Method for synthesizing 3-(2-hydroperoxy-2-propyl) phenol

Abstract

The invention discloses a method for synthesizing 3-(2-hydroperoxy-2-propyl) phenol and a preparation method of the 3-(2-hydroperoxy-2-propyl) phenol. The method comprises the following steps: in the presence of a solvent, 1, 3-bis (2-hydroperoxy-2-propyl) benzene is in contact with a potassium hydrogen sulfate catalyst for an acidolysis reaction, 3-(2-hydroperoxy-2-propyl) phenol is obtained, and the weight ratio of the 1, 3-bis (2-hydroperoxy-2-propyl) benzene to the catalyst is (15-48): 1. According to the method provided by the invention, 1, 3-bis (2-hydroperoxy-2-propyl) benzene (m-DHP) is used as a raw material, and a selective acidolysis reaction is carried out in the presence of a solid potassium hydrogen sulfate catalyst to obtain 3-(2-hydroperoxy-2-propyl) phenol m-HPP. The method has the characteristics of high yield, cleanness, environment friendliness, mild reaction conditions and easiness in industrialization.

Description

Technical Field

[0001] The present invention relates to the technical field of synthesizing organic peroxides, and more particularly to a method for synthesizing 3-(2-hydroperoxy-2-propyl)phenol. Background Art

[0002] 3-(2-Hydroperoxy-2-propyl)phenol (m-HPP) is an important fine organic intermediate. Because its molecular structure contains both phenolic hydroxyl groups and hydroperoxide groups, it is widely used in fine chemical industries such as pharmaceuticals and synthetic resins. US Patent No. 5,030,767 discloses a method for synthesizing resorcinol from m-HPP, in which m-HPP is acidolyzed in toluene under concentrated sulfuric acid to produce resorcinol. m-HPP can also be used as an epoxidizing agent in the synthesis of propylene oxide or butylene oxide. m-HPP is also an intermediate in the preparation of m-hydroxyacetophenone. Under acidic conditions and in the presence of iron or copper salt catalysts, m-HPP undergoes a demethanolysis reaction to produce m-hydroxyacetophenone. Leveraging the reactivity of the hydroperoxide and hydroxyphenol groups, m-HPP can also be used as a polymerization initiator, crosslinker, or oxidant, as well as a raw material for the synthesis of other organic peroxides.

[0003] Traditional m-HPP preparation methods use 3-(2-hydroxy-2-propyl)phenol (m-HPP) as a starting material. The hydroxyl group on the tertiary carbon atom is oxidized by hydrogen peroxide in the presence of sulfuric acid. 3-(2-hydroxy-2-propyl)phenol is first prepared through acidolysis of m-HPP (3-(2-hydroxy-2-propyl) cumene hydroperoxide) or a Grignard reaction of m-hydroxyacetophenone or m-hydroxybenzoate. The preparation of this intermediate is complex, with multiple reaction steps and low yield. The existing m-HPP synthesis reaction process is as follows:

[0004]

[0005] This synthesis method not only has many reaction steps and complicated operation, but also has complicated synthesis and separation and purification processes of the peroxide m-HPP, which has great potential safety hazards and is not suitable for large-scale production. Patent US5030767 discloses a method for preparing m-HPP, which comprises adding 1.1 grams of 60% aqueous hydrogen peroxide solution and 5 milligrams of concentrated sulfuric acid to 20 milliliters of acetic acid solution containing 3-(2-hydroxy-2-propyl)phenol, and reacting the mixture at 25°C for 4.5 hours. After completion of the reaction, the reaction mixture is neutralized with an excess of 1 gram of sodium bicarbonate, filtered, and the filtrate is concentrated under reduced pressure. 50 milliliters of ether are added to the concentrate, and the ether dispersion containing the product is added to water, thereby retaining the reaction product in the ether phase and transferring the by-products to water. The ether is then distilled off under reduced pressure and the ether extract is concentrated. The remaining solid product is recrystallized from chloroform to obtain 1.2 grams of colorless crystals with a purity of 98.4% (based on DSC method), a yield of 77%, and a melting point of 88-89°C.

[0006] The above process has the following disadvantages: 1. The synthesis of the raw material 3-(2-hydroxy-2-propyl)phenol in this preparation method requires multiple steps, is cumbersome to operate, and has low reaction conversion and yield. 2. High-concentration hydrogen peroxide is used as an oxidant in the reaction, which poses a significant safety hazard and is unsuitable for large-scale production. 3. A large amount of toxic acetonitrile solvent is used in the reaction, which is detrimental to environmental protection and unsuitable for industrial production. 4. The concentrated sulfuric acid catalyst can catalyze the further acidolysis of the product HPP to produce resorcinol. In addition, concentrated sulfuric acid is highly corrosive to equipment, and the low boiling point of the extraction solvent diethyl ether makes it unsuitable for industrialization and has adverse effects on environmental protection and occupational health.

[0007] Therefore, there is an urgent need to provide a new method for synthesizing 3-(2-hydroperoxy-2-propyl) phenol. Summary of the Invention

[0008] To address the shortcomings of existing m-HPP synthesis techniques, such as lengthy raw material preparation steps and complex post-processing, the use of 3-(2-hydroxy-2-propyl)phenol as a raw material, and the use of concentrated sulfuric acid and / or hydrogen peroxide as catalysts in the m-HPP synthesis reaction, which suffer from the drawbacks of highly corrosive acid hydrolysis, vigorous reactions, and numerous side reactions. The present invention provides a method for synthesizing 3-(2-hydroperoxy-2-propyl)phenol (m-HPP). This method overcomes these shortcomings of the existing techniques and offers high yield, clean and environmentally friendly operation, mild reaction conditions, and ease of industrialization.

[0009] The inventors of the present invention have discovered through research that the yield of 3-(2-hydroperoxy-2-propyl)phenol can be greatly improved when the weight ratio of 1,3-di(2-hydroperoxy-2-propyl)benzene to potassium hydrogen sulfate catalyst is (15-48):1, thereby completing the present invention.

[0010] The invention provides a method for synthesizing 3-(2-hydroperoxy-2-propyl)phenol. The method comprises: in the presence of a solvent, contacting 1,3-di(2-hydroperoxy-2-propyl)benzene with a potassium hydrogen sulfate catalyst to carry out an acidolysis reaction to obtain 3-(2-hydroperoxy-2-propyl)phenol; the weight ratio of the 1,3-di(2-hydroperoxy-2-propyl)benzene to the catalyst is (15-48):1.

[0011] Furthermore, preferably, the weight ratio of the 1,3-di(2-hydroperoxy-2-propyl)benzene to the catalyst is (16-30):1.

[0012] The present invention allows for a wide range of solvents to be selected, as long as they are beneficial for increasing the yield and purity of 3-(2-hydroperoxy-2-propyl)phenol. Preferably, the solvent is a ketone, or a mixed solvent of a ketone and an aromatic hydrocarbon; more preferably, a ketone and an aromatic hydrocarbon. The inventors of the present invention have further discovered that this preferred embodiment is more conducive to increasing the yield of 3-(2-hydroperoxy-2-propyl)phenol than using a single solvent.

[0013] According to the present invention, the amount of the solvent used can be selected within a wide range. Preferably, the weight ratio of the solvent to 1,3-di(2-hydroperoxy-2-propyl)benzene is (3-15):1, preferably (4-10):1, and more preferably (5-8.5):1. This preferred embodiment is more conducive to improving the yield of 3-(2-hydroperoxy-2-propyl)phenol.

[0014] Furthermore, when the solvent is ketones and aromatic hydrocarbons, the ketone content in the solvent is 10 to 80% by weight, preferably 12 to 60% by weight; the aromatic hydrocarbon content is 20 to 90% by weight, preferably 40 to 88% by weight.

[0015] In a preferred embodiment of the present invention, the ketone content in the solvent is less than the aromatic hydrocarbon content; preferably, the ketone content in the solvent is 14 to 40% by weight, and the aromatic hydrocarbon content is 60 to 86% by weight. The inventors further discovered that this preferred embodiment is more conducive to improving the yield of 3-(2-hydroperoxy-2-propyl)phenol.

[0016] Furthermore, the ketone is a ketone having 3-6 carbon atoms, and the aromatic hydrocarbon is an aromatic hydrocarbon having 6-10 carbon atoms; preferably, the ketone is selected from at least one of acetone, methyl ethyl ketone, and methyl isobutyl ketone, and the aromatic hydrocarbon is selected from at least one of toluene, xylene, ethylbenzene, and isopropylbenzene; wherein the ketone is preferably acetone, and the aromatic hydrocarbon is preferably toluene.

[0017] Furthermore, the purity of the 1,3-di(2-hydroperoxy-2-propyl)benzene is greater than 90% by weight.

[0018] Furthermore, the temperature of the acidolysis reaction is 55 to 80° C., preferably 55 to 70° C. The reaction temperature within this range is more conducive to the synthesis of 1,3-di(2-hydroperoxy-2-propyl)benzene into 1,3-(2-hydroperoxy-2-propyl)phenol, thereby increasing the yield of 1,3-(2-hydroperoxy-2-propyl)phenol. There is no limitation on the method for controlling the temperature of the acidolysis reaction. For example, the temperature of the acidolysis reaction can be controlled within the above reaction range by heating in a water bath.

[0019] Furthermore, there is no limitation on the reaction pressure during the acidolysis reaction, and it is preferably carried out under normal pressure.

[0020] Furthermore, the method further comprises performing solid-liquid separation on the reaction materials of the acidolysis reaction, washing the solid phase to obtain recovered potassium bisulfate, and recycling the recovered potassium bisulfate for the acidolysis reaction.

[0021] Furthermore, the method also includes performing solid-liquid separation on the reaction materials of the acidolysis reaction to obtain a solid phase and a liquid phase, wherein the solid phase is the catalyst potassium hydrogen sulfate and the liquid phase is the reaction liquid, and the liquid phase is distilled and extracted to obtain a 3-(2-hydroperoxy-2-propyl)phenol product.

[0022] Furthermore, in a preferred embodiment of the present invention, the method further comprises: stopping the reaction when the conversion rate of the 1,3-di(2-hydroperoxy-2-propyl)benzene reaches 97% or greater. The present invention does not limit the method for measuring the conversion rate of the 1,3-di(2-hydroperoxy-2-propyl)benzene. Generally, the composition after the reaction is determined by iodine titration and liquid chromatography, and the reaction progress is tracked based on the content of 1,3-di(2-hydroperoxy-2-propyl)benzene to obtain the conversion rate.

[0023] Furthermore, preferably, in the method of the present invention, when the conversion rate of 1,3-di(2-hydroperoxy-2-propyl)benzene reaches 97% or more, the yield of 3-(2-hydroperoxy-2-propyl)phenol reaches 70% or more, preferably 75% or more, by mass.

[0024] Furthermore, preferably, in the method of the present invention, the reaction material obtained after the acidolysis reaction is subjected to solid-liquid separation to remove the catalyst, the remaining reaction liquid is subjected to reduced pressure distillation to recover the ketone solvent, the oil phase is washed with water, the aromatic solvent is distilled off under reduced pressure, and the residue is recrystallized from chloroform to finally obtain pure m-HPP.

[0025] Furthermore, the reduced pressure distillation and recrystallization are carried out by conventional methods in the art.

[0026] The present invention aims to address the existing problem of m-HPP preparation. The conventional m-HPP preparation method uses 3-(2-hydroxy-2-propyl)phenol as a raw material, which is oxidized with high-concentration hydrogen peroxide under the catalysis of concentrated sulfuric acid to obtain m-HPP. The method first requires acid hydrolysis of 3-(2-hydroxy-2-propyl)phenol (m-HPP) or a Grignard reaction of m-hydroxyacetophenone or m-hydroxybenzoate to prepare 3-(2-hydroxy-2-propyl)phenol. The existing methods have the following disadvantages: 1. The synthesis of the raw material 3-(2-hydroxy-2-propyl)phenol used in these methods involves multiple steps, resulting in cumbersome operations and low reaction conversion and yield. 2. The reaction uses high-concentration hydrogen peroxide, which poses a significant safety hazard and is unsuitable for large-scale production. 3. The reaction uses a large amount of toxic acetonitrile solvent, which is environmentally unfriendly and unsuitable for industrial production. 4. The concentrated sulfuric acid catalyst can catalyze further acid hydrolysis of the product to produce resorcinol. Furthermore, the concentrated sulfuric acid is highly corrosive to equipment, and the low boiling point of the extraction solvent, diethyl ether, makes it unsuitable for industrialization and has adverse effects on environmental protection and occupational health.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] 1. As an important intermediate for producing resorcinol, m-DHP has been produced on a large scale in industrial scale. The present invention uses m-DHP which is easily available in industry as a raw material, is suitable for industrialization, and has low cost.

[0029] 2. The method of the present invention prepares m-HPP by selectively acidolyzing m-DHP in an organic solvent using potassium bisulfate as a catalyst. Using potassium bisulfate as a catalyst avoids low reaction yields due to a weak acidolysis ability of the catalyst, nor does it directly produce resorcinol due to excessive acidolysis ability, such as with sodium bisulfate. The m-HPP obtained by the present invention is not only high in yield but also high in purity. The potassium bisulfate catalyst can be recovered by filtration and recycled, avoiding corrosion of equipment by strong acids such as concentrated sulfuric acid and reducing the discharge of three wastes. The reaction conditions are mild, the reaction is easy to control, the reaction steps are few, and the three wastes generated are low. The method is clean and environmentally friendly, making it suitable for industrialization.

[0030]

[0031] Reaction equation for the selective acid hydrolysis of m-DHP to prepare m-HPP. DETAILED DESCRIPTION

[0032] The following examples will further illustrate the technical solutions provided by the present invention, but the protection scope of the present invention is not limited to these examples.

[0033] In the present invention, the raw materials involved are commercially available unless otherwise specified, wherein the content of m-DHP is 95 weight %, the content of m-diisopropylbenzene monohydroperoxide is 0.8 weight %, and the content of 3-(2-hydroxy-2-propyl)isopropylbenzene hydroperoxide is 4.2 weight %.

[0034] In the present invention, the analysis and evaluation of raw materials and products were performed by gas chromatography-mass spectrometry for qualitative characterization, and by iodine titration and liquid chromatography for quantitative characterization.

[0035] Example 1

[0036] In a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, 10 ml of acetone and 0.59 g of potassium bisulfate catalyst were added. Stirring was initiated and, while heating in a 55°C water bath, a solution containing 10 g of m-DHP (95% purity) and 50 ml of toluene was slowly added dropwise. The heat generated by the reaction caused the reaction solution to begin refluxing, and the DHP solution was added over approximately 20 minutes. The progress of the reaction was monitored by iodine titration and liquid chromatography. The reaction was stopped when the conversion of DHP (to HPP) in the reaction solution reached 97%. The reaction time was 3 hours. The reaction mixture was cooled to room temperature, the catalyst was filtered, and the acetone was removed under reduced pressure. The oil phase was washed with a small amount of distilled water, and the toluene was removed by reduced pressure distillation at 60°C to obtain a still solution. The residue was recrystallized from chloroform, the crystalline solid was filtered, washed with a small amount of chloroform, and dried to obtain pure meta-m-HPP with a melting point of 88-89°C and a yield of 78%.

[0037] Example 2

[0038] In a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, 10 ml of acetone and 0.32 g of potassium bisulfate catalyst were added. Stirring was initiated and, while heating in a 60°C water bath, a solution containing 10 g of m-DHP (95% purity) and 60 ml of toluene was slowly added dropwise. The heat generated by the reaction caused the reaction solution to begin refluxing. The DHP solution was added over approximately 20 minutes. The progress of the reaction was monitored by iodine titration and liquid chromatography. The reaction was stopped when the conversion of DHP (converted to HPP) in the reaction solution reached 98%. The reaction time was 3.5 hours. The reaction mixture was cooled to room temperature, the catalyst was filtered, the acetone was removed under reduced pressure, the oil phase was washed with a small amount of distilled water, and the toluene was removed by reduced pressure distillation at 60°C to obtain a still solution. The residue was recrystallized from chloroform, the crystalline solid was filtered, washed with a small amount of chloroform, and dried to obtain pure meta-m-HPP with a melting point of 88-89°C and a yield of 79%.

[0039] Example 3

[0040] In a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, 10 ml of acetone and 0.33 g of potassium bisulfate catalyst were added. Stirring was initiated and, while heating in a 65°C water bath, a solution containing 10 g of m-DHP (95% purity) and 70 ml of toluene was slowly added dropwise. The heat generated by the reaction caused the reaction solution to begin refluxing, and the DHP solution was added over approximately 20 minutes. During the reaction, the progress of the reaction was tracked using iodine titration and liquid chromatography. The reaction was stopped when the conversion of DHP (converted to HPP) in the reaction solution reached 98%. The reaction time was 4 hours. The reaction mixture was cooled to room temperature, the potassium bisulfate catalyst was filtered, the acetone was removed by distillation under reduced pressure, the oil phase was washed with a small amount of distilled water, and the toluene was removed by distillation under reduced pressure at 60°C to obtain a still liquid. The residue was recrystallized from chloroform, the crystalline solid was filtered, washed with a small amount of chloroform, and dried to obtain pure meta-m-HPP with a melting point of 88-89°C and a yield of 81%.

[0041] Example 4

[0042] In a 100 ml three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 10 ml of acetone and 0.33 g of potassium bisulfate recovered by filtration in Example 3 were added as a catalyst. Stirring was started and, under heating in a 65°C water bath, a solution of 10 g of m-DHP (95% purity) and 70 ml of toluene was slowly added dropwise. The heat of reaction caused the reaction solution to begin to reflux. The DHP solution was added over a period of approximately 20 minutes. During the reaction, the progress of the reaction was tracked using iodine titration and liquid chromatography. When the conversion of DHP (converted to HPP) in the reaction solution reached 97% as determined by liquid chromatography, the reaction was stopped. The reaction time was 4.5 hours. The reaction mixture was cooled to room temperature, the catalyst was filtered off, acetone was removed by distillation under reduced pressure, the oil phase was washed with a small amount of distilled water, and toluene was removed by distillation under reduced pressure at 60°C to obtain a still liquid. The residue was recrystallized from chloroform, the crystalline solid was suction filtered, washed with a small amount of chloroform, and dried to obtain pure meta-m-HPP with a melting point of 88-89°C and a yield of 77%.

[0043] Example 5

[0044] In a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, 10 ml of methyl ethyl ketone and 0.38 g of potassium bisulfate catalyst were added. Stirring was initiated and, while heating in a 55°C water bath, a solution containing 10 g of m-DHP (95% purity) and 50 ml of toluene was slowly added dropwise. The heat generated by the reaction caused the reaction solution to begin refluxing, and the DHP solution was added over approximately 20 minutes. The progress of the reaction was monitored by iodine titration and liquid chromatography. The reaction was stopped when the conversion of DHP (to HPP) in the reaction solution reached 97%. The reaction time was 3 hours. The reaction mixture was cooled to room temperature, the catalyst was filtered, and the acetone and methyl ethyl ketone were removed by vacuum distillation. The oil phase was washed with a small amount of distilled water, and the toluene was removed by vacuum distillation at 60°C to obtain a still solution. The residue was recrystallized from chloroform, the crystalline solid was filtered, washed with a small amount of chloroform, and dried to obtain pure meta-m-HPP with a melting point of 88-89°C and a yield of 75%.

[0045] Example 6

[0046] In a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, 10 ml of methyl isobutyl ketone (MIBK) and 0.5 g of potassium bisulfate catalyst were added. Stirring was initiated and, while heating in a 60°C water bath, a solution containing 10 g of m-DHP (95% purity) and 60 ml of toluene was slowly added dropwise. The heat generated by the reaction caused the reaction solution to begin refluxing, and the DHP solution was added over approximately 20 minutes. During the reaction, the progress of the reaction was tracked by iodine titration and liquid phase detection. The reaction was stopped when the conversion of DHP (converted to HPP) in the reaction solution reached 98%. The reaction time was 4 hours. The reaction mixture was cooled to room temperature, the catalyst was filtered, and the acetone was removed by distillation under reduced pressure. The oil phase was washed with a small amount of distilled water, and then the toluene and MIBK were removed by distillation under reduced pressure at 60°C to obtain a still liquid. The residue was recrystallized from chloroform, the crystalline solid was filtered, washed with a small amount of chloroform, and dried to obtain pure m-HPP with a melting point of 88-89°C and a yield of 76%.

[0047] Example 7

[0048] To a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, 10 ml of acetone and 0.532 g of potassium bisulfate catalyst were added. Stirring was initiated and, while heating in a 60°C water bath, a solution containing 10 g of m-DHP (95% purity) and 60 ml of acetone was slowly added dropwise. The heat generated by the reaction caused the reaction solution to begin refluxing, and the DHP solution was added over approximately 20 minutes. The progress of the reaction was monitored by iodine titration and liquid chromatography. The reaction was stopped when the conversion of DHP (to HPP) in the reaction solution reached 98%. The reaction time was 2.5 hours. The reaction mixture was cooled to room temperature, the catalyst was filtered, and the acetone was evaporated under reduced pressure to obtain a still solution. The residue was recrystallized from chloroform, the crystalline solid was filtered, washed with a small amount of chloroform, and dried to obtain pure meta-m-HPP with a melting point of 88-89°C and a yield of 74%.

[0049] Comparative Example 1

[0050] In a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, 10 ml of acetone and 0.95 g of potassium bisulfate catalyst were added. Stirring was initiated and, while heating in a 65°C water bath, a solution containing 10 g of m-DHP (95% purity) and 70 ml of toluene was slowly added dropwise. The heat generated by the reaction caused the reaction solution to begin refluxing, and the DHP solution was added over approximately 20 minutes. During the reaction, the progress of the reaction was monitored using iodine titration and liquid chromatography. The reaction was stopped when the conversion of DHP (converted to HPP and resorcinol) in the reaction solution reached 97% as determined by liquid chromatography. The reaction was then stopped for 3 hours. The reaction mixture was cooled to room temperature, the catalyst was removed by filtration, and the acetone was removed by vacuum distillation. The oil phase was washed with a small amount of distilled water (the washing water contained a relatively high amount of resorcinol), and the toluene was removed by vacuum distillation at 60°C to obtain a still solution. The residue was recrystallized from chloroform, the crystalline solid was filtered, washed with a small amount of chloroform, and dried to obtain pure m-HPP with a melting point of 88-89°C and a yield of 35%. The main by-product is resorcinol.

[0051] Comparative Example 2

[0052] To a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, 10 ml of acetone and 0.19 g of potassium bisulfate catalyst were added. Stirring was initiated and, while heating in a 65°C water bath, a solution containing 10 g of m-DHP (95% purity) and 70 ml of toluene was slowly added dropwise. The DHP solution was added over approximately 20 minutes. During the reaction, iodine titration and liquid chromatography were used to monitor the progress of the reaction. The experimental results indicated that the catalyst was insufficient, resulting in a very slow reaction. After 8 hours of reaction, approximately 50% of the DHP remained uncatalyzed by the acidolysis reaction, and the reaction was stopped. Due to the complex nature of the reaction products, no pure HPP product could be isolated.

[0053] Comparative Example 3

[0054] In a 100 ml three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 10 ml of acetone and 0.32 g of sodium bisulfate catalyst were added. Stirring was started and a solution containing 10 g of m-DHP (95% purity) and 60 ml of toluene was slowly added dropwise in a 60°C water bath. The heat generated by the reaction caused the reaction solution to begin to reflux. The DHP solution was added in approximately 20 minutes. During the reaction, the reaction progress was tracked by iodine titration and liquid chromatography. The reaction was stopped when the conversion rate of DHP (converted into resorcinol) in the reaction solution reached 98%. The reaction time was 1 hour. The reaction mixture was cooled to room temperature, the catalyst was removed by filtration, and the acetone was removed by distillation under reduced pressure. The oil phase was extracted with resorcinol twice with 50 ml of distilled water. The aqueous phases were combined and the resorcinol was extracted twice with 50 ml of MIBK. The MIBK was removed by distillation under reduced pressure. The residue was recrystallized from toluene, the crystalline solid was filtered, washed with a small amount of chloroform, and dried to obtain resorcinol with a melting point of 108-110°C and a resorcinol yield of 81%.

[0055] Comparative Example 4

[0056] In a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, 10 ml of acetone and 0.59 g of potassium bisulfate catalyst were added. Stirring was initiated and, while heating in a 45°C water bath, a solution containing 10 g of m-DHP (95% purity) and 70 ml of toluene was slowly added dropwise. The heat generated by the reaction caused the reaction solution to begin refluxing, and the DHP solution was added over approximately 20 minutes. During the reaction, the progress of the reaction was monitored using iodine titration and liquid chromatography. The reaction was stopped when the conversion of DHP (converted into HPP and resorcinol) in the reaction solution reached 98% as determined by liquid chromatography. The reaction was then stopped for 5 hours. The reaction mixture was cooled to room temperature, the catalyst removed by filtration, and the acetone removed by vacuum distillation. The oil phase was washed with a small amount of distilled water (the wash water contained a relatively high amount of resorcinol), and the toluene removed by vacuum distillation at 60°C to obtain a still solution. The residue was recrystallized from chloroform, the crystalline solid was filtered, washed with a small amount of chloroform, and dried to obtain pure m-HPP with a melting point of 88-89°C and a yield of 37%. The main by-product is resorcinol.

[0057] It can be seen from the above examples and comparative examples that a high yield of 3-(2-hydroperoxy-2-propyl)phenol can be obtained by the specific method of the present invention, and the recovered potassium bisulfate catalyst obtained after the reaction can be recycled, and a high yield of 3-(2-hydroperoxy-2-propyl)phenol can still be obtained when recycled.

[0058] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A method for synthesizing 3-(2-hydroperoxy-2-propyl)phenol, comprising: In the presence of a solvent, 1,3-di(2-hydroperoxy-2-propyl)benzene is contacted with a potassium hydrogen sulfate catalyst to carry out an acid hydrolysis reaction to obtain 3-(2-hydroperoxy-2-propyl)phenol; the weight ratio of the 1,3-di(2-hydroperoxy-2-propyl)benzene to the catalyst is (15-48):

1.

2. The method according to claim 1, characterized in that The weight ratio of the 1,3-di(2-hydroperoxy-2-propyl)benzene to the catalyst is (16-30):

1.

3. The method according to claim 1, characterized in that The weight ratio of the solvent to 1,3-di(2-hydroperoxy-2-propyl)benzene is (3-15):1, preferably (4-10):

1.

4. The method according to claim 1, characterized in that: The solvent is ketone, or ketone and aromatic hydrocarbon.

5. The method according to claim 4, characterized in that The ketones are ketones with 3 to 6 carbon atoms, and the aromatic hydrocarbons are aromatic hydrocarbons with 6 to 10 carbon atoms.

6. The method according to claim 4, characterized in that The ketone is selected from at least one of acetone, methyl ethyl ketone and methyl isobutyl ketone, and the aromatic hydrocarbon is selected from at least one of toluene, xylene, ethylbenzene and isopropylbenzene.

7. The method according to claim 1, characterized in that The solvent is ketones and aromatic hydrocarbons, wherein the ketone is acetone and the aromatic hydrocarbon is toluene.

8. The method according to claim 4 or 7, characterized in that: When the solvent is ketones and aromatic hydrocarbons, the content of ketones is 10-80% by weight, and the content of aromatic hydrocarbons is 20-90% by weight.

9. The method according to claim 1, characterized in that: The temperature of the acid hydrolysis reaction is 40-80° C., and the reaction pressure is normal pressure.

10. The method according to claim 1, characterized in that The method also includes performing solid-liquid separation on the reaction materials of the acidolysis reaction to obtain a solid phase and a liquid phase, wherein the solid phase is a catalyst potassium hydrogen sulfate and the liquid phase is a reaction liquid, and the liquid phase is distilled and extracted to obtain a 3-(2-hydroperoxy-2-propyl)phenol product.

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