A polycarbonyl compound, a preparation method and application thereof

Abstract

The application discloses a polycarbonyl compound, a preparation method and application thereof. The chemical formula of the polycarbonyl compound is shown in formula (I-1) or formula (I-2), wherein R is a flexible chain segment. The polycarbonyl compound can provide a basic construction unit for liquid crystal chiral dopants, azapolyperylene compounds, organic light emitting diodes and solar cell electrode materials, and has a good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a polycarbonyl compound, its preparation method, and its application. Background Technology

[0002] Aromatic polycarbonyl compounds are a class of organic compounds containing multiple carbonyl (C=O, or ketone) functional groups, with at least one aromatic ring in their molecular structure. Due to the presence of aromatic rings and carbonyl groups in their structure, aromatic polycarbonyl compounds exhibit unique reactivity characteristics, such as nucleophilic addition reactions, oxidation reactions, reduction reactions, Mannich reactions, electrophilic substitution reactions, metal-catalyzed deacylation cross-coupling, free radical reactions, Claisen condensation, and reverse Claisen reactions. They are playing an increasingly important role in the fields of medicine, dyes, fragrances, materials science, and optoelectronics. For example, naphthoquinone and its derivatives possess various biological activities, including anti-inflammatory, antibacterial, and antitumor effects. However, currently, the variety of aromatic polycarbonyl compounds is relatively small, and their structures are relatively simple, which to some extent affects the development and application of aromatic polycarbonyl compounds. Summary of the Invention

[0003] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the present invention proposes a polycarbonyl compound that can provide a basic building block for chiral dopants of liquid crystals, nitrogen-containing polybenzoxide compounds, organic light-emitting diodes, and solar cell electrode materials, showing promising application prospects.

[0004] The present invention also proposes a method for preparing polycarbonyl compounds.

[0005] This invention also proposes a nitrogen-containing polybenzoxene compound and its preparation method.

[0006] The present invention also proposes applications of the above-mentioned polycarbonyl compounds or nitrogen-containing polybenzobenzene compounds.

[0007] In a first aspect, the present invention provides a polycarbonyl compound having the chemical formula shown in formula (I-1) or formula (I-2):

[0008]

[0009] Where R represents a flexible chain segment.

[0010] In some embodiments of the present invention, each time R appears, a flexible chain segment with 3-20 carbon atoms in the main chain is independently selected.

[0011] In some embodiments of the present invention, the main chain of R includes at least one of carbon-carbon single bonds and carbon-heteroatom single bonds.

[0012] In some embodiments of the present invention, the heteroatom is selected from at least one of O, N, S, P or Si.

[0013] In some embodiments of the present invention, the carbon-heteroatom single bond is selected from at least one of CO, CN, CS, CP, or C-Si.

[0014] In some embodiments of the present invention, the main chain of R further includes an alkynyl group.

[0015] In some embodiments of the present invention, the R includes at least one of the following groups:

[0016]

[0017] In this context, the wavy lines in the structure of each group represent the end of the R group that is connected to the parent nucleus of the polycarbonyl compound.

[0018] In some embodiments of the present invention, the polycarbonyl compound is selected from one of the following compounds:

[0019]

[0020] A second aspect of the present invention provides a method for preparing a polycarbonyl compound, comprising the following steps: oxidizing compound G to obtain the polycarbonyl compound, wherein compound G is selected from at least one of the following compounds:

[0021]

[0022] In some embodiments of the present invention, the oxidation reaction is a Swern oxidation reaction.

[0023] In some embodiments of the present invention, the step of preparing the polycarbonyl compound specifically includes: mixing a solution containing compound G with a Swern reagent, reacting at (-60) to (-90) °C for 0.5 to 5 h, adding triethylamine, and reacting for 10 to 300 min to obtain the polycarbonyl compound. Optionally, the reaction time after adding triethylamine is selected from 10 to 200 min.

[0024] In some embodiments of the present invention, the Swern reagent contains trifluoroacetic anhydride, and the ratio of the amount of trifluoroacetic anhydride, compound G, and triethylamine in the Swern reagent is (0.8–24) mmol:(0.1–3.0) mmol:(1.5–45) mmol.

[0025] In some embodiments of the present invention, the solution containing compound G comprises compound G, dimethyl sulfoxide, and solvent I. Optionally, solvent I comprises dichloromethane.

[0026] In some embodiments of the present invention, the ratio of compound G to dimethyl sulfoxide is (0.1–3.0) mmol:(2–20) mL. In some embodiments of the present invention, the ratio of compound G, dimethyl sulfoxide, and solvent I is (0.1–3.0) mmol:(2–20) mL:(2–20) mL.

[0027] In some embodiments of the present invention, the step of preparing the polycarbonyl compound specifically includes: mixing a solution containing compound G with Swern reagent, reacting at (-60) to (-90) °C for 0.5 to 5 h, adding triethylamine and reacting at (-60) to (-90) °C for 10 to 300 min, raising the temperature to 5 to 40 °C and reacting for 5 to 60 min, adding HCl solution to terminate the reaction, and separating to obtain the polycarbonyl compound. Optionally, the separation step includes: extracting the mixture obtained after the reaction with dichloromethane, washing away triethylamine with HCl solution, washing with sodium bicarbonate solution, washing with sodium chloride solution, drying, and separating the solid and liquid to obtain the polycarbonyl compound. Optionally, the HCl solution is an aqueous HCl solution.

[0028] In some embodiments of the present invention, the Swern reagent is prepared by a method comprising the following steps: mixing trifluoroacetic anhydride, dimethyl sulfoxide, and dichloromethane at (-60) to (-90) °C under a protective atmosphere to obtain the Swern reagent. Optionally, the ratio of the amounts of trifluoroacetic anhydride, dimethyl sulfoxide, and dichloromethane is (1 to 10) mmol:(1.25 to 12.5) mmol:(5 to 50) mL.

[0029] In some embodiments of the present invention, the preparation method further includes a step of preparing compound G, specifically comprising: hydroxylating compound F to an olefin to obtain compound G, wherein compound F is selected from at least one of the following compounds:

[0030]

[0031] In some embodiments of the present invention, the step of preparing compound G specifically includes: mixing compound F with potassium ferricyanide, potassium carbonate, triethylenediamine, methanesulfonamide, potassium osmium tetroxide, and solvent II, and reacting at 5–40°C to obtain compound G. Optionally, the reaction time is 10–50 h.

[0032] In some embodiments of the present invention, the molar ratio of compound F to potassium ferricyanide, potassium carbonate, triethylenediamine, methanesulfonamide and potassium osmium tetroxide is (1-5):(6-30):(6-30):(0.1-2):(6-30):(0.05-0.5).

[0033] In some embodiments of the present invention, the ratio of the amount of compound F to solvent II is (1-5) mmol:(30-80) mL.

[0034] In some embodiments of the present invention, solvent II comprises tert-butanol and water. Optionally, the volume ratio of tert-butanol to water is (0.5–2):(0.5–2).

[0035] In some embodiments of the present invention, in the step of preparing compound G, after reacting at 5–40°C for 10–50 h, the reaction is quenched with sodium sulfite, and the mixture is separated to obtain compound G. Optionally, the separation step includes: removing the solvent from the mixture obtained after the quenching reaction, extracting with ethyl acetate, washing the organic layer successively with aqueous sodium sulfite solution and aqueous saline solution, collecting the organic layer, removing the solvent, and purifying by column chromatography to obtain compound G.

[0036] In some embodiments of the present invention, the preparation method further includes a step of preparing compound F, specifically comprising: reacting compound D and compound E via a cycloaddition reaction to obtain compound F, wherein the structures of compound D and compound E are shown below:

[0037]

[0038] In compound E, each occurrence of X1 is independently selected from at least one of F, Cl, Br, or I.

[0039] In some embodiments of the present invention, the step of preparing compound F specifically includes: mixing compound D, compound E, and solvent III under a protective atmosphere, cooling to (-30) to (-70) °C, adding n-butyllithium, reacting at (-30) to (-70) °C for 10 to 200 min, and then reacting at 5 to 40 °C for 0.5 to 10 h to obtain compound F. Optionally, after reacting at 5 to 40 °C for 0.5 to 10 h, quenching the reaction with methanol and water dropwise, separating, and obtaining compound F. Optionally, the separation step includes: removing the solvent from the mixture obtained after quenching the reaction, extracting with dichloromethane, washing with water, collecting the organic layer, drying, removing dichloromethane, and purifying by column chromatography to obtain compound F.

[0040] In some embodiments of the present invention, the molar ratio of compound D to compound E is (10-30):(1-10).

[0041] In some embodiments of the present invention, the ratio of the amount of compound D to compound E and solvent III is (3-30) mmol:(1-10) mmol:(30-120) mL.

[0042] In some embodiments of the present invention, the addition of n-butyllithium includes the addition of n-butyllithium in a hexane solution.

[0043] In some embodiments of the present invention, solvent III comprises toluene.

[0044] In some embodiments of the present invention, the preparation method further includes the step of preparing compound E, specifically including: taking tetrahalo-p-benzoquinone and subjecting it to a nucleophilic substitution reaction to obtain compound E.

[0045] In some embodiments of the present invention, the tetrahalobenzoquinone is selected from at least one of tetrafluoro-p-benzoquinone, tetrachloro-p-benzoquinone, tetrabromo-p-benzoquinone, or tetraiodo-p-benzoquinone.

[0046] In some embodiments of the present invention, R includes R1-alkynyl-, and the steps for preparing compound E specifically include: reacting tetrahalo-p-benzoquinone with R1-SH, and then reacting it with acetonitrile in the presence of stannous chloride to obtain compound E.

[0047] In some embodiments of the present invention, the step of preparing compound E specifically includes: mixing a solution of R1-SH with n-butyllithium at (-50) to (-90) °C under a protective atmosphere; raising the temperature to 4 to 40 °C; adding a solution of tetrahalo-p-benzoquinone; stirring at 4 to 40 °C for 10 to 120 min; raising the temperature to 50 to 80 °C and stirring for 5 to 30 h to quench the reaction and obtain an intermediate; mixing the intermediate with stannous chloride, water, and acetonitrile; and refluxing under a protective atmosphere to obtain compound E. Optionally, the refluxing reaction time is 10 to 30 h. Optionally, the solution of R1-SH is a tetrahydrofuran solution of R1-SH. Optionally, the solution of tetrahalo-p-benzoquinone is a tetrahydrofuran solution of tetrahalo-p-benzoquinone.

[0048] In some embodiments of the present invention, the molar ratio of R1-SH, n-butyllithium and tetrahalo-p-benzoquinone is (15-35):(14-34):(3-7).

[0049] In some embodiments of the present invention, the molar ratio of R1-SH to stannous chloride is (15-35):(30-70).

[0050] In some embodiments of the present invention, the ratio of R1-SH to water and acetonitrile is (15-35) mmol:(1-5) mL:(80-150) mL.

[0051] In some embodiments of the present invention, the preparation method further includes a step of preparing compound D, specifically comprising: compound C undergoing an elimination reaction to obtain compound D, wherein compound C is as follows:

[0052]

[0053] In compound C, each occurrence of X2 is independently selected from at least one of F, Cl, Br, or I.

[0054] In some embodiments of the present invention, the step of preparing compound D includes: mixing compound C with tetrabutylammonium iodide, solvent IV, and 1,8-diazabicycloundec-7-ene under a protective atmosphere, refluxing the mixture, adding citric acid, and reacting to obtain compound D.

[0055] In some embodiments of the present invention, the molar ratio of compound C, tetrabutylammonium iodide, 1,8-diazabicycloundec-7-ene, and citric acid is (35-65):(70-110):(350-650):(650-850).

[0056] In some embodiments of the present invention, the ratio of the amount of compound C to solvent IV is (35-65) mmol:(50-200) mL.

[0057] In some embodiments of the present invention, the reflux reaction time is 0.5 to 10 hours.

[0058] In some embodiments of the present invention, solvent IV comprises dichloromethane.

[0059] In some embodiments of the present invention, the step of preparing compound D includes: mixing compound C with tetrabutylammonium iodide, solvent IV, and 1,8-diazabicycloundec-7-ene under a protective atmosphere, refluxing the mixture, adding an aqueous solution of citric acid dropwise, reacting for 0.2–20 h, and separating to obtain compound D. Optionally, the separation step includes removing the solvent from the mixture obtained by reacting with the aqueous solution of citric acid dropwise, extracting with ethyl acetate, washing with brine, collecting the organic layer, removing the solvent, and purifying by column chromatography to obtain compound D.

[0060] In some embodiments of the present invention, the preparation method further includes a step of preparing compound C, specifically comprising: compound B undergoing a ketal reaction to obtain compound C, wherein compound B is as follows:

[0061]

[0062] In compound B, each occurrence of X2 is independently selected from at least one of F, Cl, Br, or I.

[0063] In some embodiments of the present invention, the step of preparing compound C includes: mixing compound B with 2,2-dimethoxypropane, p-toluenesulfonic acid, and solvent V under a protective atmosphere, and reacting at 5–40°C to obtain compound C.

[0064] In some embodiments of the present invention, the molar ratio of compound B to 2,2-dimethoxypropane and p-toluenesulfonic acid is (5-15):(8-20):(0.1-1.0).

[0065] In some embodiments of the present invention, the ratio of the amount of compound B, 2,2-dimethoxypropane, p-toluenesulfonic acid and solvent V is (5-15) mmol:(6-20) mmol:(0.3-1.0) mmol:(30-80) mL.

[0066] In some embodiments of the present invention, the reaction time in the step of preparing compound C is 2 to 30 hours.

[0067] In some embodiments of the present invention, solvent V comprises dichloromethane.

[0068] In some embodiments of the present invention, the preparation method further includes a step of preparing compound B, specifically comprising: compound A undergoing a Sharpless asymmetric dihydroxylation reaction to obtain compound B, wherein compound A is as follows:

[0069]

[0070] In compound A, each occurrence of X2 is independently selected from at least one of F, Cl, Br, or I.

[0071] Compound A: 4,5-Dihalocyclohex-1-ene.

[0072] In some embodiments of the present invention, the step of preparing compound B includes: mixing compound A with potassium osmium tetroxide, N-methylmorpholine oxide, solvent VI, tert-butanol and water under a protective atmosphere, and reacting at 5-40°C to obtain compound B.

[0073] In some embodiments of the present invention, the molar ratio of compound A to potassium osmium tetroxide and N-methylmorpholine oxide is (5-15):(0.05-0.3):(5-20).

[0074] In some embodiments of the present invention, the ratio of the amount of compound A, potassium osmium tetroxide, N-methylmorpholine oxide and solvent VI is (5-15) mmol:(0.1-0.3) mmol:(6-18) mmol:(20-30) mL.

[0075] In some embodiments of the present invention, the volume ratio of solvent VI, tert-butanol and water is (20-30):(5-15):(1-10).

[0076] In some embodiments of the present invention, the reaction time in the step of preparing compound B is 10 to 50 hours.

[0077] In some embodiments of the present invention, solvent VI includes acetone.

[0078] In some embodiments of the present invention, in the step of preparing compound B, after reacting at 5–40°C, the reaction is quenched with sodium sulfite, and the mixture is separated to obtain compound B. Optionally, the separation step includes removing the solvent from the reaction mixture after quenching, extracting with ethyl acetate, washing the organic layer sequentially with an aqueous sodium sulfite solution and an aqueous saline solution, collecting the organic layer, removing the solvent, and chromatographically purifying compound B.

[0079] In some embodiments of the present invention, the preparation method further includes a step of preparing compound A, specifically comprising: halogenating 1,4-cyclohexadiene to obtain compound A. Optionally, the halogenation reaction includes a bromination reaction.

[0080] In some embodiments of the present invention, the step of preparing compound A includes: mixing 1,4-cyclohexadiene with solvent VII under a protective atmosphere, cooling to (-30) to (-70) °C, adding a halogen element, and reacting at (-30) to (-70) °C to obtain compound A.

[0081] In some embodiments of the present invention, the reaction time in the step of preparing compound A is 0.5 to 5 hours.

[0082] In some embodiments of the present invention, solvent VII comprises n-hexane.

[0083] In some embodiments of the present invention, in the step of preparing compound A, the halogen element includes at least one of chlorine, bromine, or iodine.

[0084] In some embodiments of the present invention, the halogen element can be added by adding solvent VII containing halogen elements in the step of preparing compound A.

[0085] In some embodiments of the present invention, in the step of preparing compound A, the molar ratio of 1,4-cyclohexadiene to the halogen element is (0.5-2):(0.5-2).

[0086] In some embodiments of the present invention, in the step of preparing compound A, the volume ratio of 1,4-cyclohexadiene, halogen element and solvent VII is (10-30):(5-20):(200-400).

[0087] In some embodiments of the present invention, the method for preparing the polycarbonyl compound includes the following steps:

[0088] S1: Take 1,4-cyclohexadiene and brominate it to obtain compound A;

[0089] S2: Take compound A and introduce a hydroxyl group through a Sharpless asymmetric dihydroxylation reaction to obtain compound B;

[0090] S3: Take compound B and introduce 2,2-dimethoxypropane through a ketal reaction to obtain compound C;

[0091] S4: Take compound C and remove the bromine atom through an elimination reaction to obtain compound D;

[0092] S5: Tetrabromo-p-benzoquinone was taken and, through a nucleophilic substitution reaction, compound E was obtained;

[0093] S6: Take compounds D and E, and through a 4+2 cycloaddition reaction, obtain compound F;

[0094] S7: Compound F is taken and subjected to hydroxylation of an alkene to obtain compound G;

[0095] S8: Take compound G and oxidize it via Swern reaction to obtain the polycarbonyl compound.

[0096] In a third aspect, the present invention proposes the application of the above-mentioned polycarbonyl compounds in the preparation of nitrogen-containing polybenzoxene compounds, the preparation of chiral liquid crystal dopants, the preparation of electrode materials, or the preparation of semiconductor devices.

[0097] In a fourth aspect, the present invention provides a polyazinon compound selected from compounds of formula (II-1) or formula (II-2):

[0098]

[0099] Where R represents a flexible chain segment;

[0100] Each time A appears, it is independently selected from H, halogen, C1-C15 alkyl or C1-C15 alkoxy.

[0101] In some embodiments of the present invention, each occurrence of A is independently selected from H, halogens, and C1 to C5 alkyl groups.

[0102] In some embodiments of the present invention, each time R appears, a flexible chain segment with 3-20 carbon atoms in the main chain is independently selected.

[0103] In some embodiments of the present invention, the main chain of R includes at least one of carbon-carbon single bonds and carbon-heteroatom single bonds.

[0104] In some embodiments of the present invention, the heteroatom is selected from at least one of O, N, S, P or Si.

[0105] In some embodiments of the present invention, the carbon-heteroatom single bond is selected from at least one of CO, CN, CS, CP, or C-Si.

[0106] In some embodiments of the present invention, the main chain of R further includes an alkynyl group.

[0107] In some embodiments of the present invention, the R includes at least one of the following groups:

[0108]

[0109] In some embodiments of the present invention, the azapolybenzoxide compound is selected from one of the following compounds:

[0110]

[0111] In a fifth aspect of the present invention, a method for preparing a nitrogen-containing polybenzobenzene compound is provided, comprising the following steps: under a protective atmosphere, a polycarbonyl compound, compound H, and solvent VIII are reacted at 100–250 °C to obtain the nitrogen-containing polybenzobenzene compound, wherein the polycarbonyl compound is selected from the polycarbonyl compounds described in any one of the first aspects of the present invention or the polycarbonyl compounds prepared by the method described in any one of the second aspects of the present invention, and the structural formula of compound H is shown below:

[0112]

[0113] In each instance, A is independently selected from H, halogen, C1-C15 alkyl or C1-C15 alkoxy.

[0114] In some embodiments of the present invention, solvent VIII comprises imidazole. Imidazole, used as a solvent in the present invention, is favorable to acid-sensitive structures (such as ketal groups) and results in higher synthetic yields.

[0115] In some embodiments of the present invention, the reaction time is 0.5 to 10 hours.

[0116] In some embodiments of the present invention, the molar ratio of the polycarbonyl compound, compound H and solvent VIII is (0.01-0.5):(0.2-5):(20-40).

[0117] In some embodiments of the present invention, the preparation method includes the following steps: under a protective atmosphere, compound H, a polycarbonyl compound, and imidazole are reacted at 100–250°C, cooled to 5–40°C, and separated to obtain the azapolybenzoxyl compounds. Optionally, the separation step includes: extracting the mixture obtained after cooling with dichloromethane, washing the organic layer with a saline aqueous solution, collecting the organic layer, removing the solvent, and purifying by column chromatography to obtain the azapolybenzoxyl compounds.

[0118] In a sixth aspect, the present invention provides an anti-counterfeiting material comprising the aforementioned azapolybenzoxan compounds.

[0119] In a seventh aspect, the present invention provides a liquid crystal chiral dopant comprising the above-mentioned polycarbonyl compound or prepared using a raw material containing the polycarbonyl compound.

[0120] In an eighth aspect, the present invention provides an electrode material comprising the aforementioned polycarbonyl compound or prepared using a raw material containing the said polycarbonyl compound. Optionally, the electrode material comprises a solar cell electrode material.

[0121] In a ninth aspect, the present invention provides a semiconductor device comprising the aforementioned polycarbonyl compound or prepared using a raw material containing the said polycarbonyl compound. Optionally, the semiconductor device comprises an organic semiconductor device.

[0122] In some embodiments of the present invention, the semiconductor device includes at least one of an organic light-emitting diode or a solar cell.

[0123] The beneficial effects of this invention include: This invention provides a method for synthesizing aromatic polycarbonyl compounds, which exhibit cis-trans isomerism and chiral characteristics. Their unique structure endows them with distinctive properties, showing great application potential in fields such as chiral dopants for liquid crystals, nitrogen-containing polybenzobenzenes, organic light-emitting diodes, and solar cell electrodes. The molecular chemical structure of these aromatic polycarbonyl compounds is based on a tetrahalobenzoquinone skeleton, containing both ketal structures and ketone groups, with a flexible chain segment attached to the carbonyl end. These aromatic polycarbonyl compounds possess advantages such as novel structural units, strong chemical modifiability, unique molecular structure, and unique spatial configuration, providing a highly promising molecular type for the materials field. Furthermore, the raw materials used in this invention are simple to obtain, inexpensive, recyclable, and have a high synthesis yield, making them suitable for industrial production.

[0124] Explanation and Definition

[0125] In this invention, unless otherwise stated, the scientific and technical terms used herein have the meanings commonly understood by those skilled in the art. However, for a better understanding of this invention, definitions of some terms are provided below. When the definitions of terms provided in this invention differ from the meanings commonly understood by those skilled in the art, the definitions and interpretations provided in this invention shall prevail.

[0126] The protective gas in the "protective atmosphere" of this article includes at least one of an inert gas or nitrogen.

[0127] "Alkyl" refers to a branched or straight-chain saturated aliphatic alkane with a specified number of carbon atoms, after removing one hydrogen-derived group. "C1-C15 alkyl" indicates alkyl groups with a total of 1-15 carbon atoms, including C1-C15 straight-chain alkyl, C1-C15 branched alkyl, and C1-C15 cycloalkyl. A similar interpretation applies to "C1-C5 alkyl," but the number of carbon atoms differs.

[0128] "Alkoxy" refers to an alkyl group as defined herein that is linked to other groups through an oxygen atom, i.e., "alkyl-O-". "C1-C15 alkoxy" refers to alkoxy groups with a total number of carbon atoms of 1-15, including C1-C15 straight-chain alkoxy, C1-C15 branched-chain alkoxy, and C1-C15 cycloalkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, etc.

[0129] "Halogen" includes any one or more of fluorine, chlorine, bromine, and iodine. Attached Figure Description

[0130] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein:

[0131] Figure 1 This is a schematic diagram of the preparation process of compound I in Example 1 of the present invention;

[0132] Figure 2 This is the 1H NMR spectrum of trans compound I in Example 1 of the present invention;

[0133] Figure 3 This is the carbon NMR spectrum of trans compound I in Example 1 of the present invention;

[0134] Figure 4 The infrared spectrum of trans compound I in Example 1 of this invention;

[0135] Figure 5 This is the 1H NMR spectrum of cis compound I in Example 1 of the present invention;

[0136] Figure 6This is the carbon NMR spectrum of cis compound I in Example 1 of the present invention;

[0137] Figure 7 The infrared spectrum of cis compound I in Example 1 of this invention;

[0138] Figure 8 This is the 1H NMR spectrum of the trans compound K in Example 2 of the present invention;

[0139] Figure 9 This is the carbon NMR spectrum of the trans compound K in Example 2 of the present invention;

[0140] Figure 10 This is the 1H NMR spectrum of cis compound K in Example 2 of the present invention;

[0141] Figure 11 This is the carbon NMR spectrum of cis compound K in Example 2 of the present invention;

[0142] Figure 12 This is a fluorescence image of the trans compound K from Example 2 of the present invention;

[0143] Figure 13 This is a fluorescence image of cis compound K from Example 2 of the present invention;

[0144] Figure 14 The fluorescence emission spectrum of cis compound K in Example 2 of this invention;

[0145] Figure 15 The fluorescence emission spectrum of trans compound K in Example 2 of this invention;

[0146] Figure 16 This is the UV-Vis absorption spectrum and molar absorptivity test results of cis compound K in tetrahydrofuran in Example 2 of the present invention.

[0147] Figure 17 This is the UV-Vis absorption spectrum and molar absorptivity test results of the trans compound K in tetrahydrofuran in Example 2 of the present invention. Detailed Implementation

[0148] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0149] Unless otherwise specified, the experimental methods used in the following examples and comparative examples are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials and reagents used are all commercially available from the conventional market unless otherwise specified.

[0150] Unless otherwise specified, the ultra-dry reagents used below have a water content of less than 50 ppm.

[0151] Example 1

[0152] This embodiment discloses a polycarbonyl compound (compound I), the structure of which is shown below:

[0153]

[0154] The preparation process of this polycarbonyl compound includes the following steps (see schematic diagram of the preparation process). Figure 1 As shown):

[0155] (1) The synthesis of 4,5-dibromocyclohex-1-ene (compound A) includes:

[0156] Under an argon atmosphere, 1,4-cyclohexadiene (21.5 mL, 0.22 mol) and ultradry n-hexane (300 mL) were added to a reaction flask, mixed thoroughly, and cooled to -60°C. Then, a mixed solution of ultradry n-hexane (10 mL) and bromine (11.5 mL, 0.22 mol) was slowly added dropwise to the flask. After the addition was complete (the addition time should be at least 10 min, but 10–30 min is acceptable), the reaction was continued at -60°C for 2 hours, followed by a return to room temperature. The solvent was removed by vacuum rotary evaporation to obtain a pure white crystalline product (compound A) in 99% yield.

[0157] Compound A:

[0158] (2) Synthesis of 4,5-dibromocyclohexane-1,2-diol (compound B):

[0159] Under an argon atmosphere, 4,5-dibromocyclohexyl-1-ene (1.97 g, 8.2 mmol), potassium osmium tetroxide dihydrate (60 mg, 0.164 mmol), and N-methylmorpholine oxide (1.3 g, 9.84 mmol) were added to a reaction flask, followed by acetone (30 mL), tert-butanol (8 mL), and water (4 mL). The reaction was carried out at room temperature for 24 hours. After the reaction was completed, the reaction was quenched with sodium sulfite, the solvent was removed by vacuum rotary evaporation, and the product was extracted with ethyl acetate. The organic layer was washed successively with aqueous sodium sulfite solution and saturated saline solution. The organic layer was collected, the solvent was removed by vacuum rotary evaporation, and the product was purified by neutral alumina column chromatography (V = 1) to give a white solid product (compound B) in 66% yield.

[0160] Compound B:

[0161] In other embodiments of the present invention, the catalyst potassium osmium dihydrate in this step can be recycled and reused, reducing production costs.

[0162] (3) The synthesis of 5,6-dibromo-2,2-dimethyl-3a,4,5,6,7,7a-hexahydrocyclohexano[1,2-d][1,3]dioxane (compound C) includes:

[0163] Under argon protection, compound B (2.57 g, 9.38 mmol), 2,2-dimethoxypropane (1.3 g, 12.5 mmol), and p-toluenesulfonic acid monohydrate (110.45 mg, 0.564 mmol) were added to a reaction flask, followed by the addition of ultra-dry dichloromethane (50 mL). The reaction was carried out at room temperature for 6 hours. After the reaction was completed, the solvent was evaporated under vacuum, and the product was purified by column chromatography (V petroleum ether:V ethyl acetate = 3:1) to give a yellow oily product (compound C) in 91% yield.

[0164] Compound C:

[0165] (4) The synthesis of 2,2-dimethyl-3a,7a-dihydrocyclohexano[1,2-d][1,3]dioxane (compound D) includes:

[0166] Under argon protection, compound C (15.3 g, 48.7 mmol) and tetrabutylammonium iodide (38.7 g, 97.6 mmol) were added to a reaction flask, followed by 100 mL of ultradry dichloromethane. Anhydrous 1,8-diazabicycloundec-7-ene (72.8 mL, 487 mmol) was slowly added dropwise using a syringe over a period of at least 10 min (10–30 min is acceptable). The mixture was refluxed at approximately 40 °C for 2 hours. After returning to room temperature, a 200 mL aqueous solution of citric acid (154 g, 730.5 mmol) was slowly added dropwise to the reaction flask (over a period of at least 10 min, 10–30 min is acceptable). Stirring continued for 0.5 hours after the addition was complete. Dichloromethane was removed by rotary evaporation under reduced pressure. The mixture was extracted with ethyl acetate, washed with saturated brine, and the organic layer was collected. The solvent was removed by rotary evaporation under reduced pressure to obtain the crude product. Purification was performed by column chromatography (V = ethyl acetate = 1, packed with basic alumina) to give a yellow oily product (compound D) in 57% yield.

[0167] Compound D:

[0168] (5) The synthesis of [tris(propyl-2-yl)][(2,3,5,6-tetrabromo-4-{[tris(propyl-2-yl)methsilyl]ethynyl}phenyl)ethynyl]methsilane (compound E) includes:

[0169] Under argon protection, 4.44 g (23.616 mmol) of triisopropylsilylacetylene was weighed and added to a reaction flask containing 50 mL of ultra-dry tetrahydrofuran. 14.135 mL (22.616 mmol) of n-butyllithium was slowly added dropwise at -78 °C over a period of at least 10 min (10–30 min is acceptable). After stirring for 30 min, the mixture was allowed to return to room temperature. 2.084 g (4.72 mmol) of tetrabromo-p-benzoquinone was dissolved in 50 mL of ultra-dry tetrahydrofuran and added to the reaction system using a syringe. The mixture was stirred at room temperature for 30 min, then the temperature was increased to 65 °C and stirred for 12 hours. After cooling to room temperature, the reaction was quenched with 60 mL of saturated ammonium chloride solution. The tetrahydrofuran was removed by rotary evaporation under reduced pressure. The mixture was extracted with ethyl acetate, and the organic layer was collected and rotary evaporated to obtain the crude intermediate product. The intermediate was purified by column chromatography (by washing away byproducts with petroleum ether, followed by elution with ethyl acetate) to obtain a pure intermediate. The intermediate obtained in the previous step and stannous chloride (9.5 g, 49.2 mmol) were weighed into a reaction flask, and water (2 mL) and acetonitrile (100 mL) were added. The mixture was refluxed at approximately 82 °C for 18 hours under argon protection. After cooling to room temperature, the acetonitrile was removed by rotary evaporation under reduced pressure. The product was then purified by column chromatography (V petroleum ether = 1) to give a white crystalline product (compound E) in 95% yield.

[0170] Compound E:

[0171] (6) The inseparable isomer trans-structure product {{[(21Z)-8,8,18,18-tetramethyl-13-{[tris(prop-2-yl)methyl]ethynyl}-7,9,17,19-tetraoxaheptacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]tetraco-2(3),4(12),13,21,23-penten-3-yl]ethynyl}[tris(prop-2-yl)]methoxysilane and cis The synthesis of the product with the formula {[(23Z)-8,8,18,18-tetramethyl-3-{[tris(prop-2-yl)methyl]ethynyl}-7,9,17,19-tetraoxaheptacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]tetraco-2(3),4(12),13,21,23-penten-13-yl]ethynyl}[tris(prop-2-yl)]methoxysilane (referred to as the synthesis of compound F) includes:

[0172] Under argon protection, [tris(prop-2-yl)][(2,3,5,6-tetrabromo-4-{[tris(prop-2-yl)methyl]ethynyl}phenyl)ethynyl]silane (5 g, 6.63 mmol) and 2,2-dimethyl-3a,7a-dihydrocyclohexano[1,2-d][1,3]dioxane (3.03 g, 19.89 mmol) were added to a reaction flask containing ultra-dry toluene (50 mL) and cooled to -50 °C. A mixture of n-butyllithium (20.08 mL, 1.6 M in hexane) and ultra-dry n-hexane (30 mL) was slowly added dropwise to the reaction system. After the addition was complete (the addition time should be more than 10 min, but 10–30 min is acceptable), the reaction was continued at -50 °C for 30 min. After reacting at room temperature for 1 hour, methanol and water were added dropwise to quench the reaction. Toluene and n-hexane were removed by rotary evaporation under reduced pressure. The product was extracted with dichloromethane, washed repeatedly with water, and the organic layer was collected. After drying with anhydrous sodium sulfate, dichloromethane was removed by rotary evaporation under reduced pressure to obtain the crude product. The crude product was purified by column chromatography (V petroleum ether:V dichloromethane = 3:1) to give a white solid product (compound F) in 67% yield.

[0173] Compound F:

[0174]

[0175] (7) Trans-tetrahydroxy compounds 8,8,18,18-tetramethyl-3,13-bis{[tris(propyl-2-yl)silyl]ethynyl}-7,9,17,19-tetraoxaheptacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]tetracosyl-2(3),4(12),13-trien-21,22,23,24-tetraol and cis-tetrahydroxy compounds The synthesis of compound 8,8,18,18-tetramethyl-3,13-bis{[tris(propyl-2-yl)methsilyl]ethynyl}-7,9,17,19-tetraoxaheptacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]tetraco-2(3),4(12),13-trien-21,22,23,24-tetraol (abbreviated as the synthesis of compound G) includes:

[0176] Under argon protection, the trans-structure product {{[(21Z)-8,8,18,18-tetramethyl-13-{[tris(prop-2-yl)methyl]ethynyl}-7,9,17,19-tetraoxaheptacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]tetracosyl-2(3),4(12),13,21,23-pentaen-3-yl]ethynyl}[tris(prop-2-yl)]methoxysilane and the cis-structure product {[(23Z)-8,8,18,18-tetramethyl-3-{[tris(prop-2-yl)methyl]ethynyl}-7,9,17,19-tetraoxaheptacyclo[13.5.2.25,11.016,20.02,14.06,20.04,12]tetracosyl-2(3),4(12),13,21,23-pentaen-3- ... A mixture of 0.02,14.06,10.04,12]tetraco-2(3),4(12),13,21,23-penten-13-yl]ethynyl}[tris(prop-2-yl)]methylsilane (2 g, 2.705 mmol), potassium ferricyanide (5.34 g, 16.23 mmol), anhydrous potassium carbonate (2.24 g, 16.23 mmol), triethylenediamine (46 mg, 0.407 mmol), methanesulfonamide (1.54 g, 16.23 mmol) and potassium osmium dihydrate (60 mg, 0.163 mmol) was added to a reaction flask, and a mixed solution of tert-butanol (27 mL) and water (27 mL) was added. The reaction was carried out at room temperature for 24 hours. After the reaction was completed, the reaction was quenched with sodium sulfite, the solvent was removed by vacuum rotary evaporation, and the product was extracted with ethyl acetate. The organic layer was washed successively with aqueous sodium sulfite solution and saturated saline solution. The organic layer was collected, the solvent was removed by vacuum rotary evaporation, and the starting material was removed by column chromatography (V petroleum ether:V dichloromethane = 3:1). The product was then purified by column chromatography (V dichloromethane = 1) to give the trans-tetrahydroxy white solid product (trans compound G) with a yield of 31%. Finally, the product was purified by column chromatography (V petroleum ether:V ethyl acetate = 1:1) to give the cis-tetrahydroxy white solid product (cis compound G) with a yield of 18%.

[0177] Compound G:

[0178]

[0179] In other embodiments of the present invention, the unreacted raw materials in this step can be recycled and reused, and the catalyst potassium osmium dihydrate can be recycled and reused repeatedly, thereby reducing production costs.

[0180] (8) Trans-tetraketone compounds 8,8,18,18-tetramethyl-3,13-bis{[tris(propyl-2-yl)silyl]ethynyl}-7,9,17,19-tetraoxaheptacyclo[13.5.2.25,11.06,10.016,20.02,14.04,12]tetracosyl-2(3),4(12),13-trien-21,22,23,24-tetraketone and cis-tetraketone compounds The synthesis of 8,8,18,18-tetramethyl-3,13-bis{[tris(propyl-2-yl)methyl]ethynyl}-7,9,17,19-tetraoxaheptacyclo[13.5.2.25,11.06,10.016,20.02,14.04,12]tetracosyl-2(3),4(12),13-trien-21,22,23,24-tetraone (referred to as the synthesis of compound I) includes:

[0181] The preparation process of trans compound I includes:

[0182] First, prepare the Swern reagent by slowly adding trifluoroacetic anhydride (0.51 mL, 3.4 mmol) dropwise to a mixture of dimethyl sulfoxide (0.3 mL, 4.25 mmol) and dichloromethane (20 mL) under an argon atmosphere and at -78 °C, and stirring for 15 minutes.

[0183] Trans compound G (500 mg, 0.62 mmol) was dissolved in a mixed solution of dimethyl sulfoxide (7.5 mL) and dichloromethane (3.75 mL), and the solution was drawn into a 20 mL syringe. This solution was then added dropwise to Swern's reagent using a syringe pump (15 min), and the reaction was continued at -78 °C for 60 min. Triethylamine (1.15 mL, 8.25 mmol) was added dropwise to the reaction system (15 min). After 60 min, the cryogenic reactor was shut off, and the reaction was continued for another 30 min. The mixture was then removed and stirred at room temperature for 10 min. After returning to room temperature, the reaction system was terminated by adding 50 mL of a prepared 2 mol / L HCl aqueous solution. Extraction was performed with dichloromethane. Triethylamine was first washed away with a 2 mol / L HCl aqueous solution, followed by hydrochloric acid washing with a saturated sodium bicarbonate aqueous solution, and finally sodium bicarbonate washing with a saturated sodium chloride aqueous solution. The product was dried over anhydrous sodium sulfate, and rotary evaporation yielded a yellow solid trans-tetracarbonyl product (trans compound I) with a yield of 91%.

[0184] The only difference between the preparation process of cis compound I and that of trans compound I is that cis compound G is used instead of trans compound G, while the rest of the preparation process is the same as that of trans compound I. The final product is a yellow solid product of cis tetracarbonyl (cis compound I) with a yield of 94%.

[0185] Compound I:

[0186]

[0187] In this embodiment, the purity of the target product in each step is 90% to 99%.

[0188] Example 2

[0189] This embodiment discloses a azidopolybenzoxan compound (referred to as compound K): trans-bilateral azidopolybenzoxan 41,41,46,46-tetramethyl-3,22-bis{[tris(propyl-2-yl)methyl]ethynyl}-7,18,26,37-tetraaza-40,42,45,47-tetraoxa-tetrazine[22.14.5.55,20.02,23.044,48.039,43.025,38.06,19.04,21.010,15.08,17.027,36.029,34]tetraoctadecyl-2(23),3,6(7),8(17),9,11,13,15(16),18,21(22),25(26),27(28),29(30),31 ,33,35,37-Heptadecane and cis-bilateral azidophenyl 41,41,46,46-Tetramethyl-3,22-bis{[tris(prop-2-yl)methyl]ethynyl}-7,18,26,37-tetraaza-40,42,45,47-tetraoxa-tetrazine [22.14.5.55,20.04,21.039,43.025,38 .02,23.044,48.06,19.029,34.027,36.010,15.08,17] forty-eighta-2(3),4(21),6(7),8(9),10(11),12,14,16,18,22,25(38),26,28,30,32,34(35),36(37)-heptadecene:

[0190]

[0191] The preparation process of trans compound K includes:

[0192] Under an argon atmosphere, the trans-tetraone compound I-anti (50 mg, 0.0625 mmol), 2,3-naphthyldiamine (99 mg, 0.625 mmol), and imidazole (2 g) were added to a 50 mL Shrek tube and reacted at 150 °C for 2 hours. After returning to room temperature, the mixture was extracted with dichloromethane, and the organic layer was washed successively with saturated saline solution. The organic layer was collected, the solvent was removed by rotary evaporation under vacuum, and the product was purified by column chromatography (V petroleum ether:V dichloromethane = 1:2) to give the solid product trans-bilateral azapoly(benzoylbenzene) (29 mg, yield 45%).

[0193] The only difference between the preparation process of cis compound K and that of trans compound K is that cis compound I is used instead of trans compound I, while the rest of the preparation process is the same as that of trans compound K, ultimately yielding cis compound K (46 mg, yield 70%).

[0194] In this embodiment, the preparation methods of trans compound I and cis compound I are the same as in Example 1.

[0195] In this embodiment, the purity of both trans compound K and cis compound K is over 90%.

[0196] Test case

[0197] This experimental example tested the performance of the compounds obtained in the examples and comparative examples, specifically including:

[0198] (1) The proton NMR spectrum, carbon NMR spectrum, and infrared spectrum of the trans compound I prepared in Example 1 are shown below. Figures 2-4 As shown; the 1H NMR spectrum, 1C NMR spectrum, and IR spectrum of cis compound I obtained in Example 1 are shown below. Figures 5-7 As shown.

[0199] (2) The proton NMR spectrum and carbon NMR spectrum of the trans compound K obtained in Example 2 are shown below. Figures 8-9 As shown; the 1H NMR spectrum and 1C NMR spectrum of the cis compound K obtained in Example 2 are shown below. Figures 10-11 As shown.

[0200] (3) The fluorescence image of the trans compound K obtained in Example 2 is shown below. Figure 12 As shown: Figure A is the fluorescence image in a pure tetrahydrofuran solution, and Figure B is the fluorescence image in a solution where tetrahydrofuran and water each make up half the volume; the concentration of tetrahydrofuran in both Figure A and Figure B is 1×10⁻⁶. -4 mol·L -1 .

[0201] (4) The fluorescence image of the cis compound K obtained in Example 2 is shown below. Figure 13 As shown: Figure A is the fluorescence image in a pure tetrahydrofuran solution, and Figure B is the fluorescence image in a solution where tetrahydrofuran and water each make up half the volume; the concentration of tetrahydrofuran in both Figure A and Figure B is 1×10⁻⁶. -4 mol·L -1 .

[0202] (5) The fluorescence emission spectra of cis compound K and trans compound K in Example 2 are as follows: Figures 14-15 As shown. The cis-trans compound K is dissolved in tetrahydrofuran (the concentration of compound K is 1 × 10⁻⁶). –5 mol·L –1In the process of adding water, the resulting mixture was subjected to fluorescence emission testing (the weight percentage of water in the mixture is detailed in [reference needed]). Figure 14 (Data labeled for each test curve). As moisture content increases, the fluorescence emission spectrum changes. The fluorescence emission spectrum testing method for trans compound K is the same as that for cis-trans compound K.

[0203] The aggregation-induced emission (AIE) effect of cis compound K is stronger than that of trans compound K (the concentration of trans compound K in tetrahydrofuran is the same as that of cis and trans compounds). With further increase in moisture content, both exhibit aggregation-induced quenching (ACQ) effects. The AIE effect is mainly due to intramolecular motion restriction; as organic molecules aggregate, molecular motion is restricted, and energy can only be transferred from the singlet state to the ground state via radiation. The ACQ effect occurs primarily because, with further aggregation of organic molecules, energy may be transferred between molecules. The reason why the AIE effect of cis compound K is stronger than that of trans compound K is that the molecular motion of cis compound K is more restricted than that of trans compound K, and the coplanarity of the conjugated structure of the cis compound K molecule is stronger than that of the trans compound K.

[0204] Compound K in Example 2 exhibits aggregation-induced emission (AIE) effect, and the difference between cis and trans structures leads to a significant difference in fluorescence intensity, making it suitable for preparing anti-counterfeiting labels.

[0205] (6) The UV-Vis absorption spectrum and molar absorptivity test results of the cis compound K prepared in Example 2 in tetrahydrofuran, as shown in the figure. Figure 16 As shown: Figure A is the ultraviolet-visible absorption spectrum, and Figure B is the molar absorptivity test result. Figure 16 In Figure A, the concentrations of cis compound K in tetrahydrofuran are: 1 × 10⁻⁶ –6 mol·L –1 2×10 – 6 mol·L –1 4×10 –6 mol·L –1 6×10 –6 mol·L –1 8×10 –6 mol·L –1 5×10 –7 mol·L –1 The UV-Vis absorption spectrum and molar absorptivity test results of the trans compound K obtained in Example 2 in tetrahydrofuran are shown below. Figure 17 As shown: Figure A is the ultraviolet-visible absorption spectrum, and Figure B is the molar absorptivity test result. Figure 17 In Figure A, the concentrations of trans compound K in tetrahydrofuran are: 1 × 10⁻⁶ –6mol·L –1 2×10 –6 mol·L –1 4×10 – 6 mol·L –1 6×10 –6 mol·L –1 8×10 –6 mol·L –1 1×10 –5 mol·L –1 Among them, the molar absorptivity of cis compound K is greater than that of trans compound K, possibly because the coplanarity of the conjugated structure of cis compound K is stronger than that of trans compound K.

[0206] This invention discloses an aromatic polycarbonyl compound and its synthetic method, mainly including addition reaction, Sharpless asymmetric dihydroxylation reaction, ketal reaction, elimination reaction, nucleophilic substitution reaction, 4+2 cycloaddition reaction, hydroxylation reaction of olefin, and finally, the aromatic polycarbonyl compound is obtained by Swern oxidation reaction. The chemical structure of the aromatic polycarbonyl compound is based on a tetrahalobenzoquinone skeleton, containing both a ketal structure and a ketone group, exhibiting cis-trans isomerism and chirality, and the molecule can present an "X"-shaped spatial configuration. The chiral characteristics of the aromatic polycarbonyl compound make it promising for use as a chiral dopant in liquid crystals, and its rich benzene rings provide excellent electron transport characteristics, making it promising for expansion and application in fields such as organic light-emitting diodes and solar cell electrode materials. Furthermore, the aromatic polycarbonyl compounds of the present invention can be used as organic intermediates to continue chemical reactions, exhibiting enormous reaction potential. The properties of their derivatives may be quite unique, broadening the structural and application research of such compounds. For example, they can be used in the synthesis of polymer materials (after removing the triisopropylsilyl group, a double-sided triple bond is obtained, which can be used as a monomer for polymers), in the synthesis of COF materials (a carbonylamine condensation reaction with double-sided phenylenediamine can be used as a monomer for COF materials), and in the synthesis of HOF materials (after removing the ketal structure, four hydroxyl groups are obtained, which can be used in the synthesis of HOF materials).

[0207] The polycarbonyl compounds in this invention have the characteristics of complex chemical structure, strong processability, diverse properties, and wider application. Furthermore, the process design route meets the design requirements of green chemistry, and some raw materials and catalysts can be reused, which can further reduce costs and has good application prospects.

[0208] Unless otherwise specified, the term "about" in this invention actually means that the allowable error is within ±2%, for example, about 100 is actually 100 ± 2% × 100. The terms "room temperature" and "room temperature" in this invention, unless otherwise specified, are approximately 20-30°C. The phrase "between..." in this invention includes the number itself; for example, "between 2 and 3" includes the endpoints 2 and 3.

[0209] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention. Furthermore, unless otherwise specified, the embodiments of the present invention and the features thereof can be combined with each other.

Claims

1. A polycarbonyl compound, characterized in that, The chemical formula of the polycarbonyl compound is shown in formula (I-1) or formula (I-2): Wherein, R includes at least one of the following groups: 。 2. The polycarbonyl compound according to claim 1, characterized in that, The polycarbonyl compound is selected from one of the following compounds: 。 3. A method for preparing the polycarbonyl compound according to claim 1, characterized in that, The process includes the following steps: Compound G is oxidized to obtain the polycarbonyl compound, wherein compound G is selected from at least one of the following compounds: ； Wherein, group R is as described in claim 1.

4. The use of the polycarbonyl compound according to any one of claims 1 to 2 or the polycarbonyl compound prepared by the method according to claim 3 in the preparation of azahexapolybenzoxyl compounds, wherein the azahexapolybenzoxyl compounds are selected from compounds of formula (II-1) or (II-2): in, Group R is as described in claim 1; Each time A appears, it is independently selected from H, halogen, C1-C15 alkyl or C1-C15 alkoxy.

5. A nitrogen-containing polybenzoxene compound, characterized in that, The azapolybenzyl compounds are selected from compounds of formula (II-1) or formula (II-2): Wherein, group R is as described in claim 1; Each time A appears, it is independently selected from H, halogen, C1-C15 alkyl or C1-C15 alkoxy.

6. A method for preparing a nitrogen-containing polybenzoxene compound, characterized in that, The process includes the following steps: Under a protective atmosphere, a polycarbonyl compound, compound H, and solvent VIII are reacted at 100-250°C to obtain the aforementioned azapolybenzoxyl compound, wherein the polycarbonyl compound is selected from the polycarbonyl compounds described in any one of claims 1-2 or the polycarbonyl compounds prepared by the method described in claim 3, and the structural formula of compound H is shown below: ； In each instance, A is independently selected from H, halogen, C1-C15 alkyl or C1-C15 alkoxy.

7. The method for preparing azahexapolybenzoxane compounds according to claim 6, characterized in that, Solvent VIII includes imidazole.

8. An anti-counterfeiting material, characterized in that, This includes the azapolyphenylene compounds of claim 5 or the azapolyphenylene compounds prepared by the preparation method of any one of claims 6 to 7.

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