Anthracene-based photochromic compounds containing a sulfur spiro unit, and methods of making and using the same

Abstract

The application discloses an anthracene-based photochromic compound containing a sulfur heterospirocyclic unit and a preparation method and application thereof, wherein the photochromic compound has excellent compatibility in an organic solvent system or a polymer system, and has the advantages of rapid light response, fast fading rate, good fatigue resistance and the like, and can be applied to fields of color-changing glasses, photochromic glass, photochromic ink, color-changing clothes and anti-counterfeiting materials and the like.

Description

Technical Field

[0001] This invention relates to an anthracene-based photochromic compound, particularly to an anthracene-based photochromic compound containing a thiospirocyclic unit, and also to a method for preparing the above compound and its applications. Background Technology

[0002] Photochromism refers to the phenomenon where a compound changes color when exposed to light of a certain intensity wavelength. Upon exposure to light of a different wavelength, heat, or removal of the light source, the compound returns to its original state, most noticeably as a color change. Therefore, such materials are commonly referred to as photochromic materials. Photochromic materials have wide applications in information storage, optical switches, photochromic glasses, smart windows, color-changing clothing, inks and paints, and anti-counterfeiting materials.

[0003] Currently, the more mature and widely used photochromic basic molecules include azobenzene, diarylethylene and spiropyran compounds, naphthopyran compounds, and ursolic anhydride compounds. The mechanisms of organic photochromism mainly include heterolytic cleavage of chemical bonds, cis-trans isomerism, pericyclic reactions, electron transfer tautomerism, homolytic cleavage of bonds, and redox reactions. For example, under ultraviolet light, the CO bond in spiropyran breaks, the molecule rotates locally, and forms a coplanar anthocyanin structure with indole, resulting in color. The CO bond breaking time is on the picosecond scale, and the color change is extremely fast. However, it takes several minutes to several hours at room temperature to transform into a colorless spirocyclic structure, and side reactions occur during the transformation process, thus affecting the number of reversible cycles. Photochromic compounds also have disadvantages such as poor fatigue resistance, slow color change, or slow fading. For example, even after moving from outdoors to indoors, the color may remain for a period of time, or the color may not fade even when a vehicle enters a tunnel, resulting in slow recovery of forward visibility. These are defects due to the excessively slow fading reaction rate. Summary of the Invention

[0004] Purpose of the invention: The purpose of this invention is to provide an anthracene-based photochromic compound with a rapid light response and fast fading, and also to provide a method for preparing the above compound and its applications.

[0005] Technical solution: The anthracene-based photochromic compound containing a sulfur-containing heterospirocyclic unit of the present invention has the structure shown in general formula V:

[0006]

[0007] Where A is

[0008] R1 and R4 are one of hydrogen, hydroxyl, nitrile, amino, C1-C6 alkyl or C1-C6 alkoxy;

[0009] R2 and R3 are one of hydrogen, hydroxyl, amino, C1-C6 alkyl, C1-C12 alkoxy, -O-(CH2)m-CH=CH2 or -(O-CH2CH2)nZ;

[0010] m is an integer from 1 to 10, and n is an integer from 1 to 6;

[0011] Z represents hydrogen or -(CH2)p-CH3, where p is an integer from 0 to 6;

[0012] R5 is hydrogen, halogen, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0013] Preferably, the compound has the structure shown in Formula I or Formula II, or its R configuration, S configuration, or a mixture thereof:

[0014]

[0015] Among them, R1 and R4 are one of hydrogen, hydroxyl, amino, nitrile, methyl, and methoxy groups;

[0016] R2 and R3 are one of hydrogen, hydroxyl, amino, C1-C6 alkyl, C1-C12 alkoxy, -O-(CH2)m-CH=CH2 or -(O-CH2CH2)nZ;

[0017] m is an integer from 1 to 10, and n is an integer from 1 to 6;

[0018] Z represents hydrogen or -(CH2)p-CH3, where p is an integer from 0 to 6;

[0019] R5 is hydrogen, halogen, substituted or unsubstituted aryl.

[0020] Preferably, R1 and R4 are one of hydrogen, hydroxyl, and methoxy groups;

[0021] R2 and R3 are one of hydrogen, hydroxyl, amino, C1-C12 alkoxy, -O-(CH2)m-CH=CH2 or -(O-CH2CH2)nZ;

[0022] m is an integer from 1 to 10, and n is an integer from 1 to 6;

[0023] Z represents hydrogen or -(CH2)p-CH3, where p is an integer from 0 to 6;

[0024] R5 is hydrogen, substituted or unsubstituted aryl.

[0025] Preferably, R1 and R4 are one of hydrogen, hydroxyl, and methoxy groups;

[0026] R2 and R3 are one of hydrogen, hydroxyl, amino, C1-C12 alkoxy, -O-(CH2)m-CH=CH2 or -(O-CH2CH2)nZ;

[0027] m is an integer from 1 to 10, and n is an integer from 1 to 6;

[0028] Z represents hydrogen or -(CH2)p-CH3, where p is an integer from 0 to 6;

[0029] R5 is hydrogen, substituted or unsubstituted aryl.

[0030] Preferably, R1, R3, and R4 are hydrogen;

[0031] R2 is one of hydrogen, hydroxyl, amino, C1-C12 alkoxy, -O-(CH2)m-CH=CH2 or -(O-CH2CH2)nZ;

[0032] m is an integer from 1 to 10, and n is an integer from 1 to 3;

[0033] Z represents hydrogen or -(CH2)p-CH3, where p is an integer between 0 and 3;

[0034] R5 is hydrogen, substituted or unsubstituted aryl.

[0035] Preferably, the unsubstituted aryl group is phenyl or naphthyl.

[0036] The above-mentioned compounds are prepared by reacting anthracene benzoyl compounds with pentaerythritol in an organic solvent and with a catalyst.

[0037]

[0038] Preferably, the catalyst is elemental iodine and an organic acid, wherein the organic acid is formic acid, acetic acid, propionic acid, trifluoroacetic acid, p-toluenesulfonic acid, or boron trifluoride ether, etc., and the organic solvent is one or more combinations of chloroform, dichloromethane, N,N-dimethylformamide, tetrahydrofuran, or dimethyl sulfoxide.

[0039] Preferably, when at least one of R2 and R3 represents -O-(CH2CH2)mZ or C1-C12 alkoxy or -O-(CH2)m-CH=CH2, the anthracene derivative A with a hydroxyl-substituted thiaspirocyclic ring is prepared by reacting a p-toluenesulfonate derivative B or a bromoalkane or bromoalkene with a base and an organic solvent to generate a thiaspirocyclic anthracene derivative C:

[0040]

[0041] The base is sodium hydride, cesium carbonate, potassium carbonate, or sodium carbonate, and the organic solvent is one or two of N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, and dimethyl sulfoxide.

[0042] The preferred and specific preparation method is as follows:

[0043] Step 1: Anthralboronic acid is coupled with hydroxybromosubstituted benzene to prepare intermediate 1, as shown in the following reaction:

[0044]

[0045] Alternatively, a brominated anthracene compound can be coupled with a hydroxyphenylboronic acid compound to yield intermediate 1, as shown in the following reaction:

[0046]

[0047]

[0048] Step 2: The hydroxylated anthracene derivative intermediate 2 reacts with a p-toluenesulfonate derivative, a bromine-substituted alkane, or a bromine-substituted alkene in a base and organic solvent to generate anthracene derivative intermediate 2. Taking the p-toluenesulfonate derivative as the reactant as an example, the reaction formula is as follows:

[0049]

[0050] Step 3: The anthracene benzoyl compound is reacted with pentaerythritol in an organic solvent and with a catalyst to obtain the product. The steps are as follows:

[0051]

[0052] The final product is a compound of formula I or formula II.

[0053] Preferably, the first step reaction is a Suzuki coupling reaction, the selected catalyst is Pd(dppf)Cl2, Pd(PPh3)4, Pd(PPh3)2Cl2, etc., the selected reaction solvent is a mixed solvent in different proportions (toluene / water / ethanol), the selected reaction temperature is 80℃-120℃, and the reaction time is 12h-48h.

[0054] Preferably, in the second step of the reaction, the selected base is potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, etc., the selected reaction solvent is DMF, DMSO, DMA, THF, etc., the reaction temperature is 90℃-120℃, and the reaction time is 9h-24h.

[0055] Preferably, in the third step of the reaction, the selected catalyst is p-toluenesulfonic acid, boron trifluoride ether, iodine, acetic acid, etc., the reaction solvent is dichloromethane, trichloromethane, toluene, etc., the reaction temperature is 20-80℃, and the reaction time is 1h-24h.

[0056] On the other hand, the preparation method using R2 as -O-(CH2CH2)mZ, C1-C12 alkoxy, or -O-(CH2)m-CH=CH2 mainly prepares compounds with hydroxythiaspirocyclic rings, and then reacts the hydroxyl group to obtain photochromic compounds. The specific steps are as follows:

[0057] Step 1: Anthralboronic acid is coupled with hydroxybromosubstituted benzene to prepare intermediate 1, as shown in the following reaction:

[0058]

[0059] Alternatively, a brominated anthracene compound can be coupled with a hydroxyphenylboronic acid compound to yield intermediate 1, as shown in the following reaction:

[0060]

[0061] Step 2: Intermediate 1 reacts with pentaerythritol under the action of a catalyst to obtain intermediate 2, with the following steps:

[0062]

[0063] Step 3: The anthracene compound with a hydroxyl-substituted thiaspirocyclic ring reacts with p-toluenesulfonate derivative B, or a bromoalkane or bromoalkene, in a base and organic solvent to generate an anthracene photochromic compound containing a thiaspirocyclic ring. Taking p-toluenesulfonate derivative as an example, the reaction formula is as follows:

[0064]

[0065] Finally, an anthracene-based photochromic compound containing a sulfur-containing heterospirocyclic ring was obtained.

[0066] Preferably, the first step reaction is a Suzuki coupling reaction, the selected catalyst is Pd(dppf)Cl2, Pd(PPh3)4, Pd(PPh3)2Cl2, etc., the selected reaction solvent is a mixed solvent in different proportions (toluene / water / ethanol), the selected reaction temperature is 80℃-120℃, and the reaction time is 12h-48h.

[0067] Preferably, in the second step of the reaction, the selected catalyst is p-toluenesulfonic acid, boron trifluoride ether, iodine, acetic acid, etc., the reaction solvent is dichloromethane, trichloromethane, toluene, etc., the reaction temperature is 20-80℃, and the reaction time is 1h-24h.

[0068] Preferably, in the third step of the reaction, the selected base is potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, etc., the selected reaction solvent is DMF, DMSO, DMA, THF, etc., the reaction temperature is 90℃-120℃, and the reaction time is 9h-24h.

[0069] When R2 contains -O-(CH2CH2)mZ, the method for preparing the photochromic compound includes the following steps:

[0070] The reaction formula for the preparation of anthracene-based compounds with ethers under acid catalysis is as follows:

[0071]

[0072] m represents an integer from 1 to 6;

[0073] Preferably, the anthracene compound of the hydroxythiaspirocyclic ring reacts with the ether, the selected acid catalyst is p-toluenesulfonic acid or dodecylbenzenesulfonic acid, the amount of catalyst is 0.1-0.5, the reaction temperature is 50-100℃, and the reaction time is 9-24h.

[0074] The above-mentioned photochromic compounds are used as photochromic materials in photochromic glasses, photochromic glass, clothing, paints and inks.

[0075] Invention Principle: The photochromic compound of this invention is a benzene anthracene derivative linked by a thiaspirocyclic ring. It exhibits maximum absorption wavelength in the ultraviolet (230-400 nm) region, and the anthracene group is a blue fluorescent emitting group. When excited by ultraviolet light, this type of compound emits blue fluorescence; when the ultraviolet excitation stops, the compound immediately transitions from the excited state to the ground state, a process that takes only 10 seconds. -8 The color changes back to its original color, thus the compounds of this invention exhibit fast photoresponse and rapid fading. Substituents such as hydroxyl, alkyl, or ether groups improve the solubility of the compounds. These compounds can emit fluorescence under photoexcitation of solar ultraviolet light in solution or as unimolecular states.

[0076] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) Under outdoor ultraviolet irradiation, the compound is excited in the single-molecule state and emits fluorescence and shows color, that is, the photochromic compound has a fast photoresponse speed; (2) The photochromic compound fades quickly. After the compound is not excited by ultraviolet light in the single-molecule state, it immediately transforms into the ground state and returns to its original color. The time required is only 10 minutes. -8 s; (3) The preparation method of the photochromic compound of the present invention requires simple steps, the raw materials are readily available, and it is suitable for large-scale production. Attached Figure Description

[0077] Figure 1 Compound Ia (1×10-5 Images of indoor and outdoor environments with mol / L DCM (dihydrogen per cubic meter).

[0078] Figure 2 Compound Ia (1×10 -5 The ultraviolet absorption spectrum of (mol / L THF);

[0079] Figure 3 The NMR spectrum of compound Ia is shown in Figure 1.

[0080] Figure 4 The nuclear magnetic resonance C-ray spectrum of compound Ia;

[0081] Figure 5 Images of polymethyl methacrylate loaded with 5% compound Ia in indoor and outdoor environments;

[0082] Figure 6 For compound Ib (1×10 -5 The ultraviolet absorption spectrum of (mol / L THF);

[0083] Figure 7 For compound Ib (1×10 -5 Fluorescence spectra of mol / L THF at different excitation wavelengths;

[0084] Figure 8 The NMR spectrum of compound Ic is shown in Figure 1.

[0085] Figure 9 For compound Ie (1×10 -5 Excitation and emission fluorescence spectra of mol / L dichloromethane at different wavelengths;

[0086] Figure 10 Images of polymethyl methacrylate loaded with 5% compound Ie and unloaded polymethyl methacrylate in outdoor environments. Detailed Implementation

[0087] The technical solution of the present invention will be further described below with reference to the accompanying drawings.

[0088] Example 1

[0089] Synthesis of photochromic compound Ia

[0090] Step 1: Synthesis of compound A3:

[0091]

[0092] In a 250 mL three-necked flask, 9-anthraboric acid (1.70 g, 7.66 mmol) and 4-bromo-2-hydroxybenzaldehyde (1.71 g, 8.50 mmol) were added. A mixed solvent (100 mL toluene, 20 mL ethanol, 40 mL water) was added to the reaction flask, along with 2.50 g of potassium carbonate. The mixture was purged with nitrogen three times. Then, 0.40 g of tetrakis(triphenylphosphine)palladium was added, followed by three more nitrogen purgings. The mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the layers were separated. The aqueous phase was extracted with dichloromethane. The organic phases were combined and concentrated to dryness to obtain a crude product. This crude product was purified by column chromatography (eluent: petroleum ether / dichloromethane) to give 2.01 g of solid, with a yield of 88%.

[0093] A3's proton NMR spectrum: 1 H NMR(400MHz,Chloroform-d)δ11.23(d,J=22.4Hz,1H),10.10 -10.05(m,1H),8.56(s,1H),8.09(ddt,J=8.5,1.3,0.7Hz,2H),7.80(dd,J=7.7,0.6Hz,1H),7.66(dq,J= 8.8,1.0Hz,2H),7.50(ddd,J=8.3,6.6,1.3Hz,2H),7.41(ddd,J=8.9,6.6,1.3Hz,2H),7.16-7.12(m,2H).

[0094] Step 2: Synthesis of photochromic compound Ia

[0095]

[0096] 200 mg A3 and 67 mg pentaerythritol were added to a single-necked flask, followed by the addition of 10 mL of chloroform and stirring to dissolve. A catalytic amount of p-toluenesulfonic acid was then added to the system, and the mixture was heated to 65 °C and stirred for 4 h. After cooling to room temperature, the mixture was filtered, and the filter cake was dried to give 230 mg of a white solid, with a yield of 88.2%.

[0097] Compound Ia was prepared into a 1×10⁻⁶ solution. -5 A mol / L tetrahydrofuran solution was prepared, and then the UV-absorbing spectrum was measured, as shown below. Figure 2 As shown.

[0098] like Figure 3 As shown, the proton NMR spectrum of Ia: 1H NMR (400MHz, DMSO-d6) δ10.25(s,2H),8.68(s,2H),8.16(d,J=8.4Hz,4H),7.75(d, J=8.1Hz,2H),7.60(dt,J=8.6,1.1Hz,4H),7.54(ddt,J=8.3,6.5,1.6Hz,4H),7.47( ddt,J=8.1,6.5,1.5Hz,4H),6.89(dt,J=4.3,2.0Hz,4H),5.79(s,2H),4.26-4.15(m ,2H),3.47(d,J=13.9Hz,2H),3.15(d,J=14.2Hz,2H),2.75(dd,J=13.8,2.2Hz,2H).

[0099] like Figure 4 As shown, the carbon NMR spectrum of Ia: 13 C NMR(101MHz,DMSO-d6)δ154.20,139.55,136.26,131.31,129.73,129.35,128.8 9,126.44,125.97,125.84,124.30,122.59,118.27,79.65,43.95,42.73,22.20.

[0100] The obtained photochromic compound Ia was prepared into a solution of 1×10⁻⁶ ppm in dichloromethane. -5 A dilute solution of mol / L, when placed outdoors, will cause the dichloromethane solution to change from colorless to blue; upon returning indoors, the dichloromethane solution will change from blue to colorless. Figure 1 As shown; then, when irradiated with 365nm ultraviolet light, the dichloromethane solution changed from colorless to blue.

[0101] The compound was subjected to fatigue resistance tests, and no abnormalities were observed after 200 photochromic cycles, demonstrating good fatigue resistance.

[0102] Compound Ia was loaded onto polymethyl methacrylate (PMMA): 1.0 g PMMA was dissolved in 40 ml dichloromethane, and 50 mg of compound Ia was dissolved in 5 ml dichloromethane. The two solutions were mixed and added to a petri dish. The solvent was allowed to evaporate slowly, yielding PMMA loaded with compound Ia. Figure 5 As shown, PMMA loaded with compound Ia was placed indoors and outdoors. It can be seen that PMMA loaded with compound Ia is colorless indoors, while it is blue outdoors.

[0103] Example 2

[0104] Synthesis of photochromic compound Ib

[0105] Step 1: Synthesis of compound B3

[0106]

[0107] 10-Phenylacetic-9-anthraboric acid (1.00 g) and 4-bromo-2-hydroxybenzaldehyde (0.74 g) were added to a three-necked flask, followed by a mixed solvent (5 ml toluene, 10 ml ethanol, 20 ml water). 1.20 g of potassium carbonate was added to the reaction system, and the mixture was purged with nitrogen three times. Then, tetrakis(triphenylphosphine)palladium (0.20 g) was added, and the mixture was purged with nitrogen three times. The system was heated to 90 °C and reacted for 12 h. After post-reaction processing, the mixture was cooled to room temperature, and the layers were separated. The aqueous phase was extracted with dichloromethane, and the organic phases were combined and concentrated to dryness. The solution was purified by column chromatography (eluent: petroleum ether / dichloromethane) to give 1.02 g of a yellow solid, yield: 80.9%.

[0108] B3's 1H NMR spectrum: 1 H NMR (400MHz, DMSO-d6) δ11.01(s,1H),10.46(s,1H),7.94(d,J=7.7Hz,1H),7.72-7.56(m,7H),7.47(tdd,J=6.7,4.0,1.9Hz,6H),7.07(d,J=8.1Hz,2H).

[0109] Step 2: Synthesis of photochromic compound Ib

[0110]

[0111] 200 mg B3 and 53 mg pentaerythritol were added to a single-necked flask, followed by the addition of 10 mL of chloroform and stirring to dissolve. A catalytic amount of p-toluenesulfonic acid was then added to the system, and the mixture was heated to 65 °C and stirred for 4 h. After cooling to room temperature, the mixture was filtered, and the filter cake was dried to give 0.22 g of a white solid, with a yield of 89.7%.

[0112] Ib 1H NMR spectrum: 1 H NMR(400MHz, DMSO-d6)δ10.30(s,2H),7.78(d,J=8.2Hz,2H),7.71-7.54(m,14H),7.52-7.36(m,12H),6.95(dq,J=3.7, 1.7Hz, 4H), 5.81 (s, 2H), 4.22 (d, J = 14.0Hz, 2H), 3.48 (d, J = 14.0Hz, 2H), 3.17 (d, J = 5.1Hz, 2H), 2.76 (d, J = 13.8Hz, 2H).

[0113] Carbon NMR spectrum of Ib: 13 C NMR (101MHz, DMSO) δ154.25,139.76,138.59,137.16,136.51,131.39,129.62,129.44,129.17, 128.20,126.87,126.10,124.38,123.46,122.93,119.14,117.67,45.31,42.68,37.03,22.28.

[0114] The obtained photochromic compound Ib was prepared into a solution of 1×10⁻⁶ ppm in dichloromethane. -5 When a dilute solution of mol / L is placed outdoors, the dichloromethane solution changes from colorless to blue. When it is brought indoors, the dichloromethane solution changes from blue to colorless. Then, when it is irradiated with 365nm ultraviolet light, the dichloromethane solution changes from colorless to blue.

[0115] The compound was subjected to fatigue resistance tests, and no abnormalities were observed after 200 photochromic cycles, demonstrating good fatigue resistance.

[0116] Compound Ib was prepared into a 1×10⁻⁶ solution. -5 A mol / L tetrahydrofuran solution was prepared, and then the UV-absorbing spectrum was measured. (See attached image.) Figure 6 .

[0117] Compound Ib (1×10) -5 Fluorescence spectra of mol / L THF: Fluorescence emission spectra at different excitation wavelengths, namely 269 nm, 314 nm, 339 nm and 395 nm, are shown in [reference needed]. Figure 7 This indicates that compound Ib has a good emission intensity in the ultraviolet region.

[0118] Example 3

[0119] Synthesis of photochromic compound Ic

[0120] Step 1: Synthesis of compound C3

[0121]

[0122] 6.01 g of diethylene glycol monomethyl ether was dissolved in 35 ml of tetrahydrofuran and added to a 250 ml single-necked flask. 7.00 g of sodium hydroxide was dissolved in 35 ml of water and slowly added to the reaction flask. The mixture was cooled to 0 °C. 11.40 g of p-toluenesulfonyl chloride in 50 ml of tetrahydrofuran solution was slowly added dropwise to the reaction system (dropping time 2 h). After the addition was complete, the mixture was heated to room temperature and stirred for 12 h. For post-treatment, 3N HCl solution was added to the reaction system to adjust the pH to 5. The mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain 13.10 g of a pale yellow liquid, yield: 95.6%.

[0123] The proton NMR spectrum of C3: 1 H NMR(400MHz,Chloroform-d)δ7.85-7.77(m,2H),7.39-7.31(m,2H),4.22-4.15(m,2H ),3.74-3.64(m,2H),3.62-3.56(m,2H),3.52-3.46(m,2H),3.36(s,3H),2.46(s,3H).

[0124] Step 2: Synthesis of compound C5

[0125]

[0126] 0.40 g of 2-hydroxy-4-(10-phenyl-9-anthrayl)benzaldehyde (C4 and C3) (0.35 g) were added to a single-necked flask, along with 5 mL of DMF and 0.30 g of potassium carbonate. The mixture was heated to 100 °C and reacted for 10 h. The reaction was detected by TLC (petroleum ether:ethyl acetate = 3:1). After reaction, 30 mL of dichloromethane and 15 mL of water were added, and the mixture was stirred for 1 h. The layers separated, and the organic phase was washed twice with 15 mL of water and then with 15 mL of saturated sodium chloride solution. The mixture was dried over anhydrous sodium sulfate for 1 h, filtered, and concentrated to obtain 0.21 g, with a yield of 82.3%.

[0127] C5 1H NMR spectrum: 1 H NMR (400MHz, DMSO-d6) δ10.57(d,J=0.8Hz,1H),7.97(d,J=7.8Hz,1H),7.72-7.55(m,7H),7.53-7.37(m,7H),7.21 (dt,J=7.7,1.0Hz,1H),4.35-4.25(m,2H),3.83-3.74(m,2H),3.64-3.58(m,2H),3.47-3.41(m,2H),3.20(s,3H).

[0128] Step 3: Synthesis of photochromic compound Ic

[0129]

[0130] 200 mg C5 and 42 mg pentaerythritol were added to a single-necked flask, followed by 10 mL of chloroform and stirring to dissolve. A catalytic amount of p-toluenesulfonic acid was added to the system, and the mixture was heated to 65 °C and stirred for 4 h. After cooling to room temperature, the mixture was filtered, and the filter cake was dried to give 0.20 g of a white solid, with a yield of 85.4%.

[0131] like Figure 8 As shown, the 1H NMR spectrum of Ic: 1 H NMR (400MHz, DMSO-d6) δ7.88 (d, J=7.7Hz, 2H), 7.76-7.52 (m, 15H), 7.46 (dddd ,J=12.2,8.3,3.7,2.3Hz,11H),7.22(d,J=1.6Hz,2H),7.13(dd,J=7.8,1.5Hz ,2H),5.83(s,2H),4.32-4.18(m,6H),3.86-3.76(m,4H),3.70-3.64(m,4H),3 .50-3.40(m,6H),3.24(s,6H),3.14(d,J=14.2Hz,2H),2.83(d,J=13.7Hz,2H).

[0132] The obtained photochromic compound Ic was prepared into a solution of 1×10⁻⁶ ppm in dichloromethane. -5 When a dilute solution of mol / L is placed outdoors, the dichloromethane solution changes from colorless to blue. When it is brought indoors, the dichloromethane solution changes from blue to colorless. Then, when it is irradiated with 365nm ultraviolet light, the dichloromethane solution changes from colorless to blue.

[0133] The compound was subjected to fatigue resistance tests, and no abnormalities were observed after 200 photochromic cycles, demonstrating good fatigue resistance.

[0134] Example 4

[0135] Synthesis of photochromic compound Id

[0136] Step 1: Synthesis of compound D3

[0137]

[0138] 0.32 g of 2-hydroxy-4-(9-anthrayl)benzaldehyde D1 and 0.35 g of C3 were added to a single-necked flask, along with 5 ml of DMF and 0.30 g of potassium carbonate. The mixture was heated to 100 °C and reacted for 10 h. The reaction was detected by TLC (petroleum ether:ethyl acetate = 2:1). After reaction, 30 ml of dichloromethane and 15 ml of water were added, and the mixture was stirred for 1 h. The layers separated, and the organic phase was washed twice with 15 ml of water and then washed with 15 ml of saturated sodium chloride solution. The mixture was dried over anhydrous sodium sulfate for 1 h, filtered, and concentrated to obtain 0.31 g, with a yield of 72.1%.

[0139] The nuclear magnetic resonance H-spectrum of D2: 1 H NMR(400MHz,DMSO-d6)δ10.55(d,J=0.8Hz,1H),8.73(s,1H),8.18(dq,J=8.7 ,0.9Hz,2H),7.94(d,J=7.8Hz,1H),7.59-7.52(m,4H),7.47(ddd,J=8.7,6.6 ,1.3Hz,2H),7.34(d,J=1.4Hz,1H),7.13(dt,J=7.9,1.0Hz,1H),4.32-4.21( m,2H),3.83-3.73(m,2H),3.63-3.55(m,2H),3.47-3.40(m,2H),3.19(s,3H).

[0140] Step 2: Synthesis of photochromic compound Id

[0141]

[0142] 200 mg D2 and 50 mg pentaerythritol were added to a single-necked flask, followed by the addition of 10 mL of chloroform and stirring to dissolve. The catalyst, p-toluenesulfonic acid (0.05 equivalents), was added to the system. The mixture was heated to 65 °C and stirred for 4 h. After cooling to room temperature, the mixture was filtered, and the filter cake was dried to give 0.21 g of a white solid, with a yield of 87.1%.

[0143] NMR spectrum of compound Id: 1H NMR(400MHz, DMSO-d6)δ8.70(s,2H),8.17(d,J=8.3Hz,4H),7.84(d,J=7.8Hz,2H),7 .61-7.51(m,8H),7.47(ddt,J=7.9,6.5,1.3Hz,4H),7.15(d,J=1.6Hz,2H),7.06(dd, J=7.7,1.5Hz,2H),5.81(s,2H),4.25-4.16(m,6H),3.81-3.74(m,4H),3.68-3.62(m, 4H),3.48-3.44(m,4H),3.22(s,6H),3.12(d,J=14.1Hz,2H),2.81(d,J=13.8Hz,2H).

[0144] The obtained photochromic compound Id was prepared into a solution of 1×10⁻⁶ ppm in dichloromethane. -5 When a dilute solution of mol / L is placed outdoors, the dichloromethane solution changes from colorless to blue. When it is brought indoors, the dichloromethane solution changes from blue to colorless. Then, when it is irradiated with 365nm ultraviolet light, the dichloromethane solution changes from colorless to blue.

[0145] The compound was subjected to fatigue resistance tests, and no abnormalities were observed after 200 photochromic cycles, demonstrating good fatigue resistance.

[0146] Example 5

[0147] Synthesis of photochromic compound Id:

[0148]

[0149] 200 mg Ia and 216 mg C3 were added to a single-necked flask, along with 2 ml DMF and 0.11 g potassium carbonate. The mixture was heated to 100 °C and reacted for 10 h. The reaction was detected by TLC (petroleum ether: ethyl acetate = 3:1 as the developing solvent). After reaction, 10 ml dichloromethane and 5 ml water were added, the mixture was stirred, and the layers were separated. The organic phase was washed twice with 5 ml water, then washed with 5 ml saturated sodium chloride solution, dried over anhydrous sodium sulfate for 1 h, filtered, and concentrated to obtain 0.21 g, with a yield of 82.8%.

[0150] NMR spectrum of compound Id: 1H NMR(400MHz, DMSO-d6)δ8.70(s,2H),8.17(d,J=8.3Hz,4H),7.84(d,J=7.8Hz,2H),7 .61-7.51(m,8H),7.47(ddt,J=7.9,6.5,1.3Hz,4H),7.15(d,J=1.6Hz,2H),7.06(dd, J=7.7,1.5Hz,2H),5.81(s,2H),4.25-4.16(m,6H),3.81-3.74(m,4H),3.68-3.62(m, 4H),3.48-3.44(m,4H),3.22(s,6H),3.12(d,J=14.1Hz,2H),2.81(d,J=13.8Hz,2H).

[0151] Example 6

[0152] Synthesis of photochromic compound Ie

[0153] first step:

[0154]

[0155] In a 250 mL three-necked flask, 1.70 g of 9-bromoanthracene (6.61 mmol) and 1.19 g of 4-boronic acid benzaldehyde (7.93 mmol) were added. A mixed solvent (100 mL toluene, 20 mL ethanol, 40 mL water) was added to the reaction flask, along with 2.50 g of potassium carbonate. The mixture was purged with nitrogen three times. Then, 0.20 g of tetrakis(triphenylphosphine)palladium was added, followed by three more nitrogen purgings. The mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the layers were separated. The aqueous phase was extracted with dichloromethane. The organic phases were combined and concentrated to dryness to obtain a crude product. This crude product was purified by column chromatography (eluent: petroleum ether / dichloromethane) to give 1.65 g of solid, with a yield of 88.4%.

[0156] 1H NMR spectrum of 4-(9-anthrayl)benzaldehyde: 1 H NMR(400MHz,Chloroform-d)δ10.22(s,1H),8.57(s,1H),8.16-8.12(m,2H),8.10(dp,J=8.6,0.7Hz,2H),7.68- 7.64(m,2H),7.60(dq,J=8.9,1.0Hz,2H),7.51(ddd,J=8.5,6.5,1.2Hz,2H),7.40(ddd,J=8.8,6.5,1.3Hz,2H).

[0157] Step 2: Synthesis of photochromic compound Ie

[0158]

[0159] 300 mg of 4-(9-anthrayl)benzaldehyde and 106 mg of pentaerythritol were added to a single-necked flask, followed by the addition of 10 mL of chloroform and stirring to dissolve. The catalyst, p-toluenesulfonic acid (0.05 equivalents), was added to the system. The mixture was heated to 65 °C and stirred for 4 h. After cooling to room temperature, the mixture was filtered, and the filter cake was dried to give 0.31 g of a white solid, with a yield of 80.1%.

[0160] NMR spectrum of compound Ie: 1 H NMR(400MHz,Chloroform-d)δ8.53(s,2H),8.07(d,J=8.4Hz,4H),7.82-7.73(m,4H),7.72-7.65(m,4H),7.56-7.44(m,8H),7.39(ddd,J= 8.8, 6.5, 1.3Hz, 4H), 5.35 (s, 2H), 4.39 (d, J = 13.9Hz, 2H), 3.31 (d, J = 14.0Hz, 2H), 3.01 (d, J = 14.5Hz, 2H), 2.78 (dd, J = 14.0, 2.3Hz, 2H).

[0161] The obtained photochromic compound Ie was prepared into a solution of 1×10⁻⁶ ppm in dichloromethane. -5 When a dilute solution of mol / L is placed outdoors, the dichloromethane solution changes from colorless to blue. When it is brought indoors, the dichloromethane solution changes from blue to colorless. Then, when it is irradiated with 365nm ultraviolet light, the dichloromethane solution changes from colorless to blue.

[0162] The compound was subjected to fatigue resistance tests, and no abnormalities were observed after 200 photochromic cycles, demonstrating good fatigue resistance.

[0163] Figure 9 For compound Ie (1×10 -5 Excitation and emission fluorescence spectra of compound Ie at different wavelengths using dichloromethane (mol / L): Fluorescence test spectrum of compound Ie: compound Ie was prepared into a 1×10⁻⁶ solution. -5 The fluorescence emission spectrum of compound Ie was tested using mol / L THF at different excitation wavelengths. The maximum excitation was measured at the maximum fluorescence emission peak. The experimental results show that compound Ie has a wide excitation wavelength (ultraviolet region) and good fluorescence emission intensity.

[0164] Preparation of PMMA loaded with compound Ie: 1.0 g PMMA was dissolved in 40 ml of dichloromethane, and 50 mg of compound Ie was dissolved in 5 ml of dichloromethane. The two solutions were mixed and added to a petri dish. The solvent was allowed to evaporate slowly to obtain PMMA loaded with compound Ie. Alternatively, 1.0 g PMMA was dissolved in 40 ml of dichloromethane and added to a petri dish. The solvent was allowed to evaporate slowly to obtain PMMA without compound Ie loading. Figure 10 As shown, in the outdoor state, the left side is PMMA loaded with compound Ie, which is blue, and the right side is PMMA without compound Ie loading, which is colorless.

[0165] Example 7

[0166] The synthesis of photochromic compound Ie differs from Example 6 in that the type of catalyst in step two is changed:

[0167]

[0168] 300 mg of 4-(9-anthrayl)benzaldehyde and 106 mg of pentaerythritol were added to a single-necked flask, followed by the addition of 10 mL of chloroform and stirring to dissolve. Boron trifluoride diethyl ether (0.05 equivalents) was added to the system as a catalyst. The mixture was heated to 65 °C and stirred for 4 h. After cooling to room temperature, the mixture was filtered, and the filter cake was dried to give 0.33 g of a white solid, with a yield of 85.2%.

[0169] Example 8

[0170] The synthesis of photochromic compound Ie differs from Example 6 in that the type of catalyst in step two is changed:

[0171]

[0172] 300 mg of 4-(9-anthrayl)benzaldehyde and 106 mg of pentaerythritol were added to a single-necked flask, 10 ml of chloroform was added and stirred to dissolve, iodine (20 mg) catalyst was added to the system, the reaction was stirred at room temperature for 12 h, filtered, and the filter cake was dried to give 0.25 g of white solid, yield 64.6%.

[0173] Example 9

[0174] Synthesis of photochromic compound IF

[0175] Step 1: Synthesis of compound F2

[0176]

[0177] In a 250 mL three-necked flask, 9-anthraboric acid (1.70 g, 7.66 mmol) and 5-bromo-2-hydroxybenzaldehyde (1.71 g, 8.50 mmol) were added. A mixed solvent (100 mL toluene, 20 mL ethanol, 40 mL water) was added to the reaction flask, along with 2.50 g of potassium carbonate. The mixture was purged with nitrogen three times. Then, 0.40 g of tetrakis(triphenylphosphine)palladium was added, followed by three more nitrogen purgings. The mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the layers were separated. The aqueous phase was extracted with dichloromethane. The organic phases were combined and concentrated to dryness to obtain a crude product. This crude product was purified by column chromatography (eluent: petroleum ether / dichloromethane) to give 1.91 g of solid, with a yield of 83.6%.

[0178] NMR spectrum of compound F2 (H-N): 1 H NMR(400MHz,Chloroform-d)δ11.22(s,1H),9.97(s,1H),8.56(s,1H),8.09(d,J=8.4Hz,2H),7.70-7. 61(m,4H),7.51(ddd,J=8.2,6.5,1.2Hz,2H),7.42(ddd,J=8.8,6.5,1.3Hz,2H),7.26(d,J=8.4Hz,1H).

[0179] Step 2: Synthesis of photochromic compound If

[0180]

[0181] 200 mg F2 and 67 mg pentaerythritol were added to a single-necked flask, followed by the addition of 10 mL of chloroform and stirring to dissolve. A catalytic amount of p-toluenesulfonic acid was then added to the system, and the mixture was heated to 65 °C and stirred for 4 h. After cooling to room temperature, the mixture was filtered, and the filter cake was dried to give 230 mg of a white solid, with a yield of 88.2%.

[0182] The proton NMR spectrum of compound If: 1 H NMR (400MHz, DMSO-d6) δ10.27(s,2H),8.64(s,2H),8.19-8.08(m,4H),7.60-7.35(m,14H),7.16(dd,J=8.2,2.2Hz,2H),7.09(d,J=8 .2Hz,2H),5.65(s,2H),3.84(dd,J=14.5,2.1Hz,2H),3.31(d,J=14.1Hz,2H),2.89(d,J=14.2Hz,2H),2.57(dd,J=13.9,2.1Hz,2H).

[0183] Carbon NMR spectrum of compound If: 13C NMR(101MHz,DMSO)δ153.68,136.41,132.28,131.40,130.21,128.92,128.82,12 6.81,126.46,126.27,125.73,125.01,116.17,43.79,42.63,36.09,21.89,0.58.

[0184] The obtained photochromic compound IF was prepared into a solution of 1×10⁻⁶ ppm in dichloromethane. -5 When a dilute solution of mol / L is placed outdoors, the dichloromethane solution changes from colorless to blue. When it is brought indoors, the dichloromethane solution changes from blue to colorless. Then, when it is irradiated with 365nm ultraviolet light, the dichloromethane solution changes from colorless to blue.

[0185] The compound was subjected to fatigue resistance tests, and no abnormalities were observed after 200 photochromic cycles, demonstrating good fatigue resistance.

Claims

1. An anthryl photochromic compound containing a sulfur heterospirocyclic unit, characterized by, The compound has the structure shown in general formula V: ； wherein A is or ; R1 and R4 are one of hydrogen, hydroxyl, nitrile, amino, C1-C6 alkyl or C1-C6 alkoxy; R2 and R3 are one of hydrogen, hydroxyl, amino, C1-C6 alkyl, C1-C12 alkoxy, -O-(CH2)m-CH=CH2 or -(O-CH2CH2)nZ; m is an integer from 1 to 10, and n is an integer from 1 to 6; Z represents hydrogen or -(CH2)p-CH3, where p is an integer from 0 to 6; R5 is hydrogen or phenyl.

2. The compound of claim 1, wherein The compound has the structure shown in Formula I or Formula II: ； ； Among them, R1 and R4 are one of hydrogen, hydroxyl, amino, nitrile, methyl, and methoxy groups; R2 and R3 are one of hydrogen, hydroxyl, amino, C1-C6 alkyl, C1-C12 alkoxy, -O-(CH2)m-CH=CH2 or -(O-CH2CH2)nZ; m is an integer from 1 to 10, and n is an integer from 1 to 6; Z represents hydrogen or -(CH2)p-CH3, where p is an integer from 0 to 6; R5 is hydrogen or phenyl.

3. The compound of claim 1, wherein The compound has the structure shown in Formula I or Formula II: ； ； Among them, R1 and R4 are one of hydrogen, hydroxyl, and methoxy; R2 and R3 are one of hydrogen, hydroxyl, amino, C1-C12 alkoxy, -O-(CH2)m-CH=CH2 or -(O-CH2CH2)nZ; m is an integer from 1 to 10, and n is an integer from 1 to 6; Z represents hydrogen or -(CH2)p-CH3, where p is an integer from 0 to 6; R5 is hydrogen or phenyl.

4. The compound of claim 1, wherein The compound has the structure shown in Formula I or Formula II: ； ； Among them, R1, R3, and R4 are hydrogen; R2 is one of hydrogen, hydroxyl, amino, C1-C12 alkoxy, -O-(CH2)m-CH=CH2 or -(O-CH2CH2)nZ; m is an integer from 1 to 10, and n is an integer from 1 to 3; Z represents hydrogen or -(CH2)p-CH3, where p is an integer between 0 and 3; R5 is hydrogen or phenyl.

5. A process for the preparation of a compound according to any one of claims 1 to 4, characterized in that, It is obtained by reacting anthracene benzoyl compounds with pentaerythritol in an organic solvent and with a catalyst: ； or .

6. The preparation method according to claim 5, characterized in that, The catalyst is elemental iodine and an organic acid, wherein the organic acid is formic acid, acetic acid, propionic acid, trifluoroacetic acid, p-toluenesulfonic acid, or boron trifluoride ether, and the organic solvent is one or more combinations of chloroform, dichloromethane, N,N-dimethylformamide, tetrahydrofuran, or dimethyl sulfoxide.

7. The application of the photochromic compound of claim 1 as a photochromic material in the fields of photochromic glasses, photochromic glass, clothing, and paints and inks.

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