CN117756759A - Alkyl/fluoroalkyl modified benzofuranone fluorescent compounds and preparation methods and applications - Google Patents

Abstract

The invention discloses an alkyl/fluoroalkyl modified benzofuranone fluorescent compound and a preparation method and application thereof, belonging to the technical field of alkyl/fluoroalkyl modified benzofuranone fluorescent compounds, wherein the compound is simultaneously connected with two alkyl/fluoroalkyl chains and contains three benzene ring substituent structural units, and the compounds are orange fluorescent when ultraviolet light at 365nm just begins to irradiate, but the fluorescent color of the compound is changed from orange to yellow along with the irradiation time of an ultraviolet lamp being prolonged to 15min, so that the compound shows photochromic property; when the compound after illumination is heated to 110 ℃ or ground, the compound fluorescence is recovered from yellow to orange in an initial state, the thermal/mechanochromic property is shown, the reversible conversion of fluorescence can be realized under the regulation and control of light and heat, the compound can be used for preparing a photo-thermal dual-stimulus response fluorescent material, and the compound has wide application prospect in the fields of information encryption and safety, data recording and storage, photoelectric devices, molecular logic gates and biological imaging.

Description

Alkyl/fluoroalkyl modified benzofuranone fluorescent compounds and preparation methods and applications

Technical field

The invention relates to an alkyl/fluoroalkyl modified benzofuranone fluorescent compound, in particular to an alkyl/fluoroalkyl modified benzofuranone fluorescent compound and its preparation method and application, which belongs to the alkyl/fluoroalkyl modified benzene Technical field of furanone fluorescent compounds.

Background technique

The prior art provides application number CN1328109A - aromatic heterocyclic substituted dibenzofuropyran photochromic compound and its preparation method and use. The invention adopts the reversible color of the compound itself before and after photothermal stimulation. Change, suitable for preparing photochromic ink, photochromic plastic film, organic photochromic resin glasses or photochromic display materials for printing anti-counterfeiting trademarks;

The prior art also discloses a colorless benzofuranone compound and its preparation method with application number CN1680369A. This invention uses a single thermal stimulation process to realize the color change process of the compound itself, and is suitable for making Monomers for heat-sensitive dyes and polymer synthesis;

In addition, in the prior art, light, external force, temperature, magnetic field, polarity, pH, etc. are used as stimulation sources to stimulate changes in the fluorescence response of fluorescent materials;

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 reuse, and cannot meet the requirements of information encryption, security, and data. Diversified application requirements in the fields of recording and storage, optoelectronic devices, molecular logic gates and biological imaging. For this reason, an alkyl/fluoroalkyl modified benzofuranone fluorescent compound, preparation method and application are designed to solve the above technical problems.

Contents of the invention

The main purpose of the present invention is to provide alkyl/fluoroalkyl modified benzofuranone fluorescent compounds, preparation methods and applications, and solve the problems in the prior art that fluorescent compounds have a relatively simple stimulus response, poor fluorescence reversibility and are not suitable for information encryption and Issues in the areas of security, data recording and storage, optoelectronic devices, molecular logic gates, and biological imaging.

The object of the present invention can be achieved by adopting the following technical solutions:

The alkyl/fluoroalkyl modified benzofuranone fluorescent compound is shown in Formula 1:

The alkyl/fluoroalkyl modified benzofuranone fluorescent compound simultaneously connects two alkyl/fluoroalkyl chains and contains three benzene ring substituent structural units;

In formula 1, R ₁ and R ₂ are both alkyl groups, and R ₁ and R ₂ are the same alkyl group.

Preferably, R ₁ and R ₂ are ethyl, n-propyl, n-butyl, 1,1,1-trifluoroethyl, 1,1,1,2,2-pentafluoro-n-propyl, 1,1 , any one of 1,2,2,3,3-heptafluoro-n-butyl;

Among them, 423H indicates that R ₁ and R ₂ are ethyl;

433H means R ₁ and R ₂ are n-propyl;

443H indicates that R ₁ and R ₂ are n-butyl;

423F indicates that R ₁ and R ₂ are 1,1,1-trifluoroethyl;

433F indicates that R ₁ and R ₂ are 1,1,1,2,2-pentafluoro-n-propyl;

443F indicates that R ₁ and R ₂ are 1,1,1,2,2,3,3-heptafluoro-n-butyl.

The preparation method of alkyl/fluoroalkyl modified benzofuranone fluorescent compounds includes the following steps:

Step 1: Combine 2-bromo-3,4,5,6-tetramethoxytoluene, pinacol diborate, cesium carbonate, and tris(4-methoxy-3,5-dimethylphenyl) Phosphine and palladium acetate are dissolved in ethyl acetate, and the reaction is stirred after being purged with N ₂ under closed conditions. The organic layer is washed, dried and purified by column chromatography to obtain 4OMe-B. The reaction formula is detailed in Formula 2:

Step 2: Dissolve 2-bromo-1,1,2-tristyrene, 4OMe-B, potassium phosphate and tetrakis(triphenylphosphine)palladium in N,N-dimethylformamide, and pass through N under closed conditions. _2. After gas washing, a stirring reaction is carried out. The organic layer is washed, dried and purified by column chromatography to obtain TPE-4OMe. The reaction formula is detailed in Formula 3:

Step 3: Dissolve the TPE-4OMe obtained in Step 2 in methylene chloride, purge it with N ₂ under closed conditions, slowly drop BBr ₃ under ice bath conditions, stir the reaction, and then add methylene chloride. Add water to quench the reaction. The organic layer is washed, dried, filtered and spin-dried to obtain a filter residue. The obtained filter residue and p-toluenesulfonic acid monohydrate are dissolved in dichloromethane for stirring reaction. The organic layer is washed, dried and column-dried. After chromatography purification, 2OH is obtained. The reaction formula is shown in Formula 4:

Step 4: Dissolve the 2OH obtained in step 3 with any one of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, 7F-OTf and cesium carbonate in N, N-di In the methylformamide solvent, the mixture is purged with N ₂ under closed conditions and then stirred to react, and finally the compound represented by Formula 1 is obtained;

The structural formulas of the 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, and 7F-OTf are as follows:

Preferably, in step one, 2-bromo-3,4,5,6-tetramethoxytoluene, pinacol diborate, cesium carbonate, tris(4-methoxy-3,5-dimethyl The molar ratio of phenyl)phosphine, palladium acetate and ethyl acetate is 1: (1-1.5): (1-1.5): (0.005-0.011): 0.01:4;

The preferred ratio is 1:1.5:1.5:0.011:0.01:4.

Preferably, the moles of 4OMe-B, 2-bromo-1,1,2-tristyrene, potassium phosphate, tetrakis(triphenylphosphine)palladium and N,N-dimethylformamide described in step 2 The ratio is 1: (1.2-1.5): (2.0-3.0): 0.05: 6;

The preferred ratio is 1:1.2:3:0.05:6.

Preferably, in step three, the molar ratio of TPE-4OMe, BBr ₃ and methylene chloride is 1:8: (10-20);

The preferred ratio is 1:8:10.

The mass ratio of filter residue, p-toluenesulfonic acid monohydrate and methylene chloride is 1:3: (20-25);

The preferred ratio is 1:3:25.

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

The preferred ratio is 1:3:4:8.

Preferably, the temperature of the stirring reaction in step one is 80-82°C, and the time is 24-28 hours;

In step 2, the temperature of the stirring reaction is 80-85°C and the time is 24-30h;

In the first step of step three, the temperature of the stirring reaction is 0-10°C and the time is 10-12 hours;

In the second step, the temperature of the stirring reaction is 60-65°C and the time is 15-18h;

The temperature of the stirring reaction described in step 4 is 25-30°C, and the time is 5-8 hours.

Preferably, the temperature of the stirring reaction described in step 1 is 80°C and the time is 28 hours;

The temperature of the stirring reaction described in step 2 is 80°C and the time is 30h;

In Step 3, the temperature of the first step of the stirring reaction is 0°C and the time is 12h, and the temperature of the second step of the stirring reaction is 60°C and the time is 16h;

The temperature of the stirring reaction described in step 4 is 25°C and the time is 5 hours.

Preferably, the preparation method of 5H-Tos, 7H-Tos, and 9H-Tos is as follows: dissolve ethanol, propanol, n-butanol and p-toluenesulfonyl chloride in DCM, cool to 0°C, stir for 10-15min, and gradually Add triethylamine dropwise. After the addition is completed, the mixture is heated to room temperature and stirred for 12-18 hours. The organic layer is washed, dried and purified by column chromatography to obtain 5H-Tos, 7H-Tos, and 9H-Tos.

Among them, the molar ratios of ethanol, propanol, n-butanol, p-toluenesulfonyl chloride, and triethylamine are all 1:1.5:5; the reaction process is detailed in Formula 5-7:

Preferably, the preparation method of 3F-OTf, 5F-OTf, and 7F-OTf is as follows: mix pyridine and DCM evenly, purge with N ₂ three times under airtight, cool to 0°C, and then add 2,2,2-tris dropwise. Fluoroethanol, or 2,2,3,3,3-pentafluoro-1-propanol, or 2,2,3,3,4,4,4-heptafluoro-1-butanol, stir for 10-15 minutes, Add trifluoromethanesulfonic anhydride drop by drop. After the addition is completed, the temperature is raised to room temperature and stirred for 2-4 hours. The organic layer is washed, dried and purified by column chromatography to obtain 3F-OTf, 5F-OTf, and 7F-OTf;

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

Application of alkyl/fluoroalkyl modified benzofuranone fluorescent compounds as fluorescent paper for information encryption and security under light and thermal regulation.

Beneficial technical effects of the present invention:

The invention provides alkyl/fluoroalkyl modified benzofuranone fluorescent compounds, preparation methods and applications. This type of compound simultaneously connects two alkyl/fluoroalkyl chains and contains three benzene ring substituent structural units. These compounds The compound fluoresces orange when first irradiated with 365nm ultraviolet light. However, as the irradiation time of the ultraviolet light is extended to 15 minutes, the compound's fluorescence changes from orange to yellow, showing photofluorescence discoloration properties; when the irradiated compound is heated to 110°C Or when grinding, the compound's fluorescence returns from yellow to the original orange state, showing thermal/mechanical fluorescence discoloration properties;

Reversible conversion of fluorescence can be achieved under the control of light and heat, and can be used to prepare photothermal dual stimulus-responsive fluorescent materials. It has broad applications in the fields of information encryption and security, data recording and storage, optoelectronic devices, molecular logic gates, and biological imaging. prospect.

Description of drawings

Figure 1 is a reaction process diagram of the reaction of 2OH, 5H-Tos, or 7H-Tos, or 9H-Tos, and cesium carbonate dissolved in N,N-dimethylformamide solvent to obtain the compound represented by Formula 1.

Figure 2 is a reaction process diagram of the reaction of 2OH, 3F-OTf, or 5F-OTf, or 7F-OTf, and cesium carbonate dissolved in N,N-dimethylformamide solvent to obtain the compound represented by Formula 1.

Figure 3 is a single crystal structure diagram of compound 2OH.

Figure 4 is a single crystal structure diagram of compound 423F.

Figure 5 is the thermogravimetric analysis spectrum (TG spectrum) of compound 423F.

Figure 6 is the thermogravimetric analysis spectrum (TG spectrum) of compound 423H.

Figure 7 shows the UV absorption and fluorescence spectra of compound 423F in mixed solvents of water and tetrahydrofuran in different proportions.

Figure 8 shows the UV absorption and fluorescence spectra of compound 423H in mixed solvents of water and tetrahydrofuran in different proportions.

Figure 9 shows the solid fluorescence changes of compound 423F in different states.

Figure 10 shows the solid fluorescence spectra of compound 423F in different states.

Figure 11 shows the solid fluorescence change diagram and solid fluorescence spectrum diagram of compound 423H in different states.

Figure 12 shows the solid fluorescence change diagram and solid fluorescence spectrum diagram of compound 433H in different states.

Figure 13 shows the solid fluorescence change diagram and solid fluorescence spectrum diagram of compound 443H in different states.

Figure 14 shows the solid fluorescence change diagram and solid fluorescence spectrum diagram of compound 433F in different states.

Figure 15 shows the solid fluorescence change diagram and solid fluorescence spectrum diagram of compound 443F in different states.

Figure 16 shows the change of compound 423F when used to prepare fluorescent paper for information storage under light and thermal regulation.

Detailed ways

In order to make the technical solution of the present invention clearer and clearer to those skilled in the art, the present invention will be described in further detail below in conjunction with the examples and drawings, but the implementation of the present invention is not limited thereto.

The experimental methods in the following examples, unless otherwise specified, are all conventional methods. The test materials used in the following examples, unless otherwise specified, can be purchased through conventional commercial channels.

The alkyl/fluoroalkyl modified benzofuranone fluorescent compound is shown in Formula 1:

The alkyl/fluoroalkyl modified benzofuranone fluorescent compound simultaneously connects two alkyl/fluoroalkyl chains and contains three benzene ring substituent structural units;

In formula 1, R ₁ and R ₂ are both alkyl groups, and R ₁ and R ₂ are the same alkyl group.

In this embodiment, R ₁ and R ₂ are ethyl, n-propyl, n-butyl, 1,1,1-trifluoroethyl, 1,1,1,2,2-pentafluoro-n-propyl, Any one of 1,1,1,2,2,3,3-heptafluoro-n-butyl;

Among them, 423H indicates that R ₁ and R ₂ are ethyl;

433H means that R ₁ and R ₂ are n-propyl;

443H indicates that R ₁ and R ₂ are n-butyl;

423F indicates that R ₁ and R ₂ are 1,1,1-trifluoroethyl;

433F indicates that R ₁ and R ₂ are 1,1,1,2,2-pentafluoro-n-propyl;

443F indicates that R ₁ and R ₂ are 1,1,1,2,2,3,3-heptafluoro-n-butyl.

The preparation method of alkyl/fluoroalkyl modified benzofuranone fluorescent compounds includes the following steps:

Step 1: Combine 2-bromo-3,4,5,6-tetramethoxytoluene, pinacol diborate, cesium carbonate, and tris(4-methoxy-3,5-dimethylphenyl) Phosphine and palladium acetate are dissolved in ethyl acetate, and the reaction is stirred after being purged with N ₂ under closed conditions. The organic layer is washed, dried and purified by column chromatography to obtain 4OMe-B. The reaction formula is detailed in Formula 2:

Step 2: Dissolve 2-bromo-1,1,2-tristyrene, 4OMe-B, potassium phosphate and tetrakis(triphenylphosphine)palladium in N,N-dimethylformamide, and pass through N under closed conditions. _2. After gas washing, a stirring reaction is carried out. The organic layer is washed, dried and purified by column chromatography to obtain TPE-4OMe. The reaction formula is detailed in Formula 3:

Step 3: Dissolve the TPE-4OMe obtained in Step 2 in methylene chloride, purge it with N ₂ under closed conditions, slowly drop BBr ₃ under ice bath conditions, stir the reaction, and then add methylene chloride. Add water to quench the reaction. The organic layer is washed, dried, filtered and spin-dried to obtain a filter residue. The obtained filter residue and p-toluenesulfonic acid monohydrate are dissolved in dichloromethane for stirring reaction. The organic layer is washed, dried and column-dried. After chromatography purification, 2OH is obtained. The reaction formula is shown in Formula 4:

Step 4: Dissolve the 2OH obtained in step 3 with any one of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, 7F-OTf and cesium carbonate in N, N-di In the methylformamide solvent, the mixture is purged with N ₂ under closed conditions and then stirred to react, and finally the compound represented by Formula 1 is obtained;

As shown in Figures 1 and 2, the specific preparation method of alkyl/fluoroalkyl-modified benzofuranone fluorescent compounds includes the following steps:

In a 200mL round-bottomed flask, combine 2-bromo-3,4,5,6-tetramethoxytoluene (5.8228g, 20mmol), pinacol diborate (7.6182g, 30mmol), and cesium carbonate (9.7746g , 30mmol), tris(4-methoxy-3,5-dimethylphenyl)phosphine (0.0960g, 0.22mmol) and palladium acetate (0.0449g, 0.20mmol) were dissolved in 80mL ethyl acetate, sealed and passed through Purge with _N2 three times, and react with stirring and reflux at 80°C for 28 h.

After the reaction, 50 mL of DCM was added to dilute, and the organic layer was washed with water and saturated brine in sequence, and then dried over anhydrous sodium sulfate.

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

The nuclear magnetic spectrum of 4OMe-B is: ¹ H NMR (600MHz, CDCl ₃ ) δ3.90(s,3H),3.86(s,3H),3.82(s,3H),3.74(s,3H),2.21(s ,3H),1.38(s,12H).

(2) Preparation of TPE-4OMe shown in formula 12;

In a 200mL round-bottomed flask, combine 4OMe-B (3.3824g, 10mmol), 2-bromo-1,1,2-tristyrene (4.0229g, 12mmol), potassium phosphate (6.3681g, 30mmol) and Pd(PPh ₃ ) ₄ (0.5778g, 0.5mmol) was dissolved in 60mL DMF, purged with N ₂ three times under airtight, and stirred and refluxed at 80°C for 30h.

After the reaction, 50 mL of DCM was added to dilute, and the organic layer was washed with water and saturated brine in sequence, and then dried over anhydrous sodium sulfate.

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

The nuclear magnetic spectrum of TPE-4OMe is: ¹ H NMR (600MHz, CDCl ₃ ) 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).

Preparation of 2OH shown in Formula 13;

In a 250mL round-bottomed flask, dissolve TPE-4OMe (4.6621g, 10mmol) in 100mL DCM, purge it with _N2 for three times under seal, and then slowly drop 8mL of boron tribromide ( _BBr3 ) into it. After the dripping is completed, Warm up to room temperature and stir for 12h.

After the reaction, 50 mL of DCM was added to dilute, and water was added to quench the reaction. The organic layer was washed, dried, filtered, and spin-dried to obtain the filter residue.

Then dissolve the filter residue and p-toluenesulfonic acid monohydrate in DCM, stir and reflux for 16 hours at 60°C, wash the organic layer with water and saturated brine in sequence, and dry with anhydrous sodium sulfate.

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

The nuclear magnetic spectrum of 2OH is: ¹ H NMR (600MHz, DMSO-d ₆ ) 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-d ₆ )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 O ₄ for[M+ H ⁺ ] calculated 409.1434, found 409.1423.

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

Dissolve ethanol (1.17mL, 20mmol), or propanol (1.50mL, 20mmol), or butanol (1.83mL, 20mmol) and p-toluenesulfonyl chloride (5.7195g, 30mmol) in 80mL DCM in a 250mL round flask, After cooling to 0°C, stir for 10 min. Add 15 mL of triethylamine dropwise. After the dripping is completed, warm to room temperature and stir for 12 h.

After the reaction, 50 mL of DCM was added to dilute, and the organic layer was washed with water and saturated brine in sequence, and then dried over anhydrous sodium sulfate.

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

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

In a 100 mL round-bottomed flask, mix pyridine (1.48 mL, 18.75 mmol) and 50 mL DCM evenly, purge with N ₂ for three times under seal, and cool to 0°C;

Then, 2,2,2-trifluoroethanol (1.08mL, 15mmol), 2,2,3,3,3-pentafluoro-1-propanol (1.49mL, 15mmol), 2,2,3,3 were added dropwise. , 4,4,4-heptafluoro-1-butanol (1.87mL, 15mmol), stir for 10min;

Add trifluoromethanesulfonic anhydride (3.03 mL, 18 mmol) drop by drop. After the drops are completed, warm to room temperature, stir for 2 hours, add 50 mL DCM to dilute, and wash with water and saturated saline in sequence;

Dry with anhydrous sodium sulfate, and finally spin off the solvent at room temperature to obtain light yellow liquids 3F-OTf, 5F-OTf, and 7F-OTf, respectively, with yields of 25%.

Preparation of compounds 423H, 433H, 443H, 423F, 433F, 443F;

In a 50mL round bottom flask, add 2OH (0.8163g, 2mmol), Cs ₂ CO ₃ (2.6066g, 8mmol), 5H-Tos (1.2015g, 6mmol), 7H-Tos (1.2857g, 6mmol), 9H-Tos (1.3699g, 6mmol), 3F-OTf (1.3926g, 6mmol), 5F-OTf (1.6927g, 6mmol), 7F-OTf (1.9927g, 6mmol) were dissolved in 16mL DMF, and were purged with N ₂ three times under airtight. Stir and react at room temperature for 5 hours;

After the reaction, 50 mL of DCM was added to dilute, and the organic layer was washed with water and saturated brine in sequence, and then dried with anhydrous sodium sulfate. Finally, column chromatography was performed using petroleum ether: ethyl acetate (V: V = 40:1) as an eluent. After purification, yellow solid 423H, yellow solid 433H, yellow solid 443H, yellow solid 423F, yellow solid 433F, and yellow solid 423H were obtained respectively;

The yields are 28%, 25%, 23%, 35%, 30%, and 28% respectively. The single crystal structure of 423F is shown in Figure 4;

The reaction process diagram of 2OH, Cs ₂ CO ₃ , 5H-Tos, 7H-Tos, and 9H-Tos dissolved in DMF to obtain the compound represented by Formula 1 is shown in Figure 1;

The reaction process of 2OH, Cs ₂ CO ₃ , 3F-OTf, 5F-OTf, and 7F-OTf dissolved in DMF to obtain the compound represented by Formula 1 is shown in Figure 2 for details.

The nuclear magnetic spectrum of 423H is: ¹ H NMR (600MHz, DMSO-d ₆ ) 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). ¹³ C NMR (151MHz, CDCl ₃ ) δ178.79,158.87,156.99,152.20,137.33,132.77,130.04,129.73,129.32,128.92,128.34,128.03,127.64,1 22.26,101.92,68.79,68.24 ,15.92,15.65,12.77.HRMS(ESI)m/z:C ₃₁ H ₂₈ O ₄ for[M+H ⁺ ]calculated465.2060, found 465.2054.

The nuclear magnetic spectrum of 433H is: ¹ H NMR (600MHz, DMSO-d ₆ ) δ7.46–7.37 (m, 7H), 7.29 (t, J = 7.8Hz, 2H), 7.20–7.15 (m, 4H), 6.83 (dd,J＝7.8,0.6Hz,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, CDCl ₃ ) δ 178.79, 158.71, 156.77, 152.38, 137.45, 132.84, 130.34, 129.75, 129.29, 128.89, 128.33, 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 O ₄ for[M+H ⁺ ]calculated 493.2373,found493.2366.

The nuclear magnetic spectrum of 443H is: ¹ H NMR (600MHz, DMSO-d ₆ ) δ7.41 (m, 7H), 7.29 (t, J = 7.8Hz, 2H), 7.20–7.15 (m, 4H), 6.85–6.81 (m,2H),3.99(t,J＝6.6Hz,2H),3.92(t,J＝6.6Hz,2H),1.62–1.54(m,4H),1.53(s,3H),1.41–1.34( m, 4H), 0.88 (t, J = 7.2Hz, 3H), 0.82 (t, J = 7.8Hz, 3H). ¹³ C NMR (151MHz, CDCl ₃ ) 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 O ₄ for[M+H ⁺ ]calculated521.2686, found 521.2679.

The nuclear magnetic spectrum of 423F is: ¹ H NMR (600MHz, DMSO-d ₆ ) δ7.48–7.39 (m, 7H), 7.32 (t, J = 7.8Hz, 2H), 7.21–7.16 (m, 4H), 6.82 (dd, J＝7.8, 0.6Hz, 2H), 4.69 (m, 4H), 1.57 (s, 3H). ¹⁹ F NMR (564MHz, DMSO-d ₆ ) δ-73.36 (t, J＝8.5Hz, 3F ), -73.59 (t, J=9.6Hz, 3F). ¹³ C NMR (151MHz, CDCl ₃ ) δ176.65,161.44,159.91,150.37,136.37,132.06,129.83,129.44,129.27,129.03,128.52,128.26, 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 F ₆ O ₄ for[M+H ⁺ ]calculated 573.1495,found 573.1475.

The nuclear magnetic spectrum of 433F is: ¹ H NMR (600MHz, DMSO-d ₆ ) 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-d ₆ )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, CDCl ₃ ) δ 176.77, 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 O ₄ for[M+H ⁺ ]calculated673.1431, found 673.1432.

The nuclear magnetic spectrum of 443F is: ¹ H NMR (600MHz, DMSO-d ₆ ) 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-d ₆ ) 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). ¹³ C NMR(151MHz, DMSO-d ₆ )δ175.69,160.24,158.51,149.72,136.16,131.31,129.88,129.33,129.17,128.56,128.16,127.52,125.89,122.57,118.27,116.56,116. 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 O ₄ for[M+H ⁺ ]calculated 773.1367, found 773.1354.

The structural formulas of the 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, and 7F-OTf are as follows:

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

In this embodiment, it is 1:1.5:1.5:0.011:0.01:4.

In this example, 4OMe-B, 2-bromo-1,1,2-tristyrene, potassium phosphate, tetrakis(triphenylphosphine)palladium and N,N-dimethylmethylmethane were used in step 2. The molar ratio of amide is 1: (1.2-1.5): (2.0-3.0): 0.05:6;

In this embodiment, it is 1:1.2:3:0.05:6.

In this embodiment, the molar ratio of TPE-4OMe, BBr ₃ and methylene chloride in step three is 1:8: (10-20);

In this embodiment, it is 1:8:10.

The mass ratio of filter residue, p-toluenesulfonic acid monohydrate and methylene chloride is 1:3: (20-25);

In this embodiment, it is 1:3:25.

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

In this embodiment, it is 1:3:4:8.

In this embodiment, the temperature of the stirring reaction in step 1 is 80-82°C, and the time is 24-28h;

In step 2, the temperature of the stirring reaction is 80-85°C and the time is 24-30h;

In the first step of step three, the temperature of the stirring reaction is 0-10°C and the time is 10-12 hours;

In the second step, the temperature of the stirring reaction is 60-65°C and the time is 15-18h;

The temperature of the stirring reaction described in step 4 is 25-30°C, and the time is 5-8 hours.

In this example, the temperature of the stirring reaction described in step 1 is 80°C, and the time is 28 hours;

The temperature of the stirring reaction described in step 2 is 80°C and the time is 30h;

In Step 3, the temperature of the first step of the stirring reaction is 0°C and the time is 12h, and the temperature of the second step of the stirring reaction is 60°C and the time is 16h;

The temperature of the stirring reaction described in step 4 is 25°C and the time is 5 hours.

In this example, the preparation method of 5H-Tos, 7H-Tos, and 9H-Tos is as follows: dissolve ethanol, propanol, n-butanol and p-toluenesulfonyl chloride in DCM, cool to 0°C, and stir for 10- Add triethylamine dropwise for 15 minutes. After the addition is completed, the temperature is raised to room temperature and stirred for 12-18 hours. The organic layer is washed, dried and purified by column chromatography to obtain 5H-Tos, 7H-Tos, and 9H-Tos.

Among them, the molar ratios of ethanol, propanol, n-butanol, p-toluenesulfonyl chloride, and triethylamine are all 1:1.5:5; the reaction process is detailed in Formula 5-7:

In this embodiment, the preparation method of 3F-OTf, 5F-OTf, and 7F-OTf is as follows: mix pyridine and DCM evenly, purge with N ₂ three times under airtight, cool to 0°C, and then dropwise add 2,2, 2-Trifluoroethanol, or 2,2,3,3,3-pentafluoro-1-propanol, or 2,2,3,3,4,4,4-heptafluoro-1-butanol, stir for 10 -15min, add trifluoromethanesulfonic anhydride drop by drop, after the dripping is completed, warm to room temperature, stir for 2-4h, the organic layer is washed, dried and purified by column chromatography to obtain 3F-OTf, 5F-OTf, and 7F-OTf;

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

Application of alkyl/fluoroalkyl modified benzofuranone fluorescent compounds as fluorescent paper for information encryption and security under light and thermal regulation.

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

Decomposition temperature test

Compounds 423F and 423H were tested for their decomposition temperature using a thermogravimetric analyzer (TG).

As a result, it was found that the decomposition temperature of compound 423F was 217°C (Figure 5), and the decomposition temperature of compound 423H was 284°C (Figure 6).

Liquid UV absorption and fluorescence performance testing

Compounds 423F and 423H were mixed with different proportions of deionized water and tetrahydrofuran to form mixed solutions with different concentrations ⁽ 1×10 ^-3 mol/L, 1×10 ^-4 mol/L) (the water volume content was 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% and 90%), test the absorption spectrum of the mixed solution in different proportions (1×10 ^-4 mol/L), And use 330nm excitation light in a fluorescence spectrometer to test the emission spectra of mixed solutions of different proportions (1×10 ^-3 mol/L) (Figure 7 and Figure 8 in sequence).

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

Light/thermal/mechanical fluorescence discoloration performance test

Compound 423F was continuously irradiated under 365 nm ultraviolet light for 15 minutes, and then a part of the irradiated compound 423F was heated to 110°C, and the other part was ground in a mortar. During the period, the solid fluorescence change of compound 423F and the emission spectrum of the test fluorescence were observed.

The results showed that under 365nm ultraviolet light irradiation, compound 423F initially fluoresced orange, but as the irradiation time of the ultraviolet light was extended to 15 minutes, the compound's fluorescence changed from orange to yellow, showing photofluorescence discoloration properties; when the irradiation time was extended to 15 minutes, the compound 423F When the compound is heated to 110°C or ground, the fluorescence of the compound changes from yellow to orange, showing thermal/mechanical fluorescence discoloration properties.

The solid fluorescence change diagram of compound 423F in different states is shown in Figure 9.

The solid fluorescence spectra of compound 423F in different states are shown in Figure 10. The maximum emission wavelength λ _em of compound 423F in the initial state is 575nm. After irradiation with 365nm ultraviolet light for 15 minutes, the maximum emission wavelength λ _em blue-shifts to 556nm. A part of the irradiated compound 423F was ground, and the maximum emission wavelength λ _em was red-shifted to 567 nm. Another part of the irradiated compound 423F was heated to 110°C, and the maximum emission wavelength λ _em was red-shifted to 575 nm.

In this embodiment, the yellow fluorescence of compound 423F after irradiation can be restored to the original orange fluorescence by heating to 110°C.

Solid fluorescence change diagrams and solid fluorescence spectra of compounds 423H, 433H, 443H, 433F, and 443F in different states (Figure 11, Figure 12, Figure 13, Figure 14, and Figure 15, respectively).

The results showed that compounds 423H, 433H, 443H, 433F, and 443F, like compound 423F, all have photo/thermal fluorescence discoloration properties.

Compound 423F is used to prepare fluorescent paper that can be used for information storage under light and thermal regulation.

Compound 423F was loaded on high-temperature resistant black cardboard, and under 365nm ultraviolet light irradiation assisted by a photomask with a "crescent" pattern, the "crescent" pattern was recorded on the paper, and under 365nm ultraviolet light irradiation The "crescent" information can be read, and the "crescent" pattern can be made disappear by heating to 110°C, which can achieve the effect of burning after reading and can be reused (Figure 16).

In summary, it can be seen that the alkyl/fluoroalkyl modified benzofuranone fluorescent compound provided by the present invention simultaneously connects two alkyl/fluoroalkyl chains, and contains three benzene ring substituent structural units, and has light/heat/ It has strong multi-stimulus response performance and can achieve reversible conversion of fluorescence under the control of light and heat. It can be used to prepare photothermal dual stimulus-responsive fluorescent materials, which can be used in information encryption and security, data recording and storage, optoelectronic devices, molecular logic gates, and The field of biological imaging has broad application prospects.

The above are only further embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person familiar with the technical field can modify the technical solutions and concepts of the present invention within the scope disclosed by the present invention. Equivalent substitutions or changes all fall within the protection scope of the present invention.

Claims (10)

1. Alkyl/fluoroalkyl modified benzofuranone fluorescent compound, characterized in that its structural formula is as shown in Formula 1: In formula 1, R ₁ and R ₂ are both alkyl groups, and R ₁ and R ₂ are the same alkyl group. 2. The alkyl/fluoroalkyl modified benzofuranone fluorescent compound according to claim 1, characterized in that: R ₁ and R ₂ are ethyl, n-propyl, n-butyl, 1,1,1- Any one of trifluoroethyl, 1,1,1,2,2-pentafluoro-n-propyl, and 1,1,1,2,2,3,3-heptafluoro-n-butyl; Among them, 423H indicates that R ₁ and R ₂ are ethyl; 433H means R ₁ and R ₂ are n-propyl; 443H indicates that R ₁ and R ₂ are n-butyl; 423F indicates that R ₁ and R ₂ are 1,1,1-trifluoroethyl; 433F indicates that R ₁ and R ₂ are 1,1,1,2,2-pentafluoro-n-propyl; 443F indicates that R ₁ and R ₂ are 1,1,1,2,2,3,3-heptafluoro-n-butyl. 3. The preparation method of the alkyl/fluoroalkyl modified benzofuranone fluorescent compound according to claim 2, characterized in that it includes the following steps: Step 1: Combine 2-bromo-3,4,5,6-tetramethoxytoluene, pinacol diborate, cesium carbonate, and tris(4-methoxy-3,5-dimethylphenyl) Phosphine and palladium acetate are dissolved in ethyl acetate, and the reaction is stirred after being purged with N ₂ under closed conditions. The organic layer is 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-dimethylformamide, and pass through N under closed conditions. _2. After gas washing, a stirring reaction is carried out. The organic layer is washed, dried and purified by column chromatography to obtain TPE-4OMe; Step 3: Dissolve the TPE-4OMe obtained in Step 2 in methylene chloride, purge it with N ₂ under closed conditions, slowly drop BBr ₃ under ice bath conditions, stir the reaction, and then add methylene chloride. Add water to quench the reaction. The organic layer is washed, dried, filtered and spin-dried to obtain a filter residue. The obtained filter residue and p-toluenesulfonic acid monohydrate are dissolved in dichloromethane for stirring reaction. The organic layer is washed, dried and column-dried. After chromatography purification, 2OH is obtained; Step 4: Dissolve the 2OH obtained in step 3 with any one of 5H-Tos, 7H-Tos, 9H-Tos, 3F-OTf, 5F-OTf, 7F-OTf and cesium carbonate in N, N-di In the methylformamide solvent, the mixture was purged with _N2 under closed conditions and then stirred to react, and finally the compound represented by formula 1 was obtained. 4. The preparation method of alkyl/fluoroalkyl modified benzofuranone fluorescent compound according to claim 3, characterized in that in step one, 2-bromo-3,4,5,6-tetramethoxy The molar ratio of toluene, pinacol diborate, 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. 5. The preparation method of the alkyl/fluoroalkyl modified benzofuranone fluorescent compound according to claim 4, characterized in that in step two, 4OMe-B, 2-bromo-1,1,2- The molar ratio of triptyrene, potassium phosphate, tetrakis(triphenylphosphine)palladium and N,N-dimethylformamide is 1: (1.2-1.5): (2.0-3.0): 0.05:6. 6. The preparation method of alkyl/fluoroalkyl modified benzofuranone fluorescent compounds according to claim 5, characterized in that in step three, the molar ratio of TPE-4OMe, BBr ₃ and methylene chloride is 1: 8: (10-20); The mass ratio of filter residue, p-toluenesulfonic acid monohydrate and methylene chloride is 1:3: (20-25). 7. The preparation method of alkyl/fluoroalkyl modified benzofuranone fluorescent compounds according to claim 6, characterized in that in step four, the 2OH obtained in step three is the same as 5H-Tos, 7H-Tos, The molar ratio of any one of 9H-Tos, 3F-OTf, 5F-OTf, 7F-OTf and cesium carbonate dissolved in N, N-dimethylformamide solvent is 1:3: (4-6 ): (8-15). 8. The preparation method of the alkyl/fluoroalkyl modified benzofuranone fluorescent compound according to claim 7, characterized in that in step one, the temperature of the stirring reaction is 80-82°C, and the time is 24-28h; In step 2, the temperature of the stirring reaction is 80-85°C and the time is 24-30h; In the first step of step three, the temperature of the stirring reaction is 0-10°C and the time is 10-12 hours; In the second step, the temperature of the stirring reaction is 60-65°C and the time is 15-18h; The temperature of the stirring reaction described in step 4 is 25-30°C, and the time is 5-8 hours. 9. The preparation method of the alkyl/fluoroalkyl modified benzofuranone fluorescent compound according to claim 2, characterized in that the preparation method of 5H-Tos, 7H-Tos, and 9H-Tos in step four is as follows: Dissolve ethanol, propanol, n-butanol and p-toluenesulfonyl chloride in DCM, cool to 0°C, stir for 10-15min, add triethylamine drop by drop, after the dripping is completed, warm to room temperature, stir for 12-18h. The organic layer was washed, dried and purified by column chromatography to obtain 5H-Tos, 7H-Tos and 9H-Tos; Among them, the molar ratios of ethanol, propanol, n-butanol, p-toluenesulfonyl chloride and triethylamine are all 1:1.5:5; The preparation methods of 3F-OTf, 5F-OTf and 7F-OTf are: Mix pyridine and DCM evenly, purge with _N2 three times under airtight, cool to 0°C, and then add 2,2,2-trifluoroethanol and 2,2,3,3,3-pentafluoro-1-propane dropwise. Alcohol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, stir for 10-15min; Add trifluoromethanesulfonic anhydride drop by drop. After the addition is completed, the temperature is raised to room temperature and stirred for 2-4 hours. The organic layer is washed, dried and purified by column chromatography to obtain 3F-OTf, 5F-OTf, and 7F-OTf; Among them, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol The molar ratios of trifluoromethanesulfonic anhydride and triethylamine are both 1:1.2:1.25. 10. Application of the alkyl/fluoroalkyl modified benzofuranone fluorescent compound according to claim 1, characterized in that it is used as fluorescent paper for information encryption and security under light and thermal regulation.