Preparation method of 5-norbornyl octafluoro-3-oxapentane sodium sulfonate

Abstract

The invention relates to the technical field of preparation of photoacid generators, in particular to a preparation method of 5-norbornyl octafluoro-3-oxapentane sodium sulfonate. The preparation method comprises the following steps: under an oxygen-free environment condition, carrying out addition reaction and first purification treatment on 5-iodine octafluoro-3-oxygen pentane sulfonyl fluoride, norbornene and sodium p-toluenesulfinate, so as to obtain 5-(2-iodine) norbornyl octafluoro-3-oxygen pentane sulfonyl fluoride; the method comprises the following steps: under an oxygen-free environment condition, carrying out a deiodination reaction on 5-(2-iodo) norbornyl octafluoro-3-oxapentane sulfonyl fluoride and tributyltin hydride, and carrying out secondary purification treatment, so as to obtain 5-norbornyl octafluoro-3-oxapentane sulfonyl fluoride; and carrying out substitution reaction on the 5-norbornyl octafluoro-3-oxapentane sulfonyl fluoride by using sodium hydroxide, and carrying out third purification treatment, so as to obtain the 5-norbornyl octafluoro-3-oxapentane sodium sulfonate. According to the preparation method, the yield and the purity of the target product are improved while waste discharge is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photoacid generator preparation, and particularly relates to a preparation method of 5-norbornyl octafluoro-3-oxapentane sodium sulfonate. BACKGROUND

[0002] Photoresist is mainly composed of resin (polymer), photosensitizer, solvent and additive, wherein, the most important one in photosensitizer is photoacid generator (PAG), and PAG provides a key function for modern high-end photoresist. As a compound sensitive to light, under the irradiation of specific wavelength light (such as ultraviolet light, deep ultraviolet light, electron beam, extreme ultraviolet light), PAG can undergo photochemical reaction and produce acid molecules. The core value of PAG is to realize the conversion of optical signal to chemical signal, and through the chemical amplification effect, the sensitivity of photoresist is greatly improved. And with the continuous approach to the physical limit of the photoetching technology, the demand for PAG becomes more and more complex and extreme. The performance requirement of PAG in photoresist is a strict, multi-target system engineering problem, and PAG directly determines the resolution, accuracy and yield of high-end chip manufacturing. Although the existing technology has successfully synthesized the photoacid generator anion 5-norbornyl octafluoro-3-oxapentane sodium sulfonate, there are risks and drawbacks in these synthesis methods: (1) a large amount of diethyl ether is used as a solvent and an extraction reagent in the preparation process, and diethyl ether has great explosion hazards, in addition, a large amount of solvent is required to wash the excess raw materials in the reaction process, which greatly increases the production cost and the discharge amount of waste; (2) a large amount of raw materials is required in the industrialization process, which increases the processing difficulty and also increases the cost; in addition, a large amount of raw materials also reduces the synthesis efficiency and purity, prolongs the reaction time, and causes the increase of equipment energy consumption, the extension of production time and the increase of production cost. These defects greatly limit the industrial application of 5-norbornyl octafluoro-3-oxapentane sodium sulfonate. SUMMARY

[0003] The present application provides a preparation method of 5-norbornyl octafluoro-3-oxapentane sodium sulfonate, to solve the technical problem of how to improve the yield and purity of 5-norbornyl octafluoro-3-oxapentane sodium sulfonate under the premise of low waste discharge.

[0004] In a first aspect, the embodiments of the present application provide a preparation method of 5-norbornyl octafluoro-3-oxapentane sodium sulfonate, which comprises the following steps: under the condition of an oxygen-free environment, 5-iodo octafluoro-3-oxapentane sulfonyl fluoride, norbornene and sodium p-toluenesulfinate are subjected to an addition reaction to obtain an addition product; the addition product is subjected to a first purification treatment to obtain 5-(2-iodo) norbornyl octafluoro-3-oxapentane sulfonyl fluoride; Under the aforementioned anaerobic environment, 5-(2-iodo)norbornel octafluoro-3-oxapentanesulfonyl fluoride and tributyltin hydride were subjected to a deiodination reaction to obtain the deiodinated product; The deiodide product was subjected to a second purification process to obtain 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride. The 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride was substituted with sodium hydroxide to obtain the substituted product. The substituted product was subjected to a third purification process to obtain sodium 5-norbornyl octafluoro-3-oxapentane sulfonate.

[0005] Optionally, the amount of 5-iodooctafluoro-3-oxopentanesulfonyl fluoride n1, the amount of norbornene n2, and the amount of sodium p-toluenesulfinate n3 satisfy the following ratio: n1:n2:n3 = 1:1:0.2 to 1:2:0.5.

[0006] Optionally, the amount of substance n4 of 5-(2-iodo)norborneol octafluoro-3-oxapentanesulfonyl fluoride and the amount of substance n5 of tributyltin hydride satisfy: n4:n5=1:(1.0 to 1.5).

[0007] Optionally, the amount of 5-norbornyl octafluoro-3-oxapentanesulfonyl fluoride n6 and the amount of sodium hydroxide n7 satisfy: n6:n7=1:(1.0 to 3.0).

[0008] Optionally, the addition reaction can be carried out over a period of 12 to 24 hours.

[0009] Optionally, the temperature of the deiodination reaction is 30°C to 35°C, and the time of the deiodination reaction is 2 hours to 8 hours.

[0010] Optionally, the temperature of the substitution reaction is 80°C to 100°C, and the time of the substitution reaction is 2h to 10h.

[0011] Optionally, the oxygen-free environment may include a nitrogen atmosphere or an argon atmosphere.

[0012] Optionally, the first purification process sequentially includes distillation, first extraction, first separation, first drying, first concentration, and first vacuum distillation; and / or The second purification process sequentially includes quenching, second extraction, second separation, second drying, second concentration, low-temperature settling, and second vacuum distillation; and / or The third purification process includes, in sequence, cooling, precipitation, filtration, third drying, third concentration, pulping, and drying.

[0013] Optionally, the solvent used in the addition reaction is N,N-dimethylformamide; and / or The solvent used in the deiodination reaction is diethyl ether; and / or The solvent used in the substitution reaction is ultrapure water.

[0014] The technical solutions provided in this application have the following advantages compared with the prior art: This application provides a method for preparing sodium 5-norbornyloctafluoro-3-oxapentanesulfonate. The method first uses sodium p-toluenesulfinate as a free radical initiator to initiate a large number of free radicals. These free radicals undergo a regioselective double bond addition reaction with norbornene, improving the selectivity of the addition product and thus increasing its yield and purity. Then, tributyltin hydride is used to specifically deiodinate 5-(2-iodo)norbornyloctafluoro-3-oxapentanesulfonyl fluoride, suppressing side reactions and improving the purity and yield of the deiodinated product. Substituting sodium hydroxide and 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride, sodium 5-norbornyloctafluoro-3-oxapentanesulfonate can be obtained in high yield and high purity. In addition, this preparation method purifies the products after each reaction (addition reaction, deiodination reaction and substitution reaction). By purifying in a stepwise manner, impurities from each step of the reaction are avoided from accumulating in the reaction system, ensuring the purity of the raw materials for subsequent reactions and reducing side reactions caused by impurities. This effectively improves the purity of sodium 5-norbornyloctafluoro-3-oxapentanesulfonate. Attached Figure Description

[0015] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application.

[0016] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0017] Figure 1 A schematic flowchart illustrating a method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate according to an embodiment of this application; Figure 2 A schematic diagram illustrating the preparation method of sodium 5-norbornyl octafluoro-3-oxapentane sulfonate provided in this application embodiment; Figure 3 The 1H NMR spectrum of 5-(2-iodo)norbornel octafluoro-3-oxapentane sulfonyl fluoride provided in the embodiments of this application; Figure 4The carbon NMR spectrum of 5-(2-iodo)norbornel octafluoro-3-oxapentane sulfonyl fluoride provided in the embodiments of this application; Figure 5 The 1H NMR spectrum of 5-norbornel octafluoro-3-oxapentanesulfonyl fluoride provided in the embodiments of this application; Figure 6 The carbon NMR spectrum of 5-norbornyl octafluoro-3-oxapentane sulfonyl fluoride provided in the embodiments of this application; Figure 7 The 1H NMR spectrum of sodium 5-norbornyl octafluoro-3-oxapentane sulfonate provided in the embodiments of this application; Figure 8 The carbon NMR spectrum of sodium 5-norbornyl octafluoro-3-oxapentane sulfonate provided in the embodiments of this application. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0019] The range descriptions used in this application, such as numerical ranges and proportional ranges, include all possible sub-ranges and single numerical values ​​within that range. For example, the range descriptions of "1 to 6" or "1~6" cover all sub-ranges (such as 1 to 3, 2 to 5, etc.) and single numbers (such as 1, 2, 3, 4, 5, 6) between 1 and 6. Unless otherwise specified, the terms "comprising" and others used herein mean "including but not limited to"; relational terms such as "first" and "second" are used only to distinguish different entities or operations and do not imply an actual order or relationship; "and / or" indicates that multiple situations can exist individually or simultaneously; expressions such as "at least one," "multiple," and "at least one" refer to any combination of the corresponding objects, including combinations of single or multiple objects. The proportional relationships involved in this document, such as mass ratios and molar ratios, should be understood as the correspondence between the first and second terms of a proportional formula, according to the order of description. The raw materials, reagents, instruments, and equipment used herein can all be obtained by purchasing from the market or by existing methods.

[0020] Figure 1 An exemplary schematic diagram of a method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate according to an embodiment of this application is shown. Figure 2An exemplary schematic diagram illustrates the principle of a method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate according to an embodiment of this application; like Figure 1 and Figure 2 As shown in the embodiments of this application, a method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate is provided, the preparation method comprising: S1. Under anaerobic conditions, 5-iodooctafluoro-3-oxopentanesulfonyl fluoride, norbornene, and sodium p-toluenesulfinate were subjected to an addition reaction to obtain the addition product; S2. The addition product is subjected to a first purification treatment to obtain 5-(2-iodo)norbornel octafluoro-3-oxapentanesulfonyl fluoride; S3. Under the aforementioned anaerobic environment, 5-(2-iodo)norbornel octafluoro-3-oxapentanesulfonyl fluoride and tributyltin hydride are subjected to a deiodination reaction to obtain the deiodinated product; S4. The deiodinated product is subjected to a second purification treatment to obtain 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride; S5. The 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride was subjected to a substitution reaction using sodium hydroxide to obtain the substituted product; S6. The substituted product is subjected to a third purification process to obtain sodium 5-norbornyl octafluoro-3-oxapentane sulfonate.

[0021] It should be noted that in this addition reaction, 5-iodooctafluoro-3-oxopentanesulfonyl fluoride and norbornene are first dissolved in N,N-dimethylformamide, and then sodium p-toluenesulfinate is added to carry out the addition reaction.

[0022] It should be noted that in this deiodination reaction, 5-(2-iodo)norbornel octafluoro-3-oxapentanesulfonyl fluoride is first dissolved in diethyl ether, and then tributyltin hydride is slowly added dropwise to carry out the deiodination reaction.

[0023] It should be noted that in this substitution reaction, 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride is first dissolved in ultrapure water, and then sodium hydroxide is slowly added.

[0024] It should be noted that the method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate provided in this application improves the yield and purity of the target product, sodium 5-norbornyl octafluoro-3-oxapentane sulfonate, by precisely controlling reaction conditions, employing a stepwise purification strategy, and selecting highly selective reagents, while reducing waste emissions. The specific mechanism is as follows: 1. An anaerobic environment suppresses side reactions, reduces waste, and improves reaction efficiency: The entire reaction process (addition reaction and deiodination reaction) is carried out under anaerobic conditions: (1) In the addition reaction, sodium p-toluenesulfinate is used as a free radical initiator. It can stably generate active free radicals in an anaerobic environment, avoiding the combination of oxygen and free radicals to form byproducts such as peroxides (such byproducts not only consume raw materials, but also increase the complexity of waste). (2) In the deiodination reaction, tributyltin hydride is a typical free radical hydrogen source. An oxygen-free environment can prevent tributyltin hydride from being oxidized and becoming ineffective, ensuring that tributyltin hydride can efficiently provide hydrogen atoms to complete the deiodination, reducing the waste of raw materials and the generation of by-products caused by the failure of tributyltin hydride. By suppressing side reactions, the utilization rate of raw materials can be improved, and waste (such as by-products and unreacted oxidized impurities) can be significantly reduced, indirectly increasing the yield of the target product.

[0025] 2. Stepwise purification strategy: Remove impurities promptly to avoid accumulation that could affect subsequent reactions. Three targeted purification processes (first to third purification treatments): (1) First purification treatment: 5-(2-iodo)norbornyloctafluoro-3-oxapentanesulfonyl fluoride is directly separated after the addition reaction to remove unreacted norbornene, sodium p-toluenesulfinate, and other impurities. If impurities are introduced into the deiodination step, they may undergo side reactions with tributyltin hydride (e.g., sodium sulfinate is reduced), leading to a decrease in deiodination efficiency and the generation of new impurities; (2) Second purification treatment: After deiodination, 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride is obtained by purification, which can remove excess tributyltin hydride and by-products of tributyltin hydride (such as tributyltin iodide), and avoid the by-products from reacting with sodium hydroxide in subsequent substitution reactions to generate tin hydroxide and other difficult-to-treat wastes. (3) Third purification treatment: After the substitution reaction, the final product is purified to remove unreacted sulfonyl fluoride raw materials and inorganic impurities (such as NaF), directly improving the purity of the target product sodium 5-norbornyloctafluoro-3-oxapentanesulfonate.

[0026] Stepwise purification avoids the accumulation of impurities in the reaction system, ensures the purity of the raw materials in each step of the reaction, and reduces side reactions caused by impurities. This not only improves the conversion rate of each step of the reaction (and thus increases the overall yield), but also reduces the difficulty of final purification (and reduces the amount of waste to be disposed of).

[0027] 3. Highly selective reagents reduce side reactions and waste emissions: (1) Addition reaction: Sodium p-toluenesulfinate was selected as a free radical initiator. The free radicals initiated by the reaction with the double bond of norbornene have regioselectivity (preferentially attacking the active site of the double bond), reducing isomerization byproducts and improving the selectivity of the addition product. (2) Deiodination reaction: Tributyltin hydride has high specificity for the substitution of iodine atoms (only undergoes hydrogen transfer with iodine radicals), and hardly reacts with other functional groups in the molecule (such as sulfonyl fluoride, ether bond). The only byproduct is tributyltin iodide (which can be efficiently separated through a second purification to reduce the types of waste). (3) Substitution reaction: Sodium hydroxide, as a nucleophile, preferentially attacks the sulfur atom in sulfonyl fluoride (-SO2F) (fluorine is a strong leaving group). The reaction is highly selective, and the by-products are only inorganic salts, such as NaF. NaF is easily soluble in water and can be separated by a third purification process (e.g., recrystallization). It is an easy-to-handle low-pollution waste.

[0028] The use of highly selective reagents can reduce the types and amounts of byproducts at the source, reduce the pressure of waste discharge, and at the same time ensure that more raw materials are converted into target products, thereby increasing yield.

[0029] In summary, the method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate provided in this application provides a closed loop with low side reactions, high conversion rate, and easy separation and purification by inhibiting side reactions in an anaerobic environment, eliminating impurity accumulation through stepwise purification, and reducing ineffective consumption of highly selective reagents. This method significantly improves the yield and purity of sodium 5-norbornyl octafluoro-3-oxapentane sulfonate while reducing waste emissions.

[0030] In some optional embodiments, the amount n1 of 5-iodooctafluoro-3-oxopentanesulfonyl fluoride, the amount n2 of norbornene, and the amount n3 of sodium p-toluenesulfinate satisfy the following ratio: n1:n2:n3 = 1:1:0.2 to 1:2:0.5.

[0031] In these embodiments, the molar ratio of 5-iodooctafluoro-3-oxopentanesulfonyl fluoride, norbornene, and sodium p-toluenesulfinate of 1:1:0.2 to 1:2:0.5 allows the addition reaction to proceed sufficiently to form an adequate amount of the addition product.

[0032] The amounts of 5-iodooctafluoro-3-oxopentanesulfonyl fluoride (n1), norbornene (n2), and sodium p-toluenesulfinate (n3) satisfy the following: n1:n2:n3 = 1:1:0.2, 1:1:0.3, 1:1:0.4, 1:1:0.5, 1:1.5:0.2, 1:1.5:0.3, 1:1.5:0.4, 1:1.5:0.5, 1:2:0.2, 1:2:0.3, 1:2:0.4, or 1:2:0.5.

[0033] In some alternative embodiments, the amount n4 of 5-(2-iodo)norborneol octafluoro-3-oxapentanesulfonyl fluoride and the amount n5 of tributyltin hydride satisfy: n4:n5=1:(1.0 to 1.5).

[0034] In these embodiments, the molar ratio of 5-(2-iodo)norbornel octafluoro-3-oxapentanesulfonyl fluoride and tributyltin hydride in the form of 1:(1.0 to 1.5) allows the deiodination reaction to proceed sufficiently, yielding a sufficient amount of deiodinated product.

[0035] The molar amount n5 of the tributyltin hydride can be 1.0, 1.1, 1.2, 1.3, 1.4 or 1.5.

[0036] In some alternative embodiments, the amount of 5-norbornyl octafluoro-3-oxapentanesulfonyl fluoride n6 and the amount of sodium hydroxide n7 satisfy: n6:n7=1:(1.0 to 3.0).

[0037] In these embodiments, a molar ratio of 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride and sodium hydroxide of 1:(1.0 to 3.0) allows the substitution reaction to proceed sufficiently to obtain a sufficient amount of the substituted product.

[0038] The amount of sodium hydroxide, n7, can be 1.0, 1.5, 2.0, 2.5, or 3.0.

[0039] In some alternative embodiments, the addition reaction takes 12 to 24 hours.

[0040] In these embodiments, an addition reaction lasting 12 to 24 hours allows sufficient addition products to be formed between 5-iodooctafluoro-3-oxopentanesulfonyl fluoride, norbornene, and sodium p-toluenesulfinate.

[0041] The addition reaction can take 12h, 14h, 16h, 18h, 20h, 22h or 24h.

[0042] It should be noted that the addition reaction can be performed at room temperature.

[0043] In some alternative embodiments, the temperature of the deiodination reaction is 30°C to 35°C, and the time of the deiodination reaction is 2 hours to 8 hours.

[0044] In these embodiments, a deiodination reaction at a temperature of 30°C to 35°C and a time of 2h to 8h allows sufficient deiodination products to form between 5-(2-iodo)norborneol octafluoro-3-oxapentanesulfonyl fluoride and tributyltin hydride.

[0045] The temperature for the deiodination reaction can be 30℃, 31℃, 32℃, 33℃, 34℃ or 35℃.

[0046] The time for this deiodination reaction can be 2h, 3h, 4h, 5h, 6h, 7h or 8h.

[0047] In some alternative embodiments, the temperature of the substitution reaction is 80°C to 100°C, and the duration of the substitution reaction is 2 hours to 10 hours.

[0048] In these embodiments, a substitution reaction at a temperature of 80°C to 100°C and a time of 2h to 10h allows sufficient substitution products to be formed between 5-norborneyloctafluoro-3-oxapentanesulfonyl fluoride and sodium hydroxide.

[0049] The temperature for this substitution reaction can be 80℃, 85℃, 90℃, 95℃ or 100℃.

[0050] The substitution reaction can take 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, or 10h.

[0051] In some alternative implementations, the oxygen-free environment includes a nitrogen atmosphere or an argon atmosphere.

[0052] In these embodiments, using an oxygen-free environment, including a nitrogen atmosphere or an argon atmosphere, allows the addition reaction and the deiodination reaction to proceed fully under oxygen-free conditions, avoiding oxygen interference with the reaction and the generation of byproducts, which is beneficial to obtaining the target product of high purity sodium 5-norbornel octafluoro-3-oxapentane sulfonate.

[0053] In some optional embodiments, the first purification process sequentially includes distillation, first extraction, first separation, first drying, first concentration, and first vacuum distillation; and / or The second purification process sequentially includes quenching, second extraction, second separation, second drying, second concentration, low-temperature settling, and second vacuum distillation; and / or The third purification process includes, in sequence, cooling, precipitation, filtration, third drying, third concentration, pulping, and drying.

[0054] In these embodiments, a first purification process, comprising distillation, a first extraction, a first separation, a first drying, a first concentration, and a first vacuum distillation, allows the byproducts in the addition product to be separated from 5-(2-iodo)norbornyloctafluoro-3-oxapentanesulfonyl fluoride, thereby obtaining a pure 5-(2-iodo)norbornyloctafluoro-3-oxapentanesulfonyl fluoride intermediate. Furthermore, a second purification process, comprising quenching, a second extraction, a second separation, a second drying, a second concentration, low-temperature settling, and a second vacuum distillation, allows the byproducts in the deiodination product to be separated from 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride, thereby obtaining high-purity 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride. Furthermore, a third purification process, consisting of cooling, precipitation, filtration, third drying, third concentration, pulping, and drying, can separate the byproducts in the substituted product from sodium 5-norbornyloctafluoro-3-oxapentanesulfonate, thereby obtaining the target product of high purity sodium 5-norbornyloctafluoro-3-oxapentanesulfonate.

[0055] It should be noted that the specific process of the first purification treatment is as follows: the addition product is subjected to vacuum distillation using a circulating water pump to remove most of the N,N-dimethylformamide and unreacted norbornene; then, 500 mL of dichloromethane and 500 mL of water are used as the extraction solvent, and the mixture is stirred for 30 min for the first extraction, followed by standing and layering, and then the first separation is performed to obtain the organic phase and the aqueous phase; the organic phase is washed three times with water (500 mL each time), and then dried with anhydrous sodium sulfate, and then concentrated by rotary evaporation to remove the solvent; finally, pure 5-(2-iodo)norbornene octafluoro-3-oxapentanesulfonyl fluoride is obtained by the first vacuum distillation.

[0056] It should be noted that the specific process of the second purification treatment is as follows: A saturated KF solution is added to the deiodinated product for quenching to terminate the incomplete reaction of tributyltin hydride. The mixture is stirred for 30 minutes during quenching, then filtered to remove the precipitate. The remaining liquid phase is poured into 500 mL of dichloromethane and 500 mL of water for a second extraction, and stirred for another 30 minutes before standing to separate the layers. A second separation is then performed to obtain the organic phase and the aqueous phase. The organic phase is washed three times with water (500 mL each time), then dried a second time using anhydrous sodium sulfate. After the second drying, a second concentration is performed using rotary evaporation to remove the solvent. The mixture is then allowed to stand at low temperature, filtered to remove impurities precipitated during the low-temperature standing process, and finally, a second vacuum distillation is performed to obtain 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride.

[0057] It should be noted that the specific process of the third purification treatment is as follows: the substituted product is cooled to a certain temperature, and then 2000 mL of anhydrous ethanol is added for precipitation to precipitate the by-products and obtain a mixture; the mixture is dried by filtration (separation of liquid phase) to obtain a solid-phase substituted product; the solid-phase substituted product is concentrated by rotary evaporation to remove the solvent, and then pulped with isopropyl ether, and then dried to obtain sodium 5-norbornyl octafluoro-3-oxapentane sulfonate.

[0058] In some alternative embodiments, the solvent used for the addition reaction is N,N-dimethylformamide; and / or The solvent used in the deiodination reaction is diethyl ether; and / or The solvent used in the substitution reaction is ultrapure water.

[0059] In these embodiments, using N,N-dimethylformamide as a solvent allows for a sufficient addition reaction between 5-iodooctafluoro-3-oxapentanesulfonyl fluoride, norbornene, and sodium p-toluenesulfinate to yield a sufficient amount of the addition product; using diethyl ether as a solvent allows for a sufficient deiodination reaction between 5-(2-iodo)norbornyloctafluoro-3-oxapentanesulfonyl fluoride and tributyltin hydride to yield a sufficient amount of the deiodinated product; and using ultrapure water as a solvent allows for a sufficient substitution reaction between 5-(2-iodo)norbornyloctafluoro-3-oxapentanesulfonyl fluoride and sodium hydroxide to yield a sufficient amount of the substituted product.

[0060] The present application is further illustrated below with reference to specific embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national / industry standards; if there is no corresponding national / industry standard, they are performed according to general international standards, conventional conditions, or conditions recommended by the manufacturer.

[0061] Example 1 like Figure 1 and Figure 2 As shown, a method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate includes: S1. Under a nitrogen atmosphere, 1000g of 5-iodooctafluoro-3-oxopentanesulfonyl fluoride and 332g of norbornene were dissolved in 1000mL of N,N-dimethylformamide, and then 106g of sodium p-toluenesulfinate was added at room temperature for an addition reaction for 12h to obtain the addition product. S2. The addition product is subjected to a first purification treatment to obtain 5-(2-iodo)norbornyloctafluoro-3-oxapentanesulfonyl fluoride; S3. Under a nitrogen atmosphere, 1000g of 5-(2-iodo)norbornel octafluoro-3-oxapentanesulfonyl fluoride was dissolved in 1000mL of diethyl ether, and 565mL of tributyltin hydride was added dropwise under stirring to carry out a deiodination reaction at a temperature of 30℃ to 35℃ for 3h to obtain the deiodinated product. S4. The deiodination product is subjected to a second purification treatment to obtain 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride; S5. Dissolve 1000g of 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride in 1200mL of ultrapure water, then slowly add 150g of sodium hydroxide under stirring, and then carry out a substitution reaction at 80℃ for 3h to obtain the substituted product. S6. The substituted product is subjected to a third purification process to obtain sodium 5-norbornyloctafluoro-3-oxapentanesulfonate.

[0062] The specific process of the first purification treatment is as follows: The addition product is subjected to vacuum distillation by a circulating water pump to remove most of the N,N-dimethylformamide and unreacted norbornene; then, 500 mL of dichloromethane and 500 mL of water are used as the extraction solvent, and the first extraction is carried out by stirring for 30 min. After standing and separating the layers, the first separation is performed to obtain the organic phase and the aqueous phase; the organic phase is washed three times with water (500 mL each time), and then dried with anhydrous sodium sulfate. After the first drying, the first concentration is carried out by rotary evaporation to remove the solvent; finally, pure 5-(2-iodo)norbornene octafluoro-3-oxapentanesulfonyl fluoride is obtained by the first vacuum distillation.

[0063] The specific process for the second purification treatment is as follows: Saturated KF solution is added to the deiodinated product for quenching to terminate the incomplete reaction of tributyltin hydride. Stirring is performed for 30 minutes during quenching, followed by filtration to remove the precipitate. The remaining liquid phase is then poured into 500 mL of dichloromethane and 500 mL of water for a second extraction, and stirring is continued for 30 minutes. The mixture is then allowed to stand for separation, followed by a second separation to obtain an organic phase and an aqueous phase. The organic phase is washed three times with water (500 mL each time), and then dried a second time using anhydrous sodium sulfate. After the second drying, a second concentration is performed using rotary evaporation to remove the solvent. The mixture is then allowed to stand at low temperature, and filtration is used to remove impurities precipitated during the low-temperature standing process. Finally, a second vacuum distillation is performed to obtain 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride.

[0064] The specific process of the third purification treatment is as follows: the substituted product is cooled to a certain temperature, and then 2000 mL of anhydrous ethanol is added for precipitation to precipitate the by-products and obtain a mixture; the mixture is dried by filtration (separation of liquid phase) to obtain a solid substituted product; the solid substituted product is concentrated by rotary evaporation to remove the solvent, and then pulped with isopropyl ether, and then dried to obtain sodium 5-norbornyl octafluoro-3-oxapentane sulfonate.

[0065] Example 2 Compared to Example 1, the differences in this example are as follows, while the rest are the same: A method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate, comprising: S1. Under a nitrogen atmosphere, 1000g of 5-iodooctafluoro-3-oxopentanesulfonyl fluoride and 498g of norbornene were dissolved in 1000mL of N,N-dimethylformamide, and then 185g of sodium p-toluenesulfinate was added at room temperature to carry out an addition reaction for 18h to obtain the addition product. S2. The addition product is subjected to a first purification treatment to obtain 5-(2-iodo)norbornyloctafluoro-3-oxapentanesulfonyl fluoride; S3. Under a nitrogen atmosphere, 1000g of 5-(2-iodo)norbornel octafluoro-3-oxapentanesulfonyl fluoride was dissolved in 1000mL of diethyl ether, and 706mL of tributyltin hydride was added dropwise under stirring to carry out a deiodination reaction at a temperature of 30℃ to 35℃ for 3h to obtain the deiodinated product. S4. The deiodination product is subjected to a second purification treatment to obtain 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride; S5. Dissolve 1000g of 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride in 1200mL of ultrapure water, then slowly add 300g of sodium hydroxide under stirring, and then carry out a substitution reaction at 90℃ for 6h to obtain the substituted product. S6. The substituted product is subjected to a third purification process to obtain sodium 5-norbornyloctafluoro-3-oxapentanesulfonate.

[0066] Example 3 Compared to Example 1, the differences in this example are as follows, while the rest are the same: A method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate, comprising: S1. Under a nitrogen atmosphere, 1000g of 5-iodooctafluoro-3-oxopentanesulfonyl fluoride and 664g of norbornene were dissolved in 1000mL of N,N-dimethylformamide, and then 265g of sodium p-toluenesulfinate was added at room temperature to carry out an addition reaction for 24h to obtain the addition product. S2. The addition product is subjected to a first purification treatment to obtain 5-(2-iodo)norbornyloctafluoro-3-oxapentanesulfonyl fluoride; S3. Under a nitrogen atmosphere, 1000g of 5-(2-iodo)norbornel octafluoro-3-oxapentane sulfonyl fluoride was dissolved in 1000mL of diethyl ether, and 850mL of tributyltin hydride was added dropwise under stirring to carry out a deiodination reaction at a temperature of 30℃ to 35℃ for 8h to obtain the deiodinated product. S4. The deiodination product is subjected to a second purification treatment to obtain 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride; S5. Dissolve 1000g of 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride in 1200mL of ultrapure water, then slowly add 450g of sodium hydroxide under stirring, and then carry out a substitution reaction at 100℃ for 10h to obtain the substituted product. S6. The substituted product is subjected to a third purification process to obtain sodium 5-norbornyloctafluoro-3-oxapentanesulfonate.

[0067] Comparative Example 1 Compared to Example 1, the differences in this example are as follows, while the rest are the same: The solution described in CN 102799068 A is used in the prior art.

[0068] Comparative Example 2 Compared to Example 1, the differences in this example are as follows, while the rest are the same: The scheme described in Chem. Mater. 2009, 21, 4037-4046 was used.

[0069] Relevant experimental and effect data: 1. Collect the following samples from Example 1: 5-(2-iodo)norbornel octafluoro-3-oxapentanesulfonyl fluoride obtained after addition reaction and first purification treatment; 5-norbornel octafluoro-3-oxapentanesulfonyl fluoride obtained after deiodination reaction and second purification treatment; and sodium 5-norbornel octafluoro-3-oxapentanesulfonate obtained after substitution reaction and third purification treatment. Perform NMR analysis on these samples. The results are as follows: Figures 3 to 8 As shown. This indicates that the method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate provided in this application embodiment has been successfully applied. Figure 2 Materials for each step in the process.

[0070] 2. The yields and purities of 5-(2-iodo)norbornyloctafluoro-3-oxapentanesulfonyl fluoride, 5-norbornyloctafluoro-3-oxapentanesulfonyl fluoride, and sodium 5-norbornyloctafluoro-3-oxapentanesulfonate in each example were statistically analyzed, and the results are shown in Table 1.

[0071]

[0072] As shown in Table 1, the method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate provided in this application has formed a closed loop with low side reaction, high conversion rate, and easy separation and purification by inhibiting side reactions in an anaerobic environment, eliminating impurity accumulation through stepwise purification, and reducing ineffective consumption with highly selective reagents. While reducing waste emissions, this method significantly improves the yield and purity of sodium 5-norbornyl octafluoro-3-oxapentane sulfonate, so that the yield of the final target product can reach more than 90%, and the purity can reach more than 98.5%.

[0073] Compared to Example 1, Comparative Example 1 used a large amount of diethyl ether, and the amount of diethyl ether used in Comparative Example 1 was 90% higher than that used in this application. Compared to Comparative Example 1, this application used non-flammable dichloromethane instead of diethyl ether as a detergent, and also used N,N-dimethylformamide instead of diethyl ether as a solvent, effectively reducing the amount of diethyl ether used.

[0074] Compared to Example 1, Comparative Example 2 used an excessive amount of norbornene and required a large amount of diethyl ether as a solvent for subsequent extraction, which significantly increased the production cost and waste emissions of sodium 5-norbornel octafluoro-3-oxapentane sulfonate. In contrast to Comparative Example 2, this application introduces distillation operations in both the first and second purification processes, which preferentially removes large amounts of N,N-dimethylformyl and the remaining raw materials. Subsequent extraction with a small amount of dichloromethane yields the corresponding product with high purity, significantly reducing the production cost of sodium 5-norbornel octafluoro-3-oxapentane sulfonate and the amount of diethyl ether used, achieving a dual improvement in both low production cost and low use of harmful substances.

[0075] In summary, the present application provides a method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate. This method, through precise control of reaction conditions, stepwise purification strategy, and selection of highly selective reagents, reduces waste emissions while improving the yield and purity of the target product, sodium 5-norbornyl octafluoro-3-oxapentane sulfonate.

[0076] Furthermore, this application provides a method for preparing sodium 5-norbornyl octafluoro-3-oxapentanesulfonate. This method uses flammable and explosive diethyl ether only in the deiodination reaction, while using non-flammable N,N-dimethylformamide in the addition reaction. It also uses non-flammable dichloromethane instead of diethyl ether as a detergent, significantly reducing the amount of diethyl ether used in traditional preparation methods. Additionally, because this method precisely controls the amounts of 5-iodooctafluoro-3-oxapentanesulfonyl fluoride and norbornene, it reduces the additional amount of norbornene used, saving production costs. Furthermore, it increases the number of distillation operations in the first purification process, effectively removing N,N-dimethylformamide and norbornene, thus reducing the amount of detergent required for the subsequent first washing.

[0077] Furthermore, the present application provides a method for preparing sodium 5-norbornyl octafluoro-3-oxapentane sulfonate. This method has a shorter overall production time compared to Comparative Example 1 and Comparative Example 2, and the method reduces the amount of diethyl ether used, resulting in higher safety, less waste, and lower production costs. In addition, each step of this method has the advantages of high product yield and high product purity, making it a safe, green, efficient, and economical production route for sodium 5-norbornyl octafluoro-3-oxapentane sulfonate.

[0078] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed in this application.

Claims

1. A process for the preparation of sodium 5-norbornyl octafluoro-3-oxapentanesulfonate, characterized in that, The preparation method comprises: under an oxygen-free environment condition, 5-iodooctafluoro-3-oxapentane sulfonyl fluoride, norbornene and sodium p-toluenesulfinate are subjected to an addition reaction to obtain an addition product; the addition product is subjected to a first purification treatment to obtain 5-(2-iodo) norbornyl octafluoro-3-oxapentane sulfonyl fluoride; under the oxygen-free environment condition, 5-(2-iodo) norbornyl octafluoro-3-oxapentane sulfonyl fluoride and tributyltin hydride are subjected to a deiodination reaction to obtain a deiodination product; the deiodination product is subjected to a second purification treatment to obtain 5-norbornyl octafluoro-3-oxapentane sulfonyl fluoride; the 5-norbornyl octafluoro-3-oxapentane sulfonyl fluoride is subjected to a substitution reaction using sodium hydroxide to obtain a substitution product; the substitution product is subjected to a third purification treatment to obtain 5-norbornyl octafluoro-3-oxapentane sulfonate sodium.

2. The production method according to claim 1, characterized by, The amount of substance n1 of the 5-iodooctafluoro-3-oxapentane sulfonyl fluoride, the amount of substance n2 of the norbornene and the amount of substance n3 of the sodium p-toluenesulfinate satisfy: n1:n2:n3 = 1:1:0.2 to 1:2:0.

5.

3. The preparation method according to claim 1, characterized in that, The amount of substance n4 of the 5-(2-iodo) norbornyl octafluoro-3-oxapentane sulfonyl fluoride and the amount of substance n5 of the tributyltin hydride satisfy: n4:n5 = 1: (1.0 to 1.5).

4. The production method according to claim 1, characterized by, The amount of substance n6 of the 5-norbornyl octafluoro-3-oxapentane sulfonyl fluoride and the amount of substance n7 of the sodium hydroxide satisfy: n6:n7 = 1: (1.0 to 3.0).

5. The method of claim 1, wherein, The time of the addition reaction is 12h to 24h.

6. The method of claim 1, wherein, The temperature of the deiodination reaction is 30℃ to 35℃, and the time of the deiodination reaction is 2h to 8h.

7. The preparation method according to claim 1, characterized in that, The temperature of the substitution reaction is 80℃ to 100℃, and the time of the substitution reaction is 2h to 10h.

8. The method of claim 1, wherein, The oxygen-free environment comprises a nitrogen atmosphere or an argon atmosphere.

9. The method of claim 1, wherein, The first purification treatment comprises, in sequence, distillation, first extraction, first liquid separation, first drying, first concentration and first reduced-pressure distillation; and / or The second purification treatment comprises, in sequence, quenching, second extraction, second liquid separation, second drying, second concentration, low-temperature standing and second reduced-pressure distillation; and / or The third purification treatment comprises, in sequence, cooling, precipitation, filtration, third drying, third concentration, beating and drying.

10. The method of claim 1, wherein, The solvent used in the addition reaction is N,N-dimethylformamide; and / or The solvent used in the deiodination reaction is diethyl ether; and / or The solvent used in the substitution reaction is ultrapure water.

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