4- (propenyloxy)phenylsulfonyl fluoride
The preparation of 4-(propenyloxy)phenylsulfonyl fluoride via a two-step reaction catalyzed by hans ester and N,N-diisopropylethylamine solves the problem of low efficiency in existing synthetic routes, achieving high yield and high purity product preparation, suitable for industrial applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHIJIAZHUANG SAN TAI CHEM CO LTD
- Filing Date
- 2024-11-29
- Publication Date
- 2026-05-29
AI Technical Summary
In the existing technology, there are few studies on the synthetic route of 4-(propenyloxy)phenylsulfonyl fluoride, and traditional catalysts and solvents have problems such as low reaction efficiency, long reaction time and high energy consumption.
4-(propenyloxy)phenylsulfonyl fluoride was prepared by a two-step reaction using hans ester and N,N-diisopropylethylamine as catalysts. The first step used hans ester to catalyze dehalogenation and substitution reactions, and the second step used an organic weak base as an acid-binding agent. The reaction was carried out under inert gas protection, with temperature and time controlled.
It improves reaction yield and the purity of catalytic products, reduces energy consumption, and has high value for industrial application.
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Figure CN122102968A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of battery electrolyte technology, and relates to a method for preparing an additive for lithium battery electrolyte, particularly a method for preparing 4-(propenyloxy)phenylsulfonyl fluoride. Background Technology
[0002] Lithium-ion batteries mainly consist of four parts: positive electrode material, negative electrode material, separator material, and electrolyte. The electrolyte is often referred to as the "blood" of a lithium-ion battery, and its composition is closely related to the battery's high and low temperature performance, charge-discharge cycles, capacity, and safety. To improve battery performance, electrolyte additives are commonly used. Fluorinated organic substances are excellent film-forming additives that can improve battery cycle performance. This is because fluorinated additives can lower the HOMO and LUMO energies of solvent molecules, thereby enhancing the molecules' antioxidant capacity and making them more susceptible to reduction, forming a LiF-rich interfacial film.
[0003] In recent years, sulfonyl fluorides have been used as a novel electrolyte additive, and their effects have been extensively studied. Among them, 4-(propenyloxy)phenylsulfonyl fluoride, as a type of sulfonyl fluoride, has few reported studies on its synthetic routes and preparation methods. Summary of the Invention
[0004] The purpose of this invention is to develop a synthetic route for 4-(propenyloxy)phenylsulfonyl fluoride and to study its preparation method, so as to produce a product that meets the standards for use as an electrolyte additive.
[0005] The technical solution adopted in this invention is a method for preparing 4-(propenyloxy)phenylsulfonyl fluoride. The key point is that the structure of the above-mentioned 4-(propenyloxy)phenylsulfonyl fluoride is as follows:
[0006]
[0007] The above preparation method includes two steps: the first step is to prepare the intermediate p-allyloxyphenol using hydroquinone and 3-bromopropene as starting materials; the second step is to synthesize 4-(propenyloxy)phenylsulfonyl fluoride from the intermediate and thioyl fluoride under the action of an acid-binding agent; the first step requires N,N-diisopropylethylamine as the reaction solvent and hans ester as the catalyst, with a molar ratio of hydroquinone, 3-bromopropene and hans ester of 1:0.55-0.65:0.2-0.3, and the amount of N,N-diisopropylethylamine used per mole of hydroquinone is 1.0 L-1.2 L; in the second step, the molar ratio of the intermediate to thioyl fluoride is 1:2-5.
[0008] Furthermore, the aforementioned Hans ester is any one or a combination of ethylene benzoate or 1,2-propanediol dibenzoate.
[0009] Furthermore, the acid-binding agent mentioned above is an organic weak base, specifically any one of diethylamine, triethylamine, or pyridine; the molar amount of the acid-binding agent used is 1.5 to 3 times that of the intermediate.
[0010] Specifically, the reaction temperature of the first step reaction is 60℃~110℃, and the reaction time is 4h~6h; the reaction temperature of the second step reaction is 40℃~60℃, and the reaction time is 2h~4h; both the first step reaction and the second step reaction need to be carried out under the protection of an inert gas.
[0011] More specifically, after the first step reaction is completed, the reaction solution from the first step is washed with water, extracted, dried in an organic phase, filtered, evaporated, and purified by silica gel column chromatography to obtain the intermediate.
[0012] More specifically, after the second step reaction is completed, the reaction solution from the second step is washed with water, extracted, dried by organic phase filtration and rotary evaporation, purified by silica gel column chromatography, and dried by molecular sieve to obtain the 4-(propenyloxy)phenylsulfonyl fluoride product.
[0013] Preferably, the solvent used for the above extraction is ethyl acetate.
[0014] Furthermore, the reaction solvent for the second step reaction described above is any one of dichloromethane, N,N-dimethylformamide, or acetonitrile, and the amount of reaction solvent used for each mole of intermediate in the second step reaction is 1.0 L to 1.2 L.
[0015] Compared with the prior art, the present invention has the following advantages:
[0016] This invention studies a synthetic route and preparation method for a sulfonyl fluoride electrolyte additive, namely 4-(propenyloxy)phenylsulfonyl fluoride. This product can be prepared from hydroquinone and 3-bromopropene as initial starting materials through a two-step reaction. The yield of the first step reaction is the limiting factor affecting the overall yield, therefore, the study of the first step reaction is more important.
[0017] This invention utilizes hansyl ester in combination with N,N-diisopropylethylamine to catalyze the first step of the dehalogenation and substitution reaction. Hansyl ester is an organic compound containing two ester groups, with the general formula RCO(CH2)2COOR, where R is a phenyl or benzene substituent. The hansyl ester used in this invention is ethylene benzoate or 1,2-propanediol dibenzoate. Due to their reducing and oxidizing properties, these substances can be used as oxidants, reducing agents, and catalysts for esterification reactions. In this invention, it was found that when hansyl ester is used in combination with N,N-diisopropylethylamine, it can also catalyze the dehalogenation reaction. Compared to common dehalogenating agents, such as potassium carbonate commonly used in this type of reaction, it exhibits superior catalytic characteristics. This invention can improve the reaction yield and the purity of the corresponding catalytic product, and also shortens the reaction time.
[0018] Meanwhile, this invention does not use excessively high temperatures or pressures, and the preparation method has low energy consumption, making it highly valuable for industrial application. Attached Figure Description
[0019] Figure 1 This is the NMR spectrum of sample 1 of the present invention.
[0020] Figure 2 This is the gas chromatography spectrum of sample 1 of the present invention.
[0021] Figure 3 This is the high-performance gas phase spectrum of sample 1 of the present invention. Detailed Implementation
[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0023] Unless otherwise specified in the examples, the procedures can be followed according to conventional conditions; unless the manufacturers of the reagents or instruments used are specified, they are all conventional products that can be purchased commercially.
[0024] Examples 1 to 5
[0025] 4-(propenyloxy)phenylsulfonyl fluoride was prepared by the following steps:
[0026] S1. Preparation of the intermediate p-allyloxyphenol:
[0027] S1-1. Add 1 mol of hydroquinone, hansyl ester catalyst, 3-bromopropene, and N,N-diisopropylethylamine (DIPEA) sequentially to the reaction vessel. The molar ratio of hydroquinone, 3-bromopropene, and hansyl ester is 1:0.55-0.65:0.2-0.3, and the amount of DIPEA used per mole of hydroquinone is 1.0 L-1.2 L.
[0028] S1-2. Under nitrogen protection, heat the reaction solution of the first step to 60℃~110℃ and control the reaction time to 4h~6h for the first step reaction;
[0029] S1-3 After the first step reaction is completed, the reaction solution is cooled to room temperature. The reaction solution from the first step is poured into water and washed. Ethyl acetate is added for extraction. The organic phase is dried, filtered, and evaporated to dryness to obtain the crude intermediate. The crude intermediate is then purified by silica gel chromatography to obtain the sample of the intermediate p-allyloxyphenol, i.e., the intermediate sample.
[0030] S2. Preparation of the target product:
[0031] S2-1. Add 1 mol of intermediate, acid-binding agent and reaction solvent to the reactor in sequence, and pass sufficient sulfuryl fluoride gas under nitrogen protection.
[0032] S2-2. Heat the reaction solution from the second step to 40℃~60℃ and control the reaction time to 2h~4h to carry out the second step reaction.
[0033] S2-3. After the second step of the reaction is completed, the reaction solution is poured into water and washed. Ethyl acetate is added for extraction. The organic phase is dried, filtered, and evaporated to dryness to obtain the crude product of the target product. The crude product is purified by silica gel column chromatography to obtain a yellow or pale yellow liquid. After adding molecular sieves for drying and filtration, a sample of 4-(propenyloxy)phenylsulfonyl fluoride is obtained, which is the product sample.
[0034] The specific raw materials, dosage ratios, and reaction parameters in Examples 1 to 5 are shown in Tables 1 and 2, respectively, and intermediate samples 1 to 5 and product samples 1 to 5 were prepared.
[0035] Table 1: Comparison of specific raw materials, dosage ratios, and reaction parameters for step S1 in the examples
[0036]
[0037] Table 2: Comparison of specific raw materials, dosage ratios, and reaction parameters for step S2 in the examples
[0038]
[0039]
[0040] Comparative Example 1
[0041] The specific implementation process is the same as in Example 1, except that in step S1-1, DIPEA is not used as the solvent for the first step reaction. Instead, an equal volume of acetonitrile is used to prepare intermediate reference standard 1.
[0042] Comparative Example 2
[0043] The specific implementation process is the same as in Example 1, except that in step S1-1, Hans ester is not used as a catalyst, nor is DIPEA used as the solvent for the first step reaction. Instead, 0.25 mol of potassium carbonate is used as a catalyst and acetonitrile is used as a solvent. The residual amount of raw materials is monitored during the reaction until the reaction is complete. The reaction time is recorded to prepare intermediate reference standard 2, and then product reference standard 1 is prepared.
[0044] Comparative Example 3
[0045] The specific implementation process is the same as in Example 1, except that in step S1-1, Hans ester is not used as a catalyst, nor is DIPEA used as the solvent for the first step reaction. Instead, 0.8 mol of potassium carbonate is used as a catalyst and acetonitrile is used as a solvent. The amount of raw material residue is monitored during the reaction until the reaction is complete. The reaction time is recorded to prepare intermediate reference standard 3, and then product reference standard 2 is prepared.
[0046] Comparative Example 4
[0047] The specific implementation process is the same as in Example 1, except that in steps S2-3, molecular sieves are not used for drying, and product reference standard 3 is prepared.
[0048] Comparative Example 5
[0049] The specific implementation process is the same as in Example 1, except that in step S2-1, instead of using organic weak bases as acid-binding agents, inorganic strong bases, such as sodium hydroxide, are used to prepare product reference standard 4.
[0050] Analysis and Testing
[0051] The product samples prepared by this invention were analyzed by 1H NMR and HPLC-MS / MS, confirming that the obtained samples conform to the structural characteristics of 4-(propenyloxy)phenylsulfonyl fluoride. See the appendix for the analytical spectra of some product samples. Figures 1-2 .
[0052] The purity of the samples and reference standards was determined by high-performance gas chromatography (HPLC), and the yield was calculated using the following formula. The results are shown in Table 3. For the chromatograms of some product samples, please refer to the appendix. Figure 3 .
[0053] The yield calculation formula is:
[0054] Formula 1: Intermediate yield = Actual weight of intermediate obtained (g) / Theoretical yield calculated based on hydroquinone dosage (g) × 100%.
[0055] Formula 2: Product yield = Actual weight of the product obtained (g) / Theoretical yield calculated based on the amount of p-allyloxyphenol used (g) × 100%.
[0056] Formula 3: Overall yield = Intermediate yield × Product yield / 100%
[0057] Table 3: Summary of Purity and Yield Results
[0058]
[0059] As shown in Table 3, the intermediate prepared by this invention achieves a purity of over 99%, an intermediate yield of over 85%, and a product purity of over 99.4%, with moisture content controlled below 100 ppm, meeting the purity and moisture requirements for electrolyte additives. In the two-step reaction, the yield of the first step is the limiting factor for the overall yield. The overall yield of this invention reaches 80%, and the improvement in overall yield depends on the improvement of the first step's yield. During the research, it was found that changing the solvent in Comparative Example 1 resulted in an extremely low yield in the first step, indicating that the effectiveness of the first step is affected by both the selected catalyst type and the reaction solvent. Because the intermediate prepared in this comparative example had too low purity, subsequent reactions were not carried out. Furthermore, in Comparative Examples 2 and 3, it was found that potassium carbonate can also catalyze the first step reaction; however, the required reaction time is longer, approximately 12 hours (14 hours for Comparative Example 2 and 11 hours for Comparative Example 3). Simultaneously, the amount of potassium carbonate catalyst used needs to be increased to ensure the smooth progress of the reaction and the purity of the product. For the study of the second step reaction, the choice of acid-binding agent is particularly crucial. Using inorganic strong base acid-binding agents will lead to low efficiency of the second step reaction.
[0060] Impurity analysis of the product samples prepared according to this invention revealed that there were few types of impurities and their contents were low. Taking product sample 1 as an example, the impurity analysis results are shown in Table 4.
[0061] Table 4: Impurity Analysis Results of Sample 1
[0062]
[0063] As shown in Table 4, the samples prepared by this invention contain very few types of impurities, with only four. The study revealed that the impurity composition of the intermediates affects product purity; fewer types and lower impurity content in the intermediates are more conducive to preparing high-purity products. (Appendix) Figure 3 The peak appearing at 2.75 min was a solvent peak, so no relevant integral statistics were performed.
Claims
A method for preparing 1,4-(propenyloxy)phenylsulfonyl fluoride, characterized in that, The structure of the 4-(propenyloxy)phenylsulfonyl fluoride is as follows: The preparation method comprises two steps: the first step involves preparing the intermediate p-allyloxyphenol from hydroquinone and 3-bromopropene as starting materials; the second step involves synthesizing 4-(propenyloxy)phenylsulfonyl fluoride from the intermediate and thioyl fluoride under the action of an acid-binding agent. The first step requires N,N-diisopropylethylamine as the reaction solvent and hansyl ester as the catalyst. The molar ratio of hydroquinone, 3-bromopropene, and hansyl ester is 1:0.55–0.65:0.2–0.3, and the amount of N,N-diisopropylethylamine used per mole of hydroquinone is 1.0 L–1.2 L. In the second step, the molar ratio of the intermediate to thioyl fluoride is 1:2–5.
2. The method for preparing 4-(propenyloxy)phenylsulfonyl fluoride according to claim 1, characterized in that, The Hans ester is any one or a combination of ethylene benzoate or 1,2-propanediol dibenzoate.
3. The method for preparing 4-(propenyloxy)phenylsulfonyl fluoride according to claim 1, characterized in that, The acid-binding agent is an organic weak base, specifically any one of diethylamine, triethylamine, or pyridine; the molar amount of the acid-binding agent used is 1.5 to 3 times that of the intermediate.
4. The method for preparing 4-(propenyloxy)phenylsulfonyl fluoride according to claim 1, characterized in that, The reaction temperature of the first step is 60℃~110℃, and the reaction time is 4h~6h; the reaction temperature of the second step is 40℃~60℃, and the reaction time is 2h~4h; both the first step and the second step need to be carried out under the protection of an inert gas.
5. The method for preparing 4-(propenyloxy)phenylsulfonyl fluoride according to claim 1, characterized in that, After the first step reaction is completed, the reaction solution from the first step is washed with water, extracted, dried in organic phase, filtered and evaporated, and purified by silica gel column chromatography to obtain the intermediate.
6. The method for preparing 4-(propenyloxy)phenylsulfonyl fluoride according to claim 1, characterized in that, After the second step reaction is completed, the reaction solution from the second step is washed with water, extracted, dried by organic phase filtration and rotary evaporation, purified by silica gel column chromatography, and dried by molecular sieve to obtain the 4-(propenyloxy)phenylsulfonyl fluoride product.
7. The method for preparing 4-(propenyloxy)phenylsulfonyl fluoride according to any one of claims 5 or 6, characterized in that, The solvent used for the extraction is ethyl acetate.
8. The method for preparing 4-(propenyloxy)phenylsulfonyl fluoride according to claim 1, characterized in that, The reaction solvent for the second step reaction is any one of dichloromethane, N,N-dimethylformamide, or acetonitrile, and the amount of reaction solvent used for each mole of intermediate in the second step reaction is 1.0L to 1.2L.