CN111440129B - 2- (2-hydroxyphenyl) benzothiazole derivative HTPA, preparation method thereof and application thereof in fluorescence anti-counterfeiting - Google Patents

2- (2-hydroxyphenyl) benzothiazole derivative HTPA, preparation method thereof and application thereof in fluorescence anti-counterfeiting Download PDF

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CN111440129B
CN111440129B CN202010150226.5A CN202010150226A CN111440129B CN 111440129 B CN111440129 B CN 111440129B CN 202010150226 A CN202010150226 A CN 202010150226A CN 111440129 B CN111440129 B CN 111440129B
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counterfeiting
htpa
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benzothiazole derivative
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CN111440129A (en
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张大同
李斌
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Qilu University of Technology
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Abstract

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), and the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA 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, can be quickly distinguished, and improves the efficiency and safety of anti-counterfeiting technology.

Description

2- (2-hydroxyphenyl) benzothiazole derivative HTPA, preparation method thereof and application thereof in fluorescence anti-counterfeiting
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 relevant data, the loss of world economy and industry reaches over 1000 hundred million dollars because of counterfeiting various high-grade famous brand goods, counterfeit tickets and the like every year. In the international market, significant commercial 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 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. Common organic dyes in the market have good dispersibility, but the common organic dyes used for fluorescent anti-counterfeiting ink have poor stability, the fluorescent intensity is obviously attenuated after the common organic dyes are placed for a long time, and 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):
Figure BDA0002402171840000021
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 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 for 6-8 hours at 70-90 ℃, adding water to quench the reaction, extracting by using an organic solvent, washing by using water, drying, concentrating to obtain a crude product solution, and purifying by using a silica gel chromatography to obtain the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA.
Preferred according to the invention is a molar volume ratio of 2-benzothiazolyl-4-bromophenol to tetrahydrofuran: 1: 5-15, unit, mmol/mL.
According to the invention, the alkali solution is potassium carbonate aqueous solution, and the concentration of the potassium carbonate aqueous solution is 1-3 mM.
According to the invention, the preferred molar volume ratio of the 2-benzothiazolyl-4-bromophenol to the potassium carbonate aqueous solution is as follows: 1: 1-3, unit, mmol/mL.
According to the invention, the catalyst is preferably Pd (PPh) 3 ) 4 2-benzothiazolyl-4-bromophenol and Pd (PPh) 3 ) 4 The 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 anti-counterfeiting liquid;
(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 365nm.
Preferably, in step (3), the organic amine is one of piperidine, isopropylamine and pyrrolidine.
Preferably, in step (3), the anti-counterfeit goods are kept in the organic amine steam atmosphere for 20 to 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 description taken in conjunction with the accompanying drawings.
EXAMPLE 1 preparation of 2- (2-hydroxyphenyl) benzothiazole derivative HTPA
A25 mL round-bottomed flask was taken, and 306mg (1 mmol) of 2-benzothiazolyl-4-bromophenol was dissolved in 10mL of tetrahydrofuran, followed by addition of 2mL (concentration 2 mM) of an aqueous potassium carbonate solution under a nitrogen atmosphere. 290mg (1 mmol) of 4- (diphenylamino) phenylboronic acid are then added to the reaction mixture, and after stirring for 10 minutes at room temperature, 58mg of Pd (PPh) 3 ) 4 (0.05 mmol) was added to the reaction solution. The mixture was stirred at 80 ℃ for 8 hours, and then addedThe reaction was quenched with 5mL purified water, extracted three times with dichloromethane, the combined organic layers were washed with water and dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give the crude product, which was purified by silica gel chromatography (eluent: petroleum ether/ethyl acetate = 40: 1) to give 423mg of yellow 2- (2-hydroxyphenyl) benzothiazole derivative HTPA solid in 90% yield.
The synthetic route is shown as the following formula II:
Figure BDA0002402171840000041
the obtained 2- (2-hydroxyphenyl) benzothiazole derivative HTPA has a hydrogen nuclear magnetic resonance spectrum, a carbon nuclear magnetic resonance spectrum and a mass spectrum shown in FIGS. 1, 2 and 3, respectively.
Product spectral analysis data:
1 H NMR(400MHz,DMSO-d 6 ).δ11.61(s,1H),8.43(s,1H),8.16(d,J＝8.0Hz,1H),8.09(d, J＝8.1Hz,1H),7.70(d,J＝8.6Hz,1H),7.62(d,J＝8.5Hz,2H),7.55(t,J＝7.7Hz,1H),7.46(t, J＝7.5Hz,1H),7.33(t,J＝7.8Hz,4H),7.17(d,J＝8.6Hz,1H),7.08(t,J＝9.0Hz,8H)。
13 C NMR(100MHz,DMSO-d 6 )δ169.52,165.05,155.98,151.94,147.62,146.81,135.12, 134.17,131.91,130.85,130.06,127.80,126.92,126.28,125.53,124.41,124.31,123.56,122.70, 122.46,119.37,118.06.。
HRMS(ESI)calcd for[M+H] + 471.1531,found:471.1529。
2- (2-hydroxyphenyl) benzothiazole derivative HTPA solid fluorescence quantum yield phi f [％]Is 21.
Example 2 application of 2- (2-hydroxyphenyl) benzothiazole derivative HTPA in anti-counterfeiting
(1) Preparing a tetrahydrofuran solution of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA with the concentration of 50 mu M to obtain anti-counterfeiting liquid;
(2) The anti-counterfeiting liquid is arranged on an anti-counterfeiting commodity, after being dried, 365nm 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 a piperidine steam atmosphere for 30 seconds, and then irradiating the anti-counterfeiting commodity by 365nm ultraviolet light to enable the part provided with the anti-counterfeiting substance to emit blue-green fluorescence;
(4) And (3) fumigating the anti-counterfeiting commodity in an acetic acid steam atmosphere for 30 seconds to recover orange-red fluorescence, thereby realizing reversible response of solid-state fluorescence.
Experimental example 1:2- (2-hydroxyphenyl) benzothiazole derivative HTPA sensing property test
mu.L of a tetrahydrofuran solution of a 50. Mu.M concentration of 2- (2-hydroxyphenyl) benzothiazole derivative HTPA was added dropwise to a 0.8cm X1.5 cm strip of filter paper and then dried in air for 24 hours to obtain a strip of filter paper loaded with a fluorescent dye.
Piperidine vapor (15. Mu.L) was charged into a 1 cm. Times.1 cm. Times.4 cm quartz cuvette, which was then sealed and allowed to saturate at room temperature for 30 minutes to prepare piperidine vapor.
Acetic acid vapor was prepared by pouring acetic acid (15. Mu.L) into a 1 cm. Times.1 cm. Times.4 cm quartz cuvette, which was then sealed and allowed to saturate at room temperature for 30 minutes.
The dye-loaded filter paper strips were fixed to a glass plate, which was placed in a quartz cuvette. The cuvette with the glass plate mounted was placed on the solid sample holder of the fluorescence spectrometer and its fluorescence spectrum was measured. The filter paper strips were placed in piperidine vapor for 30 seconds and then tested for fluorescence spectra. The filter paper strip was removed, dried for 1 minute with a hair dryer, then placed in acetic acid vapor for 30 seconds, and tested for fluorescence spectra. Repeat 5 times.
The fluorescence spectrum change and fluorescence ratio change spectra caused by repeated exposure of the filter paper strips carrying the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA to piperidine vapor and acetic acid vapor are shown in fig. 4 and 5.
Experimental example 2:2- (2-hydroxyphenyl) benzothiazole derivative HTPA anti-counterfeiting application test
The 2- (2-hydroxyphenyl) benzothiazole derivative HTPA was formulated into a tetrahydrofuran solution at a concentration of 50 μ M.
The solution is injected into a clean gel pen, HBT characters are written on the power coupon, and the power coupon is photographed under sunlight and a 365nm ultraviolet lamp respectively.
And (4) putting the written exercise ticket into a piperidine steam atmosphere for 30 seconds, and taking a picture under sunlight and a 365nm ultraviolet lamp.
The exercise ticket was taken out from the piperidine vapor atmosphere, dried for one minute by a blower, left in the air for 5 minutes, and photographed under sunlight and a 365nm ultraviolet lamp, respectively, and the test results are shown in fig. 6.

Claims (5)

  1. 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;
    2- (2-hydroxyphenyl) benzothiazole derivative HTPA, having the structure shown in formula I:
    Figure DEST_PATH_IMAGE001
    formula I;
    is prepared by the following method:
    reacting 2-benzothiazolyl-4-bromophenol with 4- (diphenylamino) phenylboronic acid at 70-90 ℃ for 6-8 hours in the nitrogen atmosphere to obtain 2- (2-hydroxyphenyl) benzothiazole derivative HTPA;
    the specific application method is as follows:
    (1) Preparing a tetrahydrofuran solution of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA to obtain anti-counterfeiting liquid;
    (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; the wavelength of ultraviolet light is 365nm;
    (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; 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 to 30 seconds; the wavelength of ultraviolet light is 365nm;
    (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, wherein the placing time in the air is 5 minutes to 5 hours, and the placing time in the acetic acid steam atmosphere is 20 to 30 seconds.
  2. 2. The use according to claim 1, wherein the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA is prepared by the following method:
    dissolving 2-benzothiazolyl-4-bromophenol in tetrahydrofuran under nitrogen atmosphere, adding 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 for 6-8 hours at 70-90 ℃, adding water to quench the reaction, extracting by using an organic solvent, washing by using water, drying, concentrating to obtain a crude product solution, and purifying by using a silica gel chromatography to obtain the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA.
  3. 3. The use according to claim 1, wherein the molar volume ratio of 2-benzothiazolyl-4-bromophenol to tetrahydrofuran is: 1: 5-15, unit, mmol/mL.
  4. 4. The use of claim 2, wherein the alkali solution is an aqueous potassium carbonate solution, the concentration of the aqueous potassium carbonate solution is 1-3 mM, and the molar volume ratio of the 2-benzothiazolyl-4-bromophenol to the aqueous potassium carbonate solution is: 1: 1-3 unit, mmol/mL, and the catalyst is Pd (PPh) 3 ) 4 2-benzothiazolyl-4-bromophenol and Pd (PPh) 3 ) 4 The molar ratio of (A) to (B) is: 1, 0.01-0.2.
  5. 5. The use according to claim 1, wherein in step (1), the concentration of the 2- (2-hydroxyphenyl) benzothiazole derivative HTPA in the anti-counterfeiting liquid is 40-60 μ M.
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