阅读说明：本技术 一种羟基取代的苯乙烯类化合物的合成方法及光刻胶树脂单体的合成方法 (Synthesis method of hydroxyl-substituted styrene compound and synthesis method of photoresist resin monomer ) 是由 傅志伟 潘新刚 吴信 郭有壹 于 2021-10-15 设计创作，主要内容包括：本发明提供一种羟基取代的苯乙烯类化合物的合成方法及光刻胶树脂单体的合成方法。该羟基取代的苯乙烯类化合物的合成方法包括如下步骤：a)由式I-1化合物与Witting试剂反应,获得式I-2化合物。该光刻胶树脂单体的合成方法包括如下步骤：a)采用上述羟基取代的苯乙烯类化合物的合成方法获得式I-2化合物；b)将式I-2化合物与酰化试剂反应,获得所述光刻胶树脂单体,结构式见式I-3。本发明羟基取代的苯乙烯类化合物及光刻胶树脂单体的合成方法收率高、纯度高。(The invention provides a synthetic method of a hydroxyl-substituted styrene compound and a synthetic method of a photoresist resin monomer. The synthesis method of the hydroxyl-substituted styrene compound comprises the following steps: a) the compound of formula I-2 is obtained by reacting the compound of formula I-1 with Witting reagent. The synthetic method of the photoresist resin monomer comprises the following steps: a) obtaining a compound of formula I-2 by adopting the synthesis method of the hydroxyl-substituted styrene compound; b) reacting the compound shown in the formula I-2 with an acylating reagent to obtain the photoresist resin monomer shown in the formula I-3. The synthesis method of the hydroxyl-substituted styrene compound and the photoresist resin monomer has high yield and high purity.)

1. A method for synthesizing a hydroxyl-substituted styrene compound is characterized by comprising the following steps:

a) reacting a compound shown in the formula I-1 with a Witting reagent to obtain a compound shown in the formula I-2, wherein the reaction route is as follows:

wherein the reaction is carried out in the presence of a first organic solvent and a base; r₁₁、R₁₂、R₁₃、R₁₄And R₁₅Each is independent and is selected from one of hydrogen atom, alkyl and hydroxyl; r₁₁、R₁₂、R₁₃、R₁₄And R₁₅At least one of which is a hydroxyl group.

2. The method of synthesizing a hydroxy-substituted styrenic compound of claim 1 further comprising at least one of the following technical features:

a1) the Witting reagent is selected from at least one of methyl triphenyl phosphonium bromide, methyl triphenyl phosphonium iodide and methyl triphenyl phosphonium chloride;

a2) the first organic solvent is at least one selected from tetrahydrofuran, dichloromethane, chloroform, toluene and N, N' -dimethylformamide;

a3) the alkali is selected from one of sodium hydride, calcium hydride, potassium tert-butoxide, sodium tert-butoxide and sodium ethoxide;

a4) the molar ratio of the compound shown in the formula I-1 to the Witting reagent is 1: 1-1: 5;

a5) the mass ratio of the compound of the formula I-1 to the first organic solvent is 1: 5-1: 15;

a6) the molar ratio of the compound of the formula I-1 to the base is 1: 1-1: 6;

a7) the molar ratio of the Witting reagent to the alkali is 1: 0.8-1: 2;

a8) the reaction temperature is 20-25 ℃;

a9) the step a) specifically comprises the following steps: and mixing the first organic solvent and the Witting reagent, cooling for the first time, adding the alkali, cooling for the second time, and adding the compound shown in the formula I-1 for reaction.

3. The method for synthesizing a hydroxyl-substituted styrene-based compound according to claim 2, wherein the characteristic a9) further comprises at least one of the following technical characteristics:

a91) the temperature is reduced to minus 5 to minus 10 ℃ for the first time;

a92) the temperature is reduced to-65 to-75 ℃ for the second time.

4. The method of synthesizing a hydroxy-substituted styrenic compound of claim 1, further comprising: sequentially carrying out quenching reaction, pH value adjustment, liquid separation and organic phase addition on the reaction product obtained in the step a), adding a first polymerization inhibitor, carrying out reduced pressure concentration, extraction, drying, filtering and washing.

5. The method of synthesizing a hydroxy-substituted styrenic compound of claim 4 further comprising at least one of the following technical features:

11) carrying out third temperature reduction before carrying out quenching reaction;

12) the quenching reaction adopts a quenching agent selected from at least one of water, ammonium chloride solution, sodium chloride solution, hydrochloric acid and sulfuric acid;

13) adjusting the pH value to 7-8;

14) the first polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;

15) the pressure of the reduced pressure distillation is 50-200 Pa;

16) the temperature of reduced pressure distillation is 30-35 ℃;

17) the extracting agent adopted by the extraction is at least one selected from ethyl acetate, dichloromethane, dichloroethane, trichloroethane, toluene, tetrahydrofuran and methyltetrahydrofuran;

18) the drying agent is at least one of anhydrous sodium sulfate and anhydrous magnesium sulfate;

19) the washing is carried out by using a detergent selected from at least one of ethyl acetate, dichloromethane, dichloroethane, trichloroethane, toluene, tetrahydrofuran and methyltetrahydrofuran.

6. A synthetic method of a photoresist resin monomer is characterized by comprising the following steps:

a) obtaining a compound of formula I-2 using the method of synthesis of a hydroxy-substituted styrenic compound of any of claims 1 to 5;

b) reacting a compound shown in a formula I-2 with an acylating reagent to obtain the photoresist resin monomer shown in a structural formula I-3, wherein the reaction route is as follows:

wherein the reaction is carried out in the presence of a second organic solvent and a basic catalyst; r₂₁、R₂₂、R₂₃、R₂₄And R₂₅Each independently selected from one of hydrogen atom, alkyl, alkoxy and acyloxy; r₂₁、R₂₂、R₂₃、R₂₄And R₂₅At least one of them is an acyloxy group.

7. The method for synthesizing a photoresist resin monomer according to claim 6, wherein the step b) further comprises at least one of the following technical features:

b1) the acylating agent is at least one selected from acetyl chloride, acetic anhydride and acetic acid;

b2) the second organic solvent is at least one selected from tetrahydrofuran, dichloromethane, chloroform, toluene and N, N' -dimethylformamide;

b3) the basic catalyst is at least one of diethylamine, triethylamine, isopropylamine, monomethylamine, hexamethylenediamine and hexylamine;

b4) the molar ratio of the compound of the formula I-2 to the acylating reagent is 1: 1-1: 5;

b5) the molar ratio of the compound of the formula I-2 to the second solvent is 1: 5-1: 10;

b6) the molar ratio of the compound of the formula I-2 to the basic catalyst is 1: 1-1: 5;

b7) the reaction temperature is 10-20 ℃;

b8) the step b) comprises the following steps: mixing the alkaline catalyst and the second organic solvent, adding the acylating reagent, and controlling the internal temperature to be-5-0 ℃.

8. The method of synthesizing a photoresist resin monomer of claim 6, further comprising: sequentially carrying out quenching reaction on the reaction product obtained in the step b), adjusting the pH value, separating liquid, washing an organic phase by water, adding a second polymerization inhibitor, carrying out rotary evaporation, carrying out first extraction and dissolution of residues, pulping, filtering, carrying out reduced pressure concentration on the filtrate, carrying out second extraction and dissolution of residues, adding a third polymerization inhibitor, and carrying out oil pump reduced pressure distillation.

9. The method for synthesizing a photoresist resin monomer according to claim 8, further comprising at least one of the following technical features:

21) the quenching reaction adopts a quenching agent selected from at least one of water, ammonium chloride solution, sodium chloride solution, hydrochloric acid and sulfuric acid;

22) adjusting the pH value to 7-8;

23) the second polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;

24) the rotary evaporation temperature is 25-30 ℃.

10. The method for synthesizing a photoresist resin monomer according to claim 8, further comprising at least one of the following technical features:

25) the third polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;

26) the third polymerization inhibitor comprises phenothiazine and p-methoxyphenol, and the mass ratio of the phenothiazine to the p-methoxyphenol is 1: 0.1-1: 0.5;

27) the pressure of the reduced pressure distillation is 70-80 Pa;

28) the temperature of reduced pressure distillation is 90-95 ℃;

29) the top temperature of the reduced pressure distillation is 56-58 ℃.

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a synthesis method of a hydroxyl-substituted styrene compound and a synthesis method of a photoresist resin monomer.

Background

The hydroxyl-substituted styrene compound is an important chemical and medical intermediate and has wide application in the fields of photoresist technology and the like. The positive chemically amplified resist usually adopts poly-p-hydroxystyrene derivatives as acid-sensitive resin, and p-hydroxystyrene-containing high-molecular photoresists have become a key technology for photoetching 0.11 micrometer line width chips. Photoresist resin monomers (acyloxy-substituted styrenic compounds, e.g., p-acetoxystyrene) are an important aromatic compound that can be used as monomers to prepare resins, elastomers, adhesives, coatings, automotive finishes, inks, or photoresists, etc. Photoresist resin monomers (acyloxy-substituted styrenic compounds, e.g., p-acetoxystyrene) are also useful in electronic materials, as additives in elastomer and resin formulations. However, the problems of low yield and low purity exist in the prior synthesis of hydroxyl-substituted styrene compounds and photoresist resin monomers.

Disclosure of Invention

In view of the above-described drawbacks of the prior art, an object of the present invention is to provide a method for synthesizing a hydroxyl-substituted styrene compound and a method for synthesizing a photoresist resin monomer, which have high yield and high purity.

To achieve the above and other related objects, the present invention provides a method for synthesizing a hydroxy-substituted styrenic compound, comprising the steps of:

a) reacting a compound shown in the formula I-1 with a Witting reagent to obtain a compound shown in the formula I-2, wherein the reaction route is as follows:

wherein the reaction isIn the presence of a first organic solvent and a base; r₁₁、R₁₂、R₁₃、R₁₄And R₁₅Each is independent and is selected from one of hydrogen atom, alkyl and hydroxyl; r₁₁、R₁₂、R₁₃、R₁₄And R₁₅At least one of which is a hydroxyl group.

The hydroxyl-substituted styrene compound can be 2-hydroxystyrene, p-hydroxystyrene, 3, 4-dihydroxystyrene, 3, 5-dihydroxystyrene or 3,4, 5-trihydroxystyrene.

Preferably, at least one of the following technical features is also included:

a1) the Witting reagent is selected from at least one of methyl triphenyl phosphonium bromide, methyl triphenyl phosphonium iodide and methyl triphenyl phosphonium chloride;

a2) the first organic solvent is at least one selected from tetrahydrofuran, dichloromethane, chloroform, toluene and N, N' -dimethylformamide;

a3) the alkali is selected from one of sodium hydride, calcium hydride, potassium tert-butoxide, sodium tert-butoxide and sodium ethoxide;

a4) the molar ratio of the compound shown in the formula I-1 to the Witting reagent is 1: 1-1: 5, such as 1: 1-1: 3 or 1: 3-1: 5;

a5) the mass ratio of the compound of the formula I-1 to the first organic solvent is 1: 5-1: 15, such as 1: 5-1: 8.9 or 1: 8.9-1: 15;

a6) the molar ratio of the compound of the formula I-1 to the base is 1: 1-1: 6, such as 1: 1-1: 3 or 1: 3-1: 6;

a7) the molar ratio of the Witting reagent to the alkali is 1: 0.8-1: 2, such as 1: 0.8-1: 1, 1: 1-1: 1.2 or 1: 1.2-1: 2;

a8) the reaction temperature is 20-25 ℃;

a9) the step a) specifically comprises the following steps: and mixing the first organic solvent and the Witting reagent, cooling for the first time, adding the alkali, cooling for the second time, and adding the compound shown in the formula I-1 for reaction.

More preferably, in the feature a9), at least one of the following technical features is further included:

a91) the temperature is reduced to minus 5 to minus 10 ℃ for the first time, such as minus 5 to minus 8 ℃ or minus 8 to minus 10 ℃;

a92) the temperature is reduced to-65 to-75 ℃ for the second time, such as-65 to-70 ℃ or-70 to-75 ℃.

Preferably, the synthesis method further comprises: sequentially carrying out quenching reaction, pH value adjustment, liquid separation and organic phase addition on the reaction product obtained in the step a), adding a first polymerization inhibitor, carrying out reduced pressure concentration, extraction, drying, filtering and washing.

More preferably, at least one of the following technical characteristics is also included:

11) carrying out third temperature reduction before carrying out quenching reaction; even more preferably, the third temperature reduction is to-5 to-10 ℃, such as-5 to-7 ℃ or-7 to-10 ℃;

12) the quenching reaction adopts a quenching agent selected from at least one of water, ammonium chloride solution, sodium chloride solution, hydrochloric acid and sulfuric acid;

13) adjusting the pH to 7-8, such as 7-7.5 or 7.5-8;

14) the first polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;

15) the pressure of the reduced pressure distillation is 50-200 Pa, such as 50-100 Pa or 100-200 Pa;

16) the temperature of the reduced pressure distillation is 30-35 ℃, such as 30-32 ℃ or 32-35 ℃;

17) the extracting agent adopted by the extraction is at least one selected from ethyl acetate, dichloromethane, dichloroethane, trichloroethane, toluene, tetrahydrofuran and methyltetrahydrofuran;

18) the drying agent is at least one of anhydrous sodium sulfate and anhydrous magnesium sulfate;

19) the washing is carried out by using a detergent selected from at least one of ethyl acetate, dichloromethane, dichloroethane, trichloroethane, toluene, tetrahydrofuran and methyltetrahydrofuran.

The second aspect of the present invention provides a method for synthesizing a photoresist resin monomer, comprising the following steps:

a) obtaining a compound of formula I-2 by adopting the synthesis method of the hydroxyl-substituted styrene compound;

b) reacting a compound shown in a formula I-2 with an acylating reagent to obtain the photoresist resin monomer shown in a structural formula I-3, wherein the reaction route is as follows:

wherein the reaction is carried out in the presence of a second organic solvent and a basic catalyst; r₂₁、R₂₂、R₂₃、R₂₄And R₂₅Each independently selected from one of hydrogen atom, alkyl, alkoxy and acyloxy; r₂₁、R₂₂、R₂₃、R₂₄And R₂₅At least one of them is an acyloxy group.

The photoresist resin monomer can be 2-acetoxystyrene, p-acetoxystyrene, 3, 4-diacetoxystyrene, 3, 5-diacetoxystyrene, 3,4, 5-triacetoxystyrene and p-methacryloxy.

Preferably, step b) further comprises at least one of the following technical features:

b1) the acylating agent is at least one selected from acetyl chloride, acetic anhydride and acetic acid;

b2) the second organic solvent is at least one selected from tetrahydrofuran, dichloromethane, chloroform, toluene and N, N' -dimethylformamide;

b3) the basic catalyst is at least one of diethylamine, triethylamine, isopropylamine, monomethylamine, hexamethylenediamine and hexylamine;

b4) the molar ratio of the compound of formula I-2 to the acylating agent is 1: 1-1: 5, such as 1: 1-1: 2 or 1: 2-1: 5;

b5) the molar ratio of the compound of formula I-2 to the second solvent is 1: 5-1: 10, such as 1: 5-1: 6.3 or 1: 6.3-1: 10;

b6) the molar ratio of the compound of formula I-2 to the basic catalyst is 1: 1-1: 5, such as 1: 1-1: 2 or 1: 2-1: 5;

b7) the reaction temperature is 10-20 ℃, such as 10-15 ℃ or 15-20 ℃;

b8) the step b) comprises the following steps: mixing the alkaline catalyst and the second organic solvent, adding the acylating reagent, and controlling the internal temperature to be-5-0 ℃, such as-5-3 ℃ or-3-0 ℃.

Preferably, the synthesis method further comprises: sequentially carrying out quenching reaction on the reaction product obtained in the step b), adjusting the pH value, separating liquid, washing an organic phase by water, adding a second polymerization inhibitor, carrying out rotary evaporation, carrying out first extraction and dissolution of residues, pulping, filtering, carrying out reduced pressure concentration on the filtrate, carrying out second extraction and dissolution of residues, adding a third polymerization inhibitor, and carrying out oil pump reduced pressure distillation.

More preferably, at least one of the following technical characteristics is also included:

21) the quenching reaction adopts a quenching agent selected from at least one of water, ammonium chloride solution, sodium chloride solution, hydrochloric acid and sulfuric acid;

22) adjusting the pH to 7-8, such as 7-7.5 or 7.5-8;

23) the second polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;

24) the rotary evaporation temperature is 25-30 ℃, such as 25-28 ℃ or 28-30 ℃.

More preferably, at least one of the following technical characteristics is also included:

25) the third polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;

26) the third polymerization inhibitor comprises phenothiazine and p-methoxyphenol, and the mass ratio of the phenothiazine to the p-methoxyphenol is 1: 0.1-1: 0.5, such as 1: 0.1-1: 0.2, 1: 0.2-1: 0.35 or 1: 0.35-1: 0.5;

27) the pressure of the reduced pressure distillation is 70-80 Pa, such as 70-75 Pa or 75-80 Pa;

28) the temperature of reduced pressure distillation is 90-95 ℃, such as 90-94 ℃ or 94-95 ℃;

29) the top temperature of the reduced pressure distillation is 56-58 ℃, such as 56-57 ℃ or 57-58 ℃.

Compared with the prior art, the synthesis method of the hydroxyl-substituted styrene compound and the photoresist resin monomer has high yield and purity.

Drawings

FIG. 1 is a schematic representation of the HPLC purity of the reaction product obtained after the reaction of example 1 with the addition of 2-hydroxybenzaldehyde.

FIG. 2 is a schematic representation of the HPLC purity of the reaction product obtained after the addition of acetyl chloride in example 1.

FIG. 3 is a graph showing the GC purity of the residue after vacuum concentration and suction drying in example 1.

FIG. 4 is a schematic GC purity of the distillate of example 1.

FIG. 5 is an NMR spectrum of the product of example 1.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.

In the present invention, the equipment, raw materials, etc. used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.

Example 1

4450g of tetrahydrofuran, N, were added to a 10L four-necked flask₂And (3) replacing, starting mechanical stirring, adding 4400g of methyl triphenyl phosphonium bromide, cooling to-5-10 ℃, adding 1378g of potassium tert-butoxide in batches, stirring for 2h after adding, cooling to-65-75 ℃, dropwise adding 500g of 2-hydroxybenzaldehyde, stirring overnight after dropwise adding and stirring for 2h, raising the temperature to room temperature (20-25 ℃), and sampling and analyzing, wherein the HPLC purity schematic diagram is shown in figure 1 (raw materials are less than 0.1%), and the HPLC purity is 82%.

Cooling the reaction liquid to-5-10 ℃, adding 1000g of water for quenching, adding 1800g of 10% HCl for adjusting the pH value to 7-8 after quenching, separating liquid, adding 2g of phenothiazine into an organic phase, concentrating under reduced pressure at 30-35 ℃, adding 2000g of dichloromethane for dissolving after concentrating, adding anhydrous magnesium sulfate, stirring until the solution is clear, filtering, leaching a filter cake with 200g of dichloromethane, and putting the filtrate into the next step, wherein the HPLC purity is 82%.

Adding 2516g of the filtrate in the previous step and 826.4g of triethylamine into a 10L four-mouth bottle, adding 2200g of dichloromethane, mechanically stirring, cooling by a dry ice-ethanol bath, beginning to dropwise add 641.4g of acetyl chloride, wherein the dropwise addition needs 1h, and controlling the internal temperature at-5-0 ℃; after the dropwise addition is finished, removing the dry ice-ethanol bath, continuing to react at 10-20 ℃ for 3h, sampling and analyzing, wherein the HPLC purity schematic diagram is shown in figure 2 (raw materials are less than 0.2%), and the purity is 87.9%.

After the reaction is finished, 1000g of water is added into the reaction liquid for quenching, 10% of sodium hydroxide aqueous solution is added for regulating the pH value to 7-8, liquid separation is carried out, 1000g of water is added into an organic phase for washing for 1 time, 2g of phenothiazine is added after the water washing is finished, water is heated at 25-30 ℃ for rotary evaporation, an oil pump is used for pumping out solvent residues to obtain a crude product, 800g multiplied by 4 times of n-hexane is added into the crude product for pulping at room temperature, filtration is carried out, reduced pressure concentration is carried out on filtrate, then the solvent residues are pumped out, sampling analysis is carried out, a GC purity schematic diagram is shown in figure 3 (the solvent residues are less than 0.5%), the crude product 800.5g with the purity of 73%, 1g of phenothiazine and 0.2g of p-methoxyphenol are added into the crude product, then the oil pump (70-80 Pa) is used for reduced pressure distillation, the oil bath temperature is 90-95 ℃, the top temperature is 56-58 ℃ to produce a fraction 508g, the sample analysis is shown in figure 4, the GC purity schematic diagram is 98.18%, the molar yield is 76%, and an NMR spectrum is shown in figure 5.

Example 2

Tetrahydrofuran, N was added to a 10L four-necked flask₂And (2) replacement, starting mechanical stirring, adding methyl triphenyl phosphonium bromide, cooling to-5 ℃, adding potassium tert-butoxide in batches, stirring for 2h after adding, cooling to-70 ℃, dropwise adding 500g of 2-hydroxybenzaldehyde, heating to room temperature after dropwise adding and stirring for 2h, stirring overnight, sampling and analyzing, wherein the HPLC purity is 81%, wherein the molar ratio of the 2-hydroxybenzaldehyde to the methyl triphenyl phosphonium bromide is 1:1, the mass ratio of the tetrahydrofuran to the tetrahydrofuran is 1:15, and the molar ratio of the potassium tert-butoxide to the potassium tert-butoxide is 1:1.

cooling the reaction liquid to-7 ℃, adding 1000g of water for quenching, adding 10% HCl for adjusting the pH value to 7.5 after quenching, separating liquid, adding 2g of phenothiazine into the organic phase, concentrating under reduced pressure (200Pa) at 35 ℃, adding 2000g of dichloromethane for dissolving after concentrating, adding anhydrous magnesium sulfate for stirring until the solution is clear, filtering, leaching a filter cake with 200g of dichloromethane, and putting the filtrate into the next step, wherein the HPLC purity is 81%.

Adding 2514g of the filtrate in the previous step and triethylamine into a 10L four-mouth bottle, supplementing dichloromethane, mechanically stirring, cooling by a dry ice-ethanol bath, beginning to dropwise add acetyl chloride for 1h, and controlling the internal temperature at 0 ℃; after the dropwise addition is finished, removing the dry ice-ethanol bath, continuing to react at 15 ℃ for 3h, sampling and analyzing, wherein the HPLC purity is 86%, and the molar ratio of the 2-hydroxystyrene to acetyl chloride is 1: 5. the molar ratio to dichloromethane was 1: 10. the molar ratio of triethylamine to the compound is 1: 5.

after the reaction is finished, 1000g of water is added into the reaction liquid for quenching, 10% of sodium hydroxide aqueous solution is added for regulating the pH value to 8, liquid separation is carried out, 1000g of water is added into an organic phase for washing for 1 time, 2g of phenothiazine is added after the water washing is finished, the water is heated at 28 ℃ for rotary evaporation, an oil pump is used for pumping the solvent residue to obtain a crude product, 800g multiplied by 4 times of n-hexane is added into the crude product for pulping at room temperature, filtration is carried out, the filtrate is subjected to reduced pressure concentration, the solvent residue is pumped out again, sampling analysis is carried out to obtain 850g of the crude product, the GC purity is 69%, 1g of phenothiazine and 0.1g of p-methoxyphenol (the mass ratio is 1: 0.1) are added into the crude product, then the oil pump (80Pa) is used for reduced pressure distillation, the oil bath temperature is 95 ℃, the top temperature is 58 ℃, the oil bath purity is 97.1%, and the molar yield is 74.4%.

Example 3

Tetrahydrofuran, N was added to a 10L four-necked flask₂And (2) replacement, starting mechanical stirring, adding methyl triphenyl phosphonium bromide, cooling to-8 ℃, adding potassium tert-butoxide in batches, stirring for 2h after adding, cooling to-65 ℃, dropwise adding 500g of 2-hydroxybenzaldehyde, heating to room temperature after dropwise adding and stirring for 2h, stirring overnight, sampling and analyzing, wherein the HPLC purity is 80%, wherein the molar ratio of the 2-hydroxybenzaldehyde to the methyl triphenyl phosphonium bromide is 1:5, the mass ratio of the tetrahydrofuran to the tetrahydrofuran is 1:5, and the molar ratio of the potassium tert-butoxide to the potassium tert-butoxide is 1: 6.

cooling the reaction liquid to-5 ℃, adding 1000g of water for quenching, adding 10% HCl for adjusting the pH value to 7 after quenching, separating liquid, adding 2g of phenothiazine into the organic phase, concentrating under reduced pressure (50Pa) at 30 ℃, adding 2000g of dichloromethane for dissolving after concentration, adding anhydrous magnesium sulfate for stirring until the solution is clear, filtering, leaching a filter cake by 200g of dichloromethane, and putting the filtrate into the next step, wherein the HPLC purity is 80%.

Adding 2519g of the filtrate in the previous step and triethylamine into a 10L four-mouth bottle, supplementing dichloromethane, mechanically stirring, cooling by a dry ice-ethanol bath, starting dropwise adding acetyl chloride for 1h, and controlling the internal temperature to be-5 ℃; after the dropwise addition, removing the dry ice-ethanol bath, continuing to react at 20 ℃ for 3h, sampling and analyzing, wherein the HPLC purity is 85%, and the molar ratio of the 2-hydroxystyrene to acetyl chloride is 1:1. the molar ratio to dichloromethane was 1: 5. the molar ratio of triethylamine to the compound is 1:1.

after the reaction is finished, 1000g of water is added into the reaction liquid for quenching, 10% of sodium hydroxide aqueous solution is added for regulating the pH value to 7.5, liquid separation is carried out, 1000g of water is added into an organic phase for washing for 1 time, 2g of phenothiazine is added after the water washing is finished and is subjected to rotary evaporation at the temperature of 30 ℃, an oil pump is used for pumping the residue to obtain a crude product, 800g multiplied by 4 times of n-hexane is added into the crude product for pulping at room temperature, filtration is carried out, the filtrate is subjected to reduced pressure concentration, the residue is pumped and dried, sampling analysis is carried out to obtain 750g of the crude product, the GC purity is 74%, 1g of phenothiazine and 0.5g of p-methoxyphenol (the mass ratio is 1: 0.5) are added into the crude product, then the oil pump (75Pa) is used for reduced pressure distillation, the oil bath temperature is 94 ℃, the top temperature is 57 ℃, the fraction 489g is obtained, the GC purity is 98%, and the molar yield is 73.2%.

Example 4

Tetrahydrofuran, N was added to a 10L four-necked flask₂And (2) replacing, starting mechanical stirring, adding methyl triphenyl phosphonium bromide, cooling to-10 ℃, adding potassium tert-butoxide in batches, stirring for 2h after adding, cooling to-75 ℃, dropwise adding 500g of p-hydroxybenzaldehyde, heating to room temperature after dropwise stirring for 2h, stirring overnight, sampling and analyzing, wherein the HPLC purity is 81.5%, wherein the molar ratio of the p-hydroxybenzaldehyde to the methyl triphenyl phosphonium bromide is 1:3, the mass ratio of the p-hydroxybenzaldehyde to tetrahydrofuran is 1:6, and the molar ratio of the p-hydroxybenzaldehyde to the potassium tert-butoxide is 1: 6.

Cooling the reaction liquid to-10 ℃, adding 1000g of water for quenching, adding 10% HCl for adjusting the pH value to 8 after quenching, separating liquid, adding 2g of phenothiazine into an organic phase, concentrating under reduced pressure (100Pa) at 32 ℃, adding 2000g of dichloromethane for dissolving after concentration, adding anhydrous magnesium sulfate for stirring until the solution is clear, filtering, leaching a filter cake by 200g of dichloromethane, and putting the filtrate into the next step, wherein the HPLC purity is 79.9%.

Adding 2598g of the filtrate in the previous step and triethylamine into a 10L four-mouth bottle, supplementing dichloromethane, mechanically stirring, cooling by a dry ice-ethanol bath, beginning to dropwise add acetyl chloride for 1 hour, and controlling the internal temperature to be-3 ℃; after the dropwise addition, the dry ice-ethanol bath is removed, the reaction is continued at 10 ℃ for 3 hours, and then sampling analysis is carried out, wherein the HPLC purity is 81.3%, and the molar ratio of the p-hydroxystyrene to acetyl chloride is 1:3, the molar ratio of the p-hydroxystyrene to dichloromethane is 1:8, and the molar ratio of the p-hydroxystyrene to triethylamine is 1: 5.

After the reaction is finished, 1000g of water is added into the reaction liquid for quenching, 10% of sodium hydroxide aqueous solution is added for regulating the pH value to 7, liquid separation is carried out, 1000g of water is added into an organic phase for washing for 1 time, 2g of phenothiazine is added after the water washing is finished, the water is heated at 25 ℃ for rotary evaporation, an oil pump is used for pumping the solvent residue to obtain a crude product, 800g multiplied by 4 times of n-hexane is added into the crude product for pulping at room temperature, filtration is carried out, the filtrate is subjected to reduced pressure concentration, the solvent residue is pumped out again, sampling analysis is carried out to obtain 810g of the crude product, the GC purity is 69%, 1g of phenothiazine and 0.35g of p-methoxyphenol (the mass ratio is 1: 0.35) are added into the crude product, then the oil pump (70Pa) is used for reduced pressure distillation, the oil bath temperature is 90 ℃, the top temperature is 56 ℃, the oil bath is sampled and analyzed, the GC purity is 98.0%, and the molar yield is 73.8%.

The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.