A method for preparing triphenol a

Abstract

This invention provides a method for preparing pyrogallol A, relating to the field of photoresist materials technology. The method uses 2-phenyl-2-propanol as a starting material and obtains pyrogallol A in a one-pot process. Specifically, aluminum trichloride is added to dichloroethane and stirred to disperse, and acetyl chloride is added dropwise to obtain a complex solution. A dichloroethane solution of 2-phenyl-2-propanol is then added dropwise for reaction. Hydrochloric acid is added for quenching. Phenol, dodecyl mercaptan, and sodium dodecyl sulfate are then added, and the reaction is heated. After the reaction is complete, the mixture is kept at a constant temperature, filtered, washed, and dried to obtain pyrogallol A. The Friedel-Crafts reaction has a high conversion rate, and no post-processing or purification is required after quenching; condensation can be directly performed. Condensation is a heterogeneous reaction, and the reaction time is significantly shortened by adding a catalytic amount of phase transfer catalyst. The preparation method of this invention uses readily available raw materials, produces a product with high purity and high yield, has a short reaction time, is simple to operate, and is low in cost, while also reducing waste, making it suitable for industrial production.

Description

Technical Field

[0001] This invention relates to the field of photoresist materials technology, and in particular to a method for preparing pyrogallol A. Background Technology

[0002] Triphenol A is mainly used in photoresists and is a key raw material for them. Photoresists are polymeric compounds that exhibit photoresistivity after exposure to light, used to create circuit shapes on the surface of semiconductor substrates. Their formulation is typically a complex system, mainly including photosensitive materials (PAC), resins, and other beneficial materials such as stabilizers, polymerization inhibitors, viscosity control agents, dyes, plasticizers, and chemical solubilizers. The modern semiconductor industry demands increasingly smaller integrated circuits with higher integration density, progressing according to Moore's Law. The driving force behind this is the continuous development of photolithography technology. Since the 1980s, photolithography technology has evolved from I-line 365nm to deep ultraviolet (DUV, 248nm and 193nm), and the most notable next-generation photolithography technology is extreme ultraviolet (EUV, 13.5nm). Corresponding to each exposure wavelength, the photoresist components (film-forming resin, photosensitizer, and additives, etc.) have also changed accordingly. Triphenol A is one of the photosensitive substances in molecular glass system photoresists, and it is also one of the main raw materials for molecular glass system photoresists in current EUV lithography technology.

[0003] Currently available methods for preparing pyrogallol A include the following, such as the synthetic route disclosed in patent CN107011124A:

[0004]

[0005] This method has short reaction times and high yields in each step, but the raw materials are expensive, and each step requires separate processing or purification. Patent CN114436781A discloses the following synthetic route:

[0006]

[0007] This method boasts high yields at each step, but the raw materials are relatively expensive, the reaction time is long, and each step requires separate processing or purification. Patent CN102428061A discloses the following synthetic route:

[0008]

[0009] This method uses inexpensive raw materials, but each step of the reaction takes a long time and requires separate processing or purification, resulting in a low yield.

[0010] Therefore, the present invention provides a method for preparing triphenol A. Summary of the Invention

[0011] This invention provides a method for preparing pyrogallol A, which aims to solve the problems of long reaction / processing time, low overall yield, low purity of intermediates, need for step-by-step purification, and large amount of waste liquid in the preparation process of existing technologies.

[0012] To achieve the above objectives, embodiments of the present invention provide a method for preparing pyrogallol A. This method uses 2-phenyl-2-propanol as the starting material and obtains pyrogallol A in a one-pot process. The Friedel-Crafts reaction of this invention has a high conversion rate, and no post-processing or purification is required after quenching; condensation can be directly performed. Condensation is a heterogeneous reaction; adding a catalytic amount of phase transfer catalyst significantly shortens the reaction time. After the reaction is completed, holding at a certain temperature for a period of time and then filtering yields pyrogallol A with a purity of over 99% and a yield of over 85%. The raw materials of this invention are readily available, and the product has high purity and high yield. The reaction time is short, the operation is simple, and the cost is low, while also reducing waste, making it suitable for industrial production.

[0013] An embodiment of the present invention provides a method for preparing pyrogallol A, comprising the following steps:

[0014] S1: Add aluminum trichloride to dichloroethane and stir to disperse, then add acetyl chloride dropwise to obtain a complex solution;

[0015] S2: Add 2-phenyl-2-propanol to dichloroethane and stir until fully dissolved to obtain a dichloroethane solution of 2-phenyl-2-propanol;

[0016] S3: The dichloroethane solution of the 2-phenyl-2-propanol is added dropwise to the complex solution to carry out the reaction;

[0017] S4: Add hydrochloric acid dropwise to the reaction system of step S3 to quench the reaction;

[0018] S5: Add phenol, dodecyl mercaptan, and sodium dodecyl sulfate to the reaction system of step S4, heat, and carry out the reaction;

[0019] S6: After the reaction in step S5 is complete, keep warm and filter, rinse and dry to obtain triphenol A.

[0020] Preferably, in step S1, the conditions for adding acetyl chloride are: temperature 5–45°C and time 0.5 h. More preferably, the temperature for adding acetyl chloride is 5–15°C.

[0021] Preferably, in step S2, the purity of 2-phenyl-2-propanol is 99%.

[0022] Preferably, in step S3, the conditions for adding the dichloroethane solution of 2-phenyl-2-propanol are: temperature 5–45°C, time 1 h; reaction time 0.5 h. More preferably, the temperature for adding the dichloroethane solution of 2-phenyl-2-propanol is 5–15°C.

[0023] Preferably, in step S4, the quenching conditions are: temperature 15–45°C, time 1 hour; hydrochloric acid concentration 25%. More preferably, the quenching temperature is 15–25°C.

[0024] Preferably, in step S5, the reaction conditions are: temperature 15–45°C, time 1–6 h.

[0025] Preferably, in step S6, the temperature is maintained for 1 hour; the rinsing specifically involves rinsing twice with sodium bicarbonate aqueous solution and twice with dichloroethane.

[0026] Preferably, the molar ratio of 2-phenyl-2-propanol to sodium dodecyl sulfate is 1:(0.003 to 0.03).

[0027] Preferably, the molar ratio of 2-phenyl-2-propanol to sodium dodecyl sulfate is 1:0.03.

[0028] Preferably, the purity of the triphenol A is as high as 99% or more.

[0029] The above-described solution of the present invention has the following beneficial effects:

[0030] (1) The present invention uses a one-pot feeding method, with a triphenol A purity of over 99% and a total yield of over 85%.

[0031] (2) Compared with the Friedel-Crafts method of p-cumylphenol in patent CN102428061A, the following obvious byproducts will appear. This necessitates further purification, affecting the yield. However, this invention uses 2-phenyl-2-propanol as the starting material for the Friedel-Crafts reaction. Because the isopropanol group is sterically hindered, the acetyl group is difficult to substitute at the ortho position, resulting in predominantly para substitution. This leads to fewer side reactions, high purity intermediates, and no need for purification.

[0032] (3) In this invention, the main catalyst for the condensation reaction is changed from HCl gas to hydrochloric acid aqueous solution, and the solvent is dichloroethane. After the Friedel-Crafts reaction solution is quenched with hydrochloric acid, it can be directly added to the condensation reaction without extraction, separation and solvent concentration. The condensation is fed in one pot without the need for aeration and dripping operations.

[0033] (4) The solvent for the condensation reaction in this invention is dichloroethane, and the main catalyst is hydrochloric acid aqueous solution. It is a heterogeneous reaction. Introducing a catalytic amount of phase transfer catalyst can significantly shorten the reaction time. Moreover, after the reaction is completed, the temperature is maintained for 1 hour, and filtration can yield pyrogallol A with a purity of over 99%, without the need for further purification.

[0034] (5) Compared with patent CN102428061A, the reaction / processing time of the present invention is less than 1 / 5, the total yield is nearly twice as high, and the amount of solvent used to produce the same amount of pyrogallol A is only about 1 / 5, which is suitable for industrial production. Attached Figure Description

[0035] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 This is an HPLC chromatogram of pyrogallol A prepared in Example 1 of the present invention;

[0037] Figure 2 This is the pyrogallol A prepared in Example 1 of the present invention. 1 HNMR image. Detailed Implementation

[0038] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with the accompanying drawings and specific embodiments.

[0039] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0040] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0041] This invention addresses the problems of long reaction / processing time, low overall yield, low purity of intermediates, need for step-by-step purification, and large amount of waste liquid in existing technologies by providing a method for preparing pyrogallol A.

[0042] The following will be explained through specific embodiments.

[0043] Example 1

[0044] A method for preparing pyrogallol A includes the following steps:

[0045] (1) Add 375g of dichloroethane and 203.53g of aluminum trichloride (2.1eq, 1.53mol) to a 2L multi-necked reaction flask and stir to disperse. Add 119.82g of acetyl chloride (2.1eq, 1.53mol) dropwise to form a complex solution. The dropwise temperature is between 5°C and 15°C, and the dropwise time is about 0.5h.

[0046] (2) Add 250g of dichloroethane to a beaker, add 100g of 2-phenyl-2-propanol (1 eq, 0.727 mol, purity 99%), and stir until completely dissolved.

[0047] (3) The dichloroethane solution of 2-phenyl-2-propanol was added dropwise to the complex solution at a temperature between 5°C and 15°C for about 1 hour. After the addition was complete, the reaction continued for 0.5 hours.

[0048] (4) The reaction solution is quenched by adding drops into 500ml of 25% hydrochloric acid. The quenching temperature is between 15°C and 25°C, and the quenching time is about 1 hour.

[0049] (5) Add 684.11g phenol (10eq, 7.27mol), 18.39g dodecyl mercaptan (0.125eq, 0.091mol) and 6.29g sodium dodecyl sulfate (0.03eq, 0.022mol) to the reaction solution and react at 45 degrees for 6h.

[0050] (6) After the reaction was completed and kept at a constant temperature for 1 hour, the mixture was filtered, washed twice with sodium bicarbonate aqueous solution, and twice with dichloroethane. After drying, 265 g of white solid was obtained with a purity of 99.16% and a yield of 85.2%. HPLC test results are as follows: Figure 1 As shown, 1 HNMR such as Figure 2 As shown.

[0051] Example 2

[0052] A method for preparing pyrogallol A includes the following steps:

[0053] (1) Add 375g of dichloroethane and 203.53g of aluminum trichloride (2.1eq, 1.53mol) to a 2L multi-necked reaction flask and stir to disperse. Add 119.82g of acetyl chloride (2.1eq, 1.53mol) dropwise to form a complex solution. The dropwise temperature is between 5°C and 15°C, and the dropwise time is about 0.5h.

[0054] (2) Add 250g of dichloroethane to a beaker, add 100g of 2-phenyl-2-propanol (1 eq, 0.727 mol, purity 99%), and stir until completely dissolved.

[0055] (3) The dichloroethane solution of 2-phenyl-2-propanol was added dropwise to the complex solution at a temperature between 5°C and 15°C for about 1 hour. After the addition was complete, the reaction continued for 0.5 hours.

[0056] (4) The reaction solution is quenched by adding drops into 500ml of 25% hydrochloric acid. The quenching temperature is between 25°C and 45°C, and the quenching time is about 1 hour.

[0057] (5) Add 684.11g phenol (10eq, 7.27mol), 18.39g dodecyl mercaptan (0.125eq, 0.091mol) and 6.29g sodium dodecyl sulfate (0.03eq, 0.022mol) to the reaction solution and react at 45 degrees for 6h.

[0058] (6) After the reaction was completed, the mixture was kept at a constant temperature for 1 hour and then filtered. The mixture was washed twice with sodium bicarbonate aqueous solution and twice with dichloroethane. After drying, 250g of white solid was obtained with a purity of 99.02% and a yield of 80.2%.

[0059] Example 3

[0060] A method for preparing pyrogallol A includes the following steps:

[0061] (1) Add 375g of dichloroethane and 203.53g of aluminum trichloride (2.1eq, 1.53mol) to a 2L multi-necked reaction flask and stir to disperse. Add 119.82g of acetyl chloride (2.1eq, 1.53mol) dropwise to form a complex solution. The dropwise temperature is between 5°C and 15°C, and the dropwise time is about 0.5h.

[0062] (2) Add 250g of dichloroethane to a beaker, add 100g of 2-phenyl-2-propanol (1 eq, 0.727 mol, purity 99%), and stir until completely dissolved.

[0063] (3) The dichloroethane solution of 2-phenyl-2-propanol was added dropwise to the complex solution at a temperature between 5°C and 15°C for about 1 hour. After the addition was complete, the reaction continued for 0.5 hours.

[0064] (4) The reaction solution is quenched by adding drops into 500ml of 25% hydrochloric acid. The quenching temperature is between 15°C and 25°C, and the quenching time is about 1 hour.

[0065] (5) Add 684.11g phenol (10eq, 7.27mol), 18.39g dodecyl mercaptan (0.125eq, 0.091mol) and 2.10g sodium dodecyl sulfate (0.01eq, 0.007mol) to the reaction solution and react at 45 degrees for 6h.

[0066] (6) After the reaction was completed and kept at the temperature for 1 hour, the mixture was filtered, washed twice with sodium bicarbonate aqueous solution and twice with dichloroethane, and dried to obtain 210g of white solid with a purity of 99.05% and a yield of 67.4%.

[0067] Comparative Example

[0068] A method for preparing pyrogallol A includes the following steps:

[0069] Step 1: Add 70.5g of aluminum trichloride to a reaction flask, add 105.8g of chloroform, purge with nitrogen, cool to 5°C, and add 42.3g of acetyl chloride dropwise over 1 hour to form a complex solution. Separately, dissolve 50g of p-cumylphenol in 75g of chloroform and add the complex solution dropwise over 3 hours, maintaining the reaction at 5°C. After completion, continue the reaction at room temperature for 2 hours. After the reaction is complete, add 171.8g of toluene to the reaction solution, and add the mixture dropwise to 275.1g of water, maintaining the temperature at 40-50°C. After the addition is complete, add 103.1g of 35% hydrochloric acid, stir at 30°C for 1 hour, remove the aqueous layer, neutralize the organic layer with sodium hydroxide solution, and remove the solvent by distillation. Recrystallize the residue with 73.9g of toluene and 73.9g of isooctane to obtain 42.3g of a pale yellowish-white solid with 97.3% purity.

[0070] Step 2: Add 20.1g of pale yellow-white solid to a reaction flask, along with 20g of toluene, 24.0g of 16% sodium hydroxide solution, and 2g of methanol. React at 50°C for 2.5 hours. After the reaction is complete, neutralize with 75% phosphoric acid, remove the aqueous layer, and concentrate the organic phase to obtain 18g of the hydrolysis intermediate. The two-step yield is 60%.

[0071] Step 3: Add 55.6g of phenol, 1.7g of toluene, and 2.42g of dodecanethiol to a reaction flask. Purge with nitrogen and heat to 45°C, then purge with HCl, continuously purging with HCl. Add dropwise a solution of 24.6g of hydrolyzed intermediate dissolved in 24.6g of phenol over 3 hours. After the addition is complete, react at 40°C for 18 hours. Add toluene, heat to purify, filter, and purify again to obtain 30g of solid, yield 73%.

[0072] Comparison of reaction / processing time

[0073] method Fu Ke hydrolysis condensation Post-processing refined Total Time Example 1 3h 1h 6h 2h / 12h Comparative Example 7h 3h 24h 12h 18h 64h

[0074] Overall yield comparison

[0075]

[0076] Comparison of solvent usage per mole of pyrogallol A produced

[0077] method organic phase Inorganic phase Total solvent volume Example 1 1L 1L 2L Comparative Example 6.5L 3.2L 9.7L

[0078] In summary, the total time of Example 1 was 18.75% of that of the comparative example, the total yield was 1.945 times that of the comparative example, and the amount of solvent used to produce an equal amount of pyrogallol A was 20.62% of that of the comparative example.

[0079] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing pyrogallol A, characterized in that, Includes the following steps: S1: Add aluminum trichloride to dichloroethane and stir to disperse, then add acetyl chloride dropwise to obtain a complex solution; in step S1, the conditions for adding acetyl chloride dropwise are: temperature 5~45℃; S2: Add 2-phenyl-2-propanol to dichloroethane and stir until fully dissolved to obtain a dichloroethane solution of 2-phenyl-2-propanol; S3: The dichloroethane solution of 2-phenyl-2-propanol is added dropwise to the complex solution to carry out the reaction; in step S3, the conditions for adding the dichloroethane solution of 2-phenyl-2-propanol are: temperature 5~45℃; S4: Add hydrochloric acid dropwise to the reaction system of step S3 to quench the reaction; S5: Phenol, dodecyl mercaptan, and sodium dodecyl sulfate are added to the reaction system of step S4 and heated to carry out the reaction; the molar ratio of 2-phenyl-2-propanol to sodium dodecyl sulfate is 1:0.01~0.03; the reaction conditions in step S5 are: temperature 15~45℃; S6: After the reaction in step S5 is complete, keep warm and filter, rinse twice with sodium bicarbonate aqueous solution and twice with dichloroethane, dry, and obtain triphenol A; The preparation method is a one-pot method. After quenching in step S4, no post-processing or purification is required. The feeding and condensation reaction in step S5 can be carried out directly. The purity of the pyrogallol A is as high as 99% or more.

2. The method for preparing pyrogallol A according to claim 1, characterized in that, In step S1, the conditions for adding acetyl chloride are: temperature 5~45℃, time 0.5h.

3. The method for preparing pyrogallol A according to claim 1, characterized in that, In step S2, the purity of 2-phenyl-2-propanol is 99%.

4. The method for preparing pyrogallol A according to claim 1, characterized in that, In step S3, the conditions for adding the dichloroethane solution of 2-phenyl-2-propanol are: temperature 5~45℃, time 1h; reaction time 0.5h.

5. The method for preparing pyrogallol A according to claim 1, characterized in that, In step S4, the quenching conditions are: temperature 15~45℃, time 1h; hydrochloric acid concentration 25%.

6. The method for preparing pyrogallol A according to claim 1, characterized in that, In step S5, the reaction conditions are: temperature 15~45℃, time 1~6h.

7. The method for preparing pyrogallol A according to claim 1, characterized in that, In step S6, keep warm for 1 hour.

8. The method for preparing pyrogallol A according to claim 1, characterized in that, The molar ratio of 2-phenyl-2-propanol to sodium dodecyl sulfate is 1:0.03.

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