Preparation method of N-hydroxy-1, 8-naphthalimide perfluorobutyl sulfonate

Abstract

The invention provides a preparation method of N-hydroxyl-1, 8-naphthalimide perfluorobutyl sulfonate, which comprises the following steps: step 1, adding absolute ethyl alcohol, continuing to add 1, 8-naphthalic anhydride and hydroxylamine hydrochloride, dropwise adding triethylamine, and heating to reflux reaction after dropwise adding to obtain white solid N-hydroxyl-1, 8-naphthalimide; and step 2, adding tetrahydrofuran, continuing to add N-hydroxy-1, 8-naphthalimide and DMAP, controlling the temperature to be 20-25 DEG C, dropwise adding perfluorobutyl sulfonyl chloride, and after the reaction is completed, obtaining a solid product N-hydroxy-1, 8-naphthalimide perfluorobutyl sulfonate. Under the condition that the yield is not reduced, a green and clean solvent is used in the preparation method and is easy to recycle, the reaction temperature is reduced, the reaction time is greatly shortened, absolute ethyl alcohol is used as the solvent, the disadvantage of water as the solvent on the ring-closing dehydration reaction is avoided, and compared with dioxane, the method has the advantages of being environmentally friendly, simple and convenient in synthesis step and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of photochemical materials, and relates to a photoacid generator, in particular to a preparation method of N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate. BACKGROUND

[0002] A photoacid generator (PAG) is a kind of compound that can be decomposed and eventually form a specific acidic substance under external stimulation (such as light, heat, radiation, etc.), and the acidic substance generated is a photo-controllable acid that can cause acid-sensitive substances to decompose or crosslink. Sulfonium salt type acid generators appeared relatively early and are reported in many literatures; while sulfonate type acid generators appeared relatively late.

[0003] At present, the sulfonate compounds reported in the literatures mainly include N-hydroxy phthalimide p-toluenesulfonate, N-trifluoromethanesulfonyloxy succinimide, N-trifluoromethanesulfonyloxy naphthalimide, dinitrobenzyl p-toluenesulfonate, and alpha-hydroxymethyl benzoin p-toluenesulfonate, 5-norbornene-23-dicarboximide trifluoromethyl sulfonate, etc. However, the synthesis of N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate has not been reported in Chinese literatures. N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate belongs to the common N-sulfonyl dicarboximide PAG. When it is exposed to a light source of a corresponding wavelength, the sulfonate bond in the structure will break, generating a corresponding sulfonic acid with low toxicity, and the acid strength and acid diffusion degree are appropriate, so the substance is suitable for photoresists irradiated by 248 nm deep ultraviolet, 193 nm extreme deep ultraviolet and other light sources. This kind of non-ionic acid generator has good solubility in common solvents and good transparency at 248 nm. Although the existing process uses 1,8-naphthalic anhydride and hydroxylamine hydrochloride as raw materials to synthesize N-hydroxy-1,8-naphthalimide by one step, this synthesis route has been widely concerned and researched due to its advantages of simple process, less by-products and high yield. However, the reaction solvent system has the following defects.

[0004] First, the alkaline system: referring to the synthesis of N-hydroxy phthalimide (NHPI), people make the carbonate of alkali metal participate in the reaction, and the yield of NHPI prepared at a temperature of 80-100 ℃ can reach 80%-85%. Although the yield of the reaction is high, there is a problem of difficult separation of the product and the generated inorganic salt, which increases the difficulty of the purification step.

[0005] Second, the organic solvent system: people use dioxane as the reaction solvent. It is found through experiments that when the volume ratio of dioxane in the overall solvent system reaches 90%, although the reactants are reacted at 100-105 DEG C for 2h, the yield reaches 90%-95%, and the purity can reach 97%. This method has the advantages of easy availability of raw materials and simple synthesis steps, but dioxane is a toxic solvent, which is expensive and pollutes the environment.

[0006] Some scholars choose pyridine as the reaction medium, and the yield can reach 81%. Although this method has the advantages of simple product post-treatment and high conversion rate, the pyridine reagent used has toxicity and certain harm to the environment and human body. Liu Jianguo et al. synthesized NHPI using phthalic anhydride and hydroxylamine hydrochloride as raw materials and methanol as solvent, and the yield was 84% and the purity was 98.5%. The reaction selects the easily recyclable methanol as the solvent, and the product with high yield can be obtained. However, the reaction time of this method is long, and the steps are complicated. SUMMARY

[0007] In view of the deficiencies of the prior art, the purpose of the present application is to provide a preparation method of N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate, which solves the technical problems that the preparation method in the prior art cannot simultaneously consider environmental protection and simplicity without reducing the yield.

[0008] In order to solve the above technical problems, the technical scheme is adopted as follows: A preparation method of N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate, which is carried out according to the following steps: Step one, synthesis of N-hydroxy-1,8-naphthalimide: Add anhydrous ethanol, start stirring, continue to add 1,8-naphthalic anhydride and hydroxylamine hydrochloride, start stirring, stir at room temperature, add triethylamine dropwise, heat to reflux after dropwise addition is completed, first concentrate under reduced pressure until solid appears, cool, add ultrapure water dropwise, and finally filter the wet product after crystallization, filtration and washing, and dry the material to obtain white solid N-hydroxy-1,8-naphthalimide.

[0009] Step two, synthesis of N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate: Add tetrahydrofuran, open the stirring, continue to add the N-hydroxy-1,8-naphthalene dicarboxylic acid imide prepared in step one and DMAP, control temperature 20-25℃, drop the addition of perfluorobutyl sulfonyl chloride, after the reaction is completed, drop the addition of ultrapure water, there is solid precipitation, stirring, cooling, filtration to obtain wet product, again through water washing, filtration to obtain filter cake, filter cake is added to acetone, stirring to completely dissolve, filter out the insoluble, add water to the filtrate, heating, stirring, solid is completely dissolved, keep warm, cooling, filtration to obtain product, drying, obtain solid product N-hydroxy-1,8-naphthalene dicarboxylic acid imide perfluorobutyl sulfonate.

[0010] The present application also has the following technical features: Preferably, the method is carried out according to the following steps Step one, synthesis of N-hydroxy-1,8-naphthalene dicarboxylic acid imide: Add anhydrous ethanol to the three-port bottle, open the stirring, continue to add 1,8-naphthalene anhydride and hydroxylamine hydrochloride, open the stirring, stirring at room temperature for 0.5-1h, control the temperature ≤45℃, drop the addition of triethylamine, after the drop addition is completed, heating to reflux reaction for 2h, after the reaction is completed, first reduce pressure concentration to remove most of the solvent until solid appears, transfer to a beaker, cooling to below 10℃, drop the addition of ultrapure water, through crystallization, filtration, again use ultrapure water for water washing, hydrochloric acid for acid washing, ultrapure water for water washing, finally filtration to obtain wet product, drying to moisture ≤0.5wt%, obtain white solid N-hydroxy-1,8-naphthalene dicarboxylic acid imide.

[0011] Step two, synthesis of N-hydroxy-1,8-naphthalene dicarboxylic acid imide perfluorobutyl sulfonate: Add tetrahydrofuran to the three-port bottle, open the stirring, continue to add the N-hydroxy-1,8-naphthalene dicarboxylic acid imide prepared in step one and DMAP, control temperature 20-25℃, drop the addition of perfluorobutyl sulfonyl chloride, after the reaction is completed, drop the addition of ultrapure water, there is solid precipitation, stirring, cooling to 10-15℃, filtration to obtain wet product, again through ultrapure water for water washing, filtration to obtain filter cake, filter cake is added to acetone, stirring to completely dissolve at 20-25℃, filter out the insoluble, add ultrapure water to the filtrate, heating to 55-60℃, stirring, solid is completely dissolved, keep warm, cooling to 10-15℃, filtration to obtain product, drying to moisture ≤0.5wt%, obtain solid product N-hydroxy-1,8-naphthalene dicarboxylic acid imide perfluorobutyl sulfonate.

[0012] Preferably, the molar ratio of 1,8-naphthalene anhydride and hydroxylamine hydrochloride is 1: (1.1-2.0).

[0013] Preferably, the molar ratio of hydroxylamine hydrochloride and triethylamine is 1: (1.1-2.0).

[0014] Preferably, the molar ratio of N-hydroxy-1,8-naphthalimide to DMAP is 1: (1.5-2.0).

[0015] Preferably, the molar ratio of N-hydroxy-1,8-naphthalimide to perfluoroalkylsulfonyl chloride is 1: (1.5-2.0).

[0016] Most preferably, the method is performed according to the following steps: Step one, synthesis of N-hydroxy-1,8-naphthalimide: Into a 100ml three-necked flask, 50g of anhydrous ethanol was added, stirring was started, and then 5.0g of 1,8-naphthalic anhydride and 1.9g of hydroxylamine hydrochloride were added, stirring was started, and then the temperature was controlled at room temperature for 0.5h, 3.8g of triethylamine was added dropwise, the temperature was raised to reflux after the addition was completed, and the reaction was carried out for 2h, after the reaction was completed, most of the solvent was removed under reduced pressure until solid appeared, it was transferred to a 1L beaker, the temperature was lowered to below 10℃, 166g of ultrapure water was added dropwise, it was crystallized, filtered, washed with 300g of ultrapure water, acid washed with 100mL of 0.1wt% hydrochloric acid, washed with 300g of ultrapure water, and finally filtered to obtain wet product, the temperature of the vacuum oven was 60℃, the material was dried until the moisture content was ≤0.5wt%, and 4.6g of white solid N-hydroxy-1,8-naphthalimide was obtained.

[0017] Step two, synthesis of N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate: Into a 100ml three-necked flask, 22.6g of tetrahydrofuran was added, stirring was started, and then 1.02g of N-hydroxy-1,8-naphthalimide prepared in step one and 1.17g of DMAP were added, the temperature was controlled at 20℃, and 2.33g of perfluorobutylsulfonyl chloride was added dropwise for 0.5h; after the reaction was completed, 74.2g of ultrapure water was added dropwise, solid was precipitated, stirring was carried out for 0.5h, the temperature was lowered to 10℃, and then filtration was carried out to obtain 27.95g of wet product, which was then washed with 113.3g of ultrapure water, and filtration was carried out to obtain 27.53g of filter cake, 30g of acetone was added to the filter cake, stirring was carried out at 20℃ until complete dissolution, the insoluble matter was filtered out, 11.33g of ultrapure water was added to the filtrate, the temperature was raised to 55℃, stirring was carried out for 1h, the solid was completely dissolved, the temperature was maintained for 10min, the temperature was lowered to 10℃, and then filtration was carried out, 2.17g of product was obtained, the temperature of the oven was 35℃, and the material was dried until the moisture content was ≤0.5wt%, and 1.73g of solid product N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate was obtained.

[0018] Compared with the prior art, the present application has the following technical effects: (I) The present application adopts 1,8-naphthalene dicarboxylic anhydride and hydroxylamine hydrochloride as raw materials, changes the solvent to anhydrous ethanol, and uses triethylamine (TEA) as an acid binding agent to synthesize the target product without reducing the yield. The preparation method of the present application uses green and clean solvents and is easy to recycle and reuse, reduces the reaction temperature, greatly shortens the reaction time, and uses anhydrous ethanol as a solvent to avoid the adverse effects of water as a solvent on the ring-closing dehydration reaction, and is more environmentally friendly than dioxane, and has the advantages of simple synthesis steps.

[0019] (II) The synthesis route of the present application does not produce waste solids, is environmentally friendly, and reduces production costs.

[0020] The specific content of the present application is further explained and described in detail below in conjunction with the examples. DETAILED DESCRIPTION

[0021] It should be noted that all materials and instruments in the present application, unless otherwise specified, are known materials and instruments in the art.

[0022] The preparation method of N-hydroxy-1,8-naphthalene dicarboxamide perfluorobutyl sulfonate of the present application is carried out according to the following reaction formula:

[0023] The reaction mechanism of the preparation method is as follows: Step one, hydroxylamine hydrochloride generates free hydroxylamine under the action of triethylamine, the nitrogen atom in free hydroxylamine has a lone pair of electrons and can act as a nucleophile, the carbonyl carbon atom in 1,8-naphthalene anhydride has a higher positive charge and is more susceptible to nucleophilic attack, and 1,8-naphthalene anhydride and hydroxylamine hydrochloride can interact to form a transition complex under the action of pyridine, and finally undergo intramolecular isomerization to form an intermediate (amide acid), which is heated to remove one molecule of water and then undergoes ring-closing reaction to obtain N-hydroxy-1,8-naphthalene dicarboxamide.

[0024] Step two, the oxygen in N-hydroxy-1,8-naphthalene dicarboxamide can act as a nucleophile, and the chlorine in perfluorobutylsulfonyl chloride has good leaving ability, so nucleophilic substitution occurs to obtain N-hydroxy-1,8-naphthalene dicarboxamide perfluorobutyl sulfonate.

[0025] N-hydroxy-1,8-naphthalene dicarboxamide perfluorobutyl sulfonate of the present application is used as a photo-induced acid generator.

[0026] The following gives specific examples of the present application, it should be noted that the present application is not limited to the following specific examples, any equivalent transformation based on the technical solutions of the present application falls within the protection scope of the present application.

[0027] Example: The present example gives a preparation method of N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate, which is carried out according to the following steps: Step one, synthesis of N-hydroxy-1,8-naphthalimide: .

[0028] Into a 100ml three-necked flask, 50g of anhydrous ethanol was added, stirring was started, and then 5.0g of 1,8-naphthalic anhydride and 1.9g of hydroxylamine hydrochloride were added, stirring was started, and then the mixture was stirred at room temperature for 0.5h, 3.8g of triethylamine was slowly added at a temperature controlled at ≤45℃, and then the temperature was raised to reflux for reaction for 2h, after the reaction was completed, most of the solvent was first concentrated under reduced pressure until solid appeared, and then the mixture was transferred to a 1L beaker, the temperature was lowered to below 10℃, 166g of ultrapure water was added dropwise, and then the mixture was crystallized, filtered, washed with 300g of ultrapure water, acid washed with 100mL of 0.1wt% hydrochloric acid, and then washed with 300g of ultrapure water, and finally filtered to obtain wet product, which was dried in a vacuum oven at a temperature of 60℃ until the moisture content was ≤0.5wt%, and then 4.6g of white solid N-hydroxy-1,8-naphthalimide was obtained (yield = 85.22wt%).

[0029] Step two, synthesis of N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate: .

[0030] Into a 100ml three-necked flask, 22.6g of tetrahydrofuran was added, stirring was started, and then 1.02g of N-hydroxy-1,8-naphthalimide prepared in step one and 1.17g of DMAP (4-dimethylaminopyridine) were added, the temperature was controlled at 20℃, and then 2.33g of perfluorobutylsulfonyl chloride was slowly added dropwise for 0.5h. After the reaction was completed, 74.2g of ultrapure water was added dropwise, and then solid was precipitated, the mixture was stirred for 0.5h, the temperature was lowered to 10℃, and then the mixture was filtered to obtain 27.95g of wet product, which was then washed with 113.3g of ultrapure water, and then filtered to obtain 27.53g of filter cake, 30g of acetone was added to the filter cake, the mixture was stirred at 20℃ until it was completely dissolved, the insoluble matter was filtered out, 11.33g of ultrapure water was added to the filtrate, the temperature was raised to 55℃, and then the mixture was stirred for 1h, the solid was completely dissolved, the mixture was kept at the temperature for 10min, the temperature was lowered to 10℃, and then the mixture was filtered, 2.17g of product was obtained, which was dried in an oven at a temperature of 35℃ until the moisture content was ≤0.5wt%, and then 1.73g of solid product N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate was obtained (yield = 73.4wt%).

[0031] The structural characterization data of the solid product prepared in the present example are as follows: LC-MS: molecular weight is 495, (M+39)*2; 1 H NMR: 1H -NMR (400MHz, CDCl3, ), δ: 8.69 (d, J =7.6Hz, 2H), 8.34 (d, J =8Hz, 2H), 8.69 (t, J =8Hz, 2H); 19 F NMR: δ: -106 (t, J =8.9Hz, 2F), -80 (t, J =9.1Hz, 3F), -120 (tt, J 1=9.1Hz, J 2=8.9Hz, 2F), -126 (tt, J 1=8.9Hz, J 2=8.9Hz, 2F); IR: 1738 cm -1 , 1714 cm -1 -1 as the characteristic absorption peak of imide, 1582 cm -1 -1 as the characteristic absorption peak of imide, 1582 cm -1 , 1356 cm -1 -1 as the characteristic absorption peak of imide, 1582 cm

[0032] From the above structural characterization data, it can be seen that the solid product prepared in the embodiment is the target product N-hydroxy-1,8-naphthalene dicarboxylic acid imide perfluorobutyl sulfonate.

[0033] The present application uses 1,8-naphthalene anhydride and hydroxylamine hydrochloride as raw materials, and mainly prepares N-hydroxy-1,8-naphthalene dicarboxylic acid imide perfluorobutyl sulfonate by changing the reaction environment. The 1,8-naphthalene anhydride and hydroxylamine hydrochloride undergo ammonolysis reaction under the action of triethylamine to obtain 1,8-naphthalene dicarboxylic acid imide; under heating, the 1,8-naphthalene dicarboxylic acid imide loses one molecule of water to close the ring to obtain N-hydroxy-1,8-naphthalene dicarboxylic acid imide; the chlorine in perfluorobutyl sulfuryl chloride has good leaving ability, and the oxygen in N-hydroxy-1,8-naphthalene dicarboxylic acid imide can act as a nucleophile, so that nucleophilic substitution with perfluorobutyl sulfuryl chloride can occur to obtain N-hydroxy-1,8-naphthalene dicarboxylic acid imide perfluorobutyl sulfonate. The main advantage of the synthetic route lies in that the steps are simple, the raw materials are easy to obtain, the reaction is feasible, the equipment requirement is low, and it is suitable for large-scale production. This method uses green and clean solvent and is easy to recycle, reduces the reaction temperature, greatly shortens the reaction time, and uses anhydrous ethanol as a solvent to avoid the adverse effects of water as a solvent on the closed ring dehydration reaction, and is more environmentally friendly than dioxane. The synthetic route has the advantages of simple synthesis steps, etc. The present application does not produce waste solids, is environmentally friendly, and reduces production costs.

Claims

1. A process for the preparation of N-hydroxy-l,8-naphthalimide perfluorobutyl sulfonate, characterized in that, The method is carried out according to the following steps: Step one, synthesis of N-hydroxy-1,8-naphthalene dicarboxamide: Add anhydrous ethanol, start stirring, continue to add 1,8-naphthalene anhydride and hydroxylamine hydrochloride, start stirring, stir at room temperature, add triethylamine dropwise, after the dropwise addition is completed, warm to reflux reaction, after the reaction is completed, first reduce pressure concentration until solid appears, cool, add ultrapure water dropwise, through crystallization, filtration and washing, finally filter the wet product, dry the material, and obtain white solid N-hydroxy-1,8-naphthalene dicarboxamide; Step two, synthesis of N-hydroxy-1,8-naphthalene dicarboxamide perfluorobutyl sulfonate: Add tetrahydrofuran, start stirring, continue to add N-hydroxy-1,8-naphthalene dicarboxamide prepared in step one and DMAP, control the temperature at 20-25℃, add perfluorobutylsulfonyl chloride dropwise, after the reaction is completed, add ultrapure water dropwise, solid is precipitated, stir, cool, filter to obtain the wet product, then wash with ultrapure water, filter to obtain the filter cake, add acetone to the filter cake, stir until completely dissolved, filter out the insoluble substances, add ultrapure water to the filtrate, warm, stir, solid is completely dissolved, keep warm, cool, and extract by filtration to obtain the product, dry the material to obtain solid product N-hydroxy-1,8-naphthalene dicarboxamide perfluorobutyl sulfonate.

2. The process for the preparation of N-hydroxy-l,8-naphthalimide perfluorobutyl sulfonate according to claim 1, characterized in that, The method is carried out according to the following steps Step one, synthesis of N-hydroxy-1,8-naphthalene dicarboxamide: Add anhydrous ethanol to a three-necked flask, start stirring, continue to add 1,8-naphthalene anhydride and hydroxylamine hydrochloride, start stirring, stir at room temperature for 0.5-1h, control the temperature at ≤45℃, add triethylamine dropwise, after the dropwise addition is completed, warm to reflux reaction for 2h, after the reaction is completed, first reduce pressure concentration to remove most of the solvent until solid appears, transfer to a beaker, cool to ≤10℃, add ultrapure water dropwise, through crystallization, filtration, then wash with ultrapure water, acid wash with hydrochloric acid, and finally wash with ultrapure water, filter the wet product, dry the material to ≤0.5wt%, and obtain white solid N-hydroxy-1,8-naphthalene dicarboxamide; Step two, synthesis of N-hydroxy-1,8-naphthalene dicarboxamide perfluorobutyl sulfonate: Add tetrahydrofuran to a three-necked flask, start stirring, continue to add N-hydroxy-1,8-naphthalene dicarboxamide prepared in step one and DMAP, control the temperature at 20-25℃, add perfluorobutylsulfonyl chloride dropwise, after the reaction is completed, add ultrapure water dropwise, solid is precipitated, stir, cool to 10-15℃, filter to obtain the wet product, then wash with ultrapure water, filter to obtain the filter cake, add acetone to the filter cake, stir until completely dissolved at 20-25℃, filter out the insoluble substances, add ultrapure water to the filtrate, warm to 55-60℃, stir, solid is completely dissolved, keep warm, cool to 10-15℃, and extract by filtration to obtain the product, dry the material to ≤0.5wt%, and obtain solid product N-hydroxy-1,8-naphthalene dicarboxamide perfluorobutyl sulfonate.

3. The process for the preparation of N-hydroxy-l,8-naphthalimide perfluorobutyl sulfonate according to claim 1, characterized in that, The molar ratio of 1,8-naphthalene anhydride and hydroxylamine hydrochloride is 1: (1.1-2.0).

4. The process for the preparation of N-hydroxy-l,8-naphthalimide perfluorobutyl sulfonate according to claim 1, characterized in that, The molar ratio of hydroxylamine hydrochloride and triethylamine is 1: (1.1-2.0).

5. The process for the preparation of N-hydroxy-l,8-naphthalimide perfluorobutyl sulfonate according to claim 1, characterized in that, The molar ratio of N-hydroxy-1,8-naphthalene dicarboxamide and DMAP is 1: (1.5-2.0).

6. The process for the preparation of N-hydroxy-l,8-naphthalimide perfluorobutyl sulfonate according to claim 1, characterized in that, The molar ratio of N-hydroxy-1,8-naphthalimide to perfluoroalkylsulfonyl chloride is 1: (1.5-2.0).

7. The process for the preparation of N-hydroxy-l,8-naphthalimide perfluorobutyl sulfonate according to claim 1, characterized in that, The method is performed according to the following steps: Step one, synthesis of N-hydroxy-1,8-naphthalimide: Into a 100ml three-necked flask, 50g of anhydrous ethanol was added, stirring was started, and then 5.0g of 1,8-naphthalic anhydride and 1.9g of hydroxylamine hydrochloride were added, stirring was started, and then the mixture was stirred at room temperature for 0.5h, 3.8g of triethylamine was added dropwise while controlling the temperature to be ≤45℃, and then the temperature was increased to reflux for 2h after the dropwise addition was completed, and then the reaction was completed, the most of the solvent was first concentrated under reduced pressure until solid appeared, the mixture was transferred to a 1L beaker, and then the temperature was decreased to ≤10℃, 166g of ultrapure water was added dropwise, and then the mixture was crystallized, filtered, washed with 300g of ultrapure water, acid-washed with 100mL of 0.1wt% hydrochloric acid, and then washed with 300g of ultrapure water, and finally, the mixture was filtered to obtain wet product, the mixture was dried in a vacuum oven at 60℃ until the moisture content was ≤0.5wt%, and then 4.6g of white solid N-hydroxy-1,8-naphthalimide was obtained; Step two, synthesis of N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate: Into a 100ml three-necked flask, 22.6g of tetrahydrofuran was added, stirring was started, and then 1.02g of N-hydroxy-1,8-naphthalimide obtained in step one and 1.17g of DMAP were added, the temperature was controlled to be 20℃, and then 2.33g of perfluorobutylsulfonyl chloride was added dropwise for 0.5h, the reaction was completed, 74.2g of ultrapure water was added dropwise after the reaction was completed, and then solid appeared, the mixture was stirred for 0.5h, the temperature was decreased to 10℃, and then the mixture was filtered to obtain 27.95g of wet product, the wet product was washed with 113.3g of ultrapure water, and then the mixture was filtered to obtain 27.53g of filter cake, 30g of acetone was added to the filter cake, the mixture was stirred at 20℃ until the filter cake was completely dissolved, the undissolved substances were filtered out, 11.33g of ultrapure water was added to the filtrate, the temperature was increased to 55℃, and then the mixture was stirred for 1h, the solid was completely dissolved, the temperature was maintained for 10min, the temperature was decreased to 10℃, and then the mixture was filtered, 2.17g of product was obtained, the product was dried in an oven at 35℃ until the moisture content was ≤0.5wt%, and then 1.73g of solid product N-hydroxy-1,8-naphthalimide perfluorobutyl sulfonate was obtained.

Images