CN118084858B - A preparation method of bis(2,3-ethylpropyl) sulfide - Google Patents
A preparation method of bis(2,3-ethylpropyl) sulfide Download PDFInfo
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- CN118084858B CN118084858B CN202410220350.2A CN202410220350A CN118084858B CN 118084858 B CN118084858 B CN 118084858B CN 202410220350 A CN202410220350 A CN 202410220350A CN 118084858 B CN118084858 B CN 118084858B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
- C07D331/02—Three-membered rings
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Abstract
本发明公开了一种双(2,3‑乙基丙基)硫化物的制备方法，属于精细化工技术领域。所述制备方法包括：第一步，环氧氯/溴丙烷与硫化试剂进行氧硫交换反应得到2‑(氯/溴甲基)环硫乙烷；第二步，2‑(氯/溴甲基)环硫乙烷与硫化钾在碱性溶液中硫醚化反应得到双(2,3‑乙基丙基)硫化物。本发明提供的制备方法，反应路线简单，条件温和，易于控制，避免应用硫化氢，工艺相比更安全，同时也提高产品的品质。The invention discloses a method for preparing bis(2,3-ethylpropyl) sulfide, and belongs to the technical field of fine chemicals. The preparation method comprises: a first step, epoxy chlorine/bromopropane and a sulfiding agent undergo an oxygen-sulfur exchange reaction to obtain 2-(chloro/bromomethyl) ethylene sulfide; a second step, 2-(chloro/bromomethyl) ethylene sulfide and potassium sulfide undergo a thioetherification reaction in an alkaline solution to obtain bis(2,3-ethylpropyl) sulfide. The preparation method provided by the present invention has a simple reaction route, mild conditions, is easy to control, avoids the use of hydrogen sulfide, is safer than the process, and also improves the quality of the product.
Description
Technical Field
The invention relates to the field of organic material synthesis, in particular to a preparation method of bis (2, 3-ethyl propyl) sulfide.
Background
Bis (2, 3-ethylpropyl) sulfide is one of sulfur heterocyclic compounds, which are important medical intermediates, optical materials and are widely applied to various fields. The bis (2, 3-ethylpropyl) sulfide is a thioepoxy group, and at present, the bis (2, 3-ethylpropyl) sulfide can be polymerized to obtain a thioepoxy group spectacle lens with high light transmittance, high diopter, high hardness and difficult abrasion. With the development of polymer chemistry, it is believed that the use of bis (2, 3-ethylpropyl) sulfide as a starting material is more widespread.
The patent US2012/309987, JP2015/44880 or EP2805949 uses epichlorohydrin to open the ring with a vulcanizing agent (H 2 S or NaHS), then closes the ring under strong alkaline conditions, and finally exchanges oxygen and sulfur with the vulcanizing agent (thiourea) to prepare bis (2, 3-ethylpropyl) sulfide. The method is applied to hydrogen sulfide or is easy to generate hydrogen sulfide, has high requirements on equipment and safety, has longer steps, is easy to generate incomplete conversion of symmetrical two side functional groups in the process of ring closure and oxygen-sulfur exchange, and does not give a pure product of the bis (2, 3-ethyl propyl) sulfide.
The specific reaction route is as follows:
in order to make up for the shortages of the existing patent synthesis methods, therefore, a new method needs to be developed and introduced, and the invention is particularly provided.
Disclosure of Invention
The invention aims to provide a preparation method of bis (2, 3-ethyl propyl) sulfide, which is synthesized by two steps of oxygen-sulfur exchange and thioetherification reaction, has a simple route and mild conditions, is easy to control, avoids the application of hydrogen sulfide, is safer in process, and improves the quality of products.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the bis (2, 3-ethyl propyl) sulfide comprises the following steps:
the first step: performing oxygen-sulfur exchange reaction on epoxy chlorine/bromopropane and a vulcanizing reagent to obtain 2- (chlorine/bromomethyl) ethylene sulfide;
And a second step of: carrying out a thioetherification reaction on 2- (chloro/bromomethyl) ethylene sulfide and potassium sulfide in an alkaline solution to obtain bis (2, 3-ethyl propyl) sulfide;
the reaction scheme is shown below:
further, the specific feeding sequence in the first step is as follows: under the protection of nitrogen, the thio reagent and the solvent are firstly mixed, then the catalyst is added, and finally the epoxy chlorine/bromopropane is added dropwise for reaction.
Further, in the first step, the reaction temperature is selected from 15-80 ℃.
Further, in the first step, the vulcanizing agent is selected from ammonium thiocyanate, sodium thiocyanate or thiourea.
Further, in the first step, the solvent is selected from acetonitrile or water.
Further, in the first step, the catalyst is selected from cerium sulfate or aluminum oxide.
Further, in the first step, the molar ratio of epoxy chlorine to bromopropane to vulcanizing agent to catalyst is 1:1.5-2.0:0.05-0.10.
Further, the specific feeding sequence in the second step is as follows: under the protection of nitrogen, alkali liquor and a reducing agent are mixed, potassium sulfide is rapidly added, and 18-crown ether-6 is added while 2- (chloro/bromomethyl) ethylene sulfide is dropwise added.
Further, in the second step, the reaction temperature is 20-25 ℃.
Further, in the second step, the alkaline solution is selected from an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution.
Further, in the second step, the reducing agent is selected from 40-80% hydrazine hydrate.
Further, in the second step, the molar ratio of the 2- (chloro/bromomethyl) ethylene sulfide, the potassium sulfide and the alkaline solution to the reducing agent is 1:1.8-2.0:4.0-6.0:1.5.
Compared with the prior art, the method has the advantages of simple synthetic route, mild reaction conditions and continuous two-step reaction.
Drawings
FIG. 1 is a 1 HNMR spectrum of the product of example 9;
FIG. 2 is a 13 CNMR spectrum of the product of example 9.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Preparation of 2- (chloro/bromomethyl) cyclothioethane
Examples 1 to 4
Examples 1-3 were prepared using the reagents in Table 1 as follows:
Under the protection of nitrogen, sequentially adding a thio reagent (ammonium thiocyanate, sodium thiocyanate or thiourea) (0.2 mol) and 40mL of acetonitrile into a four-port reaction bottle, mixing, adding cerium (IV) sulfate (0.005 mol,1.2 g), dropwise adding epichlorohydrin (0.1 mol,9.3 g), heating to 77-82 ℃ for reaction after the dropwise adding is finished, performing GC detection, concentrating under reduced pressure to evaporate solvent, adding cyclopentane, filtering, adding 0.5g of phenol-pyrazine into filtrate, concentrating under reduced pressure to evaporate cyclopentane, and performing reduced pressure distillation to obtain 2- (chloromethyl) ethylene sulfide.
Example 4 was prepared using the reagents in table 1 as follows:
thiourea (0.2 mol,15.2 g) and water (55 mL) are sequentially added into a four-port reaction bottle under the protection of nitrogen, mixed, added with aluminum oxide (0.01 mol,1.0 g), added with epichlorohydrin (0.1 mol,9.3 g) dropwise for reaction for 3 hours at 25 ℃, sampled and extracted by methylene dichloride, after the GC detection reaction is finished, extracted by methylene dichloride, dried by magnesium sulfate, added with 0.5g of phenothiazine into filtrate, concentrated under reduced pressure to evaporate methylene dichloride, and distilled under reduced pressure to obtain 2- (chloromethyl) ethylene sulfide .GC-MS(M+1)109.7;1HNMR(400MHz,CDCl3):3.70-3.53(d,2H),3.08-3.02(m,1H),2.45-2.34(m,1H),2.18(dd,1H).
Examples 5 to 8
Examples 5-7 were prepared using the reagents in table 2, with reference to examples 1-3.
Example 8 was prepared using the reagents in table 2, see example 4 for the procedure.
Preparation of 2- (bromomethyl) cyclothiane GCMS(M+1)155.1;1HNMR(400MHz,CDCl3):3.61-3.42(d,2H),3.18-3.12(m,1H),2.42-2.33(m,1H),2.17(dd,1H). bis (2, 3-ethylpropyl) sulphide
Example 9
Under the protection of nitrogen, 10 percent of potassium hydroxide solution (0.5 mol,280.5 g) and 80 percent of hydrazine hydrate (0.15 mol,6 g) are added into a four-port reaction bottle in sequence for mixing, potassium sulfide (0.18 mol,20 g) is added, the temperature is controlled to be 20-25 ℃, 18-crown ether-6 (2.0 g) is added, 2- (chloromethyl) ethylene sulfide (0.1 mol, 10.9) is added dropwise at the same time for reacting for 7 hours at 20-25 ℃, the sampling is extracted by methylene dichloride, GC (gas) detection, methylene dichloride extraction, citric acid washing, magnesium sulfate drying, 0.5g of phenol-pyrazine is added into filtrate, methylene dichloride is distilled off by vacuum concentration, and 7.3g of bis (2, 3-ethyl propyl) sulfide is obtained by vacuum distillation, the yield is obtained 81.9％,GC 98.6％.GC-MS(M+1)＝180.1;1HNMR(400MHz,CDCl3):3.00-3.09(m,4H),2.55-2.67(m,4H),2.23-2.25(m,2H).13CNMR(100MHz,CDCl3):37.96,33.85,25.86.
Example 10
Under the protection of nitrogen, 10% sodium hydroxide solution (0.6 mol,240 g) and 40% hydrazine hydrate (0.15 mol,12 g) are sequentially added into a four-port reaction bottle to be mixed, potassium sulfide (0.18 mol, about 20 g) is added, the temperature is controlled to be 15-20 ℃, 18-crown ether-6 (2.0 g) is added, 2- (bromomethyl) ethylene sulfide (0.1 mol,15.3 g) is dropwise added at the same time, the reaction is carried out for 5 hours at the temperature of 15-20 ℃, the sampling is carried out, dichloromethane extraction, GC detection, dichloromethane extraction, citric acid washing, magnesium sulfate drying are carried out, 0.5g of phenol-pyrazine is added into filtrate, dichloromethane is distilled off through reduced pressure concentration, and then 7.9g of bis (2, 3-ethyl propyl) sulfide is obtained through reduced pressure distillation, and the yield is 88.6%, and the GC is 98.7%.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (5)
1. A method for preparing bis (2, 3-ethyl propyl) sulfide, which is characterized by comprising the following steps:
The first step: epoxy chlorine/bromine propane and a vulcanizing reagent are subjected to oxygen-sulfur exchange reaction in the presence of a catalyst to obtain 2- (chlorine/bromine methyl) ethylene sulfide; the vulcanizing agent is selected from ammonium thiocyanate, sodium thiocyanate or thiourea; the catalyst is selected from cerium sulfate or aluminum oxide;
and a second step of: carrying out a thioetherification reaction on 2- (chloro/bromomethyl) ethylene sulfide and potassium sulfide in an alkaline solution and a reducing agent to obtain bis (2, 3-ethyl propyl) sulfide; the reducing agent is selected from 40-80% hydrazine hydrate.
2. The method for producing bis (2, 3-ethylpropyl) sulfide according to claim 1, wherein: in the first step, the oxygen-sulfur exchange is carried out in acetonitrile or water.
3. The method for producing bis (2, 3-ethylpropyl) sulfide according to claim 1, wherein: in the first step, the mol ratio of the epoxy chlorine/bromopropane to the vulcanizing agent to the catalyst is 1:1.5-2.0:0.05-0.10.
4. The method for producing bis (2, 3-ethylpropyl) sulfide according to claim 1, wherein: in the second step, the alkaline solution is selected from aqueous sodium hydroxide or aqueous potassium hydroxide.
5. The method for producing bis (2, 3-ethylpropyl) sulfide according to claim 1, wherein: in the second step, the mol ratio of the 2- (chlorine/bromomethyl) ethylene sulfide, the potassium sulfide, the alkaline solution and the reducing agent is 1:1.8-2.0:4.0-6.0:1.5.
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| CN106068260A (en) * | 2014-03-11 | 2016-11-02 | 三井化学株式会社 | The manufacture method of optical material episulfide compound, the compositions containing episulfide and comprise the polymerizable composition for optical material of said composition |
| CN110156748A (en) * | 2019-06-18 | 2019-08-23 | 江苏可奥熙光学材料科技有限公司 | A kind of preparation method of high refractive index lens monomer |
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| GB968424A (en) * | 1960-10-21 | 1964-09-02 | Shell Int Research | Epithio ethers, their preparation and polymers |
| KR20210014257A (en) * | 2019-07-29 | 2021-02-09 | 주식회사 케이오씨솔루션 | Composition for improving light resistance of optical materials and a method for improving the light resistance of the optical material using the same |
| KR20210105219A (en) * | 2020-02-18 | 2021-08-26 | 주식회사 케이오씨솔루션 | Methods for Manufacturing Episulfide Compounds for Optical Materials, Compositions for Optical Materials Containing the Same, and High Refractive Optical Materials |
| CN112480095B (en) * | 2020-11-25 | 2022-06-10 | 益丰新材料股份有限公司 | Preparation method of bis (2, 3-thiocyclopropyl) sulfide |
| CN117567428A (en) * | 2023-11-21 | 2024-02-20 | 益丰新材料股份有限公司 | Preparation method of bis (2, 3-cyclothiopropyl) sulfide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106068260A (en) * | 2014-03-11 | 2016-11-02 | 三井化学株式会社 | The manufacture method of optical material episulfide compound, the compositions containing episulfide and comprise the polymerizable composition for optical material of said composition |
| CN110156748A (en) * | 2019-06-18 | 2019-08-23 | 江苏可奥熙光学材料科技有限公司 | A kind of preparation method of high refractive index lens monomer |
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Effective date of registration: 20250102 Address after: 230031 Building 20, Liandong U-Valley High tech Enterprise Port, Nangang Science and Technology Park, Hefei City, Anhui Province, at the intersection of Kongquetai Road and Huguang West Road Patentee after: Hefei hechen Biotechnology Co.,Ltd. Country or region after: China Patentee after: Jiangsu Huaijin New Material Technology Co.,Ltd. Address before: 230031 Building 20, Liandong U-Valley High tech Enterprise Port, Nangang Science and Technology Park, Hefei City, Anhui Province, at the intersection of Kongquetai Road and Huguang West Road Patentee before: Hefei hechen Biotechnology Co.,Ltd. Country or region before: China |