CN112940006B - Tetraphenyl ethylene-oxazine material and synthetic method and application thereof - Google Patents

Abstract

Translated fromChinese

本发明开发出了一类四苯乙烯‑噁嗪材料及其合成方法，通过共轭双键将四苯乙烯功能单元和吲哚并噁嗪分子开关相连接，兼具有分子开关和聚集诱导发光性能，能够针对多种刺激做出荧光和颜色改变响应，具体结构如式(1)所示。该类染料在信息存储、荧光防伪和生物成像领域有着重要的应用。

The present invention has developed a class of tetraphenylethylene-oxazine materials and their synthesis methods, which connect tetraphenylethylene functional units and indoloxazine molecular switches through conjugated double bonds, and have both molecular switches and aggregation-induced luminescence Performance, can respond to various stimuli with fluorescence and color changes, and the specific structure is shown in formula (1). Such dyes have important applications in the fields of information storage, fluorescent anti-counterfeiting and biological imaging.

Description

Translated fromChinese

一类四苯乙烯-噁嗪材料及其合成方法和应用A class of tetraphenylethylene-oxazine materials and their synthesis methods and applications

技术领域technical field

本发明属于有机发光材料领域，具体涉及一类四苯乙烯-噁嗪材料及其合成方法，以及在信息存储、荧光防伪和生物成像领域的应用。The invention belongs to the field of organic luminescent materials, and in particular relates to a class of tetraphenylethylene-oxazine materials and a synthesis method thereof, as well as applications in the fields of information storage, fluorescent anti-counterfeiting and biological imaging.

背景技术Background technique

荧光防伪作为一种防伪手段，不止是政府在制造纸币上重视使用，也是很多民用企业当中广泛使用的一种防伪技术。荧光防伪使用特殊的荧光油墨在产品的某的特定的位置上，将文字信息或者图案隐藏其中，当想要辨别的时候，使用紫外线灯照射方可识别出来。目前，很多企业喜欢定制荧光和隐形防伪技术相结合的产品，隐形技术不易被发觉，更不易复制仿造，便能起到双重防伪的效果，大大提高增强了产品的防伪性能。As an anti-counterfeiting method, fluorescent anti-counterfeiting is not only used by the government in the manufacture of banknotes, but also an anti-counterfeiting technology widely used in many civilian enterprises. Fluorescent anti-counterfeiting uses special fluorescent ink to hide text information or patterns in a specific position of the product. When you want to identify it, you can use ultraviolet light to identify it. At present, many companies like to customize products that combine fluorescence and invisible anti-counterfeiting technology. Invisible technology is not easy to be detected, and it is not easy to copy and imitate. It can achieve double anti-counterfeiting effects and greatly enhance the anti-counterfeiting performance of products.

四苯乙烯是经典的聚集诱导发光材料，因其合成步骤简单，原料廉价易得、性能优越且人们对其研究最为深入，成为聚集诱导发光材料家族的明星分子。而噁嗪作为新型分子开关因其具有响应速度快、不易光降解、抗疲劳性优良等优异的性能，受到科研工作者的青睐。分子开关作为功能分子可赋予聚集诱导发光材料刺激响应性能，即能够在外界刺激下发生吸收及荧光波长的可逆变化。截至目前，噁嗪类分子开关的聚集诱导发光材料还未见报道，为了发展该分子开关的性能，丰富市场对刺激响应聚集诱导发光材料的需求，设计合成该类四苯乙烯-噁嗪材料就显得尤为重要。Tetraphenylethylene is a classic aggregation-induced luminescent material. Because of its simple synthesis steps, cheap and easy-to-obtain raw materials, superior performance and the most in-depth research on it, it has become a star molecule in the family of aggregation-induced luminescent materials. As a new type of molecular switch, oxazines are favored by researchers because of their excellent properties such as fast response, low photodegradation, and excellent fatigue resistance. Molecular switches, as functional molecules, can endow aggregation-induced luminescent materials with stimuli-responsive properties, that is, reversible changes in absorption and fluorescence wavelengths can occur under external stimuli. Up to now, aggregation-induced luminescent materials for oxazine molecular switches have not been reported. In order to develop the performance of the molecular switch and enrich the market demand for stimuli-responsive aggregation-induced luminescent materials, it is necessary to design and synthesize this type of tetraphenylethylene-oxazine materials. appears to be particularly important.

发明内容Contents of the invention

本发明的目的之一是提供一类四苯乙烯-噁嗪材料，共轭双键将四苯乙烯功能单元和吲哚并噁嗪分子开关相连接，兼具有分子开关和聚集诱导发光性能，能够针对多种刺激做出荧光和颜色改变响应，刺激响应固态发光材料，该材料可应用在信息存储、荧光防伪和生物成像领域。One of the objectives of the present invention is to provide a class of tetraphenylethylene-oxazine materials, the conjugated double bond connects the tetraphenylethylene functional unit and the indoloxazine molecular switch, which has both molecular switch and aggregation-induced luminescent properties, It can respond to various stimuli with fluorescence and color changes, and the stimuli-responsive solid-state luminescent material can be applied in the fields of information storage, fluorescent anti-counterfeiting and biological imaging.

本发明的另一目的是提供该类四苯乙烯-噁嗪材料的制备方法，该方法具有步骤简单、容易分离、原料价廉等优点。Another object of the present invention is to provide a preparation method of this tetraphenylethylene-oxazine material, which has the advantages of simple steps, easy separation, and cheap raw materials.

该类四苯乙烯-噁嗪材料具有如下结构：Such tetraphenylethylene-oxazine materials have the following structures:

其中：in:

X,Y,Z,W为相同或不同的取代基；X, Y, Z, W are the same or different substituents;

X,Y,Z,W具体为C_mH_2m+1、F、Cl、Br、OH、C5H5N、OCH3、N(C_mH_2m+1)₂或C₆H₆中的任何一种基团；X, Y, Z, W are specifically any one of C_m H_2m+1 , F, Cl, Br, OH, C5H5N, OCH3, N(C_m H_2m+1 )₂ or C₆ H₆ ;

m是0～20之间的整数。m is an integer between 0 and 20.

其具体合成路线，如下：Its specific synthetic route is as follows:

具体合成步骤如下：Concrete synthetic steps are as follows:

其特征步骤如下：Its characteristic steps are as follows:

(1)中间体1-(4-溴苯基)-1,2,2-三苯乙烯的合成(1) Synthesis of intermediate 1-(4-bromophenyl)-1,2,2-triphenylethylene

搅拌下，将超干四氢呋喃加入氮气氛围下的Z、W二取代的二苯基甲烷，低温下，加入正丁基锂，继续搅拌1-2小时；保持低温，将Y取代的4-溴二苯甲酮的四氢呋喃溶液加入上述反应体系中，升温回流6-12小时；用氯化铵水溶液淬灭反应后，继续用二氯甲烷萃取，并用无水硫酸钠干燥有机相，最后经减压蒸馏除去溶剂，残余物经硅胶层析柱分离得到白色固体化合物1，即中间体1-(4-溴苯基)-1,2,2-三苯乙烯。Under stirring, add ultra-dry tetrahydrofuran to Z, W disubstituted diphenylmethane under nitrogen atmosphere, add n-butyllithium at low temperature, and continue stirring for 1-2 hours; keep the low temperature, add Y-substituted 4-bromodiphenylmethane Add the tetrahydrofuran solution of benzophenone into the above reaction system, raise the temperature and reflux for 6-12 hours; quench the reaction with ammonium chloride aqueous solution, continue to extract with dichloromethane, dry the organic phase with anhydrous sodium sulfate, and finally distill under reduced pressure The solvent was removed, and the residue was separated by silica gel column chromatography to obtain whitesolid compound 1, namely the intermediate 1-(4-bromophenyl)-1,2,2-triphenylethylene.

Z、W二取代的二苯基甲烷和Y取代的4-溴二苯甲酮的摩尔比为1.1-3.0；正丁基锂的物质的量应为Z、W二取代的二苯基甲烷的0.6-1.0当量，且于零下二十度加入正丁基锂。The molar ratio of Z, W disubstituted diphenylmethane and Y substituted 4-bromobenzophenone is 1.1-3.0; the amount of n-butyllithium should be Z, W disubstituted diphenylmethane 0.6-1.0 equivalent, and add n-butyllithium at minus twenty degrees.

(2)中间体4-(1,2,2-三苯乙烯基)苯甲醛的合成：(2) Synthesis of intermediate 4-(1,2,2-tristyryl)benzaldehyde:

将步骤(1)得到的化合物1置于氮气气氛下搅拌，随后加入超干四氢呋喃，于低温下，加入正丁基锂，保持低温继续搅拌1-2小时；再室温搅拌1-2小时后，再次降低反应温度，加入二甲基甲酰胺，缓慢升至室温，继续搅拌6-12小时即可；用2M盐酸水溶液淬灭反应后，再用二氯甲烷萃取，将有机相用无水硫酸钠干燥后减压蒸馏除去溶剂，残余物用硅胶层析柱分离得到黄色化合物2，即为中间体4-(1,2,2-三苯乙烯基)苯甲醛。Stir thecompound 1 obtained in step (1) under a nitrogen atmosphere, then add ultra-dry tetrahydrofuran, add n-butyllithium at low temperature, keep stirring at low temperature for 1-2 hours; after stirring at room temperature for 1-2 hours, Lower the reaction temperature again, add dimethylformamide, slowly rise to room temperature, and continue to stir for 6-12 hours; quench the reaction with 2M hydrochloric acid aqueous solution, then extract with dichloromethane, and wash the organic phase with anhydrous sodium sulfate After drying, the solvent was distilled off under reduced pressure, and the residue was separated by silica gel column chromatography to obtain yellow compound 2, which is the intermediate 4-(1,2,2-tristyryl)benzaldehyde.

化合物1和二甲基甲酰胺的摩尔比为1：5-10；化合物1与四氢呋喃的质量体积比为1:5-10(mg:ml)。The molar ratio ofcompound 1 to dimethylformamide is 1:5-10; the mass volume ratio ofcompound 1 to tetrahydrofuran is 1:5-10 (mg:ml).

(3)中间体3的合成：(3) Synthesis of intermediate 3:

将X取代的2,3,3-三甲基吲哚和2-羟基-5-硝基溴苄溶于乙腈，加热至回流反应6-18小时后，冷却至室温，将溶剂经减压蒸馏除去，残余物用硅胶层析柱分离，得到粉红色化合物3。Dissolve X-substituted 2,3,3-trimethylindole and 2-hydroxy-5-nitrobenzyl bromide in acetonitrile, heat to reflux for 6-18 hours, cool to room temperature, and distill the solvent under reduced pressure The residue was separated by silica gel column chromatography to obtain pink compound 3.

X取代的2,3,3-三甲基吲哚和2-羟基-5-硝基溴苄的摩尔比为1：0.8-1.2；且X取代的2,3,3-三甲基吲哚与乙腈的质量体积比为1：5-10(mg:ml)。The molar ratio of X-substituted 2,3,3-trimethylindole to 2-hydroxy-5-nitrobenzyl bromide is 1:0.8-1.2; and X-substituted 2,3,3-trimethylindole The mass volume ratio with acetonitrile is 1:5-10 (mg:ml).

(4)四苯乙烯-噁嗪的合成：(4) Synthesis of tetraphenylethylene-oxazine:

将化合物2和化合物3溶于无水乙醇，升温至回流搅拌6-20小时，冷却至室温后，经减压蒸馏除去溶剂，用硅胶层析柱分离得到四苯乙烯-噁嗪(化合物4)。Dissolve compound 2 and compound 3 in absolute ethanol, raise the temperature to reflux and stir for 6-20 hours, after cooling to room temperature, remove the solvent by distillation under reduced pressure, and separate with silica gel column to obtain tetraphenylethylene-oxazine (compound 4) .

化合物2和化合物3的摩尔比为1：0.8-1.2；且化合物2与无水乙醇的质量体积比为1：5-10(mg:ml)。The molar ratio of compound 2 to compound 3 is 1:0.8-1.2; and the mass volume ratio of compound 2 to absolute ethanol is 1:5-10 (mg:ml).

本发明的有益效果：Beneficial effects of the present invention:

本发明涉及的四苯乙烯-噁嗪材料具有原料廉价易得、合成方法简单易行、产物分离容易且产率较高等优点。The tetraphenylethylene-oxazine material involved in the invention has the advantages of cheap and easy-to-obtain raw materials, simple and easy synthesis method, easy product separation and high yield, and the like.

本发明涉及的四苯乙烯-噁嗪材料同时具有固态酸碱及光热可逆的荧光开关性质。The tetraphenylethylene-oxazine material involved in the invention has both solid-state acid-base and photothermal reversible fluorescent switch properties.

基于该四苯乙烯-噁嗪材料的特征合成方法及酸碱和光热可逆的特点，其化学结构、合成方法及其在信息存储、荧光防伪和生物成像领域的应用均受此专利保护。Based on the characteristic synthesis method of the tetraphenylethylene-oxazine material and the characteristics of acid-base and photothermal reversibility, its chemical structure, synthesis method and its application in the fields of information storage, fluorescent anti-counterfeiting and biological imaging are all protected by this patent.

附图说明：Description of drawings:

图1：为中间体1的氢核磁谱图。Figure 1: is the proton magnetic spectrum ofintermediate 1.

图2：为中间体2的氢核磁谱图。Figure 2: is the proton magnetic spectrum of intermediate 2.

图3：为P1的氢核磁谱图。Figure 3: Proton Magnetic Spectrum of P1.

图4：为P1的碳核磁谱图。Figure 4: C NMR spectrum of P1.

图5：为P1在不同溶剂中的紫外可见吸收光谱。Figure 5: UV-Vis absorption spectra of P1 in different solvents.

图6：为P1的荧光发射光谱随水含量变化情况。Figure 6: Fluorescence emission spectrum of P1 as a function of water content.

图7：为P1的有机溶液在酸碱刺激下的紫外可见吸收光谱。Figure 7: The UV-Vis absorption spectrum of the organic solution of P1 under acid-base stimulation.

图8：为P1的有机溶液的三氟乙酸滴定的紫外可见吸收光谱Figure 8: UV-Vis absorption spectrum of the TFA titration of the organic solution of P1

图9：为P1的有机溶液在紫外光的照射下其紫外可见吸收光谱随时间的变化情况。Figure 9: The change of the UV-Vis absorption spectrum with time of the organic solution of P1 under the irradiation of UV light.

图10：为P1的固体在紫外光照射前后的紫外可见吸收光谱。Figure 10: UV-Vis absorption spectra of solid P1 before and after UV irradiation.

图11：为P1的固体在紫外光照射前后的荧光发射光谱。Figure 11: Fluorescence emission spectra of solid P1 before and after UV irradiation.

图12：光照前后P1的固体分别在日光灯和紫外灯下的显微图片。Figure 12: Micrographs of the solid P1 before and after illumination under fluorescent lamp and ultraviolet lamp.

图13：为P1的固体在酸刺激前后的紫外可见吸收光谱。Figure 13: UV-Vis absorption spectra of solid P1 before and after acid stimulation.

图14：为P1的固体在酸刺激前后的荧光发射光谱。Figure 14: Fluorescence emission spectra of P1 solid before and after acid stimulation.

图15：酸刺激前后P1的固体分别在日光灯和紫外灯下的显微图片。Fig. 15: Micrographs of P1 solid before and after acid stimulation under fluorescent lamp and ultraviolet lamp respectively.

图16：通过喷涂方式负载在滤纸上的P1对酸碱及光热的可逆刺激响应。Figure 16: The reversible stimulus response of P1 loaded on filter paper by spraying to acid-base and light-heat.

具体实施方式Detailed ways

以下结合具体优选的实施例对本发明作进一步描述，但并不因此而限制本发明的保护范围。The present invention will be further described below in conjunction with specific preferred embodiments, but the protection scope of the present invention is not limited thereby.

实施例1Example 1

当X,Y,Z,W均为H时，一类四苯乙烯-噁嗪材料P1的合成路线和产物结构如下：When X, Y, Z, and W are all H, the synthetic route and product structure of a class of tetraphenylethylene-oxazine materials P1 are as follows:

中间体1的合成：Synthesis of Intermediate 1:

将2,3,3-三甲基吲哚(1.6ml,10mmol)和2-羟基-5-硝基溴苄(2.3g,10mmol)置于单口圆底烧瓶中，用30ml乙腈溶解，将反应体系升温至回流，搅拌下持续反应24小时。反应结束后，将体系冷却至室温，通过减压蒸馏除去反应溶剂，随后用二氯甲烷将残余物溶解，再用碳酸钾的饱和溶液萃取3-5次，合并所有有机相并用无水硫酸钠干燥。将溶剂通过减压蒸馏除去后，残余物通过硅胶柱层析(10/1；石油醚/乙酸乙酯；v/v)分离得到黄色固体即为化合物1(2.8g,产率90％)。2,3,3-Trimethylindole (1.6ml, 10mmol) and 2-hydroxy-5-nitrobenzyl bromide (2.3g, 10mmol) were placed in a single-necked round bottom flask, dissolved with 30ml of acetonitrile, and the reaction The system was heated to reflux, and the reaction was continued for 24 hours under stirring. After the reaction, the system was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure, and the residue was dissolved with dichloromethane, then extracted 3-5 times with a saturated solution of potassium carbonate, all organic phases were combined and washed with anhydrous sodium sulfate dry. After the solvent was distilled off under reduced pressure, the residue was separated by silica gel column chromatography (10/1; petroleum ether/ethyl acetate; v/v) to obtaincompound 1 as a yellow solid (2.8 g, yield 90%).

其高分辨质谱数据如下：Its high-resolution mass spectrometry data are as follows:

高分辨质谱C₁₈H₁₈N₂O₃[M+H]⁺计算值：311.1396；实验值：311.1370。High resolution mass spectrum_Calcd . for_C18H18N2O3 [M+H]⁺ :_311.1396 ; found:_311.1370 .

其核磁谱图氢谱数据如下：Its nuclear magnetic spectrum hydrogen spectrum data are as follows:

¹H NMR(400MHz,CDCl₃)δ8.07(d,J＝2.7Hz,1H),7.94(dd,J＝9.1,2.8Hz,1H),7.11(dd,J＝7.3,0.7Hz,1H),7.07(dd,J＝7.7,1.2Hz,1H),6.83(td,J＝7.5,0.8Hz,1H),6.71(d,J＝9.1Hz,1H),6.56(d,J＝7.8Hz,1H),4.61(s,2H),1.58(s,3H),1.54(d,J＝3.7Hz,3H),1.19(d,J＝6.6Hz,3H).¹ H NMR (400MHz, CDCl₃ ) δ8.07 (d, J = 2.7Hz, 1H), 7.94 (dd, J = 9.1, 2.8Hz, 1H), 7.11 (dd, J = 7.3, 0.7Hz, 1H) ,7.07(dd,J=7.7,1.2Hz,1H),6.83(td,J=7.5,0.8Hz,1H),6.71(d,J=9.1Hz,1H),6.56(d,J=7.8Hz, 1H), 4.61(s, 2H), 1.58(s, 3H), 1.54(d, J=3.7Hz, 3H), 1.19(d, J=6.6Hz, 3H).

经鉴定，其产物结构为化合物1，如图1所示。After identification, the structure of the product wascompound 1, as shown in Figure 1.

中间体2的合成：Synthesis of Intermediate 2:

将二苯基甲烷(5.0ml,29.7mmol)置于两口圆底烧瓶中，氮气气氛下，用50ml超干四氢呋喃溶解，紧接着将反应体系的温度降低至0℃，将正丁基锂(11mL,2.4M in hexane)缓慢滴加到上述反应体系，保持低温反应30分钟，将反应体系的温度降至-78℃，将4-溴苯甲酰苯(5.94g,22.8mmol)的四氢呋喃溶液滴加进反应体系后缓慢升至室温后继续搅拌反应6小时后，反应停止。用氯化铵的饱和溶液淬灭反应后，再用二氯甲烷萃取3-5次，合并所有有机相后用无水硫酸钠干燥，通过减压蒸馏除去溶剂后，残余物用100ml甲苯溶解，将对甲苯磺酸(378mg,2.30mmol)加入上述甲苯溶液，升温至回流，持续搅拌反应12h。反应结束后。冷却至室温，通过减压蒸馏出去溶剂后，残余物通过硅胶柱层析(20/1石油醚/乙酸乙酯,v/v)分离得到白色固体即为化合物2(3.90g,产率70％)。Diphenylmethane (5.0ml, 29.7mmol) was placed in a two-necked round-bottomed flask, dissolved in 50ml ultra-dry tetrahydrofuran under a nitrogen atmosphere, and then the temperature of the reaction system was lowered to 0°C, and n-butyllithium (11mL , 2.4M in hexane) was slowly added dropwise to the above reaction system, and the reaction was kept at low temperature for 30 minutes, and the temperature of the reaction system was lowered to -78°C. After adding to the reaction system, it was slowly raised to room temperature and continued to stir for 6 hours. After that, the reaction stopped. After quenching the reaction with a saturated solution of ammonium chloride, extract with dichloromethane 3-5 times, combine all organic phases and dry with anhydrous sodium sulfate. After removing the solvent by distillation under reduced pressure, the residue is dissolved in 100ml of toluene. Add p-toluenesulfonic acid (378mg, 2.30mmol) to the above toluene solution, raise the temperature to reflux, and continue stirring for 12h. After the reaction is over. After cooling to room temperature and removing the solvent by distillation under reduced pressure, the residue was separated by silica gel column chromatography (20/1 petroleum ether/ethyl acetate, v/v) to obtain a white solid which was compound 2 (3.90g, yield 70% ).

其高分辨质谱数据如下：Its high-resolution mass spectrometry data are as follows:

高分辨质谱C²⁶H²⁰Br[M+H]⁺计算值：411.0748；实验值：411.0742。High resolution mass spectrum Calcd. for^C26H20Br [M+H]⁺ : 411.0748; found^: 411.0742.

其核磁谱图氢谱数据如下：Its nuclear magnetic spectrum hydrogen spectrum data are as follows:

¹H NMR(400MHz,CDCl3)δ7.23–7.19(m,2H),7.13–7.07(m,9H),7.01(ddd,J＝7.0,4.7,1.6Hz,6H),6.91–6.87(m,2H)。¹ H NMR (400MHz, CDCl3) δ7.23–7.19(m,2H),7.13–7.07(m,9H),7.01(ddd,J=7.0,4.7,1.6Hz,6H),6.91–6.87(m, 2H).

经鉴定，其产物结构为化合物2，如图2所示。After identification, the product structure is compound 2, as shown in Figure 2.

中间体3的合成：Synthesis of intermediate 3:

将中间体2(3.9g,9.5mmol)置于两口圆底烧瓶中，氮气气氛下，加入40ml超干四氢呋喃将固体溶解，随后将反应体系降温至-78℃,将正丁基锂(12mL,2.4M in hexane)缓慢滴加至上述反应体系，保持低温继续搅拌2h。继续保持-78℃，加入超干N,N-二甲基甲酰胺(3.66ml,47.5mmol)，-78℃再反应30分钟后,缓慢升温至室温持续搅拌过夜。反应结束后，用2M盐酸水溶液淬灭反应，再用二氯甲烷萃取有机相3-5次，合并所有有机相后用无水硫酸钠干燥，将溶剂通过减压蒸馏除去，残余物用硅胶柱层析(10/1；石油醚/乙酸乙酯；v/v)分离得到黄色化合物3(1.8g,产率68％)。Intermediate 2 (3.9g, 9.5mmol) was placed in a two-neck round-bottomed flask, under a nitrogen atmosphere, 40ml of ultra-dry tetrahydrofuran was added to dissolve the solid, and then the reaction system was cooled to -78°C, and n-butyllithium (12mL, 2.4M in hexane) was slowly added dropwise to the above reaction system, and kept stirring at low temperature for 2h. Continue to maintain -78°C, add ultra-dry N,N-dimethylformamide (3.66ml, 47.5mmol), react at -78°C for another 30 minutes, then slowly warm up to room temperature and continue stirring overnight. After the reaction is over, quench the reaction with 2M hydrochloric acid aqueous solution, then extract the organic phase with dichloromethane for 3-5 times, combine all the organic phases and dry with anhydrous sodium sulfate, remove the solvent by distillation under reduced pressure, and the residue is purified by silica gel column Chromatography (10/1; petroleum ether/ethyl acetate; v/v) gave yellow compound 3 (1.8 g, yield 68%).

其高分辨质谱数据如下：Its high-resolution mass spectrometry data are as follows:

高分辨质谱C₂₇H₂₁O[M+H]⁺计算值：361.1592；实验值：361.1600。High resolution mass spectrum Calcd. for C₂₇ H₂₁ O [M+H]⁺ : 361.1592; found: 361.1600.

经鉴定，其产物结构为化合物3。The structure of the product was identified as compound 3.

P1的合成：Synthesis of P1:

将化合物1(1.55g,5.0mmol)和化合物3(1.8g,5.0mmol)置于单口圆底烧瓶中，再用30ml无水乙醇将固体溶解。搅拌下，缓慢升温至回流，持续反应16h。反应结束后，将体系冷却至室温，通过减压蒸馏除去反应溶剂，随后用二氯甲烷将残余物溶解，再用碳酸钾的饱和溶液萃取3-5次，合并所有有机相并用无水硫酸钠干燥。将溶剂通过减压蒸馏除去后，残余物通过硅胶柱层析(50/1；石油醚/乙酸乙酯；v/v)分离得到黄色固体即为P1(1.2g,产率36％)。其高分辨质谱数据如下：Compound 1 (1.55g, 5.0mmol) and compound 3 (1.8g, 5.0mmol) were placed in a single-necked round bottom flask, and then 30ml of absolute ethanol was used to dissolve the solids. Under stirring, the temperature was slowly raised to reflux, and the reaction was continued for 16h. After the reaction, the system was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure, and the residue was dissolved with dichloromethane, then extracted 3-5 times with a saturated solution of potassium carbonate, all organic phases were combined and washed with anhydrous sodium sulfate dry. After the solvent was distilled off under reduced pressure, the residue was separated by silica gel column chromatography (50/1; petroleum ether/ethyl acetate; v/v) to obtain a yellow solid P1 (1.2 g, yield 36%). Its high-resolution mass spectrometry data are as follows:

高分辨质谱C₄₅H₃₆N₂O₃[M+H]⁺计算值：653.2804；实验值：653.2827。High resolution mass spectrum Calcd. for C₄₅ H₃₆ N₂ O₃ [M+H]⁺ : 653.2804; Found: 653.2827.

其核磁谱图氢谱数据如下：Its nuclear magnetic spectrum hydrogen spectrum data are as follows:

¹H NMR(400MHz,CDCl₃)δ7.99(d,J＝2.4Hz,0H),7.95(dd,J＝9.0,2.7Hz,1H),7.15–6.95(m,11H),6.87–6.80(m,1H),6.69(d,J＝16.2Hz,1H),6.60(d,J＝7.8Hz,1H),6.25(d,J＝16.1Hz,1H),4.55(s,2H),1.52(s,1H),1.26(s,2H)。¹ H NMR (400MHz, CDCl₃ ) δ7.99 (d, J=2.4Hz, 0H), 7.95 (dd, J=9.0, 2.7Hz, 1H), 7.15–6.95 (m, 11H), 6.87–6.80 ( m,1H),6.69(d,J=16.2Hz,1H),6.60(d,J=7.8Hz,1H),6.25(d,J=16.1Hz,1H),4.55(s,2H),1.52( s,1H), 1.26(s,2H).

其核磁谱图碳谱数据如下：Its nuclear magnetic spectrum carbon spectrum data are as follows:

¹³C NMR(101MHz,CDCl3)δ159.20,146.38,144.25,143.56,143.52,141.43,140.60,140.19,138.18,135.84,133.44,131.69,131.28,131.26,127.81,127.71,127.62,126.57,126.54,126.20,123.99,123.47,123.21,122.27,120.68,119.94,117.62,108.74,103.78,50.09,40.67,31.57,22.64,14.10。¹³ C NMR(101MHz,CDCl3)δ159.20,146.38,144.25,143.56,143.52,141.43,140.60,140.19,138.18,135.84,133.44,131.69,131.28,131.26,127.81,127.71,127.62,126.57,126.54,126.20,123.99, 123.47, 123.21, 122.27, 120.68, 119.94, 117.62, 108.74, 103.78, 50.09, 40.67, 31.57, 22.64, 14.10.

经鉴定，其产物结构为P1，如图3和图4所示。After identification, the product structure is P1, as shown in Figure 3 and Figure 4.

实施例2Example 2

将P1溶解在超干的二甲基亚砜中，使其终浓度为1mM。将前述母液分别溶解在二甲基亚砜、二甲基甲酰胺、乙腈、乙醇、氯仿、乙酸乙酯、四氢呋喃和甲苯中，使其终浓度为10^-5M。然后分别测试上述八种溶液的紫外可见吸收光谱。如图5所示，二甲基亚砜和二甲基甲酰胺这两个大极性溶剂可使P1开环，而其他质子性溶剂和小极性溶剂不能导致P1开环。以上现象说明P1是一个溶剂极性敏感的化合物，有可能与溶剂中少量的酸性物质相关。Dissolve P1 in ultra-dry DMSO to a final concentration of 1 mM. The aforementioned mother liquor was dissolved in dimethyl sulfoxide, dimethylformamide, acetonitrile, ethanol, chloroform, ethyl acetate, tetrahydrofuran and toluene, respectively, so that the final concentration was 10^-5 M. Then test the ultraviolet-visible absorption spectra of the above eight solutions respectively. As shown in Figure 5, two large polar solvents, dimethyl sulfoxide and dimethyl formamide, can open the ring of P1, while other protic solvents and low polar solvents cannot lead to ring opening of P1. The above phenomena indicate that P1 is a compound sensitive to solvent polarity, which may be related to a small amount of acidic substances in the solvent.

实施例3Example 3

将适量体积P1的1mM母液分别与不同体积的去离子水配成终浓度为10^-5M的测试液，其体积比分别为二甲基亚砜比去离子水为：99:1；80:20；60:40；40:60；35:65；30:70；25:75；20:80；15:85；10:90。然后分别测试它们的荧光发射光谱。如图6所示，随着水含量的逐渐增加，P1的荧光发射轻度逐渐增强，且在去离子水含量达到80％时，荧光发射强度最强。此时，噁嗪分子开关处于关闭状态，四苯乙烯显示出自身波段的聚集诱导发光性质。Prepare a test solution with a final concentration of 10^-5 M by mixing an appropriate volume of 1 mM mother solution of P1 with different volumes of deionized water, and the volume ratios are: 99:1; 80: dimethyl sulfoxide todeionized water 20;60:40;40:60;35:65;30:70;25:75;20:80;15:85;10:90. Then test their fluorescence emission spectra respectively. As shown in Figure 6, with the gradual increase of water content, the fluorescence emission of P1 was slightly enhanced, and the fluorescence emission intensity was the strongest when the deionized water content reached 80%. At this time, the oxazine molecular switch is in the off state, and the tetraphenylethylene exhibits aggregation-induced luminescent properties in its own band.

实施例4Example 4

首先将P1配制成浓度为10^-5M的乙醇溶液，测试其紫外可见吸收光谱；其次，在前述溶液中加入一当量的三氟乙酸，测试其紫外可见吸收光谱；最后，在前述溶液中加入两当量的氢氧化钠，测试其紫外可见吸收光谱。如图7所示，P1的乙醇溶液在酸碱刺激下具有可逆开关性能。First, prepare P1 into an ethanol solution with a concentration of 10^-5 M, and test its UV-visible absorption spectrum; secondly, add one equivalent of trifluoroacetic acid to the aforementioned solution, and test its UV-visible absorption spectrum; finally, add Two equivalents of sodium hydroxide, test its ultraviolet-visible absorption spectrum. As shown in Figure 7, the ethanol solution of P1 has reversible switching properties under acid-base stimulation.

实施例5Example 5

将P1配制成浓度为10^-5M的多个乙腈溶液，分别加入不同当量比(0，0.2，0.4，0.6，0.8，1.0)的三氟乙酸，然后逐一测试上述乙腈混合溶液的紫外可见吸收光谱。如图8所示，上述三氟乙酸滴定实验表明，随着三氟乙酸含量的增加，P1的开环比也随之增加，且在一当量时开环比达到最大；说明P1是对酸敏感的化合物，这与噁嗪分子开关的性质相符。Prepare P1 into multiple acetonitrile solutions with a concentration of 10^-5 M, add trifluoroacetic acid with different equivalent ratios (0, 0.2, 0.4, 0.6, 0.8, 1.0) respectively, and then test the UV-visible absorption of the above-mentioned acetonitrile mixed solutions one by one spectrum. As shown in Figure 8, the above trifluoroacetic acid titration experiment shows that with the increase of the trifluoroacetic acid content, the ring-opening ratio of P1 also increases, and the ring-opening ratio reaches the maximum at one equivalent; indicating that P1 is an acid-sensitive compound , which is consistent with the properties of oxazine molecular switches.

实施例6Example 6

将P1配制成浓度为10^-5M的四氢呋喃溶液，用手提式紫外灯照射前述样品，分别采集不同时刻(0，5，10，15，20，30，40，50，60，120，240，480，960，1920，3000秒)该体系的紫外可见吸收光谱。如图9所示，随着光照时间的增加，P1的开环比逐渐增大，且在60秒左右达到最大，继续光照则发生光降解；说明P1对紫外光敏感，这现象与噁嗪分子开关的性质相符。Prepare P1 into a tetrahydrofuran solution with a concentration of 10^-5 M, irradiate the aforementioned samples with a portable ultraviolet lamp, and collect samples at different times (0, 5, 10, 15, 20, 30, 40, 50, 60, 120, 240, 480, 960, 1920, 3000 seconds) the ultraviolet-visible absorption spectrum of this system. As shown in Figure 9, as the illumination time increases, the open-loop ratio of P1 gradually increases, and reaches the maximum at about 60 seconds, and photodegradation occurs when the illumination continues; this shows that P1 is sensitive to ultraviolet light, and this phenomenon is related to the molecular switch match in nature.

实施例7Example 7

分别采集P1的固体粉末在紫外光照射前后的紫外可见吸收光谱。如图10所示，紫外光照射后P1在长波长处有新的吸收峰出现，表明有开环化合物存在，与该化合物在溶液中的性质一致，说明该化合物是具有固体光刺激响应的有机变色材料。The ultraviolet-visible absorption spectra of the solid powder of P1 were collected before and after ultraviolet light irradiation. As shown in Figure 10, after ultraviolet light irradiation, P1 has a new absorption peak at a long wavelength, indicating the existence of a ring-opening compound, which is consistent with the properties of the compound in solution, indicating that the compound is an organic color-changing compound with a solid light-stimulus response. Material.

实施例8Example 8

分别采集P1的固体粉末在紫外光照射前后的荧光发射光谱。如图11所示，紫外光照射后P1的荧光发射峰红移，表明开环化合物相较于闭环化合物具有更大的共轭体系，说明该化合物是具有固体光刺激响应的有机发光材料。The fluorescence emission spectra of the solid powder of P1 were collected before and after ultraviolet light irradiation. As shown in Figure 11, the fluorescence emission peak of P1 shifted red after ultraviolet light irradiation, indicating that the open-ring compound has a larger conjugated system than the closed-ring compound, indicating that the compound is an organic light-emitting material with a solid light-stimulus response.

实施例9Example 9

将P1的固体粉末置于干净的载玻片上，在倒置显微镜下观察。分别采集紫外光照射前后该固体粉末的显微图像。如图12所示，P1为白色固体且具有四苯乙烯的蓝色荧光；紫外光照射后，P1转变为橙色固体有深红色荧光。Place the solid powder of P1 on a clean glass slide and observe under an inverted microscope. Microscopic images of the solid powder were collected before and after ultraviolet light irradiation. As shown in Figure 12, P1 is a white solid with blue fluorescence of tetraphenylethylene; after ultraviolet light irradiation, P1 turns into an orange solid with deep red fluorescence.

实施例10Example 10

分别采集P1的固体粉末在酸刺激前后的紫外可见吸收光谱。如图13所示，酸刺激后P1在长波长处有新的吸收峰出现，表明有开环化合物存在，与该化合物在溶液中的性质一致，说明该化合物是具有固体酸刺激响应的有机变色材料。The ultraviolet-visible absorption spectra of the solid powder of P1 were collected before and after acid stimulation. As shown in Figure 13, after acid stimulation, P1 has a new absorption peak at a long wavelength, indicating the existence of a ring-opening compound, which is consistent with the properties of the compound in solution, indicating that the compound is an organic color-changing material that responds to solid acid stimulation. .

实施例11Example 11

分别采集P1的固体粉末在酸刺激前后的荧光发射光谱。如图14所示，酸刺激后P1的荧光发射峰红移，表明开环化合物相较于闭环化合物具有更大的共轭体系，说明该化合物是具有固体酸刺激响应的有机发光材料。Fluorescence emission spectra of the solid powder of P1 were collected before and after acid stimulation. As shown in Figure 14, the fluorescence emission peak of P1 shifted red after acid stimulation, indicating that the open-ring compound has a larger conjugated system than the closed-ring compound, indicating that the compound is an organic light-emitting material that responds to solid acid stimulation.

实施例12Example 12

将P1的固体粉末置于干净的载玻片上，在倒置显微镜下观察。分别采集酸刺激前后该固体粉末的显微图像。如图15所示，P1为白色固体且具有四苯乙烯的蓝色荧光；酸刺激后，P1转变为橙红色固体有较强深红色荧光。Place the solid powder of P1 on a clean glass slide and observe under an inverted microscope. Microscopic images of the solid powder were collected before and after acid stimulation. As shown in Figure 15, P1 is a white solid with blue fluorescence of tetraphenylethylene; after acid stimulation, P1 turns into an orange-red solid with strong deep red fluorescence.

实施例13Example 13

将P1用二氯甲烷溶解，用喷枪喷涂在有掩膜的滤纸片上，吹干纸片后，分别采集日光和紫外灯下该纸片的图像；然后分别用紫外光和酸碱刺激并采集信息。如图16所示，P1在纸片上几乎看不见，同时具有蓝色四苯乙烯的荧光，说明其固体在可见光区吸收很弱，可用作一重荧光防伪；紫外光照射后，P1在纸片上显示橙色，同时有较弱的红色荧光，说明紫外光刺激下该化合物变色同时还发光，可用作二重荧光防伪；三氟乙酸刺激后，P1在纸片上显示橙红色，同时有较强的深红色荧光，说明酸刺激下该化合物变色同时也发光，可用作三重荧光防伪；与此同时，紫外光刺激后的化合物会继续对酸响应，酸响应后的P1在三乙胺的作用下恢复到初始状态，这是一个可多次重复的可逆过程，可用作多重荧光防伪。Dissolve P1 in dichloromethane, spray it on a masked filter paper with a spray gun, and dry the paper, collect images of the paper under sunlight and ultraviolet light respectively; then stimulate and collect information with ultraviolet light and acid-base respectively . As shown in Figure 16, P1 is almost invisible on the paper, and at the same time has the fluorescence of blue tetraphenylethylene, indicating that its solid absorbs very weakly in the visible light region, and can be used as a fluorescent anti-counterfeiting; after ultraviolet light irradiation, P1 is on the paper. It shows orange and has weak red fluorescence at the same time, indicating that the compound changes color and emits light under the stimulation of ultraviolet light, which can be used as double fluorescence anti-counterfeiting; after trifluoroacetic acid stimulation, P1 shows orange-red on the paper, and has a strong Deep red fluorescence, indicating that the compound changes color and also emits light under acid stimulation, which can be used as triple fluorescence anti-counterfeiting; at the same time, the compound after ultraviolet light stimulation will continue to respond to acid, and P1 after acid response is under the action of triethylamine Returning to the original state is a reversible process that can be repeated many times and can be used as multiple fluorescent anti-counterfeiting.

Claims (7)

1. A tetraphenylethylene-oxazine material is characterized in that the structural formula of the tetraphenylethylene-oxazine material is as follows:

wherein:

x, Y, Z and W are H.

2. The method for synthesizing the tetraphenylethylene-oxazine material of claim 1, which comprises the following specific steps:

(1) Synthesis of intermediate 1- (4-bromophenyl) -1,2,2-triphenylethylene

Adding the super-dry tetrahydrofuran into Z, W disubstituted diphenylmethane under the nitrogen atmosphere under stirring, adding n-butyl lithium at low temperature, and continuing stirring for 1-2 hours; keeping the temperature low, adding tetrahydrofuran solution of the Y-substituted 4-bromobenzophenone into the reaction system, and heating and refluxing for 6-12 hours; quenching the reaction with ammonium chloride aqueous solution, continuously extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, removing the solvent by reduced pressure distillation, and separating the residue with silica gel chromatographic column to obtain a white solid compound 1, namely an intermediate 1- (4-bromophenyl) -1,2,2-triphenylethylene;

(2) Synthesis of intermediate 4- (1,2,2-triphenylvinyl) benzaldehyde:

placing the compound 1 obtained in the step (1) in a nitrogen atmosphere for stirring, then adding ultra-dry tetrahydrofuran, adding n-butyllithium at a low temperature, and keeping the low temperature for continuously stirring for 1-2 hours; stirring at room temperature for 1-2 hours, reducing the reaction temperature again, adding dimethylformamide, slowly heating to room temperature, and continuously stirring for 6-12 hours; quenching the reaction by using 2M hydrochloric acid aqueous solution, then extracting by using dichloromethane, drying an organic phase by using anhydrous sodium sulfate, then distilling under reduced pressure to remove the solvent, and separating the residue by using a silica gel chromatographic column to obtain a yellow compound 2, namely an intermediate 4- (1,2,2-tristyryl) benzaldehyde;

(3) Synthesis of intermediate compound 3:

dissolving X-substituted 2,3,3-trimethylindole and 2-hydroxy-5-nitrobenzyl bromide in acetonitrile, heating to reflux reaction for 6-18 hours, cooling to room temperature, removing the solvent by reduced pressure distillation, and separating the residue by using a silica gel chromatographic column to obtain a pink compound 3;

(4) Synthesis of tetraphenylethylene-oxazine material:

and dissolving the compound 2 and the compound 3 in absolute ethyl alcohol, heating to reflux and stirring for 6-20 hours, cooling to room temperature, removing the solvent through reduced pressure distillation, and separating by using a silica gel chromatographic column to obtain a compound 4, namely the tetraphenylethylene-oxazine.

3. The method for synthesizing the tetraphenylethylene-oxazine material according to claim 2, wherein in the step (1): z, W disubstituted diphenylmethane and Y substituted 4-bromobenzophenone in a molar ratio of 1.1 to 3.0; the amount of n-butyllithium material should be 0.6 to 1.0 equivalent of Z, W disubstituted diphenylmethane and n-butyllithium added at twenty degrees below zero.

4. A method for synthesizing tetraphenylethylene-oxazine material as claimed in claim 2, wherein in step (2): the molar ratio of compound 1 to dimethylformamide is 1:5-10; the mass-to-volume ratio of compound 1 to tetrahydrofuran was 1:5-10 (mg: ml).

5. The method for synthesizing the tetraphenylethylene-oxazine material according to claim 2, wherein in the step (3): the molar ratio of the X-substituted 2,3,3-trimethylindole to the 2-hydroxy-5-nitrobenzyl bromide is 1:0.8 to 1.2; and the mass-to-volume ratio of the X-substituted 2,3,3-trimethylindole to the acetonitrile is 1:5-10 (mg: ml).

6. The method for synthesizing the tetraphenylethylene-oxazine material according to claim 2, wherein in the step (4): the molar ratio of compound 2 to compound 3 is 1:0.8-1.2; and the mass-to-volume ratio of the compound 2 to the absolute ethyl alcohol is 1:5-10 (mg: ml).

7. The use of the tetraphenylethylene-oxazine material of claim 1 in fluorescence anti-counterfeiting.

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