CN102093269A - Synthesis method of 4,4'-thiobisbenzenethiol - Google Patents
Synthesis method of 4,4'-thiobisbenzenethiol Download PDFInfo
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- CN102093269A CN102093269A CN201110069713XA CN201110069713A CN102093269A CN 102093269 A CN102093269 A CN 102093269A CN 201110069713X A CN201110069713X A CN 201110069713XA CN 201110069713 A CN201110069713 A CN 201110069713A CN 102093269 A CN102093269 A CN 102093269A
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- thiophenol
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Abstract
The invention discloses a synthesis method of 4,4'-thiobisbenzenethiol. The method comprises the following steps of: 1) esterfying, namely adding acetic anhydride into phenthiol serving as an initiative raw material dropwise for reacting, and laminating; 2) etherifying, namely adding a solvent, iodine and sulfur dichloride into an organic layer I obtained in the step 1) for reacting, laminating, decompressing an organic layer II and removing the solvent to obtain a yellow solid; 3) hydrolyzing, namely adding sodium hydroxide and the yellow solid into water for a warming reflux reaction, adding hydrochloric acid solution dropwise, and filtering to obtain a white solid; and 4) recrystallizing, namely recrystallizing the white solid with a recrystallizing solvent to obtain white crystalline 4,4'-thiobisbenzenethiol. The 4,4'-thiobisbenzenethiol synthesized by the method has the characteristics of simple process and high yield.
Description
Technical field
The present invention relates to a kind of 4, the synthetic method of 4 '-dimercapto diphenyl sulfide.
Background technology
Suc as formula 4 shown in the I, 4 '-dimercapto diphenyl sulfide is widely used in fine chemicals intermediates such as medicine, agricultural chemicals and dyestuff.
Formula I
CN02114837.6 has reported that with diphenyl sulfide, chlorsulfonic acid be starting raw material, makes 4 through chlorosulphonation, zinc powder reduction, 4 '-dimercapto diphenyl sulfide; The required zinc consumption amount of this method is big, cost an arm and a leg, and prepared product isomer is many, content is not high.JP06032773 and JP04264064 have reported with diphenyl sulfide and dichloro two reaction of Salmon-Saxl, make 4 through the triphenylphosphine reduction, 4 '-dimercapto diphenyl sulfide, this method exists isomer many too, deficiencies such as triphenylphosphine costs an arm and a leg have limited its suitability for industrialized production greatly.
Summary of the invention
The technical problem to be solved in the present invention provide that a kind of technology is succinct, yield is high 4, the synthetic method of 4 '-dimercapto diphenyl sulfide.
In order to solve the problems of the technologies described above, the invention provides a kind ofly 4, the synthetic method of 4 '-dimercapto diphenyl sulfide may further comprise the steps:
1), esterification:
Drip aceticanhydride in thiophenol, being warming up to 80～90 ℃ of reactions has not then had thiophenol until the GC analysis; After the reaction product for the treatment of gained is cooled to 5～15 ℃, add water, get the organic layer I that is positioned at lower floor of gained after the layering; The mol ratio of thiophenol and aceticanhydride is 1: 1.1～1.5;
2), etherificate:
In the organic layer I of step 1) gained, add solvent and as the iodine of catalyzer, and drip sulfur dichloride down in 10～15 ℃, in 10～15 ℃ of insulation reaction 2～4h; In the product of reaction gained, add water, get the organic layer II that is positioned at the upper strata of gained after the layering; After solvent is sloughed in organic layer II decompression, get yellow solid; The weight ratio of iodine and thiophenol is 0.9%～2%, and the mol ratio of thiophenol and sulfur dichloride is 1: 1.1～1.3;
3), hydrolysis:
In water, add sodium hydroxide and step 2) yellow solid of gained, temperature rising reflux reaction 1～3h; Be cooled to room temperature then, the dropping mass concentration is 20～40% hydrochloric acid soln, filters, and gets white solid; The mass ratio of sodium hydroxide and thiophenol is 1～2: 1, and the mol ratio of hydrochloric acid and sodium hydroxide is 1.0～1.2: 1;
4), recrystallization: white solid is carried out recrystallization with recrystallization solvent, get 4 of white crystal shape, 4 '-dimercapto diphenyl sulfide.
As of the present invention 4, the improvement of the synthetic method of 4 '-dimercapto diphenyl sulfide: the reaction times of step 1) is 1～3 hour.
As of the present invention 4, the further improvement of the synthetic method of 4 '-dimercapto diphenyl sulfide: the solvent step 2) is at least a in hexanaphthene, ethyl acetate and the ethylene dichloride.
As of the present invention 4, the further improvement of the synthetic method of 4 '-dimercapto diphenyl sulfide: the recrystallization solvent in the step 4) is benzene, toluene, sherwood oil or hexanaphthene.
Of the present invention 4, the synthetic method that 4 '-dimercapto diphenyl sulfide is new generates acetate thiophenol ester with thiophenol and aceticanhydride, directly generate 4 with the sulfur dichloride reaction again, 4 '-dithio ethyl ester diphenyl sulfide, the ester hydrolysis obtains 4 again, 4 '-dimercapto diphenyl sulfide, total molar yield is more than 60%.The present invention has that isomer is few, reaction temperature and, be fit to advantage such as suitability for industrialized production.Reaction formula is suc as formula shown in the II.
Formula II
Embodiment
Embodiment 1, a kind of 4, the synthetic method of 4 '-dimercapto diphenyl sulfide, carry out following steps successively:
1), esterification: add dropping 7g aceticanhydride under 11g thiophenol, the room temperature under the whipped state in the 250ml there-necked flask, drip and finish, intensification 80-90 ℃ is reacted 2h, and GC analyzes has not had thiophenol; Be cooled to 10 ℃ then, Dropwise 5 0ml water, the layering fetch bit is standby in the organic layer I of lower floor.
2), etherificate: whipped state adds the organic layer I of step 1) gained down in the 500ml there-necked flask, the mixing solutions of 75ml hexanaphthene and 25ml ethyl acetate, 0.1g iodine, be cooled to 10 ℃, 10～15 ℃ of following Dropwise 5 .5g sulfur dichloride of temperature control, drip and finish, insulation reaction 3h adds 100ml water in the reaction product of gained.The layering fetch bit is in the organic layer II on upper strata, and solvent is sloughed in decompression (0.01MPa), gets the 25g yellow solid.
3), hydrolysis: whipped state adds 80ml water, 16g sodium hydroxide down in the 250ml there-necked flask, stirring and dissolving, adding step 2) yellow solid of gained, temperature rising reflux 2h, be cooled to room temperature (20～25 ℃) then, Dropwise 5 0g (mass concentration 30%) technical hydrochloric acid, filter white solid 20g.
4), recrystallization: with the 20g white solid with 100ml benzene recrystallization, dry the 16g white crystal, fusing point: 115-116 ℃, total molar yield is 64%.Products therefrom is correct through characterizing structure.
Embodiment 2, a kind of 4, the synthetic method of 4 '-dimercapto diphenyl sulfide, carry out following steps successively:
1), esterification: whipped state adds dropping 7g aceticanhydride under 11g thiophenol, the room temperature down in the 250ml there-necked flask, drips and finishes, and 80～90 ℃ of reaction 2h heat up, GC analyzes has not had thiophenol, be cooled to 10 ℃, Dropwise 5 0ml water, the layering fetch bit is standby in the organic layer I of lower floor.
2), etherificate: whipped state adds the organic layer I of step 1) gained, 100ml hexanaphthene, 0.1g iodine down in the 500ml there-necked flask, be cooled to 10 ℃, 10～15 ℃ of following Dropwise 5 .5g sulfur dichloride of temperature control drip and finish, insulation reaction 3h adds 100ml water in the reaction product of gained.The layering fetch bit is in the organic layer II on upper strata, and solvent is sloughed in decompression (0.01MPa), gets the 23g yellow solid.
3), hydrolysis: whipped state adds down 80ml water, 16g sodium hydroxide in the 250ml there-necked flask, and stirring and dissolving adds step 2 again) yellow solid of gained, temperature rising reflux 2h, be cooled to room temperature, Dropwise 5 0g (mass concentration 30%) technical hydrochloric acid, filter white solid 19g.
4), recrystallization: with the 19g white solid with 100ml benzene recrystallization, dry the 15g white crystal, fusing point: 114-116 ℃, total molar yield is 60%.Products therefrom is correct through characterizing structure.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. 4, the synthetic method of 4 '-dimercapto diphenyl sulfide is characterized in that with the thiophenol being starting raw material, may further comprise the steps:
1), esterification:
Drip aceticanhydride in thiophenol, being warming up to 80 ~ 90 ℃ of reactions has not then had thiophenol until the GC analysis; After the reaction product for the treatment of gained is cooled to 5 ~ 15 ℃, add water, get the organic layer I that is positioned at lower floor of gained after the layering; The mol ratio of described thiophenol and aceticanhydride is 1:1.1～1.5;
2), etherificate:
In the organic layer I of step 1) gained, add solvent and as the iodine of catalyzer, and drip sulfur dichloride down in 10 ~ 15 ℃, in 10 ~ 15 ℃ of insulation reaction 2 ~ 4h; In the product of reaction gained, add water, get the organic layer II that is positioned at the upper strata of gained after the layering; After solvent is sloughed in described organic layer II decompression, get yellow solid; The weight ratio of described iodine and thiophenol is 0.9%～2%, and the mol ratio of described thiophenol and sulfur dichloride is 1:1.1～1.3;
3), hydrolysis:
In water, add sodium hydroxide and step 2) yellow solid of gained, temperature rising reflux reaction 1 ~ 3h; Be cooled to room temperature then, the dropping mass concentration is 20 ~ 40% hydrochloric acid soln, filters, and gets white solid; The mass ratio of described sodium hydroxide and thiophenol is 1 ~ 2:1, and the mol ratio of described hydrochloric acid and sodium hydroxide is 1.0 ~ 1.2:1;
4), recrystallization: white solid is carried out recrystallization with recrystallization solvent, get 4 of white crystal shape, 4 '-dimercapto diphenyl sulfide.
2. according to claim 14, the synthetic method of 4 '-dimercapto diphenyl sulfide is characterized in that: the reaction times of described step 1) is 1 ~ 3 hour.
3. according to claim 1 and 24, the synthetic method of 4 '-dimercapto diphenyl sulfide is characterized in that: the solvent described step 2) is at least a in hexanaphthene, ethyl acetate and the ethylene dichloride.
4. according to claim 34, the synthetic method of 4 '-dimercapto diphenyl sulfide is characterized in that: the recrystallization solvent in the described step 4) is benzene, toluene, sherwood oil or hexanaphthene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367464A (en) * | 2015-09-18 | 2016-03-02 | 浙江农林大学暨阳学院 | Efficient method for selectively synthesizing 2-hydroxybenzene sulfur ether compound |
| CN105566183A (en) * | 2016-03-21 | 2016-05-11 | 太原理工大学 | Preparation method of 4,4'-dimercaptodiphenylsulfide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04264064A (en) * | 1991-02-18 | 1992-09-18 | Sumitomo Seika Chem Co Ltd | Production of 4,4'-thiobisbenzenethiol |
| CN1364758A (en) * | 2002-02-07 | 2002-08-21 | 中国科学院广州化学研究所 | Synthesis process for aroamtic dithiol |
| CN1718581A (en) * | 2005-06-03 | 2006-01-11 | 何连岐 | Preparation method of biothion |
-
2011
- 2011-03-22 CN CN 201110069713 patent/CN102093269B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04264064A (en) * | 1991-02-18 | 1992-09-18 | Sumitomo Seika Chem Co Ltd | Production of 4,4'-thiobisbenzenethiol |
| CN1364758A (en) * | 2002-02-07 | 2002-08-21 | 中国科学院广州化学研究所 | Synthesis process for aroamtic dithiol |
| CN1718581A (en) * | 2005-06-03 | 2006-01-11 | 何连岐 | Preparation method of biothion |
Non-Patent Citations (2)
| Title |
|---|
| 《武汉工程大学学报》 20100331 刘安昌等 4,4'-二巯基二苯硫醚的合成 25-27,30 1-4 第32卷, 第3期 * |
| 刘安昌等: "4,4’-二巯基二苯硫醚的合成", 《武汉工程大学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367464A (en) * | 2015-09-18 | 2016-03-02 | 浙江农林大学暨阳学院 | Efficient method for selectively synthesizing 2-hydroxybenzene sulfur ether compound |
| CN105566183A (en) * | 2016-03-21 | 2016-05-11 | 太原理工大学 | Preparation method of 4,4'-dimercaptodiphenylsulfide |
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