A preparation method of 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]propane

Abstract

The invention provides a method for preparing 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl] propane, comprising the steps of: adding 3-(N-R substituted) benzamide to a first polar solvent, adding a first catalyst, heating in the first stage, dropping a polar solution of 2,2-bis(4-hydroxy-3-bromophenyl) propane after reaching a certain temperature, adjusting the reaction solution to the second stage for stabilization after the reaction of the raw material, adding a deprotecting agent, recovering 60% of the polar solvent under reduced pressure after the reaction of the intermediate product, adding the residue to water, cooling to 0 DEG C and stirring for 2 hours, filtering to obtain a crude product; adding the crude product obtained by S1 to a second polar solvent, adding ultrapure water for washing, recovering 50% of acetonitrile under reduced pressure after filtering with an organic membrane, cooling to 0 DEG C and stirring for 1 hour, and vacuum drying to obtain 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl] propane. The process conditions of the present invention are mild, the yield is high, the quality is good, the solvent can be recovered and applied, and it is suitable for mass production.

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemistry, and in particular relates to a method for preparing 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]propane. Background Art

[0002] 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane (m-BAP for short) can be used in photosensitive materials to make photosensitive resins because it contains both amide bonds and hydroxyl groups in its structure. Its terminal applications are photoresist semiconductors, photosensitive inks, photocurable adhesives, etc.

[0003] Patent WO2024111466A1 discloses a method for preparing m-BAP, which is a patent for semiconductor photosensitive resin. The preparation method is a two-step reaction:

[0004] Step 1: dissolve 2,2-bis(4-hydroxy-3-aminophenyl)propane in acetone and propylene oxide, cool to -15°C, add dropwise an acetone solution of m-nitrobenzoyl chloride, react at this temperature for 4 hours, warm to room temperature, filter, and dry under vacuum at 50°C to obtain a solid;

[0005] Step 2: Add the solid from the first step into a stainless steel autoclave, add palladium carbon, methanol, introduce hydrogen, react at room temperature for 2 hours, filter after the reaction is completed, and concentrate the filtrate to obtain the product m-BAP.

[0006] The preparation method provided by the above patent does not disclose detailed information such as product yield and quality. The above two-step reaction formula is as follows:

[0007] Summary of the invention

[0008] In view of this, the present invention aims to provide a method for preparing 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]propane to improve the product yield and quality so that it can meet the needs of use in the semiconductor field.

[0009] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0010] A method for preparing 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]propane comprises the following steps:

[0011] S1: Crude product preparation steps:

[0012] After adding 3-(NR substituted)benzamide to the first polar solvent, adding the first catalyst, performing the first stage heating, and after reaching a certain temperature, adding dropwise the polar solution of 2,2-bis(4-hydroxy-3-bromophenyl)propane, after the reaction of the raw materials is completed, adjusting the reaction solution to the second stage stability, then adding the deprotecting agent, after the reaction of the intermediate product is completed, reducing the pressure to recover 60% of the polar solvent, adding the residue to water, cooling to 0°C and stirring for 2 hours, and filtering to obtain a crude product;

[0013] S2: Refining step:

[0014] The crude product obtained in S1 is added to a second polar solvent, washed with ultrapure water, filtered with an organic membrane, and then 50% acetonitrile is recovered under reduced pressure. The product is cooled to 0°C and stirred for 1 hour, and then dried under vacuum to obtain 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]propane;

[0015] The above reaction formula is as follows:

[0016]

[0017] Furthermore, R is benzyloxycarbonyl, tert-butyloxycarbonyl, 9-fluorenylmethylester, trifluoroacetate, allylformate, methyl(ethyl)oxycarbonyl, phthalate or p-toluenesulfonate.

[0018] Furthermore, the R is benzyloxycarbonyl.

[0019] Further, the deprotecting agent is a hydrogen donor or a combination of the second catalyst and a hydrogen donor;

[0020] The hydrogen donor is acetic acid, trifluoroacetic acid, hydrogen, ammonium formate or methanol;

[0021] When the second catalyst is palladium carbon and the deprotecting agent is a combination of the second catalyst and a hydrogen donor, the mass of the second catalyst is 1%-15% of 2,2-bis(4-hydroxy-3-bromophenyl)propane.

[0022] Furthermore, the first polar solvent and the second polar solvent include one or more of methanol, acetonitrile, methyl tert-ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, N-methyl pyrrolidone, acetone, toluene, propylene glycol dimethyl ether, dimethyl sulfoxide, ethyl acetate, trimethylbenzene, butanol, xylene, methyl isobutyl ketone, and isopropyl ether.

[0023] Furthermore, the molar ratio of the 2,2-bis(4-hydroxy-3-bromophenyl)propane, 3-(NR substituted)benzamide, the first polar solvent, and the hydrogen donor is 1:(2-2.1):(20-60):(1-10).

[0024] Furthermore, the molar ratio of the 2,2-bis(4-hydroxy-3-bromophenyl)propane, 3-(NR substituted)benzamide, the first polar solvent, and the hydrogen donor is 1:2.01:40:2.

[0025] Further, the first catalyst includes phenylphosphine rhodium chloride, (bicyclo[2,2,1]hept-2,5-diene)[1,4-bis(diphenylphosphino)butane] rhodium tetrafluoroborate, pentamethylcyclopentadienylcarbonyl cobalt diiodide, dodecacarbonyl triruthenium, copper acetate, copper formate, copper iodide, potassium fluoride, bromo(o-phenanthroline)(triphenyl)copper, silver trifluoromethanesulfonate, trifluoroacetylacetonate copper, trimethylphosphine(hexafluoroacetylacetonate)copper, One or more of trimethylphosphine (hexafluoroacetylacetonate) silver, silver citrate, acetylmethionine silver, M-oxy-bis-tetraphenylporphyrin manganese, (1,10-phenanthroline) copper dibromide, pentaammine cobalt chloride, copper hydroxide phosphate, methylcyclopentadiene tricarbonyl manganese, [1,1'-bis(diphenylphosphino)ferrocene] cobalt dichloride, tris(triphenylphosphine) copper bromide, tetra-p-tolyl manganese porphyrin, hexaammine cobalt chloride, and tris(ethylenediamine) cobalt chloride.

[0026] Furthermore, the mass of the first catalyst is 0.5%-6%, preferably 2.2%, of 2,2-bis(4-hydroxy-3-bromophenyl)propane.

[0027] Furthermore, the reaction temperature in the first stage is 50°C-180°C, and the temperature in the second stage is 30°C-80°C.

[0028] Furthermore, the contents of 28 kinds of metal ions in the ultrapure water in S2 are less than 1 ppb, the volume ratio of ultrapure water to acetonitrile is 1:1, and the ultrapure water is added for washing for 5 times.

[0029] The 28 metal ions are shown in the attached Figure 2 .

[0030] Furthermore, the pore size of the organic membrane in S2 is 0.2-2 microns.

[0031] Furthermore, the pore size of the organic membrane in S2 is 0.45 micrometers.

[0032] Compared with the prior art, the method for preparing 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]propane of the present invention has the following advantages:

[0033] The present invention adopts a one-pot method to prepare high-purity m-BAP, with mild process conditions, high yield, good quality, and solvent recovery, which is suitable for mass production. Secondly, the method can also be used for the preparation of other amide compounds, such as m-6FDAP (CAS: 220426-92-6), p-6FDAP (CAS: 129 197-38-2), and sulfone compounds, such as 3,3'-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]diphenyl sulfone. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0035] Figure 1 This is the m-BAP liquid chromatogram described in Example 1 of the present invention;

[0036] Figure 2 This is the detection result of metal ions of m-BAP using ICPMS7900 in Example 1 of the present invention. DETAILED DESCRIPTION

[0037] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other.

[0038] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0039] Detection equipment: Liquid phase: Agilent 1260; Colorimetric YI: Konica Minolta CM5; Metal ion: Agilent ICPMS7900.

[0040] Example 1

[0041] S1: Add 271g 3-(N-benzyloxycarbonyl)benzamide, 965mL N-methylpyrrolidone, 4.2g potassium fluoride, 4.2g copper formate to the reaction bottle, heat to 110°C, and drop 193g 2,2-bis(4-hydroxy-3-bromophenyl)propane in 965mL N-methylpyrrolidone solution. After the reaction of the raw materials is completed, cool to 50°C and add 3.8g palladium carbon and 63g ammonium formate. Continue to react until the reaction of the intermediate product is completed, filter at this temperature, and recover 60% of the polar solvent by decompression of the filtrate. Add the reaction solution to water, cool to 0°C and stir for 2 hours to precipitate solids, and filter to obtain 750g of wet crude product.

[0042] S2: 750g of the wet crude product was added to 6750mL of acetonitrile, and washed 5 times with 2000mL of ultrapure water. The acetonitrile solution after separation was filtered once with a 0.45 micron organic membrane, and then 50% of the acetonitrile was recovered under reduced pressure. The reaction solution was cooled to 0°C and stirred for 1 hour, then filtered, and vacuum dried at 120°C in a vacuum drying oven for 12 hours to obtain m-BAP, 463.5g. White solid, yield 93.34%, liquid content 99.69%, chromaticity YI 3.3, 28 metal ion contents were all <1ppm.

[0043] Example 2

[0044] S1: Add 272.3g 3-(N-benzyloxycarbonyl)benzamide, 1200mL N-methylpyrrolidone (containing 50% recovered N-methylpyrrolidone), 7.7g potassium fluoride, 7.7g copper formate to the reaction bottle, heat to 110°C, and drop 193g 2,2-bis(4-hydroxy-3-bromophenyl)propane in 1200mL N-methylpyrrolidone solution (containing 50% recovered N-methylpyrrolidone). After the reaction of the raw materials is completed, cool to 50°C and add 5.8g palladium carbon and 126g ammonium formate. Continue to react until the reaction of the intermediate product is completed, filter at this temperature, and recover 60% of the polar solvent by decompression of the filtrate. Add the reaction solution into water, cool to 0°C and stir for 2 hours to precipitate solids, and filter to obtain 783g of wet crude product.

[0045] S2: 783g of the wet crude product was added to 7050mL of acetonitrile, and washed 5 times with 3000mL of ultrapure water. The acetonitrile solution after separation was filtered once with a 0.45 micron organic membrane, and then 50% of the acetonitrile was recovered under reduced pressure. The reaction solution was cooled to 0°C and stirred for 1 hour, then filtered, and vacuum dried at 120°C in a vacuum drying oven for 12 hours to obtain m-BAP, 470g. White solid, yield 94.65%, liquid content 99.72%, chromaticity YI 3.1, 28 metal ion contents were all <1ppm.

[0046] Example 3

[0047] S1: Add 271g 3-(N-benzyloxycarbonyl)benzamide, 1000mL N-methylpyrrolidone, 7.7g potassium fluoride, 4.5g bromo(o-phenanthroline)(triphenyl)copper to the reaction bottle, heat to 105°C, and drop 193g 2,2-bis(4-hydroxy-3-bromophenyl)propane in 1000mL N-methylpyrrolidone solution. After the reaction of the raw materials is completed, cool to 50°C and add 5.8g palladium carbon and 89g ammonium formate. Continue to react until the reaction of the intermediate product is completed, filter at this temperature, and recover 60% of the polar solvent by decompression of the filtrate. Add the reaction solution to water, cool to 0°C and stir for 2 hours to precipitate solids, and filter to obtain 638g of wet crude product.

[0048] S2: 638g of the wet crude product was added to 5700mL of acetonitrile, and washed five times with 1600mL of ultrapure water. The acetonitrile solution after separation was filtered once with a 0.45 micron organic membrane, and then 50% of the acetonitrile was recovered under reduced pressure. The reaction solution was cooled to 0°C and stirred for 1 hour, then filtered, and vacuum dried at 120°C in a vacuum drying oven for 12 hours to obtain m-BAP, 296g. White solid, yield 59.61%, liquid content 99.36%, color YI 3.5, 28 metal ion contents were all <1ppm.

[0049] Example 4

[0050] S1: Add 271g 3-(N-benzyloxycarbonyl)benzamide, 1100mL N-methylpyrrolidone, 11.6g tri(ethylenediamine)cobalt chloride to the reaction bottle, heat to 120°C, and drop 193g 2,2-bis(4-hydroxy-3-bromophenyl)propane in 1100mL N-methylpyrrolidone solution. After the reaction of the raw materials is completed, cool to 50°C and add 4.9g palladium carbon and 105g ammonium formate. Continue to react until the reaction of the intermediate product is completed, filter at this temperature, and recover 60% of the polar solvent by decompression of the filtrate. Add the reaction solution to water, cool to 0°C and stir for 2 hours to precipitate solids, and filter to obtain 593g of wet crude product.

[0051] S2: 593 g of the wet crude product was added to 5400 mL of acetonitrile, and washed five times with 1300 mL of ultrapure water. The acetonitrile solution after separation was filtered once with a 0.45 μm organic membrane, and then 50% of the acetonitrile was recovered under reduced pressure. The reaction solution was cooled to 0°C and stirred for 1 hour, then filtered, and vacuum dried at 120°C in a vacuum drying oven for 12 hours to obtain m-BAP, 223 g. White solid, yield 44.90%, liquid content 98.57%, color YI 4.3, 28 metal ion contents were all <1 ppm.

[0052] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]propane, characterized in that: The steps include: S1: Crude product preparation steps: After adding 3-(NR substituted)benzamide to the first polar solvent, adding the first catalyst, performing the first stage heating, and after reaching a certain temperature, adding dropwise the polar solution of 2,2-bis(4-hydroxy-3-bromophenyl)propane, after the reaction of the raw materials is completed, adjusting the reaction solution to the second stage stability, then adding the deprotecting agent, after the reaction of the intermediate product is completed, reducing the pressure to recover 60% of the polar solvent, adding the residue to water, cooling to 0°C and stirring for 2 hours, and filtering to obtain a crude product; S2: Refining step: The crude product obtained in S1 is added to a second polar solvent, washed with ultrapure water, filtered with an organic membrane, and then 50% acetonitrile is recovered under reduced pressure. The product is cooled to 0°C and stirred for 1 hour, and then dried under vacuum to obtain 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]propane; The above reaction formula is as follows:

2. The method for preparing 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane according to claim 1, characterized in that: The R is benzyloxycarbonyl, tert-butyloxycarbonyl, 9-fluorenylmethoxy, trifluoroacetoxy, allylmethoxy, methyl(ethyl)oxycarbonyl, phthalate or p-toluenesulfonate, preferably benzyloxycarbonyl.

3. The method for preparing 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane according to claim 1, characterized in that: The deprotecting agent is a hydrogen donor or a combination of the second catalyst and a hydrogen donor; The hydrogen donor is acetic acid, trifluoroacetic acid, hydrogen, ammonium formate or methanol; When the second catalyst is palladium carbon and the deprotecting agent is a combination of the second catalyst and a hydrogen donor, the mass of the second catalyst is 1%-15% of 2,2-bis(4-hydroxy-3-bromophenyl)propane.

4. The method for preparing 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane according to claim 1, characterized in that: The first polar solvent and the second polar solvent include one or more of methanol, acetonitrile, methyl tert-ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, N-methyl pyrrolidone, acetone, toluene, propylene glycol dimethyl ether, dimethyl sulfoxide, ethyl acetate, trimethylbenzene, butanol, xylene, methyl isobutyl ketone, and isopropyl ether.

5. The method for preparing 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane according to claim 3, characterized in that: The molar ratio of the 2,2-bis(4-hydroxy-3-bromophenyl)propane, 3-(NR substituted)benzamide, the first polar solvent and the hydrogen donor is 1:(2-2.1):(20-60):(1-10), preferably 1:2.01:40:

2.

6. The method for preparing 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane according to claim 1, characterized in that: The first catalyst includes phenylphosphine rhodium chloride, (bicyclo[2,2,1]hept-2,5-diene)[1,4-bis(diphenylphosphino)butane] rhodium tetrafluoroborate, pentamethylcyclopentadienylcarbonyl cobalt diiodide, dodecacarbonyl triruthenium, copper acetate, copper formate, copper iodide, potassium fluoride, bromo(o-phenanthroline)(triphenyl)copper, silver trifluoromethanesulfonate, trifluoroacetylacetonate copper, trimethylphosphine(hexafluoroacetylacetonate)copper, trimethyl One or more of silver hexafluoroacetylacetonate, silver citrate, silver acetylmethionine, M-oxy-bis-tetraphenylporphyrin manganese, (1,10-phenanthroline) copper dibromide, cobalt pentaammine chloride, copper hydroxide phosphate, methylcyclopentadiene tricarbonyl manganese, [1,1'-bis(diphenylphosphino)ferrocene] cobalt dichloride, tris(triphenylphosphine) copper bromide, tetra-p-tolyl manganese porphyrin, hexaammine cobalt chloride, and tris(ethylenediamine) cobalt chloride.

7. The method for preparing 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane according to claim 1, characterized in that: The mass of the first catalyst is 0.5%-6% of 2,2-bis(4-hydroxy-3-bromophenyl)propane, preferably 2.2%.

8. The method for preparing 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane according to claim 1, characterized in that: The reaction temperature of the first stage is 50°C-180°C, and the temperature of the second stage is 30°C-80°C.

9. The method for preparing 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane according to claim 1, characterized in that: The contents of 28 kinds of metal ions in the ultrapure water in S2 are less than 1 ppb, the volume ratio of ultrapure water to the second polar solvent is 1:1, and the ultrapure water is added for 5 washing times.

10. The method for preparing 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane according to claim 1, characterized in that: The pore size of the organic membrane in S2 is 0.2-2 microns, preferably 0.45 microns.

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