Polycarbonyl compound as well as preparation method and application thereof

Abstract

The invention discloses a polycarbonyl compound as well as a preparation method and application thereof. The chemical formula of the polycarbonyl compound is shown as a formula (I-1) or a formula (I-2), and R is a flexible chain segment. The polycarbonyl compound provided by the invention can provide a basic construction unit for liquid crystal chiral dopants, aza-polyacene compounds, organic light-emitting diodes and solar cell electrode materials, and has a good application prospect. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a polycarbonyl compound and a preparation method and application thereof. Background Art

[0002] Aromatic polycarbonyl compounds are organic compounds containing multiple carbonyl (C=O, such as keto) functional groups, and their molecular structure contains at least one aromatic ring. Aromatic polycarbonyl compounds can exhibit some unique reaction characteristics, such as nucleophilic addition reaction, oxidation reaction, reduction reaction, Mannich reaction, electrophilic substitution reaction, metal-catalyzed deacylation cross-coupling, free radical reaction, Claisen condensation and reverse Claisen reaction, because they contain aromatic rings and carbonyl groups in their structure. They are playing an increasingly important role in medicine, dyes, fragrances, materials science and optoelectronics. For example, naphthoquinone and its derivatives have a variety of biological activities, including anti-inflammatory, antibacterial, anti-tumor, etc. However, at present, there are few types of aromatic polycarbonyl compounds 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 solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a polycarbonyl compound, which can provide a basic structural unit for liquid crystal chiral dopants, nitrogen-polybenzoic compounds, organic light-emitting diodes, and solar cell electrode materials, and has good application prospects.

[0004] The invention also provides a method for preparing the polycarbonyl compound.

[0005] The invention also provides an azapolyacene compound and a preparation method thereof.

[0006] The present invention also proposes the application of the above-mentioned polycarbonyl compounds or azapolyacene compounds.

[0007] In the first aspect of the present invention, a polycarbonyl compound is provided, wherein the chemical formula of the polycarbonyl compound is as shown in formula (I-1) or formula (I-2):

[0008]

[0009] Among them, R is a flexible segment.

[0010] In some embodiments of the present invention, each occurrence of R is independently selected from a flexible segment having 3 to 20 carbon atoms in the main chain.

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

[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 comprises at least one of the following groups:

[0016]

[0017] The wavy line in each group structure represents the end of the R group connected to the polycarbonyl compound core.

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

[0019]

[0020] In a second aspect of the present invention, a method for preparing a polycarbonyl compound is provided, comprising the following steps: subjecting a compound G to an oxidation reaction to obtain the polycarbonyl compound, wherein the 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 comprises: mixing a solution containing compound G with a Swern reagent, reacting at (-60) to (-90)°C for 0.5 to 5 hours, adding triethylamine and reacting for 10 to 300 minutes to obtain the polycarbonyl compound. Optionally, the reaction time after adding triethylamine is selected from 10 to 200 minutes.

[0024] In some embodiments of the present invention, the Swern reagent contains trifluoroacetic anhydride, and the ratio of trifluoroacetic anhydride to 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, the 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 a Swern reagent, reacting at (-60) to (-90) ° C for 0.5 to 5 hours, adding triethylamine and reacting at (-60) to (-90) ° C for 10 to 300 minutes, heating to 5 to 40 ° C and reacting for 5 to 60 minutes, 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 the triethylamine with HCl solution, washing with sodium bicarbonate solution, washing with sodium chloride solution, drying, and solid-liquid separation 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: under a protective atmosphere, trifluoroacetic anhydride, dimethyl sulfoxide and dichloromethane are mixed at (-60) to (-90)° C. to prepare the Swern reagent. Optionally, the ratio 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 comprises the step of preparing compound G, specifically comprising: subjecting compound F to hydroxylation of 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 comprises: mixing compound F with potassium ferrocyanide, potassium carbonate, triethylenediamine, methanesulfonamide, potassium osmate and solvent II, and reacting at 5 to 40° C. to obtain compound G. Optionally, the reaction time is 10 to 50 hours.

[0032] In some embodiments of the present invention, the molar ratio of compound F to potassium ferrocyanide, potassium carbonate, triethylenediamine, methanesulfonamide and potassium osmate 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 the compound F to the solvent II is (1-5) mmol: (30-80) mL.

[0034] In some embodiments of the present invention, the solvent II comprises tert-butyl alcohol and water. Optionally, the volume ratio of the tert-butyl alcohol 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 to 40° C. for 10 to 50 hours, the reaction is quenched with sodium sulfite, and separated to obtain compound G. Optionally, the separation step comprises: removing the solvent from the mixture obtained after quenching the reaction, extracting with ethyl acetate, washing the organic layer with sodium sulfite aqueous solution and saline solution in sequence, collecting the organic layer, removing the solvent, and purifying with column chromatography to obtain compound G.

[0036] In some embodiments of the present invention, the preparation method further comprises the step of preparing compound F, specifically comprising: compound D and compound E, through a cycloaddition reaction, to obtain compound F, wherein the structures of compound D and compound E are as follows:

[0037]

[0038] Among them, in compound E, X 1 Each occurrence 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 comprises: mixing compound D, compound E and solvent III under a protective atmosphere, cooling to (-30) to (-70) ° C, adding n-butyl lithium, reacting at (-30) to (-70) ° C for 10 to 200 minutes, and then reacting at 5 to 40 ° C for 0.5 to 10 hours to obtain compound F. Optionally, after reacting at 5 to 40 ° C for 0.5 to 10 hours, methanol and water are added dropwise to quench the reaction, and separated to obtain compound F. Optionally, the separation step comprises: 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 adding of n-butyl lithium comprises adding n-butyl lithium in an n-hexane solution.

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

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

[0045] In some embodiments of the present invention, the tetrahalogen p-benzoquinone 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 comprises R 1 -alkynyl-, the step of preparing compound E specifically comprises: reacting tetrahalogen p-benzoquinone with R 1 -SH reaction, and then reacting with acetonitrile under the action of stannous chloride to obtain the compound E.

[0047] In some embodiments of the present invention, the step of preparing compound E specifically comprises: in a protective atmosphere, at (-50) to (-90) ° C, 1 -SH solution is mixed with n-butyl lithium, and after the temperature is raised to 4-40°C, a tetrahalogen p-benzoquinone solution is added, and the mixture is stirred at 4-40°C for 10-120 min, and then the mixture is heated to 50-80°C and stirred for 5-30 h, and the reaction is quenched to obtain an intermediate; the intermediate is mixed with stannous chloride, water, and acetonitrile, and refluxed under a protective atmosphere to obtain the compound E. Optionally, the reflux reaction time is 10-30 h. Optionally, R 1 The solution of -SH is R 1 Alternatively, the solution of tetrahalogen p-benzoquinone is a tetrahydrofuran solution of tetrahalogen p-benzoquinone.

[0048] In some embodiments of the present invention, the R 1 The molar ratio of -SH, n-butyllithium and tetrahalogenoquinone is (15-35):(14-34):(3-7).

[0049] In some embodiments of the present invention, the R 1 The molar ratio of -SH and stannous chloride is (15-35):(30-70).

[0050] In some embodiments of the present invention, the R 1 The ratio of -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 comprises the step of preparing compound D, specifically comprising: subjecting compound C to an elimination reaction to obtain compound D, wherein compound C is as follows:

[0052]

[0053] Among them, in compound C, X 2 Each occurrence 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: under a protective atmosphere, mixing compound C with tetrabutylammonium iodide, solvent IV, and 1,8-diazabicycloundec-7-ene, 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 the compound C to the 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 h.

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

[0059] In some embodiments of the present invention, the step of preparing compound D comprises: mixing compound C with tetrabutylammonium iodide, solvent IV, and 1,8-diazabicycloundec-7-ene under a protective atmosphere, reflux reaction, dripping an aqueous solution of citric acid, reacting for 0.2 to 20 hours, and separating to obtain compound D. Optionally, the separation step comprises removing the solvent from the mixture obtained by dripping the aqueous solution of citric acid, extracting with ethyl acetate, washing with saline, 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 comprises the step of preparing compound C, specifically comprising: compound B undergoes a ketal reaction to obtain compound C, wherein compound B is as follows:

[0061]

[0062] Among them, in compound B, X 2 Each occurrence 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: under a protective atmosphere, mixing compound B with 2,2-dimethoxypropane, p-toluenesulfonic acid, and solvent V, and reacting at 5 to 40° C. to obtain compound C.

[0064] In some embodiments of the present invention, the molar ratio of the 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 the 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, in the step of preparing compound C, the reaction time is 2 to 30 hours.

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

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

[0069]

[0070] Among them, in compound A, X 2 Each occurrence 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: under a protective atmosphere, mixing compound A with potassium osmate, N-methylmorpholine oxide, solvent VI, tert-butanol and water, and reacting at 5 to 40° C. to obtain compound B.

[0073] In some embodiments of the present invention, the molar ratio of compound A to potassium osmate 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 osmate, 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 the solvent VI, tert-butyl alcohol and water is (20-30):(5-15):(1-10).

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

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

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

[0079] In some embodiments of the present invention, the preparation method further comprises the step of preparing compound A, specifically comprising: subjecting 1,4-cyclohexadiene to a halogenation reaction to obtain compound A. Optionally, the halogenation reaction comprises 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, in the step of preparing compound A, the reaction time is 0.5 to 5 hours.

[0082] In some embodiments of the present invention, the 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, in the step of preparing compound A, the halogen element may be added by adding a solvent VII containing the halogen element.

[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 comprises the following steps:

[0088] S1: Take 1,4-cyclohexadiene and obtain compound A through bromination reaction;

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

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

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

[0092] S5: Take tetrabromo-p-benzoquinone and obtain compound E through nucleophilic substitution reaction;

[0093] S6: Compounds D and E are subjected to a 4+2 cycloaddition reaction to obtain compound F;

[0094] S7: taking compound F and subjecting it to hydroxylation of olefin to obtain compound G;

[0095] S8: Take compound G and subject it to a Swern oxidation reaction to obtain the polycarbonyl compound.

[0096] The third aspect of the present invention proposes the use of the above-mentioned polycarbonyl compounds in the preparation of azapolyacene compounds, the preparation of liquid crystal chiral dopants, the preparation of electrode materials or the preparation of semiconductor devices.

[0097] In a fourth aspect of the present invention, an azapolyacene compound is provided, wherein the azapolyacene compound is selected from the compound of formula (II-1) or the compound of formula (II-2):

[0098]

[0099] Among them, R is a flexible segment;

[0100] Each occurrence of A 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, halogen, and C1-C5 alkyl.

[0102] In some embodiments of the present invention, each occurrence of R is independently selected from a flexible segment having 3 to 20 carbon atoms in the main chain.

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

[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 comprises at least one of the following groups:

[0108]

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

[0110]

[0111] In a fifth aspect of the present invention, a method for preparing an azapolybenzoic compound is provided, comprising the following steps: taking a polycarbonyl compound, a compound H and a solvent VIII under a protective atmosphere, reacting at 100 to 250° C. to obtain the azapolybenzoic compound, wherein the polycarbonyl compound is selected from the polycarbonyl compound described in any one of the first aspect of the present invention or the polycarbonyl compound obtained by the method described in any one of the second aspect, and the structural formula of the compound H is as follows:

[0112]

[0113] Wherein, each occurrence of A is independently selected from H, halogen, C1-C15 alkyl or C1-C15 alkoxy.

[0114] In some embodiments of the present invention, the solvent VIII includes imidazole. In the present invention, imidazole is used as a solvent, which is friendly to acid-sensitive structures (such as ketal groups) and has a higher synthesis yield.

[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 comprises the following steps: under a protective atmosphere, taking compound H, a polycarbonyl compound and imidazole, reacting at 100 to 250°C, cooling to 5 to 40°C, and separating to obtain the azapolybenzoic compound. Optionally, the separation step comprises: extracting the mixture obtained after cooling with dichloromethane, washing the organic layer with a saline solution, collecting the organic layer, removing the solvent, and purifying by column chromatography to obtain the azapolybenzoic compound.

[0118] The sixth aspect of the present invention provides an anti-counterfeiting material, comprising the above-mentioned azapolybenzoic acid compound.

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

[0120] In an eighth aspect of the present invention, an electrode material is provided, comprising the above-mentioned polycarbonyl compound or prepared by using a raw material containing the polycarbonyl compound. Optionally, the electrode material comprises a solar cell electrode material.

[0121] In a ninth aspect of the present invention, a semiconductor device is provided, comprising the above-mentioned polycarbonyl compound or prepared by using a raw material containing the 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 the present invention include: the present invention provides a method for synthesizing an aromatic polycarbonyl compound, wherein the aromatic polycarbonyl compound has cis-trans isomerism and chiral characteristics, and its unique structure makes it have peculiar properties, and has great application potential in the fields of liquid crystal chiral dopants, nitrogen-polybenzones, organic light-emitting diodes, solar cell electrodes, etc. The molecular chemical structure of this type of aromatic polycarbonyl compound is based on a tetrahalogen parabenzoquinone skeleton, and contains a ketal structure and a keto group, and the carbonyl end is connected to a flexible chain segment. This type of aromatic polycarbonyl compound has the advantages of novel structural units, strong chemical modifiability, unique molecular structure and unique spatial configuration, and provides a very potential molecular type in the field of materials. In addition, the raw materials used in the present invention are simple in source, cheap, recyclable, and have a high synthesis yield, which is suitable for industrial production.

[0124] Description and Definition

[0125] In the present invention, unless otherwise specified, the scientific and technical terms used herein have the meanings commonly understood by those skilled in the art, but in order to better understand the present invention, the definitions of some terms are provided below. When the definitions of terms provided by the present invention are inconsistent with the meanings commonly understood by those skilled in the art, the definitions and interpretations of the terms provided by the present invention shall prevail.

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

[0127] "Alkyl" refers to a group derived from a branched or straight chain saturated aliphatic alkane with a specified number of carbon atoms by removing one hydrogen. "C1-C15 alkyl" means an alkyl group with a total carbon atom count of 1 to 15, including C1-C15 straight chain alkyl, C1-C15 branched chain alkyl and C1-C15 cycloalkyl. "C1-C5 alkyl" etc. have a similar explanation, except that the number of carbon atoms is different.

[0128] "Alkoxy" means an alkyl group as defined herein connected to another group through an oxygen atom, i.e. "alkyl-O-". "C1-C15 alkoxy" means an alkoxy group having a total carbon atom count of 1 to 15, including C1-C15 straight-chain alkoxy groups, C1-C15 branched-chain alkoxy groups and C1-C15 cycloalkoxy groups, such as methoxy, ethoxy, n-propoxy, isopropoxy, etc.

[0129] The "halogen" includes any one or two or more of fluorine, chlorine, bromine and iodine. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0131] Figure 1Schematic diagram of the preparation process of Compound I in Example 1 of the present invention;

[0132] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of the trans compound I in Example 1 of the present invention;

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

[0134] Figure 4 This is the infrared spectrum of the trans compound I in Example 1 of the present invention;

[0135] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the cis-form compound I in Example 1 of the present invention;

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

[0137] Figure 7 This is the infrared spectrum of the cis-form compound I in Example 1 of the present invention;

[0138] Figure 8 This is the hydrogen nuclear magnetic resonance spectrum of the trans compound K of Example 2 of the present invention;

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

[0140] Fig.10 This is the hydrogen nuclear magnetic resonance spectrum of the cis-form compound K of Example 2 of the present invention;

[0141] Fig.11 This is the carbon NMR spectrum of the cis-form compound K of Example 2 of the present invention;

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

[0143] Fig.13 This is a fluorescence image of the cis-form compound K of Example 2 of the present invention;

[0144] Fig.14 is the fluorescence emission spectrum of the cis-form compound K of Example 2 of the present invention;

[0145] Fig.15 is the fluorescence emission spectrum of the trans compound K in Example 2 of the present invention;

[0146] Fig.16 The figure is a UV-visible absorption spectrum diagram and molar absorption coefficient test result diagram of the cis-form compound K in tetrahydrofuran of Example 2 of the present invention;

[0147] Fig.17It is a graph showing the UV-visible absorption spectrum of the trans compound K in tetrahydrofuran according to Example 2 of the present invention and a graph showing the test results of the molar absorption coefficient. DETAILED DESCRIPTION

[0148] The following will be combined with the embodiments to clearly and completely describe the concept of the present invention and the technical effects produced, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0149] The experimental methods without specific conditions in the following examples and comparative examples are generally based on conventional conditions in the art or conditions recommended by the manufacturers; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents available from commercial channels such as conventional markets.

[0150] Unless otherwise specified, the water content of the super dry reagent used below is 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 the polycarbonyl compound comprises the following steps (the preparation process schematic diagram is shown in Figure 1 shown):

[0155] (1) Synthesis of 4,5-dibromocyclohex-1-ene (Compound A), comprising:

[0156] Under argon atmosphere, 1,4-cyclohexadiene (21.5mL, 0.22mol) and super dry n-hexane (300mL) were added to the reaction bottle, mixed evenly and cooled to -60°C, and then a mixed solution of super dry n-hexane (10mL) and bromine (11.5mL, 0.22mol) was slowly added dropwise to the reaction bottle. After the addition was completed (the addition time was more than 10min, and the addition time was 10 to 30min), the reaction was continued at -60°C for 2 hours, and then returned to room temperature. The solvent was removed by vacuum rotary evaporation to obtain a pure white crystalline product (Compound A) with a yield of 99%.

[0157] Compound A:

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

[0159] Under argon atmosphere, 4,5-dibromocyclohex-1-ene (1.97 g, 8.2 mmol), potassium osmate dihydrate (60 mg, 0.164 mmol) and N-methylmorpholine oxide (1.3 g, 9.84 mmol) were put into a reaction bottle, and acetone (30 mL), tert-butyl alcohol (8 mL) and water (4 mL) were added in sequence, and 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 organic layer was washed with sodium sulfite aqueous solution and saturated salt water solution in sequence, the organic layer was collected, the solvent was removed by vacuum rotary evaporation, and the product (compound B) was obtained by purification by neutral alumina column chromatography (V ethyl acetate = 1) with a yield of 66%.

[0160] Compound B:

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

[0162] (3) Synthesis of 5,6-dibromo-2,2-dimethyl-3a,4,5,6,7,7a-hexahydrocyclohexane[1,2-d][1,3]dioxolane (Compound C), comprising:

[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 put into a reaction bottle, and then ultra-dry dichloromethane (50 mL) was added to react at room temperature for 6 hours. After the reaction was completed, the solvent was dried in vacuo and purified by column chromatography (V petroleum ether: V ethyl acetate = 3: 1) to obtain a yellow oily product (compound C) with a yield of 91%.

[0164] Compound C:

[0165] (4) Synthesis of 2,2-dimethyl-3a,7a-dihydrocyclohexa[1,2-d][1,3]dioxolane (Compound D), comprising:

[0166] Under argon protection, compound C (15.3g, 48.7mmol) and tetrabutylammonium iodide (38.7g, 97.6mmol) were added to the reaction bottle, and then ultra-dry dichloromethane (100mL) was added, and anhydrous 1,8-diazabicycloundec-7-ene (72.8mL, 487mmol) was slowly added dropwise with a syringe, and the addition time was more than 10min (if the addition time was 10-30min), and the reaction was refluxed at about 40°C for 2 hours. After returning to room temperature, citric acid (154g, 730.5mmol) was used to prepare a 200mL aqueous solution and slowly added dropwise into the reaction bottle (the addition time was more than 10min, if the addition time was 10-30min), and stirring was continued for 0.5 hours after the addition was completed. Dichloromethane was removed by vacuum rotary evaporation, extracted with ethyl acetate, washed with saturated brine, the organic layer was collected, and the solvent was removed by vacuum rotary evaporation to obtain a crude product. The residue was purified by column chromatography (V ethyl acetate = 1, filled with basic alumina) to give a yellow oily product (Compound D) in a yield of 57%.

[0167] Compound D:

[0168] (5) Synthesis of [tri(propan-2-yl)][(2,3,5,6-tetrabromo-4-{[tri(propan-2-yl)silyl]ethynyl}phenyl)ethynyl]silane (Compound E), comprising:

[0169] Under argon protection, weigh triisopropylsilyl acetylene (4.44g, 23.616mmol) and put it into a reaction bottle containing ultra-dry tetrahydrofuran (50mL). Slowly add n-butyl lithium (14.135mL, 22.616mmol) at -78℃, the addition time is more than 10min (if the addition time is 10-30min), stir for 30 minutes and return to room temperature. Dissolve tetrabromobenzoquinone (2.084g, 4.72mmol) in ultra-dry tetrahydrofuran (50mL), and add the solution to the reaction system with a syringe, stir at room temperature for 30 minutes, then increase the temperature of the reaction system to 65℃ and stir for 12 hours. After cooling to room temperature, quench the reaction with saturated ammonium chloride solution (60mL), remove tetrahydrofuran by vacuum rotary evaporation, extract with ethyl acetate, collect the organic layer and rotary evaporate to obtain the crude intermediate product. Purify by column chromatography (first wash away the byproducts with petroleum ether, then elute with ethyl acetate) to obtain a pure intermediate. Weigh the intermediate obtained in the previous step and stannous chloride (9.5g, 49.2mmol) into a reaction flask, add water (2mL) and acetonitrile (100mL), and reflux at about 82°C for 18 hours under argon protection. After the reaction is cooled to room temperature, acetonitrile is removed by vacuum rotary evaporation, and purified by column chromatography (V petroleum ether = 1) to obtain a white crystalline product (Compound E) with a yield of 95%.

[0170] Compound E:

[0171] (6) Inseparable isomeric trans-structure products {{[(21Z)-8,8,18,18-tetramethyl-13-{[tri(prop-2-yl)silyl]ethynyl}-7,9,17,19-tetraoxacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]twenty-tetra-2(3),4(12),13,21,23-pentaen-3-yl]ethynyl}[tri(prop-2-yl)]silane and cis The synthesis of the product of the formula {[(23Z)-8,8,18,18-tetramethyl-3-{[tri(propan-2-yl)methylsilyl]ethynyl}-7,9,17,19-tetraoxacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]twenty-tetra-2(3),4(12),13,21,23-pentaen-13-yl]ethynyl}[tri(propan-2-yl)]silane (hereinafter referred to as the synthesis of compound F) comprises:

[0172] Under argon protection, [tri(propan-2-yl)][(2,3,5,6-tetrabromo-4-{[tri(propan-2-yl)silyl]ethynyl}phenyl)ethynyl]silane (5g, 6.63mmol) and 2,2-dimethyl-3a,7a-dihydrocyclohexane[1,2-d][1,3]dioxolane (3.03g, 19.89mmol) were added to a reaction bottle containing ultra-dry toluene (50mL) and cooled to -50°C. A mixture of n-butyl lithium (20.08mL, 1.6M in hexane) and ultra-dry n-hexane (30mL) was slowly injected and dripped into the reaction system. After the addition was completed (the addition time was more than 10min, and the addition time was 10 to 30min), the reaction was continued at -50°C for 30 minutes. After the reaction was reacted at room temperature for 1 hour, methanol and water were added to quench the reaction. The toluene and n-hexane were removed by rotary evaporation under reduced pressure, and the mixture was extracted with dichloromethane. The organic layer was collected after multiple washings, dried over anhydrous sodium sulfate, and dichloromethane was removed by rotary evaporation under reduced pressure to obtain a crude product. The product was purified by column chromatography (V petroleum ether: V dichloromethane = 3:1) to obtain a white solid product (Compound F) with a yield of 67%.

[0173] Compound F:

[0174]

[0175] (7) Trans-tetrahydroxy compounds 8,8,18,18-tetramethyl-3,13-bis{[tri(prop-2-yl)methylsilyl]ethynyl}-7,9,17,19-tetraoxacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]twenty-tetra-2(3),4(12),13-triene-21,22,23,24-tetraol and cis-tetrahydroxy compounds The synthesis of compound 8,8,18,18-tetramethyl-3,13-bis{[tri(propan-2-yl)methylsilyl]ethynyl}-7,9,17,19-tetraoxacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]twenty-tetra-2(3),4(12),13-triene-21,22,23,24-tetraol (hereinafter referred to as the synthesis of compound G) comprises:

[0176] Under argon protection, the trans-structured product {{[(21Z)-8,8,18,18-tetramethyl-13-{[tri(propan-2-yl)silyl]ethynyl}-7,9,17,19-tetraoxacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]twenty-tetra-2(3),4(12),13,21,23-pentaen-3-yl]ethynyl}[tri(propan-2-yl)]silane and the cis-structured product {[(23Z)-8,8,18,18-tetramethyl-3-{[tri(propan-2-yl)silyl]ethynyl}-7,9,17,19-tetraoxacyclo[13.5.2.25,11.016,20.02,14.06,10.04,12]twenty-four-2(3),4(12),13,21,23-pentaen-3-yl]ethynyl}[tri(propan-2-yl)]silane A mixed product of [0.02, 14.06, 10.04, 12]twenty-tetra-2(3), 4(12), 13, 21, 23-pentaen-13-yl]ethynyl}[tri(propan-2-yl)]silane (2 g, 2.705 mmol), potassium ferrocyanide (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 osmate dihydrate (60 mg, 0.163 mmol) were put into a reaction bottle, and a mixed solution of tert-butyl alcohol (27 mL) and water (27 mL) was added and reacted at room temperature for 24 hours. After the reaction, 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 with an aqueous sodium sulfite solution and a saturated saline solution in turn. The organic layer was collected and the solvent was removed by vacuum rotary evaporation. The raw material was removed by column chromatography (V petroleum ether: V dichloromethane = 3:1), and then purified by column chromatography (V dichloromethane = 1) to obtain a trans-tetrahydroxy white solid product (trans compound G) with a yield of 31%. Finally, the cis-tetrahydroxy white solid product (cis compound G) was purified by column chromatography (V petroleum ether: V ethyl acetate = 1:1) to obtain a 18% yield.

[0177] Compound G:

[0178]

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

[0180] (8) Trans-tetraketone compounds 8,8,18,18-tetramethyl-3,13-bis{[tri(prop-2-yl)methylsilyl]ethynyl}-7,9,17,19-tetraoxacyclo[13.5.2.25,11.06,10.016,20.02,14.04,12]twenty-tetra-2(3),4(12),13-triene-21,22,23,24-tetraketone and cis-tetraketone compounds The synthesis of 8,8,18,18-tetramethyl-3,13-bis{[tri(propan-2-yl)methylsilyl]ethynyl}-7,9,17,19-tetraoxacyclo[13.5.2.25,11.06,10.016,20.02,14.04,12]twenty-tetra-2(3),4(12),13-triene-21,22,23,24-tetraone (hereinafter referred to as the synthesis of compound I) comprises:

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

[0182] First, the Swern reagent was prepared, including: slowly dropping trifluoroacetic anhydride (0.51 mL, 3.4 mmol) into a mixture of dimethyl sulfoxide (0.3 mL, 4.25 mmol) and dichloromethane (20 mL) under an argon atmosphere at -78°C to obtain the Swern reagent, and stirring for 15 minutes.

[0183] After dissolving the trans compound G (500 mg, 0.62 mmol) in a mixed solution of dimethyl sulfoxide (7.5 mL) and dichloromethane (3.75 mL), the mixture was extracted with a 20 mL syringe and then dripped into the Swern reagent (15 min) with a syringe pump, and the reaction was continued at -78 ° C for 60 minutes. Triethylamine (1.15 mL, 8.25 mmol) was added dropwise into the reaction system (the dropping time was 15 min), and the low-temperature reactor was closed after 60 minutes. After continuing the reaction for 30 minutes, it was taken out and stirred at room temperature for 10 minutes. After returning to room temperature, the reaction system was poured into 50 mL of a prepared 2 mol / L HCl aqueous solution to terminate the reaction. Extract with dichloromethane, first wash away the triethylamine with a 2 mol / L HCl aqueous solution, then wash away the hydrochloric acid with a saturated sodium bicarbonate aqueous solution, and finally wash away the sodium bicarbonate with a saturated sodium chloride aqueous solution. Dry with anhydrous sodium sulfate and rotary evaporate to obtain a trans tetracarbonyl yellow solid product (trans compound I) with a yield of 91%.

[0184] The preparation process of cis-compound I is different from that of trans-compound I only in that cis-compound G is used instead of trans-compound G. The other steps are the same as those of trans-compound I, and finally a cis-tetracarbonyl yellow solid product (cis-compound I) is obtained with a yield of 94%.

[0185] Compound I:

[0186]

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

[0188] Example 2

[0189] This embodiment discloses an azapolyacene compound (referred to as compound K): trans-bilateral azapolyacene 41,41,46,46-tetramethyl-3,22-bis{[tri(propyl-2-yl)methylsilyl]ethynyl}-7,18,26,37-tetraaza-40,42,45,47-tetraoxatridecacyclic [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]tetraocta-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-heptadecene and cis-bi-anhydro-41,41,46,46-tetramethyl-3,22-bis{[tri(prop-2-yl)methylsilyl]ethynyl}-7,18,26,37-tetraaza-40,42,45,47-tetraoxatridecacyclo[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]Tetraoctadecene-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 argon atmosphere, trans-tetraketone compound I-anti (50 mg, 0.0625 mmol), 2,3-naphthalenediamine (99 mg, 0.625 mmol) and imidazole (2 g) were placed in a 50 mL Shrek tube and reacted at 150 ° C for 2 hours. After returning to room temperature, it was extracted with dichloromethane, and the organic layer was washed with saturated saline solution in turn, the organic layer was collected, and the solvent was removed by vacuum rotary evaporation. Column chromatography was used for purification (V petroleum ether: V dichloromethane = 1:2) to obtain a solid product trans-bilateral aza-polyacene (29 mg, yield 45%).

[0193] The preparation process of cis compound K differs from that of trans compound K only in that cis compound I is used instead of trans compound I. The other steps are the same as those of trans compound K, and cis compound K (46 mg, yield 70%) is finally obtained.

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

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

[0196] Test example

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

[0198] (1) The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and infrared spectrum of the trans compound I prepared in Example 1 are as follows: Figures 2 to 4 The hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and infrared spectrum of the cis-form compound I prepared in Example 1 are shown as follows: Figures 5 to 7 shown.

[0199] (2) The hydrogen nuclear magnetic resonance spectrum and carbon nuclear magnetic resonance spectrum of the trans compound K prepared in Example 2 are as follows: Figures 8-9 The hydrogen nuclear magnetic resonance spectrum and carbon nuclear magnetic resonance spectrum of the cis-form compound K prepared in Example 2 are shown as follows: Figures 10-11 shown.

[0200] (3) The fluorescence image of the trans compound K prepared in Example 2 is as follows: Fig.12 As shown: Figure A is a fluorescence image of a pure tetrahydrofuran solution, and Figure B is a fluorescence image of a solution in which tetrahydrofuran and water each account for half of the volume; the concentration of tetrahydrofuran in Figure A and Figure B is 1×10 -4 mol·L -1 .

[0201] (4) The fluorescence image of the cis-form compound K prepared in Example 2 is as follows: Fig.13 As shown: Figure A is a fluorescence image of a pure tetrahydrofuran solution, and Figure B is a fluorescence image of a solution in which tetrahydrofuran and water each account for half of the volume; the concentration of tetrahydrofuran in Figure A and Figure B is 1×10 -4 mol·L -1 .

[0202] (5) The fluorescence emission spectra of the cis-form compound K and the trans-form compound K in Example 2 are respectively as follows: Figures 14-15 As shown. The cis-trans compound K was dissolved in tetrahydrofuran (the concentration of compound K was 1×10 –5 mol·L –1), after adding water, the resulting mixed liquid was subjected to a fluorescence emission test (the weight percentage of water in the mixed liquid is detailed in Fig.14 Each test curve is labeled with data). As the water content increases, the fluorescence emission spectrum changes. The fluorescence emission spectrum test method of trans compound K is the same as that of 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 compound K). As the water content continues to increase, both exhibit aggregation-induced quenching (ACQ) effect. The main reason for the AIE effect is the restriction of intramolecular motion. As organic molecules aggregate, the molecular motion is restricted, and energy can only be transferred from the singlet state to the ground state in the form of radiation. The main reason for the ACQ effect is that as organic molecules further aggregate, 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 degree of restriction of molecular motion of cis compound K is greater than that of trans compound K, and the coplanarity of the conjugated structure of cis compound K molecules is stronger than that of trans compound K.

[0204] Compound K in Example 2 has aggregation-induced emission (AIE) effect, and the difference in cis and trans structures leads to significant difference in fluorescence intensity, and can be used to prepare anti-counterfeiting labels.

[0205] (6) The UV-visible absorption spectrum of the cis-form compound K prepared in Example 2 in tetrahydrofuran and the molar absorption coefficient test result are shown in FIG. Fig.16 As shown: Figure A is a UV-visible absorption spectrum, and Figure B is a molar absorption coefficient test result diagram; Fig.16 In Figure A, the concentrations of cis compound K in tetrahydrofuran are: 1×10 –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-visible absorption spectrum of the trans compound K prepared in Example 2 in tetrahydrofuran and the molar absorption coefficient test result are shown in FIG. Fig.17 As shown: Figure A is a UV-visible absorption spectrum, and Figure B is a molar absorption coefficient test result diagram; Fig.17 In Figure A, the concentrations of trans compound K in tetrahydrofuran are: 1×10 –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 absorption coefficient of the cis compound K is greater than that of the trans compound K. The possible reason is that the coplanarity of the conjugated structure of the cis compound K is stronger than that of the trans compound K.

[0206] The present invention discloses an aromatic polycarbonyl compound and a synthesis method thereof, which mainly include addition reaction, Sharpless asymmetric dihydroxylation reaction, ketal reaction, elimination reaction, nucleophilic substitution reaction, 4+2 cycloaddition reaction, hydroxylation reaction of olefins, and finally obtain the aromatic polycarbonyl compound through Swern oxidation reaction. The chemical structure of the aromatic polycarbonyl compound is based on a tetrahalogen para-benzoquinone skeleton, and contains a ketal structure and a keto group, has cis-trans isomerism and chirality, and the molecule can present an "X"-type spatial configuration. The chiral characteristics of the aromatic polycarbonyl compound make it possible to play a role in the field of liquid crystal chiral dopants, and the fact that it is rich in benzene rings and has excellent electron transmission characteristics makes it possible to expand and apply in the fields of organic light-emitting diodes, solar cell electrode materials, etc. In addition, the aromatic polycarbonyl compound of the present invention can be used as an organic intermediate to continue chemical reactions, and has great reaction potential. The properties of its derivatives may be very peculiar, broadening the structural and application research of the molecules of this type of compound, such as: it can be used for the synthesis of polymer materials (after removing the triisopropylsilyl group, a double-sided triple bond is obtained, which can be used as a polymer monomer), it can be used for the synthesis of COF materials (after undergoing carbonyl-amine condensation reaction with double-sided phenylenediamine, it can be used as a monomer of COF materials), and it can be used for the synthesis of HOF materials (after removing the ketal structure, four hydroxyl groups are obtained, which can be used for the synthesis of HOF materials).

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

[0208] If there is no special explanation, the actual meaning of "about" in the present invention is that the error is allowed within the range of ±2%, for example, about 100 is actually 100±2%×100. The "normal temperature" and "room temperature" in the present invention, if there is no special explanation, are about 20-30°C. The "between" in the present invention includes the number itself, for example, "between 2-3" includes the endpoint values ​​2 and 3.

[0209] The embodiments of the present invention are described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. A polycarbonyl compound, characterized in that The chemical formula of the polycarbonyl compound is as shown in formula (I-1) or formula (I-2): Among them, R is a flexible segment.

2. The polycarbonyl compound according to claim 1, characterized in that Each occurrence of R is independently selected from a flexible chain segment having 3 to 20 carbon atoms in the main chain; Preferably, the main chain of R includes at least one of a carbon-carbon single bond and a carbon-heteroatom single bond; Preferably, the heteroatom is selected from at least one of O, N, S, P or Si; Preferably, the carbon-heteroatom single bond is selected from at least one of CO, CN, CS, CP or C-Si; Preferably, the main chain of R further includes an alkynyl group; Preferably, the R comprises at least one of the following groups: Preferably, the polycarbonyl compound is selected from one of the following compounds:

3. A method for preparing a polycarbonyl compound according to claim 1, characterized in that: The method comprises the following steps: compound G is subjected to an oxidation reaction to obtain the polycarbonyl compound, wherein compound G is selected from at least one of the following compounds:

4. Use of the polycarbonyl compound according to any one of claims 1 to 2 or the polycarbonyl compound prepared by the preparation method according to claim 3 in the preparation of azapolyacene compounds, preparation of liquid crystal chiral dopants, preparation of electrode materials or preparation of semiconductor devices.

5. An azapolyacene compound, characterized in that: The azapolyacene compound is selected from the compound of formula (II-1) or the compound of formula (II-2): Among them, R is a flexible segment; Each occurrence of A is independently selected from H, halogen, C1-C15 alkyl or C1-C15 alkoxy.

6. A method for preparing an azapolyacene compound, characterized in that: The method comprises the following steps: taking a polycarbonyl compound, a compound H and a solvent VIII under a protective atmosphere, reacting at 100 to 250° C. to obtain the azapolybenzoic compound, wherein the polycarbonyl compound is selected from the polycarbonyl compound according to any one of claims 1 to 2 or the polycarbonyl compound obtained by the preparation method according to claim 3, and the structural formula of the compound H is as follows: wherein each occurrence of A is independently selected from H, halogen, C1-C15 alkyl or C1-C15 alkoxy; Preferably, the solvent VIII comprises imidazole.

7. An anti-counterfeiting material, characterized in that: The invention comprises the azapolybenzoic acid compound as described in claim 5 or the azapolybenzoic acid compound prepared by the preparation method as described in claim 6.

8. A liquid crystal chiral dopant, characterized in that: It comprises a polycarbonyl compound or is prepared by using a raw material containing the polycarbonyl compound, wherein the polycarbonyl compound comprises the polycarbonyl compound according to any one of claims 1 to 2 or the polycarbonyl compound prepared by the preparation method according to claim 3.

9. An electrode material, characterized in that: It comprises a polycarbonyl compound or is prepared by using a raw material containing the polycarbonyl compound, wherein the polycarbonyl compound comprises the polycarbonyl compound according to any one of claims 1 to 2 or the polycarbonyl compound prepared by the preparation method according to claim 3.

10. A semiconductor device, characterized in that: Comprising a polycarbonyl compound or being prepared by using a raw material containing the polycarbonyl compound, wherein the polycarbonyl compound comprises the polycarbonyl compound according to any one of claims 1 to 2 or the polycarbonyl compound prepared by the preparation method according to claim 3; Preferably, the semiconductor device includes at least one of an organic light emitting diode or a solar cell.

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