Method for preparing vinyl sulfide compound under ball milling condition
By using arylsulfonium salt, potassium tert-butoxide and tetrahydrofuran for grinding reactions under ball milling conditions, the problem of using flammable and explosive gases and expensive catalysts in the prior art is solved, and high efficiency, environmentally friendly and low-cost ethylene is achieved. Preparation of sulfide compounds.
Patent Information
- Application Number
- CN202411599816.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-11
- Publication Date
- 2025-02-18
AI Technical Summary
The existing preparation methods for vinyl sulfide compounds have problems such as using high-pressure flammable and explosive acetylene gas, expensive transition metal catalysts, and a large number of organic solvents, resulting in safety hazards, environmental pollution and high preparation costs.
Under ball milling conditions, arylsulfonium salt is used as the starting material, potassium tert-butoxide is used as the base, and tetrahydrofuran is used as the liquid auxiliary abrasive agent. The grinding reaction is carried out in a stainless steel ball mill, and mechanical stress and shear force are used as the organic chemical reaction. Energy source, avoiding the use of large amounts of organic solvents.
It effectively shortens the reaction time, reduces the preparation cost, avoids environmental pollution, and has mild reaction conditions, good substrate universality, and high reaction yield, providing a highly efficient synthesis method for vinyl sulfide compounds.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of preparation of vinyl sulfide compounds, and in particular to a method for preparing vinyl sulfide compounds under ball milling conditions. Background Art
[0002] Vinyl sulfide is an important structural unit in organic synthesis and materials science. For example, vinyl sulfide can participate in Michael addition, cycloaddition, and Heck reaction in organic synthesis, and can also be used as a substitute for enol ether. In addition to the synthesis of small molecules, vinyl sulfide can also produce sulfur-containing polymers through mature polymerization pathways. Sulfur-containing functional groups are the most commonly used structural units to improve the mechanical properties of polymers, which can further expand their application in advanced optoelectronic materials. Therefore, the synthesis of vinyl sulfide compounds has always attracted much attention.
[0003] At present, there are many methods for preparing vinyl sulfide compounds. For example, the most atom-economical strategy for constructing vinyl sulfide compounds is the direct addition reaction of thiol and acetylene (Russ. Chem. Bull. Int. Ed., 2013, 62, 438.). However, this method often requires the use of high-pressure, flammable and explosive acetylene gas as a reactant, which requires cumbersome experimental operation steps and has great safety hazards, thus limiting the application of this method in actual production; another method is to use transition metals to catalyze thiols and terminal alkynes through direct hydrosulfanation to synthesize the corresponding 1,1-disubstituted alkenyl sulfide compounds (J. Am. Chem. Soc. 1992, 114, 5902), but this method requires the use of expensive transition metals and usually generates 1,2-disubstituted alkenyl sulfide by-products; another major drawback of the existing method is that it requires a large amount of organic solvents and a long reaction time, and under certain conditions, it also requires the operation of inert gas protection. The use of a large amount of organic solvents is prone to environmental pollution, and the inert gas protection increases the preparation cost. Although a variety of strategies have been developed for the preparation of vinyl sulfide compounds, existing methods still have many defects. Given that vinyl sulfide compounds play an important role in drug synthesis and material preparation, it is necessary to develop more efficient and green synthesis methods. Summary of the invention
[0004] The object of the present invention is to provide a method for preparing a vinyl sulfide compound under ball milling conditions to solve the problems existing in the prior art mentioned in the above background technology.
[0005] To achieve the above object, the present invention provides the following technical solutions:
[0006] A method for preparing a vinyl sulfide compound under ball milling conditions comprises the following steps:
[0007] S1: Select arylsulfonium salt as the starting material, potassium tert-butoxide as the base, and tetrahydrofuran as the liquid auxiliary grinding agent, add the raw materials into the grinding tank of the ball mill according to a certain proportion, and grind with grinding balls;
[0008] S2: neutralizing the ground raw material in S1 with a saturated sodium chloride aqueous solution, and extracting the solution;
[0009] S3: The organic phases were combined and dried with anhydrous sodium sulfate. The solvent was removed by rotary evaporation on a rotary evaporator, and the crude product was separated and purified by a silica gel column to obtain a vinyl sulfide compound.
[0010] Preferably, the arylsulfonium salt is any one of the following:
[0011]
[0012] Preferably, the molar ratio of the arylsulfonium salt to potassium tert-butoxide is 1:1.5 to 1:2.5.
[0013] Preferably, the molar ratio of the arylsulfonium salt to tetrahydrofuran is 1:3.0 to 1:5.0.
[0014] Preferably, the gas atmosphere in the grinding jar is air, and the reaction time is 0.5 to 1.0 h.
[0015] Preferably, the grinding jar and grinding balls are made of stainless steel.
[0016] Preferably, the grinding balls have a particle size of 10.0 mm.
[0017] Compared with the prior art, the present invention has the following beneficial effects:
[0018] 1. The present invention uses a stainless steel ball mill instead of a traditional glass reaction container, and uses the mechanical stress and shear force generated by the left and right vibration of the stainless steel grinding balls in the ball mill as the energy source for the organic chemical reaction, thereby avoiding the environmental pollution problem caused by the use of a large amount of organic solvents. The entire preparation process can be carried out under air conditions, and does not require expensive transition metal catalysts and a complex anhydrous and oxygen-free preparation environment, thereby effectively reducing the preparation cost.
[0019] 2. The present invention effectively utilizes the mechanical force generated by the ball mill, greatly shortens the reaction time, and has mild reaction conditions, good substrate universality, and high reaction yield. It is an efficient method for synthesizing vinyl sulfide compounds. DETAILED DESCRIPTION
[0020] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further explained below in conjunction with specific implementation methods.
[0021] The present invention provides the following technical solutions:
[0022] Example 1
[0023] A 5 mL stainless steel grinding jar equipped with a 10 mm grinding ball was selected, and compound 1 (172.2 mg, 0.5 mmol), tetrahydrofuran (160 μL, 1.0 mmol), potassium tert-butoxide (112.2 mg, 1.0 mmol) were added in turn under air conditions, and a ball mill (model Retsch MM 400) was used to vibrate at 30 Hz for one hour. After the reaction was completed, a saturated sodium chloride aqueous solution was used for neutralization, and the mixture was extracted with dichloromethane. The organic phases were combined and dried with anhydrous sodium sulfate. After the solvent was removed by rotary evaporation on a rotary evaporator, the crude product was separated and purified by silica gel column using petroleum ether or ethyl acetate as a developing agent to obtain compound 2 (113.1 mg, yield 85%), and the reaction formula is shown below:
[0024]
[0025] Among them, MeO represents methoxy, KO t Bu stands for potassium tert-butoxide, jar stands for stainless steel ball mill, THF stands for tetrahydrofuran, and ball milling stands for ball milling.
[0026] The product structure characterization data are as follows:
[0027] 1 H NMR (400 MHz, CDCl 3 )δ7.40–7.34(m,2H),6.92–6.86(m,2H),6.47(dd,J=16.5,9.7Hz,1H),5.22(d,J=9.7Hz,1H),5.10(d,J=16.6Hz,1H),3.81(s,3H).
[0028] 13 C NMR (101 MHz, CDCl 3 )δ159.6,134.1,133.6,123.5,114.8,112.6,55.3.
[0029] HRMS m / z(APCI):calcd for C 9 H 10 OS(M+H) + 167.0525, found 167.0511.
[0030] Example 2
[0031] A 5 mL stainless steel reaction tank equipped with a 10 mm grinding ball was selected, and compound 3 (197.4 mg, 0.5 mmol), tetrahydrofuran (160 μL, 1.0 mmol), potassium tert-butoxide (112.2 mg, 1.0 mmol) were added in turn under air conditions, and a ball mill (model Retsch MM 400) was used to vibrate at 30 Hz for one hour. After the reaction was completed, a saturated sodium chloride aqueous solution was used for neutralization, and dichloromethane was used for extraction. The organic phase was combined and dried with anhydrous sodium sulfate. After the solvent was removed by rotary evaporation on a rotary evaporator, petroleum ether or ethyl acetate was used as a developing agent for the crude product, and the silica gel column was separated and purified to obtain compound 4 (86.5 mg, yield 80%), and the reaction formula is shown below:
[0032]
[0033] The product structure characterization data are as follows:
[0034] 1 H NMR (400 MHz, CDCl 3 )δ8.34(d,J=8.4Hz,2H),7.72(d,J=8.0Hz,1H),7.64–7.58(m,1H),7.57–7.51(m,1H),6.81(d,J=8. 0Hz,1H),6.48(dd,J=16.5,9.7Hz,1H),5.17(d,J=9.7Hz,1H),4.88(d,J=16.5Hz,1H),4.02(s,3H).
[0035] 13 C NMR (101 MHz, CDCl 3 )δ156.7,134.6,134.2,133.4,127.4,126.3,125.7,125.6,122.5,119.6,111.6,103.9,55.6.
[0036] HRMS m / z(APCI):calcd for C 13 H 12 OS(M+H) + 217.0682, found 217.0662.
[0037] Example 3
[0038] A 5 mL stainless steel reaction tank equipped with a 10 mm grinding ball was selected, and compound 5 (164.2 mg, 0.5 mmol), tetrahydrofuran (160 μL, 1.0 mmol), potassium tert-butoxide (112.2 mg, 1.0 mmol) were added in turn under air conditions, and a ball mill (model Retsch MM 400) was used to vibrate at 30 Hz for one hour. After the reaction was completed, a saturated sodium chloride aqueous solution was used for neutralization, and the mixture was extracted with dichloromethane. The organic phases were combined and dried with anhydrous sodium sulfate. After the solvent was removed by rotary evaporation on a rotary evaporator, the crude product was separated and purified by silica gel column using petroleum ether or ethyl acetate as a developing agent to obtain compound 6 (59.0 mg, yield 79%), and the reaction formula is shown below:
[0039]
[0040] The product structure characterization data are as follows:
[0041] 1 H NMR (400 MHz, CDCl 3 )δ7.30(d,J=8.1Hz,2H),7.15(d,J=7.9Hz,2H),6.51(dd,J=16.6,9.6Hz,1H),5.29(d,J=9.6Hz,1H),5.25(d,J=16.6Hz,1H),2.35(s,3H).
[0042] 13 C NMR (101 MHz, CDCl 3 )δ137.4,132.6,131.2,130.1,129.9,114.1,21.1.
[0043] HRMS m / z(APCI):calcd for C9H10S(M+H)+151.0576,found 151.0556.
[0044] Example 4
[0045] A 5 mL stainless steel reaction tank equipped with a 10 mm grinding ball was selected, and compound 7 (160.2 mg, 0.5 mmol), tetrahydrofuran (160 μL, 1.0 mmol), potassium tert-butoxide (112.2 mg, 1.0 mmol) were added in turn under air conditions, and a ball mill (model Retsch MM 400) was used to vibrate at 30 Hz for one hour. After the reaction was completed, a saturated sodium chloride aqueous solution was used for neutralization, and the mixture was extracted with dichloromethane. The organic phases were combined and dried with anhydrous sodium sulfate. After the solvent was removed by rotary evaporation on a rotary evaporator, the crude product was separated and purified by using petroleum ether / ethyl acetate as a developing agent on a silica gel column to obtain compound 6 (64.0 mg, yield 90%), and the reaction formula is shown below:
[0046]
[0047] The product structure characterization data are as follows:
[0048] 1 H NMR (400 MHz, CDCl 3 )δ7.44(dd,J=5.3,1.2Hz,1H),7.19(dd,J=3.6,1.2Hz,1H),7.05(dd,J=5.3,3.6Hz ,1H),6.43(dd,J=16.5,9.6Hz,1H),5.24(d,J=9.6Hz,1H),5.11(d,J=16.5Hz,1H).
[0049] 13 C NMR (101 MHz, CDCl 3 )δ134.6,134.0,130.4,130.2,127.8,112.5.
[0050] HRMS m / z(APCI):calcd for C 6 H 6 S 2 (M+H) + 142.9984, found 142.9973.
[0051] According to the above Examples 1-4, it can be concluded that the method for preparing vinyl sulfide compounds provided by the present invention does not require the use of a large amount of solvents and transition metal catalysts, so that the reaction time is shortened, the reaction conditions are mild, the substrate universality is good, and the reaction yield is high. It is an efficient method for synthesizing vinyl sulfide compounds.
[0052] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A method for preparing a vinyl sulfide compound under ball milling conditions, characterized in that: The following steps are involved: S1: Select arylsulfonium salt as the starting material, potassium tert-butoxide as the base, and tetrahydrofuran as the liquid auxiliary grinding agent, add the raw materials into the grinding tank of the ball mill according to a certain proportion, and grind with grinding balls; S2: neutralizing the ground raw material in S1 with a saturated sodium chloride aqueous solution, and extracting the solution; S3: The organic phases were combined and dried with anhydrous sodium sulfate. The solvent was removed by rotary evaporation on a rotary evaporator, and the crude product was separated and purified by a silica gel column to obtain a vinyl sulfide compound.
2. The method for preparing a vinyl sulfide compound under ball milling conditions according to claim 1, characterized in that: The arylsulfonium salt is any one of the following:
3. The method for preparing a vinyl sulfide compound under ball milling conditions according to claim 1, characterized in that: The feeding molar ratio of the arylsulfonium salt and potassium tert-butoxide is 1:1.5 to 1:2.
5.
4. The method for preparing a vinyl sulfide compound under ball milling conditions according to claim 1, characterized in that: The molar ratio of the arylsulfonium salt to tetrahydrofuran is 1:3.0 to 1:5.
0.
5. The method for preparing a vinyl sulfide compound under ball milling conditions according to claim 1, characterized in that: The gas atmosphere in the grinding jar is air, and the reaction time is 0.5 to 1.0 h.
6. The method for preparing a vinyl sulfide compound under ball milling conditions according to claim 1, characterized in that: The grinding jar and grinding balls are made of stainless steel.
7. The method for preparing a vinyl sulfide compound under ball milling conditions according to claim 1, characterized in that: The grinding balls used are grinding balls with a particle size of 10.0 mm.