A nitrogen-containing heterocyclic compound and its preparation method and application

Abstract

The present invention provides a nitrogen-containing heterocyclic compound, the nitrogen-containing heterocyclic compound structural formula is as follows: The synthesis path is as follows: wherein the substituent R is selected from any one of bromine, N,N-dimethylaminophenyl, and p-cyanophenyl. The nitrogen-containing heterocyclic compound can be combined with acrylic resin and polyvinyl pyrrolidone to form a film, and a clear fluorescent image is formed under a 365nm ultraviolet lamp. The nitrogen-containing heterocyclic compound has simple synthesis steps, mild reaction conditions, easy purification, high yield, high solid fluorescence quantum yield, is conducive to industrial production, and has great potential in the field of fluorescent anti-counterfeiting applications.

Description

Technical Field

[0001] The invention belongs to the technical field of fluorescent materials, and specifically relates to a nitrogen-containing heterocyclic compound and a preparation method and application thereof. Background Art

[0002] Anti-counterfeiting technology refers to measures taken to achieve the purpose of anti-counterfeiting. It can accurately identify the authenticity within a certain range and is not easy to be imitated and copied. Simply put, it is a technology to prevent imitation and counterfeiting. It is a preventive technical measure taken to protect corporate brands, protect the market, and protect the legitimate rights and interests of consumers.

[0003] Ultraviolet fluorescent anti-counterfeiting technology is a common anti-counterfeiting technology. Under ultraviolet light (200-400nm), special inks of different colors of light (400-800nm) can be seen. According to the wavelength of the excitation light source, it can be divided into short-wave ultraviolet excited fluorescent anti-counterfeiting ink (excitation wavelength 254nm) and long-wave ultraviolet excited fluorescent anti-counterfeiting ink (excitation wavelength is 365nm). Colored fluorescent ink (a certain color under natural light) is a common fluorescent anti-counterfeiting ink. Fluorescent anti-counterfeiting materials are made by mixing dyes and resins. At present, fluorescent anti-counterfeiting dyes have problems such as low solid fluorescence yield, unstable physical properties, and poor solubility. Summary of the invention

[0004] In view of this, the present invention provides a nitrogen-containing heterocyclic compound and application thereof in an optical anti-counterfeiting film. The nitrogen-containing compound has a high fluorescence quantum yield, and the raw materials are simple and easily available, and can be used in the anti-counterfeiting film.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A nitrogen-containing heterocyclic compound, the nitrogen-containing heterocyclic compound has the following structural formula:

[0007]

[0008] The substituent R is any one selected from bromine, N,N-dimethylaminophenyl, and p-cyanophenyl.

[0009] The preparation method of the above-mentioned nitrogen-containing heterocyclic compound, the synthesis route of the nitrogen-containing heterocyclic compound is as follows:

[0010]

[0011] Wherein, the substituent R is any one selected from bromine, N,N-dimethylaminophenyl, and p-cyanophenyl;

[0012] The preparation of the nitrogen-containing heterocyclic compound comprises the following steps:

[0013] S1. Add I-1, DMF and compound 2 to a reaction bottle at room temperature, stir to dissolve, then add tetrakistriphenylphosphine palladium and potassium carbonate aqueous solution, and heat to obtain a reaction solution;

[0014] S2. Wash the reaction solution with water, extract, dry, concentrate and purify to obtain the nitrogen-containing heterocyclic compound.

[0015] Furthermore, in step S1, the concentration of the potassium carbonate aqueous solution is 1.79 mol / mL to 3.57 mol / mL.

[0016] In some specific embodiments, preferably, in step S1, the concentration of the potassium carbonate aqueous solution is 3.57 mol / mL.

[0017] Furthermore, the order of adding materials in step S1 is compound I-1, DMF, compound 2, tetrakistriphenylphosphine palladium, and potassium carbonate aqueous solution.

[0018] The order of adding materials is solid first and then liquid, that is, first add a solid reactant with a smaller equivalent, then add the solvent, then add another solid reactant, then add the catalyst, and finally add the inorganic substance, so as to ensure the smooth progress of the reaction.

[0019] Furthermore, the order of adding materials in step S1 is compound I-1, DMF, compound 2, tetrakistriphenylphosphine palladium, and potassium carbonate aqueous solution.

[0020] Furthermore, in step S1, the molar ratio of compound I-1, compound 2, tetrakistriphenylphosphine palladium, and potassium carbonate is 1:(1-2):(0.001-0.002):(1-2);

[0021] When the molar amount of compound I-1 is 1 mmol, the amount of DMF added is (30-60) mL.

[0022] In some specific embodiments, preferably, in step S1, the molar ratio of compound I-1, compound 2, tetrakistriphenylphosphine palladium, and potassium carbonate is 1:2:0.002:2;

[0023] When the molar amount of compound I-1 was 1 mmol, the amount of DMF added was 30 mL.

[0024] Furthermore, in step S1, the heating temperature is 30-150° C., and the heating time is 2-18 hours.

[0025] In some specific embodiments, preferably, the heating temperature in step S1 is 90° C. and the heating time is 8 h.

[0026] Application of the above nitrogen-containing heterocyclic compounds in optical anti-counterfeiting films.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The nitrogen-containing heterocyclic compound prepared by the present invention has simple synthesis steps, mild reaction conditions, easy purification, high yield, and high solid fluorescence quantum yield.

[0029] (2) The fluorescent anti-counterfeiting film prepared by using the nitrogen-containing heterocyclic compound prepared by the present invention has a simpler production method compared with other types of anti-counterfeiting films. The two types of nitrogen-containing heterocyclic compounds provided have good optical properties, reduce the risk of counterfeiting, and have huge production potential.

[0030] (3) The anti-counterfeiting film itself is a rigid entity. Once formed, its shape is not easy to change. The nitrogen-containing heterocyclic compound prepared by the present invention can be directly coated when manufacturing the fluorescent anti-counterfeiting film. It has universal applicability and has good adhesion to the glass and metal packaging of high-end wines and precision instruments. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is the absorption spectrum of the nitrogen-containing heterocyclic compound I-2 prepared in Example 1 of the present invention.

[0032] Figure 2 This is the absorption spectrum of the nitrogen-containing heterocyclic compound I-3 prepared in Example 9 of the present invention.

[0033] Figure 3 A clear fluorescence image was obtained for Experimental Example 1 of the present invention.

[0034] Figure 4 A clear fluorescence image was obtained for Experimental Example 2 of the present invention.

[0035] Figure 5 A clear fluorescence image was obtained for Experimental Example 3 of the present invention.

[0036] Figure 6 A clear fluorescence image was obtained for Experimental Example 4 of the present invention.

[0037] Figure 7 This is the hydrogen spectrum of the nitrogen-containing heterocyclic compound I-2 prepared in Example 1 of the present invention.

[0038] Figure 8 This is the hydrogen spectrum of the nitrogen-containing heterocyclic compound I-3 prepared in Example 9 of the present invention.

[0039] Fig. 9 This is a graph of the solid fluorescence quantum yield of the nitrogen-containing heterocyclic compound I-2 prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0040] The present invention is further described in detail below in conjunction with specific embodiments so that those skilled in the art can understand the present invention more clearly.

[0041] Sources and physical and chemical parameters of key test materials:

[0042] Compound I-1 was prepared in the laboratory with a purity of more than 90%. The specific preparation process is as follows:

[0043]

[0044] S1. Dissolve 4-bromophenylhydrazine hydrochloride (4.47 g, 20 mmol) in acetic acid (30 mL), stir to dissolve, add methyl isopropyl ketone (4.29 mL, 40 mmol) to the solution, and heat to 125° C. for 5 h.

[0045] S2. The reaction solution in S1 is washed with water, extracted, dried, concentrated and purified to obtain the compound a.

[0046] S3. Dissolve a (1.19 g, 5 mmol) in toluene (30 mL), stir to dissolve, add pyrrole-2-carboxaldehyde (584 mg, 6.25 mmol), piperidine (494 μL, 5 mmol), and acetic acid (288 μL, 5 mmol) to the solution, heat to 120°C and react for 12 h.

[0047] S4, washing, extracting, drying, concentrating and purifying the reaction solution in S3 to obtain the compound I-1.

[0048] The prepared compound I-1 is a yellow solid with a yield of 28%.

[0049] The mass spectrometry results of compound I-1 are as follows:

[0050] 1 HNMR (400MHz, CDCl3) δ15.57 (s, 1H), 7.48-7.39, (m, 2H), 7.26, (s, 1H), 7.09, (d, J=1.1Hz, 1H), 6.76, (dt, J=5.9, 2.0Hz, 1H), 6.69, (s, 1H), 6.65, (d, 1H), 6.53-6.44, (m, 2H), 4.72, (s, 2H), 1.63, (s, 6H).

[0051] 13 CNMR (101MHz, CDCl3) δ181.05, 151.34, 148.64, 139.82, 130.58, 129.20, 128.65, 124.97, 12 4.43, 122.35, 119.90, 117.92, 117.63, 114.82, 109.56, 106.95, 99.66, 54.89, 54.49, 25.46.

[0052] HRMS(APCI)Calcd.for C 21 H 19 N3Br[M+H]+: 392.0762, found: 392.0752.

[0053] The specific raw materials not described in the present invention are all existing materials and can be directly purchased from the market.

[0054] Example 1

[0055] This embodiment provides a nitrogen-containing heterocyclic compound, and the preparation method thereof is as follows:

[0056] Weigh compound I-1 (391 mg, 1 mmol), take 30.00 mL N, N-dimethylformamide (DMF) and mix and dissolve, then add 4-diphenylaminophenylboronic acid (289 mg, 1 mmol), tetrakistriphenylphosphine palladium (11.6 mg, 0.001 mmol), potassium carbonate aqueous solution (potassium carbonate 138 mg, 1 mmol, deionized water 560 μL) in sequence, heat and stir at 90 ° C for 8 hours to react completely, wash the reactant with water, dry it, and purify it by column chromatography to obtain an orange solid I-2 (192.6 mg) with a yield of 34.7%. The specific absorption spectrum is shown in Figure 1 , hydrogen spectrum see Figure 7 .

[0057] Example 2

[0058] This embodiment provides a nitrogen-containing heterocyclic compound, and its steps and methods are basically the same as those in Example 1, except that the amount of 4-diphenylaminophenylboronic acid is 578 mg (2 mmol), and the rest remain unchanged, and finally an orange solid I-2 (328.6 mg) is obtained, and the yield is 59.2%. At this time, when the amount of 4-diphenylaminophenylboronic acid is increased by 1 times relative to Example 1, the yield increases by 24.5%.

[0059] Example 3

[0060] This example provides a nitrogen-containing heterocyclic compound, and its steps and methods are basically the same as those in Example 1, except that: the reaction temperature is 120°C, the stirring time is 6 hours, and the rest remain unchanged, and finally an orange solid I-2 (391.3 mg) is obtained, and the yield is 70.5%. At this time, the reaction temperature is increased by 30°C relative to Example 1, the reaction time is reduced by 2 hours, and the yield is increased by 35.8%.

[0061] Example 4

[0062] This embodiment provides a nitrogen-containing heterocyclic compound, and its steps and methods are basically the same as those in Example 1, except that the amount of tetrakistriphenylphosphine palladium is 23.2 mg (0.002 mmol), and the rest remain unchanged, and finally an orange solid I-2 (305.8 mg) is obtained, and the yield is 55.1%. At this time, when the amount of tetrakistriphenylphosphine palladium is increased by 1 times relative to Example 1, the yield increases by 20.4%.

[0063] Example 5

[0064] This embodiment provides a nitrogen-containing heterocyclic compound, and its steps and methods are basically the same as those in Example 1, except that: the potassium carbonate aqueous solution is changed to (potassium carbonate 276 mg, 2 mmol, deionized water 1120 μL), and the rest remains unchanged, and finally an orange solid I-2 (238.1 mg) is obtained, and the yield is 42.9%. At this time, when the concentration and amount of the potassium carbonate solution are increased by 1 times relative to Example 1, the yield increases by 8.2%.

[0065] Example 6

[0066] This example provides a nitrogen-containing heterocyclic compound, and its steps and methods are basically the same as those in Example 1, except that the amount of DMF is 60.00 mL, and the rest remain unchanged, and finally an orange solid I-2 (178.7 mg) is obtained, and the yield is 32.2%. At this time, when the amount of DMF is increased by 1 times relative to Example 1, the yield does not change significantly.

[0067] Example 7

[0068] This example provides a nitrogen-containing heterocyclic compound, and its steps and methods are basically the same as those in Example 1, except that: the reaction temperature is 60°C, the stirring time is 16h, and the rest remains unchanged, and finally an orange solid I-2 (83.3mg) is obtained with a yield of 15.0%. At this time, when the reaction temperature is reduced by 30°C relative to Example 1, the reaction time is increased by 8h, and the yield is reduced by 19.7%.

[0069] Example 8

[0070] This embodiment provides a nitrogen-containing heterocyclic compound, and its steps and methods are basically the same as those in Example 1, except that: the potassium carbonate aqueous solution is changed to (potassium carbonate 276 mg, 2 mmol, deionized water 560 μL), and the rest remain unchanged, and finally an orange solid I-2 (295.8 mg) is obtained, and the yield is 53.3%. At this time, when the concentration of the potassium carbonate solution is increased by 1 times relative to Example 1 and the amount is unchanged, the yield increases by 18.6%.

[0071] Example 9

[0072] This embodiment provides a nitrogen-containing heterocyclic compound, and the preparation method thereof is as follows:

[0073] Weigh compound I-1 (391 mg, 1 mmol), take 30.00 mL DMF to mix and dissolve, then add 4-cyanophenylboronic acid (146.9 mg, 1 mmol), tetrakistriphenylphosphine palladium (11.6 mg, 0.001 mmol), potassium carbonate aqueous solution (potassium carbonate 138 mg, 1 mmol, deionized water 560 μL) in sequence, heat and stir at 90 ° C for 8 hours to react completely, wash the reactant with water, dry it, and purify it by column chromatography to obtain an orange solid I-3 (171.0 mg) with a yield of 41.3%. The specific absorption spectrum is shown in Figure 2 , hydrogen spectrum see Figure 8 .

[0074] Furthermore, in order to understand the application effect of the nitrogen-containing heterocyclic compound prepared above in optical anti-counterfeiting, the following test examples were also carried out.

[0075] Test Example 1

[0076] Weigh compound I-2 (5.55 mg, 0.01 mmol) in Example 1, dissolve in 1 mL of ethyl acetate to prepare a 0.01 mol / L mother solution, then dissolve 10 μL of the mother solution in 10 μL of acrylic resin, and evenly apply it on the cling film, and dry it at 30°C. Put the cling film under a (365 nm) ultraviolet light, take a photo with an iPhone 12, and get a clear picture, as shown below. Figure 3 As shown, clear fluorescence can be observed.

[0077] Test Example 2

[0078] The steps and methods of this test example are basically the same as those of test example 1, except that 5 μL of the mother solution is dissolved in 10 μL of acrylic resin, and the rest is the same. The final fluorescence image is shown in Figure 4 At this time, it was observed that the fluorescence intensity was weaker than that of Experimental Example 1, which was not conducive to the preparation of the anti-counterfeiting film.

[0079] Test Example 3

[0080] The steps and methods of this test example are basically the same as those of test example 1, except that 20 μL of the mother solution is dissolved in 10 μL of acrylic resin, and the rest is the same. The final fluorescence image is shown in Figure 5 At this time, the film-forming speed on the cling film was slow, and when the film of Test Example 1 was formed, the film of Test Example 3 was still in liquid state on the cling film.

[0081] Test Example 4

[0082] The steps and methods of this test example are basically the same as those of test example 1, except that 20 μL of the mother solution is dissolved in 10 μL of polyvinyl pyrrolidone, and the rest is the same. The final fluorescence image is shown in Figure 6At this time, it was observed that when the acrylic resin was replaced with polyvinyl pyrrolidone, the fluorescence intensity was further enhanced compared with that of Test Example 1.

[0083] The above are only preferred embodiments of the present invention and are not intended to limit the protection scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A nitrogen-containing heterocyclic compound, characterized in that The nitrogen-containing heterocyclic compound has the following structural formula: ； The substituent R is any one selected from N,N-diphenylamino-4-phenyl and p-cyanophenyl.

2. The method for preparing the nitrogen-containing heterocyclic compound according to claim 1, characterized in that: The synthesis route of the nitrogen-containing heterocyclic compound is as follows: ； Wherein, the substituent R is any one selected from N,N-diphenylamino-4-phenyl and p-cyanophenyl; The preparation of the nitrogen-containing heterocyclic compound comprises the following steps: S1. Add I-1, DMF and compound 2 to a reaction bottle at room temperature, stir to dissolve, then add tetrakistriphenylphosphine palladium and potassium carbonate aqueous solution, and heat to obtain a reaction solution; S2. Wash the reaction solution with water, extract, dry, concentrate and purify to obtain the nitrogen-containing heterocyclic compound.

3. The preparation method according to claim 2, characterized in that: In step S1, the concentration of the potassium carbonate aqueous solution is 1.79 mol / mL to 3.57 mol / mL.

4. The preparation method according to claim 3, characterized in that: In step S1, the concentration of the potassium carbonate aqueous solution is 3.57 mol / mL.

5. The preparation method according to claim 2, characterized in that: The order of adding materials in step S1 is compound I-1, DMF, compound 2, tetrakistriphenylphosphine palladium, and potassium carbonate aqueous solution.

6. The preparation method according to claim 2, characterized in that: In step S1, the molar ratio of compound I-1, compound 2, tetrakistriphenylphosphine palladium and potassium carbonate is 1:(1-2):(0.001-0.002):(1-2); Among them, when the molar feeding amount of compound I-1 is 1 mmol, the feeding amount of DMF is (30~60) mL.

7. The preparation method according to claim 6, characterized in that: In step S1, the molar ratio of compound I-1, compound 2, tetrakistriphenylphosphine palladium, and potassium carbonate is 1:2:0.002:2; When the molar amount of compound I-1 was 1 mmol, the amount of DMF added was 30 mL.

8. The preparation method according to claim 2, characterized in that: In step S1, the heating temperature is 30-150° C. and the heating time is 2-18 hours.

9. The preparation method according to claim 8, characterized in that: In step S1, the heating temperature is 90° C. and the heating time is 8 h.

10. Use of the nitrogen-containing heterocyclic compound according to claim 1 in an optical anti-counterfeiting film.

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