Polyquinazoline derivative as well as preparation method and application thereof
By preparing high molecular weight polyquinazoline derivatives, the problem of limited existing structural types has been solved, and the diversity and functionality of polymers have been improved. They have excellent thermal stability and optical properties and are suitable for the fields of biomedicine, materials science and environmental science.
Patent Information
- Application Number
- CN202510665254.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-22
- Publication Date
- 2025-12-16
AI Technical Summary
The existing polyquinazoline derivatives have a limited range of structures, which makes it difficult to meet the needs of modern technology for diversity and functionality.
A novel polyquinazoline derivative and its preparation method are provided. The method involves reacting isonitrile monomers, amine monomers, sulfonyl azide monomers and catalysts under mild conditions, combined with a precipitation method to prepare polyquinazoline imine and polyquinazoline ketone. The isonitrile monomers and sulfonyl azide monomers are activated with a cobalt-based catalyst to generate a carbodiimide intermediate, which is then cyclized with the amine monomer to prepare a high molecular weight polymer.
The prepared polymers have high molecular weights, with absolute weight-average molecular weights ranging from 41,000 to 4,064,000 g/mol and polymer dispersion indices ranging from 1.42 to 3.90. They exhibit excellent thermal stability, morphological stability, and good solubility, and demonstrate aggregated luminescence properties and chiral optical properties.
Smart Images
Figure CN121136069A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic polymer technology, and in particular to polyquinazoline derivatives, their preparation methods and applications. Background Technology
[0002] Polyquinazoline derivatives are a large class of fused heterocyclic functional polymers, whose repeating units form the structural core of various alkaloids, exhibiting diverse biological activities. Simultaneously, the heteroatom-rich fused-ring structure endows these materials with excellent chemical, thermal, optoelectronic, and mechanical properties, making them widely applicable in optoelectronic devices, fluorescence-based chemical / biological sensors, bioimaging, and stimulus-responsive materials. Furthermore, the structure of quinazoline derivatives possesses multiple hydrogen bonding sites and is easily modified / functionalized; the introduction of chiral structures can further enhance the materials' potential optical activity. These superior properties enable polyquinazoline derivatives to play a crucial role in biomedicine, materials science, and environmental science.
[0003] However, the existing structural types of polyquinazoline derivatives are still relatively limited, which to some extent restricts their performance and application development and cannot meet the diverse needs of modern technology for polyquinazoline derivatives.
[0004] Therefore, existing technologies still need to be improved and developed. Summary of the Invention
[0005] Based on the shortcomings of the prior art, the purpose of this invention is to provide polyquinazoline derivatives, their preparation methods and applications, and to provide polyquinazoline derivatives with novel structures to solve the problem that the structural types of existing polyquinazoline derivatives are still relatively limited, thereby enriching the structural library of polyquinazoline derivatives.
[0006] The technical solution of the present invention is as follows:
[0007] In a first aspect, the present invention provides a polyquinazoline derivative of Formula I:
[0008]
[0009] Where a is an integer from 1 to 200; R 1 R 2 Each group is independently an aryl group, an aryl derivative, an aromatic heterocyclic group, an ester group, a bioactive fragment, or an aliphatic substituent; the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins; It is an aryl, aryl derivative or aryl heterocyclic group, where R is NH or O.
[0010] Optionally, Choose from one of the following structures:
[0011]
[0012] Where * represents the linking site; X is selected from CH2, O, S, or Se, Y is selected from C, S, or Si; R 1 R 2 Each can be independently an aryl group, aryl derivative, aromatic heterocyclic group, ester group, bioactive fragment, or aliphatic substituent; R 3 R 4 R 5 and R 6 Each can be independently a hydrogen atom, halogen atom, allyl group, ester group, nitro group, cyano group, bioactive fragment, or M group;
[0013] The bioactive fragments include one of terpenes, steroids, fatty alcohols, and vitamins;
[0014] The M group is one of the following groups, which may or may not be chiral:
[0015] Alkylamines, alkyl groups, alkoxy groups, aromatic heterocyclic groups, aryl groups, and aryl derivatives.
[0016] Optionally, R 1 R 2 Each of the following groups, whether chiral or not, is independently one of them:
[0017] Alkylamines, alkyl groups, alkoxy groups, aromatic heterocyclic groups, aryl groups, and aryl derivatives.
[0018] Optionally, R 1 R 2 Each is independently selected from one of the following structures:
[0019]
[0020] Where * represents a connection site; m and n are integers from 1 to 20; X is selected from NH, O, S, or Se; R 3 R 4 Each group is independently a hydrogen atom, a halogen atom, an allyl group, an ester group, a nitro group, a cyano group, a bioactive fragment, or an M group; the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins; the M group is one of the following groups, which may or may not be chiral:
[0021] Alkylamines, alkyl groups, alkoxy groups, aromatic heterocyclic groups, aryl groups, and aryl derivatives.
[0022] A second aspect of the present invention provides a method for preparing the polyquinazoline derivative as described above, wherein, when R is NH, the method for preparing the polyquinazoline derivative includes the following steps:
[0023] The isonitrile monomer, amine monomer, sulfonyl azide monomer, catalyst and solvent are mixed and reacted to obtain the first reaction solution;
[0024] The first reaction solution was added to a precipitant to precipitate the polyquinazoline derivative.
[0025] The general structural formula of the isonitrile monomer is:
[0026] The general structural formula of the amine monomer is: H2N-R 1 -NH2;
[0027] The general structural formula of the sulfonyl azide monomer is: N3O2S-R 2 -SO2N3;
[0028] in, It is an aryl, aryl derivative, or aromatic heterocyclic group; R 1 R 2 Each group is independently an aryl group, an aryl derivative, an aromatic heterocyclic group, an ester group, a bioactive fragment, or an aliphatic substituent; the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins.
[0029] A third aspect of the present invention provides a method for preparing the polyquinazoline derivative as described above, wherein, when R is O, the preparation of the polyquinazoline derivative includes the following steps:
[0030] The isonitrile monomer, amine monomer, sulfonyl azide monomer, catalyst and solvent are mixed and reacted to obtain the first reaction solution;
[0031] The first reaction solution is added to a precipitant for precipitation, and the product obtained after precipitation is added to an acidic solution for reaction to obtain a second reaction solution;
[0032] The second reaction solution was added to a precipitant to precipitate the polyquinazoline derivative.
[0033] The general structural formula of the isonitrile monomer is:
[0034] The general structural formula of the amine monomer is: H2N-R 1 -NH2;
[0035] The general structural formula of the sulfonyl azide monomer is: N3O2S-R 2 -SO2N3;
[0036] It is an aryl, aryl derivative, or aromatic heterocyclic group; R 1 R 2Each group is independently an aryl group, an aryl derivative, an aromatic heterocyclic group, an ester group, a bioactive fragment, or an aliphatic substituent; the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins.
[0037] Optionally, the molar ratio of the isonitrile monomer, amine monomer, and sulfonyl azide monomer is (2-2.5):1:1; and / or,
[0038] The reaction concentration of the amine monomer is 0.05–0.20 mol / L; and / or,
[0039] The molar amount of the catalyst is 5% to 10% of the molar amount of the amine monomer.
[0040] Optionally, the precipitant includes at least one selected from hexane, methanol, diethyl ether, and acetone; and / or,
[0041] The solvent comprises at least one selected from toluene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, 1,4-dioxane, and 1,2-dichloroethane; and / or,
[0042] The catalyst includes at least one of cobalt-based catalyst, nickel-based catalyst, copper-based catalyst and iron-based catalyst; and / or, in the step of reacting isonitrile monomer, amine monomer, sulfonyl azide monomer, catalyst and solvent, the reaction temperature is 80-120°C and the reaction time is 12-24 h.
[0043] A fourth aspect of the present invention provides the application of the polyquinazoline derivative of the present invention as described above, or the polyquinazoline derivative prepared by the preparation method of the present invention as described above, in the fields of biomedicine, materials science, or environmental science.
[0044] Alternatively, polyquinazoline derivatives can be used as fluorescent or polarizing materials.
[0045] Beneficial effects: The polyquinazoline derivative provided by this invention has a novel structure, enriching the structural library of polyquinazoline derivatives. This polyquinazoline derivative has a high molecular weight, with an absolute weight-average molecular weight of 41,000 to 4,064,000 g / mol and a polymer dispersion index (PDI) of 1.42 to 3.90. It also has excellent thermal stability, morphological stability, and good solubility, and exhibits aggregated luminescence or chiral optical properties. It has broad application prospects in the fields of biomedicine, materials science, and environmental science. Attached Figure Description
[0046] Figure 1 This is the general structural formula for polyquinazoline derivatives.
[0047] Figure 2The image shows the 1H NMR spectrum of polyquinazoline imine P1 in deuterated dimethyl sulfoxide from Example 1.
[0048] Figure 3 In Example 1, (A) is the photofluorescence emission spectrum of polyquinazoline imine P1 in dimethyl sulfoxide solutions with different ethanol contents, and (B) is the curve of the relative peak emission intensity (I / I0) of polyquinazoline imine P1 in dimethyl sulfoxide solutions with different ethanol contents as a function of ethanol content.
[0049] Figure 4 The image shows the 1H NMR spectrum of polyquinazoline imine P2 in deuterated dimethyl sulfoxide from Example 2.
[0050] Figure 5 The image shows the 1H NMR spectrum of polyquinazoline imine P3 in deuterated dimethyl sulfoxide from Example 3.
[0051] Figure 6 The image shows the 1H NMR spectrum of polyquinazoline imine P4 in deuterated chloroform from Example 4.
[0052] Figure 7 The image shows the 1H NMR spectrum of polyquinazoline imine P5 in deuterated chloroform from Example 5.
[0053] Figure 8 Scanning electron microscope (SEM) images of the self-assembly morphology of polyquinazoline imine P5 in Example 5 in mixed solutions of tetrahydrofuran and water at different volume ratios.
[0054] Figure 9 The image shows the 1H NMR spectrum of polyquinazolinone P6 in deuterated chloroform from Example 6.
[0055] Figure 10 The image shows the 1H NMR spectrum of polyquinazolinone P7 in deuterated chloroform from Example 7.
[0056] Figure 11 The images show circular dichroism chromatograms of different polymers in tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and a mixture of dimethyl sulfoxide and ethanol. (A) shows the circular dichroism chromatograms of polyquinazoline imide P4 in Example 4 and polyquinazoline imide P5 in Example 5; (B) shows the circular dichroism chromatograms of polyquinazoline ketone P6 in Example 6 and polyquinazoline ketone P7 in Example 7.
[0057] Figure 12The images show the circularly polarized emission spectra of different polymers in tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and a mixture of dimethyl sulfoxide and ethanol. (A) shows the circularly polarized emission spectra of polyquinazoline imide P4 in Example 4 and polyquinazoline imide P5 in Example 5; (B) shows the circularly polarized emission spectra of polyquinazoline ketone P6 in Example 6 and polyquinazoline ketone P7 in Example 7. Detailed Implementation
[0058] This invention provides polyquinazoline derivatives, their preparation methods, and applications. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.
[0059] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
[0060] like Figure 1 As shown, embodiments of the present invention provide polyquinazoline derivatives represented by Formula I:
[0061]
[0062] Where a is an integer from 1 to 200; R 1 R 2 Each group is independently an aryl group, an aryl derivative, an aromatic heterocyclic group, an ester group, a bioactive fragment, or an aliphatic substituent (such as alkyl, alkylamine, alkoxy, allyl, etc.); the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins; It is an aryl, aryl derivative or aryl heterocyclic group, where R is NH or O.
[0063] The polyquinazoline derivatives provided in this embodiment have novel structures, high molecular weights (absolute weight-average molecular weight of 41,000 to 4,064,000 g / mol, PDI of 1.42 to 3.90), and excellent thermal stability, morphological stability, good solubility, and aggregated luminescence or chiral optical properties.
[0064] In this embodiment, the polyquinazoline derivative is a polyquinazoline imine or a polyquinazoline ketone, wherein the structural formula of the polyquinazoline imine is: The structural formula of polyquinazolinone is:
[0065]
[0066] In some implementations... Choose from one of the following structures:
[0067]
[0068] Where * represents a connection site; when X is selected from CH2, O, S, or Se, Y is selected from C, S, or Si; R 1 R 2 Each can be independently an aryl group, aryl derivative, aromatic heterocyclic group, ester group, bioactive fragment, or aliphatic substituent; R 3 R 4 R 5 and R 6 Each group is independently a hydrogen atom, a halogen atom, an allyl group, an ester group, a nitro group, a cyano group, a bioactive fragment, or an M group; the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins; the M group is one of the following groups, which may or may not be chiral:
[0069] Alkylamines, alkyl groups, alkoxy groups, aromatic heterocyclic groups, aryl groups, and aryl derivatives.
[0070] In this embodiment, having chirality means having a chiral center, a chiral axis, or a chiral surface.
[0071] In some implementations, R 1 R 2 Each of the following groups, whether chiral or not, is independently one of them:
[0072] Alkylamines, alkyl groups, alkoxy groups, aromatic heterocyclic groups, aryl groups, and aryl derivatives.
[0073] In some implementations, R 1 R 2 Each is independently selected from one of the following structures:
[0074]
[0075] Where * represents a connection site; m and n are integers from 1 to 20; X is selected from NH, O, S, or Se; R 3 R 4 Each group is independently a hydrogen atom, a halogen atom, an allyl group, an ester group, a nitro group, a cyano group, a bioactive fragment, or an M group; the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins; the M group is one of the following groups, which may or may not be chiral: alkylamines, alkyl groups, alkoxy groups, aromatic heterocyclic groups, aryl groups, and aryl derivatives.
[0076] in, Can be wait.
[0077] The existing structural variety of polyquinazoline derivatives remains relatively limited, primarily due to the numerous challenges encountered in synthesizing polymers with such structures using traditional polymerization methods. Traditional methods typically require the pre-synthesis of monomers with quinazoline structures and cumbersome pre-functionalization steps. Currently, the variety of functionalized reactive monomers containing quinazoline structures is still very limited, resulting in a relatively limited range of corresponding polyquinazoline derivatives and high difficulty in structural control. Introducing chiral units into the polymer structure further increases the difficulty of monomer and polymer synthesis. Therefore, developing a simple and efficient method for preparing polyquinazoline derivatives with unique structures and advanced functions has significant academic and industrial value. Based on this, this invention provides two methods for preparing polyquinazoline derivatives: one for preparing polyquinazoline imines and the other for preparing polyquinazoline ketones.
[0078] The preparation method of polyquinazoline imine includes the following steps:
[0079] S11. The isonitrile monomer, amine monomer, sulfonyl azide monomer, catalyst and solvent are mixed and reacted to obtain the first reaction solution;
[0080] S12. The first reaction solution is added to a precipitant to precipitate the polyquinazoline imine.
[0081] The general structural formula of the isonitrile monomer is:
[0082] The general structural formula of the amine monomer is: H2N-R 1 -NH2;
[0083] The general structural formula of the sulfonyl azide monomer is: N3O2S-R 2 -SO2N3;
[0084] in, R 1 and R 2 The selected functional groups are described above and will not be repeated here.
[0085] The preparation method provided by this invention utilizes a wide variety of readily available and inexpensive substrates, employs relatively mild reaction conditions, achieves high polymerization yields, and demonstrates excellent economic efficiency. The catalyst used is a high-yield metal catalyst, and the polyquinazoline imine is easily separated; only one precipitation in a precipitant is required to obtain polyquinazoline imine with high purity. The polyquinazoline derivative, i.e., polyquinazoline imine, prepared by the method provided by this invention exhibits a novel structure, high molecular weight (absolute weight-average molecular weight of 41,000–4,064,000 g / mol), a PDI of 1.42–3.90, and excellent thermal stability, morphological stability, good solubility, and aggregated luminescence properties. Furthermore, the polyquinazoline imine prepared based on chiral amine monomers possesses unique self-assembly properties and excellent chiral optical properties.
[0086] In this embodiment of the invention, a catalyst such as a cobalt catalyst activates the isonitrile monomer and the sulfonyl azide monomer, removing one molecule of nitrogen gas to generate a carbodiimide intermediate. Then, the amine monomer nucleophilically attacks the carbon atom of this carbodiimide intermediate, followed by a cyclization reaction with a cyano group to obtain the target product.
[0087] In step S11, in some embodiments, the molar ratio of the isonitrile monomer, amine monomer and sulfonyl azide monomer is (2-2.5):1:1, for example, it can be 2:1:1, 2.1:1:1, 2.2:1:1, 2.3:1:1, 2.4:1:1 or 2.5:1:1, etc.
[0088] In some embodiments, the molar amount of the catalyst is 5% to 10% of the molar amount of the amine monomer, for example, it can be 5%, 6%, 7%, 8%, 9% or 10%.
[0089] In some embodiments, the reaction concentration of the amine monomer is 0.05 to 0.20 mol / L, for example, it can be 0.05 mol / L, 0.1 mol / L, 0.15 mol / L or 0.20 mol / L.
[0090] In some embodiments, the solvent includes at least one selected from toluene, dimethyl sulfoxide (DMSO), N,N-dimethylformamide, acetonitrile, 1,4-dioxane, and 1,2-dichloroethane.
[0091] In some embodiments, the catalyst includes at least one of a cobalt-based catalyst, a nickel-based catalyst, a copper-based catalyst, and an iron-based catalyst, but is not limited thereto. The cobalt-based catalyst includes at least one of cobalt acetylacetonate (Co(acac)3), cobalt dichloride, cobalt oxalate, hydrated cobalt acetate, and cobalt sulfate, but is not limited thereto; the nickel-based catalyst includes at least one of nickel chloride, nickel acetate, and cyclooctadiene nickel, but is not limited thereto; the copper-based catalyst includes copper chloride, but is not limited thereto; the iron-based catalyst includes ferric chloride, but is not limited thereto.
[0092] In some embodiments, in the step of reacting the isonitrile monomer, amine monomer, sulfonyl azide monomer, catalyst, and solvent, the reaction temperature is 80–120°C (e.g., 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, or 120°C), and the reaction time is 12–24 h (e.g., 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 18 h, 19 h, 20 h, 21 h, 22 h, 23 h, or 24 h).
[0093] In step S12, in some embodiments, the precipitant includes at least one of n-hexane, methanol, diethyl ether, and acetone, but is not limited to these.
[0094] In some implementations, the precipitation process also includes steps of filtration and drying.
[0095] Furthermore, the preparation method of polyquinazoline includes the following steps:
[0096] S21. The polyquinazoline imine prepared above is added to an acidic solution (such as a mixed solution of hydrochloric acid and tetrahydrofuran, or a mixed solution of hydrochloric acid and dimethyl sulfoxide) to carry out the reaction (reaction temperature is 65-70℃) to obtain a second reaction solution;
[0097] S22. The second reaction solution is added to a precipitant to precipitate the polyquinazolinone.
[0098] In this invention, polyquinazoline imine can be obtained simply by adding it to an acidic solution for hydrolysis.
[0099] Step S22 includes filtration and drying after precipitation.
[0100] The polyquinazoline derivatives (polyquinazoline imine and polyquinazoline ketone) prepared by the preparation method described above in this invention all have good optical properties and unique application value in fluorescence emission, circular dichroism spectroscopy, circular polarization luminescence and self-assembly.
[0101] The present invention also provides an application of the polyquinazoline derivative of the present invention as described above, or the polyquinazoline derivative prepared by the preparation method of the present invention as described above, in the fields of biomedicine, materials science, or environmental science.
[0102] In some implementations, polyquinazoline derivatives are used as fluorescent or polarizing materials in the field of optics.
[0103] The present invention will be further described below through specific embodiments.
[0104] Unless otherwise specified, the raw materials used in the following embodiments are all commercially available products.
[0105] In the following examples, the 2-isocyanobenzonitrile used was prepared according to the methods disclosed in the literature (S.Jiang, W.-B.Cao, X.-P.Xu, S.-J.Ji, Org.Lett.2021,23,6740-6744), and the 4,4'-oxobis(benzenesulfonyl)azides used were prepared according to the methods disclosed in the literature (AR.Katritzky, J.W.Rogers, R.M.Witek, A.V.A.Kakulenko, P.P.Mohapatra, P.S.Teel, R.D.Damavarapu, J.Energ.Mater.2007,25,79-109).
[0106] Example 1
[0107] This embodiment provides a polyquinazoline imine P1, the structural formula of which is:
[0108]
[0109] The synthetic route for the polyquinazoline imine P1 is as follows:
[0110]
[0111] According to the above synthetic route, the preparation method of the polyquinazoline imine P1 includes the following steps:
[0112] 2-Isocyanobenzonitrile (64.0 mg, 0.50 mmol), 4,4'-oxobis(benzenesulfonyl)azonium (76.7 mg, 0.20 mmol), 1,4-phenylenediamine (21.6 mg, 0.20 mmol), and Co(acac)3 (7.2 mg, 0.02 mmol) were sequentially added to a 25 mL sealed tube. Then, DMSO (1 mL) was added to the tube in a glove box. The mixture was then stirred at 120 °C for 24 hours in an oil bath. After the reaction was complete, the reaction solution was cooled to room temperature and diluted with methanol (2 mL), then passed through a 4 cm thick neutral Al2O3 column to obtain a mixture. This mixture was added dropwise to 150 mL of diethyl ether under vigorous stirring to precipitate the precipitate, which was then collected. The precipitate was then dried under vacuum at 65 °C to constant weight to obtain polyquinazoline imine P1 with a yield of 97%, a weight-average molecular weight of 41800 g / mol, and a PDI of 1.52.
[0113] The 1H NMR spectrum of polyquinazoline imine P1 in deuterated dimethyl sulfoxide provided in this embodiment is as follows: Figure 2 As shown. From Figure 2As can be seen, the solvent peak of deuterated dimethyl sulfoxide is located at 2.50 ppm, and the water peak is located at 3.33 ppm. All other peaks are hydrogen atom signals from polyquinazoline imine P1, and these characteristic hydrogen atom signals can be assigned accordingly. The peak at 9.33 ppm is the characteristic peak of the ortho-amino hydrogen at the sulfonyl group in polyquinazoline imine P1.
[0114] Photofluorescence emission spectra of polyquinazoline imine P1 in dimethyl sulfoxide solutions with different ethanol contents are shown below. Figure 3 As shown in (A), the fluorescence intensity remains almost constant with increasing ethanol content, except for a slight decrease when the ethanol content exceeds 70% (volume fraction). The curves showing the relative peak emission intensity (I / I0) of polyquinazoline imine P1 in dimethyl sulfoxide solutions with different ethanol contents are shown below. Figure 3 As shown in (B), polyquinazoline imine P1 exhibits a clear dual-state luminescence phenomenon, where I represents the fluorescence emission intensity and I0 represents the fluorescence emission intensity in dimethyl sulfoxide.
[0115] Example 2
[0116] This embodiment provides a polyquinazoline imine P2, the structural formula of which is:
[0117]
[0118] The synthetic route for the polyquinazoline imine P2 is as follows:
[0119]
[0120] According to the above synthetic route, the preparation method of the quinazoline imine P2 includes the following steps:
[0121] 2-Isocyanobenzonitrile (64.0 mg, 0.50 mmol), 4,4'-oxobisbenzenesulfonyl azide (76.7 mg, 0.20 mmol), N 1 -(4-Aminophenyl)-N 11,4-Phenyl-1,4-phenylenediamine (55.3 mg, 0.20 mmol) and Co(acac)3 (7.2 mg, 0.02 mmol) were sequentially added to a 25 mL sealed tube. Then, DMSO (1 mL) was added to the tube in a glove box. The mixture was then stirred at 120 °C for 24 hours in an oil bath. After the reaction was complete, the reaction solution was cooled to room temperature and diluted with methanol (2 mL). The solution was then passed through a 4 cm thick neutral Al2O3 column to obtain a mixture. This mixture was added dropwise to 150 mL of diethyl ether under vigorous stirring to precipitate the precipitate, which was then collected. The precipitate was then dried under vacuum at 65 °C to constant weight to give polyquinazoline imine P2 in 82% yield, with a weight-average molecular weight of 138,900 g / mol and a PDI of 1.70.
[0122] The 1H NMR spectrum of polyquinazoline imine P2 in deuterated dimethyl sulfoxide provided in this embodiment is as follows: Figure 4 As shown. From Figure 4 As can be seen, the solvent peak and water peak of deuterated dimethyl sulfoxide are located at 2.50 ppm and 3.33 ppm, respectively. All other peaks are hydrogen atom signals from polyquinazoline imine P2.
[0123] Example 3
[0124] This embodiment provides a polyquinazoline imine P3, the structural formula of which is:
[0125]
[0126] The synthetic route for the polyquinazoline imine P3 is as follows:
[0127]
[0128] According to the above synthetic route, the preparation method of the polyquinazoline imine P3 includes the following steps:
[0129] 2-Isocyanobenzonitrile (64.0 mg, 0.50 mmol), 4,4'-oxobis(benzenesulfonyl)azonium (76.7 mg, 0.20 mmol), 4,4'-methylenediphenylamine (39.6 mg, 0.20 mmol), and Co(acac)3 (7.2 mg, 0.02 mmol) were sequentially added to a 25 mL sealed tube. Then, DMSO (1 mL) was added to the tube in a glove box. The mixture was then stirred at 120 °C for 24 hours in an oil bath. After the reaction was complete, the reaction solution was cooled to room temperature and diluted with methanol (2 mL). The solution was then passed through a 4 cm thick neutral Al2O3 column to obtain a mixture. This mixture was added dropwise to 150 mL of diethyl ether under vigorous stirring to precipitate the product, and the precipitate was collected. The precipitate was then dried under vacuum at 65 °C to constant weight to obtain polyquinazoline imine P3 with a yield of 99%, a weight-average molecular weight of 49000 g / mol, and a PDI of 1.94.
[0130] The 1H NMR spectrum of polyquinazoline imine P3 in deuterated dimethyl sulfoxide provided in this embodiment is as follows: Figure 5 As shown. From Figure 5 As can be seen, the solvent peak and water peak of deuterated dimethyl sulfoxide are located at 2.50 ppm and 3.33 ppm, respectively. All other peaks are hydrogen atom signals from polyquinazoline imine P3.
[0131] Example 4
[0132] This embodiment provides a polyquinazoline imine P4, the structural formula of which is:
[0133]
[0134] The synthetic route for the polyquinazoline imine P4 is as follows:
[0135]
[0136] Following the above synthetic route, the preparation method of the polyquinazoline imine P4 includes the following steps:
[0137] 2-Isocyanobenzonitrile (64.0 mg, 0.50 mmol), 4,4'-oxobis(benzenesulfonyl)azonium (76.7 mg, 0.20 mmol), (1R,2R)-1,2-diphenylethane-1,2-diamine (42.4 mg, 0.20 mmol), and Co(acac)3 (7.2 mg, 0.02 mmol) were sequentially added to a 25 mL sealed tube. Then, DMSO (1 mL) was added to the tube in a glove box. The mixture was then stirred at 120 °C for 24 hours in an oil bath. After the reaction was complete, the reaction solution was cooled to room temperature and diluted with methanol (2 mL). The solution was then passed through a 4 cm thick neutral Al2O3 column to obtain a mixture. This mixture was added dropwise to 150 mL of diethyl ether under vigorous stirring to precipitate the precipitate, which was then collected. Then, it was vacuum dried at 65°C to constant weight to obtain polyquinazoline imine P4 with a yield of 47%, a weight-average molecular weight of 683,600 g / mol, and a PDI of 2.68.
[0138] The 1H NMR spectrum of polyquinazoline imine P4 in deuterated chloroform provided in this embodiment is as follows: Figure 6 As shown. From Figure 6 As can be seen, the solvent peak and water peak of deuterated chloroform are located at 7.26 ppm and 1.56 ppm, respectively, while the solvent peaks of a small amount of residual dimethyl sulfoxide and silicone grease are located at 2.62 ppm and 1.26 ppm, respectively. All other peaks are hydrogen atom signals from polyquinazoline imine P4.
[0139] Example 5
[0140] This embodiment provides a polyquinazoline imine P5, the structural formula of which is:
[0141]
[0142] The synthetic route for the polyquinazoline imine P5 is as follows:
[0143]
[0144] According to the above synthetic route, the preparation method of the polyquinazoline imine P5 includes the following steps:
[0145] 2-Isocyanobenzonitrile (64.0 mg, 0.50 mmol), 4,4'-oxobis(benzenesulfonyl)azonium (76.7 mg, 0.20 mmol), (1S,2S)-1,2-diphenylethane-1,2-diamine (42.4 mg, 0.20 mmol), and Co(acac)3 (7.2 mg, 0.02 mmol) were sequentially added to a 25 mL sealed tube. Then, DMSO (1 mL) was added to the tube in a glove box. The mixture was then stirred at 120 °C for 24 hours in an oil bath. After the reaction was complete, the reaction solution was cooled to room temperature and diluted with methanol (2 mL). The solution was then passed through a 4 cm thick neutral Al2O3 column to obtain a mixture. This mixture was added dropwise to 150 mL of diethyl ether under vigorous stirring to precipitate the precipitate, which was then collected. Then, it was vacuum dried at 65°C to constant weight to obtain polyquinazoline imine P5 with a yield of 35%, a weight-average molecular weight of 4,064,000 g / mol, and a PDI of 3.90.
[0146] The 1H NMR spectrum of polyquinazoline imine P5 in deuterated chloroform provided in this embodiment is as follows: Figure 7 As shown. From Figure 7 As can be seen, the solvent peak and water peak of deuterated chloroform are located at 7.26 ppm and 1.56 ppm, respectively; the internal standard peak of TMS (tetramethylsilane) is located at 0.00 ppm; and the solvent peak and silicone grease peak of a small amount of residual dimethyl sulfoxide are located at 2.62 ppm and 1.26 ppm, respectively. All other signals are hydrogen atom signals from polyquinazoline imine.
[0147] The scanning electron microscope (SEM) images of the self-assembly morphology of polyquinazoline imine P5 in mixed solutions of tetrahydrofuran and water at different volume ratios provided in this embodiment are as follows: Figure 8 As shown. From Figure 8 It can be seen that polyquinazoline imine P5 can self-assemble into a structure with helical morphology.
[0148] Example 6
[0149] This embodiment provides a polyquinazolinone P6 with the following structural formula:
[0150]
[0151] The synthetic route for polyquinazoline ketone P6 is as follows:
[0152]
[0153] According to the above synthetic route, the preparation method of polyquinazolinone P6 includes the following steps:
[0154] The polyquinazoline imine P4 (50 mg, 0.063 mmol) provided in Example 4 and 1 mL of dimethyl sulfoxide were added to a 10 mL flask, followed by the addition of hydrochloric acid (1 M, 1 mL). The mixture was stirred vigorously at 65 °C until complete. The reaction solution was then passed dropwise through a 4 cm thick neutral Al₂O₃ column into 150 mL of diethyl ether to precipitate the product. The precipitate was collected and dried under vacuum at 65 °C to constant weight to obtain polyquinazoline ketone P6 in 74% yield.
[0155] The 1H NMR spectrum of polyquinazolinone P6 in deuterated chloroform provided in this embodiment is as follows: Figure 9 As shown.
[0156] Example 7
[0157] This embodiment provides a polyquinazolinone P7, whose structural formula is as follows:
[0158]
[0159] The synthetic route for the polyquinazolinone P7 is as follows:
[0160]
[0161] According to the above synthetic route, the preparation method of polyquinazolinone P7 includes the following steps:
[0162] The polyquinazoline imine P5 (50 mg, 0.063 mmol) provided in Example 5 and 1 mL of dimethyl sulfoxide were added to a 10 mL flask, followed by the addition of hydrochloric acid (1 M, 1 mL). The mixture was stirred vigorously at 65 °C until complete. The reaction solution was then passed dropwise through a 4 cm thick neutral Al₂O₃ column into 150 mL of diethyl ether to precipitate the product. The precipitate was collected and dried under vacuum at 65 °C to constant weight to obtain polyquinazoline ketone P7 in 72% yield.
[0163] The 1H NMR spectrum of polyquinazolinone P7 in deuterated chloroform provided in this embodiment is as follows: Figure 10 As shown.
[0164] Figure 11 The figures show circular dichroism chromatograms of different polymers in tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and a mixture of dimethyl sulfoxide and ethanol (dimethyl sulfoxide to ethanol volume ratio 40:60). Figure (A) shows the circular dichroism chromatograms of polyquinazoline imine P4 in Example 4 and polyquinazoline imine P5 in Example 5; Figure (B) shows the circular dichroism chromatograms of polyquinazoline ketone P6 in Example 6 and polyquinazoline ketone P7 in Example 7. It can be seen that there are significant differences in wavelength before and after hydrolysis.
[0165] Figure 12The images show the circularly polarized emission spectra of different polymers in tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and a mixture of dimethyl sulfoxide and ethanol. Figure (A) shows the circularly polarized emission spectra of polyquinazoline imide P4 from Example 4 and polyquinazoline imide P5 from Example 5; Figure (B) shows the circularly polarized emission spectra of polyquinazoline ketone P6 from Example 6 and polyquinazoline ketone P7 from Example 7. It can be seen that the circularly polarized emission of polyquinazoline imide P4 and polyquinazoline imide P5, and their hydrolyzed products polyquinazoline ketone P6 and polyquinazoline ketone P7, almost disappears.
[0166] In summary, this invention provides polyquinazoline derivatives, their preparation methods, and applications. The polyquinazoline derivatives possess novel structures, high biomolecular weight (41,000–4,064,000 g / mol absolute weight average), and polymer dispersion index (PDI) of 1.42–3.90. They also exhibit excellent thermal stability, morphological stability, and good solubility, as well as aggregated-state luminescence or chiral optical properties, demonstrating unique application value in fluorescence emission, circular dichroism spectroscopy, circularly polarized luminescence, and self-assembly. Furthermore, the preparation method provided by this invention utilizes a wide variety of inexpensive and readily available substrates, employs relatively mild reaction conditions, achieves high polymerization yields, and demonstrates good economic efficiency. The catalyst used is a high-yield metal catalyst, and the polyquinazoline imine is easily separated; only one precipitation in a precipitant is required to obtain highly pure polyquinazoline imine. Simultaneously, hydrolysis of the polyquinazoline imine yields polyquinazoline ketone.
[0167] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.
Claims
1. The polyquinazoline derivative shown in Formula I: in, a is an integer from 1 to 200; R 1 R 2 Each group is independently an aryl group, an aryl derivative, an aromatic heterocyclic group, an ester group, a bioactive fragment, or an aliphatic substituent; the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins; It is an aryl, aryl derivative or aryl heterocyclic group, where R is NH or O.
2. The polyquinazoline derivative according to claim 1, characterized in that, Choose from one of the following structures: Where * represents the linking site; X is selected from CH2, O, S, or Se, Y is selected from C, S, or Si; R 1 R 2 Each can be independently an aryl group, aryl derivative, aromatic heterocyclic group, ester group, bioactive fragment, or aliphatic substituent; R 3 R 4 R 5 and R 6 Each can be independently a hydrogen atom, halogen atom, allyl group, ester group, nitro group, cyano group, bioactive fragment, or M group; The bioactive fragments include one of terpenes, steroids, fatty alcohols, and vitamins; The M group is one of the following groups, which may or may not be chiral: Alkylamines, alkyl groups, alkoxy groups, aromatic heterocyclic groups, aryl groups, and aryl derivatives.
3. The polyquinazoline derivative according to claim 1, characterized in that, R 1 R 2 Each of the following groups, whether chiral or not, is independently one of them: Alkylamines, alkyl groups, alkoxy groups, aromatic heterocyclic groups, aryl groups, and aryl derivatives.
4. The polyquinazoline derivative according to claim 1, characterized in that, R 1 R 2 Each is independently selected from one of the following structures: Where * represents a connection site; m and n are integers from 1 to 20; X is selected from NH, O, S, or Se; R 3 R 4 Each group is independently a hydrogen atom, a halogen atom, an allyl group, an ester group, a nitro group, a cyano group, a bioactive fragment, or an M group; the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins; the M group is one of the following groups, which may or may not be chiral: Alkylamines, alkyl groups, alkoxy groups, aromatic heterocyclic groups, aryl groups, and aryl derivatives.
5. A method for preparing the polyquinazoline derivative according to any one of claims 1-4, characterized in that, When R is NH, the preparation method of the polyquinazoline derivative includes the following steps: The isonitrile monomer, amine monomer, sulfonyl azide monomer, catalyst and solvent are mixed and reacted to obtain the first reaction solution; The first reaction solution was added to a precipitant to precipitate the polyquinazoline derivative. The general structural formula of the isonitrile monomer is: The general structural formula of the amine monomer is: H2N-R 1 -NH2; The general structural formula of the sulfonyl azide monomer is: N3O2S-R 2 -SO2N3; in, It is an aryl, aryl derivative, or aromatic heterocyclic group; R 1 R 2 Each group is independently an aryl group, an aryl derivative, an aromatic heterocyclic group, an ester group, a bioactive fragment, or an aliphatic substituent; the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins.
6. A method for preparing the polyquinazoline derivative according to any one of claims 1-4, characterized in that, When R is O, the preparation of the polyquinazoline derivative includes the following steps: The isonitrile monomer, amine monomer, sulfonyl azide monomer, catalyst and solvent are mixed and reacted to obtain the first reaction solution; The first reaction solution is added to a precipitant for precipitation, and the product obtained after precipitation is added to an acidic solution for reaction to obtain a second reaction solution; The second reaction solution was added to a precipitant to precipitate the polyquinazoline derivative. The general structural formula of the isonitrile monomer is: The general structural formula of the amine monomer is: H2N-R 1 -NH2; The general structural formula of the sulfonyl azide monomer is: N3O2S-R 2 -SO2N3; It is an aryl, aryl derivative, or aromatic heterocyclic group; R 1 R 2 Each group is independently an aryl group, an aryl derivative, an aromatic heterocyclic group, an ester group, a bioactive fragment, or an aliphatic substituent; the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins.
7. The preparation method according to claim 5 or 6, characterized in that, The molar ratio of the isonitrile monomer, amine monomer, and sulfonyl azide monomer is (2–2.5):1:1; and / or, The reaction concentration of the amine monomer is 0.05–0.20 mol / L; and / or, The molar amount of the catalyst is 5% to 10% of the molar amount of the amine monomer.
8. The preparation method according to claim 5 or 6, characterized in that, The precipitant includes at least one selected from n-hexane, methanol, diethyl ether, and acetone; and / or, The solvent comprises at least one selected from toluene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, 1,4-dioxane, and 1,2-dichloroethane; and / or, The catalyst includes at least one selected from cobalt-based catalysts, nickel-based catalysts, copper-based catalysts, and iron-based catalysts; and / or, In the step of reacting isonitrile monomer, amine monomer, sulfonyl azide monomer, catalyst and solvent, the reaction temperature is 80-120°C and the reaction time is 12-24 h.
9. The application of a polyquinazoline derivative according to any one of claims 1-4 or a polyquinazoline derivative prepared by the preparation method according to any one of claims 5-8 in the fields of biomedicine, materials science or environmental science.
10. The application according to claim 9, characterized in that, Polyquinazoline derivatives are used as fluorescent or polarizing materials.