Anthracene compounds, methods for manufacturing the same, and uses of the same as solar fuel

Abstract

The present invention provides an anthracene-based compound, a method for manufacturing the same, and its use as a solar fuel, and relates to the field of the energy chemical industry. The anthracene-based compound of the present invention can be converted into a dimer under UV irradiation at 365 nm to store light energy as chemical energy, and can release heat as a photodepolymerization reaction occurs under UV irradiation at 254 nm; that is, this anthracene-based solar fuel can store or release photothermal energy through a reversible photodimerization / depolymerization reaction. Furthermore, this anthracene-based compound possesses the unique advantage of a light-tunable reversible solid-liquid phase transition and can simultaneously store photon energy and phase transition energy. The energy storage density of the anthracene-based compound is approximately 65 kJ / mol, and the storage half-life is up to 60 days. The anthracene-based compound and the method for manufacturing the same provided in the present invention provide a novel strategy for the storage and utilization of light energy.

Description

Technology Field

[0001] The present invention relates to the field of energy chemistry, and in particular to anthracene compounds, a method for manufacturing the same, and the use of the same as solar fuel. Background Technology

[0002] Anthracene is a polycyclic aromatic hydrocarbon composed of three rings that is widely utilized in various chemical production fields. In industry, anthracene is generally first oxidized and then undergoes processes such as nitrification and sulfonation to provide intermediates for fields such as dyes, pharmaceuticals, and optoelectronic materials. Anthracene is present in high concentrations in coal tar, and Patent CN115141077B discloses a method for separating anthracene from coal tar under simple operation, mild conditions, and low cost. Furthermore, anthracene offers the advantages of controllable luminescence, easy energy and charge transfer, and the ability to perform unique photo-thermal reversible dimerization. However, existing methods for manufacturing anthracene-based compounds are relatively complex, and there are few reports on the development of anthracene-based solar fuels based on photodimerization / depolymerization reactions. Solar fuels are a type of molecular photoswitch that realizes photoenergy storage and thermal energy release based on reversible changes in molecular spatial arrangement; they exhibit stable circulation during utilization processes and do not emit gases or pollutants. Anthracene compounds possess an extended aromatic π-system and exhibit a relatively low electronic band gap, allowing them to easily form dimers and rapidly depolymerize under bright conditions. Therefore, the preparation of new anthracene compounds and their exploration as solar fuels hold significant application value in expanding the applications of anthracene, a polycyclic aromatic hydrocarbon. The problem to be solved

[0003] The present invention aims to provide an anthracene compound, a method for manufacturing the same, and the use of the same as a solar fuel. means of solving the problem

[0004] To achieve the above-mentioned objective, the present invention provides the following technical solution:

[0005] The present invention provides an anthracene compound represented by Chemical Formula 1:

[0006] Chemical formula 1;

[0007] In [Chemical Formula 1], n is 10 to 16.

[0008] The above n is preferably 10, 13, or 16.

[0009] The present invention provides a method for producing an anthracene compound according to the above technical solution, and the method comprises the following steps:

[0010] A step of mixing anthracene, N-methylformanilide, phosphorus oxychloride, and a first solvent, and performing a formylation-condensation reaction to obtain anthracene-9-carbaldehyde;

[0011] A step of mixing the above anthracene-9-carbaldehyde, sodium borohydride, and a second solvent, and performing a reduction reaction to obtain 9-anthracenemethanol;

[0012] A step of mixing the above 9-anthracen methanol, succinic anhydride, 4-dimethylaminopyridine, and a third solvent, and performing a substitution reaction to obtain 4-(anthracen-9-ylmethoxy)-4-oxobutyric acid;

[0013] A step of mixing the above 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, long-chain fatty alcohol, and a fourth solvent, and performing an esterification reaction to obtain an anthracene-based compound;

[0014] The number of carbon atoms in the above long-chain fatty alcohol is 12 to 18.

[0015] Preferably, the anthracene is derived from coal tar.

[0016] Preferably, the molar ratio of the anthracene, N-methylformanilide, and phosphorus oxychloride is 1:2:2 to 1:4:4, and the volume ratio of the N-methylformanilide and the first solvent is 10:1 to 5:1;

[0017] The temperature of the above formylation-condensation reaction is 90 to 100°C, and the reaction time is 2 to 8 hours.

[0018] Preferably, the molar ratio of the anthracene-9-carbaldehyde to the sodium borohydride is 1:2 to 1:3, the temperature of the reduction reaction is 25°C, and the reaction time is 4 to 8 hours.

[0019] Preferably, the third solvent comprises dichloromethane and pyridine, and the volume ratio of dichloromethane to pyridine is 1:1 to 3:1.

[0020] Preferably, the molar ratio of the 9-anthracenmethanol, 4-dimethylaminopyridine, and succinic anhydride is 1:1:4 to 1:2:6;

[0021] The temperature of the above substitution reaction is 25℃, and the time is 24 to 48 hours.

[0022] Preferably, the molar ratio of the 4-(anthracen-9-ylmethoxy)-4-oxobutyric acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, and long-chain fatty alcohol is 1:4:2:1 to 1:6:5:3;

[0023] The temperature of the above esterification reaction is 25℃, and the time is 24 to 48 hours.

[0024] The present invention provides the use of an anthracene compound described in the technical solution or an anthracene compound produced by the manufacturing method described in the technical solution as a solar fuel.

[0025] The present invention provides an anthracene-based compound, wherein the anthracene-based compound undergoes a photodimerization reaction under ultraviolet irradiation of a specific wavelength to store photothermal energy, and undergoes a photodepolymerization reaction under ultraviolet irradiation of a different wavelength to release heat. In other words, the anthracene-based compound can effectively induce reversible photodimerization / depolymerization reactions to store or release photothermal energy, and also possesses the unique advantage of a reversible solid-liquid phase transition that allows for light control. Furthermore, this anthracene-based compound has a high energy storage density (65 kJ / mol) and a long storage half-life (3 days), enabling it to simultaneously store photon energy and phase transition energy, thereby effectively improving the storage performance of solar thermal fuel, ensuring stable circulation in the utilization process, and emitting no greenhouse gases.

[0026] The present invention produces anthracene-based compounds through a formylation-condensation reaction, a substitution reaction, and an esterification reaction using a reversible photodimerization / depolymerization reaction of anthracene. The produced anthracene-based compounds can be photodimerized under 365 nm light irradiation and undergo a solid-liquid phase change to simultaneously store photon energy and phase change energy, and can be depolymerized under 254 nm light irradiation and undergo a liquid-solid phase change to release the stored photon energy and phase change energy in the form of thermal energy.

[0027] The anthracene used as a manufacturing raw material in this invention is a commercially available product or a product obtained by separation from coal tar, and utilizing this anthracene-based compound as a solar fuel can not only expand various application routes but also further enrich the solar fuel molecular system.

[0028] The anthracene compound of the present invention has a simple synthesis process, high yield, easy mass production, stable circulation, and an environmentally friendly utilization process, which can improve the clean utilization rate of coal tar. Brief explanation of the drawing

[0029] FIG. 1 is a synthesis pathway of an anthracene compound of the present invention; FIG. 2 shows the hydrogen nuclear magnetic resonance spectrum (deuterated chloroform) of 9-anthracene methanol (a) prepared in Example 1, the intermediate product 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid (b), and anthracene compound (c), and the mass spectrum of anthracene compound (d); FIG. 3 shows the anthracene-based compound of Example 1 irradiated with 365 nm ultraviolet light (a) and 254 nm ultraviolet light (b) (irradiance 10 mW / cm² 2 This is the ultraviolet-visible absorption spectrum after irradiating ) for different times, and a schematic diagram (c) of the photodimerization / depolymerization reaction of anthracene compounds when irradiated alternately with 365 nm and 254 nm ultraviolet light; FIG. 4 shows the alternating ultraviolet excitation (irradiance 50 mW / cm²) of the anthracene compound prepared in Example 2. 2 This is an optical photograph of a photoreversible solid-liquid phase transition under ); Figure 5 shows the energy storage density test curve (a) and recovery half-life curve (b) of the anthracene compound of Example 3. Specific details for implementing the invention

[0030] The present invention provides an anthracene compound represented by Chemical Formula 1:

[0031] Chemical formula 1;

[0032] In [Chemical Formula 1], n is 10 to 16.

[0033] In the present invention, n is 10, 13, or 16.

[0034] As illustrated in FIG. 1, the present invention provides a method for producing an anthracene compound according to the technical solution, which comprises the following steps:

[0035] A step of mixing anthracene, N-methylformanilide, phosphorus oxychloride, and a first solvent, and performing a formylation-condensation reaction to obtain anthracene-9-carbaldehyde;

[0036] A step of mixing the above anthracene-9-carbaldehyde, sodium borohydride, and a second solvent, and performing a reduction reaction to obtain 9-anthracenemethanol;

[0037] A step of mixing the above 9-anthracen methanol, succinic anhydride, 4-dimethylaminopyridine, and a third solvent, and performing a substitution reaction to obtain 4-(anthracen-9-ylmethoxy)-4-oxobutyric acid;

[0038] A step of mixing the above 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, long-chain fatty alcohol, and a fourth solvent, and performing an esterification reaction to obtain an anthracene-based compound;

[0039] The number of carbon atoms in the above long-chain fatty alcohol is 12 to 18.

[0040] In the present invention, unless otherwise specified, the raw materials or reagents required for manufacturing are commercially available products well known to those skilled in the art.

[0041] In the present invention, anthracene, N-methylformanilide, phosphorus oxychloride, and a first solvent are mixed and a formylation-condensation reaction is performed to obtain anthracene-9-carbaldehyde.

[0042] In the present invention, the anthracene is preferably obtained by using a commercially available product or by separating it from coal tar, and more preferably by extracting the anthracene by adopting the method of separating anthracene from coal tar disclosed in Patent CN115141077B.

[0043] In the present invention, the molar ratio of anthracene, N-methylformanilide, and phosphorus oxychloride is preferably 1:2:2 to 1:4:4, more preferably 1:3:3.

[0044] In the present invention, the first solvent is preferably o-dichlorobenzene, and the volume ratio of the N-methylformanilide to the first solvent is preferably 10:1 to 5:1, more preferably 7 to 9:1.

[0045] In the present invention, it is preferable to mix anthracene, N-methylformanilide, and phosphorus oxychloride, add a first solvent, heat the mixture in an oil bath to the reaction temperature while stirring, maintain it for 30 to 60 minutes, more preferably 50 minutes, until the anthracene dissolves to form a deep red solution and the hydrochloric acid precipitates, and then carry out a formylation-condensation reaction.

[0046] In the present invention, the temperature of the formylation-condensation reaction is preferably 90 to 100°C, more preferably 95 to 98°C, and the reaction time is preferably 2 to 8 hours, more preferably 3 to 6 hours.

[0047] After the formylation-condensation reaction is completed, dichloromethane is added to the obtained product and washed several times with a saturated sodium chloride solution, the obtained organic phase is dried with magnesium sulfate and filtered, and then the solvent is evaporated to obtain anthracene-9-carbaldehyde. The present invention does not impose any particular limitations on the washing, drying, filtration, and solvent evaporation, and can be carried out by methods known in the art.

[0048] In the present invention, the anthracene-9-carbaldehyde, sodium borohydride, and a second solvent are mixed, and a reduction reaction is performed to obtain 9-anthracene methanol.

[0049] In the present invention, the molar ratio of anthracene-9-carbaldehyde and sodium borohydride is preferably 1:2 to 1:3, and the second solvent is preferably ethanol, and the present invention does not impose any special limit on the amount of the second solvent used as long as the reaction proceeds smoothly.

[0050] In the present invention, sodium borohydride is added to a solvent containing anthracene-9-carbaldehyde at 0°C and a reduction reaction is carried out while stirring, and the temperature of the reduction reaction is preferably 25°C and the reaction time is preferably 4 to 8 hours.

[0051] After the above reduction reaction is completed, the present invention preferably adds concentrated hydrochloric acid dropwise to the obtained product to decompose unreacted sodium borohydride, then adds water until neutral, then adds dichloromethane to separate the organic layer, washes several times with a saturated sodium chloride solution, then dries with anhydrous magnesium sulfate, filters, and recrystallizes the crude product obtained by vacuum distillation into ethanol to obtain 9-anthracenmethanol.

[0052] In the present invention, the mass concentration of the concentrated hydrochloric acid is preferably 12 M, the volume ratio of the concentrated hydrochloric acid to the second solvent is preferably 1:15 to 1:10, more preferably 1:12.5, the volume ratio of the dichloromethane to the saturated sodium chloride solution is preferably 1:2 to 1:6, more preferably 1:3 to 4.8, the number of washes with the saturated sodium chloride solution is preferably 2 to 6 times, more preferably 3 to 4 times, and the number of recrystallizations is preferably 2 to 5 times, more preferably 3 times.

[0053] In the present invention, 9-anthracen methanol, succinic anhydride, 4-dimethylaminopyridine, and a third solvent are mixed and subjected to a substitution reaction to obtain 4-(anthracen-9-ylmethoxy)-4-oxobutyric acid.

[0054] In the present invention, the molar ratio of the 9-anthracen methanol, 4-dimethylaminopyridine, and succinic anhydride is preferably 1:1:4 to 1:2:6, more preferably 1:1:5 to 1:2:6.

[0055] In the present invention, the third solvent preferably comprises dichloromethane and pyridine, and the volume ratio of the dichloromethane and pyridine is preferably 1:1 to 3:1, more preferably 2:1, and the present invention has no particular limitation on the amount of the third solvent as long as the reaction proceeds smoothly.

[0056] In the present invention, it is preferable to mix 9-anthracen methanol, 4-dimethylaminopyridine, and succinic anhydride, add a third solvent to dissolve them, and then carry out a substitution reaction while stirring.

[0057] In the present invention, the temperature of the substitution reaction is preferably 25°C, and the reaction time is preferably 24 to 48 hours, more preferably 36 hours.

[0058] After the above substitution reaction is completed, the obtained mixture is poured into an ice / water mixture and heated to room temperature, dichloromethane is added to separate the organic layer, the organic layer is extracted several times with a saturated sodium chloride solution, the collected organic layer is dried with anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure to obtain 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid. In the present invention, the volume ratio of the dichloromethane and the saturated sodium chloride solution is preferably 1:2 to 1:6, more preferably 1:2.5, and the number of times the mixture is extracted with the saturated sodium chloride solution is preferably 2 to 5 times, more preferably 4 times.

[0059] The present invention obtains an anthracene-based compound by mixing the above 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, long-chain fatty alcohol, and a fourth solvent, and performing an esterification reaction.

[0060] In the present invention, the molar ratio of the 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, and long-chain fatty alcohol is preferably 1:4:2:1 to 1:6:5:3, more preferably 1:5:3:3, and the number of carbon atoms of the long-chain fatty alcohol is 12 to 18, preferably 12, 15, or 18.

[0061] In the present invention, the fourth solvent is preferably chloroform, and the present invention does not impose any particular limit on the amount of the fourth solvent used as long as the reaction proceeds smoothly.

[0062] In the present invention, it is preferable to mix 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride (EDAC), and 4-dimethylaminopyridine (DMAP), then add a fourth solvent, dissolve the solid through magnetic stirring, then add a long-chain fatty alcohol, and carry out an esterification reaction under continuous stirring conditions.

[0063] In the present invention, the temperature of the esterification reaction is preferably 25°C, and the reaction time is preferably 24 to 48 hours, more preferably 36 hours.

[0064] In the present invention, it is preferable to obtain an anthracene compound by adding a 5 wt% dilute aqueous hydrochloric acid solution to the product system obtained after the esterification reaction is completed, extracting the combined organic layer with a saturated aqueous sodium bicarbonate solution, drying the obtained organic layer with magnesium sulfate, filtering under reduced pressure, concentrating by rotary evaporation, and purifying by column chromatography.

[0065] In the present invention, the volume ratio of the dilute aqueous hydrochloric acid solution and the fourth solvent is preferably 1:3 to 1:6, more preferably 1:3.75 to 5, the number of times extraction with the saturated aqueous sodium bicarbonate solution is preferably 3 to 5 times, the developing agent used for the column chromatography purification is preferably ethyl acetate and n-hexane, and the volume ratio of the ethyl acetate and n-hexane is preferably 1:1 to 1:3, more preferably 1:2.

[0066] The present invention provides the use of an anthracene compound described in the technical solution or an anthracene compound produced by the manufacturing method described in the technical solution as a solar fuel.

[0067] The present invention does not particularly limit the method of use, and the anthracene-based compound can be used directly as solar fuel.

[0068] The technical solution provided by the present invention will be described in detail below with reference to specific embodiments, but this should not be understood as a limitation on the scope of protection of the present invention.

[0069] Example 1

[0070] 1) Anthracene (5.00 g, 28.00 mmol), N-methylformanilide (6.3 mL, 7.58 g, 56.00 mmol), and phosphorus oxychloride (8.56 g, 56.00 mmol) were placed in a 100 mL round-bottom flask containing 0.7 mL of o-dichlorobenzene, heated in an oil bath at 1500 r / min to 95 °C while stirring, and maintained for 30 minutes; during this period, the anthracene dissolved to form a deep red solution and hydrochloric acid precipitated, and heating continued for 3 hours; after the reaction was complete, 25 mL of dichloromethane was added first, followed by washing three times with 50 mL of saturated sodium chloride solution, the organic phase was dried with magnesium sulfate at room temperature for 12 hours, filtered, and the solvent was evaporated at 30 °C for 1 hour to obtain anthracene-9-carbaldehyde; Sodium borohydride (0.34 g, 9.60 mmol) was added to an ethanol solution (50 mL) containing anthracene-9-carbaldehyde (1.00 g, 4.80 mmol) at 0°C, and the reaction mixture was stirred at 25°C at 1500 r / min for 4 hours; 5 mL of concentrated hydrochloric acid (concentration 12 M) was added dropwise, followed by the addition of water to neutralize the mixture; 25 mL of dichloromethane was added to separate the organic layer, and after washing three times with 50 mL of saturated sodium chloride solution, 150 g of anhydrous magnesium sulfate was dried at 45°C for 12 hours, filtered, and the crude product obtained by vacuum distillation (0.02 MPa, 30°C, 1 hour) was recrystallized twice in 50 mL of ethanol at 4°C for 12 hours to obtain pale yellow 9-anthracenemethanol;

[0071] 2) A mixture of 9-anthracenmethanol (2.08 g, 10.00 mmol), 4-dimethylaminopyridine (1.23 g, 10.01 mmol), and succinic anhydride (4.00 g, 40.02 mmol) was placed in a 250 mL round-bottom flask, and a mixed solution of 50 mL of dichloromethane anhydride and 50 mL of pyridine anhydride was added to obtain a mixed solution, and the obtained mixed solution was stirred at 1500 r / min at 25°C for 24 hours; After the reaction was complete, the mixed solution was poured into 200 mL of an ice / water mixed solution and heated to room temperature. Then, 50 mL of dichloromethane was added to separate the organic layer, the organic layer was washed three times with 100 mL of saturated sodium chloride solution, the collected organic layer was dried in 150 g of anhydrous magnesium sulfate at room temperature for 12 hours, filtered, and vacuum concentrated at 0.02 MPa and 30°C for 1 hour to obtain the intermediate product, 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid.

[0072] 3) 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid (1.48 g, 4.80 mmol), 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride (3.67 g, 19.20 mmol), and p-dimethylaminopyridine (1.17 g, 9.60 mmol) were sequentially added to a 250 mL single-neck round-bottom flask, 150 mL of chloroform was added, and the mixture was dissolved by magnetic stirring at 1500 r / min; then, n-dodecanol (0.89 g, 4.80 mmol) was added to the round-bottom flask, and the mixture was continuously stirred at 25°C for 24 hours; After the reaction was completed, 50 mL of a 5 wt% dilute aqueous hydrochloric acid solution was added, and the mixture was washed three times with 50 mL of a saturated aqueous sodium bicarbonate solution. The resulting organic layer was then dried with 150 g of magnesium sulfate, filtered under reduced pressure of 0.02 MPa, concentrated by rotary evaporation at 45°C for 1 hour, and purified by column chromatography (ethyl acetate and n-hexane, volume ratio 1:2) to obtain an anthracene compound.

[0073] Example 2

[0074] 1) Anthracene (5.00 g, 28.00 mmol), N-methylformanilide (9.45 mL, 11.34 g, 84.00 mmol), and phosphorus oxychloride (12.85 g, 84.00 mmol) were placed in a 100 mL round-bottom flask containing 1.35 mL of o-dichlorobenzene, heated in an oil bath at 1500 r / min to 98 °C with stirring, and maintained for 50 minutes; during this period, the anthracene dissolved to form a deep red solution and hydrochloric acid precipitated, and heating continued for 6 hours; after the reaction was complete, 25 mL of dichloromethane was added first, followed by washing 4 times with 75 mL of saturated sodium chloride solution; the organic phase was dried with magnesium sulfate at room temperature for 12 hours, filtered, and the solvent was evaporated at 30 °C for 1 hour to obtain anthracene-9-carbaldehyde; Sodium borohydride (0.34 g, 9.60 mmol) was added to an ethanol solution (50 mL) containing anthracene-9-carbaldehyde (1.00 g, 4.80 mmol) at 0°C, and the reaction mixture was stirred at 25°C at 1500 r / min for 4 hours; 4 mL of concentrated hydrochloric acid (concentration 12 M) was added dropwise, followed by the addition of water until neutral; after the reaction was complete, 25 mL of dichloromethane was added to separate the organic layer, and the organic layer was washed 4 times with 75 mL of saturated sodium chloride solution, dried with 150 g of anhydrous magnesium sulfate for 12 hours at 45°C, filtered, and then subjected to vacuum distillation (0.02 MPa, 30°C, 1 hour). The crude product obtained was recrystallized 3 times in 50 mL of ethanol at 4°C for 12 hours to obtain pale yellow 9-anthracenemethanol.

[0075] 2) A mixture of 9-anthracenmethanol (2.08 g, 10.00 mmol), 4-dimethylaminopyridine (2.44 g, 20.01 mmol), and succinic anhydride (5.00 g, 50.02 mmol) was placed in a 250 mL round-bottom flask, then a mixed solution of 100 mL of dichloromethane anhydride and 50 mL of pyridine anhydride was added, and the resulting mixed solution was reacted by stirring at 1500 r / min at 25°C for 36 hours; After the reaction was complete, the mixed solution was poured into 200 mL of an ice / water mixture and heated to room temperature, then 100 mL of dichloromethane was added to separate the organic layer, the organic layer was washed four times with 250 mL of saturated sodium chloride solution, the collected organic layer was dried with 150 g of anhydrous magnesium sulfate at room temperature for 12 hours, filtered, and then vacuum concentrated at 0.02 MPa and 30°C for 1 hour to obtain the intermediate 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid;

[0076] 3) 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid (1.48 g, 4.80 mmol), 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride (3.67 g, 19.20 mmol), and p-dimethylaminopyridine (1.17 g, 9.60 mmol) were sequentially added to a 250 mL one-neck round-bottom flask, 150 mL of chloroform was added, and the mixture was dissolved by magnetic stirring at 1500 r / min; then, n-dodecanol (1.78 g, 9.60 mmol) was added to the round-bottom flask, and the mixture was reacted by stirring at 25°C for 36 hours; after the reaction was complete, 30 mL of 5 wt% dilute hydrochloric acid was added, and the mixture was washed 4 times with 50 mL of saturated sodium bicarbonate aqueous solution; The obtained organic layer was dried with 150 g of magnesium sulfate, filtered under reduced pressure at 0.02 MPa, concentrated by rotary evaporation at 45°C for 1 hour, and purified by column chromatography (ethyl acetate and n-hexane, volume ratio 1:3) to obtain an anthracene compound.

[0077] Example 3

[0078] 1) Anthracene (2.50 g, 14.00 mmol), N-methylformanilide (6.3 mL, 7.56 g, 56.00 mmol), and phosphorus oxychloride (8.57 g, 56.00 mmol) were placed in a 100 mL round-bottom flask containing 1.20 mL of o-dichlorobenzene, then heated in an oil bath at 1500 r / min to 100 °C while stirring, and maintained for 60 minutes; during this period, the anthracene dissolved to form a deep red solution and hydrochloric acid precipitated, and heating was continued for 8 hours; after the reaction was complete, 25 mL of dichloromethane was added first, followed by 5 washes with 150 mL of saturated sodium chloride solution; the organic phase was dried with magnesium sulfate at room temperature for 12 hours, filtered, and the solvent was evaporated at 30 °C for 1 hour to obtain anthracene-9-carbaldehyde; Sodium borohydride (0.51 g, 14.40 mmol) was added to an ethanol solution (50 mL) containing anthracene-9-carbaldehyde (1.00 g, 4.80 mmol) at 0°C, and the reaction mixture was stirred at 25°C at 1500 r / min for 8 hours; 5 mL of concentrated hydrochloric acid (concentration 12 M) was added dropwise, and then water was added until neutral; After the reaction was complete, 25 mL of dichloromethane was added to separate the organic layer, and after washing 5 times with a saturated sodium chloride solution (120 mL), the mixture was dried with 150 g of anhydrous magnesium sulfate at 45°C for 12 hours, filtered, and then subjected to vacuum distillation (0.02 MPa, 30°C, 1 hour). The resulting crude product was added to 50 mL of ethanol and recrystallized 3 times at 4°C for 12 hours to obtain pale yellow 9-anthracenmethanol;

[0079] 2) A mixture of 9-anthracenmethanol (2.08 g, 10.00 mmol), 4-dimethylaminopyridine (2.44 g, 20.01 mmol), and succinic anhydride (6.00 g, 60.02 mmol) was placed in a 250 mL round-bottom flask, then a mixed solution of 150 mL of dichloromethane anhydride and 50 mL of pyridine anhydride was added, and the resulting mixed solution was stirred at 1500 r / min at 25°C for 48 hours; After the reaction was complete, the mixed solution was poured into a 200 mL ice / water mixture and heated to room temperature, then 150 mL of dichloromethane was added to separate the organic layer, the organic layer was washed 5 times with 300 mL of saturated sodium chloride solution, the collected organic layer was dried with 150 g of anhydrous magnesium sulfate at room temperature for 12 hours, filtered, and then vacuum concentrated at 30°C for 1 hour under a pressure of 0.02 MPa to obtain the intermediate product 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid;

[0080] 3) 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid (1.48 g, 4.80 mmol), 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride (4.58 g, 24.00 mmol), and 4-dimethylaminopyridine (1.75 g, 14.40 mmol) were sequentially added to a 250 mL single-neck round-bottom flask, 150 mL of chloroform was added, and the mixture was dissolved by magnetic stirring at 1500 r / min; then, n-dodecanol (2.68 g, 14.40 mmol) was added to the round-bottom flask and the mixture was stirred continuously at 25°C for 48 hours; After the reaction was completed, 40 mL of a 5 wt% dilute aqueous hydrochloric acid solution was added, and the mixture was washed 5 times with 50 mL of a saturated aqueous sodium bicarbonate solution. The resulting organic layer was then dried with 150 g of magnesium sulfate, filtered under reduced pressure at 0.02 MPa, concentrated by rotary evaporation at 45°C for 1 hour, and purified by column chromatography (ethyl acetate and n-hexane = 1:2) to obtain an anthracene compound.

[0081] Characterization and performance testing

[0082] FIG. 2 shows the hydrogen nuclear magnetic resonance spectrum (deuterated chloroform) of 9-anthracene methanol (a), the intermediate product 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid (b), and the mass spectrum of the anthracene compound (c) prepared in Example 1, and the mass spectrum of the anthracene compound (d). As can be seen in FIG. 2, the product 9-anthracene methanol, the intermediate product 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid, and the target product anthracene compound were successfully synthesized.

[0083] FIG. 3 shows the anthracene-based compound of Example 1 irradiated with 365 nm ultraviolet (a) and 254 nm ultraviolet (b) (methanol solution, 1 M, illuminance 10 mW / cm² 2 It shows the ultraviolet-visible absorption spectra after irradiating for different times and a schematic diagram (c) of the photodimerization / depolymerization reaction of anthracene compounds when irradiated alternately with 365 nm and 254 nm ultraviolet light. As can be seen in FIG. 3, anthracene compounds can effectively achieve a reversible photodimerization / depolymerization reaction under ultraviolet irradiation.

[0084] FIG. 4 shows the alternating ultraviolet excitation (irradiance 50 mW / cm²) of the anthracene compound prepared in Example 2. 2 This is an optical photograph of the photoreversible solid-liquid phase change under ) As can be seen in Fig. 4, the prepared anthracene-based compound can achieve a reversible solid-liquid phase change under ultraviolet irradiation.

[0085] Figure 5 shows the energy storage density test curve (a) and recovery half-life curve (b) of the anthracene compound of Example 3. As can be calculated from Figure 5, the energy density of the anthracene compound is 65 kJ / mol, and the energy storage time is up to 60 days.

[0086] The above is merely a preferred embodiment of the present invention, and it should be noted that a person skilled in the art may make some improvements and modifications without departing from the principles of the present invention, and such improvements and modifications also fall within the scope of protection of the present invention.

Claims

Claim 1 As an anthracene compound characterized by having a structure represented by the following chemical formula 1: Chemical formula 1; an anthracene compound in which n is 10 to 16 in [Chemical formula 1] above. Claim 2 An anthracene compound according to claim 1, characterized in that n is 10, 13, or 16. Claim 3 A method for preparing an anthracene-based compound as described in claim 1, characterized by comprising the following steps: a step of mixing anthracene, N-methylformanilide, phosphorus oxychloride, and o-dichlorobenzene as a first solvent, and performing a formylation-condensation reaction to obtain anthracene-9-carbaldehyde; a step of mixing the anthracene-9-carbaldehyde, sodium borohydride, and ethanol as a second solvent, and performing a reduction reaction to obtain 9-anthracenemethanol; a step of mixing the 9-anthracenemethanol, succinic anhydride, 4-dimethylaminopyridine, and a third solvent, and performing a substitution reaction to obtain 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid, wherein the third solvent comprises dichloromethane and pyridine; and the 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid, A method for preparing an anthracene compound by mixing 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, a long-chain fatty alcohol, and chloroform as a fourth solvent and performing an esterification reaction; wherein the number of carbon atoms of the long-chain fatty alcohol is 12 to 18. Claim 4 A manufacturing method according to paragraph 3, characterized in that the anthracene is separated from coal tar. Claim 5 A method for manufacturing according to claim 3, characterized in that the molar ratio of the anthracene, N-methylformanilide, and phosphorus oxychloride is 1:2:2 to 1:4:4, the volume ratio of the N-methylformanilide to the first solvent is 10:1 to 5:1, the temperature of the formylation-condensation reaction is 90 to 100°C, and the reaction time is 2 to 8 hours. Claim 6 A manufacturing method according to claim 3, characterized in that the molar ratio of anthracene-9-carbaldehyde to sodium borohydride is 1:2 to 1:3, the temperature of the reduction reaction is 25℃, and the reaction time is 4 to 8 hours. Claim 7 A manufacturing method according to claim 3, characterized in that, in the third solvent, the volume ratio of dichloromethane to pyridine is 1:1 to 3:

1. Claim 8 A method of preparation according to claim 3, characterized in that the molar ratio of 9-anthracenmethanol, 4-dimethylaminopyridine, and succinic anhydride is 1:1:4 to 1:2:6, the temperature of the substitution reaction is 25℃, and the time is 24 to 48 hours. Claim 9 A method of preparation according to claim 3, characterized in that the molar ratio of 4-(anthracene-9-ylmethoxy)-4-oxobutyric acid, 1-ethyl(3-dimethylaminopropyl)-3-carbodiimide hydrochloride, 4-dimethylaminopyridine, and long-chain fatty alcohol is 1:4:2:1 to 1:6:5:3, the temperature of the esterification reaction is 25℃, and the time is 24 to 48 hours. Claim 10 Solar fuel comprising an anthracene compound described in any one of claims 1 to 2 or an anthracene compound produced by the manufacturing method of any one of claims 3 to 9.

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