CN106631937B - A kind of synthetic method of 4,4 '-dimercapto diphenyl sulfides - Google Patents
A kind of synthetic method of 4,4 '-dimercapto diphenyl sulfides Download PDFInfo
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- CN106631937B CN106631937B CN201610817093.6A CN201610817093A CN106631937B CN 106631937 B CN106631937 B CN 106631937B CN 201610817093 A CN201610817093 A CN 201610817093A CN 106631937 B CN106631937 B CN 106631937B
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- dimercapto
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- diphenyl
- diphenyl sulfide
- sulfides
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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
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
Abstract
The invention discloses one kind 4; the synthetic method of 4 '-dimercapto diphenyl sulfides reacts with chlorosulfonic acid using diphenyl sulfide as starting material and is made 4; 4 '-two (chlorosulfonyl) diphenyl sulfides; then it under red phosphorus, iodine effect, is restored with glacial acetic acid and 4,4 '-two (acetylthio) diphenyl sulfides is made; then hydrolysis is made 4; 4 '-dimercapto diphenyl sulfide crude products are finally recrystallized to give 4,4 '-dimercapto diphenyl sulfide fine work.Raw material used in the present invention is easy to get, technique is advanced, is easy to industrialized production.
Description
Technical field
The present invention relates to a kind of 4,4 '-dimercapto diphenyl sulfide preparation methods.
Technical background
4,4 '-dimercapto diphenyl sulfides are a kind of novel high polymer material monomers, are widely used in medicine, pesticide and dye
The fine chemicals intermediates such as material.In particular for the aspect of conductive photoelectric material.Small with ray refractive index, permeability is high,
The features such as gained polymeric material water white transparency degree is high.
The method that CN02114837.6 reports a kind of 4,4 '-dimercapto diphenyl sulfides of synthesis；Zinc powder needed for the method disappears
Consumption is big, expensive, and obtained product isomers is more, content is not high.
JP06032773 and JP04264064 is reported with two reaction of Salmon-Saxl of diphenyl sulfide and dichloro, is restored and is made through triphenylphosphine
4,4 '-dimercapto diphenyl sulfides are obtained, which similarly has the deficiencies of isomers is more, and triphenylphosphine is expensive, greatly limit
Its industrialized production is made.
Liu Anchang, Li Gaofeng of Wuhan Engineering Univ et al. exist《Wuhan Engineering Univ's journal》With Feng of Qingdao University of Science and Technology
Bai Cheng, well is beautiful pretty, and Liu Peng et al. exists《Qingdao University of Science and Technology's journal (natural science edition)》Equal pertinent literatures report 4,4 '-two mercaptos
The related synthesis and preparation process of base diphenyl sulfide, but to there is production process seriously polluted for these techniques, is unsuitable for industrializing
Production.
Invention content
It is an object of the invention to overcome many drawbacks of existing synthetic method, a kind of concise in technology, high income, energy are provided
The method of the synthesis 4,4 '-dimercapto diphenyl sulfide of enough industrial applications.
In order to achieve the above technical purposes, the present invention adopts the following technical scheme that：
A kind of preparation method of 4,4 '-dimercapto diphenyl sulfides, 4,4 '-dimercapto diphenyl sulfides tool prepared by the method
Have with lower structure：
Further, the preparation method specifically comprises the following steps：
The preparation of (1) 4,4 '-two (chlorosulfonyl) diphenyl sulfide (I)
Diphenyl sulfide, inert organic solvents are added in a kettle, sulfonation accelerating agent is refrigerated to 0--10 DEG C.It is slowly added dropwise
Chlorosulfonic acid, drop finish, and warm naturally to 10-20 DEG C, and heating is finished, and start that aryl chloride transforming agent is added dropwise, drop finishes, and is warming up to 25-30
DEG C, it reacts 3-8 hours, obtains pale yellow solution.It waits for that sulfonated liquid is naturally cooling to 10 DEG C or so, is added into another reaction kettle a large amount of
Ice water, sulfonated liquid is slowly added dropwise into reaction kettle at 10 DEG C or so, it is solid to drip off within about 2 hours a large amount of whites of appearance control temperature
Body stops stirring, is poured into liquid separation kettle and divides water.Organic layer with distillation still depressurize precipitation, until substantially it is solvent-free steam after stop
Distillation.It then cools to room temperature, filters.White particle sprills are obtained, it is dry, obtain product 4,4 '-two (chlorosulfonyl) diphenyl sulfide
Ether (I).
The preparation of (2) 4,4 '-two (acetylthio) diphenyl sulfides (II)
Glacial acetic acid, iodine grain, red phosphorus are added into reaction kettle, temperature rising reflux 30-60min is subsequently cooled to 35-60 DEG C, adds
Enter 4,4 '-two (chlorosulfonyl) diphenyl sulfides (I), be to slowly warm up to reflux after the reaction was continued 3-5 hours, obtain purple liquid.It takes advantage of
Heat filters, and recycles red phosphorus, and filtrate, which is cooled to room temperature, becomes yellowish-brown slurry, and a large amount of cold water, stirred crystallization is added in when room temperature
It 1-2 hours, filters, dry 4,4 '-two (acetylthio) diphenyl sulfides (II).
The preparation of (3) 4,4 '-dimercapto diphenyl sulfide (III) crude products
In a kettle, it takes inorganic base soluble in water, 4,4 '-two (acetylthio) diphenyl sulfides (II) is added, stir back
Stream 2-4 hours, makes solid fully dissolve, filters while hot, removes insoluble matter, filtrate is cooled to room temperature, it is dense that quality is slowly added dropwise
The hydrochloric acid of degree 30%, it is 2.5-3.5 to make pH.Stirring and crystallizing 3-4 hours filters, and it is thick to obtain 4,4 '-dimercapto diphenyl sulfides (III)
Product.With re crystallization from toluene, faint yellow flat crystal is obtained.
The preparation of (4) 4,4 '-dimercapto diphenyl sulfide (IV) fine work
Into reaction kettle, 4,4 '-dimercapto diphenyl sulfide (III) crude products, toluene, water, zinc powder, heating, side heating is added
While mass concentration 10-20% hydrochloric acid is slowly added dropwise, interior temperature rises to 80 DEG C or so after being added dropwise.Solution becomes colourless clear at this time
Night, fast filtering, while hot liquid separation, upper toluene crystallization obtain white plates crystal 4,4 '-dimercapto diphenyl sulfide (IV) fine work.
The inert organic solvents are one in nitrobenzene, o-dichlorohenzene, dichloroethanes, tetrachloroethanes, carbon tetrachloride
Kind is a variety of.Preferably dichloroethanes.Inert organic solvents, which are added, can effectively reduce the dosage of sulfonating agent chlorosulfonic acid.Simultaneously
Dilute reaction solution local concentration keeps reaction mild.
The sulfonation accelerating agent is any one in sodium chloride, sodium sulphate.Preferably sodium chloride.Sulfonation is added to promote
Agent can make the sulfuric acid conversion produced in chlorosulfonation be niter cake, and reaction balance moves to right, and improves reaction yield, reduces chlorine
The dosage of sulfonic acid.
The aryl chloride transforming agent is any one in phosphorus trichloride, phosphorus pentachloride, thionyl chloride.Preferably chlorination
Sulfoxide.It is a reversible reaction that sulfo group, which is converted into sulfuryl chlorio, individually sulfo group cannot be made to be completely converted into sulfonic acid chloride with chlorosulfonic acid
Base, aryl chloride transforming agent, which is added, can greatly improve reaction yield.
The molar ratio of the diphenyl sulfide and chlorosulfonic acid is 1:6-8.The mass ratio of diphenyl sulfide and inert organic solvents
It is 1:5-10.The mass ratio of diphenyl sulfide and sulfonation accelerating agent is 1:0.1-0.3.The matter of diphenyl sulfide and aryl chloride transforming agent
Amount is than being 1:0.3-0.6.
The molar ratio of 4,4 '-two (chlorosulfonyl) diphenyl sulfides and red phosphorus is 1:2-5.4,4 '-two (chlorine sulphonyl
Base) mass ratio of diphenyl sulfide and glacial acetic acid is 1:2-4.The mass ratio of 4,4 '-two (chlorosulfonyl) diphenyl sulfides and iodine grain is
1:0.01-0.02。
The molar ratio of 4,4 '-two (acetylthio) diphenyl sulfides and inorganic base is 1:3-6.Lye mass concentration is
5%-10%.
The inorganic base is any one of potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, preferably hydroxide
Sodium.
Described 4,4 '-dimercapto diphenyl sulfide crude product, toluene, water, zinc powder, mass concentration 10%-20% hydrochloric acid solutions
Mass ratio be 1:5-10:3-5:0.05-0.1:5-8.
The present invention is a kind of synthetic method of 4,4 '-dimercapto diphenyl sulfides, is had compared with existing other methods as follows
Remarkable advantage：
1. total yield of products is high, reach 80% or more；
2. product purity is high, HPLC reaches 99.5% or more；
3. being easy to industrialize.
Net reaction of the present invention is as follows：
Specific implementation mode
Embodiment 1：
The preparation of (1) 4,4 '-two (chlorosulfonyl) diphenyl sulfide
20kg diphenyl sulfides, 180kg dichloroethanes are added in 500L reaction kettles, 3kg sodium chloride is refrigerated to -2 DEG C.It is slow
It is slow that 90kg chlorosulfonic acids are added dropwise, it is added dropwise within about 2 hours.Drop finishes, and warms naturally to 15 DEG C, and heating is finished, and starts that 10kg chlorinations are added dropwise
Sulfoxide, about 20min are added dropwise.Drop finishes, and is warming up to 27 DEG C, reacts 5 hours, obtains pale yellow solution.Wait for sulfonated liquid Temperature fall
To 10 DEG C or so, a large amount of ice water is added into another reaction kettle, control temperature is slowly added dropwise at 10 DEG C or so into reaction kettle
Sulfonated liquid drips off and a large amount of white solids occurs for about 2 hours, stops stirring, is poured into liquid separation kettle and divides water.Organic layer distillation still
Depressurize precipitation, until substantially it is solvent-free steam after stop distillation.It then cools to room temperature, filters.White particle sprills are obtained, are done
It is dry, obtain product 4,4 '-two (chlorosulfonyl) diphenyl sulfide (I) 39kg, yield 94.6%.
The preparation of (2) 4,4 '-two (acetylthio) diphenyl sulfides
In the reaction kettle of 100L, glacial acetic acid 80kg, iodine grain 0.6kg, red phosphorus 17kg, temperature rising reflux 40min is added, then
It is cooled to 45 DEG C, is added 35kg4,4 '-two (chlorosulfonyl) diphenyl sulfides (I), it is 3 small to be to slowly warm up to after reflux that the reaction was continued
When, obtain purple liquid.It filters while hot, recycles red phosphorus, filtrate, which is cooled to room temperature, becomes yellowish-brown slurry, and when room temperature is added
250kg cold water, stirred crystallization 1 hour filter, dry 4,4 '-two (acetylthio) diphenyl sulfide (II) 29kg, yield
95%.
The preparation of (3) 4,4 '-dimercapto diphenyl sulfide crude products
In the reaction kettle of 500L, 15kg sodium hydroxides is taken to be dissolved in 200L water, 4,4 '-two (acetylthios) are added
Diphenyl sulfide (II) 25kg, is stirred at reflux 3 hours, so that solid is fully dissolved, filter while hot, removes insoluble matter, filtrate is cooled down
To room temperature, the hydrochloric acid of mass concentration 30% is slowly added dropwise, it is 3 to make pH.Stirring and crystallizing 3 hours filters, obtains 4,4 '-dimercaptos two
Diphenyl sulfide (III) crude product 18.5kg.With 200kg re crystallization from toluene, 4,4 '-dimercapto diphenyl sulfide of faint yellow flat crystal
(III) 18kg, yield 96.3%, HPLC 99.25%.
The preparation of (4) 4,4 '-dimercapto diphenyl sulfide fine work
In 500L reaction kettles, 4,4 '-dimercapto diphenyl sulfide (III) crude product 15kg, 100kg toluene of addition, 60kg water,
15% hydrochloric acid 100kg of mass concentration is slowly added dropwise in heating in 1kg zinc powders, heating, and interior temperature rises to 80 DEG C or so after being added dropwise.
Solution becomes the colourless stillness of night at this time, fast filtering, liquid separation while hot, and upper toluene crystallization obtains 14.4kg white plates crystals 4,4 '-
Dimercapto diphenyl sulfide (IV) fine work.HPLC99.68%, yield 96%.Total recovery 83%.
Embodiment 2：
Changing the inert organic solvents in step (1) into 150kg carbon tetrachloride, thionyl chloride changes 8kg phosphorus pentachlorides into,
He obtains 4,4 '-two (chlorosulfonyl) diphenyl sulfide (I) 37kg, yield 89.8% with embodiment 1.
Embodiment 3：
Change the sodium hydroxide in step (3) into 20kg potassium hydroxide, other obtain 4,4 '-dimercapto hexichol with embodiment 1
Thioether (III) 18.2kg, yield 97.3%, HPLC 99.38%.
Embodiment 4：
Change the sodium chloride in step (1) into 4kg sodium sulphate, other obtain 4,4 '-two (chlorosulfonyls) two with embodiment 1
Diphenyl sulfide (I) 37.5kg, yield 91%.
Embodiment 5：Zinc powder weight in step (4) is reduced into 0.8kg, other obtain 14.2kg white plates with embodiment 1
Crystal 4,4 '-dimercapto diphenyl sulfide (IV) fine work.HPLC99.75%, yield 94.7%.
Finally illustrate, the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to compared with
Good embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the right of invention.
Claims (9)
1. the preparation method of 4,4 '-dimercapto diphenyl sulfide of one kind, 4,4 '-dimercapto diphenyl sulfides prepared by the method have
Such as lower structure：
Preparation method includes the following steps：
The preparation of (1) 4,4 '-two (chlorosulfonyl) diphenyl sulfide (I)
Be added diphenyl sulfide in a kettle, inert organic solvents, sulfonation accelerating agent, the sulfonation accelerating agent be sodium chloride,
Any one in sodium sulphate, is refrigerated to 0--10 DEG C, and chlorosulfonic acid is slowly added dropwise, and drop finishes, and warms naturally to 10-20 DEG C, heating
Finish, starts that aryl chloride transforming agent is added dropwise, drop finishes, and is warming up to 25-30 DEG C, reacts 3-8 hours, obtains pale yellow solution, wait for sulfonation
Liquid is naturally cooling to 10 DEG C, a large amount of ice water is added into another reaction kettle, control temperature is at 8-15 DEG C, slowly into reaction kettle
Sulfonated liquid is added dropwise, drips off within 1-3 hours and a large amount of white solids occurs, stops stirring, is poured into liquid separation kettle and divides water, organic layer steams
Evaporate kettle decompression precipitation, until substantially it is solvent-free steam after stop distillation, then cool to room temperature, filter, obtain white particle sprills,
It is dry, obtain product 4,4 '-two (chlorosulfonyl) diphenyl sulfide (I)；
The preparation of (2) 4,4 '-two (acetylthio) diphenyl sulfides (II)
Glacial acetic acid, iodine grain, red phosphorus are added into reaction kettle, temperature rising reflux 30-60min is subsequently cooled to 35-60 DEG C, is added 4,
4 '-two (chlorosulfonyl) diphenyl sulfides (I), be to slowly warm up to reflux after the reaction was continued 3-5 hours, obtain purple liquid, take out while hot
Red phosphorus is recycled in filter, and filtrate, which is cooled to room temperature, becomes yellowish-brown slurry, and a large amount of cold water is added in when room temperature, and stirred crystallization 1-2 is small
When, it filters, dry 4,4 '-two (acetylthio) diphenyl sulfides (II)；
The preparation of (3) 4,4 '-dimercapto diphenyl sulfide (III) crude products
In a kettle, it takes inorganic base soluble in water, 4,4 '-two (acetylthio) diphenyl sulfides (II) is added, are stirred at reflux 2-4
Hour, so that solid is fully dissolved, filter while hot, removes insoluble matter, filtrate is cooled to room temperature, mass concentration 30% is slowly added dropwise
Hydrochloric acid, make pH be 2.5-3.5, stirring and crystallizing 3-4 hour, suction filtration, obtain 4,4 '-dimercapto diphenyl sulfide (III) crude products, use first
Benzene recrystallizes, and obtains faint yellow flat crystal；
The preparation of (4) 4,4 '-dimercapto diphenyl sulfide (IV) fine work
Into reaction kettle, 4,4 '-dimercapto diphenyl sulfide (III) crude products, toluene, water, zinc powder is added, heating is delayed in heating
Slow that mass concentration 10-20% hydrochloric acid is added dropwise, interior temperature rises to 70-90 DEG C after being added dropwise, and solution becomes colorless clear liquid at this time, quickly
Filtering, liquid separation while hot, upper toluene crystallization obtain white plates crystal 4,4 '-dimercapto diphenyl sulfide (IV) fine work.
2. the preparation method of described in claim 14,4 '-dimercapto diphenyl sulfides, which is characterized in that described in step (1)
Inert organic solvents are one or more in nitrobenzene, o-dichlorohenzene, dichloroethanes, tetrachloroethanes, carbon tetrachloride.
3. the preparation method of described in claim 14,4 '-dimercapto diphenyl sulfides, which is characterized in that described in step (1)
Sulfonation accelerating agent is sodium chloride.
4. the preparation method of described in claim 14,4 '-dimercapto diphenyl sulfides, which is characterized in that described in step (1)
Aryl chloride transforming agent is thionyl chloride.
5. the preparation method of described in claim 14,4 '-dimercapto diphenyl sulfides, which is characterized in that described in step (1)
The molar ratio of diphenyl sulfide and chlorosulfonic acid is 1：The mass ratio of 6-8, diphenyl sulfide and inert organic solvents is 1：5-10, diphenyl sulfide
The mass ratio of ether and sulfonation accelerating agent is 1:The mass ratio of 0.1-0.3, diphenyl sulfide and aryl chloride transforming agent is 1：0.3-
0.6。
6. the preparation method of described in claim 14,4 '-dimercapto diphenyl sulfides, which is characterized in that described in step (2)
The molar ratio of 4,4 '-two (chlorosulfonyl) diphenyl sulfides and red phosphorus is 1：2-5；4,4 '-two (chlorosulfonyl) diphenyl sulfides and ice
The mass ratio of acetic acid is 1：2-4；The mass ratio of 4,4 '-two (chlorosulfonyl) diphenyl sulfides and iodine grain is 1：0.01-0.02.
7. the preparation method of described in claim 14,4 '-dimercapto diphenyl sulfides, which is characterized in that described in step (3)
The molar ratio of 4,4 '-two (acetylthio) diphenyl sulfides and inorganic base is 1：3-6；Lye mass concentration is 5%-10%.
8. the preparation method of described in claim 14,4 '-dimercapto diphenyl sulfides, which is characterized in that described in step (3)
Inorganic base is any one of potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide.
9. the preparation method of described in claim 14,4 '-dimercapto diphenyl sulfides, which is characterized in that described in step (4)
4,4 '-dimercapto diphenyl sulfide crude products, toluene, water, zinc powder, mass concentration 10%-20% hydrochloric acid solutions mass ratio be 1：5-
10：3-5：0.05-0.1：5-8.
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| JP4257558B2 (en) * | 1999-12-15 | 2009-04-22 | ソニー株式会社 | Viewing detection system, video playback apparatus, and viewing detection method |
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| JPH0314557A (en) * | 1989-06-09 | 1991-01-23 | Sumitomo Seika Chem Co Ltd | Production of 4,4'-thiobisbenzene thiol |
| JP2785876B2 (en) * | 1989-11-10 | 1998-08-13 | 住友精化株式会社 | Method for producing aromatic dithiol |
| JPH04257558A (en) * | 1991-02-07 | 1992-09-11 | Sumitomo Seika Chem Co Ltd | Production of 4,4'-thiobisbenzenethiol |
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| JP4257558B2 (en) * | 1999-12-15 | 2009-04-22 | ソニー株式会社 | Viewing detection system, video playback apparatus, and viewing detection method |
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| Title |
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| 光学树脂单体4，4"-二巯基二苯硫醚双甲基丙烯酸酯的合成;张勇，等;《化学世界》;20101231(第2期);105-107 * |
| 张勇，等.光学树脂单体4，4"-二巯基二苯硫醚双甲基丙烯酸酯的合成.《化学世界》.2010,(第2期),105-107. * |
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