CN118307471A - Novel azaphenanthrene structural compound and synthesis method thereof - Google Patents

Abstract

The present invention provides a novel azaphenanthrene structure compound and a synthesis method thereof, belonging to the technical field of organic compound synthesis, wherein an aryl borate is coupled with bromoarene through a Suzuki coupling reaction to obtain an intermediate; and then the intermediate is reacted with POCl ₃ and P ₂ O ₅ to obtain a novel azaphenanthrene structure compound. That is, the present invention utilizes the Suzuki reaction to obtain a synthesis method with simple operation, and the synthesized compound has the advantages of high yield and strong stability.

Description

A novel azophenanthrene structure compound and its synthesis method

Technical Field

The invention belongs to the technical field of organic compound synthesis, and in particular relates to a novel azophenanthrene structure compound and a synthesis method thereof.

Background technique

Room temperature phosphorescence (RTP) materials are a promising class of luminescent materials with unique physical and chemical properties such as large Stokes shift and long-life luminescence. Compared with inorganic phosphorescent materials, pure organic RTP materials have superior advantages in organic light-emitting diodes (OLEDs), high-sensitivity chemical sensing, information encryption, high-resolution biological imaging, data storage, etc., and have the advantages of low cost, simple preparation process, and easy color tuning. In recent years, new design ideas for ultralong organic room temperature phosphorescence (UORTP) materials have attracted widespread attention. Generally, the phosphorescence properties of a luminophor are closely related to its surrounding environment. Rigid environments such as intermolecular interactions and H-aggregation will greatly suppress the non-radiative decay of triplet excitons, resulting in high quantum yield and long-life RTP. The flexibility and tunability of luminescent color are a significant advantage of UORTP materials.

At present, the more commonly used method for regulating single-component luminescence is to adjust the energy gap ( _ΔEST ) between the lowest singlet state and the triplet state through molecular engineering means, or to change the stacking method of the crystal to adjust the luminescence color, but the preparation process is cumbersome.

Therefore, there is an urgent need to provide a functional luminescent small molecule compound and a method thereof with a simple synthesis method, high yield and strong product stability.

Summary of the invention

In order to solve the above technical problems, the present invention proposes a novel azophenanthrene structure compound and a synthesis method thereof.

To achieve the above object, the present invention provides the following technical solutions:

One of the technical solutions of the present invention:

A new type of azophenanthrene structure compound, the structural formula is:

, or .

The second technical solution of the present invention:

The synthesis method of the novel azaphenanthrene structure compound comprises the following steps: subjecting an aryl borate ester to a halogenated aromatic hydrocarbon through a Suzuki coupling reaction to obtain an intermediate; and then reacting the intermediate with POCl ₃ and P ₂ O ₅ to prepare the novel azaphenanthrene structure compound.

Preferably, the aryl borate ester is N-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pivalamide;

The halogenated aromatic hydrocarbon is 9-bromophenanthrene, 3-bromophenanthrene or 2-bromoanthracene.

Beneficial effects: Since the reaction between chlorinated compounds (especially chlorinated compounds with large steric hindrance) and some heterocyclic boronic acids is difficult to carry out, the present invention uses bromine-substituted aromatic hydrocarbons to react with aromatic borate esters to increase the reaction rate.

Preferably, the method comprises the following steps:

S1. dissolving an aryl borate, a halogenated aromatic hydrocarbon and an alkaline solution in an organic solvent to obtain a mixed solution, adjusting the pH of the mixed solution to alkaline, and then adding tetrakis(triphenylphosphine)palladium thereto to cause a Suzuki coupling reaction to obtain an intermediate;

S2. Mixing the intermediate with POCl ₃ and P ₂ O ₅ , reacting, and preparing the novel azophenanthrene structure compound.

Furthermore, the molar volume ratio of the halogenated aromatic hydrocarbon, aryl borate and organic solvent is: 3.55mmol:4.26mmol:70mL;

The molar volume ratio of the intermediate, POCl ₃ and P ₂ O ₅ is: 0.63 mmol: 10 mL: 6.3 mmol.

Furthermore, the synthesis method of the novel azophenanthrene structure compound 9SF comprises the following steps:

S1: 9-bromophenanthrene, N-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pivalamide and alkaline solution are dissolved in an organic solvent to obtain a mixed solution, and then the pH of the mixed solution is adjusted to alkaline, and then tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) is quickly added to cause a Suzuki coupling reaction. After the reaction is completed, the mixture is cooled to room temperature, and then extracted, dried, filtered, evaporated under reduced pressure, and purified to obtain an intermediate 9F;

S2: Under a nitrogen atmosphere, the intermediate 9F, POCl ₃ and P ₂ O ₅ were mixed and reacted. After the reaction was completed, the mixture was cooled to room temperature, poured into ice water and ethyl acetate, neutralized with sodium hydroxide solution to alkalinity, and then extracted, dried, filtered, evaporated and purified in sequence to obtain a white solid, a novel azophenanthrene structure compound 9SF.

The synthesis process of the novel azaphenanthrene structure compound 9SF is as follows:

.

Furthermore, the synthesis method of the novel azophenanthrene structure compound 3SF comprises the following steps:

S1: 3-bromophenanthrene, N-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pivalamide and alkaline solution are dissolved in an organic solvent to obtain a mixed solution, and then the pH of the mixed solution is adjusted to alkaline, and then tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) is quickly added to cause a Suzuki coupling reaction. After the reaction is completed, the mixture is cooled to room temperature, and then extracted, dried, filtered, evaporated under reduced pressure, and purified to obtain intermediate 3F;

S2: Under a nitrogen atmosphere, the intermediate 3F, POCl ₃ and P ₂ O ₅ were mixed and reacted. After the reaction was completed, the mixture was cooled to room temperature, poured into ice water and ethyl acetate, neutralized with sodium hydroxide solution to alkalinity, and then extracted, dried, filtered, evaporated and purified in sequence to obtain a white solid, a novel azophenanthrene structure compound 3SF.

Further, the synthesis method of the novel azaphenanthrene structure compound 2SE comprises the following steps:

S1: 2-bromoanthracene, N-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pivalamide and alkaline solution are dissolved in an organic solvent to obtain a mixed solution, and then the pH of the mixed solution is adjusted to alkaline, and then tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) is quickly added to cause a Suzuki coupling reaction. After the reaction is completed, the mixture is cooled to room temperature, and then extracted, dried, filtered, evaporated under reduced pressure, and purified to obtain intermediate 2E;

S2: Under a nitrogen atmosphere, the intermediate 2E, POCl ₃ and P ₂ O ₅ were mixed and reacted. After the reaction was completed, the mixture was cooled to room temperature, poured into ice water and ethyl acetate, neutralized with sodium hydroxide solution to alkalinity, and then extracted, dried, filtered, evaporated and purified in sequence to obtain a white solid, a new type of azaphenanthrene structure compound 2SE.

Furthermore, in step S1, the reaction temperature of the Suzuki coupling reaction is 70-120° C., and the reaction time is 48 h.

Furthermore, in step S1, the organic solvent includes one or more of methanol, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide.

Furthermore, in step S1, the alkaline solution is K ₂ CO ₃ .

Furthermore, in step S1, before adding tetrakis(triphenylphosphine)palladium, the mixed solution needs to be purged with nitrogen for 30 minutes.

Beneficial effect: The existing Suzuki reaction is sensitive to oxygen, and a small amount of oxygen dissolved in the solvent may lead to the generation of byproducts of boric acid self-coupling. Therefore, the present invention performs nitrogen purge on the mixed liquid to discharge the oxygen therein, thereby ensuring that there is no oxygen in the reaction system, thereby ensuring the formation of the polymer and improving the purity of the finally prepared compound.

Furthermore, in step S2, the conditions during the reaction are: reaction temperature is 110° C., and reaction time is 16-24 h.

Technical solution three:

A composite film, the raw material of which includes the novel azophenanthrene structure compound.

Preferably, the preparation process of the composite film is: blending the novel azophenanthrene structure compound with a polymer, and heating the mixture to prepare the doping system with a long afterglow.

Furthermore, the mass ratio of the novel azophenanthrene structure compound to the polymer is 1:200.

Furthermore, the polymer is PMMA.

Preferably, the heating conditions are: first heating at 100° C. for 30 minutes; and then heating at 140° C. until the solvent is completely evaporated to obtain the composite film.

Technical solution 4:

The application of the above composite film in information storage and anti-counterfeiting.

Compared with the prior art, the present invention has the following advantages and technical effects:

The present invention uses a simple synthesis method to prepare a new type of nitrogen-containing phenanthroline structure with high yield, strong product stability and a certain planar configuration. That is, the present invention prepares a condensed-ring nitrogen-phenanthroline structure, which is synthesized for the first time and is blended with a polymer (such as PMMA) to form a doping system with a long afterglow, which can be used in information storage and anti-counterfeiting applications.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings constituting a part of the present application are used to provide a further understanding of the present application. The illustrative embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

FIG1 is a nuclear magnetic resonance image of the 9SF compound prepared in Example 1;

FIG2 is a carbon spectrum of the 9SF compound prepared in Example 1;

FIG3 is a chemical structure diagram of the 9SF compound prepared in Example 1;

FIG4 is a HR MS graph of the 9SF compound prepared in Example 1;

FIG5 is a nuclear magnetic resonance image of the 3SF compound prepared in Example 2;

FIG6 is a carbon spectrum of the 3SF compound prepared in Example 2;

FIG7 is a chemical structure diagram of the 3SF compound prepared in Example 2;

FIG8 is a HR MS graph of the 3SF compound prepared in Example 2;

FIG9 is a nuclear magnetic resonance image of the 2SE compound prepared in Example 3;

FIG10 is a carbon spectrum of the 2SE compound prepared in Example 3;

FIG11 is a HR MS graph of the 2SE compound prepared in Example 3;

FIG12 is a luminescent image of the film prepared in Example 1-3 under 365 nm ultraviolet light excitation;

Among them, (a) is effect example 1; (b) is effect example 2; (c) is effect example 3.

Detailed ways

Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and/or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

All raw materials used in the examples of the present invention are purchased from the market. Specific raw materials are shown in Table 1 below.

Table 1

The technical solution of the present invention is further illustrated by the following embodiments.

Example 1

A method for synthesizing a novel azophenanthrene structure compound comprises the following steps:

S1: A round-bottom flask was charged with 9-bromophenanthrene (912.35 mg, 3.55 mmol), N-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pivalamide (1.59 g, 4.26 mmol), K ₂ CO ₃ (5.3 g, 38.41 mmol), tetrahydrofuran (THF, 70 mL), and deionized water (10 mL). The mixed solution was purged with nitrogen for 30 minutes, and then Pd(PPh ₃ ) ₄ (89 mg, 0.077 mmol) was quickly added. The mixture was stirred at 90°C for 48 hours. After cooling to room temperature, it was extracted three times with saturated brine and DCM (50 mL). The organic layers were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and evaporated to dryness under reduced pressure. The crude product was purified on a silica gel column using PE:EtOAc = 20:1 (v/v) as the eluent to obtain intermediate 9F.

S2: Under nitrogen atmosphere, a mixture of 9F (222 mg, 0.63 mmol), POCl ₃ (10 mL) and phosphorus pentoxide (P ₂ O ₅ , 0.89 g, 6.3 mmol) was stirred at 110 °C for 20 h. After cooling to room temperature, the resulting mixture was poured into ice water (150 mL) and ethyl acetate (20 mL), slowly neutralized to pH = 9 with aqueous sodium hydroxide solution (8 M NaOH), and then extracted 3 times with DCM (50 mL). The combined organic phase was dried over anhydrous Na ₂ SO ₄ , filtered, and evaporated to dryness. The crude product was purified on a silica gel column using PE∶EA = 20∶1 (v/v) as the eluent to obtain 9SF (168 mg, 89.1%) as a white solid. The NMR spectrum of compound 9SF is shown in Figure 1, the carbon spectrum is shown in Figure 2, the single crystal XRD diffraction pattern is shown in Figure 3, and the HR MS pattern is shown in Figure 4; the relevant characterization data are as follows:

9SF: ¹ H NMR (600 MHz, CDCl ₃ ): δ 8.74 (d, J = 5.36 Hz, 1H), 8.63 (t, J = 5.12 Hz, 2H), 8.51 (d, J = 5.36 Hz, 1H), 8.16 (dd, J = 5.36 Hz, 2H), 7.76 (t, J = 4.76 Hz, 1H), 7.71-7.66 (m, 2H), 7.60 (t, J = 4.76 Hz, 1H), 7.53 (q, J = 4.80 Hz, 2H), 1.58 (s, 9H). ¹³ C NMR (100 MHz, CDCl3): δ 165.55, 144.82, 134.94, 132.14, 130.80, 130.49, 129.62, 129.42, _{128.58, 128.37, 128.14, 128.07, 126.98, 126.87, 126.52, 125.54, 125.32, 123.69, 123.14, 121.90, 121.81, 41.52, 32.58, 32.58, 32.58. HR MS C25H21N m} /z: Calculated for [M] ⁺ , Exact mass: 335.45, Found: 336.06 [M ⁺ H] ⁺ .

Example 2

The difference from Example 1 is that

In S1, 9-bromophenanthrene was replaced by 3.55 mmol of 3-bromophenanthrene; the intermediate obtained in this step was 3F;

In S2, 9F was replaced by 0.63 mmol of 3F;

The other conditions were consistent with those in Example 1, and the final compound prepared was 3SF with a yield of 87%.

The NMR image of compound 3SF is shown in Figure 5, the carbon spectrum is shown in Figure 6, the single crystal XRD diffraction pattern is shown in Figure 7, and the HR MS pattern is shown in Figure 8. The relevant characterization data of 3SF are as follows:

3SF: ¹ H NMR (600 MHz, CDCl ₃ ): δ 9.97 (s, 1H), 9.12 (s, 1H), 9.00 (d, J = 5.40 Hz, 1H), 8.84 (d, J = 5.24 Hz, 1H), 8.17 (d, J = 3.96 Hz, 1H), 7.93 (t, J = 5.16 Hz, 2H), 7.80– 7.77 (m, 2H), 7.75-7.70 (m, 3H), 1.84 (s, 9H). ¹³ C NMR (100 MHz, CDCl3): δ 167.11, 132.71, 131.60, 130.64, 130.44, 129.97, 129.85, 129.76, _{128.85, 128.50, 127.84, 127.70, 127.56, 127.12, 126.72, 123.70, 123.17, 122.74, 121.76, 119.93, 116.49, 41.52, 32.58, 32.58, 32.58. HR MS C25H21N m} /z: Calculated for [M] ⁺ , Exact mass: 335.45, Found: 336.09 [M ⁺ H] ⁺ .

Example 3

The difference from Example 1 is that

In S1, 9-bromophenanthrene was replaced with 3.55 mmol of 2-bromoanthracene; the intermediate obtained in this step was 2E;

In S2, 9F was replaced by 0.63 mmol of 2E;

The other conditions were consistent with those in Example 1, and the final compound prepared was 2SE with a yield of 75%.

The NMR image of compound 2SE is shown in Figure 9, the carbon spectrum is shown in Figure 10, and the HR MS image is shown in Figure 11. The relevant characterization data of 2SE are as follows:

2SE: ¹ H NMR (600 MHz, CDCl ₃ ): δ 9.04 (s, 1H), 8.48 (d, J = 5.56 Hz, 1H), 8.40 (t, J = 8.12 Hz, 2H), 8.13 (t, J = 4.56 Hz, 2H), 8.09 (t, J = 5.24 Hz, 2H), 7.73 (t, J = 5.32 Hz, 1H), 7.62 – 7.57 (m, 3H), 1.67 (s, 9H). ¹³ C NMR (100 MHz, CDCl3): δ 166.24, 143.60, 134.07, 131.44, 130.81, 130.06, 129.90, 128.86, 128.48, 128.27, 127.65, 126.12, 126.11, 125.68, 125.19, 122.18, 122.11, 121.84, 120.00, 41.67, 32.56, 32.56 _{, 32.56, 33.37, 14.08. HR MS C25H21N m} /z: Calculated: Exact mass for [M] ⁺ : 335.45, Found: 336.08 [M ⁺ H] ⁺ .

Effect verification

Effect Example 1

The compound 9SF prepared in Example 1 was combined with PMMA to prepare a film, which was recorded as 9SF@PMMA. The preparation process of the film was as follows:

(1) Dissolve PMMA in the organic reagent dimethyl sulfoxide (DMSO) to form a uniform polymer solution with a concentration of 200 mg/mL;

(2) 9SF was dissolved in the organic reagent N,N-dimethylformamide (DMF) to form a uniform solution with a concentration of 10 mg/mL;

(3) Prepare a mixed solution of PMMA:9SF=200:1 (mass ratio) and mix well.

(4) Take 200 μL of the mixed solution and drop it onto a 2.5*2.5 cm glass slide at 100 °C. After heating for 30 min, raise the temperature to 140 °C and continue heating until the solvent evaporates completely to form a stable and uniform film, which is recorded as 9SF@PMMA.

Effect Example 2

The difference from Example 1 is that the compound 3SF prepared in Example 2 is used as a raw material, and the other conditions are the same as those in Example 1. The prepared film is recorded as 3SF@PMMA.

Effect Example 3

The difference from Example 1 is that the compound 2SE prepared in Example 3 is used as the raw material, and the other conditions are the same as those in Example 1. The prepared film is recorded as 2SE@PMMA.

The films prepared in Example 1-3 were excited under 365 nm ultraviolet light, and the corresponding luminescence diagram is shown in Figure 12. It can be seen from the figure that the steady-state fluorescence color of 9SF@PMMA changes from blue-green to light purple, the long afterglow luminescence color changes from yellow to green, and its luminescence time is the best, which is 14s; the steady-state fluorescence color of 3SF@PMMA is purple-red, the long afterglow luminescence color changes from orange to green, and its luminescence time is second, which is 8s; the steady-state fluorescence color of 2SE@PMMA is blue, the long afterglow color is light yellow-green, and the time is 2s.

The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with the technical field within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims (10)

1. A novel azaphenanthrene structural compound is characterized by having the structural formula:

、 Or (b) 。

2. The method for synthesizing the novel azaphenanthrene structural compound according to claim 1, which comprises the following steps: performing suzuki coupling reaction on aryl borate and halogenated aromatic hydrocarbon to obtain an intermediate; and then reacting the intermediate with POCl ₃ and P ₂O₅ to prepare the novel azaphenanthrene structural compound.

3. The method for synthesizing a novel azaphenanthrene structural compound according to claim 2, wherein the arylboronic acid ester is N- (2- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) pivalamide;

The halogenated aromatic hydrocarbon is 9-bromophenanthrene, 3-bromophenanthrene or 2-bromophenanthrene.

4. The method for synthesizing the novel azaphenanthrene structural compound according to claim 2, which comprises the following steps:

s1, dissolving aryl borate, halogenated aromatic hydrocarbon and alkaline solution in an organic solvent to obtain mixed solution, adjusting the pH value of the mixed solution to be alkaline, adding tetrakis (triphenylphosphine) palladium into the mixed solution, and performing suzuki coupling reaction to obtain an intermediate;

S2, mixing the intermediate with POCl ₃ and P ₂O₅, and reacting to prepare the novel azaphenanthrene structural compound.

5. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S1, the molar volume ratio of the halogenated aromatic hydrocarbon, the arylboronic acid ester and the organic solvent is as follows: 3.55 mmol:4.26 mmol:70 mL;

The molar volume ratio of the intermediate, POCl ₃ and P ₂O₅ is: 0.63 mmol: 10 mL: 6.3mmol.

6. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S1, the reaction temperature of the suzuki coupling reaction is 70-120 ℃ and the reaction time is 48h.

7. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S1, the organic solvent comprises one or more of methanol, tetrahydrofuran, acetonitrile, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.

8. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S1, the alkaline solution is K ₂CO₃.

9. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S1, nitrogen purging is performed on the mixed solution for 30min before adding tetrakis (triphenylphosphine) palladium.

10. The method for synthesizing a novel azaphenanthrene structural compound according to claim 4, wherein in the step S2, the reaction process is performed under the following conditions: the reaction temperature is 110 ℃, and the reaction time is 16-24h.