A pyridazinoindole derivative, a preparation method and application thereof

Abstract

The application discloses a pyridazinoindole derivative, and a structure formula of the pyridazinoindole derivative is as follows: The pyridazinoindole derivative can effectively absorb ultraviolet light with a wavelength range of 200-250 nm and 350-400 nm. The pyridazinoindole derivative prepared by the application can be used as an ultraviolet absorber, and is expected to improve the light stability of a high polymer material.

Description

Technical Field

[0001] This invention relates to the field of organic ultraviolet absorbers, and in particular to a pyridazine-indole derivative that can be used for organic ultraviolet absorption and its preparation method. Background Technology

[0002] Short-wave ultraviolet (UVC) radiation is widely used for disinfection of water, air, and object surfaces. However, UVC also has a strong destructive effect on many polymer materials. The development of ultraviolet absorbers, especially high-performance UVC absorbers, is crucial for extending the lifespan of polymer products used in UVC applications. The structural design and synthesis of small organic molecules are core research areas in the field of ultraviolet absorbers. Organic ultraviolet absorbers are diverse, easy to modify and control structurally, and have a wide range of applications. However, some application areas still lack ideal organic ultraviolet absorbers. The research and development of organic ultraviolet absorbers with a broad absorption wavelength coverage or specific wavelength absorption ranges remains an urgent problem to be solved. Summary of the Invention

[0003] To address the aforementioned problems, this invention provides a pyridazindoindole derivative with a simple preparation method, concise operation steps, complex product structure, and broad ultraviolet absorption range, as well as a method for preparing the derivative.

[0004] This invention discloses a novel compound, a pyridazindoindole derivative, with the following structural formula: .

[0005] This invention patent also discloses a method for preparing the above-mentioned novel compound pyridazindoindole derivative, specifically including the following steps: Step 1) A certain amount of 1-naphthalenesulfonyl-3-(3-chlorophenylazo)indole, 2-vinyl-1H-indole, 1,10-bis(anthracene-9-yl)-12-hydroxy-4,5,6,7-tetrahydrodiindenzo[7,1-de:1',7'-fg][1,3,2]dioxophosphacyclohexane-12-oxide and solvent are reacted under certain temperature conditions;

[0006] Step 2) After the reaction is complete, the solvent is removed under reduced pressure, and the product is purified by column chromatography to obtain a pure pyridazindoindole derivative; wherein the structural formula of the pyridazindoindole derivative is as follows: .

[0007] The above-mentioned pyridazinindole derivatives were prepared in anhydrous ethanol to form 10 -5 The solution, at room temperature, exhibits good UV absorption properties when tested for UV absorption at a concentration of mol / L.

[0008] Preferably, the solvent is mesitylene, dichloromethane, 1,2-dichloroethane, or toluene.

[0009] Preferably, the reaction temperature is -15 to -25°C. o C.

[0010] Preferably, the molar ratio of 1-naphthalenesulfonyl-3-(3-chlorophenylazo)indole, 2-vinyl-1H-indole, and 1,10-bis(anthracene-9-yl)-12-hydroxy-4,5,6,7-tetrahydrodiindenzo[7,1-de:1',7'-fg][1,3,2]dioxophosphacyclohexane-12-oxide is 1:1-2:0.01-0.1.

[0011] Preferably, the ratio of 1-naphthalenesulfonyl-3-(3-chlorophenylazo)indole to solvent is 1 mmol: 20-50 mL.

[0012] This patent also discloses the application of novel compounds, pyridazine-indole derivatives, as ultraviolet absorbers.

[0013] The above technical solution has the following beneficial effects: the pyridazindoindole derivative synthesized by this invention has good ultraviolet absorption performance and a wide ultraviolet absorption wavelength coverage. The preparation method of this pyridazindoindole derivative has the advantages of simple synthesis steps, high chemical selectivity of reaction, and convenient post-processing. Attached Figure Description

[0014] Figure 1 The target compound of the present invention 1 H NMR spectrum.

[0015] Figure 2 The target compound of the present invention 13 C10 NMR spectrum.

[0016] Figure 3 This is the ultraviolet-visible absorption spectrum of the target compound in an embodiment of the present invention. Detailed Implementation

[0017] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.

[0018] Exemplary embodiments will now be described more fully with reference to the accompanying drawings. However, these exemplary embodiments can be implemented in many forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided to make the invention more comprehensive and complete, and to fully convey the concept of the exemplary embodiments to those skilled in the art. The described features, structures, or characteristics can be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to give a full understanding of embodiments of the invention. However, those skilled in the art will recognize that the technical solutions of the invention may be practiced with one or more of these specific details omitted, or other methods, components, apparatus, steps, etc., may be employed. In other instances, well-known technical solutions are not shown or described in detail to avoid obscuring various aspects of the invention.

[0019] The present invention will be further described in detail below with reference to the embodiments.

[0020] Example 1:

[0021] This invention patent discloses a pyridazindoindole derivative, the structural formula of which is as follows: .

[0022] Example 2: A method for preparing 2-(3-chlorophenyl)-3-(1H-indol-2-yl)-5-(1-naphthyl)sulfonyl-2,3,4,4a-tetrahydro-5H-pyridazine[4,3-b]indole.

[0023] Step 1) Under argon protection, add 0.1 mmol of 1-naphthalenesulfonyl-3-(3-chlorophenylazo)indole, 0.15 mmol of 2-vinyl-1H-indole, 0.005 mmol of 1,10-bis(anthracene-9-yl)-12-hydroxy-4,5,6,7-tetrahydrodiindenzo[7,1-de:1',7'-fg][1,3,2]dioxophosphazenecyclohexane-12-oxide, and 2 mL of 1,2-dichloroethane to a 10 mL reactor. Then, heat at 25 °C... o The reaction was carried out for 36 hours under C conditions.

[0024] Step 2) After the reaction was completed, the solvent was removed under reduced pressure, and the product was purified by column chromatography to obtain pure 2-(3-chlorophenyl)-3-(1H-indol-2-yl)-5-(1-naphthyl)sulfonyl-2,3,4,4a-tetrahydro-5H-pyridazine[4,3-b]indole, with the following structural formula:

[0025]

[0026] Yield: 59%; yellow solid; as shown Figures 1 to 2As shown, its 1H NMR spectrum (Acetone-d6, 400 MHz) is as follows: δ 10.16 (s, 1H), 8.90 (d, J = 8.8 Hz, 1H), 8.28 (d, J = 7.2 Hz, 1H), 8.19 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 8.4 Hz, 1H), 7.77 (t, J = 7.2 Hz, 2H), 7.69 (t, J = 7.2 Hz, 1H), 7.63 – 7.56 (m, 2H), 7.46 – 7.42 (m, 3H), 7.25 – 7.20 (m, 2H), 7.14 (d, J = 8.0 Hz, 1H), 7.06 – 6.92 (m, 3H), 6.69 (d, J = 8.0 Hz, 1H), 6.45(s, 1H), 5.70 (t, J = 8.8 Hz, 1H), 4.98 – 4.94 (m, 1H), 3.65 – 3.59 (m, 1H), 2.45 – 2.36 (m, 1H). Carbon NMR spectrum (Acetone-d6, 101 MHz): δ 150.9, 148.2, 147.0, 138.4, 137.5, 135.9, 135.4, 134.5, 134.3, 132.3, 130.3, 130.2, 130.0, 129.5, 129.4, 129.0, 128.1, 125.4, 125.31, 125.26, 125.2, 122.3, 122.1, 120.7, 120.09, 120.07, 116.0, 115.7, 114.1, 111.9, 102.1, 58.8, 51.7, 38.8. High-resolution mass spectrometry (ESI) calcd for C 34 H 26 ClN4O2S [M+H] + 589.1460, found 589.1466.

[0027] Example 3: A method for preparing 2-(3-chlorophenyl)-3-(1H-indol-2-yl)-5-(1-naphthyl)sulfonyl-2,3,4,4a-tetrahydro-5H-pyridazine[4,3-b]indole.

[0028] Step 1) Under argon protection, add 0.1 mmol of 1-naphthalenesulfonyl-3-(3-chlorophenylazo)indole, 0.15 mmol of 2-vinyl-1H-indole, 0.005 mmol of 1,10-bis(anthracene-9-yl)-12-hydroxy-4,5,6,7-tetrahydrodiindenzo[7,1-de:1',7'-fg][1,3,2]dioxophosphazenecyclohexane-12-oxide, and 2 mL of 1,2-dichloroethane to a 10 mL reactor. Then, heat at -15 °C. o The reaction was carried out for 36 hours under C conditions.

[0029] Step 2) After the reaction was completed, the solvent was removed under reduced pressure, and the product was purified by column chromatography to obtain pure 2-(3-chlorophenyl)-3-(1H-indol-2-yl)-5-(1-naphthyl)sulfonyl-2,3,4,4a-tetrahydro-5H-pyridazine[4,3-b]indole, with a yield of 74%.

[0030] Example 4: A method for preparing 2-(3-chlorophenyl)-3-(1H-indol-2-yl)-5-(1-naphthyl)sulfonyl-2,3,4,4a-tetrahydro-5H-pyridazine[4,3-b]indole.

[0031] Step 1) Under argon protection, add 0.1 mmol of 1-naphthalenesulfonyl-3-(3-chlorophenylazo)indole, 0.15 mmol of 2-vinyl-1H-indole, 0.005 mmol of 1,10-bis(anthracene-9-yl)-12-hydroxy-4,5,6,7-tetrahydrodiindenzo[7,1-de:1',7'-fg][1,3,2]dioxophosphazenecyclohexane-12-oxide, and 2 mL of toluene to a 10 mL reactor. Then, heat at -15 °C. o The reaction was carried out for 36 hours under C conditions.

[0032] Step 2) After the reaction was completed, the solvent was removed under reduced pressure, and the product was purified by column chromatography to obtain pure 2-(3-chlorophenyl)-3-(1H-indol-2-yl)-5-(1-naphthyl)sulfonyl-2,3,4,4a-tetrahydro-5H-pyridazine[4,3-b]indole, with a yield of 77%.

[0033] Example 5: A method for preparing 2-(3-chlorophenyl)-3-(1H-indol-2-yl)-5-(1-naphthyl)sulfonyl-2,3,4,4a-tetrahydro-5H-pyridazine[4,3-b]indole.

[0034] Step 1) Under argon protection, add 0.1 mmol of 1-naphthalenesulfonyl-3-(3-chlorophenylazo)indole, 0.15 mmol of 2-vinyl-1H-indole, 0.005 mmol of 1,10-bis(anthracene-9-yl)-12-hydroxy-4,5,6,7-tetrahydrodiindenzo[7,1-de:1',7'-fg][1,3,2]dioxophosphazenecyclohexane-12-oxide, and 2 mL of mesitylene to a 10 mL reactor. Then, heat at -15 °C. o The reaction was carried out for 36 hours under C conditions.

[0035] Step 2) After the reaction was completed, the solvent was removed under reduced pressure, and the product was purified by column chromatography to obtain pure 2-(3-chlorophenyl)-3-(1H-indol-2-yl)-5-(1-naphthyl)sulfonyl-2,3,4,4a-tetrahydro-5H-pyridazine[4,3-b]indole, with a yield of 83%.

[0036] The preparation method is simple in its synthesis steps, has high chemical selectivity, and is convenient in its post-processing. The pyridazindoindole derivative synthesized in this invention has good ultraviolet absorption properties and a wide ultraviolet absorption wavelength coverage.

[0037] Experimental example: in 10 -5 The UV-Vis absorption spectra of 2-(3-chlorophenyl)-3-(1H-indol-2-yl)-5-(1-naphthyl)sulfonyl-2,3,4,4a-tetrahydro-5H-pyridazine[4,3-b]indole were measured at room temperature at a concentration of mol / L.

[0038] like Figure 3 It is known that 2-(3-chlorophenyl)-3-(1H-indol-2-yl)-5-(1-naphthyl)sulfonyl-2,3,4,4a-tetrahydro-5H-pyridazine[4,3-b]indole has strong ultraviolet absorption at 200-250 nm and 350-400 nm.

[0039] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

[0040] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A pyridazindoindole derivative, characterized in that: Its structural formula is as follows: .

2. A method for preparing the pyridazindoindole derivative of claim 1, characterized in that, It includes the following steps: Step 1) Under argon protection, a certain amount of 1-naphthalenesulfonyl-3-(chlorophenylazo)indole, 2-vinyl-1H-indole, 1,10-bis(anthracene-9-yl)-12-hydroxy-4,5,6,7-tetrahydrodiindenzo[7,1-de:1',7'-fg][1,3,2]dioxophosphanecyclohexane-12-oxide and solvent are reacted under certain temperature conditions; Step 2) After the reaction is complete, the solvent is removed under reduced pressure, and the product is purified by column chromatography to obtain a pure pyridazindoindole derivative; wherein the structural formula of the pyridazindoindole derivative is as follows: .

3. The method for preparing the pyridazindoindole derivative according to claim 2, characterized in that: The solvents are mesitylene, dichloromethane, 1,2-dichloroethane, and toluene.

4. The method for preparing the pyridazindoindole derivative according to claim 2, characterized in that: The reaction temperature is -15 to -25°C. o C.

5. The method for preparing the pyridazindoindole derivative according to claim 2, characterized in that: The molar ratio of 1-naphthalenesulfonyl-3-(chlorophenylazo)indole, 2-vinyl-1H-indole, and 1,10-bis(anthracene-9-yl)-12-hydroxy-4,5,6,7-tetrahydrodiindenzo[7,1-de:1',7'-fg][1,3,2]dioxophosphacyclohexane-12-oxide is 1:1-2:0.01-0.

1.

6. The method for preparing the pyridazindoindole derivative according to claim 2, characterized in that: The feeding ratio of 1-naphthalenesulfonyl-3-(chlorophenylazo)indole to solvent is 1 mmol: 20-50 mL.

7. An application of the pyridazindoindole derivative according to claim 1, characterized in that: It is used to prepare ultraviolet absorbers from high molecular weight polymers.

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