Organic conjugated compound taking naphtho ring aza-bodipy as basic skeleton, and preparation method and application thereof

Abstract

This invention relates to the field of functional organic conjugated molecular materials technology, specifically to an organic conjugated compound with a naphthenic ring Aza-BODIPY as its basic framework, its preparation method, and its applications. The structure of the organic conjugated compound is shown in formula (G): where R1 is an alkyl group; R2 is an alkoxy group, halogen, or hydrogen. This invention overcomes the limitations of existing technologies where similar Aza-BODIPY molecules require complex synthetic routes and are not conducive to the flexible construction of various ring structures. A naphthenic ring-based Aza-BODIPY molecule and its simple preparation method are disclosed.

Description

Technical Field

[0001] This invention relates to the field of functional organic conjugated molecular materials technology, specifically to an organic conjugated compound with a naphthalene ring-Aza-BODIPY as its basic skeleton, its preparation method, and its application. Background Technology

[0002] Aza-BODIPY dye molecules, as near-infrared organic fluorescent dyes, have wide applications in optoelectronic devices, bioimaging, and photodynamic therapy. In existing technologies, to improve the photoelectronic properties of these molecular materials, heavy atoms are introduced into organic conjugated compounds with Aza-BODIPY as the basic framework. However, the introduction of heavy atoms leads to a decrease in fluorescence quantum yield and reactive oxygen species production. Furthermore, the synthesis of organic conjugated compounds with Aza-BODIPY as the basic framework involves complex intermediate synthesis pathways and structural instability, resulting in low yields of the target product, which is unfavorable for mass production and application. Summary of the Invention

[0003] The purpose of this invention is to overcome the problem in the prior art that the introduction of heavy atoms into organic conjugated compounds with Aza-BODIPY as the basic framework leads to a decrease in their fluorescence quantum yield. It also overcomes the problem that in the synthesis of organic conjugated compounds with Aza-BODIPY as the basic framework, the intermediate synthesis route is complex and the structure is unstable, and the yield of the target product is low, which is not conducive to the mass production and application.

[0004] To achieve the above objectives, the present invention provides an organic conjugated compound with Aza-BODIPY as its basic framework, the structure of which is shown in formula (G):

[0005]

[0006] Where R1 is C1-C 12 Alkyl group; R2 is C1-C 12 Alkoxy, halogen, or hydrogen.

[0007] A second aspect of the present invention provides a method for preparing the above-mentioned organic conjugated compound with Aza-BODIPY as the basic skeleton, the method comprising:

[0008] S1. In the presence of an inorganic base and a first alcohol solvent, the benzocyclohexanone compound shown in formula (A) and the benzaldehyde compound shown in formula (B) are brought into contact to carry out a first reaction (aldol condensation reaction) to obtain the compound shown in formula (C).

[0009] S2. In the presence of a first organic base and a second alcohol solvent, the compound shown in formula (C) is contacted with nitromethane to carry out a second reaction (Michael addition) to obtain the compound shown in formula (D);

[0010] S3. In the presence of a third alcohol solvent, the compound shown in formula (D) is contacted with ammonium acetate to carry out a third reaction to obtain the compound shown in formula (E);

[0011] S4. In the presence of 1,2-dichloroethane and a second organic base, the compound shown in formula (E) is contacted with boron trifluoride diethyl ether to carry out a fourth reaction to obtain the compound shown in formula (F).

[0012] S5. In the presence of chloroform, the compound shown in formula (F) is contacted with dichlorocyanobenzoquinone to carry out the fifth reaction, yielding the compound shown in formula (G);

[0013]

[0014] A third aspect of the present invention provides an application of the above-mentioned organic conjugated compound with a naphthenic ring Aza-BODIPY as the basic framework as a fluorescent material, wherein the organic conjugated compound has an absorption wavelength of 300-900 nm.

[0015] Compared with existing technologies, this invention has the following technical advantages: This invention provides a novel Aza-BODIPY molecule with a β-naphthyl ring. This invention overcomes the difficulty in constructing a fused ring at the β-position in existing Aza-BODIPY molecular structures, providing a simple and convenient method for synthesizing Aza-BODIPY molecules with a β-naphthyl ring. Introducing the fused ring structure can further redshift the absorption and emission wavelengths of the molecule, meeting the requirements of near-infrared applications. Furthermore, introducing the fused ring structure can increase intermolecular interactions, thereby improving the photoelectronic properties of this type of molecular material.

[0016] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0017] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0018] Figure 1 The absorption spectra of the compounds (G1-G3) shown in Example 1 in dichloromethane are shown.

[0019] Figure 2 The absorption spectra of the compound shown in formula G1 in Test Example 1 in different solvents;

[0020] Figure 3 The absorption spectra of the compound G2 shown in Test Example 1 in different solvents are shown.

[0021] Figure 4 The absorption spectra of the compound shown in formula G3 in Test Example 1 in different solvents;

[0022] Figure 5 This is the proton spectrum of formula G1 in test example two;

[0023] Figure 6 This is the carbon spectrum of formula G1 in test example 2;

[0024] Figure 7 This is the proton spectrum of G2 in test example two;

[0025] Figure 8 This is the carbon spectrum of formula G2 in test example two;

[0026] Figure 9 This is the proton spectrum of formula G3 in test example two;

[0027] Figure 10 This is the mass spectrum of formula G1 in test example 3;

[0028] Figure 11 This is the mass spectrum of formula G2 in test example three;

[0029] Figure 12 This is the mass spectrum of formula G3 in test example three. Detailed Implementation

[0030] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further explained below with reference to specific embodiments.

[0031] This invention provides an organic conjugated compound with a naphthocyclic Aza-BODIPY as its basic skeleton, the structure of which is shown in formula (G):

[0032]

[0033] Where R1 is C1-C 12 Alkyl group; R2 is C1-C 12 Alkoxy, halogen, or hydrogen.

[0034] The present invention also provides a method for preparing the above-described organic conjugated compound with Aza-BODIPY as the basic skeleton, the method comprising:

[0035] S1. In the presence of an inorganic base and a first alcohol solvent, the compound shown in formula (A) and the compound shown in formula (B) are brought into contact to carry out a first reaction to obtain the compound shown in formula (C).

[0036] S2. In the presence of a first organic base and a second alcohol solvent, the compound shown in formula (C) is contacted with nitromethane to carry out a second reaction to obtain the compound shown in formula (D);

[0037] S3. In the presence of a third alcohol solvent, the compound shown in formula (D) is contacted with ammonium acetate to carry out a third reaction to obtain the compound shown in formula (E);

[0038] S4. In the presence of a second organic base, the compound shown in formula (E) is contacted with boron trifluoride diethyl ether to carry out a fourth reaction to obtain the compound shown in formula (F).

[0039] S5. In the presence of chloroform, the compound shown in formula (F) is contacted with dichlorodicyanobenzoquinone to undergo a fifth reaction, yielding the compound shown in formula (G).

[0040]

[0041] In the above method, the amount of raw materials can be selected within a wide range. However, in order to further improve the fluorescence quantum yield and reactive oxygen generation ability of the prepared organic conjugated compound, preferably, the conditions of the first reaction include: the molar ratio of the compound shown in formula (A), the compound shown in formula (B) and the inorganic base is 1:(1-1.2):(1-3).

[0042] The conditions for the second reaction include: the molar ratio of the compound shown in formula (C), nitromethane, and the first organic base is 1:(6-10):(1-6);

[0043] The conditions for the third reaction include: the molar ratio of the compound represented by formula (D) to ammonium acetate is 1:(10-30);

[0044] The conditions for the fourth reaction include a molar ratio of the compound represented by formula (E), the second organic base, and boron trifluoride diethyl ether of 1:(20-30):(20-30).

[0045] The conditions for the fifth reaction include a molar ratio of the compound represented by formula (F) to dichlorocyanobenzoquinone of 1:(2-10).

[0046] In the above method, the conditions of each reaction can be selected within a wide range, but in order to further improve the fluorescence quantum yield and reactive oxygen generation ability of the prepared organic conjugated compound, preferably, the conditions of the first reaction include: a temperature of 0-40℃.

[0047] The conditions for the second reaction include: a temperature of 60-100℃;

[0048] The conditions for the third reaction include: a temperature of 80-120℃;

[0049] The conditions for the fourth reaction include a temperature of 20-60℃.

[0050] The conditions for the fifth reaction include: a temperature of 60-80℃.

[0051] In the above method, the type of inorganic base used in step S1 can be selected from a wide range. Preferably, the inorganic base is potassium hydroxide and / or sodium hydroxide.

[0052] In the above method, the types of the first organic base used in step S2 and the second organic base used in step S4 can be selected from a wide range. However, in order to further improve the fluorescence quantum yield and reactive oxygen generation ability of the prepared organic conjugated compound, preferably, the first organic base and the second organic base are each independently selected from at least one of sodium ethoxide, potassium tert-butoxide, triethylamine, diethylamine, DBU and piperidine.

[0053] In the above method, the types of the first alcohol solvent used in step S1, the second alcohol solvent used in step S2, and the third alcohol solvent used in step S3 can be selected from a wide range. Preferably, the first alcohol solvent, the second alcohol solvent, and the third alcohol solvent are each independently selected from at least one of methanol, ethanol, and isopropanol.

[0054] The present invention further provides the application of organic conjugated compounds with Aza-BODIPY as the basic framework as photosensitizer materials, as described above. When the concentration of the organic conjugated compound is 0-1 mol / L, it can generate reactive oxygen species under light irradiation with a wavelength of 300-700 nm.

[0055] The present invention further provides the application of organic conjugated compounds with Aza-BODIPY as the basic framework as absorbent materials, wherein the absorption wavelength of the organic conjugated compounds is 300-900 nm.

[0056] The present invention will be described in detail below through specific examples.

[0057] In the following examples, all chemical reagents (chloroform, toluene, acetonitrile, methanol, tetrahydrofuran) are analytical grade reagents and are generally used directly without further processing unless otherwise specified.

[0058] The reaction was monitored using a 0.25 mm thick fluorescent TLC plate and a ZF-1 type three-purpose ultraviolet analyzer;

[0059] 1H NMR and 13 C NMR was performed using a Bruker AVANCE III Spectrometers 400 or Bruker AVANCE III Spectrometers 500MHz NMR spectrometer, with CDCl3 as the solvent.

[0060] The instrument used for absorption spectroscopy was a UV-2450 ultraviolet spectrophotometer; the instrument used for fluorescence spectroscopy was an Edinburgh FlS-920 fluorescence spectrometer.

[0061] Preparation Example 1

[0062]

[0063] This preparation example provides a method for preparing a compound as shown in structural formula G1, the method comprising the following steps:

[0064] S1. The compound shown in formula (A1) and the compound shown in formula (B1) and potassium hydroxide are reacted in a molar ratio of 1:1:1 in methanol at 20°C for 1 hour to obtain the compound shown in formula (C1).

[0065] S2. The compound shown in formula (C1) was mixed with nitromethane and potassium tert-butoxide in a molar ratio of 1:6:1 and reacted at 80°C for 12 hours in the presence of ethanol to obtain the compound shown in formula (D1).

[0066] S3. The compound shown in formula (D1) is mixed with ammonium acetate in a molar ratio of 1:10, and reacted in ethanol at 80°C for 24 hours to obtain the compound shown in formula (E1).

[0067] S4. The compound shown in formula (E1) was reacted with triethylamine and boron trifluoride diethyl ether in a molar ratio of 1:20:20 in the presence of 1,2-dichloroethane at 60°C for 2 hours, and purified to give the compound shown in formula (F1) (yield 82%).

[0068] S5. The compound shown in formula (F1) was reacted with dichlorodicyanobenzoquinone in a molar ratio of 1:4 in the presence of chloroform at 60°C for 12 hours, and purified to obtain the compound shown in formula (G1) (yield 72%).

[0069]

[0070] The characterization data for the compound shown in formula (G1) are as follows: 1H NMR (400MHz, CDCl3, ppm) δ9.37(d,J=8.4Hz,2H),7.86(d,J=8.4Hz,4H),7.72-7.61(m,8H),7.55(d,J=8.4,4H),7.30(d,J=9.2Hz,2H),1.41(s,18H). 13 C NMR (100MHz, CDCl3, ppm) δ152.8,151.8,149.1,139.8,137.7,131.6,130.9,129.6, 129.5,129.3,127.7,126.4,125.5,123.5,120.4,34.9,31.2.HRMS(ESI)Calcd.for C 44 H 39 BF2N3 + [M+H] + 658.3200, found 658.3198.

[0071] Preparation Example 2

[0072]

[0073] This preparation example provides a method for preparing a compound as shown in structural formula G2, the method comprising the following steps:

[0074] S1. The compound shown in formula (A2) is reacted with the compound shown in formula (B1) and potassium hydroxide in a molar ratio of 1:1:1 in methanol at 20°C for 1 hour to obtain the compound shown in formula (C2).

[0075] S2, the compound shown in formula (C2) is mixed with nitromethane and diethylamine in a molar ratio of 1:6:6 and reacted at 65°C for 12 hours in the presence of methanol to obtain the compound shown in formula (D2).

[0076] S3. The compound shown in formula (D2) is mixed with ammonium acetate in a molar ratio of 1:10, and reacted in ethanol at 80°C for 24 hours to obtain the compound shown in formula (E2).

[0077] S4. The compound shown in formula (E2) was reacted with triethylamine and boron trifluoride diethyl ether in a molar ratio of 1:20:20 in the presence of 1,2-dichloroethane at 60°C for 2 hours, and purified to give the compound shown in formula (F2) (yield 78%).

[0078] S5. The compound shown in formula (F2) was reacted with dichlorodicyanobenzoquinone in a molar ratio of 1:4 in the presence of chloroform at 60°C for 12 hours, and purified to obtain the compound shown in formula (G2) (yield 62%).

[0079]

[0080] The characterization data for the compound shown in formula (G2) are as follows: 1 H NMR (400MHz, CDCl3, ppm) δ9.25 (d, J = 9.2Hz, 2H), 7.82 (d, J = 8.4Hz, 4H), 7.70-7.61 (m, 6H), 7.54 (d, J = 8.4Hz, 4H), 7.21 (d, J = 8.8Hz, 2H), 1.41 (s, 18H). 13 C NMR (100MHz, CDCl3, ppm) δ153.2,151.0,149.2,140.3,138.7,137.2,131.6,130.8,129 .3,129.0,128.7,128.1,125.6,125.3,121.8,121.7,34.9,31.2.HRMS(ESI)calcd.for C 44 H 37 BCl2F2N3 + [M+H] + :726.2426,found 726.2421.

[0081] Preparation Example 3

[0082]

[0083] This preparation example provides a method for preparing a compound as shown in structural formula G3, the method comprising the following steps:

[0084] S1. The compound shown in formula (A3) is reacted with the compound shown in formula (B1) and potassium hydroxide in a molar ratio of 1:1:1 in methanol at 20°C for 1 hour to obtain the compound shown in formula (C3).

[0085] S2. The compound shown in formula (C3) was mixed with nitromethane and diethylamine in a molar ratio of 1:6:6 and reacted at 65°C for 12 hours in the presence of methanol to obtain the compound shown in formula (D3).

[0086] S3. The compound shown in formula (D3) is mixed with ammonium acetate in a molar ratio of 1:10, and reacted in ethanol at 80°C for 24 hours to obtain the compound shown in formula (E3).

[0087] S4. The compound shown in formula (E3) was reacted with triethylamine and boron trifluoride diethyl ether in a molar ratio of 1:20:20 in the presence of 1,2-dichloroethane at 60°C for 2 hours, and purified to give the compound shown in formula (F3) (yield 68%).

[0088] S5. The compound shown in formula (F3) was reacted with dichlorodicyanobenzoquinone in a molar ratio of 1:4 in the presence of chloroform at 60°C for 12 hours, and purified to obtain the compound shown in formula (G3) (yield 74%).

[0089]

[0090] The characterization data for the compound shown in formula (G3) are as follows: 1 H NMR (400MHz, CDCl3, ppm) δ9.31(d,J=9.6Hz,2H),7.85(d,J=8.4Hz,4H),7.62(d,J=9.6Hz,2H),7.53(d,J=8.4Hz ,4H),7.30(d,J=8.8Hz,2H),7.21(d,J=8.8Hz,2H),7.12(s,2H),4.00(s,6H)1.40(s,18H).HRMS(ESI)calcd.For C 46 H 42 BF2N3O2[M] + :717.3338, found 717.3330.

[0091] Test Example 1: Absorption Spectroscopy Test

[0092] Weigh 1-1.5 mg of the compound shown in formulas (G1-G3) and dissolve it in 2 mL of chloroform. Then, dilute it with n-hexane, toluene, dichloromethane, tetrahydrofuran, and acetonitrile to prepare a molar concentration of 10. -6 A solution of mol / L was prepared; absorption spectra were performed on each solution, and the results are as follows: Figure 1-4 As shown.

[0093] comprehensive Figure 1 , Figure 2 This demonstrates that the compound shown in formula (G1) has absorption capacity in the range of 300-900 nm.

[0094] Test Example 2: 1H NMR Spectroscopy

[0095] The compounds prepared in Examples 1, 2, and 3, as shown in formula (G1 / G2 / G3), were subjected to 1H NMR and 1C NMR spectroscopy. The original 1H and 1C NMR spectra are shown below. Figure 3-9 As shown.

[0096] Test Example 3: High-Resolution Mass Spectrometry Test

[0097] High-resolution mass spectrometry (HMS) was performed on the compounds prepared in Examples 1, 2, and 3, which are shown in formula (G1 / G2 / G3). The obtained HMS spectra are shown below. Figure 10 , Figure 11 , Figure 12 As shown.

[0098] The foregoing has shown and described the basic principles, main features, and characteristics of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method of preparing an organic conjugated compound having a basic skeleton of naphtho-cyclo Aza-BODIPY, characterized by, The method comprises: S1, contacting a benzocyclohexanone compound shown in formula (A) and a benzaldehyde compound shown in formula (B) in the presence of an inorganic base and a first alcohol solvent to perform a first reaction (aldol condensation reaction) to obtain a compound shown in formula (C); S2, contacting the compound shown in formula (C) and nitromethane in the presence of a first organic base and a second alcohol solvent to perform a second reaction (Michael addition) to obtain a compound shown in formula (D); S3, contacting the compound shown in formula (D) and ammonium acetate in the presence of a third alcohol solvent to perform a third reaction to obtain a compound shown in formula (E); S4, contacting the compound shown in formula (E) and boron trifluoride etherate in the presence of 1,2-dichloroethane and a second organic base to perform a fourth reaction to obtain a compound shown in formula (F); S5, contacting the compound shown in formula (F) and dichlorodicyanoquinone in chloroform to perform a fifth reaction to obtain a compound shown in formula (G); ； wherein R1 is tert-butyl, and R2 is selected from methoxy, chlorine or hydrogen.

2. The method of claim 1, wherein, The conditions of the first reaction include that the molar ratio of the compound shown in formula (A), the compound shown in formula (B) and the inorganic base is 1: (1-1.2): (1-3).

3. The method of claim 1, wherein, The conditions of the second reaction include that the molar ratio of the compound shown in formula (C), nitromethane and the first organic base is 1: (6-10): (1-6).

4. The method of claim 1, wherein, The conditions of the third reaction include that the molar ratio of the compound shown in formula (D) and ammonium acetate is 1: (10-30).

5. The method of claim 1, wherein, The conditions of the fourth reaction include that the molar ratio of the compound shown in formula (E), the second organic base and boron trifluoride etherate is 1: (20-30): (20-30).

6. The method of claim 1, wherein, The conditions of the fifth reaction include that the molar ratio of the compound shown in formula (F) and dichlorodicyanoquinone is 1: (2-10).

7. The method of claim 1, wherein, The conditions of the first reaction include that the temperature is 0-40℃; The conditions of the second reaction include that the temperature is 60-100℃; The conditions of the third reaction include that the temperature is 80-120℃; The conditions of the fourth reaction include that the temperature is 20-60℃; The conditions of the fifth reaction include that the temperature is 60-80℃ The inorganic base is potassium hydroxide and / or sodium hydroxide; The first organic base and the second organic base are each independently selected from at least one of sodium ethoxide, potassium tert-butoxide, triethylamine, diethylamine, DBU and piperidine; The first alcohol solvent, the second alcohol solvent and the third alcohol solvent are each independently selected from at least one of methanol, ethanol and isopropanol.

8. Use of the organic conjugated compound prepared according to the method of claim 1 as an organic dye, characterized in that, The absorption wavelength of the organic conjugated compound is 300-900nm.

Images