WO2019095636A1

WO2019095636A1 - Method for synthesizing benzenesulfonate derivative

Info

Publication number: WO2019095636A1
Application number: PCT/CN2018/084559
Authority: WO
Inventors: 闫彩桥; 刘鹏; 侯荣雪
Original assignee: 石家庄圣泰化工有限公司
Priority date: 2017-11-14
Filing date: 2018-04-26
Publication date: 2019-05-23
Also published as: KR102144626B1; CN107840812A; JP2021502950A; KR20190105493A

Abstract

Disclosed is a method for synthesizing a benzenesulfonate derivative, which belongs to the technical field of compound synthesis. Formula (I) is used as a raw material and reacted with ethylene glycol or R2-OH to produce formula (II) or formula (III), wherein R1 is selected from an alkyl, H or F, and R2 is selected from allyl, propargyl or phenyl. The specific operations are: adding ethylene glycol or R2-OH and dichloromethane to a reactor, adding an organic base under stirring, then cooling to 15ºC or less, and starting to dropwise add formula (I); after addition is complete, bringing same to room temperature and continuing to stir for 0.5-1 h, and then raising the temperature and refluxing the reaction for 1-2 h; and after the reaction is complete, carrying out an de-ice treatment, layering, and dry concentration to obtain a benzenesulfonate derivative product. The synthesis method of the present invention is simple, the reaction process is mild and stable, the yield is high, and the resulting product has a high purity.

Description

Method for synthesizing besylate derivatives

Technical field

The invention belongs to the technical field of compound synthesis, and particularly relates to a method for synthesizing a benzenesulfonate derivative. The synthesis method of the invention is simple, the reaction process is mild, stable, and the yield is high, and the obtained product has high purity.

Background technique

With the development of China's electronic information industry, the demand for chemical power sources is increasing, and its performance requirements are getting higher and higher. Because lithium-ion batteries have the advantages of small size, good safety performance, light weight, high specific energy, high voltage, long life, no pollution and other chemical power sources, it has become a mobile phone, handheld computer, notebook computer, and miniature. The main power source for portable electronic devices such as camera digital cameras. In recent years, basic research and application development of lithium-ion batteries have become one of the hot spots. The lithium battery includes a positive electrode, a negative electrode, an electrolyte, and a separator. However, during charging and discharging, the battery releases heat, resulting in a decrease in battery performance. In the process of charging and discharging, the battery will release heat, which will cause the battery performance to be degraded. When the existing electrolyte additive encounters high temperature in use, the performance of the battery is poor and the damage is severe. After the high temperature cycle of the battery without additives, 50 weeks later In order to overcome the above shortcomings, we are working on an electrolyte additive that can effectively improve the performance of the battery under high temperature conditions.

The besylate derivative is an important organic synthesis intermediate and has a wide range of applications. We have found that it can be applied to battery electrolytes, but its synthesis method is complicated. At present, there is no way to prepare it to meet the battery electrolyte. Claim.

Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a synthesis method which can be prepared to conform to a benzene sulfonate derivative for battery electrolyte requirements. The technical solution adopted by the present invention for achieving the purpose is:

a method for synthesizing a besylate derivative,

Take

As a raw material, react with ethylene glycol or R ₂ -OH to form

Wherein R _{1 is} selected from alkyl, H or F, and R _{2 is} selected from allyl, propargyl or benzene, in particular by adding ethylene glycol or R ₂ —OH and dichloromethane to the reactor with stirring Adding an organic base, the amount of the organic base added is 1-5% of the mass of the raw material, and then the temperature is lowered to below 15 ° C, and the dropping is started.

After the completion of the dropwise addition, the mixture is stirred at room temperature for 0.5-1 h, then the temperature is raised and refluxed for 1-2 h. After the reaction is completed, the mixture is ice-dissolved, ice-dissolved with 5-10 times of ice water, layered, and dried to give benzenesulfonic acid. Ester derivative products.

The organic base is triethylamine or pyridine.

Control when using ethylene glycol

The molar ratio to ethylene glycol is (2-2.3): 1; when R ₂ -OH is used, control

The molar ratio to R ₂ -OH is (1-1.3):1.

The obtained benzenesulfonate derivative is subjected to recrystallization (for example, DMC) to obtain a pure benzenesulfonate derivative.

The beneficial effects of the invention are:

The synthesis method of the invention is simple and efficient, and is suitable for industrial large-scale production, the yield is up to 90% or more, and the purity is up to 99.9% or more, and the process parameter control, the process matching, the three-stage temperature control method and the material selection are made. The prepared benzenesulfonic acid derivative has a water content of less than ≤50 ppm and a low acid value of ≤50 ppm, which lays a foundation for enhancing the high and low temperature stability of the battery after application.

DRAWINGS

Figure 1 is a 1H NMR spectrum of 1-phenylbenzenesulfonate.

Figure 2 is a 13C NMR spectrum of 1-phenylbenzenesulfonate.

Figure 3 is a 1H NMR spectrum of allyl benzenesulfonate.

Figure 4 is a 13C NMR spectrum of allyl benzenesulfonate.

Figure 5 is a 1H NMR spectrum of ethylene glycol dibenzenesulfonate.

Figure 6 is a 13C NMR spectrum of ethylene glycol dibenzenesulfonate.

Detailed ways

The invention will now be further described in conjunction with specific embodiments.

First, the specific embodiment

Example 1

Add 1.0 mol of phenol and 500 ml of dichloromethane to the reaction flask respectively, add triethylamine under stirring, then cool to below 15 ° C, start adding 1.1 mol of benzenesulfonyl chloride, drop, return to room temperature and continue stirring for 1 h, then heat up. The reaction was continued at reflux for 2 h, and after the gas phase reaction was completed, the mixture was subjected to ice-reaction, layered, and concentrated to give a crude product which was then recrystallized to afford 222.3 g of pure product. The yield of the product was 95%. The purity of the test was 99.93%, the moisture content was 30 ppm, the acid value was 34 ppm, the measured density was 1.277 g/cm ³ , the boiling point was 375.4 ° C 760 mmHg, the 1H NMR spectrum thereof is shown in Fig. 1, and the 13C NMR spectrum is shown in Fig. 2.

The synthetic route is:

Example 2

Add 1.0 mol of allyl alcohol and 500 ml of dichloromethane to the reaction flask respectively, add pyridine with stirring, then cool to below 15 ° C, start adding 2.1 mol of benzenesulfonyl chloride, drop, return to room temperature and continue stirring for 1 h, then warm up to The reaction was further refluxed for 2 h, and after the gas phase reaction was completed, the mixture was subjected to ice-reaction, layered, and concentrated to give a crude product which was then recrystallized to give a pure product of 189.3 g, and the yield of the product was 95.5%. The purity was 99.95%, the moisture content was 30 ppm, and the acid value was 40 ppm. The 1H NMR spectrum is shown in Fig. 3, and the 13C NMR spectrum is shown in Fig. 4.

The synthetic route is:

Example 3

Add 1.0mol of propargyl alcohol and 500ml of dichloromethane to the reaction flask respectively, add triethylamine under stirring, then cool down to below 15 °C, start adding 2.1mol of benzenesulfonyl chloride, drop, return to room temperature and continue stirring for 1h, then The temperature was raised to reflux and the reaction was continued for 2 hours. After the gas phase detection reaction was completed, the mixture was subjected to ice-clearing, layered, and concentrated to give a crude product which was then recrystallized to yield 187.77 g of pure product. The calculated yield was 95.8%. The purity was 99.93%, the moisture content was 28 ppm, the acid value was 36 ppm, and the density was 1.244 g/mL.

The synthetic route is:

Example 4

Add 1.0mol of ethylene glycol and 500ml of dichloromethane to the reaction flask respectively, add pyridine with stirring, then cool down to below 15 °C, start adding 2.1mol of benzenesulfonyl chloride, drop, return to room temperature and continue stirring for 1h, then heat up to The reaction was further refluxed for 2 hours, and after the gas phase detection reaction was completed, it was subjected to ice-clear treatment, layered, and concentrated to give a crude product which was then recrystallized to give a pure product, and the yield of the product was calculated to be 94.3%. The purity was 99.91%, the moisture content was 26 ppm, the acid value was 35 ppm, the density was 1.387 g/cm ³ , the boiling point was 516.1 ° C, and 760 mmHg. The 1H NMR spectrum is shown in Fig. 5, and the 13C spectrum is shown in Fig. 6.

The synthetic route is:

Example 5

1.0mol of ethylene glycol and 500ml of dichloromethane were respectively added to the reaction flask, triethylamine was added under stirring, and then the temperature was lowered to below 15 ° C, and 2.1 mol of 2,4,6-trimethylbenzenesulfonyl chloride was added dropwise. After returning to room temperature, stirring was continued for 1 h, then the temperature was raised to reflux to continue the reaction for 2 h. After the gas phase detection reaction was completed, the mixture was subjected to ice-clearing, layered, and dried to give a crude product which was then recrystallized to obtain a pure product (CAS No. 128584-68-9). The calculated yield was 94.6%. The purity was 99.9%, the moisture content was 38 ppm, the acid value was 45 ppm, the density was 1.239 g/cm ³ , and the boiling point was 588.8 ° C and 760 mmHg.

The synthetic route is:

Example 6

1.0 mol of ethylene glycol and 500 ml of dichloromethane were respectively added to the reaction flask, pyridine was added thereto with stirring, and then the temperature was lowered to 15 ° C or lower, and 2.1 mol of 2,4,6-trifluorobenzenesulfonyl chloride was added dropwise, and the mixture was dropped. Stirring was continued for 1 h at room temperature, then the temperature was raised to reflux and the reaction was continued for 2 h. After the reaction was completed in the gas phase, the mixture was subjected to ice-reaction, layered, and concentrated to give a crude product which was recrystallized to give a pure product. The yield of the product was calculated to be 93.8%. The purity was 99.94%, the moisture content was 35 ppm, and the acid value was 42 ppm.

The synthetic route is:

Second, the application test

1. A lithium battery to which a 1% by weight of an electrolyte solution is added, a lithium battery without a lithium battery, and a lithium battery to which a conventional benzenesulfonate derivative is added are respectively circulated at 65 ° C. For comparison, the product obtained in Example 1 is taken as an example, wherein the purity of the besylate derivative of the present invention is 99.93%, the moisture content is 30 ppm, and the acid value is 34 ppm; the purity of the existing benzenesulfonic acid derivative Control 1 is 99.93%. The acid value is 150 ppm and the moisture content is 138 ppm; the purity of the existing benzenesulfonic acid derivative control 2 is 95%, the acid value is 150 ppm, and the moisture content is 138 ppm. The results are shown in Table 1:

Table 1

As is apparent from Table 1, the benzenesulfonate derivative of the present invention can improve the high temperature cycle performance of the battery.

2, battery high-temperature storage performance evaluation: 60 ° C / 30D and 85 ° C / 7D storage performance test, the following list 2 is the battery after the standard charge and discharge, then stored at 60 ° C for 30 days and 85 ° C for 7 days, then measure the battery capacity retention Rate and capacity recovery rate.

Table 2

As can be seen from Table 2, the benzenesulfonate derivative of the present invention can improve the high-temperature storage performance of the battery.

3, battery low-temperature storage performance evaluation; Table 3 is to leave the battery in the low-temperature box, respectively control the temperature of -30 ° C or -40 ° C, hold time 240 min, then measure the capacity retention rate of the battery.

table 3

As is apparent from Table 3, the benzenesulfonate derivative of the present invention can improve the low-temperature storage performance of the battery. The above performance tests are all taken as an example. The performance of other benzenesulfonate derivatives is basically the same as the above properties, and the difference in properties fluctuates between 2-4%, indicating the purity, acid value and the benzenesulfonate derivative. The moisture content has a critical influence on the battery performance after application to the battery, and Tables 2 and 3 indirectly prove that the besylate derivative of the present invention can improve the stability of the battery and improve the service life of the battery.

Claims

A method for synthesizing a besylate derivative, characterized in that

Take
As a raw material, react with ethylene glycol or R 2 -OH to form
Wherein R 1 is selected from alkyl, H or F, and R 2 is selected from allyl, propargyl or benzene, in particular by adding ethylene glycol or R 2 —OH and dichloromethane to the reactor with stirring Add organic base, then cool down to below 15 °C and start dropping
After the completion of the dropwise addition, the mixture was stirred at room temperature for 0.5-1 h, and then the temperature was raised and refluxed for 1-2 h. After completion of the reaction, the mixture was ice-dissolved, layered, and dried to give a benzenesulfonate derivative product.
The method for synthesizing a benzenesulfonate derivative according to claim 1, wherein the organic base is triethylamine or pyridine.
The method for synthesizing a benzenesulfonate derivative according to claim 1, wherein when ethylene glycol is used, control
The molar ratio to ethylene glycol is (2-2.3): 1; when R 2 -OH is used, control
The molar ratio to R 2 -OH is (1-1.3):1.
The method for synthesizing a benzenesulfonate derivative according to claim 1, wherein the obtained benzenesulfonate derivative is recrystallized to obtain a pure benzenesulfonate derivative.