A meta-disubstituted tetraphenyl ethene compound, and a preparation method and application thereof

Abstract

The present application relates to the technical field of organic synthesis, and particularly provides a meta-disubstituted tetraphenyl ethylene compound, a preparation method and application thereof. The present application introduces trifluoromethyl, cyano, aldehyde group or methoxyformyl into the meta-position of tetraphenyl ethylene, and through the interaction of the specific substituent at the meta-position with the large conjugated group formed by the four benzene rings, the substituted tetraphenyl ethylene compound has more significant photochromic and mechanochromic dual functions, the compound can realize photo-mechanical synergistic color change effect, provides a basis for developing intelligent materials with multi-functional response characteristics, has great application potential in intelligent display, anti-fake identification, wearable devices and the like, and can effectively expand the application range of tetraphenyl ethylene compounds.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a meta-disubstituted tetraphenyl ethene compound and a preparation method and application thereof. BACKGROUND

[0002] The tetraphenyl ethene compound has the optical properties of aggregation-induced fluorescence and high quantum yield, can efficiently release more energy in the form of fluorescence, emits brighter and more persistent fluorescence, and has the advantages of high quantum yield, which can ensure excellent performance of a system in the fields of a fluorescence sensor pursuing high sensitivity and an optoelectronic material application scene requiring strong light signal output. In addition, the tetraphenyl ethene compound has the advantages of strong modifiability and mild preparation conditions, and researchers can accurately and diversely modify the molecule according to different application requirements, and prepare derivatives with different functions, and therefore, the tetraphenyl ethene compound is widely applied in the fields of optoelectronic materials, fluorescence sensors, biological fluorescence markers and the like.

[0003] The photochromic material is a kind of optical material capable of changing color under ultraviolet or visible light irradiation, and has a wide application in the fields of optical switches, optical memories, anti-fake marks, intelligent windows, color-changing glasses and the like. The mechanochromic material is a kind of intelligent sensing material capable of sensing external force stimulation and changing fluorescence intensity or color, and plays a huge role in the fields of damage detection, inkless writing, anti-fake marks and information storage.

[0004] However, the current mechanochromic material or photochromic material synthesized by people has the defects of single function, single color change recovery mode, difficult control of color change recovery and great synthesis difficulty. In the modern society, the rapid development of science and technology promotes the diversification and refinement of the demand for material functions in various fields, and the material with the properties of photochromism and mechanochromism has great application potential in many key fields, and therefore, it is necessary to develop a new material with the properties of photochromism and mechanochromism to meet the increasingly complex and diversified social needs. SUMMARY

[0005] In view of the problems of the single function, single color change recovery mode, difficult control of color change recovery and great synthesis difficulty of the mechanochromic material or photochromic material in the prior art, the present application provides a meta-disubstituted tetraphenyl ethene compound and a preparation method and application thereof. The meta-disubstituted tetraphenyl ethene compound provided by the present application has the dual properties of mechanofluorochromism and photochromism, has mild synthesis conditions, a simple preparation method and high application prospect.

[0006] To solve the above technical problems, the technical scheme provided by the present application is as follows:

[0007] A meta-disubstituted tetraphenyl ethylene compound, the structural formula of which is shown as formula I:

[0008]

[0009] R is -CF3, -CN, -CHO or -COOCH3.

[0010] Compared with the prior art, the present application introduces trifluoromethyl, cyano, aldehyde group or methoxyformyl group into the meta position of tetraphenyl ethylene, and through the interaction of the meta specific substituent and the large conjugated group formed by the four benzene rings, the substituted tetraphenyl ethylene compound has more significant photochromic and piezochromic dual functions, the compound can realize photo-piezochromic synergistic effect, provides a basis for developing intelligent materials with multi-functional response characteristics, has great application potential in intelligent display, anti-fake identification, wearable devices and the like, and can effectively expand the application range of tetraphenyl ethylene compounds.

[0011] Most of the tetraphenyl ethylene compounds currently only have a single piezofluorescence color change function and do not have a photochromic function, the meta-disubstituted tetraphenyl ethylene compound provided by the present application has significant photochromic characteristics in addition to piezofluorescence color change, improves the reliability of the compound in the field of fluorescent anti-fake, information security materials and the like, and makes a significant progress compared with existing materials.

[0012] The present application also provides a preparation method of the above-mentioned meta-disubstituted tetraphenyl ethylene compound, comprising the following steps:

[0013] S1, under the condition of inert atmosphere and catalyst a, diphenylacetylene is subjected to addition reaction with pinacol diboronic acid to obtain diphenylstyryl pinacol diboronic acid shown as formula II;

[0014]

[0015] S2, under the condition of inert atmosphere, catalyst b and acid binding agent, the diphenylstyryl pinacol diboronic acid is subjected to coupling reaction with meta-halogenated benzene shown as formula III to obtain the meta-disubstituted tetraphenyl ethylene compound shown as formula I;

[0016]

[0017] R is -CF3, -CN, -CHO or -COOCH3; X is Cl, Br or I.

[0018] The preparation method of the meta-disubstituted tetraphenyl ethylene compound provided by the present application only needs two steps of reaction, has a short preparation route, simple process, high reaction conversion rate and high production safety, and is convenient for realizing large-scale production application.

[0019] Further, in S1, the reaction solvent of the addition reaction is selected from at least one of N,N-dimethylformamide, dioxane, tetrahydrofuran or acetonitrile.

[0020] The preferred reaction solvent can improve the yield and purity of the product obtained by reacting diphenylacetylene with pinacol diboron.

[0021] Further, in S1, the catalyst a is tetrakis(triphenylphosphine)platinum.

[0022] The preferred catalyst and the amount added above can promote the forward progress of the addition reaction, improve the yield of the product, and reduce the production cost.

[0023] Further, in S1, the molar ratio of diphenylacetylene to pinacol diboron is 1:1.5-1:3.

[0024] Further, in S1, the molar ratio of the catalyst a to diphenylacetylene is 0.01:1-0.03:1.

[0025] Further, in S1, the temperature of the addition reaction is 80-100°C, and the time of the addition reaction is 6-10h.

[0026] It should be noted that after the addition reaction in S1 is completed, a post-treatment process is also included: the reaction solution is rotary evaporated to remove the solvent, cooled and solidified, then dichloromethane is added for dissolution, followed by the addition of n-hexane for recrystallization to obtain diphenylstyrylpinacol diboron.

[0027] Specifically, in S1, the volume ratio of the above n-hexane to dichloromethane is 1:(2.5-3.5).

[0028] Illustratively, in S2, the meta-halogenated benzene is one of 3-trifluoromethyl halogenated benzene, 3-cyano halogenated benzene, 3-aldehyde halogenated benzene, and 3-carboxymethyl halogenated benzene.

[0029] Further, in S2, the reaction solvent of the coupling reaction is a mixed solution of an organic solvent and water, and the organic solvent is N,N-dimethylformamide, toluene, dioxane or xylene.

[0030] Further, in S2, the catalyst b includes tetrakis(triphenylphosphine)palladium and tetrabutylammonium bromide.

[0031] Further, in S2, the acid binding agent includes potassium carbonate.

[0032] Further, in S2, the mass ratio of diphenylstyrylpinacol diboron, meta-halogenated benzene, tetrakis(triphenylphosphine)palladium, potassium carbonate and tetrabutylammonium bromide is 1:(1.8-2.4):(0.012-0.02):(1.2-1.8):1.

[0033] Furthermore, in S2, the volume ratio of the organic solvent to water in the reaction solvent is 2:1 to 4:1.

[0034] Furthermore, in S2, the coupling reaction temperature is 85° C. to 105° C., and the coupling reaction time is 10 h to 16 h.

[0035] It should be noted that, in S2, after the coupling reaction is completed, a post-treatment process is also included: after the reaction is completed, dichloromethane is added to the reaction solution for extraction, the extraction is repeated three times, the extract is evaporated to remove the solvent, and then silica gel column chromatography is performed for separation and purification, the eluate is collected and concentrated to obtain an m-disubstituted tetraphenylethylene compound.

[0036] Specifically, the eluent for column chromatography separation and purification is a mixed solvent of dichloromethane and petroleum ether in a volume ratio of (2-5):1.

[0037] The preparation method of the meta-disubstituted tetraphenylethylene compound provided by the present invention is a normal pressure reaction with a reaction temperature not exceeding 110° C., and the reaction solvent does not need to be strictly dehydrated, the conditions are mild, and at the same time, the reaction route is short, the reaction raw materials are easily available, the reaction conversion rate is high, the economy is good, and it is easy to realize industrial production and application.

[0038] The present invention also provides the use of the above-mentioned meta-disubstituted tetraphenylethylene compound in intelligent sensing materials, photosensitive materials or anti-counterfeiting materials.

[0039] The present invention also provides a mechanofluorescent color-changing material, comprising the meta-disubstituted tetraphenylethylene compound.

[0040] The present invention also provides a photochromic material, comprising the meta-disubstituted tetraphenylethylene compound.

[0041] The present invention also provides a material having both mechanofluorescence and photochromism, comprising the meta-disubstituted tetraphenylethylene compound.

[0042] The meta-disubstituted tetraphenylethylene compound provided by the present invention can exhibit both photochromic and mechanochromic fluorescence, and can undergo significant changes in optical properties under the action of light and force. It is a multi-stimulus responsive material that can be applied to anti-counterfeiting markings, information storage materials, optoelectronic materials and other fields. Compared with single mechanochromic or photochromic response materials, it has stronger applicability.

[0043] In the field of intelligent sensing, a material can be used to detect light intensity and pressure changes simultaneously, reducing the number of sensors and system complexity, and improving integration. In information storage and display, light and force can be used as information input means, and different stimulus combinations can achieve more rich information coding and display effects, providing possibilities for the development of high-density information storage and multifunctional display devices. In intelligent wearable devices such as smart clothing and smart bracelets, the material can change color or display information in real time according to the movement of the human body (force) and changes in environmental light. In the field of anti-counterfeiting, the dual color-changing function increases the difficulty and complexity of counterfeiting, as it is difficult for counterfeiters to replicate the exact same effect by simulating the specific response characteristics of the material to light and force. In the field of security identification, such as important documents and certificates, the material's properties can be used to create tamper-resistant identification that will immediately change color if the document is damaged by external force or attempts to counterfeit, serving as a warning and identification. Therefore, the material provided by the present application, which has both force-induced color change and photochromic dual functions, has a wide range of applications and great application potential. With the continuous development of materials science and related technologies, its application in various fields will continue to expand and deepen, bringing more convenience and innovation to people's lives and social development. BRIEF DESCRIPTION OF DRAWINGS

[0044] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0045] Figure 1 is the fluorescence emission spectrum of the meta-disubstituted tetraphenyl ethylene compound prepared in Embodiment 1 to Embodiment 4 before and after grinding;

[0046] Figure 2 is the force-induced color change fluorescence chart of the meta-disubstituted tetraphenyl ethylene compound prepared in Embodiment 1 to Embodiment 4 under 365nm ultraviolet light before and after grinding;

[0047] Figure 3 is the ultraviolet-visible absorption spectrum of the meta-disubstituted tetraphenyl ethylene compound prepared in Embodiment 1 to Embodiment 4 before and after light irradiation;

[0048] Figure 4 is the color change chart of the meta-disubstituted tetraphenyl ethylene compound prepared in Embodiment 1 to Embodiment 4 under 365nm ultraviolet light before and after irradiation. DETAILED DESCRIPTION

[0049] In order to make the purposes, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with examples. It should be understood that the specific examples described herein are only used to explain the present application and not to limit the present application.

[0050] Example 1

[0051] A meta-disubstituted tetraphenyl ethene compound has the following structural formula:

[0052]

[0053] The preparation method of the above meta-disubstituted tetraphenyl ethene compound comprises the following steps:

[0054] Step a, weigh 10.108 g (0.04 mol) of pinacol diboronic acid and 0.249 g (0.2 mmol) of tetrakis(triphenylphosphine) platinum, dissolve in 30 mL of N,N-dimethylformamide, and add to a 250 mL three-necked flask, and then introduce nitrogen. Then weigh 3.56 g (0.02 mol) of diphenylacetylene, dissolve in 30 mL of N,N-dimethylformamide, and add to the above flask. Then heat to 90°C, and react for 8 hours. After the reaction is completed, spin the solvent, cool and solidify, then dissolve in 60 mL of dichloromethane, add 40 mL of n-hexane, heat to boiling point, and then cool to room temperature. A white solid compound 7.69 g is obtained, with a yield of 89%;

[0055] Step b, weigh 4.32 g (0.01 mol) of the diphenyl ethene-based pinacol diboronic acid obtained in the above step, 4.5 g (0.02 mol) of 3-bromotrifluorotoluene, 0.223 g (0.2 mmol) of tetrakis(triphenylphosphine) palladium, 3.22 g (0.01 mol) of tetrabutylammonium bromide, and 1.66 g (0.012 mol) of K2CO3 into a three-necked flask, and then add 80 mL of toluene and 40 mL of deionized water to the three-necked flask. Introduce nitrogen, and heat the oil bath to 95°C. React for 12 hours. After the reaction is completed, extract the organic matter with dichloromethane, repeat three times, spin to remove the solvent, and then perform silica gel column chromatography (eluent: a mixture of dichloromethane and petroleum ether in a volume ratio of 5:1). Concentrate to obtain 4.31 g of a colorless solid powder, with a yield of 92%.

[0056] The product is characterized by nuclear magnetic resonance, and the spectrum analysis data are as follows:

[0057] 1 H NMR (500 MHz, CDCl3): δ 7.36 (d, 2H), 7.23 (m, 4H), 7.18 (d, 2H), 7.13 (m, 6H), 7.02 (m, 4H).

[0058] FT-IR (cm-1 ) : 3059, 3025, 1609, 1598, 1493, 1439, 1336, 1276, 1255, 1203, 1167, 1128, 1094, 1074, 1031, 1001, 992, 908, 800, 789, 743, 716, 701, 670, 657, 608, 571).

[0059] ESI: m / z found for C 28 H 19 F6 [M+H + ] : 469.1385; calc'd: 469.1391.

[0060] Example 2

[0061] A meta-disubstituted tetraphenyl ethene compound has the following structural formula:

[0062]

[0063] The preparation method of the above meta-disubstituted tetraphenyl ethene compound comprises the following steps:

[0064] Step a, weigh 7.581 g (0.03 mol) of pinacol diboronic acid and 0.374 g (0.3 mmol) of tetrakis(triphenylphosphine) platinum, dissolve in 30 mL of dioxane, then add to a 250 mL three-necked flask, and then introduce nitrogen. Then weigh 3.56 g (0.02 mol) of diphenylacetylene, dissolve in 30 mL of dioxane, and then add to the above flask. Then heat to 80°C, and react for 10 hours. After the reaction is completed, remove the solvent by rotary evaporation, cool and solidify, then dissolve in 60 mL of dichloromethane, add 40 mL of n-hexane, heat to boiling point, and then cool to room temperature. A white solid compound 7.52 g is obtained, with a yield of 87%.

[0065] Step b, weigh 4.32 g (0.01 mol) of the diphenyl ethene-based pinacol diboronic acid obtained in the above step, 5.04 g (0.022 mol) of 3-iodobenzonitrile, 0.173 g (0.15 mmol) of tetrakis(triphenylphosphine) palladium, 3.22 g (0.01 mol) of tetrabutylammonium bromide, and 1.93 g (0.014 mol) of K2CO3, and then add to a three-necked flask. Then add 150 mL of N,N-dimethylformamide and 40 mL of deionized water to the three-necked flask, introduce nitrogen, and then heat to 105°C in an oil bath. React for 10 hours. After the reaction is completed, extract the organic matter with dichloromethane, repeat three times, remove the solvent by rotary evaporation, and then perform silica gel column chromatography (eluent: a mixture of dichloromethane and petroleum ether in a volume ratio of 2:1). Concentrate to obtain 3.37 g of a colorless solid powder, with a yield of 88%.

[0066] 1H NMR (500 MHz, CDC13): δ 7.54 (m, 2H), 7.41 (s, 2H), 7.36 (m, 2H), 7.26 (m, 6H), 7.08 (m, 4H).

[0067] FT-IR (cm -1 ): 3058, 3026, 2230, 1598, 1576, 1490, 1478, 1444, 1417, 1275, 1266, 1174, 1157, 1076, 1030, 1000, 907, 801, 764, 749, 698, 599, 570, 555.

[0068] ESI: m / z found for C 28 H 18 N2Na [M+Na + ]: 405.1372; Found: 405.1368.

[0069] Example 3

[0070] A meta-disubstituted tetraphenyl ethene compound has the following structural formula:

[0071]

[0072] The preparation method of the above meta-disubstituted tetraphenyl ethene compound comprises the following steps:

[0073] Step a, weigh 15.162 g (0.06 mol) of pinacol diboronic acid and 0.498 g (0.4 mmol) of tetrakis(triphenylphosphine) platinum, dissolve in 30 mL of toluene, then add to a 250 mL three-necked flask, introduce nitrogen, then weigh 3.56 g (0.02 mol) of diphenylacetylene, dissolve in 30 mL of toluene, and then add to the above flask, heat to 100°C, and react for 6 h. After the reaction is completed, the solvent is removed by rotary evaporation, and after cooling and solidification, 60 mL of dichloromethane is added for dissolution, 40 mL of n-hexane is added, heated to boiling point, and then cooled to room temperature to obtain 7.86 g of white solid compound with a yield of 91%.

[0074] Step b, diphenylstilbene diboronic acid pinacol ester 4.32 g (0.01 mol), 3- chlorobenzaldehyde 2.53 g (0.018 mol) and 0.139 g (0.12 mmol) of tetrakis(triphenylphosphine)palladium, 3.22 g (0.01 mol) of tetrabutylammonium bromide and 2.21 g (0.016 mol) of K2CO3 were weighed into a three-necked flask. 120 mL of dioxane and 40 mL of deionized water were added to the flask, which was then purged with nitrogen. The oil bath was heated to 90 °C, and the reaction was allowed to proceed for 16 h. After the reaction was completed, dichloromethane was added to extract the organic matter, which was repeated three times. After the solvent was removed by rotary evaporation, silica gel column chromatography was performed for separation and purification (eluent: a mixture of dichloromethane and petroleum ether in a volume ratio of 3:1). After concentration, 3.01 g of colorless solid powder was obtained, with a yield of 86%.

[0075] 1 H NMR (500 MHz, CDC13): δ 9.80 (s, 2H), 7.63 (d, 2H), 7.54 (m, 2H), 7.32 (m, 4H), 7.14 (m, 6H), 7.02 (m, 4H).

[0076] FT-IR (cm -1 ): 3056, 2827, 2728, 1699, 1596, 1578, 1492, 1444, 1379, 1270, 1229, 1193, 1157, 1118, 1029, 913, 816, 789, 737, 700, 651, 633, 575.

[0077] ESI: m / z found for C 28 H 20 O2Na[M+Na + ]: 411.1365; Calculated: 411.1361.

[0078] Example 4

[0079] A meta-disubstituted tetraphenyl ethene compound has the following structural formula:

[0080]

[0081] The preparation method of the above meta-disubstituted tetraphenyl ethene compound comprises the following steps:

[0082] a. Weigh 12.635 g (0.05 mol) of bis(pinacolato)diboron and 0.747 g (0.6 mmol) of tetrakis(triphenylphosphine) palladium, dissolve in 30 mL of acetonitrile, then add to a 250 mL three-necked flask, and then pass nitrogen gas. Weigh 3.56 g (0.02 mol) of diphenylacetylene, dissolve in 30 mL of acetonitrile, and then add to the above flask. Warm to 80°C, and react for 9 h. After the reaction is complete, remove the solvent by rotary evaporation, cool and solidify, dissolve in 60 mL of dichloromethane, add 40 mL of n-hexane, warm to the boiling point, and then cool to room temperature to obtain 7.34 g of white solid, with a yield of 85%.

[0083] Step b. Weigh 4.32 g (0.01 mol) of the diphenylstyryl bis(pinacolato)diboron obtained in the previous step, 5.16 g (0.024 mol) of methyl 3-bromobenzoate, 0.208 g (0.18 mmol) of tetrakis(triphenylphosphine) palladium, 3.22 g (0.01 mol) of tetrabutylammonium bromide, and 2.48 g (0.018 mol) of K2CO3, and add to a three-necked flask. Add 160 mL of xylene and 40 mL of deionized water to the three-necked flask, pass nitrogen gas, and warm to 85°C in an oil bath. React for 14 h. After the reaction is complete, extract the organic matter with dichloromethane, repeat three times, remove the solvent by rotary evaporation, and then perform silica gel column chromatography (eluent: a mixture of dichloromethane and petroleum ether at a volume ratio of 4:1) to purify and concentrate to obtain 4.04 g of colorless solid powder, with a yield of 90%.

[0084] 1 H NMR (500 MHz, CDCl3): δ 7.81 (d, 2H), 7.74 (s, 2H), 7.22 (d, 2H), 7.14 (m, 2H), 7.12 (m, 6H), 7.01 (m, 4H), 3.84 (s, 6H).

[0085] FT-IR (cm -1 ): 3057, 3025, 2950, 1724, 1599, 1579, 1491, 1438, 1295, 1242, 1204, 1139, 1108, 1084, 1007, 819, 750, 704, 630, 621, 576.

[0086] ESI: m / z found for C 30 H 24 O4Na[M+Na + ]: 471.1573, the theoretical value: 471.1572.

[0087] Test Example 1

[0088] Force-induced fluorescence color change detection:

[0089] The meta-disubstituted tetraphenyl ethylene compounds prepared in Example 1 to Example 4 were respectively placed in a mortar and ground by a pestle for about 1 min to obtain rubbed samples. The un-rubbed and rubbed samples were respectively placed in a sample groove of a Hitachi F-7000 fluorescence spectrophotometer, and the fluorescence emission spectra of the un-rubbed and rubbed powder samples were tested, with 365 nm ultraviolet light as excitation light, to obtain the emission spectra as shown in Figure 1 Table 1, and the peak values are summarized in Table 1. To show the effect, the solid powder products prepared in Example 1 to Example 4 were placed on a weighing paper, the powder was uniformly coated using a spoon, and then the sample was rubbed in a specific direction using a spoon or the like hard object, and was observed under a 365 nm ultraviolet lamp, and the change in fluorescence of the rubbed sample was observed, and the effect is shown in Figure 2 .

[0090] Table 1 Force-induced fluorescence color change detection results

[0091]

[0092] As can be seen from Table 1, after irradiation by 365 nm ultraviolet light, the four meta-disubstituted tetraphenyl ethylene compounds prepared in Example 1 to Example 4 all have a new absorption peak at about 500 nm. Due to the appearance of this absorption peak, the material absorbs green light from the environment, and appears pink, which is the photochromic phenomenon. After being subjected to external force rubbing, the four meta-disubstituted tetraphenyl ethylene compounds all have a red shift phenomenon of the fluorescence emission peak, i.e. the wavelength moves to a longer wavelength, which is the force-induced fluorescence color change phenomenon. As can be seen from Table 1, the four meta-disubstituted tetraphenyl ethylene compounds have both photochromic properties and force-induced fluorescence color change properties, and are expected to be applied in the fields of information security, optoelectronic materials, fluorescent anti-counterfeiting, etc.

[0093] Test Example 2

[0094] Photochromic detection:

[0095] The meta-disubstituted tetraphenyl ethylene compounds prepared in Example 1 to Example 4 were respectively added to dichloromethane to prepare a 1×10 -5 mol / L solution, which was placed in a Shimadzu UV-2600 ultraviolet-visible spectrophotometer, and a reference solution (dichloromethane) was placed therein, and the absorption spectrum of the solution at 350 nm to 750 nm was tested. Then the solution was irradiated by a 365 nm ultraviolet lamp for about 1 min, and then the ultraviolet-visible absorption spectrum was immediately tested, and the spectrum data is shown in Figure 3 , and the color change effect is shown in Figure 4 .

[0096] Figure 3The UV-Vis absorption spectra of the four kinds of meta-disubstituted tetraphenyl ethylene compounds prepared in Example 1 to Example 4 before and after light irradiation can be seen from the figure, and it can be seen that after UV light irradiation, an absorption peak appears in the visible light part of the dye. Figure 4 The photo can reflect the discoloration effect of the four kinds of compounds caused by light irradiation.

[0097] Comparative Example 1

[0098] The present comparative example provides a para-disubstituted tetraphenyl ethylene compound, and its structural formula is as follows:

[0099]

[0100] The preparation method of the above para-disubstituted tetraphenyl ethylene compound comprises the following steps:

[0101] Step a, weigh 12.635 g (0.05 mol) of pinacol diboronic acid and 0.747 g (0.6 mmol) of tetrakis(triphenylphosphine) platinum, dissolve in 30 mL of N,N-dimethylformamide, then introduce into a 250 mL three-necked flask, introduce nitrogen, then weigh 3.56 g (0.02 mol) of diphenylacetylene, dissolve in 30 mL of dioxane, and then introduce into the above flask, heat to 80°C, and react for 6 h. After the reaction is completed, the solvent is rotary evaporated, and after cooling and solidification, 60 mL of dichloromethane is added for dissolution, 40 mL of n-hexane is added, heated to boiling point, and then cooled to room temperature to obtain 7.52 g of white solid compound, with a yield of 87%;

[0102] Step b, weigh 4.32 g (0.01 mol) of the diphenyl ethylene-based pinacol diboronic acid obtained in the above step, 4.05 g (0.018 mol) of 4-bromotrifluorotoluene, 0.201 g (0.18 mmol) of tetrakis(triphenylphosphine) palladium, 3.22 g (0.01 mol) of tetrabutylammonium bromide, and 1.66 g (0.012 mol) of K2CO3 into a three-necked flask, then introduce 160 mL of toluene and 40 mL of deionized water into the three-necked flask, introduce nitrogen, and heat to 95°C in an oil bath for 16 h. After the reaction is completed, dichloromethane is added to extract the organic matter, which is repeated three times. After the solvent is rotary evaporated, silica gel column chromatography is performed for separation and purification (eluent is a mixture of dichloromethane and petroleum ether in a volume ratio of 5:1), concentrated, and 4.12 g of colorless solid powder is obtained, with a yield of 88%.

[0103] 1 H NMR (500 MHz, CDCl3): δ 7.393-7.351 (m, 4H), 7.159-7.126 (m, 10H), 7.007-6.987 (d, 4H).

[0104] FT-IR (cm -1) : 3057, 3023, 1610, 1595, 1492, 1438, 1337, 1278, 1253, 1201, 1169, 1130, 1096, 1075, 1032, 1005, 994, 912, 827, 745, 718, 703, 671, 650, 606, 573).

[0105] ESI: m / z found for C 28 H 19 F6 [M+H + ]: 469.1387; calc: 469.1391.

[0106] After the sample was irradiated with ultraviolet light for 1 minute, no color change was observed, and no new absorption peak was found using ultraviolet-visible spectrophotometry, indicating that the sample had no photochromic properties.

[0107] Comparative Example 2

[0108] The present comparative example provides a para-disubstituted tetraphenyl ethane compound, which has the following structural formula:

[0109]

[0110] The preparation method of the para-disubstituted tetraphenyl ethane compound includes the following steps:

[0111] Step a, weigh 7.581 g (0.03 mol) of pinacol diboronic acid and 0.249 g (0.2 mmol) of tetrakis(triphenylphosphine) platinum, dissolve in 30 mL of N,N-dimethylformamide, then add to a 250 mL three-necked flask, introduce nitrogen, then weigh 3.56 g (0.02 mol) of diphenylacetylene, dissolve in 30 mL of dioxane, and then add to the above flask, heat to 100°C, and react for 10 h. After the reaction is completed, the solvent is rotary evaporated, and after cooling and solidification, 60 mL of dichloromethane is added for dissolution, 40 mL of n-hexane is added, heated to boiling point, and then cooled to room temperature to obtain 7.77 g of white solid compound with a yield of 90%.

[0112] Step b, diphenylstilbene diboronic acid pinacol ester 4.32 g (0.01 mol), 4-iodobenzonitrile 4.58 g (0.02 mol), 0.231 g (0.2 mmol) of tetrakis(triphenylphosphine)palladium, 3.22 g (0.01 mol) of tetrabutylammonium bromide and 1.93 g (0.014 mol) of K2CO3 were weighed into a three-necked flask, 130 mL of N,N-dimethylformamide and 40 mL of deionized water were added to the three-necked flask, nitrogen was bubbled, the oil bath was heated to 85 °C, and the reaction was carried out for 10 h. After the reaction was completed, dichloromethane was added to extract the organic matter, which was repeated three times. After the solvent was removed by rotary evaporation, silica gel column chromatography was performed for separation and purification (eluent: dichloromethane: petroleum ether mixed solvent with a volume ratio of 2:1). After concentration, 3.29 g of colorless solid powder was obtained, with a yield of 86%.

[0113] 1 H NMR (500 MHz, CDCl3): δ 8.016-7.969 (m, 4H), 7.201-7.145 (m, 10H), 6.991-6.975 (m, 4H).

[0114] FT-IR (cm -1 ): 3056, 3023, 2231, 1597, 1578, 1491, 1477, 1447, 1418, 1276, 1262, 1178, 1158, 1072, 1031, 1002, 909, 831, 747, 697, 598, 570, 554.

[0115] ESI: m / z found: C 28 H 18 N2Na[M+Na + ]: 405.1374; theoric: 405.1368.

[0116] After the sample was irradiated with ultraviolet light for 1 min, no color change was observed, and no new absorption peak was found by testing with an ultraviolet visible spectrophotometer, indicating that the sample had no photochromic properties.

[0117] Comparative Example 3

[0118] This comparative example provides a para-disubstituted tetraphenyl ethylene compound, which has the following structural formula:

[0119]

[0120] The preparation method of the para-disubstituted tetraphenyl ethylene compound described above includes the following steps:

[0121] Step a, 10.108 g (0.04 mol) of bis(pinacolato)diboron and 0.374 g (0.3 mmol) of tetrakis(triphenylphosphine) palladium were weighed into a 250 mL three-necked flask, and nitrogen was bubbled through the flask. Then, 3.56 g (0.02 mol) of diphenylacetylene was dissolved in 30 mL of acetonitrile and added to the flask. The temperature was raised to 90°C, and the reaction was allowed to proceed for 10 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the white solid was dissolved in 60 mL of dichloromethane and 40 mL of n-hexane. The temperature was raised to the boiling point, and then the temperature was lowered to room temperature to obtain 7.6 g of a white solid, with a yield of 88%.

[0122] Step b, 4.32 g (0.01 mol) of the diphenylstyryl bis(pinacolato)diboron obtained in the previous step, 2.25 g (0.016 mol) of 4-chlorobenzaldehyde, 0.185 g (0.16 mmol) of tetrakis(triphenylphosphine) palladium, 3.22 g (0.01 mol) of tetrabutylammonium bromide, and 2.21 g (0.016 mol) of K2CO3 were weighed into a three-necked flask. Then, 80 mL of dioxane and 40 mL of deionized water were added to the flask, and nitrogen was bubbled through the flask. The temperature was raised to 105°C in an oil bath, and the reaction was allowed to proceed for 14 hours. After the reaction was completed, the organic matter was extracted with dichloromethane, and the extraction was repeated three times. After the solvent was removed by rotary evaporation, the product was purified by silica gel column chromatography (eluent: a mixture of dichloromethane and petroleum ether in a volume ratio of 3:1). After concentration, 3.08 g of a colorless solid powder was obtained, with a yield of 88%.

[0123] 1 H NMR (500 MHz, CDCl3): δ 9.91 (s, 2H), 7.65-7.63 (m, 4H), 7.16 (m, 4H), 7.14 (m, 6H), 7.02 (m, 4H).

[0124] FT-IR (cm -1 ): 3055, 2827, 2729, 1701, 1594, 1575, 1493, 1445, 1380, 1271, 1226, 1195, 1158, 1120, 1027, 915, 829, 734, 702, 651, 635, 574.

[0125] ESI: m / z found for C 28 H 20 O2Na[M+Na + ]: 411.1366; the theoretical value: 411.1361.

[0126] After the sample was irradiated with ultraviolet light for 1 minute, no color change was observed, and no new absorption peak was found when the sample was tested using an ultraviolet-visible spectrophotometer, indicating that the sample had no photochromic properties.

[0127] Comparative Example 4

[0128] The present comparative example provides a para-disubstituted tetraphenyl ethene compound, which has the following structural formula:

[0129]

[0130] The preparation method of the para-disubstituted tetraphenyl ethene compound includes the following steps:

[0131] Step a, weigh 15.162 g (0.06 mol) of pinacol diboronic acid and 0.498 g (0.4 mmol) of tetrakis(triphenylphosphine) platinum, dissolve in 30 mL of acetonitrile, then add to a 250 mL three-necked flask, and then add 3.56 g (0.02 mol) of diphenylacetylene, which is dissolved in 30 mL of toluene, to the flask, and then heat to 80°C and react for 9 hours. After the reaction is completed, the solvent is rotary evaporated, and then cooled and solidified, and then dissolved in 60 mL of dichloromethane, and then added with 40 mL of n-hexane, and then heated to boiling point, and then cooled to room temperature to obtain 7.43 g of a white solid, with a yield of 86%;

[0132] Step b, weigh 4.32 g (0.01 mol) of the diphenyl ethene-based pinacol diboronic acid obtained in the previous step, 5.16 g (0.024 mol) of methyl 4-bromobenzoate, 0.139 g (0.12 mmol) of tetrakis(triphenylphosphine) palladium, 3.22 g (0.01 mol) of tetrabutylammonium bromide, and 2.48 g (0.018 mol) of K2CO3, and then add them to a three-necked flask, and then add 160 mL of xylene and 40 mL of deionized water to the three-necked flask, and then introduce nitrogen, and then heat to 95°C in an oil bath, and then react for 12 hours. After the reaction is completed, the organic matter is extracted with dichloromethane, and then the extraction is repeated three times, and then the solvent is rotary evaporated, and then column chromatography is performed on silica gel (eluent: a mixture of dichloromethane and petroleum ether in a ratio of 4:1), and then concentrated to obtain 3.90 g of a colorless solid powder, with a yield of 87%.

[0133] 1 H NMR (500 MHz, CDCl3): δ 7.435-7.384 (m, 4H), 7.182-7.104 (m, 10H), 6.975-6.956 (d, 4H), 3.84 (s, 6H).

[0134] FT-IR (cm -1 ): 3054, 3026, 2951, 1725, 1597, 1581, 1492, 1436, 1294, 1241, 1208, 1141, 1106, 1084, 1008, 837, 751, 705, 631, 622, 578.

[0135] ESI: m / z found: C 30 H 24 O4Na[M+Na + ]: 471.1574; calc: 471.1572.

[0136] After UV irradiation for 1 min, no color change was observed for this sample, and no new absorption peak was found by testing with a UV-Vis spectrophotometer. This sample has no photochromic properties.

[0137] The above description is merely preferred embodiments of the present application, but not to limit the present application. Any modification, equivalent replacement or improvement made within the spirit and principle of the present application should be included in the scope of protection of the present application.

Claims

1. A meta-disubstituted tetraphenylethylene compound, characterized in that: Its structure is shown in Formula I: Formula I; Wherein, R is -CHO.

2. A method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 1, characterized in that: The following steps are involved: S1, under an inert atmosphere and in the presence of catalyst a, diphenylacetylene and diboronic acid pinacol ester undergo an addition reaction to obtain distyryl diboronic acid pinacol ester represented by formula II; Formula II S2, under an inert atmosphere, in the presence of catalyst b and an acid-binding agent, the distyryl diboronic acid pinacol ester undergoes a coupling reaction with the meta-halogenated benzene represented by formula III to obtain the meta-disubstituted tetraphenylethylene compound represented by formula I; Formula III Wherein, R is -CHO; X is Cl, Br or I.

3. The method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 2, wherein: In S1, the reaction solvent of the addition reaction is selected from at least one of N,N-dimethylformamide, dioxane, tetrahydrofuran or acetonitrile.

4. The method for preparing a meta-disubstituted tetraphenylethylene compound according to claim 2, wherein: In S1, the catalyst a is selected from tetrakis(triphenylphosphine)platinum.

5. The method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 2 or 3, wherein: In S1, the molar ratio of diphenylacetylene to diboric acid pinacol ester is 1:1.5 to 1:

3.

6. The method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 2 or 3, wherein: In S1, the molar ratio of the catalyst a to diphenylacetylene is 0.01:1 to 0.03:

1.

7. The method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 2 or 3, wherein: In S1, the temperature of the addition reaction is 80° C. to 100° C., and the time of the addition reaction is 6 h to 10 h.

8. The method for preparing a meta-disubstituted tetraphenylethylene compound according to claim 2, wherein: In S2, the reaction solvent of the coupling reaction is a mixed solution of an organic solvent and water, wherein the organic solvent is N,N-dimethylformamide, toluene, dioxane or xylene.

9. The method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 8, wherein: In S2, the catalyst b includes tetrakis(triphenylphosphine)palladium and tetrabutylammonium bromide.

10. The method for preparing a meta-disubstituted tetraphenylethylene compound according to claim 9, wherein: In S2, the acid binding agent is selected from potassium carbonate.

11. The method for preparing a meta-disubstituted tetraphenylethylene compound according to claim 10, wherein: In S2, the molar ratio of the distyryl diboronic acid pinacol ester, m-halobenzene, tetrakis(triphenylphosphine)palladium, potassium carbonate and tetrabutylammonium bromide is 1:(1.8-2.4):(0.012-0.02):(1.2-1.8):

1.

12. The method for preparing a meta-disubstituted tetraphenylethylene compound according to claim 8 to 10, wherein: In S2, the volume ratio of the organic solvent to water in the reaction solvent is 2:1 to 4:

1.

13. The method for preparing a meta-disubstituted tetraphenylethylene compound according to claim 2, wherein: In S2, the coupling reaction temperature is 85° C. to 105° C., and the coupling reaction time is 10 h to 16 h.

14. Use of the meta-disubstituted tetraphenylethylene compound according to claim 1 in smart sensing materials, photosensitive materials or anti-counterfeiting materials.

15. A mechanoluminescent material, characterized in that: The invention comprises the meta-disubstituted tetraphenylethylene compound according to claim 1.

16. A photochromic material, characterized in that: The invention comprises the meta-disubstituted tetraphenylethylene compound according to claim 1.

17. A material having both mechanoluminescent and photochromic properties, characterized in that: The invention comprises the meta-disubstituted tetraphenylethylene compound according to claim 1.

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