CN111440103A - Preparation method of tert-butyl disulfide - Google Patents
Preparation method of tert-butyl disulfide Download PDFInfo
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- CN111440103A CN111440103A CN202010352387.2A CN202010352387A CN111440103A CN 111440103 A CN111440103 A CN 111440103A CN 202010352387 A CN202010352387 A CN 202010352387A CN 111440103 A CN111440103 A CN 111440103A
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Abstract
The invention discloses a preparation method of tert-butyl disulfide, which comprises the following steps of reacting di-tert-butyl sulfite with a disodium disulfide solution, and purifying to obtain a product. The invention adopts the di-tert-butyl sulfite as the raw material, compared with the prior route which generally adopts tert-butyl mercaptan or tert-butyl chloride as the raw material, the invention has innovative advantages, and the method and the raw material for preparing the di-tert-butyl sulfite are cheap and easy to purchase, have small odor and easy control, have mild reaction conditions, simple post-treatment operation, can be used for production only by using conventional equipment, and solve the problems of large production odor, difficult environmental management, high production cost and inapplicability to industrial production in the prior art.
Description
Technical Field
The invention relates to a preparation method, in particular to a preparation method of tert-butyl disulfide.
Background
Tert-butyl disulfide is an important intermediate for synthesizing various chiral drugs and bioactive substances. The tert-butyl disulfide is used as an important intermediate, can be used for synthesizing important raw materials such as tert-butyl sulfenamide, tert-butyl sulfenyl chloride and the like, and has wide application in medicine synthesis; are industrially useful as vulcanizing agents for rubbers and elastomers, and are also monomers for the synthesis of proteins and other biologically active molecules. The synthesis and post-treatment method of tert-butyl disulfide has been reported, and the problems of difficult environmental management, high production cost and the like exist in the processes of using tert-butyl mercaptan with large odor as a raw material or using tert-butyl chloride as a raw material.
Patent CN106995395A reports a process for preparing tert-butyl disulfide by reacting tert-butyl mercaptan as a starting material with sulfur powder and sodium hydroxide to give the product in 90% yield.
Patent CN101665454B also reports a method for preparing tert-butyl disulfide, in which tert-butyl mercaptan gas is passed into an absorption kettle of a mixed solution of sulfur and isopropanol, and mercaptan reacts with sulfur while passing through an isopropanol solution to form tert-butyl disulfide.
The literature, "synthesis of di-tert-butyl disulfide by elemental bromine oxidation" (chemical reagent, 2008,30(9), 709-710) also reports that tert-butyl disulfide is obtained by oxidation of elemental bromine with tert-butyl mercaptan as a raw material, and the total yield is 92.3%.
Although the improvement is made on the basis of the prior people, the problem that the odor of the raw material tert-butyl mercaptan is large and the environment is difficult to treat still exists; and the raw materials are high in price, and the transportation and storage have great risks.
The literature, microwave-assisted phase transfer catalytic synthesis of tert-butyl disulfide (chemical reagent, 2010,32(10),94 l-943) and the literature Syn. Comm.,2002,32(7), 963-substituted sodium benzoate 969 report a method for obtaining a product by reacting tert-butyl chloride serving as a raw material with disodium disulfide under the action of microwaves. However, the method needs microwave, and the industrial production is difficult to quickly find suitable equipment matching; the production cost is high.
Disclosure of Invention
The invention aims to solve the technical problems that the existing method has large production smell, is difficult to treat in environment, high in production cost and not suitable for industrial production, and aims to provide a preparation method of tert-butyl disulfide to solve the problems.
The invention is realized by the following technical scheme:
a preparation method of tert-butyl disulfide is characterized in that the tert-butyl disulfide is prepared from disodium disulfide aqueous solution and di-tert-butyl sulfite.
The invention adopts the di-tert-butyl sulfite as the raw material, compared with the prior route which generally adopts tert-butyl mercaptan or tert-butyl chloride as the raw material, the invention has innovative advantages, and the method and the raw material for preparing the di-tert-butyl sulfite are cheap and easy to purchase, have small odor and easy control, have mild reaction conditions, simple post-treatment operation, can be used for production only by using conventional equipment, and solve the problems of large production odor, difficult environmental management, high production cost and inapplicability to industrial production in the prior art.
The preparation method of tert-butyl disulfide is characterized by comprising the following specific steps:
s1, preparing a disodium disulfide aqueous solution: adding sodium sulfide and purified water into a reaction kettle, heating until the reaction is dissolved and becomes clear, adding sulfur powder, reacting until the solid is basically dissolved and becomes clear, and filtering to obtain a disodium disulfide aqueous solution;
s2, preparing di-tert-butyl sulfite: adding tert-butyl alcohol liquid into a reaction kettle, dropwise adding thionyl chloride at the temperature of 20-40 ℃, continuously stirring for 0.5 hour after dropwise adding, then adding water into the reaction system, and washing with water until the pH value is close to neutral to obtain colorless oily substance di-tert-butyl sulfite;
s3, placing the disodium disulfide aqueous solution obtained in the step S1 into a reaction kettle, cooling to 20-65 ℃, then dropwise adding di-tert-butyl sulfite, reacting after dropwise adding is completed until the raw materials react, and purifying to obtain the tert-butyl disulfide product.
Di-tert-butyl sulfite reacts with a disodium disulfide solution, and then the product is obtained after purification. The invention provides a novel method with low cost and simple route for preparing tert-butyl disulfide.
Preferably, the sodium sulfide described in step S1 is sodium sulfide nonahydrate.
Preferably, the sulfur powder described in step S1 is sublimed sulfur.
Preferably, the temperature is reduced to 20-40 ℃ in step S3.
Preferably, the molar ratio of the disodium disulfide to the di-tert-butyl sulfite in the disodium disulfide aqueous solution is: 1.0-1.5: 1.0. The invention optimizes the optimal proportioning range according to the raw material cost and the product performance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation method of the tert-butyl disulfide adopts the di-tert-butyl sulfite as the raw material, has little smell, is environment-friendly and is beneficial to environmental management;
2. the preparation method of the tert-butyl disulfide has the advantages of simple preparation process, mild whole reaction conditions and convenience for large-scale production;
3. the preparation method of the tert-butyl disulfide has the advantages of easily obtained raw materials, reasonable control of production cost and contribution to industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a schematic diagram of the reaction of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
The invention relates to a preparation method of tert-butyl disulfide, which is used for preparing tert-butyl disulfide according to a synthetic route shown in figure 1 and comprises the following specific steps:
step S1, preparing disodium disulfide aqueous solution
Adding 200g of deionized water and 96g of sodium sulfide nonahydrate into a 500m L three-necked bottle, heating, setting the temperature of a water bath to be 55 ℃, dissolving and clearing the sodium sulfide nonahydrate and stirring for 0.5 hour, then adding 17g of sublimed sulfur, continuing the heat preservation reaction, filtering the system, and filtering undissolved solid to obtain filtrate.
Step S2, preparing di-tert-butyl sulfite
111g of tert-butyl alcohol liquid is added into a 250m L three-necked bottle, 60g of thionyl chloride is dropwise added into a single-necked bottle at the temperature of 20-40 ℃, after the dropwise addition, the mixture is continuously stirred for 0.5 hour, water is added into a reaction system, and the mixture is washed twice (50m L x 2) until the pH value approaches to neutral, so that 95g of colorless oily matter is obtained.
Step S3 preparation of tert-butyl disulfide
Adding the filtrate of S1 into a flask, keeping the temperature at 45 ℃, adding 2g of phase transfer catalyst (PEG-400) and dropwise adding 90g of di-tert-butyl sulfite, keeping the temperature for continuously reacting for 1 hour, stopping the reaction, cooling to room temperature of 15 ℃, carrying out phase separation to obtain an organic phase, washing with water, and carrying out rotary evaporation and concentration to obtain 94.6g of a target product, wherein the total yield of the product is 86% and the GC purity is 99.4%.
Example 2
Step S1, preparing disodium disulfide aqueous solution
240g of sodium sulfide nonahydrate and 500g of purified water are added into a 3L three-neck flask, the mixture is heated to 55 ℃ for reaction, then the stirring is continued for 0.5h, 38.4g of sublimed sulfur is added into the three-neck flask, and the reaction is stirred until the mixture is clear.
Step S2, preparing di-tert-butyl sulfite
1110g of tert-butyl alcohol liquid is added into a three-necked 3L bottle, 600g of thionyl chloride is dropwise added into a single-necked bottle at the temperature of 20-40 ℃, after the dropwise addition, the stirring is continued for 0.5 hour, water is added into the reaction system, and the pH is nearly neutral after twice water washing (500m L X2), so that 935g of colorless oily matter is obtained.
Step S3: preparation of tert-butyl disulfide
Cooling sodium disulfide solution (778.4g) to 30-40 ℃, adding 20g of phase transfer catalyst (PEG-400) and dropwise adding 900g of di-tert-butyl sulfite, reacting for 1.5 hours after dropwise adding, wherein T L C shows generation of a large amount of target products, standing, carrying out phase splitting to obtain an upper layer organic product, washing with water, carrying out rotary evaporation and concentration to obtain 560g of product with GC purity of 99.2%, extracting and recovering a water phase product with methyl tert-butyl ether, and carrying out rotary evaporation and concentration to obtain 355g of product with GC purity of 98.5% and total yield of 83%.
It can be known from the combination of the embodiment 1 and the embodiment 2 that the yield of the product obtained by the invention is more than 80%, which is not much different from the yield achieved by the prior art, and can meet the actual production requirement, but the purity of the product of the invention is far higher than the purity of the product prepared by the prior synthesis method, in addition, the embodiment 2 enlarges the production compared with the embodiment 1, the yield and the purity are still higher, the adopted process means and the required reaction conditions are the same, the enlargement of the production does not increase the process difficulty, and the invention is suitable for industrial production. The method avoids the use of tert-butyl mercaptan, which has high toxicity and large production odor and is difficult to treat in the environment, is environment-friendly, and solves the problem that the existing method has large production odor and is difficult to treat in the environment; compared with the microwave method, the microwave method is difficult to realize amplification production; compared with the method of the simple substance bromine, the method has low cost and avoids using bromine with high toxicity. The method has mild conditions, good reproducibility and environmental friendliness, and can realize industrial production only by a corresponding reaction kettle and a simple distillation device.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A preparation method of tert-butyl disulfide is characterized in that the tert-butyl disulfide is prepared from disodium disulfide aqueous solution and di-tert-butyl sulfite.
2. The preparation method of tert-butyl disulfide according to claim 1, characterized by comprising the following specific steps:
s1, preparing a disodium disulfide aqueous solution: adding sodium sulfide and purified water into a reaction kettle, heating until the reaction is dissolved and becomes clear, adding sulfur powder, reacting until the solid is basically dissolved and becomes clear, and filtering to obtain a disodium disulfide aqueous solution;
s2, preparing di-tert-butyl sulfite: adding tert-butyl alcohol liquid into a reaction kettle, dropwise adding thionyl chloride at the temperature of 20-40 ℃, continuously stirring for 0.5 hour after dropwise adding, then adding water into the reaction system, and washing with water until the pH value is close to neutral to obtain colorless oily substance di-tert-butyl sulfite;
s3, placing the disodium disulfide aqueous solution obtained in the step S1 into a reaction kettle, cooling to 20-65 ℃, then dropwise adding di-tert-butyl sulfite, reacting after dropwise adding is completed until the raw materials react, and purifying to obtain the tert-butyl disulfide product.
3. The process according to claim 2, wherein the sodium sulfide in step S1 is sodium sulfide nonahydrate.
4. The method according to claim 2, wherein the sulfur powder in step S1 is sublimed sulfur.
5. The method according to claim 2, wherein the temperature in step S3 is reduced to 20-40 ℃.
6. The method for preparing tert-butyl disulfide according to claim 1, wherein the molar ratio of disodium disulfide to di-tert-butyl sulfite in the aqueous solution of disodium disulfide is: 1.0-1.5: 1.0.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508662A (en) * | 2009-03-11 | 2009-08-19 | 郑州大学 | Solvent-free phase transfer catalysis synthesis method of sec-butyl disulfide |
| CN104592070A (en) * | 2015-01-13 | 2015-05-06 | 湖北兴发化工集团股份有限公司 | Preparation method of dimethyl disulfide |
| CN104945286A (en) * | 2015-06-25 | 2015-09-30 | 成都百事兴科技实业有限公司 | Method for compounding high-purity sulfuric acid esters |
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- 2020-04-28 CN CN202010352387.2A patent/CN111440103A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508662A (en) * | 2009-03-11 | 2009-08-19 | 郑州大学 | Solvent-free phase transfer catalysis synthesis method of sec-butyl disulfide |
| CN104592070A (en) * | 2015-01-13 | 2015-05-06 | 湖北兴发化工集团股份有限公司 | Preparation method of dimethyl disulfide |
| CN104945286A (en) * | 2015-06-25 | 2015-09-30 | 成都百事兴科技实业有限公司 | Method for compounding high-purity sulfuric acid esters |
Non-Patent Citations (1)
| Title |
|---|
| 何柱生等: "高纯二甲基二硫醚制备工艺研究与开发", 《宝鸡文理学院学报（自然科学版）》 * |
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Application publication date: 20200724 |