Preparation method of photoacid generator 1-(4-alkoxy naphthyl)-1H-cyclosulfonium perfluorobutyl sulfonate

Abstract

The invention discloses a preparation method of a photoacid generator 1-(4-alkoxy naphthyl)-1H-cyclosulfonium perfluorobutyl sulfonate, and belongs to the field of synthesis of photoacid generator compounds in the field of photoresist. The preparation method specifically comprises the following steps: by taking 1-naphthyl alkyl ether, a sulfoxide compound and a fluoroalkyl sulfonic acid derivative compound (anhydride or acyl chloride) as reaction raw materials, reacting in a solvent at-5 to 5 DEG C to obtain the 1-(4-alkoxy naphthyl) tetrahydro-1H-thiophene-1-perfluorobutyl sulfonate. On the basis of certain reports of previous people, synthesis and purification methods of the photoacid generator are reported for the first time. The preparation method disclosed by the invention is high in conversion rate and simple in purification process, and a product with the purity of 99% or above can be obtained by washing, concentrating and pulping reaction liquid; wherein the reaction solvent can be recycled, so that the production cost is further saved.

Description

Technical Field

[0001] The invention belongs to the field of synthesis of photoacid generator compounds, in particular to a method for preparing photoacid generator 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutyl sulfonate. Background Art

[0002] Photoacid generator is a light-sensitive compound that decomposes to produce hydrogen ions, i.e., acid, under light conditions. During the post-exposure baking process, these acids act as catalysts to cause unstable groups on the polymer to fall off and produce new acids. The shedding of unstable groups changes the polarity of the polymer. When enough unstable groups fall off, the photoresist can be dissolved in the developer. Photoacid generator is the core part of photoresist, and a corresponding reaction will occur in the environment of radiation energy in the form of light, especially in the ultraviolet region.

[0003] There are two main types of commonly used photoacid generators, one is positive iodide ion salts, such as diaryl iodonium salts; the other is positive sulfonium salts, such as triaryl sulfonium salts and naphthyl cyclosulfonium salts. Compared with other onium salt photoacid generators, the acid generated by diaryl iodonium salt photoacid generators has a higher quantum yield, and triaryl sulfonium salt photoacid generators have high thermal stability. These two major types of photoacid generators have greatly promoted the development of the semiconductor industry.

[0004] The 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutyl sulfonate of this invention belongs to the naphthyl cyclosulfonium salt type photoacid generator, which is a variant of the triarylsulfonium salt type photoacid generator, and it replaces the benzene ring of the triarylsulfonium salt with a substituted naphthalene ring and a thioether ring. Its advantage is that it further amplifies the effect of the triarylsulfonium salt type photoacid generator in the field of photoresists. The structure and overview of the cation of this type of photoacid generator have been mentioned in previous patents, such as ZL02160643.9, CN 1916760B, US2012 / 0003590 A1, WO 2013 / 180314 Al and other patents, but in order to expand the substrate cases, these patents only generally describe this type of photoacid generator, and do not provide a detailed synthesis method.

[0005] Based on this, the present invention specifically synthesizes one type of photoacid generator cation in combination with a perfluorobutanesulfonate anion. Summary of the invention

[0006] The purpose of the present invention is to provide a preparation method of a photoacid generator 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutane sulfonate for the first time; the preparation method is simple, and the purity and yield of the obtained product are both high.

[0007] The objective of the present invention is achieved through the following technical solutions:

[0008] A method for preparing a photoacid generator 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutyl sulfonate, characterized in that 1-naphthalene ether, a cyclic sulfoxide compound and a fluoroalkyl sulfonic acid derivative compound are used as reaction raw materials, and the 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutyl sulfonate is obtained by reacting in an organic solvent system and at low temperature;

[0009] The chemical reaction equation is as follows:

[0010]

[0011] Wherein, m = 1 to 5, n = 1 or 2, and X is Or -Cl. That is, the fluoroalkyl sulfonic acid derivative compound is any one of perfluorobutylsulfonic anhydride and perfluorobutylsulfonyl chloride.

[0012] The above reaction is a one-pot process with simple conditions and no need for other catalysts.

[0013] As one possible embodiment of the present application, the organic solvent is dichloromethane or 1,2-dichloroethane.

[0014] As one possible embodiment of the present application, the molar ratio of the 1-naphthalene ether, the cyclic sulfoxide compound and the fluoroalkyl sulfonic acid derivative compound is 1:1-2:1-2.

[0015] As one of the embodiments of the present application, the preparation method of the 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutanesulfonate specifically includes the following preparation steps:

[0016] S1, adding 1-naphthalene ether, an organic solvent and a cyclic sulfoxide compound into a reaction container and stirring evenly, and then slowly dropping a fluoroalkyl sulfonic acid derivative compound and allowing it to react fully;

[0017] S2, after the reaction of S1 is completed, the obtained reaction solution is subjected to alkaline solution and water extraction and separation, and then the organic phase is dried and the organic solvent is evaporated to obtain a crude product;

[0018] S3. The crude product obtained in step S2 is subjected to pulping treatment to obtain a solid, namely 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutanesulfonate.

[0019] As one possible embodiment of the present application, in step S1, the reaction time is 6-12 hours, and the reaction temperature is -5 to 5°C.

[0020] As one possible embodiment of the present application, in step S2, the extracting and washing agents used in the extraction and washing are a bicarbonate aqueous solution and water; the carbonate solution is sodium bicarbonate; and the reagent used in drying the organic phase is anhydrous sodium sulfate.

[0021] As one of the embodiments of the present application, in step S3, the solvent used for pulping is ether or methyl tert-butyl ether.

[0022] The beneficial effects of the present invention are:

[0023] The present invention discloses for the first time the synthesis and purification process of the photoacid generator 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutyl sulfonate. The successful preparation of the monomer fills the gap in the relevant synthesis field at home and abroad, and lays the foundation for the research and development of a new generation of advanced photoacid generators. Specifically, the photoacid generator can be prepared by reacting 1-naphthalene ether, cyclic sulfoxide compounds and fluoroalkyl sulfonic acid derivative compounds (anhydrides or acid chlorides) in an organic solvent at -5 to 5°C.

[0024] The preparation method of the invention has high conversion rate and simple purification process. The reaction liquid can obtain a product with purity of more than 99% through alkali washing, water washing, concentration and pulping. In addition, the reaction solvent can be recycled, further saving production cost.

[0025] The purity of the product prepared by the method of the present invention is >99%, and the total yield is >85%, which indicates that the conversion rate and purification efficiency are extremely high. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 :1-(4-Butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate product 1 H NMR nuclear magnetic resonance spectrum;

[0027] Figure 2 :1-(4-Butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate product 19 F NMR nuclear magnetic resonance spectrum;

[0028] Figure 3 :1-(4-Butoxynaphthyl)-1H-thiophene trifluoromethylsulfonate product 1 H NMR nuclear magnetic resonance spectrum;

[0029] Figure 4 :1-(4-Butoxynaphthyl)-1H-thiophene trifluoromethylsulfonate product 19 F NMR nuclear magnetic resonance spectrum. DETAILED DESCRIPTION

[0030] The following examples take the preparation of 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutylsulfonate and 1-(4-butoxynaphthyl)-1H-thiophene trifluoromethylsulfonate as examples, but the protection scope of the present invention is not limited thereto.

[0031] Example 1

[0032] A method for preparing a photoacid generator 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate, the reaction formula is as follows:

[0033]

[0034] The specific steps include:

[0035] S1. Add 300 mL of dichloromethane to a 1L four-necked flask equipped with a stirring paddle, a condenser and a thermometer, start stirring, add 0.3 mol of 1-naphthylbutyl ether and 0.3 mol of tetramethylene sulfoxide to the four-necked flask, then slowly add 0.3 mol of perfluorobutylsulfonyl chloride, and react at -5°C for 6 h;

[0036] S2, sampling to monitor the reaction process, until 1-naphthyl ether reacts completely, the reaction solution is washed once with a saturated sodium bicarbonate aqueous solution and twice with water, and the above extraction and washing process is stirred for 0.5h each time. 1 mol of anhydrous sodium sulfate is added to the organic layer, dried, filtered, and the organic phase is spin-dried to obtain a crude product;

[0037] S3. Add 500 mL of ether to the crude product, stir for 1 h, and then filter to obtain 158 g of 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate, with a yield of 89.8% and a purity of 99.1% (LC). 1 H NMR (400MHz, CDCl3) δ8.38(d,J=8.4Hz,1H),8.23(d,J=8.4Hz,1H),8.03(d,J=8.6H z,1H),7.72(tt,J=8.3,4.1Hz,1H),7.67-7.58(m,1H),7.08(d,J=8.6Hz,1H),4.30 -4.13(m,1H),3.70(dt,J=12.7,6.3Hz,1H),2.73-2.62(m,1H),2.54(td,J=13.2,7 .4Hz,1H),1.92(tt,J=12.5,6.4Hz,1H),1.65-1.50(m,1H),1.03(q,J=7.8Hz,1H). 19F NMR (376MHz, CDCl3) δ-80.88 (t, J = 9.3Hz), -114.50 (t, J = 12.0Hz), -121.55 (dd, J = 11.6, 6.5Hz), -125.58--126.09 (m). Product NMR 1 H NMR spectrum Figure 1 As shown, the product NMR 19 F NMR spectrum Figure 2 shown.

[0038] Example 2

[0039] A method for preparing a photoacid generator 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate, the reaction formula is as follows:

[0040]

[0041] The specific steps include:

[0042] S1. Add 300 mL of 1,2-dichloroethane to a 1L four-necked flask equipped with a stirring paddle, a condenser and a thermometer, start stirring, add 0.3 mol of 1-naphthylbutyl ether and 0.3 mol of tetramethylene sulfoxide to the four-necked flask, then slowly add 0.3 mol of perfluorobutylsulfonyl chloride, and react at -5°C for 8 h;

[0043] S2, sampling to monitor the reaction process, until 1-naphthyl ether reacts completely, the reaction solution is washed once with a saturated sodium bicarbonate aqueous solution and twice with water, and the above extraction and washing process is stirred for 0.5h each time. 1 mol of anhydrous sodium sulfate is added to the organic layer, dried, filtered, and the organic phase is spin-dried to obtain a crude product;

[0044] S3. Add 500 mL of ether to the crude product, stir for 1 h, and then filter to obtain 150 g of the product 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate, with a yield of 85.2% and a purity of 99.0% (LC, i.e., data obtained by liquid chromatography testing).

[0045] Example 3

[0046] A method for preparing a photoacid generator 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate, the reaction formula is as follows:

[0047]

[0048] The specific steps include:

[0049] S1. Add 300 mL of dichloromethane to a 1L four-necked flask equipped with a stirring paddle, a condenser and a thermometer, start stirring, add 0.3 mol of 1-naphthylbutyl ether and 0.3 mol of tetramethylene sulfoxide to the four-necked flask, then slowly add 0.3 mol of perfluorobutylsulfonyl anhydride, and react at -5 °C for 10 h;

[0050] S2, sampling to monitor the reaction process, until 1-naphthyl ether reacts completely, the reaction solution is washed once with a saturated sodium bicarbonate aqueous solution and twice with water, and the above extraction and washing process is stirred for 0.5h each time. 1 mol of anhydrous sodium sulfate is added to the organic layer, dried, filtered, and the organic phase is spin-dried to obtain a crude product;

[0051] S3. Add 500 mL of ether to the crude product, stir for 1 h, and then filter to obtain 155 g of 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate with a yield of 88.1% and a purity of 99.3% (LC).

[0052] Example 4

[0053] A method for preparing a photoacid generator 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate, the reaction formula is as follows:

[0054]

[0055] The specific steps include:

[0056] S1. Add 300 mL of dichloromethane to a 1L four-necked flask equipped with a stirring paddle, a condenser and a thermometer, start stirring, add 0.3 mol of 1-naphthylbutyl ether and 0.6 mol of tetramethylene sulfoxide to the four-necked flask, and then slowly add 0.6 mol of perfluorobutylsulfonic anhydride, and react at 5 °C for 12 h;

[0057] S2, sampling to monitor the reaction process, until 1-naphthyl ether reacts completely, the reaction solution is washed once with a saturated sodium bicarbonate aqueous solution and twice with water, and the above extraction and washing process is stirred for 0.5h each time. 1 mol of anhydrous sodium sulfate is added to the organic layer, dried, filtered, and the organic phase is spin-dried to obtain a crude product;

[0058] S3. Add 500 mL of ether to the crude product, stir for 1 h, and then filter to obtain 161 g of 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate with a yield of 91.5% and a purity of 99.5% (LC).

[0059] Example 5

[0060] A method for preparing a photoacid generator 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate, the reaction formula is as follows:

[0061]

[0062] The specific steps include:

[0063] S1. Add 300 mL of 1,2-dichloroethane to a 1L four-necked flask equipped with a stirring paddle, a condenser and a thermometer, start stirring, add 0.3 mol of 1-naphthylbutyl ether and 0.6 mol of tetramethylene sulfoxide to the four-necked flask, and then slowly add 0.6 mol of perfluorobutylsulfonic anhydride, and react at 5°C for 12 h;

[0064] S2, sampling to monitor the reaction process, until 1-naphthyl ether reacts completely, the reaction solution is washed once with a saturated sodium bicarbonate aqueous solution and twice with water, and the above extraction and washing process is stirred for 0.5h each time. 1 mol of anhydrous sodium sulfate is added to the organic layer, dried, filtered, and the organic phase is spin-dried to obtain a crude product;

[0065] S3. Add 500 mL of ether to the crude product, stir for 1 h, and then filter to obtain 157 g of 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate with a yield of 89.2% and a purity of 99.2% (LC).

[0066] Example 6

[0067] A method for preparing a photoacid generator 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate, the reaction formula is as follows:

[0068]

[0069] The specific steps include:

[0070] S1. Add 300 mL of dichloromethane to a 1L four-necked flask equipped with a stirring paddle, a condenser and a thermometer, start stirring, add 0.3 mol of 1-naphthylbutyl ether and 0.6 mol of tetramethylene sulfoxide to the four-necked flask, and then slowly add 0.6 mol of perfluorobutylsulfonic anhydride, and react at 5 °C for 12 h;

[0071] S2, sampling to monitor the reaction process, until 1-naphthyl ether reacts completely, the reaction solution is washed once with a saturated sodium bicarbonate aqueous solution and twice with water, and the above extraction and washing process is stirred for 0.5h each time. 1 mol of anhydrous sodium sulfate is added to the organic layer, dried, filtered, and the organic phase is spin-dried to obtain a crude product;

[0072] S3. Add 500 mL of methyl tert-butyl ether to the crude product, stir for 1 h, and then filter to obtain 164 g of 1-(4-butoxynaphthyl)-1H-thiophene perfluorobutyl sulfonate with a yield of 93.2% and a purity of 99.5% (LC).

[0073] Example 7

[0074] A method for preparing a photoacid generator 1-(4-butoxynaphthyl)-1H-thiophene trifluoromethylsulfonate, the reaction formula is as follows:

[0075]

[0076] The specific steps include:

[0077] S1, add 300mL of dichloromethane to a 1L four-necked flask equipped with a stirring paddle, a condenser and a thermometer, start stirring, add 0.3mol of 1-naphthylbutyl ether and 0.6mol of tetramethylene sulfoxide to the four-necked flask, then slowly add 0.6mol of trifluoromethanesulfonic anhydride, and react at 5°C for 7h;

[0078] S2, sampling to monitor the reaction process, until 1-naphthyl ether reacts completely, the reaction solution is washed once with a saturated sodium bicarbonate aqueous solution and twice with water, and the above extraction and washing process is stirred for 0.5h each time. 1 mol of anhydrous sodium sulfate is added to the organic layer, dried, filtered, and the organic phase is spin-dried to obtain a crude product;

[0079] S3. Add 500 mL of methyl tert-butyl ether to the crude product, stir for 1 h, and then filter to obtain 118 g of 1-(4-butoxynaphthyl)-1H-thiophene trifluoromethylsulfonate with a yield of 90.0% and a purity of 99.0% (LC).

[0080] Example 8

[0081] A method for preparing a photoacid generator 1-(4-butoxynaphthyl)-1H-thiophene trifluoromethylsulfonate, the reaction formula is as follows:

[0082]

[0083] The specific steps include:

[0084] S1. Add 300 mL of dichloromethane to a 1L four-necked flask equipped with a stirring paddle, a condenser and a thermometer, start stirring, add 0.3 mol of 1-naphthylbutyl ether and 0.3 mol of tetramethylene sulfoxide to the four-necked flask, then slowly add 0.3 mol of trifluoromethanesulfonyl chloride, and react at -5°C for 6 h;

[0085] S2, sampling to monitor the reaction process, until 1-naphthyl ether reacts completely, the reaction solution is washed once with a saturated sodium bicarbonate aqueous solution and twice with water, and the above extraction and washing process is stirred for 0.5h each time. 1 mol of anhydrous sodium sulfate is added to the organic layer, dried, filtered, and the organic phase is spin-dried to obtain a crude product;

[0086] S3. Add 500 mL of methyl tert-butyl ether to the crude product, stir for 1 h, and then filter to obtain 115 g of 1-(4-butoxynaphthyl)-1H-thiophene trifluoromethylsulfonate with a yield of 87.8% and a purity of 99.1% (LC). 1 H NMR (400MHz, CDCl3) δ8.38(d,J=8.1Hz,1H),8.24(d,J=8.5Hz,1H),8.03(d,J=8. 6Hz,1H),7.74(ddd,J=8.4,7.0,1.2Hz,1H),7.67-7.58(m,1H),7.08(d,J=8.6Hz ,1H),4.29-4.13(m,5H),3.78-3.59(m,2H),2.75-2.62(m,2H),2.62-2.41(m,2H ),1.92(tt,J=12.4,6.4Hz,2H),1.67-1.49(m,2H),1.04(dt,J=14.8,7.4Hz,3H). 19 F NMR (376MHz,CDCl3)δ-78.14(s).Product NMR 1 H NMR spectrum Figure 3 As shown, the product NMR 19 F NMR spectrum Figure 4 shown.

Claims

1. A method for preparing a photoacid generator 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutanesulfonate, characterized in that: Using 1-naphthalene ether, cyclic sulfoxide compounds and fluoroalkyl sulfonic acid derivative compounds as reaction raw materials, reacting in an organic solvent system and at low temperature to obtain 1-(4-alkoxynaphthyl)-1H-cyclic sulfonium perfluorobutyl sulfonate; The chemical reaction equation is as follows: Wherein, m = 1 to 5, n = 1 or 2, and X is or -Cl.

2. The method for preparing a photoacid generator 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutanesulfonate according to claim 1, characterized in that: The organic solvent is dichloromethane or 1,2-dichloroethane.

3. The method for preparing a photoacid generator 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutanesulfonate according to claim 1, characterized in that: The molar ratio of the 1-naphthalene ether, the cyclic sulfoxide compound and the fluoroalkyl sulfonic acid derivative compound is 1:1-2:1-2.

4. The method for preparing 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutanesulfonate according to any one of claims 1 to 3, characterized in that: The specific preparation steps include: S1, adding 1-naphthalene ether, an organic solvent and a cyclic sulfoxide compound into a reaction container and stirring evenly, and then slowly dropping a fluoroalkyl sulfonic acid derivative compound and allowing it to react fully; S2, after the reaction of S1 is completed, the obtained reaction solution is subjected to alkaline solution and water extraction and separation, and then the organic phase is dried and the organic solvent is evaporated to obtain a crude product; S3. The crude product obtained in step S2 is subjected to pulping treatment to obtain a solid, namely 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutanesulfonate.

5. The method for preparing a photoacid generator 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutanesulfonate according to claim 4, characterized in that: In the step S1, the reaction time is 6-12 hours and the reaction temperature is -5 to 5°C.

6. The method for preparing a photoacid generator 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutanesulfonate according to claim 4, characterized in that: In the step S2, the washing agents used in the washing are bicarbonate aqueous solution and water; the carbonate solution is sodium bicarbonate; and the reagent used in the drying of the organic phase is anhydrous sodium sulfate.

7. The method for preparing a photoacid generator 1-(4-alkoxynaphthyl)-1H-cyclosulfonium perfluorobutanesulfonate according to claim 4, characterized in that: In step S3, the solvent used for pulping is diethyl ether or methyl tert-butyl ether.

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