A method for preparing tonone
By using high-temperature reaction of 2-phenoxybenzoic acid with anhydrous zinc chloride and solvent treatment, the problems of long reaction time, high cost and complicated post-processing in existing tonne preparation methods have been solved, and high-purity tonne has been prepared efficiently.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HUBEI JIUTIAN BIO-MEDICAL TECH CO LTD
- Filing Date
- 2026-04-13
- Publication Date
- 2026-06-02
AI Technical Summary
Existing methods for preparing tonone suffer from problems such as long reaction time, high cost, complex post-processing, and the need for column chromatography purification.
Using 2-phenoxybenzoic acid and anhydrous zinc chloride as raw materials, the reaction is carried out at high temperature, followed by cooling and solidification, pulverization, and then solvent treatment and separation. Combined with activated carbon treatment and solvent extraction, the post-processing steps are simplified to directly obtain high-purity phenoxybenzoic acid.
It achieves short reaction time, low cost, simple operation, and post-processing only requires solvent separation to obtain ketone with a purity of over 97%.
Smart Images
Figure CN122127300A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of organic compound preparation, and particularly relates to a method for preparing ketone. Background Technology
[0002] Benzophenone, also known as dibenzo-γ-pyranone, is widely used in the preparation of organic synthesis, pharmaceuticals, dyes, and fluorescent agents. It is also the basic molecular skeleton of many medicinal plants, and its derivatives have a wide range of pharmacological activities.
[0003] In the pharmaceutical field, derivatives of tonone are widely found in plants and fungi and have a variety of pharmacological activities. Studies have shown that its derivatives can inhibit tumor cell proliferation by regulating cell cycle and apoptosis mechanisms. Specific uses include: (1) Anti-tumor effect: inhibiting the proliferation of human glioma cells and inducing apoptosis of liver cancer cells; (2) Cardiovascular protection: reducing myocardial ischemia damage by inhibiting platelet aggregation and dilating blood vessels; (3) Antibacterial and antiviral: inhibiting methicillin-resistant Staphylococcus aureus and hepatitis B virus; (4) Hypoglycemic and antioxidant: lowering blood sugar by inhibiting α-glucosidase and having a higher free radical scavenging ability than vitamin C.
[0004] In the dye industry, tannin derivatives such as 6'-(diethylamino)-1',3'-dimethyl-spiro[isobenzofuran-1(3H),9'[9H]tannin]-3-one can be used as an orange-red color developer for thermal paper. The application of tannin and its derivatives in the dye industry is mainly based on their special chemical structures: (1) the multi-benzene ring conjugated system provides good electron delocalization ability; (2) the planar rigid structure is conducive to the stability of dye molecules; (3) dyes with different color characteristics can be obtained through structural modification. These characteristics make tannin compounds have continuous application value in the fields of specialty dyes and functional dyes.
[0005] In terms of fluorescent agent applications, thallium ketone and its derivatives have various applications in OLED display technology. For example, thallium ketone derivatives such as DPA-XT and TDPA-XT have been developed as thermally activated delayed fluorescence (TADF) materials for use in organic light-emitting diode (OLED) display devices. The fluorescence properties of thallium ketone and its derivatives stem from their unique molecular structure and electronic characteristics. Thrallium ketone has a three-benzene-ring conjugated system with the oxygen atom located at the 9-position of the central pyran ring, forming a rigid planar structure. This structure facilitates electron delocalization, enhancing the fluorescence quantum yield, similar to the principle of dye applications.
[0006] The preparation of zentonone can be basically divided into two categories. The first category uses xanthracene as a raw material to synthesize zentonone, and the second category uses 2-phenoxybenzoic acid as a raw material to synthesize zentonone.
[0007] The first type of reaction uses xanthracene as a raw material, and reacts at 70°C for 24 h under the catalysis of N-hydroxyphthalimide and cobalt(III) acetylacetonate, with oxygen introduced. The disadvantages of this method are the long reaction time, high oxygen cost, and the need for column chromatography purification as a post-treatment method.
[0008] Alternatively, xanthracene can be used as a raw material, reacted under a CO2 atmosphere for 9 hours, followed by the addition of an aqueous sodium chlorite solution. The reaction solution is then treated with a saturated sodium sulfite aqueous solution and extracted with ethyl acetate. This method involves high CO2 costs, a long reaction time, and requires drying and column chromatography purification after extraction, making the operation relatively complex.
[0009] The second type of reaction uses 2-phenoxybenzoic acid as a raw material and trifluoroacetic acid as a solvent to react with trifluoroacetic anhydride at room temperature for 12 hours. This method requires both trifluoroacetic acid and trifluoroacetic anhydride, resulting in high costs, complicated post-processing, and a long reaction time, necessitating column chromatography purification.
[0010] Summary of the Invention
[0011] The present invention aims to provide a method for preparing tonne, which uses 2-phenoxybenzoic acid as a raw material and reacts with anhydrous zinc chloride to form a cyclization reaction to obtain a light gray product tonne with a purity of over 97%.
[0012] The technical solution adopted by this invention to achieve its purpose is as follows: A method for preparing tannin is described, which uses 2-phenoxybenzoic acid and anhydrous zinc chloride as raw materials. After high-temperature reaction, the reaction solution is poured into an iron pan while hot. After cooling, the reaction solution solidifies, is crushed, and then a solvent is added for dissolution treatment. The liquid is separated to obtain an organic phase, and after treatment of the organic phase, tannin is obtained.
[0013] Preferably, the mass ratio of 2-phenoxybenzoic acid to anhydrous zinc chloride is 1:(0.95-2).
[0014] Preferably, the reaction conditions for the high-temperature reaction are 190-215℃ and 20-30 min.
[0015] Preferably, the solvent used for the dissolution treatment is one or any combination of DCE, water, trichloroethylene, 5% NaOH, and 5% HCl.
[0016] Preferably, the temperature for the solvent treatment is 60-70℃.
[0017] Preferably, the organic phase treatment involves adding the organic phase to activated carbon, stirring at 60°C for 30 min, hot filtering, adding methanol, hot slurrying at 65°C for 30 min, cooling, filtering, and drying the filter cake to obtain ketone.
[0018] Preferably, the organic phase treatment involves adding the organic phase to water, washing and separating the liquid at 70°C, separating the lower organic phase, removing the solvent, adding methanol, hot-beating at 65°C for 30 min, cooling, filtering, and drying the filter cake to obtain ketone.
[0019] Preferably, the organic phase treatment involves acid washing and water washing of the organic phase, or direct water washing of the organic phase, followed by separation of the lower organic phase and concentration of the organic phase under reduced pressure to obtain ketone.
[0020] Preferably, the organic phase treatment involves washing the organic phase twice with water, separating the lower organic phase, decolorizing at 60°C for 30 min, filtering, obtaining the filtrate, and concentrating it to obtain ketone.
[0021] The beneficial effects of this invention are: The method of this invention has a short reaction time, is simple to operate, and has low cost. The reaction is solvent-free, and the post-treatment only requires a good solvent and water solution. After the organic phase is decolorized, hot-beaten, or concentrated, the product can be obtained with a purity of over 97%. Attached Figure Description
[0022] Figure 1 This is the NMR spectrum of the ketone prepared in this invention. Detailed Implementation
[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention. Example 1
[0024] 2-Phenoxybenzoic acid (85 g) and anhydrous zinc chloride (137.38 g) were reacted at 215℃ for 30 min. The reaction solution was poured evenly into an iron pan while hot, and solidified into a hard solid after cooling. The solid was broken into small pieces, and 475 mL of DCE and 552 mL of water were added. After dissolving at 70℃, the mixture was allowed to stand and separated. The lower organic phase was separated, and 1.36 g of activated carbon was added to the organic phase. The mixture was stirred at 60℃ for 30 min and then hot filtered. When the total weight of the filtrate remaining in the desolvation flask was 149 g, 400 mL of methanol was added, and the mixture was hot-beaten at 65℃ for 30 min. After cooling, the mixture was filtered, and the filter cake was dried to obtain 57.07 g of ketone, with a yield of 72.56% and a purity of 98.60%. 1H NMR (400MHz, CDCl3) δ 8.35 (d, 2H); δ 7.74 (t, 2H); δ 7.49 (d, 2H); δ7.39 (t, 2H). Example 2
[0025] 2-Phenoxybenzoic acid (5 g) and anhydrous zinc chloride (6.36 g) were reacted at 195 °C for 30 min. The reaction solution was poured evenly into an iron pan while hot, and solidified into a hard solid after cooling. The solid was broken into small pieces, and 35 mL of trichloroethylene and 25 g of 5% NaOH were added. After dissolving at 70 °C, the mixture was allowed to stand and separated. The lower organic phase was separated, and 25 g of water was added to the organic phase. The mixture was washed with water at 70 °C and separated. The lower organic phase was separated, and after solvent removal, 25 mL of methanol was added. The mixture was hot-beaten at 65 °C for 30 min, cooled, filtered, and the filter cake was dried to obtain 4.41 g of thionone, with a yield of 95.32% and a purity of 97.58%. Example 3
[0026] 2-Phenoxybenzoic acid (5 g) and anhydrous zinc chloride (4.77 g) were reacted at 195 °C for 20 min. The reaction solution was poured evenly into an iron pan while hot and allowed to solidify into a hard solid after cooling. The solid was broken into small pieces, and 35 mL of trichloroethylene and 4.77 g of 5% HCl were added. The mixture was dissolved at 70 °C and allowed to stand for separation. The lower organic phase was separated. 10 g of 2.5% HCl was added to the organic phase, and the mixture was dissolved at 70 °C and separated. The lower organic phase was separated. 10 g of water was added, and the mixture was dissolved at 70 °C and separated. The lower organic phase was then concentrated to obtain 3.83 g of phenoxybenzoic acid, with a yield of 82.78% and a purity of 97.91%. Example 4
[0027] 2-Phenoxybenzoic acid (5 g) was reacted with anhydrous zinc chloride (10 g) at 190 °C for 20 min. The reaction solution was poured evenly into an iron pan while hot and solidified into a hard solid after cooling. The solid was broken into small pieces, and 35 mL of trichloroethylene and 20 mL of water were added. The mixture was dissolved at 60 °C and allowed to stand for separation. The lower organic phase was separated and washed with 20 g of water. The lower organic phase was separated again and concentrated under reduced pressure to obtain 3.89 g of phenoxybenzoic acid, with a yield of 84.08% and a purity of 98.34%. Example 5
[0028] 2-Phenoxybenzoic acid (5 g) and anhydrous zinc chloride (4.77 g) were reacted at 195 °C for 20 min. The reaction solution was poured evenly into an iron pan while hot and solidified into a hard solid after cooling. The solid was broken into small pieces, and 10 g of 2.5% HCl solution and 35 mL of trichloroethylene were added. The solvent was stirred at 70 °C, and the lower organic phase was separated by liquid separation. The lower organic phase was washed twice with 20 g of water (10 g × 2), and 0.3 g of activated carbon was added. The mixture was decolorized at 60 °C for 30 min, filtered, and the filtrate was concentrated to obtain 3.83 g of thionone, with a yield of 82.72% and a purity of 98.00%.
[0029] Finally, it should be noted that the above-described embodiments are merely specific implementations of the present invention, used to illustrate the technical solutions of the present invention, and not to limit them. The scope of protection of the present invention is not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that any person skilled in the art can still modify or easily conceive of changes to the technical solutions described in the foregoing embodiments within the scope of the technology disclosed in the present invention, or make equivalent substitutions for some of the technical features; and these modifications, changes, or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention, and should all be covered within the scope of protection of the present invention.
Claims
1. A method for preparing ketone, characterized in that, Using 2-phenoxybenzoic acid and anhydrous zinc chloride as raw materials, the reaction solution was poured into an iron pan while hot after high-temperature reaction. After cooling, the reaction solution solidified, was crushed, and then a solvent was added for dissolution treatment. The organic phase was obtained by separation, and the organic phase was then treated to obtain tannin.
2. The method for preparing ketone according to claim 1, characterized in that, The mass ratio of 2-phenoxybenzoic acid to anhydrous zinc chloride is 1:(0.95-2).
3. The method for preparing ketone according to claim 1, characterized in that, The reaction conditions for the high-temperature reaction are 190-215℃ and 20-30 min.
4. The method for preparing ketone according to claim 1, characterized in that, The solvent used for the dissolution treatment is one or any combination of DCE, water, trichloroethylene, 5% NaOH, and 5% HCl.
5. The method for preparing ketone according to claim 1, characterized in that, The temperature for solvent treatment is 60-70℃.
6. The method for preparing ketone according to claim 1, characterized in that, The organic phase treatment involved adding the organic phase to activated carbon, stirring at 60°C for 30 min, hot filtering, adding methanol, hot slurrying at 65°C for 30 min, cooling, filtering, and drying the filter cake to obtain tonone.
7. The method for preparing ketone according to claim 1, characterized in that, The organic phase treatment involved adding the organic phase to water, washing and separating the liquid at 70°C, separating the lower organic phase, removing the solvent, adding methanol, hot-beating at 65°C for 30 min, cooling, filtering, and drying the filter cake to obtain tonone.
8. The method for preparing ketone according to claim 1, characterized in that, The organic phase treatment involves acid washing and water washing of the organic phase, or direct water washing of the organic phase, followed by separation of the lower organic phase, and concentration of the organic phase under reduced pressure to obtain ketone.
9. The method for preparing ketone according to claim 1, characterized in that, The organic phase treatment involved washing the organic phase twice with water, separating the lower organic phase, decolorizing at 60°C for 30 min, filtering, obtaining the filtrate, and concentrating it to obtain tonone.