Synthesis method of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate photoacid generator anions

Abstract

The invention provides a synthesis method of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate photoacid generator anions, and relates to a photoacid generator anion synthesis method of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate photoacid generator anions. The preparation method comprises the following steps: S1, uniformly mixing a solvent and difluorobromoacetic acid, then adding CDI, fully stirring, then adding 3-hydroxy-1-adamantane methanol, fully reacting, then adding bicarbonate, carrying out liquid separation to obtain an organic phase A, washing the organic phase A, and carrying out drying and spin-drying; s2, fully mixing the spin-dried substance with NaHCO3, Na2S2O4, acetonitrile and ultrapure water, then carrying out liquid separation to obtain an organic phase B, and carrying out drying and spin-drying on the organic phase B; and S3, dissolving the spin-dried substance in water, then adding an H2O2 solution, carrying out a full reaction, and then carrying out cooling and post-treatment so as to obtain the photoacid generator anions. According to the method, 3-hydroxy-1-adamantane methanol and difluorobromoacetic acid are used as reaction raw materials, esterification reaction is performed under the condition of adding CDI to obtain a first-step reaction intermediate, then acylation sulfonation and oxidation reaction are performed to obtain the target product photoacid generator anion, the reaction process is mild in condition, and the product purity is high.

Description

Technical Field

[0001] The invention relates to the technical field of organic compound synthesis, in particular to a method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate. Background Art

[0002] Photoresist is an indispensable material in the field of semiconductor chips, and photoacid generator is a key component of photoresist. When photoacid generator is exposed to light, it will decompose and produce acid. During the post-exposure baking (PEB) process, these acids act as catalysts to cause chemical changes in the polymers in the photoresist, such as causing the acid-labile groups hanging on the polymer to fall off, thereby changing its solubility.

[0003] In 193nm photoresist, there are two main types of commonly used photoacid generators, one is iodonium salts; the other is sulfonium salts, among which the common structure of sulfonate photoacid generators is sulfonate. Currently, relevant patents have mentioned the structure of sulfonate photoacid generators, such as JP 2016-210983 A, US20140302438A1, etc., but there are few reports on their specific synthesis methods. Summary of the invention

[0004] The purpose of the present invention is to provide a method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate salts, aiming to fill the gap in the reports of less synthetic methods. 3-hydroxy-1-adamantane methanol and difluorobromoacetic acid are used as main reaction raw materials, and the target product photoacid generator anion is obtained through three-step reaction post-treatment.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] A method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate salt type comprises the following steps:

[0007] S1. The solvent and difluorobromoacetic acid were mixed uniformly, and then CDI was added in batches. After sufficient stirring, 3-hydroxy-1-adamantane methanol was added. After sufficient reaction at room temperature, a bicarbonate solution was added and extracted to obtain an organic phase A. The organic phase A was then washed, dried and spin-dried to obtain a substance P-1;

[0008] S2. The substance P-1 and NaHCO3, Na2S2O4, acetonitrile and ultrapure water are thoroughly mixed, and then separated to obtain an organic phase B, and the organic phase B is dried and spin-dried to obtain a substance P-2;

[0009] S3. Dissolve substance P-2 in water, then add H2O2 solution in batches, and after sufficient reaction, cool and post-treat to obtain substance P-3, i.e., the photoacid generator anion.

[0010] In this application, the reaction formula is as follows:

[0011]

[0012] The invention mainly reports a synthesis method of a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate salt type, aiming to fill the blank of less reported synthesis methods. 3-hydroxy-1-adamantane methanol and difluorobromoacetic acid are used as main reaction raw materials, and the target product photoacid generator anion is obtained through three-step reaction post-treatment. The reaction process conditions are mild and the product purity is high, thereby providing a route for efficiently preparing the photoacid generator anion.

[0013] As one possible embodiment of the present application, in step S1, the solvent is selected from dichloromethane, 1,2-dichloroethane and chloroform.

[0014] As one possible embodiment of the present application, in step S1, the mass fraction of the bicarbonate solution is 8%.

[0015] As one possible embodiment of the present application, in step S1, the molar ratio of difluorobromoacetic acid, CDI and 3-hydroxy-1-adamantanemethanol is (1-2): (1-2): 1. Preferably, the molar ratio of the three is 1.5:1.5:1.

[0016] As one possible embodiment of the present application, in step S2, the molar ratio of NaHCO3, Na2S2O4 and substance P-1 is (1-2): (1-2): 1. Preferably, the molar ratio of the three is 1.3:1.5:1.

[0017] As one possible embodiment of the present application, in step S2, the volume ratio of acetonitrile to ultrapure water is 1:1.

[0018] As one possible embodiment of the present application, in step S2, the temperature for thorough mixing is 60° C., and the mixing time is 18 hours.

[0019] As one possible embodiment of the present application, in step S3, the molar ratio of H2O2 to P-2 is 1 to 3: 1. Preferably, the molar ratio of H2O2 to P-2 is 2:1.

[0020] As one possible embodiment of the present application, in step S3, the specific operation of the post-processing is as follows:

[0021] Sodium bisulfite is added to the reaction system to quench the reaction, and then sodium chloride is added for liquid separation to obtain an organic phase C. The organic phase C is dried and spun dry, and a mixed solution of ethyl acetate and methyl tert-butyl ether is added and slurried for multiple times. The phase is then filtered and dried to obtain a photoacid generator anion.

[0022] As one of the embodiments of the present application, the volume ratio of the ethyl acetate and methyl tert-butyl ether mixed solution is 1:(1-20). Preferably, the molar ratio of the two is 1:5.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. The present invention uses 3-hydroxy-1-adamantanemethanol and difluorobromoacetic acid as reaction raw materials, performs an esterification reaction under the condition of adding CDI to obtain a first step reaction intermediate, and then performs acylation, sulfonation and oxidation reactions to obtain a target product, a photoacid generator anion. The reaction process is simple to operate and has a high conversion rate, and provides a route for efficiently preparing a photoacid generator anion.

[0025] 2. The present application can significantly improve the purity of the product by performing multiple pulping in the post-processing process.

[0026] 3. The product purity and total yield obtained by the preparation method of the present invention are high, specifically, the product purity is >98%, and the total yield is >55%. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 : The product H NMR spectrum of Example 1;

[0028] Figure 2 : The product NMR fluorine spectrum of Example 1;

[0029] Figure 3 : The product H NMR spectrum of Example 2;

[0030] Figure 4 : The product NMR fluorine spectrum of Example 2. DETAILED DESCRIPTION

[0031] The preparation method of the anion of the sulfonate photoacid generator of the present application is further described in detail below in conjunction with specific embodiments.

[0032] Example 1

[0033] S1. Add 250mL of dichloromethane to a 1L three-necked reaction bottle, add 65.6g of difluorobromoacetic acid, and stir for 10min until completely dissolved. Slowly add 60.8g of CDI, and the addition process takes about 20min. Bubbles are generated during the dropwise addition process, and the color of the reaction system turns yellow. Add 30mL of dichloromethane and stir for 2h. Add 45.5g of 3-hydroxy-1-adamantane methanol, and add 20mL of dichloromethane as a wash, heat to 45℃ and react for 18h. After cooling, add 500g of 8% sodium bicarbonate solution, stir for 20min, and separate after standing. Add 400mL of ultrapure water to the organic phase, wash once, and then dry with anhydrous sodium sulfate to obtain 47.2g of yellow-white solid.

[0034] S2. Add 35.3g NaHCO3, 48.8g Na2S2O4 and 180mL H2O into a 1L reaction bottle and stir for 10min. Then slowly add acetonitrile solution (the yellow-white solid in step S1 is dissolved in 180mL acetonitrile). React at 60℃ for about 18h. After cooling, separate the liquids, the upper layer is acetonitrile phase, and the lower layer is water phase. Dry the organic phase and spin dry to obtain 39.8g yellow viscous liquid product.

[0035] S3. Dissolve the 39.8g yellow viscous liquid product in 100mL H2O. Then slowly add 15.6g 30% H2O2 solution, and then add 200mL acetonitrile, the solution becomes light yellow, clear and transparent. React at 50℃ for about 3h. After cooling, add 100mL of aqueous solution of sodium bisulfite (0.138mol, 14.5g). Add sodium chloride to promote the separation of the reaction system. After the organic phase is spin-dried, add a mixed solvent of ethyl acetate and methyl tert-butyl ether, beat twice, and then filter and dry to obtain 50g of the target product with a yield of 55% and a purity of 98.5%.

[0036] The product H NMR spectrum is Figure 1 As shown, the NMR fluorine spectrum results of the product are as follows Figure 2 shown.

[0037] Example 2

[0038] S1. Add 250mL of 1,2-dichloroethane to a 1L three-necked reaction bottle, add 65.6g of difluorobromoacetic acid, and stir for 10min until completely dissolved. Slowly add 60.8g of CDI, the addition process takes about 20min, bubbles are generated during the dropwise addition, and the color of the reaction system turns yellow. Add 30mL of dichloromethane and stir for 2h. Add 45.5g of 3-hydroxy-1-adamantane methanol, and add 20mL of 1,2-dichloroethane as a wash, heat to 45℃ and react for 18h. Cool the reaction, add 500g of 8% sodium bicarbonate solution, stir for 20min, and separate after standing. Add 400mL of ultrapure water to the organic phase, wash once, and then dry with anhydrous sodium sulfate to obtain 44.8g of yellow-white solid.

[0039] S2. Add 33.5g NaHCO3, 46.4g Na2S2O4 and 170mL H2O into a 1L reaction bottle and stir for 10min. Then slowly add the acetonitrile solution containing the product of the first step (the yellow-white solid in step S1 is dissolved in 170mL acetonitrile). React at 60℃ for about 18h. After cooling, separate the liquids, the upper layer is the acetonitrile phase, and the lower layer is the water phase. Dry the organic phase and spin dry to obtain 37.8g of yellow viscous liquid product.

[0040] S3. Dissolve 37.8g of the yellow viscous liquid product in 100mL H2O. Then slowly add 14.8g of 30% H2O2 solution, and then add 200mL of acetonitrile, and the solution becomes slightly yellow, clear and transparent. React at 50℃ for about 3h. After cooling, add 100mL of an aqueous solution of sodium bisulfite (0.13mol, 13.7g). Add sodium chloride to promote the separation of the reaction system. After the organic phase is spin-dried, add a mixed solvent of ethyl acetate and methyl tert-butyl ether, beat twice, and then filter and dry to obtain 45g of the target product, with a yield of 50% and a product purity of 98%.

[0041] The product H NMR spectrum is Figure 3 As shown, the NMR fluorine spectrum results of the product are as follows Figure 4 shown.

Claims

1. A method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate, characterized in that: The steps include: S1. The solvent and difluorobromoacetic acid were mixed uniformly, and then CDI was added in batches. After sufficient stirring, 3-hydroxy-1-adamantane methanol was added. After sufficient reaction at room temperature, a bicarbonate solution was added and extracted to obtain an organic phase A. The organic phase A was then washed, dried and spin-dried to obtain a substance P-1; S2. The substance P-1 and NaHCO3, Na2S2O4, acetonitrile and ultrapure water are thoroughly mixed, and then separated to obtain an organic phase B, and the organic phase B is dried and spin-dried to obtain a substance P-2; S3. Dissolve substance P-2 in water, then add H2O2 solution in batches, and after sufficient reaction, cool and post-treat to obtain substance P-3, i.e., the photoacid generator anion.

2. The method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate according to claim 1, characterized in that: In step S1, the solvent is selected from dichloromethane, 1,2-dichloroethane and chloroform.

3. The method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate according to claim 1, characterized in that: In step S1, the mass fraction of the bicarbonate solution is 8%.

4. The method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate according to claim 1, characterized in that: In step S1, the molar ratio of difluorobromoacetic acid, CDI and 3-hydroxy-1-adamantanemethanol is (1-2):(1-2):

1.

5. The method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate according to claim 1, characterized in that: In step S2, the molar ratio of NaHCO3, Na2S2O4 and substance P-1 is (1-2):(1-2):

1.

6. The method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate according to claim 1, characterized in that: In step S2, the volume ratio of acetonitrile to ultrapure water is 1:

1.

7. The method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate according to claim 1, characterized in that: In step S2, the temperature for thorough mixing is 60° C. and the mixing time is 18 h.

8. The method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate according to claim 1, characterized in that: In step S3, the molar ratio of H2O2 to P-2 is 1 to 3:

1.

9. The method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate according to claim 1, characterized in that: In step S3, the specific operation of the post-processing is as follows: Sodium bisulfite is added to the reaction system to quench the reaction, and then sodium chloride is added for liquid separation to obtain an organic phase C. The organic phase C is dried and spun dry, and a mixed solution of ethyl acetate and methyl tert-butyl ether is added and slurried for multiple times. The phase is then filtered and dried to obtain a photoacid generator anion.

10. The method for synthesizing a photoacid generator anion of (3-hydroxyadamantane-1-methoxycarbonyl) difluoromethanesulfonate according to claim 9, characterized in that: The volume ratio of the ethyl acetate and methyl tert-butyl ether mixed solution is 1:(1-20).

Images