CN101774953A - Preparation method for substituted diphenyl sulfide - Google Patents
Preparation method for substituted diphenyl sulfide Download PDFInfo
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- CN101774953A CN101774953A CN201010101517A CN201010101517A CN101774953A CN 101774953 A CN101774953 A CN 101774953A CN 201010101517 A CN201010101517 A CN 201010101517A CN 201010101517 A CN201010101517 A CN 201010101517A CN 101774953 A CN101774953 A CN 101774953A
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Abstract
本发明属于有机化学物质制备技术领域，涉及一种有机化合物质的新的合成方法，特别是取代二苯硫醚的制备方法，在路易斯酸催化剂存在条件下，控制反应温度为-10℃～70℃，使取代苯次磺酰氯在氯代烷烃溶剂中与取代苯发生傅克反应生成取代二苯硫醚；所选用的氯代烷烃溶剂为混合溶剂，属于一氯甲烷、二氯甲烷、氯仿、四氯化碳、二氯乙烷和四氯乙烷中的一种或几种的混合；所选用的催化剂为无水三氯化铁、无水三氯化铝、四氯化钛和无水三氟化硼中的一种或几种的混合；具有原料价格低、合成反应温和平稳、原料转化率高、产品选择性好、产品易于从溶剂中分离、产品收率高等特点。The invention belongs to the technical field of preparation of organic chemical substances, and relates to a new synthesis method of organic compound substances, especially a preparation method of substituted diphenyl sulfide. In the presence of a Lewis acid catalyst, the reaction temperature is controlled at -10°C to 70°C. ℃, make substituted benzenesulfenyl chloride react with substituted benzene in a chlorinated alkane solvent to generate substituted diphenyl sulfide; A mixture of one or more of carbon tetrachloride, dichloroethane and tetrachloroethane; the selected catalysts are anhydrous ferric chloride, anhydrous aluminum trichloride, titanium tetrachloride and anhydrous A mixture of one or several boron trifluorides; it has the characteristics of low raw material price, mild and stable synthesis reaction, high conversion rate of raw materials, good product selectivity, easy separation of products from solvents, and high product yield.
Description
Technical field:
The invention belongs to the organic chemicals preparing technical field, relate to a kind of preparation method of new synthetic method, particularly a kind of substituted diphenyl sulfide of organic compound material.
Background technology:
As everyone knows, fragrance sulfide especially substituted diphenyl sulfide is the organism that a class has pharmaceutical activity, it is widely used in various treatments field as pharmaceutical intermediate, such as diabetes, anti-infective, immunity, alzheimer's disease and parkinsonism etc., modern medicine preparing technical field particularly, substituted diphenyl sulfide has more development prospect widely.At present, many both at home and abroad scholars and unit carry out the research and the experiment of this respect, particularly to the preparation of substituted diphenyl sulfide or synthetic technology carrying out in various degree a large amount of discussion and research and development; For example the people such as Joseph Levy of AP Oil company take at mineral alkali K in the U.S. Pat 3254125 of application in 1966
2CO
3Synthesized the chloro diphenyl sulfide according to following reaction formula under the existence condition:
Experimental results show that, when this method prepares the chloro diphenyl sulfide, its long reaction time, yield is on the low side less than 50%, can not obtain target product with high purity by ordinary methods such as crystallizations, and have only when strong electron-withdrawing group is arranged on the aromatic nucleus above-mentioned reaction just can carry out.People such as the Wang Zhi of Chinese Academy of Sciences duty is arranged again in the technology in the 462-465 page or leaf record of " organic chemistry " the 8th phase in 1988, in no divide power slot be that raw material uses methylene dichloride to make chlorizating agent to have synthesized 4-chloro diphenyl sulfide with 35% yield with the diphenyl sulfide, obtained simultaneously 60.1% 4,4 '-dichloro-diphenyl sulfide, this method can use this variation route of electrolysis to synthesize substituted diphenyl sulfide, its shortcoming is that the selectivity of target product is low, and the task of separate targets product is heavy and will realize that suitability for industrialized production has certain difficulty.Also have people such as Yugen Zhang in the technical scheme in the 3495th page of record of " Organic Letters " the 9th phase in 2007, in the DMF solvent, under Ni class catalyzer and potassium tert.-butoxide condition, successfully synthesize substituted diphenyl sulfide by following route:
X＝Cl，Br，I
The shortcoming of this method is that to select the phenyl-iodide compounds for use be raw material, and it costs an arm and a leg, and is difficult to the synthetic target product of high yield under the reaction process complexity, normal condition.End is got up, and have not yet to see the technological process of ideal substituted diphenyl sulfide preparation, and existing preparation or synthesis technique ubiquity the reaction process complexity, and product yield is low, and the cost height is difficult to obtain the target product of high yield under the normal condition.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that prior art exists, seek to provide a kind of new preparation process of substituted diphenyl sulfide, this method is under solvent action, and the substituted diphenyl sulfide product is prepared in control reaction temperature and the chemosynthesis of catalyzer condition.
To achieve these goals, the present invention is under the lewis acid catalyst existence condition, and control reaction temperature is-10 ℃～70 ℃, makes substituted benzene time SULPHURYL CHLORIDE generate substituted diphenyl sulfide with substituted benzene generation Friedel-Crafts reaction in chlorinated paraffin solvent; Earlier in the containers such as flask that prolong and chlorine inlet tube are housed, add substituted diphenylamine disulfide and tetracol phenixin by weight percentage, dissolve the chlorine that slow feeding vitriol oil drying is crossed in back 3 hours fully in stirring and also be no more than 20 ℃ with water-bath maintenance reaction solution internal temperature during the course, keep 2 hours stopped reaction of this temperature stirring then; Normal pressure steams tetracol phenixin, and vacuum distilling obtains the red benzene time SULPHURYL CHLORIDE of boiling point 40-49 ℃/2mmHg; Add substituted benzene, chloroparaffin and lewis acid catalyst again in flask by weight percentage, the interior temperature of water-bath maintenance flask is 25 ℃ under the agitation condition, drips the inferior SULPHURYL CHLORIDE of the substituted benzene that has prepared then 1 hour; Dropwise under this temperature, to continue to stir and finished reaction in 2 hours; Then reaction mixture is slowly poured in the mixture of ice and water of stirring into layering, anhydrous magnesium sulfate drying; Chloroparaffin and unreacted substituted benzene are removed in air distillation; Last vacuum distilling is collected target fraction and is obtained colourless liquid substituted diphenyl sulfide product; The equation general formula of its Fu Ke chemical reaction is:
Wherein R is a kind of among H, C1～C4 alkyl, C1～C4 alkoxyl group, ethanoyl, propionyl, F, Cl or the Br; R ' is a kind of among H, C1～C4 alkyl, C1～C4 alkoxyl group, ethanoyl, propionyl, F, Cl or the Br.
The selected chlorinated paraffin solvent of the present invention is a mixed solvent, belongs to one or more the mixing in monochloro methane, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride and the tetrachloroethane; Temperature of reaction is-10 ℃～70 ℃, more preferably 0 ℃～40 ℃, is preferably 20～30 ℃; Selected catalyzer is one or more the mixing in FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous), titanium tetrachloride and the anhydrous boron trifluoride.
The present invention compared with prior art has that cost of material is low, building-up reactions is gentle steadily, feed stock conversion is high, product selectivity good, product is easy to characteristics such as separation, product yield height from solvent.
Embodiment:
Below by embodiment the present invention is further described.The substituted diphenyl sulfide that substituted diphenyl sulfide involved in the present invention is not limited only among the embodiment to be comprised.
Synthesizing of embodiment 1:4-fluorine diphenyl sulfide
In the 1000mL flask that prolong (the alkali lye device of termination monochlor(in)ate calcium drying tube and absorption chlorine on the prolong) and chlorine inlet tube are housed, add diphenyl disulfide (88g earlier, 0.4mol), the 300mL tetracol phenixin, open magnetic agitation, treat to dissolve fully the back and slowly fed the dry chlorine of crossing of the vitriol oil 3 hours; In this process, keep the reaction solution internal temperature to be no more than 20 ℃, keep this temperature to stir 2 hours stopped reaction then with water-bath; Air distillation tetracol phenixin, vacuum distilling obtain the red benzene time SULPHURYL CHLORIDE 51g of boiling point 40-49 ℃/2mmHg, yield 88%; Add 100mL fluorobenzene and 100mL tetracol phenixin again in the 500mL flask, (16g 0.12mol), starts stirring to aluminum trichloride (anhydrous), and it is 25 ℃ that water-bath keeps the interior temperature of bottle, and (11.3g 0.1mol), dripped 1 hour to drip the benzene time SULPHURYL CHLORIDE that has prepared then; Dropwise under this temperature, to continue to stir and finished reaction in 2 hours; Then reaction mixture is slowly poured in the 200g mixture of ice and water of stirring into layering, anhydrous magnesium sulfate drying; Tetracol phenixin and unreacted fluorobenzene are removed in air distillation; The cut that 160-165 ℃/266Pa of boiling point is collected in last vacuum distilling obtains colourless liquid 18g, and yield 82% is 4-fluorine diphenyl sulfide product;
1HNMR (400M, CDCl
3, TMS): δ=7.01 (ddt, J=8.8Hz, 2H), 7.20-7.22 (m, 1H), 7.23-7.29 (m, 4H), 7.36 (ddt, 8.8Hz, 2H).
Synthesizing of embodiment 2:4-chloro diphenyl sulfide
Earlier according to corresponding steps among the embodiment 1 and the synthetic 4-chlorobenzene time SULPHURYL CHLORIDE of mode; Add 100mL benzene and 100mL tetracol phenixin again in the 500mL flask, (16g 0.12mol), starts stirring to aluminum trichloride (anhydrous), and water-bath keeps 25 ℃ of the interior temperature of bottle, and (18g 0.1mol), dripped 2 hours to drip the 4-chlorobenzene time SULPHURYL CHLORIDE that has prepared then; Dropwise under 25 ℃ of temperature, to continue to stir and finished reaction in 2 hours; Then reaction mixture is slowly poured in the 200g mixture of ice and water of stirring into layering, anhydrous magnesium sulfate drying; The cut that tetracol phenixin and 190-196 ℃/266Pa of unreacted benzene final vacuum distillation collection boiling point are removed in last air distillation obtains colourless liquid 19.5g, and yield 74% is 4-chloro diphenyl sulfide product;
1HNMR (400M, CDCl
3, TMS): δ=7.03 (ddt, J=8.8Hz, 2H), 7.22-7.24 (m, 1H), 7.25-7.29 (m, 4H), 7.38 (ddt, 8.8Hz, 2H).
Synthesizing of embodiment 3:4-chloro-4 '-methyldiphenyl thioether
Earlier according to corresponding steps among the embodiment 1 and the synthetic 4-chlorobenzene time SULPHURYL CHLORIDE of mode; Add 100mL toluene and 100mL ethylene dichloride again in the 500mL flask, (16g 0.12mol), starts stirring to Zinc Chloride Anhydrous, and water-bath keeps 25 ℃ of the interior temperature of bottle, and (18g 0.1mol), dripped 2 hours to drip the 4-chlorobenzene time SULPHURYL CHLORIDE that has prepared then; Dropwise under 25 ℃ of temperature, to continue to stir and finished reaction in 2 hours; Then reaction mixture is slowly poured in the 200g mixture of ice and water of stirring into layering, anhydrous magnesium sulfate drying; The cut that tetracol phenixin and 183-185 ℃/266Pa of unreacted toluene final vacuum distillation collection boiling point are removed in last air distillation obtains colourless liquid 16.7g, and yield 71% is 4-chloro-4 '-methyldiphenyl thioether product;
1HNMR (400M, CDCl
3, TMS): δ=7.12-7.29 (m, 8H), 1.56 (s, 3H).
Claims (2)
1. the preparation method of a substituted diphenyl sulfide, it is characterized in that under the lewis acid catalyst existence condition, control reaction temperature is-10 ℃～70 ℃, makes substituted benzene time SULPHURYL CHLORIDE generate substituted diphenyl sulfide with substituted benzene generation Friedel-Crafts reaction in chlorinated paraffin solvent; Earlier in the flask that prolong and chlorine inlet tube are housed, add substituted diphenylamine disulfide and tetracol phenixin by weight percentage, dissolve the chlorine that slow feeding vitriol oil drying is crossed in back 3 hours fully in stirring and also be no more than 20 ℃ with water-bath maintenance reaction solution internal temperature during the course, keep 2 hours stopped reaction of this temperature stirring then; Normal pressure steams tetracol phenixin, and vacuum distilling obtains the red benzene time SULPHURYL CHLORIDE of boiling point 40-49 ℃/2mmHg; Add substituted benzene, chloroparaffin and lewis acid catalyst again in flask by weight percentage, the interior temperature of water-bath maintenance flask is 25 ℃ under the agitation condition, drips the inferior SULPHURYL CHLORIDE of the substituted benzene that has prepared then 1 hour; Dropwise under this temperature, to continue to stir and finished reaction in 2 hours; Then reaction mixture is slowly poured in the mixture of ice and water of stirring into layering, anhydrous magnesium sulfate drying; Chloroparaffin and unreacted substituted benzene are removed in air distillation; Last vacuum distilling is collected target fraction and is obtained colourless liquid substituted diphenyl sulfide product; The equation general formula of its Fu Ke chemical reaction is:
Wherein R is a kind of among H, C1～C4 alkyl, C1～C4 alkoxyl group, ethanoyl, propionyl, F, Cl or the Br; R ' is a kind of among H, C1～C4 alkyl, C1～C4 alkoxyl group, ethanoyl, propionyl, F, Cl or the Br.
2. the preparation method of substituted diphenyl sulfide according to claim 1, it is characterized in that selected chlorinated paraffin solvent is a mixed solvent, belong to one or more the mixing in monochloro methane, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride and the tetrachloroethane; Selected catalyzer is one or more the mixing in FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous), titanium tetrachloride and the anhydrous boron trifluoride.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351622A (en) * | 2011-08-19 | 2012-02-15 | 浙江大学 | Method for preparing (Z)-1,2-disulfide-1-olefin by catalysis of metal copper salt |
| CN102516139A (en) * | 2011-11-02 | 2012-06-27 | 浙江工业大学 | Synthesis method of phenyl sulfide compound |
| CN104961694A (en) * | 2015-06-23 | 2015-10-07 | 天津师范大学 | Diphenyl sulfide compound displaced with double triazole and preparing method and application thereof |
| CN108997180A (en) * | 2018-09-10 | 2018-12-14 | 浙江扬帆新材料股份有限公司 | A kind of method of one pot process substituted diphenyl sulfide |
| TWI652254B (en) | 2017-08-01 | 2019-03-01 | 財團法人工業技術研究院 | Method for preparing compound and method for preparing polymer employing the same |
| CN109734636A (en) * | 2018-12-29 | 2019-05-10 | 天津久日新材料股份有限公司 | A kind of preparation method of 4- benzoyl -4 '-methyl-diphenyl sulfide |
| US10723841B2 (en) | 2017-08-01 | 2020-07-28 | Industrial Technology Research | Method for preparing compound and method for preparing polymer employing the same |
| CN116273169A (en) * | 2021-12-20 | 2023-06-23 | 安庆莱霆光电科技有限公司 | Supported catalyst and its preparation method |
-
2010
- 2010-01-21 CN CN201010101517A patent/CN101774953A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351622A (en) * | 2011-08-19 | 2012-02-15 | 浙江大学 | Method for preparing (Z)-1,2-disulfide-1-olefin by catalysis of metal copper salt |
| CN102351622B (en) * | 2011-08-19 | 2013-12-25 | 浙江大学 | Method for preparing (Z)-1,2-disulfide-1-olefin by catalysis of metal copper salt |
| CN102516139A (en) * | 2011-11-02 | 2012-06-27 | 浙江工业大学 | Synthesis method of phenyl sulfide compound |
| CN104961694A (en) * | 2015-06-23 | 2015-10-07 | 天津师范大学 | Diphenyl sulfide compound displaced with double triazole and preparing method and application thereof |
| TWI652254B (en) | 2017-08-01 | 2019-03-01 | 財團法人工業技術研究院 | Method for preparing compound and method for preparing polymer employing the same |
| US10723841B2 (en) | 2017-08-01 | 2020-07-28 | Industrial Technology Research | Method for preparing compound and method for preparing polymer employing the same |
| CN108997180A (en) * | 2018-09-10 | 2018-12-14 | 浙江扬帆新材料股份有限公司 | A kind of method of one pot process substituted diphenyl sulfide |
| CN109734636A (en) * | 2018-12-29 | 2019-05-10 | 天津久日新材料股份有限公司 | A kind of preparation method of 4- benzoyl -4 '-methyl-diphenyl sulfide |
| CN116273169A (en) * | 2021-12-20 | 2023-06-23 | 安庆莱霆光电科技有限公司 | Supported catalyst and its preparation method |
| CN116273169B (en) * | 2021-12-20 | 2024-11-01 | 安庆莱霆光电科技有限公司 | Supported catalyst and preparation method thereof |
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Application publication date: 20100714 |