Alkyl / fluoroalkyl-modified benzofuranone fluorescent compounds, methods of making and uses thereof

Abstract

This invention discloses alkyl / fluoroalkyl-modified benzofuranone fluorescent compounds, their preparation methods, and applications. Belonging to the technical field of alkyl / fluoroalkyl-modified benzofuranone fluorescent compounds, these compounds simultaneously connect two alkyl / fluoroalkyl chains and contain three benzene ring substituent structural units. These compounds exhibit orange fluorescence initially upon initial irradiation with 365nm ultraviolet light, but as the irradiation time increases to 15 minutes, the fluorescence changes from orange to yellow, demonstrating photoluminescence color-changing properties. When the irradiated compound is heated to 110℃ or ground, the fluorescence reverts from yellow to its initial orange state, exhibiting thermo / mechanical fluorescence color-changing properties. Reversible fluorescence conversion can be achieved under light and heat regulation, making them suitable for preparing photothermal dual-stimulus responsive fluorescent materials. They have broad application prospects in information encryption and security, data recording and storage, optoelectronic devices, molecular logic gates, and bioimaging.

Description

Technical Field

[0001] This invention relates to an alkyl / fluoroalkyl modified benzofuranone fluorescent compound, and particularly to an alkyl / fluoroalkyl modified benzofuranone fluorescent compound, its preparation method, and its application, belonging to the technical field of alkyl / fluoroalkyl modified benzofuranone fluorescent compounds. Background Technology

[0002] The prior art provides a photochromic compound of the form of benzofuran-pyran with aromatic heterocyclic substitution, its preparation method and use. The invention uses the reversible change of the color of the compound itself before and after photothermal stimulation. It is suitable for preparing photochromic ink for printing anti-counterfeiting trademarks, photochromic plastic film, organic photochromic resin glasses or photochromic display materials.

[0003] The prior art also discloses a colorless benzofuranone compound of the bisindole class and its preparation method, which uses a single thermal stimulation process to achieve the color change process of the compound itself and is suitable for making thermosensitive dyes and monomers for polymer synthesis.

[0004] In addition, existing technologies also use stimuli such as light, external force, temperature, magnetic field, polarity and pH as stimuli to stimulate changes in the fluorescence response of fluorescent materials;

[0005] However, as mentioned above, most stimulus-responsive fluorescent materials in the prior art only have the characteristic of fluorescence response to a single stimulus source. Secondly, their fluorescence reversibility is unsatisfactory, making it difficult to meet the requirements for repeated use. They also cannot meet the diverse application needs in the fields of information encryption and security, data recording and storage, optoelectronic devices, molecular logic gates, and biological imaging. To address these issues, an alkyl / fluoroalkyl modified benzofuranone fluorescent compound, its preparation method, and its application are designed to solve the above-mentioned technical problems. Summary of the Invention

[0006] The main objective of this invention is to provide alkyl / fluoroalkyl modified benzofuranone fluorescent compounds, their preparation methods, and applications, thereby solving the problems of existing fluorescent compounds having relatively simple stimulus responses, poor fluorescence reversibility, and being unsuitable for information encryption and security, data recording and storage, optoelectronic devices, molecular logic gates, and biological imaging.

[0007] The objective of this invention can be achieved by adopting the following technical solution:

[0008] Alkyl / fluoroalkyl modified benzofuranone fluorescent compounds are shown in Formula 1:

[0009]

[0010] Alkyl / fluoroalkyl modified benzofuranone fluorescent compounds simultaneously connect two alkyl / fluoroalkyl chains and contain three benzene ring substituent structural units;

[0011] In Formula 1, R1 and R2 are both alkyl groups, and R1 and R2 are the same alkyl group.

[0012] Preferably, R1 and R2 are any one of ethyl, n-propyl, n-butyl, 1,1,1-trifluoroethyl, 1,1,1,2,2-pentafluoron-propyl, and 1,1,1,2,2,3,3-heptafluoron-butyl.

[0013]

[0014] Wherein, 423H indicates that R1 and R2 are ethyl groups;

[0015] 433H indicates that R1 and R2 are n-propyl;

[0016] 443H indicates that R1 and R2 are n-butyl;

[0017] 423F indicates that R1 and R2 are 1,1,1-trifluoroethyl;

[0018] 433F indicates that R1 and R2 are 1,1,1,2,2-pentafluoropropyl;

[0019] 443F indicates that R1 and R2 are 1,1,1,2,2,3,3-heptafluorobutyl.

[0020] A method for preparing alkyl / fluoroalkyl modified benzofuranone fluorescent compounds includes the following steps:

[0021] Step 1: 2-Bromo-3,4,5,6-Tetramethoxytoluene, pinacol diborate, cesium carbonate, tris(4-methoxy-3,5-dimethylphenyl)phosphine, and palladium acetate were dissolved in ethyl acetate. The mixture was stirred under N2 gas scrubbing conditions. The organic layer was washed, dried, and purified by column chromatography to obtain 4OMe-B. The reaction formula is detailed in Formula 2.

[0022]

[0023] Step 2: Dissolve 2-bromo-1,1,2-tristyrene, 4OMe-B, potassium phosphate, and tetrakis(triphenylphosphine)palladium in N,N-dimethylformamide. After washing with N2 gas under a sealed environment, the mixture is stirred and reacted. The organic layer is washed, dried, and purified by column chromatography to obtain TPE-4OMe. See Formula 3 for the detailed reaction formula.

[0024]

[0025] Step 3: Dissolve the TPE-4OMe obtained in Step 2 in dichloromethane. Under sealed conditions, wash with N2 gas, slowly add BBr3 dropwise under ice bath conditions, and stir the reaction. Then add dichloromethane and quench the reaction with water. After washing, drying, filtering, and rotary drying, obtain the filter residue. Dissolve the obtained filter residue and p-toluenesulfonic acid monohydrate in dichloromethane and stir the reaction. After washing, drying, and column chromatography purification, obtain 2OH. See Equation 4 for the reaction formula.

[0026]

[0027] Step 4: Dissolve the 2OH obtained in Step 3 together with any one of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, 7F-OTf and cesium carbonate in N,N-dimethylformamide solvent, wash with N2 gas under closed conditions and then stir to react, finally obtaining the compound shown in Formula 1;

[0028] The structural formulas of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, and 7F-OTf are shown below:

[0029]

[0030] Preferably, in step one, the molar ratio of 2-bromo-3,4,5,6-tetramethoxytoluene, pinacol diboronate, cesium carbonate, tris(4-methoxy-3,5-dimethylphenyl)phosphine, palladium acetate, and ethyl acetate is 1:(1-1.5):(1-1.5):(0.005-0.011):0.01:4;

[0031] The preferred ratio is 1:1.5:1.5:0.011:0.01:4.

[0032] Preferably, in step two, the molar ratio of 4OMe-B, 2-bromo-1,1,2-tristyrene, potassium phosphate, tetrakis(triphenylphosphine)palladium to N,N-dimethylformamide is 1:(1.2-1.5):(2.0-3.0):0.05:6;

[0033] The preferred ratio is 1:1.2:3:0.05:6.

[0034] Preferably, in step three, the molar ratio of TPE-4OMe, BBr3 and dichloromethane is 1:8:(10-20);

[0035] The preferred ratio is 1:8:10.

[0036] The mass ratio of filter residue, p-toluenesulfonic acid monohydrate, and dichloromethane is 1:3:(20-25);

[0037] The preferred ratio is 1:3:25.

[0038] Preferably, in step four, the molar ratio of 2OH obtained in step three, any one of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, 7F-OTf, and cesium carbonate dissolved together in N,N-dimethylformamide solvent is 1:3:(4-6):(8-15).

[0039] The preferred ratio is 1:3:4:8.

[0040] Preferably, the temperature of the stirring reaction in step one is 80-82℃, and the time is 24-28h;

[0041] In step two, the stirring reaction is carried out at a temperature of 80-85℃ for 24-30 hours.

[0042] In step three, the temperature of the first stirring reaction is 0-10℃, and the time is 10-12h;

[0043] The second step of the stirring reaction is carried out at a temperature of 60-65℃ for 15-18 hours.

[0044] The stirring reaction in step four is carried out at a temperature of 25-30℃ for 5-8 hours.

[0045] Preferably, the stirring reaction in step one is carried out at a temperature of 80°C for 28 hours.

[0046] The stirring reaction in step two is carried out at a temperature of 80°C for 30 hours.

[0047] Step 3 describes the first step of the stirring reaction as having a temperature of 0°C and a time of 12 hours, and the second step of the stirring reaction as having a temperature of 60°C and a time of 16 hours.

[0048] The stirring reaction in step four is carried out at a temperature of 25°C for 5 hours.

[0049] Preferably, the preparation method of 5H-Tos, 7H-Tos, and 9H-Tos is as follows: ethanol, propanol, n-butanol and p-methylbenzenesulfonyl chloride are dissolved in DCM and cooled to 0°C. The mixture is stirred for 10-15 min, and triethylamine is added dropwise. After the addition is complete, the temperature is raised to room temperature and stirred for 12-18 h. The organic layer is washed, dried and purified by column chromatography to obtain 5H-Tos, 7H-Tos, and 9H-Tos.

[0050] The molar ratio of ethanol, propanol, n-butanol, p-toluenesulfonyl chloride, and triethylamine is 1:1.5:5; the reaction process is detailed in Equation 5-7.

[0051]

[0052] Preferred preparation methods for 3F-OTf, 5F-OTf, and 7F-OTf are as follows: pyridine and DCM are mixed evenly, washed three times with N2 gas under a sealed environment, cooled to 0°C, and then 2,2,2-trifluoroethanol, or 2,2,3,3,3-pentafluoro-1-propanol, or 2,2,3,3,4,4,4-heptafluoro-1-butanol are added dropwise. The mixture is stirred for 10-15 min, and then trifluoromethanesulfonic anhydride is added dropwise. After the addition is complete, the temperature is raised to room temperature and stirred for 2-4 h. The organic layer is washed, dried, and purified by column chromatography to obtain 3F-OTf, 5F-OTf, and 7F-OTf.

[0053] The molar ratio of 2,2,2-trifluoroethanol, or 2,2,3,3,3-pentafluoro-1-propanol, or 2,2,3,3,4,4,4-heptafluoro-1-butanol, trifluoromethanesulfonic anhydride, and triethylamine is 1:1.2:1.25; the reaction process is detailed in Formula 8-10.

[0054]

[0055] Applications of alkyl / fluoroalkyl modified benzofuranone fluorescent compounds as fluorescent paper for information encryption and security under light and heat regulation.

[0056] Beneficial technical effects of the present invention:

[0057] This invention provides alkyl / fluoroalkyl modified benzofuranone fluorescent compounds, their preparation methods, and applications. These compounds simultaneously connect two alkyl / fluoroalkyl chains and contain three benzene ring substituent structural units. These compounds exhibit orange fluorescence at the initial stage of 365nm ultraviolet light irradiation, but as the irradiation time is extended to 15 minutes, the fluorescence changes from orange to yellow, demonstrating photoluminescence properties. When the irradiated compounds are heated to 110°C or ground, the fluorescence returns from yellow to the initial orange state, exhibiting thermo / mechanical fluorescence properties.

[0058] Reversible fluorescence conversion can be achieved under the regulation of light and heat, which can be used to prepare photothermal dual-stimulus responsive fluorescent materials. It has broad application prospects in the fields of information encryption and security, data recording and storage, optoelectronic devices, molecular logic gates and biological imaging. Attached Figure Description

[0059] Figure 1 The reaction process diagram is shown in Figure 1, in which 2OH, 5H-Tos, 7H-Tos, or 9H-Tos, or cesium carbonate are dissolved in N,N-dimethylformamide solvent to obtain the compound shown in Figure 1.

[0060] Figure 2The reaction process diagram is shown in Figure 1, in which 2OH, 3F-OTf, or 5F-OTf, or 7F-OTf, or cesium carbonate are dissolved in N,N-dimethylformamide solvent to obtain the compound shown in Figure 1.

[0061] Figure 3 This is a single-crystal structure diagram of compound 2OH.

[0062] Figure 4 This is a single-crystal structure diagram of compound 423F.

[0063] Figure 5 The thermogravimetric analysis (TG) spectrum of compound 423F.

[0064] Figure 6 The thermogravimetric analysis (TG) spectrum of compound 423H is shown.

[0065] Figure 7 The UV absorption and fluorescence spectra of compound 423F in mixed solvents of water and tetrahydrofuran in different proportions are shown.

[0066] Figure 8 The UV absorption and fluorescence spectra of compound 423H in mixed solvents of water and tetrahydrofuran in different proportions are shown.

[0067] Figure 9 This is a graph showing the solid fluorescence changes of compound 423F in different states.

[0068] Figure 10 The solid-state fluorescence spectra of compound 423F in different states are shown.

[0069] Figure 11 The graph shows the solid-state fluorescence changes and solid-state fluorescence spectra of compound 423H in different states.

[0070] Figure 12 The graph shows the solid-state fluorescence changes and solid-state fluorescence spectra of compound 433H in different states.

[0071] Figure 13 The graph shows the solid-state fluorescence changes and solid-state fluorescence spectra of compound 443H in different states.

[0072] Figure 14 The graph shows the solid-state fluorescence changes and solid-state fluorescence spectra of compound 433F in different states.

[0073] Figure 15 The graph shows the solid-state fluorescence changes and solid-state fluorescence spectra of compound 443F in different states.

[0074] Figure 16 Compound 423F is used to prepare fluorescent paper for information storage under light and heat regulation. Detailed Implementation

[0075] To enable those skilled in the art to understand the technical solution of the present invention more clearly, the present invention will be further described in detail below with reference to the embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto.

[0076] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.

[0077] Alkyl / fluoroalkyl modified benzofuranone fluorescent compounds are shown in Formula 1:

[0078]

[0079] Alkyl / fluoroalkyl modified benzofuranone fluorescent compounds simultaneously connect two alkyl / fluoroalkyl chains and contain three benzene ring substituent structural units;

[0080] In Formula 1, R1 and R2 are both alkyl groups, and R1 and R2 are the same alkyl group.

[0081] In this embodiment, R1 and R2 are any one of ethyl, n-propyl, n-butyl, 1,1,1-trifluoroethyl, 1,1,1,2,2-pentafluoron-propyl, and 1,1,1,2,2,3,3-heptafluoron-butyl.

[0082]

[0083] Wherein, 423H indicates that R1 and R2 are ethyl groups;

[0084] 433H indicates that R1 and R2 are n-propyl;

[0085] 443H indicates that R1 and R2 are n-butyl;

[0086] 423F indicates that R1 and R2 are 1,1,1-trifluoroethyl;

[0087] 433F indicates that R1 and R2 are 1,1,1,2,2-pentafluoropropyl;

[0088] 443F indicates that R1 and R2 are 1,1,1,2,2,3,3-heptafluorobutyl.

[0089] A method for preparing alkyl / fluoroalkyl modified benzofuranone fluorescent compounds includes the following steps:

[0090] Step 1: 2-Bromo-3,4,5,6-Tetramethoxytoluene, pinacol diborate, cesium carbonate, tris(4-methoxy-3,5-dimethylphenyl)phosphine, and palladium acetate were dissolved in ethyl acetate. The mixture was stirred under N2 gas scrubbing conditions. The organic layer was washed, dried, and purified by column chromatography to obtain 4OMe-B. The reaction formula is detailed in Formula 2.

[0091]

[0092] Step 2: Dissolve 2-bromo-1,1,2-tristyrene, 4OMe-B, potassium phosphate, and tetrakis(triphenylphosphine)palladium in N,N-dimethylformamide. After washing with N2 gas under a sealed environment, the mixture is stirred and reacted. The organic layer is washed, dried, and purified by column chromatography to obtain TPE-4OMe. See Formula 3 for the detailed reaction formula.

[0093]

[0094] Step 3: Dissolve the TPE-4OMe obtained in Step 2 in dichloromethane. Under sealed conditions, wash with N2 gas, slowly add BBr3 dropwise under ice bath conditions, and stir the reaction. Then add dichloromethane and quench the reaction with water. After washing, drying, filtering, and rotary drying, obtain the filter residue. Dissolve the obtained filter residue and p-toluenesulfonic acid monohydrate in dichloromethane and stir the reaction. After washing, drying, and column chromatography purification, obtain 2OH. See Equation 4 for the reaction formula.

[0095]

[0096] Step 4: Dissolve the 2OH obtained in Step 3 together with any one of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, 7F-OTf and cesium carbonate in N,N-dimethylformamide solvent, wash with N2 gas under closed conditions and then stir to react, finally obtaining the compound shown in Formula 1;

[0097] like Figure 1 and Figure 2 As shown, the specific preparation method of the alkyl / fluoroalkyl modified benzofuranone fluorescent compound includes the following steps:

[0098]

[0099] In a 200 mL round-bottom flask, 2-bromo-3,4,5,6-tetramethoxytoluene (5.8228 g, 20 mmol), pinacol diborate (7.6182 g, 30 mmol), cesium carbonate (9.7746 g, 30 mmol), tris(4-methoxy-3,5-dimethylphenyl)phosphine (0.0960 g, 0.22 mmol) and palladium acetate (0.0449 g, 0.20 mmol) were dissolved in 80 mL of ethyl acetate. The mixture was washed three times with N2 gas under a closed system and then stirred and refluxed at 80 °C for 28 h.

[0100] After the reaction, 50 mL of DCM was added for dilution. The organic layer was washed successively with water and saturated brine, and then dried with anhydrous sodium sulfate.

[0101] Finally, column chromatography was performed using petroleum ether:ethyl acetate (V:V = 40:1) as eluent to obtain a colorless and transparent liquid, namely 4OMe-B, with a yield of 74%.

[0102] The NMR spectrum of 4OMe-B is as follows: 1 H NMR (600MHz, CDCl3) δ3.90(s,3H),3.86(s,3H),3.82(s,3H),3.74(s,3H),2.21(s,3H),1.38(s,12H).

[0103] (2) Preparation of TPE-4OMe as shown in Formula 12;

[0104]

[0105] In a 200 mL round-bottom flask, 4OMe-B (3.3824 g, 10 mmol), 2-bromo-1,1,2-triphenylene (4.0229 g, 12 mmol), potassium phosphate (6.3681 g, 30 mmol) and Pd(PPh3)4 (0.5778 g, 0.5 mmol) were dissolved in 60 mL of LDM. The mixture was washed three times with N2 gas under a closed system and stirred and refluxed at 80 °C for 30 h.

[0106] After the reaction, 50 mL of DCM was added for dilution. The organic layer was washed successively with water and saturated brine, and then dried with anhydrous sodium sulfate.

[0107] Finally, column chromatography was performed using petroleum ether:ethyl acetate (V:V = 20:1) as eluent to obtain a white solid, namely TPE-4OMe, in 60% yield.

[0108] The NMR spectrum of TPE-4OMe is as follows: 1H NMR (600MHz, CDCl3) δ7.16–6.99(m,15H),3.88(s,3H),3.83(s,3H),3.58(s,3H),3.19(s,3H),2.05(s,3H).

[0109] Preparation of 2OH as shown in Formula 13;

[0110]

[0111] In a 250 mL round-bottom flask, TPE-4OMe (4.6621 g, 10 mmol) was dissolved in 100 mL of DCM. The mixture was then washed three times with N2 under a sealed environment. 8 mL of boron tribromide (BBr3) was then slowly added dropwise. After the addition was complete, the mixture was heated to room temperature and stirred for 12 h.

[0112] After the reaction, 50 mL of DCM was added for dilution, and the reaction was quenched with water. The organic layer was washed, dried, filtered, and evaporated to obtain the filter residue.

[0113] The filter residue and p-toluenesulfonic acid monohydrate were then dissolved in DCM and stirred under reflux at 60°C for 16 hours. The organic layer was washed successively with water and saturated brine, and then dried with anhydrous sodium sulfate.

[0114] Finally, column chromatography was performed using petroleum ether:ethyl acetate (V:V = 5:1) as eluent to obtain a red solid, 2OH, in 85% yield. Its single-crystal structure is shown below. Figure 3 As shown.

[0115] The NMR spectrum of 2OH is as follows: 1 H NMR(600MHz,DMSO-d6)δ9.15(s,1H),8.76(s,1H),7.43–7.33(m,7H),7.27(t ,J=7.8Hz,2H),7.21–7.16(m,4H),6.82(dd,J=8.4,1.2Hz,2H),1.47(s,3H). 13 C NMR(151MHz,DMSO-d6)δ175.67,153.26,152.18,148.30,137.50,132.52,129.63,129.10, 128.84,128.41,127.89,127.58,127.46,126.99,106.16,100.72,11.52.HRMS(ESI)m / z:C 27 H 20 O4 for[M+H + ]calculated 409.1434, found 409.1423.

[0116] (4) Preparation of compounds 5H-Tos, 7H-Tos, and 9H-Tos;

[0117]

[0118] In a 250 mL round flask, ethanol (1.17 mL, 20 mmol), or propanol (1.50 mL, 20 mmol), or butanol (1.83 mL, 20 mmol) and p-toluenesulfonyl chloride (5.7195 g, 30 mmol) were dissolved in 80 mL of DCM. The mixture was cooled to 0 °C and stirred for 10 min. 15 mL of triethylamine was added dropwise. After the addition was complete, the mixture was heated to room temperature and stirred for 12 h.

[0119] After the reaction, 50 mL of DCM was added for dilution. The organic layer was washed successively with water and saturated brine, and then dried with anhydrous sodium sulfate.

[0120] Finally, after purification by column chromatography using petroleum ether:ethyl acetate (V:V = 5:1) as eluent, colorless and transparent liquids 5H-Tos (yield 50%), 7H-Tos (yield 67%), and 9H-Tos (yield 55%) were obtained.

[0121] (5) Preparation of compounds 3F-OTf, 5F-OTf, and 7F-OTf;

[0122]

[0123] In a 100 mL round-bottom flask, pyridine (1.48 mL, 18.75 mmol) and 50 mL DCM were mixed thoroughly, washed three times with N2 under a sealed environment, and cooled to 0 °C.

[0124] Then add dropwise 2,2,2-trifluoroethanol (1.08 mL, 15 mmol), 2,2,3,3,3-pentafluoro-1-propanol (1.49 mL, 15 mmol), and 2,2,3,3,4,4,4-heptafluoro-1-butanol (1.87 mL, 15 mmol), and stir for 10 min;

[0125] Trifluoromethanesulfonic anhydride (3.03 mL, 18 mmol) was added dropwise. After the addition was complete, the temperature was raised to room temperature and stirred for 2 hours. Then, 50 mL of DCM was added to dilute the mixture. The mixture was then washed with water and saturated saline solution in sequence.

[0126] The solution was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation at room temperature to obtain pale yellow liquids 3F-OTf, 5F-OTf, and 7F-OTf, respectively, with a yield of 25% for each.

[0127] Preparation of compounds 423H, 433H, 443H, 423F, 433F, and 443F;

[0128]

[0129] In a 50 mL round-bottom flask, 2OH (0.8163 g, 2 mmol), Cs2CO3 (2.6066 g, 8 mmol), 5H-Tos (1.2015 g, 6 mmol), 7H-Tos (1.2857 g, 6 mmol), 9H-Tos (1.3699 g, 6 mmol), 3F-OTf (1.3926 g, 6 mmol), 5F-OTf (1.6927 g, 6 mmol), and 7F-OTf (1.9927 g, 6 mmol) were dissolved in 16 mL of DMF. The mixture was then washed three times with N2 gas under a sealed environment and stirred at room temperature for 5 h.

[0130] After the reaction, 50 mL of DCM was added for dilution. The organic layer was washed successively with water and saturated brine, dried with anhydrous sodium sulfate, and finally purified by column chromatography with petroleum ether:ethyl acetate (V:V = 40:1) as eluent to obtain yellow solids 423H, 433H, 443H, 423F, 433F, and 423H, respectively.

[0131] The yields were 28%, 25%, 23%, 35%, 30%, and 28%, respectively, among which the single crystal structure of 423F was as follows: Figure 4 As shown;

[0132] The reaction process of 2OH, Cs2CO3, 5H-Tos, 7H-Tos, and 9H-Tos dissolving in DMF to obtain the compound shown in Formula 1 is detailed in the diagram. Figure 1 ;

[0133] The reaction process of 2OH, Cs2CO3, 3F-OTf, 5F-OTf, and 7F-OTf dissolving in DMF to obtain the compound shown in Formula 1 is detailed in the diagram. Figure 2 .

[0134] The NMR spectrum of 423H is as follows: 1 H NMR (600MHz, DMSO-d6) δ7.47–7.35(m,7H),7.29(t,J=7.8Hz,2H),7.20–7.14(m,4H),6.83(dd,J=7.8 ,0.6Hz,2H),4.04(q,J=7.2Hz,2H),3.97(q,J=7.2Hz,2H),1.53(s,3H),1.22(td,J=7.2,4.2Hz,6H). 13C NMR (151MHz, CDCl3) δ178.79,158.87,156.99,152.20,137.33,132.77,130.04,129.73,129.32,12 8.92,128.34,128.03,127.64,122.26,101.92,68.79,68.24,15.92,15.65,12.77.HRMS(ESI)m / z:C 31 H 28 O4 for[M+H + ]calculated465.2060, found 465.2054.

[0135] The NMR spectrum of 433H is as follows: 1 H NMR (600MHz, DMSO-d6) δ7.46–7.37(m,7H),7.29(t,J=7.8Hz,2H),7.20–7.15(m,4H),6.83(dd,J=7.8,0.6H z,2H),3.96(t,J=6.0Hz,2H),3.88(t,J=6.6Hz,2H),1.65–1.57(m,4H),1.53(s,3H),0.91(t,J=7.2Hz,6H). 13 C NMR (151MHz, CDCl3) δ178.79,158.71,156.77,152.38,137.45,132.84,130.34,129.75,129.29,128.89,1 28.33,128.03,127.72,121.88,101.86,74.73,74.38,23.72,23.33,12.69,10.54,10.46.HRMS(ESI)m / z:C 33 H 32 O4 for[M+H + ]calculated 493.2373,found493.2366.

[0136] The NMR spectrum of 443H is as follows: 1¹H NMR (600 MHz, DMSO-d₆) δ 7.41 (m, 7H), 7.29 (t, J = 7.8 Hz, 2H), 7.20–7.15 (m, 4H), 6.85–6.81 (m, 2H), 3.99 (t, J = 6.6 Hz, 2H), 3.92 (t, J = 6.6 Hz, 2H), 1.62–1.54 (m, 4H), 1.53 (s, 3H), 1.41–1.34 (m, 4H), 0.88 (t, J = 7.2 Hz, 3H), 0.82 (t, J = 7.8 Hz, 3H). 13 ¹³C NMR (151 MHz, CDCl₃) δ 178.81, 158.77, 156.75, 152.43, 137.46, 132.85, 130.32, 129.77, 129.29, 128.89, 128.33, 128.04, 127.74, 121.91, 101.87, 72.94, 72.57, 32.55, 32.18, 19.27, 19.17, 14.02, 13.99, 12.70. HRMS (ESI) m / z: C 35 H 36 O₄ for [M+H + calculated 521.2686, found 521.2679.

[0137] The NMR spectrum of 423F is: 1 ¹H NMR (600 MHz, DMSO-d₆) δ 7.48–7.39 (m, 7H), 7.32 (t, J = 7.8 Hz, 2H), 7.21–7.16 (m, 4H), 6.82 (dd, J = 7.8, 0.6 Hz, 2H), 4.69 (m, 4H), 1.57 (s, 3H). 19 ¹⁹F NMR (564 MHz, DMSO-d₆) δ -73.36 (t, J = 8.5 Hz, 3F), -73.59 (t, J = 9.6 Hz, 3F). 13 ¹³C NMR (151 MHz, CDCl₃) δ 176.65, 161.44, 159.91, 150.37, 136.37, 132.06, 129.83, 129.44, 129.27, 129.03, 128.52, 128.26, 127.97, 126.49, 126.44, 124.59, 123.35, 103.06, 68.76, 68.70, 12.50. HRMS (ESI) m / z: C 31 H 22 F₆O₄ for [M+H +]calculated 573.1495, found 573.1475.

[0138] The NMR spectrum of 433F is as follows: 1 H NMR (600MHz, DMSO-d6) δ7.48–7.38(m,7H),7.32(t,J=7.8Hz,2H),7.18(m,4H),6.82(dd,J=7.8,0.6Hz,2H),4.79(q,J=15Hz,4H),1.57(s,3H). 19 F NMR(564MHz, DMSO-d6)δ-82.55(s,3F),-82.67(s,3F),-123.48(t,J=13.5Hz,2F),-123.69(t,J=14.7Hz,2F). 13 C NMR (151MHz, CDCl3) δ176.77,161.43,159.70,150.43,136.52,132.13,129.86,129.47,129.27,128.53,128 .28,127.96,126.58,123.13,117.87,114.49,112.80,111.11,103.08,68.08,67.92,12.43.HRMS(ESI)m / z:C 33 H 22 F 10 O4 for[M+H + ]calculated673.1431, found 673.1432.

[0139] The NMR spectrum of 443F is as follows: 1 H NMR (600MHz, DMSO-d6) δ7.47–7.37(m,7H),7.32(t,J=7.8Hz,2H),7.18(m,4H),6.83(dd,J=8.4,1.2Hz,2H),4.83(m,4H),1.57(s,3H). 19 F NMR(564MHz, DMSO-d6)δ-80.45(dd,J=22.0,9.0Hz,6F),-120.69(d,J=7.9Hz,2F),-120.96(d,J=7.3Hz,2F),-126.92(s,2F),-127.03(s,2F). 13C NMR(151MHz,DMSO-d6)δ175.69,160.24,158.51,149.72,136.16,131.31,129.88,129.33,129.17,128.56,128.16,12 7.52,125.89,122.57,118.27,116.56,116.36,116.13,114.71,114.46,102.52,67.15,67.03,11.86.HRMS(ESI)m / z:C 35 H 22 F 14 O4 for[M+H + ]calculated 773.1367, found 773.1354.

[0140] The structural formulas of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, and 7F-OTf are shown below:

[0141]

[0142] In this embodiment, the molar ratio of 2-bromo-3,4,5,6-tetramethoxytoluene, pinacol diborate, cesium carbonate, tris(4-methoxy-3,5-dimethylphenyl)phosphine, palladium acetate, and ethyl acetate in step one is 1:(1-1.5):(1-1.5):(0.005-0.011):0.01:4;

[0143] In this embodiment, the ratio is 1:1.5:1.5:0.011:0.01:4.

[0144] In this embodiment, the molar ratio of 4OMe-B, 2-bromo-1,1,2-tristyrene, potassium phosphate, tetrakis(triphenylphosphine)palladium and N,N-dimethylformamide in step two is 1:(1.2-1.5):(2.0-3.0):0.05:6;

[0145] In this embodiment, the ratio is 1:1.2:3:0.05:6.

[0146] In this embodiment, the molar ratio of TPE-4OMe, BBr3 and dichloromethane in step three is 1:8:(10-20);

[0147] In this embodiment, the ratio is 1:8:10.

[0148] The mass ratio of filter residue, p-toluenesulfonic acid monohydrate, and dichloromethane is 1:3:(20-25);

[0149] In this embodiment, the ratio is 1:3:25.

[0150] In this embodiment, in step four, the molar ratio of 2OH obtained in step three to any one of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, 7F-OTf, and cesium carbonate dissolved together in N,N-dimethylformamide solvent is 1:3:(4-6):(8-15).

[0151] In this embodiment, the ratio is 1:3:4:8.

[0152] In this embodiment, the temperature of the stirring reaction in step one is 80-82℃, and the time is 24-28h;

[0153] In step two, the stirring reaction is carried out at a temperature of 80-85℃ for 24-30 hours.

[0154] In step three, the temperature of the first stirring reaction is 0-10℃, and the time is 10-12h;

[0155] The second step of the stirring reaction is carried out at a temperature of 60-65℃ for 15-18 hours.

[0156] The stirring reaction in step four is carried out at a temperature of 25-30℃ for 5-8 hours.

[0157] In this embodiment, the temperature of the stirring reaction in step one is 80°C and the time is 28 hours;

[0158] The stirring reaction in step two is carried out at a temperature of 80°C for 30 hours.

[0159] Step 3 describes the first step of the stirring reaction as having a temperature of 0°C and a time of 12 hours, and the second step of the stirring reaction as having a temperature of 60°C and a time of 16 hours.

[0160] The stirring reaction in step four is carried out at a temperature of 25°C for 5 hours.

[0161] In this embodiment, the preparation methods of 5H-Tos, 7H-Tos, and 9H-Tos are as follows: ethanol, propanol, n-butanol, and p-methylbenzenesulfonyl chloride are dissolved in DCM, cooled to 0°C, stirred for 10-15 min, and triethylamine is added dropwise. After the addition is complete, the temperature is raised to room temperature and stirred for 12-18 h. The organic layer is washed, dried, and purified by column chromatography to obtain 5H-Tos, 7H-Tos, and 9H-Tos.

[0162] The molar ratio of ethanol, propanol, n-butanol, p-toluenesulfonyl chloride, and triethylamine is 1:1.5:5; the reaction process is detailed in Equation 5-7.

[0163]

[0164] In this embodiment, the preparation methods of 3F-OTf, 5F-OTf, and 7F-OTf are as follows: pyridine and DCM are mixed evenly, washed three times with N2 gas under a sealed environment, cooled to 0°C, and then 2,2,2-trifluoroethanol, or 2,2,3,3,3-pentafluoro-1-propanol, or 2,2,3,3,4,4,4-heptafluoro-1-butanol are added dropwise. The mixture is stirred for 10-15 min, and then trifluoromethanesulfonic anhydride is added dropwise. After the addition is complete, the temperature is raised to room temperature and stirred for 2-4 h. The organic layer is washed, dried, and purified by column chromatography to obtain 3F-OTf, 5F-OTf, and 7F-OTf.

[0165] The molar ratio of 2,2,2-trifluoroethanol, or 2,2,3,3,3-pentafluoro-1-propanol, or 2,2,3,3,4,4,4-heptafluoro-1-butanol, trifluoromethanesulfonic anhydride, and triethylamine is 1:1.2:1.25; the reaction process is detailed in Formula 8-10.

[0166]

[0167] Applications of alkyl / fluoroalkyl modified benzofuranone fluorescent compounds as fluorescent paper for information encryption and security under light and heat regulation.

[0168] Example 2 Performance characterization of alkyl / fluoroalkyl modified benzofuranone fluorescent compounds: Compounds 423F and 423H were used for performance characterization.

[0169] Decomposition temperature test

[0170] The decomposition temperatures of compounds 423F and 423H were tested using a thermogravimetric analyzer (TG).

[0171] The results showed that the decomposition temperature of compound 423F was 217℃. Figure 5 The decomposition temperature of compound 423H is 284℃. Figure 6 ).

[0172] Liquid UV absorption and fluorescence performance testing

[0173] Compounds 423F and 423H were prepared into different concentrations (1×10⁻⁶) by mixing deionized water and tetrahydrofuran in different proportions. - 3 mol / L, 1×10 -4 A mixed solution (water volume contents of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90% by volume) was prepared, and its absorption spectrum (1×10⁻⁶) was measured at different proportions. -4 (mol / L), and the emission spectra of mixed solutions with different proportions were measured using a fluorescence spectrometer with 330 nm excitation light (1×10). -3mol / L (in order) Figure 7 , Figure 8 ).

[0174] The results showed that as the proportion of deionized water increased (0%-90%), the fluorescence intensity of compounds 423F and 423H gradually increased, both exhibiting aggregation-induced emission (AIE) properties.

[0175] Photo / thermal / mechanical fluorescence color change performance test

[0176] Compound 423F was continuously irradiated under 365 nm ultraviolet light for 15 min. Then, a portion of the irradiated compound 423F was heated to 110 °C, while the other portion was ground in a mortar. The changes in solid fluorescence of compound 423F and the emission spectrum of the fluorescence were observed during the process.

[0177] The results showed that under 365 nm ultraviolet light irradiation, compound 423F initially exhibited orange fluorescence, but as the irradiation time was extended to 15 min, the fluorescence of the compound changed from orange to yellow, showing photoluminescence color change performance; when the irradiated compound was heated to 110 °C or ground, the fluorescence of the compound changed from yellow to orange, showing thermo / mechanical fluorescence color change performance.

[0178] The solid fluorescence changes of compound 423F in different states are shown in the figure below. Figure 9 As shown.

[0179] Solid-state fluorescence spectra of compound 423F in different states are shown below. Figure 10 As shown, the maximum emission wavelength λ of compound 423F in its initial state is... em The wavelength is 575nm. After being irradiated with 365nm ultraviolet light for 15 minutes, the maximum emission wavelength λ em The blue shift was 556 nm. A portion of the irradiated compound 423F was then ground to achieve the maximum emission wavelength λ. em The redshift was 567 nm. Heating another portion of the irradiated compound 423F to 110 °C resulted in the maximum emission wavelength λ. em The redshift is 575nm.

[0180] In this embodiment, the yellow fluorescence of the irradiated compound 423F can be restored to its initial orange fluorescence by heating it to 110°C.

[0181] Solid-state fluorescence changes and solid-state fluorescence spectra of compounds 423H, 433H, 443H, 433F, and 443F in different states (in order) Figure 11 , Figure 12 , Figure 13 , Figure 14 , Figure 15 ).

[0182] The results showed that compounds 423H, 433H, 443H, 433F, and 443F, like compound 423F, all exhibit photo / thermal induced fluorescence color-changing properties.

[0183] Compound 423F was used to prepare fluorescent paper that can be used for information storage under light and heat modulation.

[0184] Compound 423F was loaded onto high-temperature resistant black cardstock. Under 365nm ultraviolet light irradiation assisted by a photomask with a crescent pattern, the crescent pattern was recorded on the paper. The information of the crescent pattern could be read under 365nm ultraviolet light irradiation, and the pattern could be removed by heating to 110℃, achieving a self-extinguishing effect and allowing for reuse. Figure 16 ).

[0185] In summary, the alkyl / fluoroalkyl modified benzofuranone fluorescent compound provided by this invention, which simultaneously connects two alkyl / fluoroalkyl chains and contains three benzene ring substituent structural units, exhibits photo / thermal / mechanical multi-stimulus response properties. Under the regulation of light and heat, reversible fluorescence conversion can be achieved. It can be applied to the preparation of photothermal dual-stimulus responsive fluorescent materials and has broad application prospects in the fields of information encryption and security, data recording and storage, optoelectronic devices, molecular logic gates, and bioimaging.

[0186] The above are merely further embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope disclosed in the present invention, based on the technical solution and concept of the present invention, shall fall within the scope of protection of the present invention.

Claims

1. An alkyl / fluoroalkyl-modified benzofuranone fluorescent compound, characterized in that, The fluorescent compound is selected from: 。 2. The method for preparing the alkyl / fluoroalkyl modified benzofuranone fluorescent compound as described in claim 1, characterized in that, Includes the following steps: Step 1: 2-bromo-3,4,5,6-tetramethoxytoluene, pinacol diborate, cesium carbonate, tris(4-methoxy-3,5-dimethylphenyl)phosphine and palladium acetate were dissolved in ethyl acetate. The mixture was stirred and reacted under N2 gas under closed conditions. The organic layer was washed, dried and purified by column chromatography to obtain 4OMe-B. ； Step 2: Dissolve 2-bromo-1,1,2-tristyrene, 4OMe-B, potassium phosphate, and tetrakis(triphenylphosphine)palladium in... N, N In dimethylformamide, the reaction was carried out under closed conditions with N2 washing and stirring. The organic layer was washed, dried and purified by column chromatography to obtain TPE-4OMe. ; Step 3: Dissolve the TPE-4OMe obtained in Step 2 in dichloromethane, wash with N2 gas under closed conditions, slowly add BBr3 dropwise under ice bath conditions and stir the reaction, then add dichloromethane, add water to quench the reaction, and the organic layer is washed, dried, filtered and rotary dried to obtain filter residue. Dissolve the obtained filter residue and p-toluenesulfonic acid monohydrate in dichloromethane and stir the reaction. The organic layer is washed, dried and purified by column chromatography to obtain 2OH. ； Step 4: Dissolve the 2OH obtained in Step 3 together with any one of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, 7F-OTf, and cesium carbonate in... N , N In dimethylformamide solvent, the mixture was washed with N2 gas under closed conditions and then stirred to finally obtain fluorescent compounds 423H, 433H, 443H, 423F, 433F and 443F; The structural formulas of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, and 7F-OTf are shown below: 。 3. The method for preparing the alkyl / fluoroalkyl modified benzofuranone fluorescent compound according to claim 2, characterized in that, In step one, the molar ratio of 2-bromo-3,4,5,6-tetramethoxytoluene, pinacol diboronate, cesium carbonate, tris(4-methoxy-3,5-dimethylphenyl)phosphine, palladium acetate, and ethyl acetate is 1:(1-1.5):(1-1.5):(0.005-0.011):0.01:

4.

4. The method for preparing the alkyl / fluoroalkyl modified benzofuranone fluorescent compound according to claim 3, characterized in that, In step two, 4OMe-B, 2-bromo-1,1,2-tristyrene, potassium phosphate, tetrakis(triphenylphosphine)palladium and N, N The molar ratio of dimethylformamide is 1:(1.2-1.5):(2.0-3.0):0.05:

6.

5. The method for preparing the alkyl / fluoroalkyl modified benzofuranone fluorescent compound according to claim 4, characterized in that, In step three, the molar ratio of TPE-4OMe, BBr3 and dichloromethane is 1:8:(10-20); the mass ratio of filter residue, p-toluenesulfonic acid monohydrate and dichloromethane is 1:3:(20-25).

6. The method for preparing the alkyl / fluoroalkyl modified benzofuranone fluorescent compound according to claim 5, characterized in that, In step four, the 2OH obtained in step three is dissolved together with any one of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, 7F-OTf, and cesium carbonate in... N, N The molar ratio of the dimethylformamide solvent is 1:3:(4-6):(8-15).

7. The method for preparing the alkyl / fluoroalkyl modified benzofuranone fluorescent compound according to claim 6, characterized in that, In step one, the stirring reaction is carried out at a temperature of 80-82℃ for 24-28 hours. In step two, the stirring reaction is carried out at a temperature of 80-85℃ for 24-30 hours. In step three, the temperature of the first stirring reaction is 0-10℃, and the time is 10-12h; The second step of the stirring reaction is carried out at a temperature of 60-65 ℃ for 15-18 hours. The stirring reaction in step four is carried out at a temperature of 25-30℃ for 5-8 hours.

8. The method for preparing the alkyl / fluoroalkyl modified benzofuranone fluorescent compound according to claim 2, characterized in that, The preparation methods for 5H-Tos, 7H-Tos, and 9H-Tos in step four are as follows: Ethanol, propanol or n-butanol were dissolved in p-methylbenzenesulfonyl chloride in DCM, cooled to 0°C, stirred for 10-15 min, and triethylamine was added dropwise. After the addition was complete, the temperature was raised to room temperature and stirred for 12-18 h. The organic layer was washed, dried and purified by column chromatography to obtain 5H-Tos, 7H-Tos and 9H-Tos. The molar ratio of ethanol, propanol or n-butanol to p-methylbenzenesulfonyl chloride and triethylamine is 1:1.5:

5.

9. The method for preparing the alkyl / fluoroalkyl modified benzofuranone fluorescent compound according to claim 2, characterized in that, The preparation method of 3F-OTf, 5F-OTf, or 7F-OTf in step four is as follows: Pyridine and dichloromethane were mixed evenly, washed three times with N2 gas under a sealed environment, and cooled to 0°C. Then, one of 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol, or 2,2,3,3,4,4,4-heptafluoro-1-butanol was added dropwise. The mixture was stirred for 10-15 min, and then trifluoromethanesulfonic anhydride was added dropwise. After the addition was complete, the mixture was heated to room temperature and stirred for 2-4 h. The organic layer was washed, dried, and purified by column chromatography to obtain 3F-OTf, 5F-OTf, or 7F-Otf, respectively. The molar ratios of 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol, or 2,2,3,3,4,4,4-heptafluoro-1-butanol to trifluoromethanesulfonic anhydride and pyridine are all 1:1.2:1.

25.

10. The application of the alkyl / fluoroalkyl modified benzofuranone fluorescent compound according to claim 1 in the preparation of fluorescent paper, wherein the fluorescent paper is used for information encryption, and the information encryption is achieved through light and heat modulation.

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