Meta-disubstituted tetraphenyl ethylene compound as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic synthesis, and particularly provides a meta-disubstituted tetraphenyl ethylene compound as well as a preparation method and application thereof. According to the invention, trifluoromethyl, cyano, aldehyde group or methoxyformyl is introduced into the meta-position of tetraphenyl ethylene, and the substituted tetraphenyl ethylene compound has more remarkable photochromic and mechanochromic dual functions through the interaction of a specific meta-position substituent and a large conjugated group formed by four benzene rings; the compound can realize a light-force synergistic color change effect, provides a basis for developing intelligent materials with multifunctional response characteristics, has great application potential in the aspects of intelligent display, anti-counterfeiting marks, wearable equipment and the like, and can effectively expand the application range of tetraphenyl ethylene compounds.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a meta-disubstituted tetraphenylethylene compound and a preparation method and application thereof. Background Art

[0002] Tetraphenylethylene compounds have optical properties such as aggregation-induced fluorescence and high quantum yield. They can efficiently release more energy in the form of fluorescence, emitting brighter and longer-lasting fluorescence. This advantage of high quantum yield ensures that the system has excellent performance, whether in the field of fluorescence sensors that pursue high sensitivity or in the application scenarios of optoelectronic materials that require strong light signal output. In addition, tetraphenylethylene compounds have the advantages of strong modifiability and mild preparation conditions. Researchers can accurately and diversely modify molecules according to different application requirements to prepare derivatives with different functions. Therefore, they have been widely used in optoelectronic materials, fluorescence sensors, and bioluminescent markers.

[0003] Photochromic materials are a type of optical material that can change color under ultraviolet or visible light, and are widely used in optical switches, optical storage, anti-counterfeiting labels, smart windows, photochromic glasses, etc. Mechanochromic materials are a type of intelligent sensing material that can sense external force stimulation and change fluorescence intensity or color, and play a huge role in damage detection, inkless writing, anti-counterfeiting labels, information storage, etc.

[0004] However, the mechanochromic materials or photochromic materials synthesized by people currently have the disadvantages of single function, single color recovery mode, difficult to control color recovery and great difficulty in synthesis. In modern society, the rapid development of science and technology has led to the increasingly diversified and refined demand for material functions in various fields. Materials with both photochromic and mechanochromic properties have great application potential in many key fields. Therefore, it is necessary to develop a new material with both photochromic and mechanochromic properties to meet the increasingly complex and diverse social needs. Summary of the invention

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

[0006] In order to solve the above technical problems, the technical solution provided by the present invention is:

[0007] A meta-disubstituted tetraphenylethylene compound, the structural formula of which is shown in Formula I:

[0008]

[0009] Where R is -CF 3 , -CN, -CHO or -COOCH 3 .

[0010] Compared with the prior art, the present invention introduces a trifluoromethyl group, a cyano group, an aldehyde group or a methoxycarbonyl group into the meta-position of tetraphenylethylene. Through the interaction between the specific meta-position substituent and the large conjugated group formed by the four benzene rings, the substituted tetraphenylethylene compound has more significant photochromic and mechanochromic dual functions. The compound can achieve a light-mechanical synergistic color-changing effect, provides a basis for the development of smart materials with multifunctional response characteristics, has great application potential in smart displays, anti-counterfeiting labels, wearable devices, etc., and can effectively expand the application scope of tetraphenylethylene compounds.

[0011] At present, most of the tetraphenylethylene compounds only have a single mechanofluorescent color-changing function, but do not have a photochromic function. The meta-disubstituted tetraphenylethylene compound provided by the present invention has not only mechanofluorescent color-changing properties but also significant photochromic properties, thereby improving its reliability in the fields of fluorescent anti-counterfeiting, information confidentiality materials, etc., and has achieved significant progress compared with existing materials.

[0012] The present invention also provides a method for preparing the above-mentioned meta-disubstituted tetraphenylethylene compound, comprising the following steps:

[0013] S1, under the condition of inert atmosphere and catalyst a, diphenylacetylene and diboric acid pinacol ester undergo addition reaction to obtain distyryl diboric acid pinacol ester shown in formula II;

[0014]

[0015] S2, in an inert atmosphere, in the presence of catalyst b and an acid-binding agent, the distyryl diboric acid pinacol ester is subjected to a coupling reaction with the meta-halogenated benzene shown in formula III to obtain the meta-disubstituted tetraphenylethylene compound shown in formula I;

[0016]

[0017] Where R is -CF 3 , -CN, -CHO or -COOCH 3 ; X is Cl, Br or I.

[0018] The preparation method of the meta-disubstituted tetraphenylethylene compound provided by the present invention requires only two-step reactions, has a short preparation route, a simple process, a high reaction conversion rate, and high production safety, and is easy to realize large-scale production and application.

[0019] Furthermore, 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 the reaction of diphenylacetylene and diboric acid pinacol ester.

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

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

[0023] Furthermore, in S1, the molar ratio of the diphenylacetylene to the diboric acid pinacol ester is 1:1.5 to 1:3.

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

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

[0026] It should be noted that in S1, after the addition reaction is completed, a post-treatment process is also included: the reaction solution is subjected to rotary evaporation to remove the solvent, cooled and solidified, dichloromethane is added to dissolve, and then n-hexane is added to recrystallize to obtain distyryl diboric acid pinacol ester.

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

[0028] Illustratively, in S2, the meta-halobenzene is one of 3-trifluoromethylhalobenzene, 3-cyanohalobenzene, 3-formylhalobenzene, and 3-methylformylhalobenzene.

[0029] Furthermore, 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] Furthermore, in S2, the catalyst b includes tetrakis(triphenylphosphine)palladium and tetrabutylammonium bromide.

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

[0032] Furthermore, in S2, the molar ratio of the distyryl diboric acid pinacol ester, 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 10h to 16h.

[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 meta-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, the reaction temperature does not exceed 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 easy to obtain, 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 have 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 labels, 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, it can be used to detect changes in light intensity and pressure at the same time. One material can monitor multiple physical quantities, reducing the number of sensors and the complexity of the system, and improving the integration. In terms of information storage and display, light and force can be used as means of information input, and different stimulus combinations can be used to achieve richer information encoding and display effects, which provides possibilities for the development of high-density information storage and multi-functional display devices. In smart wearable devices, such as smart clothing and smart bracelets, this material can change color or display information in real time according to human body movement (force) and ambient light changes. In the field of anti-counterfeiting, the dual color-changing function increases the difficulty and complexity of counterfeiting, because it is necessary to simulate the specific response characteristics of the material to light and force at the same time, and it is difficult for counterfeiters to replicate exactly the same effect. In terms of security identification, such as some important documents and certificates, the characteristics of this material can be used to make identification that is not easy to be tampered with. Once the document is damaged by external force or attempted to be forged, the color change of the material will immediately appear, which plays a warning and identification role. Therefore, the material with both mechanochromic and photochromic functions provided by the present invention has a broad application range and huge 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 THE DRAWINGS

[0044] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0045] Figure 1 is the fluorescence emission spectra of the meta-disubstituted tetraphenylethylene compounds prepared in Examples 1 to 4 of the present invention before and after grinding;

[0046] Figure 2 It is a mechanochromic fluorescence image of the meta-disubstituted tetraphenylethylene compound prepared in Examples 1 to 4 of the present invention before and after grinding under a 365nm ultraviolet lamp;

[0047] Figure 3 It is the ultraviolet-visible absorption spectrum of the meta-disubstituted tetraphenylethylene compound prepared in Examples 1 to 4 of the present invention before and after irradiation;

[0048] Figure 4 This is a color change diagram of the meta-disubstituted tetraphenylethylene compounds prepared in Examples 1 to 4 of the present invention before and after irradiation with a 365nm ultraviolet lamp. DETAILED DESCRIPTION

[0049] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0050] Example 1

[0051] A meta-disubstituted tetraphenylethylene compound, the structural formula of which is as follows:

[0052]

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

[0054] Step a, weighing 10.108g (0.04mol) of biboric acid pinacol ester and 0.249g (0.2mmol) of tetrakis (triphenylphosphine) platinum, dissolving them in 30mL N, N-dimethylformamide, adding them to a 250mL three-necked flask, passing nitrogen, then weighing 3.56g (0.02mol) of diphenylacetylene, dissolving them in 30mL of N, N-dimethylformamide, adding them to the above flask, heating to 90°C, reacting for 8h, and after the reaction, rotary evaporating the solvent, cooling and solidifying, adding 60mL of dichloromethane to dissolve, then adding 40mL of n-hexane, heating to boiling point, and cooling to room temperature to obtain 7.69g of compound as a white solid, with a yield of 89%;

[0055] Step b: Weigh 4.32 g (0.01 mol) of distyryl diboric acid pinacol ester obtained in the previous 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 K 2 CO 3 Add to a three-necked flask, then add 80 mL of toluene and 40 mL of deionized water to the three-necked flask, introduce nitrogen, raise the oil bath temperature to 95°C, react for 12 hours, and after the reaction is completed, add dichloromethane to extract the organic matter, repeat three times, and after rotary evaporation to remove the solvent, purify by silica gel column chromatography (the eluent is a mixed solvent of dichloromethane: petroleum ether in a volume ratio of 5:1), and concentrate to obtain 4.31 g of colorless solid powder with a yield of 92%.

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

[0057] 1 H NMR (500 MHz, CDCl 3 ): δ7.36(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 test value: C 28 H 19 F 6 [M+H + ]:469.1385;Theoretical value:469.1391.

[0060] Example 2

[0061] A meta-disubstituted tetraphenylethylene compound, the structural formula of which is as follows:

[0062]

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

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

[0065] Step b: Weigh 4.32 g (0.01 mol) of distyryl diboronic acid pinacol ester obtained in the previous 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 K 2 CO 3Add to a three-necked flask, then add 150mL of N,N-dimethylformamide and 40mL of deionized water to the three-necked flask, introduce nitrogen, raise the oil bath temperature to 105°C, react for 10 hours, after the reaction is completed, add dichloromethane to extract the organic matter, repeat three times, remove the solvent by rotary evaporation, and purify by silica gel column chromatography (the eluent is a mixed solvent of dichloromethane: petroleum ether in a volume ratio of 2:1), and concentrate to obtain 3.37g of colorless solid powder with a yield of 88%.

[0066] 1 H NMR (500 MHz, CDCl 3 ): δ7.54(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 test value: C 28 H 18 N 2 Na[M+Na + ]:405.1372;Theoretical value:405.1368.

[0069] Example 3

[0070] A meta-disubstituted tetraphenylethylene compound, the structural formula of which is as follows:

[0071]

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

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

[0074] Step b: Weigh 4.32 g (0.01 mol) of distyryl diboronic acid pinacol ester obtained in the previous step, 2.53 g (0.018 mol) of 3-chlorobenzaldehyde 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 K 2 CO 3 Add to a three-necked flask, then add 120mL of dioxane and 40mL of deionized water to the three-necked flask, introduce nitrogen, raise the oil bath temperature to 90°C, react for 16 hours, after the reaction is completed, add dichloromethane to extract the organic matter, repeat three times, remove the solvent by rotary evaporation, and separate and purify by silica gel column chromatography (the eluent is a mixed solvent of dichloromethane: petroleum ether in a volume ratio of 3:1), and concentrate to obtain 3.01 g of colorless solid powder with a yield of 86%.

[0075] 1 H NMR (500 MHz, CDCl 3 ): δ9.80(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 test value: C 28 H 20 O 2 Na[M+Na + ]:411.1365;theoretical value:411.1361.

[0078] Example 4

[0079] A meta-disubstituted tetraphenylethylene compound, the structural formula of which is as follows:

[0080]

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

[0082] a. Weigh 12.635 g (0.05 mol) of biboric acid pinacol ester and 0.747 g (0.6 mmol) of tetrakis(triphenylphosphine)platinum, dissolve them in 30 mL of acetonitrile, then add them to a 250 mL three-necked flask, pass nitrogen, weigh 3.56 g (0.02 mol) of diphenylacetylene, dissolve them in 30 mL of acetonitrile, add them to the above flask, heat to 80°C, react for 9 hours, and remove the solvent by rotary evaporation after the reaction is completed. After cooling and solidification, add 60 mL of dichloromethane to dissolve, add 40 mL of n-hexane, heat to boiling point, and cool to room temperature to obtain 7.34 g of compound as a white solid with a yield of 85%.

[0083] Step b: Weigh 4.32 g (0.01 mol) of distyryl diboronic acid pinacol ester 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 K 2 CO 3 Add to a three-necked flask, then add 160 mL of xylene and 40 mL of deionized water to the three-necked flask, introduce nitrogen, raise the oil bath temperature to 85°C, react for 14 hours, after the reaction is completed, add dichloromethane to extract the organic matter, repeat three times, remove the solvent by rotary evaporation, and separate and purify by silica gel column chromatography (the eluent is a mixed solvent of dichloromethane: petroleum ether in a volume ratio of 4:1), and concentrate to obtain 4.04 g of colorless solid powder with a yield of 90%.

[0084] 1 H NMR (500 MHz, CDCl 3 ): δ7.81(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 test value: C 30 H 24 O 4 Na[M+Na + ]:471.1573, theoretical value:471.1572.

[0087] Test Example 1

[0088] Force-induced fluorescence color change detection:

[0089] The meta-disubstituted tetraphenylethylene compounds prepared in Examples 1 to 4 were placed in a mortar and ground vigorously with a pestle for about 1 minute to obtain a rubbed sample. The unrubbed and rubbed samples were placed in the sample slot of a Hitachi F-7000 fluorescence spectrophotometer, and the fluorescence emission spectra of the unrubbed and rubbed powder samples were tested. The excitation light was 365nm ultraviolet light, and the emission spectra were obtained as shown in FIG. Figure 1 , and its peak values ​​are summarized in Table 1. To demonstrate the effect, the solid powder products prepared in Examples 1 to 4 were placed on weighing paper, and the powder was evenly coated with a medicine spoon, and then the sample was rubbed along a specific direction with a hard object such as a medicine spoon, and then the fluorescence change of the sample at the rubbing point was observed under a 365nm ultraviolet lamp. The effect is as follows Figure 2 shown.

[0090] Table 1 Results of fluorescence color change detection

[0091]

[0092] As can be seen from Table 1, after irradiation with 365nm ultraviolet light, the four meta-disubstituted tetraphenylethylene compounds prepared in Examples 1 to 4 show a new absorption peak at around 500nm. Due to the appearance of this absorption peak, the material absorbs the green light in the environment and appears pink, which is the photochromic phenomenon. After the four meta-disubstituted tetraphenylethylene compounds are subjected to external friction, the fluorescence emission peak undergoes a red shift, that is, the wavelength moves to a long wavelength, which is the mechanofluorescent color change phenomenon. As can be seen from Table 1, the four meta-disubstituted tetraphenylethylene compounds have both photochromic properties and mechanofluorescent color change properties, and are expected to be used in the fields of information confidentiality, optoelectronic materials, fluorescent anti-counterfeiting, etc.

[0093] Test Example 2

[0094] Photochromic detection:

[0095] The meta-disubstituted tetraphenylethylene compounds prepared in Examples 1 to 4 were added to dichloromethane to prepare 1×10 -5 mol / L solution was placed in a Shimadzu UV-2600 UV-visible spectrophotometer, and a reference solution (dichloromethane) was added to test its absorption spectrum at 350nm to 750nm. The solution was then irradiated with a 365nm UV lamp for about 1 minute, and then the UV-visible absorption spectrum was tested immediately. The spectral data is shown in Figure 3 As shown, the color change effect is as Figure 4 shown.

[0096] Figure 3These are the UV-visible absorption spectra of the four meta-disubstituted tetraphenylethylene compounds prepared in Examples 1 to 4 before and after irradiation with light. It can be seen from the figure that after irradiation with ultraviolet light, the dyes all exhibit an absorption peak in the visible light part. Figure 4 The photos show the effect of light causing the four compounds to change color.

[0097] Comparative Example 1

[0098] This comparative example provides a para-disubstituted tetraphenylethylene compound, the structural formula of which is as follows:

[0099]

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

[0101] Step a, weighing 12.635g (0.05mol) of biboric acid pinacol ester and 0.747g (0.6mmol) of tetrakis (triphenylphosphine) platinum, dissolving them in 30mL of N, N-dimethylformamide, then adding them to a 250mL three-necked flask, passing nitrogen, then weighing 3.56g (0.02mol) of diphenylacetylene, dissolving them in 30mL of dioxane, adding them to the above flask, heating to 80°C, reacting for 6h, and after the reaction, rotary evaporation of the solvent, cooling and solidifying, adding 60mL of dichloromethane to dissolve, adding 40mL of n-hexane, heating to boiling point, and cooling to room temperature to obtain 7.52g of compound as a white solid, with a yield of 87%;

[0102] Step b: Weigh 4.32 g (0.01 mol) of distyryl diboric acid pinacol ester obtained in the previous 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 K 2 CO 3 Add to a three-necked flask, then add 160 mL of toluene and 40 mL of deionized water to the three-necked flask, introduce nitrogen, raise the oil bath temperature to 95°C, react for 16 hours, after the reaction is completed, add dichloromethane to extract the organic matter, repeat three times, remove the solvent by rotary evaporation, and separate and purify by silica gel column chromatography (the eluent is a mixed solvent of dichloromethane: petroleum ether in a volume ratio of 5:1), and concentrate to obtain 4.12 g of colorless solid powder with a yield of 88%.

[0103] 1 H NMR (500 MHz, CDCl 3 ): δ7.393-7.351(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 test value: C 28 H 19 F 6 [M+H + ]:469.1387;Theoretical value:469.1391.

[0106] After the sample was irradiated with ultraviolet light for 1 minute, there was no color change. No new absorption peak was found when tested using a UV-visible spectrophotometer, indicating that this sample has no photochromic properties.

[0107] Comparative Example 2

[0108] This comparative example provides a para-disubstituted tetraphenylethylene compound, the structural formula of which is as follows:

[0109]

[0110] The preparation method of the above-mentioned para-disubstituted tetraphenylethylene compound comprises the following steps:

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

[0112] Step b: Weigh 4.32 g (0.01 mol) of distyryl diboronic acid pinacol ester obtained in the previous step, 4.58 g (0.02 mol) of 4-iodobenzonitrile, 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 K 2 CO 3Add to a three-necked flask, then add 130mL of N,N-dimethylformamide and 40mL of deionized water to the three-necked flask, introduce nitrogen, raise the oil bath temperature to 85°C, react for 10 hours, after the reaction is completed, add dichloromethane to extract the organic matter, repeat three times, remove the solvent by rotary evaporation, and separate and purify by silica gel column chromatography (the eluent is a mixed solvent of dichloromethane: petroleum ether in a volume ratio of 2:1), and concentrate to obtain 3.29g of colorless solid powder with a yield of 86%.

[0113] 1 H NMR (500 MHz, CDCl 3 ): δ8.016-7.969(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 test value: C 28 H 18 N 2 Na[M+Na + ]:405.1374;Theoretical value:405.1368.

[0116] After the sample was irradiated with ultraviolet light for 1 minute, there was no color change. No new absorption peak was found when tested using a UV-visible spectrophotometer, indicating that this sample has no photochromic properties.

[0117] Comparative Example 3

[0118] This comparative example provides a para-disubstituted tetraphenylethylene compound, the structural formula of which is as follows:

[0119]

[0120] The preparation method of the above-mentioned para-disubstituted tetraphenylethylene compound comprises the following steps:

[0121] Step a, weighing 10.108g (0.04mol) of biboric acid pinacol ester and 0.374g (0.3mmol) of tetrakis (triphenylphosphine) platinum, dissolving them in 30mL of toluene, then adding them to a 250mL three-necked flask, passing nitrogen, then weighing 3.56g (0.02mol) of diphenylacetylene, dissolving them in 30mL of acetonitrile, adding them to the above flask, heating to 90°C, reacting for 10h, and after the reaction, rotary evaporating the solvent, cooling and solidifying, adding 60mL of dichloromethane to dissolve, adding 40mL of n-hexane, heating to boiling point, and cooling to room temperature to obtain 7.6g of compound as a white solid, with a yield of 88%;

[0122] Step b: Weigh 4.32 g (0.01 mol) of distyryl diboric acid pinacol ester 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 K 2 CO 3 Add to a three-necked flask, then add 80 mL of dioxane and 40 mL of deionized water to the three-necked flask, introduce nitrogen, raise the oil bath temperature to 105°C, react for 14 hours, after the reaction is completed, add dichloromethane to extract the organic matter, repeat three times, remove the solvent by rotary evaporation, and separate and purify by silica gel column chromatography (the eluent is a mixed solvent of dichloromethane: petroleum ether in a volume ratio of 3:1), and concentrate to obtain 3.08 g of colorless solid powder with a yield of 88%.

[0123] 1 H NMR (500 MHz, CDCl 3 ): δ9.91(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 test value: C 28 H 20 O 2 Na[M+Na + ]:411.1366;Theoretical value:411.1361.

[0126] After the sample was irradiated with ultraviolet light for 1 minute, there was no color change. No new absorption peak was found when tested using a UV-visible spectrophotometer, indicating that this sample has no photochromic properties.

[0127] Comparative Example 4

[0128] This comparative example provides a para-disubstituted tetraphenylethylene compound, the structural formula of which is as follows:

[0129]

[0130] The preparation method of the above-mentioned para-disubstituted tetraphenylethylene compound comprises the following steps:

[0131] Step a, weighing 15.162g (0.06mol) of biboric acid pinacol ester and 0.498g (0.4mmol) of tetrakis (triphenylphosphine) platinum, dissolving them in 30mL of acetonitrile, then adding them to a 250mL three-necked flask, passing nitrogen, then weighing 3.56g (0.02mol) of diphenylacetylene, dissolving them in 30mL of toluene, adding them to the above flask, heating to 80°C, reacting for 9h, and after the reaction, rotary evaporating the solvent, cooling and solidifying, adding 60mL of dichloromethane to dissolve, adding 40mL of n-hexane, heating to boiling point, and cooling to room temperature to obtain 7.43g of compound as a white solid, with a yield of 86%;

[0132] Step b: Weigh 4.32 g (0.01 mol) of distyryl diboronic acid pinacol ester 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 K 2 CO 3 Add to a three-necked flask, then add 160 mL of xylene and 40 mL of deionized water to the three-necked flask, introduce nitrogen, raise the oil bath temperature to 95°C, react for 12 hours, after the reaction is completed, add dichloromethane to extract the organic matter, repeat three times, remove the solvent by rotary evaporation, and separate and purify by silica gel column chromatography (eluent is a 4:1 dichloromethane: petroleum ether mixed solvent), concentrate to obtain 3.90 g of colorless solid powder, with a yield of 87%.

[0133] 1 H NMR (500 MHz, CDCl 3 ): δ7.435-7.384(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 test value: C 30 H 24 O 4 Na[M+Na + ]:471.1574;Theoretical value:471.1572.

[0136] After the sample was exposed to ultraviolet light for 1 minute, there was no color change, and no new absorption peak was found when tested with a UV-visible spectrophotometer, indicating that the sample had no photochromic properties.

[0137] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent substitution or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A meta-disubstituted tetraphenylethylene compound, characterized in that: Its structure is shown in Formula I: Wherein, R is -CF3, -CN, -CHO or -COOCH3.

2. A method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 1, characterized in that: The following steps are involved: S1, under the condition of inert atmosphere and catalyst a, diphenylacetylene and diboric acid pinacol ester undergo addition reaction to obtain distyryl diboric acid pinacol ester shown in formula II; S2, in an inert atmosphere, in the presence of catalyst b and an acid-binding agent, the distyryl diboric acid pinacol ester is subjected to a coupling reaction with the meta-halogenated benzene shown in formula III to obtain the meta-disubstituted tetraphenylethylene compound shown in formula I; Wherein, R is -CF3, -CN, -CHO or -COOCH3; X is Cl, Br or I.

3. The method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 2, characterized in that: In S1, the reaction solvent of the addition reaction is selected from at least one of N,N-dimethylformamide, dioxane, tetrahydrofuran or acetonitrile; and / or In S1, the catalyst a comprises tetrakis(triphenylphosphine)platinum.

4. The method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 2 or 3, characterized in that: In S1, the molar ratio of diphenylacetylene to diboric acid pinacol ester is 1:1.5 to 1:3; and / or In S1, the molar ratio of the catalyst a to diphenylacetylene is 0.01:1 to 0.03:1; and / or In S1, the temperature of the addition reaction is 80°C to 100°C, and the time of the addition reaction is 6h to 10h.

5. The method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 2, characterized in that: 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; and / or In S2, the catalyst b comprises tetrakis(triphenylphosphine)palladium and tetrabutylammonium bromide; and / or In S2, the acid binding agent includes potassium carbonate.

6. The method for preparing the meta-disubstituted tetraphenylethylene compound according to claim 5, characterized in that: In S2, the molar ratio of distyryl diboric acid pinacol ester, 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; and / or In S2, the volume ratio of the organic solvent to water in the reaction solvent is 2:1 to 4:1; and / or In S2, the coupling reaction temperature is 85°C to 105°C, and the coupling reaction time is 10h to 16h.

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

8. A mechanoluminescent material, characterized in that: The invention comprises the meta-disubstituted tetraphenylethylene compound as claimed in claim 1.

9. A photochromic material, characterized in that: The invention comprises the meta-disubstituted tetraphenylethylene compound as claimed in claim 1.

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

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