阅读说明：本技术 2-（2-羟基苯基）苯并噻唑衍生物htpa及其制备方法与在荧光防伪中的应用 (2- (2-hydroxyphenyl) benzothiazole derivative HTPA, preparation method thereof and application thereof in fluorescence anti-counterfeiting ) 是由 张大同 李斌 于 2020-03-06 设计创作，主要内容包括：本发明涉及2-(2-羟基苯基)苯并噻唑衍生物HTPA及其制备方法与在其荧光防伪中的应用,2-(2-羟基苯基)苯并噻唑衍生物HTPA,具有式(I)所示的结构,本发明的2-(2-羟基苯基)苯并噻唑衍生物HTPA荧光强度强,材料性质稳定,可以长时间放置,对胺蒸气和醋酸蒸汽响应快并且可逆,实现了双色荧光显示,荧光颜色对比度高,用肉眼即可区分,作为荧光防伪材料使用,可以快速辨别,提高了防伪技术的效率和安全性。<Image he="489" wi="669" file="DDA0002402171860000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to a 2- (2-hydroxyphenyl) benzothiazole derivative HTPA and a preparation method and application thereof in fluorescence anti-counterfeiting, wherein the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA has a structure shown in a formula (I), has strong fluorescence intensity and stable material property, can be placed for a long time, has quick response and reversibility to amine steam and acetic acid steam, realizes double-color fluorescence display, has high fluorescence color contrast, can be distinguished by naked eyes, can be used as a fluorescence anti-counterfeiting material and can be quickly distinguished,the efficiency and the security of the anti-counterfeiting technology are improved.)

A2- (2-hydroxyphenyl) benzothiazole derivative HTPA having the structure shown in formula (I):

a preparation method of 2- (2-hydroxyphenyl) benzothiazole derivative HTPA comprises the following steps:

reacting 2-benzothiazolyl-4-bromophenol with 4- (diphenylamino) phenylboronic acid at 70-90 ℃ for 6-8 hours in the nitrogen atmosphere to obtain the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA.

A preparation method of 2- (2-hydroxyphenyl) benzothiazole derivative HTPA comprises the following steps:

dissolving 2-benzothiazolyl-4-bromophenol in tetrahydrofuran under nitrogen atmosphere, adding an alkali solution, and then adding 4- (diphenylamino) phenylboronic acid to ensure that the molar ratio of 2-benzothiazolyl-4-bromophenol to 4- (diphenylamino) phenylboronic acid is 1: 1-1.2, stirring the reaction mixture for 10 minutes, adding a catalyst into the reaction mixture, reacting at 70-90 ℃ for 6-8 hours, adding water to quench the reaction, extracting with an organic solvent, washing with water, drying, concentrating to obtain a crude product solution, and purifying by silica gel chromatography to obtain the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA.

4. The preparation method according to claim 3, wherein the molar volume ratio of 2-benzothiazolyl-4-bromophenol to tetrahydrofuran is 1: 5-15 units (mmol/m L).

5. The preparation method of claim 3, wherein the alkali solution is potassium carbonate aqueous solution, the concentration of the potassium carbonate aqueous solution is 1-3 mM, the molar volume ratio of the 2-benzothiazolyl-4-bromophenol to the potassium carbonate aqueous solution is 1: 1-3, unit, mmol/m L, and the catalyst is Pd (PPh)₃)₄2-benzothiazolyl-4-bromophenol and Pd (PPh)₃)₄The molar ratio of (A) to (B) is: 1: 0.01-0.2.

6. Use of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA according to claim 1 as a fluorescent security material in banknotes, securities, checks, documents, invoices or in organic amine vapour sensing.

7. The application of claim 6, wherein the specific application method is as follows:

(1) preparing a tetrahydrofuran solution of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA to obtain an anti-counterfeiting solution;

(2) the anti-counterfeiting liquid is arranged on the anti-counterfeiting commodity, and after the anti-counterfeiting liquid is dried, ultraviolet light is adopted for irradiation, and the part provided with the anti-counterfeiting substance emits orange red fluorescence;

(3) placing the anti-counterfeiting commodity in an organic amine steam atmosphere, and then irradiating by adopting ultraviolet light, wherein the part provided with the anti-counterfeiting substance emits blue-green fluorescence;

(4) and (3) placing the anti-counterfeiting commodity in the air for a period of time or in an acetic acid steam atmosphere, recovering orange-red fluorescence, and realizing solid-state fluorescence reversible response.

8. The use according to claim 7, wherein in the step (1), the concentration of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA in the anti-counterfeiting liquid is 40-60 μ M.

9. The use of claim 7, wherein in step (2) and step (3), the ultraviolet light has a wavelength of 365 nm; in the step (3), the organic amine is one of piperidine, isopropylamine and pyrrolidine, and the anti-counterfeiting commodity is placed in the organic amine steam atmosphere for 20-30 seconds.

10. The use according to claim 7, wherein in the step (4), the air is kept for 5 minutes to 5 hours, and the acetic acid vapor atmosphere is kept for 20 to 30 seconds.

Technical Field

The invention relates to a 2- (2-hydroxyphenyl) benzothiazole derivative HTPA, a preparation method thereof and application thereof in fluorescence anti-counterfeiting, belonging to the technical field of fluorescent materials and anti-counterfeiting application.

Background

Along with the development of commodity economy, the physical living standard of people is also greatly improved. However, as interest drives, counterfeit and shoddy commodities are increasing in the consumer market, the market is getting stronger, and the interests of consumers are greatly harmed. According to the statistics of related data, the loss of the world economy and industry reaches over 1000 billion dollars due to the counterfeiting of various high-grade famous brand goods, counterfeit tickets and the like every year. In the international market, significant commodity counterfeiting events have been recorded for only five years, which has exceeded 2000. More worried that in the fields of medicine, food, cigarette, wine and beverage, the counterfeit package is more rampant and often makes people defend. Not only causes economic loss, but also directly endangers the health and the life of people. People are also aware of the importance of anti-counterfeiting technology for the first time of the pain.

The current common anti-counterfeiting technologies include: laser holography, fluorescence anti-counterfeiting, watermarking, bar codes, magnetic codes, two-dimensional codes and other anti-counterfeiting technologies, but the technologies generally have the problems of high cost, complex operation and easiness in copying. The fluorescent anti-counterfeiting has the advantages of simple and convenient operation, time saving, strong anti-counterfeiting performance and the like, so that the fluorescent anti-counterfeiting has wide application in the aspect of high-tech anti-counterfeiting technology.

The fluorescent anti-counterfeiting technology is mainly applied to fluorescent anti-counterfeiting ink, namely, the anti-counterfeiting ink is prepared by adding anti-counterfeiting materials with special properties into ink caking materials and processing the anti-counterfeiting ink through a special process, and the special ink can emit visible light under the irradiation of ultraviolet light. The fluorescent dyes currently used for manufacturing anti-counterfeiting ultraviolet fluorescent ink are mainly rare earth metal complexes and organic fluorescent dyes. The rare earth metal complex fluorescent dye has good stability, but has poor uniformity and water resistance in an oil medium, and can corrode a plate material and influence the printing effect when added into printing ink. The common organic dye in the market has good dispersibility, but has poor stability when being used for fluorescent anti-counterfeiting ink, and the fluorescent intensity is obviously attenuated after being placed for a long time, so that the anti-counterfeiting effect is weakened. In addition, most of the currently applied fluorescent anti-counterfeiting materials are monochromatic fluorescence, so that the effectiveness and safety of the traditional fluorescent anti-counterfeiting material face serious challenges.

In order to further enhance the anti-counterfeiting effect, a novel fluorescent anti-counterfeiting material needs to be developed.

Disclosure of Invention

Aiming at the defects of the existing fluorescent material for anti-counterfeiting, the invention provides a 2- (2-hydroxyphenyl) benzothiazole derivative HTPA, a preparation method thereof and application thereof in fluorescent anti-counterfeiting.

The invention achieves the following aims:

1. the fluorescent material for anti-counterfeiting has strong fluorescence intensity, stable material property and slower fluorescence intensity attenuation after being placed for a long time;

2. realizes double-color fluorescent display and has high fluorescent color contrast.

The invention is realized by the following technical scheme for achieving the aim:

2- (2-hydroxyphenyl) benzothiazole derivative HTPA having the structure shown in formula (I):

the second object of the invention is to provide a preparation method of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA.

A preparation method of 2- (2-hydroxyphenyl) benzothiazole derivative HTPA comprises the following steps:

reacting 2-benzothiazolyl-4-bromophenol with 4- (diphenylamino) phenylboronic acid at 70-90 ℃ for 6-8 hours in the nitrogen atmosphere to obtain the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA.

Specifically, the preparation method of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA comprises the following steps:

dissolving 2-benzothiazolyl-4-bromophenol in tetrahydrofuran under nitrogen atmosphere, adding an alkali solution, and then adding 4- (diphenylamino) phenylboronic acid to ensure that the molar ratio of 2-benzothiazolyl-4-bromophenol to 4- (diphenylamino) phenylboronic acid is 1: 1-1.2, stirring the reaction mixture for 10 minutes, adding a catalyst into the reaction mixture, reacting at 70-90 ℃ for 6-8 hours, adding water to quench the reaction, extracting with an organic solvent, washing with water, drying, concentrating to obtain a crude product solution, and purifying by silica gel chromatography to obtain the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA.

According to the invention, the preferable molar volume ratio of the 2-benzothiazolyl-4-bromophenol to the tetrahydrofuran is 1: 5-15 units, mmol/m L.

According to the invention, the alkali solution is preferably a potassium carbonate aqueous solution, and the concentration of the potassium carbonate aqueous solution is 1-3 mM.

According to the invention, the preferable molar volume ratio of the 2-benzothiazolyl-4-bromophenol to the potassium carbonate aqueous solution is 1: 1-3, unit, mmol/m L.

According to the invention, the catalyst is preferably Pd (PPh)₃)₄2-benzothiazolyl-4-bromophenol and Pd (PPh)₃)₄The molar ratio of (A) to (B) is: 1: 0.01-0.2.

The third purpose of the invention is to provide the application of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA.

The application of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA as a fluorescent anti-counterfeiting material in paper money, securities, checks, documents and invoices or in the aspect of organic amine steam sensing.

The preferred application method of the fluorescent anti-counterfeiting material is as follows:

(1) preparing a tetrahydrofuran solution of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA to obtain an anti-counterfeiting solution;

(2) the anti-counterfeiting liquid is arranged on the anti-counterfeiting commodity, and after the anti-counterfeiting liquid is dried, ultraviolet light is adopted for irradiation, and the part provided with the anti-counterfeiting substance emits orange red fluorescence;

(3) placing the anti-counterfeiting commodity in an organic amine steam atmosphere, and then irradiating by adopting ultraviolet light, wherein the part provided with the anti-counterfeiting substance emits blue-green fluorescence;

(4) and (3) placing the anti-counterfeiting commodity in the air for a period of time or in an acetic acid steam atmosphere, recovering orange-red fluorescence, and realizing solid-state fluorescence reversible response.

According to the invention, in the step (1), the concentration of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA in the anti-counterfeiting liquid is preferably 40-60 mu M.

According to the invention, in the step (2) and the step (3), the wavelength of the ultraviolet light is preferably 365 nm.

Preferably, in step (3), the organic amine is one of piperidine, isopropylamine and pyrrolidine.

According to the invention, in the step (3), the anti-counterfeiting commodity is preferably placed in the organic amine steam atmosphere for 20-30 seconds.

Preferably, in the step (4), the air is kept for 5 minutes to 5 hours, and the acetic acid vapor atmosphere is kept for 20 to 30 seconds.

The invention has the technical characteristics and advantages that:

1. the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA has strong fluorescence intensity and stable material property, and can be placed for a long time.

2. The 2- (2-hydroxyphenyl) benzothiazole derivative HTPA has quick and reversible response to amine steam and acetic acid steam, realizes two-color fluorescent display, has high contrast of fluorescent colors, can be distinguished by naked eyes, can be used as a fluorescent anti-counterfeiting material, can be quickly distinguished, and improves the efficiency and the safety of anti-counterfeiting technology.

3. The raw materials involved in the preparation process of the fluorescent material are wide in source, high in synthesis yield, stable in product fluorescence performance, convenient for large-scale application and popularization, and wide in application prospect.

Drawings

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 2- (2-hydroxyphenyl) benzothiazole derivative HTPA obtained in example 1;

FIG. 2 is a nuclear magnetic resonance carbon spectrum of 2- (2-hydroxyphenyl) benzothiazole derivative HTPA obtained in example 1;

FIG. 3 is a mass spectrum of 2- (2-hydroxyphenyl) benzothiazole derivative HTPA obtained in example 1;

FIG. 4 is a graph showing the change of fluorescence spectra of a filter paper strip carrying a 2- (2-hydroxyphenyl) benzothiazole derivative HTPA after repeated exposure to piperidine vapor and acetic acid vapor;

FIG. 5 is a graph showing fluorescence ratio changes caused by repeated exposure of filter paper strips loaded with 2- (2-hydroxyphenyl) benzothiazole derivative HTPA to piperidine vapor and acetic acid vapor;

FIG. 6 is a graph showing the application effect of 2- (2-hydroxyphenyl) benzothiazole derivative HTPA in anti-counterfeiting: wherein, a, under sunlight, b, under sunlight after fumigation by piperidine steam, c, under a 365nm ultraviolet lamp, d, under a 365nm ultraviolet lamp after fumigation by piperidine steam, e, under sunlight after exposure in air for 5 minutes, and f, under a 365nm ultraviolet lamp after exposure in air for 5 minutes.

Detailed Description

For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings.