Large-pi conjugated phosphorus-doped fused ring compound as well as preparation method and application thereof

Abstract

The invention discloses a large-pi conjugated phosphorus-doped fused ring compound as well as a preparation method and application thereof, and belongs to the technical field of organic synthesis. The preparation method comprises the following steps: by adopting a series strategy of combining visible light catalysis and acid treatment, carrying out dehydrophosphine free radical addition / cyclization reaction on commercially available bicycloolefin and a secondary phosphine oxide compound serving as raw materials under the irradiation of visible light in the presence of cobalt oxime complex catalysis and organic alkali to generate a phosphorus heterocyclic intermediate; then the intermediate is heated and refluxed in concentrated hydrochloric acid for deoxidation aromatization, and large-pi conjugated phosphorus-doped condensed ring structures such as naphthalene ring benzo-phosphorus cyclopentadiene are efficiently constructed. The method provided by the invention overcomes the defects of tedious steps and large substrate limitation of the traditional alkyne route, has the advantages of mild reaction conditions, simple operation, good to excellent yield (up to 70-90%), and realization of one-pot synthesis, and is suitable for large-scale production. A series of prepared novel phosphorus-doped fused ring compounds show strong fluorescence under ultraviolet irradiation, and have application potential in the field of organic photoelectric materials.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and more specifically to a large π-conjugated phosphorus heterocyclic compound, its preparation method, and its application. Background Technology

[0002] π-conjugated ladder molecules with highly fused structures are fundamental materials in the field of organic electronics. Their rigid frameworks exhibit unique optoelectronic advantages, including strong luminescence and high charge carrier mobility. To further modulate the electronic and structural properties of these materials, altering the chemical composition of the conjugated system is one of the main approaches to optimizing the performance of organic materials. The most common strategy is to synthesize molecules containing different C(sp) groups. 2 All-carbon macromolecules with C(sp) structural units (such as aryl, alkynes, alkenes, etc.) and the introduction of substituents with specific functions onto the skeletal side chains are also effective methods. Another highly effective approach is to introduce heteroatoms into the conjugated framework. Numerous studies have reported ladder-frame materials using heteroatoms such as boron (B), silicon (Si), nitrogen (N), and sulfur (S) as bridging units, some of which have demonstrated excellent performance in organic light-emitting diodes (OLEDs) and transistors.

[0003] It is noteworthy that phosphorus atoms are highly promising heteroatom candidates due to their unique chemical modifiability. Because they are readily oxidized to phosphine oxides or phosphine sulfides, or complexed with Lewis acids and transition metals, the electronic and optical properties of compounds can be easily modulated. This property has been well-validated in various π-conjugated systems containing skeletons such as phosphacyclopentadiene, dibenzophosphacyclopentadiene, and dithiophenephosphacyclopentadiene.

[0004] Despite the unique electronic topological properties of polycyclic aromatic hydrocarbons with a phosphacene-containing heterocyclic pentadiene skeleton, their synthesis remains challenging based on current research. First, the construction of phosphacene-containing fused-ring aromatic compounds typically requires lengthy synthetic steps and complex starting materials. Second, existing strategies, such as the synthesis of benzo[b]phosphacene oxides, are still limited to endynylene substrates, and methods involving other unsaturated bonds have not yet been observed. Furthermore, endynylenes as substrates have limitations in the synthesis of certain large π-conjugated phosphacene heterocyclic molecules.

[0005] Visible light is abundant in nature and is a green, pollution-free, and renewable natural resource. In recent years, visible light-catalyzed organic synthesis chemistry has become a cutting-edge research field internationally. Due to the importance of organophosphorus oxides in medicine, materials, catalysis, and other fields, visible light redox-catalyzed phosphine radical reactions have developed rapidly. Therefore, developing a visible light-catalyzed technique for preparing large π-conjugated phosphorus heterocyclic compounds has become an urgent problem to be solved in this field. Summary of the Invention

[0006] To address the aforementioned problems, this invention proposes a strategy of photoinduced cobalt oxime complex-catalyzed dehydrogenation radical addition cyclization of bicyclic alkenes and diphenylphosphine oxides. The resulting phosphorus heterocyclic compounds can be synthesized into large π-conjugated phosphorus heterocyclic compounds through simple transformation. This study is the first to utilize the intramolecular cyclization characteristics of bicyclic alkenes, combined with a photoinduced cobalt oxime complex catalytic system, to overcome the spatial limitations of the alkyne route. It enables the generation of large π-conjugated phosphorus heterocyclic compounds in moderate to good yields under mild conditions, providing a new approach for the synthesis of phosphorus heterocyclic compounds.

[0007] To achieve the above objectives, the present invention first provides a method for preparing a large π-conjugated phosphorus heterocyclic compound, comprising the following steps: S1, under an inert atmosphere, using a cobalt oxime complex as a catalyst, and in the presence of an organic base and under visible light irradiation, a dicyclic olefin compound and a secondary phosphine oxide compound undergo a dehydrophosphine radical addition / cyclization reaction in an organic solvent to generate a phosphorus heterocyclic intermediate.

[0008] S2, the phosphorus heterocyclic intermediate obtained in S1 is heated under reflux in acid to carry out deoxyaromatization reaction. After the reaction is completed, it is cooled to room temperature, separated by dichloromethane extraction, dried with magnesium sulfate, and separated by silica gel column chromatography to obtain the large π-conjugated phosphorus heterocyclic compound.

[0009] The specific chemical reaction formula is as follows:

[0010] Step S2 can be replaced by: separating the phosphorus heterocyclic intermediate obtained in S1 by silica gel column chromatography, heating the separated product under reflux in acid for deoxyaromatization, cooling to room temperature after the reaction is completed, separating by dichloromethane extraction, drying with magnesium sulfate, and separating by silica gel column chromatography to obtain the large π-conjugated phosphorus heterocyclic compound.

[0011] The specific chemical reaction formula is as follows:

[0012] The bicyclic olefin compound in step S1 is 1,4-epoxy-1,4-dihydronaphthalene or a derivative thereof; the secondary phosphine oxide compound is diphenylphosphine oxide or a derivative thereof with electron-donating or electron-withdrawing substituents on its benzene ring; The molar ratio of the bicyclic olefin compound to the secondary phosphine oxide compound is 2:1.

[0013] Further, the derivatives of the 1,4-epoxy-1,4-dihydronaphthalene are 6,7-dimethyl-1,4-epoxy-1,4-dihydronaphthalene, 6,7-dimethoxy-1,4-epoxy-1,4-dihydronaphthalene, 6,7-difluoro-1,4-epoxy-1,4-dihydronaphthalene, 5,8-dimethoxy-1,4-epoxy-1,4-dihydronaphthalene, and 5,8-dihydro-5,8-epoxynaphthalene[2,3- d [1,3]dioxolane, 1,4-epoxy-1,4-dihydroanthracene; The diphenylphosphine oxide derivatives with electron-donating or electron-withdrawing substituents on their benzene rings are one of bis([1,1'-biphenyl]-4-yl)phosphine oxide, bis(4-methoxyphenyl)phosphine oxide, and bis(4-tert-butylphenyl)phosphine oxide.

[0014] In step S1, the cobalt oxime complex is Co(dmgH)₂PyCl, and its amount is 1-10 mol% of the molar amount of the bicyclic olefin compound; the organic base is 4-dimethylaminopyridine, and its amount is 10-50 mol% of the molar amount of the bicyclic olefin compound; the organic solvent is dichloroethane, and the molar amount of the bicyclic olefin compound to the volume ratio of dichloroethane is 0.4 mmol:4 mL; the visible light wavelength is 450 nm; the reaction temperature is 25 °C, and the time is 24-72 h.

[0015] The acid mentioned in step S2 is concentrated hydrochloric acid with a concentration of 12N, and the volume ratio of the concentrated hydrochloric acid to the organic solvent is 1:1; the reflux temperature is 80-100℃, and the reaction time is 4-12h.

[0016] The raw materials required for this invention, diphenylphosphine oxide and bicyclic olefin substrates, are commercially available.

[0017] Another object of the present invention is to provide a large π-conjugated phosphorus heterocyclic compound, the general structural formula of which is as follows:

[0018] in: R is monosubstituted or polysubstituted, selected from one of H, F, Cl, Br, C1-C6 straight-chain or branched alkyl, C1-C6 straight-chain or branched alkenyl, C1-C6 straight-chain or branched alkoxy, and when R is polysubstituted, different substituents can form a ring. R 1 It can be monosubstituted or polysubstituted, and is selected from H, phenyl, C1-C6 straight-chain or branched hydrocarbon group, and C1-C6 straight-chain or branched alkoxy group; Ar is a phenyl or substituted phenyl group, wherein the substitution is a phenyl group, a C1-C6 straight-chain or branched hydrocarbon group, or a C1-C6 straight-chain or branched alkoxy group.

[0019] Another object of the present invention is to provide an application of the large π-conjugated phosphorus heterocyclic compound as described above in organic optoelectronic devices, including organic light-emitting diodes, fluorescent sensors, and organic solar cells.

[0020] The present invention also provides the application of the above-described large π-conjugated phosphorus heterocyclic compound in the preparation of trivalent phosphine compounds.

[0021] Furthermore, the prepared trivalent phosphine compounds are used to prepare organometallic complexes.

[0022] As can be seen from the above technical solution, this invention discloses a large π-conjugated phosphorus heterocyclic compound, its preparation method, and its applications. Compared with the prior art, its beneficial effects are as follows: 1) By using bicyclic olefins and diphenylphosphine oxides as substrates, this invention not only breaks through the spatial limitations of the alkyne route, but also generates large π-conjugated phosphorus heterocyclic compounds in moderate and good yields under mild conditions, providing a new green synthetic route for expanding the synthesis of large π-conjugated phosphorus heterocyclic compounds.

[0023] 2) This invention overcomes the drawbacks of traditional alkyne routes, such as lengthy steps and limited substrates. It features mild reaction conditions, simple operation, and good to excellent yields (70%–90%). Furthermore, it allows for one-pot synthesis, making it suitable for large-scale production. The resulting series of novel phosphorus heterocyclic compounds exhibit strong fluorescence under ultraviolet light irradiation, demonstrating potential applications in organic optoelectronic materials. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0025] Figure 1 These are two synthetic route diagrams for the present invention.

[0026] Figure 2 The 5-phenyldibenzo[ b,f ] Phosphadinium-5-oxide and 5-phenylbenzo[ b Naphthalene[2,3- f Luminescence diagram of phosphanin-5-oxide.

[0027] Figure 3 Fluorescence emission spectra of π-conjugated phosphorus heterocyclic aromatic compounds provided by this invention.

[0028] Figure 4The table shows the photophysical properties of the compounds in Examples 1-10 of this invention (including fluorescence quantum yield and Stokes shift).

[0029] Figure 5 The 5-phenyldibenzo[] provided by the present invention b , f Synthetic route for preparing trivalent phosphine and its complexes from phosphanin-5-oxide. Detailed Implementation

[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] General Method The catalyst Co(dmgH)₂pyCl, the organic base 4-dimethylaminopyridine, and the bicyclic olefin compound were placed in a 10 mL Schlenk tube equipped with a magnetic inlet and dried in an oven. The Schlenk tube was then introduced into an argon-filled glove box, and a secondary phosphine oxide compound was added. The tube was removed from the glove box and connected to a vacuum line, evacuated using a vacuum pump, and backfilled with argon three times. After adding 4 mL of dichloroethane under argon, the resulting mixture was degassed using a "freeze-pump-thaw" procedure (three times) under argon. The mixture was then stirred at 25°C for 36 hours under 450 nm blue LED (40 W) illumination, and the results were monitored by TLC analysis.

[0032] Method A: After the reaction was complete, the mixture was concentrated under reduced pressure and purified by silica gel column chromatography. The purified product was refluxed in 4 mL of 12 N concentrated hydrochloric acid at 85 °C for 8 hours. After cooling to room temperature, the reaction mixture was diluted in 20 mL of dichloromethane (DCM), and the organic layer was separated. The aqueous layer was extracted three times with 20 mL of DCM. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure to obtain the corresponding product.

[0033] Method B: After the reaction was complete, the mixture was concentrated under reduced pressure and refluxed directly in 4 mL of 12 N concentrated hydrochloric acid at 85 °C for 8 hours. After cooling to room temperature, the reaction mixture was diluted in 20 mL of dichloromethane (DCM), and the organic layer was separated. The aqueous layer was extracted three times with 20 mL of DCM, and the combined organic layers were dried over magnesium sulfate and separated by silica gel column chromatography to obtain the corresponding product.

[0034] Example 1

[0035] The bicyclic olefin compound was 1,4-epoxy-1,4-dihydronaphthalene, used in an amount of 0.4 mmol; the secondary phosphine oxide compound was diphenylphosphine oxide, used in an amount of 0.2 mmol; the catalyst Co(dmgH)₂pyCl was used in an amount of 10 mol% of the molar amount of 1,4-epoxy-1,4-dihydronaphthalene; and the organic base 4-dimethylaminopyridine was used in an amount of 30 mol% of the molar amount of 1,4-epoxy-1,4-dihydronaphthalene. The final product was: 5-phenyldibenzo[ b,f Phosphanin-5-oxide, chemical formula as follows:

[0036] Yield: Method A: 88%; Method B: 90%.

[0037] Pale yellow solid, mp 167.1-168.8 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.24 (dd, J = 7.3, 4.1 Hz, 2H), 8.01 (dd, J= 7.8, 2.9 Hz, 1H), 7.92 (d, J = 8.2 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1H), 7.76(dd, J = 9.8, 7.4 Hz, 1H), 7.73-7.62 (m, 3H), 7.61-7.55 (m, 1H), 7.54-7.46(m, 2H), 7.44-7.37 (m, J = 10.6, 7.4, 3.1 Hz, 3H); 13 C NMR (100 MHz, CDCl3) δ 142.1 (d, J C-P = 20.2 Hz), 137.3 (d, J C-P =22.2 Hz), 135.8, 133.503 (d, J C-P = 2.2 Hz), 133.502 (d, J C-P = 12.3 Hz), 133.4 (d, J C-P = 105.9 Hz), 132.1 (d, J C-P = 2.9 Hz), 131.8 (d, J C-P = 9.4 Hz), 131.4(d, J C-P = 104.0 Hz), 131.1 (d, J C-P= 10.9 Hz), 130.9 (d, J C-P = 107.2 Hz), 129.9 (d, J C-P = 9.4 Hz), 129.5 (d, J C-P = 11.1 Hz), 129.2, 128.7, 128.60,128.55, 127.1, 121.5 (d, J C-P = 9.7 Hz), 120.0 (d, J C-P = 9.7 Hz); 31 P NMR (162 MHz, CDCl3) δ 32.8; HRMS (ESI) Calcd for C 22 H 15 OPNa [M +Na] + 349.0753, found 349.0760.

[0038] Example 2

[0039] The bicyclic olefin compound was 6,7-dimethyl-1,4-epoxy-1,4-dihydronaphthalene, used in an amount of 0.4 mmol; the secondary phosphine oxide compound was diphenylphosphine oxide, used in an amount of 0.2 mmol; the catalyst Co(dmgH)₂pyCl was used in an amount of 10 mol% of the molar amount of 6,7-dimethyl-1,4-epoxy-1,4-dihydronaphthalene; and the organic base 4-dimethylaminopyridine was used in an amount of 30 mol% of the molar amount of 6,7-dimethyl-1,4-epoxy-1,4-dihydronaphthalene. The final product was 8,9-dimethyl-5-phenyldibenzo[…]. b,f Phosphanin-5-oxide, chemical formula as follows:

[0040] Yield: Method A: 67%; Method B: 82%.

[0041] Pale yellow solid, mp 212.9-214.6 ℃; 1H NMR (400 MHz, CDCl3) δ 8.16-8.08(m, 2H), 7.97 (dd, J = 7.9, 2.9 Hz, 1H), 7.74 (dd, J = 9.7, 7.5 Hz, 1H),7.71-7.64 (m, 3H), 7.62 (t, J = 7.6 Hz, 1H), 7.57 (s, 1H), 7.48 (t, J = 7.4Hz, 1H), 7.41-7.35 (m, 3H), 2.45 (s, 3H), 2.41 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 142.3 (d, JC-P = 20.4 Hz), 138.8, 137.1,136.4 (d, J C-P = 22.4 Hz), 134.6 (d, J C-P = 1.9 Hz), 133.3 (d, J C-P = 2.2 Hz),133.2 (d, J C-P = 105.9 Hz), 132.4 (d, J C-P = 12.4 Hz), 131.9 (d, J C-P = 2.9 Hz),131.7 (d, J C-P = 104.0 Hz), 131.0 (d, J C-P = 10.8 Hz), 130.7 (d, J C-P = 9.6 Hz),129.7 (d, J C-P = 9.5 Hz), 129.6 (d, J C-P = 107.6 Hz), 129.1 (d, J C-P = 11.3 Hz),128.6, 128.5, 128.1, 121.3 (d, J C-P = 9.9 Hz), 119.0 (d, J C-P = 9.8 Hz), 20.3,20.0; 31 P NMR (162 MHz, CDCl3) δ 33.1; HRMS (ESI) Calcd for C 24 H 19 OPNa [M +Na] +377.1066, found 377.1075.

[0042] Example 3

[0043] The bicyclic olefin compound was 6,7-dimethoxy-1,4-epoxy-1,4-dihydronaphthalene, used in an amount of 0.4 mmol; the secondary phosphine oxide compound was diphenylphosphine oxide, used in an amount of 0.2 mmol; the catalyst Co(dmgH)₂pyCl was used in an amount of 8 mol% of the molar amount of 6,7-dimethoxy-1,4-epoxy-1,4-dihydronaphthalene; and the organic base 4-dimethylaminopyridine was used in an amount of 30 mol% of the molar amount of 6,7-dimethoxy-1,4-epoxy-1,4-dihydronaphthalene. The final product was 8,9-dimethoxy-5-phenyldibenzo[ b,f Phosphanin-5-oxide, chemical formula as follows:

[0044] Yield: Method A: 83%; Method B: 85%.

[0045] Pale yellow solid, mp 82.6-84.5 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.15-8.02 (m, 2H), 7.95-7.89 (m, 1H), 7.76-7.65 (m, 3H), 7.61 (t, J = 7.6 Hz, 1H), 7.50-7.45 (m, 1H), 7.41-7.35 (m, 3H),7.21 (s, 1H), 7.10 (s, 1H), 4.05 (s, 3H), 3.98 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 151.5, 150.2, 142.4 (d, J C-P = 20.8 Hz), 136.2 (d, J C-P = 22.2 Hz), 133.4 (d, J C-P = 1.8 Hz), 133.1 (d, J C-P = 106.2 Hz), 132.1 (d, J C-P = 1.6 Hz), 132.0 (d, J C-P = 2.9 Hz), 131.7 (d, J C-P = 103.6 Hz), 131.1 (d, J C-P= 10.9 Hz), 129.83 (d, J C-P = 9.3 Hz), 129.77 (d, J C-P = 10.0Hz), 129.4 (d, J C-P = 12.6 Hz), 129.0 (d, J C-P = 11.1 Hz), 128.63 (d, J C-P =108.9 Hz), 128.62 (d, J C-P = 12.5 Hz), 121.1 (d, J C-P = 9.9 Hz), 118.6 (d, J C-P = 10.2 Hz), 107.5, 106.9, 56.0, 55.9; 31 P NMR (162 MHz, CDCl3) δ 33.1; HRMS (ESI) Calcd for C 24 H 20 O3P [M + H] + 387.1145, found 387.1153.

[0046] Example 4

[0047] The bicyclic olefin compound was 6,7-difluoro-1,4-epoxy-1,4-dihydronaphthalene, used in an amount of 0.4 mmol; the secondary phosphine oxide compound was diphenylphosphine oxide, used in an amount of 0.2 mmol; the catalyst Co(dmgH)₂pyCl was used in an amount of 10 mol% of the molar amount of 6,7-difluoro-1,4-epoxy-1,4-dihydronaphthalene; and the organic base 4-dimethylaminopyridine was used in an amount of 30 mol% of the molar amount of 6,7-difluoro-1,4-epoxy-1,4-dihydronaphthalene. The final product was 8,9-difluoro-5-phenyldibenzo[…]. b,f Phosphanin-5-oxide, chemical formula as follows:

[0048] Yield: Method A: 73%; Method B: 84%.

[0049] Pale yellow solid, mp 221.9-223.6 ℃; 1H NMR (400 MHz, CDCl3) δ 8.20-8.09 (m, 2H), 7.96 (dd, J = 7.9, 2.9Hz, 1H), 7.75 (t, J = 8.7 Hz, 1H), 7.71-7.59 (m, 4H), 7.58-7.48 (m, 2H),7.46-7.36 (m, 3H); 13 C NMR (100 MHz, CDCl3) δ 151.6 (dd, J C-F = 252.9, 15.6 Hz), 150.4(dd, J C-F = 252.1, 15.7 Hz), 141.5 (d, J C-P = 20.0 Hz), 137.8 (dd, J C-P = 22.3,J C-F = 2.5 Hz), 133.7 (d, J C-P = 2.1 Hz), 133.1 (d, J C-P = 106.8 Hz), 132.9 (d,J C-F = 8.1 Hz), 132.3 (d, J C-P = 2.9 Hz), 131.7 (dd, J C-P = 107.0, J C-F = 2.4Hz), 131.0 (d, J C-P = 11.0 Hz), 130.9 (d, J C-P = 105.1 Hz), 130.9-130.5 (m),130.3-130.1 (m), 130.0 (d, J C-P = 9.3 Hz), 129.9 (d, J C-P = 10.9 Hz), 128.8 (d,J C-P = 12.7 Hz), 121.6 (d, J C-P = 9.9 Hz), 119.2 (ddd, J C-P = 9.3, J C-F = 4.9,J C-F = 1.8 Hz), 115.0 (d, J C-F = 17.0 Hz), 114.4 (d, J C-F= 17.3 Hz); 19 F NMR (377 MHz, CDCl3) δ -132.6 (d, J = 20.8 Hz), -134.6 (d, J =20.7 Hz); 31 P NMR (162 MHz, CDCl3) δ 32.5; HRMS (ESI) Calcd for C 22 H 14 F2OP [M + H] + 363.0745, found 363.0751.

[0050] Example 5

[0051] The bicyclic olefin compound was 5,8-dimethoxy-1,4-epoxy-1,4-dihydronaphthalene, used in an amount of 0.4 mmol; the secondary phosphine oxide compound was diphenylphosphine oxide, used in an amount of 0.2 mmol; the catalyst Co(dmgH)₂pyCl was used in an amount of 10 mol% of the molar amount of 5,8-dimethoxy-1,4-epoxy-1,4-dihydronaphthalene; and the organic base 4-dimethylaminopyridine was used in an amount of 30 mol% of the molar amount of 5,8-dimethoxy-1,4-epoxy-1,4-dihydronaphthalene. The final product was: 7,10-dimethoxy-5-phenyldibenzo[ b, f Phosphanin-5-oxide, chemical formula as follows:

[0052] Yield: Method A: 75%; Method B: 80%.

[0053] Yellow solid, mp 173.6-175.4 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.66 (d, J = 11.7 Hz, 2H), 8.62 (d, J = 2.9Hz, 1H), 8.05 (dd, J = 8.0, 2.9 Hz, 1H), 7.74 (t, J = 8.6 Hz, 1H), 7.72-7.58(m, 3H), 7.47 (t, J = 7.5 Hz, 1H), 7.44-7.33 (m, 3H), 6.82 (d, J = 8.4 Hz,1H), 6.72 (d, J = 8.4 Hz, 1H), 4.01 (s, 3H), 3.91 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 150.2, 149.6, 142.3 (d, J C-P = 20.4 Hz), 137.3 (d, J C-P = 22.7 Hz), 133.41 (d, J C-P = 2.3 Hz), 133.40 (d, J C-P = 105.8Hz), 132.0 (d, J C-P = 2.9 Hz), 131.4 (d, J C-P = 104.1 Hz), 131.1 (d, J C-P = 10.9Hz), 130.2 (d, J C-P = 108.2 Hz), 129.8 (d, J C-P = 9.4 Hz), 129.4 (d, J C-P = 11.2Hz), 128.7, 128.5, 126.2 (d, J C-P = 12.2 Hz), 126.1 (d, J C-P = 10.8 Hz), 121.7(d, J C-P = 9.8 Hz), 114.3 (d, J C-P = 9.5 Hz), 106.4, 104.7, 55.8, 55.7; 31 P NMR (162 MHz, CDCl3) δ 33.3; HRMS (ESI) Calcd for C 24 H 19 O3PNa [M +Na] + 409.0964, found 409.0973.

[0054] Example 6

[0055] The bicyclic olefin compound is 5,8-dihydro-5,8-epoxynaphtho[2,3- d [1,3]dioxolane, 0.4 mmol; secondary phosphine oxide, 0.2 mmol; catalyst Co(dmgH)2pyCl, 5,8-dihydro-5,8-epoxynaphtho[2,3- d[1,3] 10 mol% of dioxolane molar amount, with the organic base 4-dimethylaminopyridine used in an amount of 5,8-dihydro-5,8-epoxynaphtho[2,3- d The final product was 30 mol% of the molar amount of [1,3]dioxolane. d [1,3]dioxane-6-oxide, with the following chemical formula:

[0056] Yield: Method A: 79%; Method B: 83%.

[0057] Yellow solid, mp 257.3-259.1 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.06-7.98 (m, 2H), 7.90 (dd, J = 8.0, 2.9Hz, 1H), 7.75-7.64 (m, 3H), 7.63-7.56 (m, 1H), 7.51-7.45 (m, 1H), 7.40-7.34(m, 3H), 7.17 (s, 1H), 7.08 (s, 1H), 6.06 (s, 2H) 13 C NMR (100 MHz, CDCl3) δ 149.7, 148.5, 142.2 (d, J = 20.7 Hz), 136.4 (d, J = 22.4 Hz), 133.6 (d, J = 1.9 Hz), 133.4 (d, J = 2.3 Hz), 133.1 (d, J =106.9 Hz), 132.0 (d, J = 2.9 Hz), 131.5 (d, J = 103.5 Hz), 131.1 (d, J = 11.0Hz), 130.8 (d, J = 12.7 Hz), 130.2 (d, J = 10.1 Hz), 129.8 (d, J = 9.5 Hz),129.1 (d, J = 11.2 Hz), 128.9 (d, J = 109.3 Hz), 128.6 (d, J = 12.7 Hz), 121.1 (d, J = 10.1 Hz), 119.2 (d, J = 10.2 Hz), 105.1, 104.5, 101.6; 31P NMR (162 MHz, CDCl3) δ 33.1; HRMS (ESI) Calcd for C 23 H 16 O3P [M + H] + 371.0831, found 371.0843.

[0058] Example 7

[0059] The bicyclic olefin compound was 1,4-epoxy-1,4-dihydroanthracene, used in an amount of 0.4 mmol; the secondary phosphine oxide compound was diphenylphosphine oxide, used in an amount of 0.2 mmol; the catalyst Co(dmgH)₂pyCl was used in an amount of 10 mol% of the molar amount of 1,4-epoxy-1,4-dihydroanthracene; and the organic base 4-dimethylaminopyridine was used in an amount of 30 mol% of the molar amount of 1,4-epoxy-1,4-dihydroanthracene. The final product was: 5-phenylbenzo[ b Naphthalene[2,3- f Phosphanin-5-oxide, chemical formula as follows:

[0060] Yield: Method A: 73%; Method B: 86%.

[0061] Yellow solid, mp 203.4-204.9 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.48 (s, 1H), 8.44 (d, J = 11.9 Hz, 1H), 8.41 (s, 1H), 8.38 (d, J = 2.9 Hz, 1H), 8.07 (dd, J = 8.0, 2.9 Hz, 1H), 8.00(dd, J = 11.8, 8.2 Hz, 2H), 7.78 (dd, J = 9.7, 7.5 Hz, 1H), 7.73 (d, J = 7.5Hz, 1H), 7.71-7.64 (m, 2H), 7.55-7.47 (m, 3H), 7.46-7.38 (m, J = 7.5, 3.3 Hz, 3H); 13 C NMR (100 MHz, CDCl3) δ 142.2 (d, J C-P = 19.6 Hz), 135.9 (d, J C-P =22.6 Hz), 133.54 (d, J C-P= 2.2 Hz), 133.49 (d, J C-P = 106.0 Hz), 133.3, 133.1(d, J C-P = 9.2 Hz), 132.7 (d, J C-P = 1.6 Hz), 132.3, 132.1 (d, J C-P = 3.0 Hz),131.2, 131.1, 130.6 (d, J C-P = 81.9 Hz), 130.0 (d, J C-P = 9.3 Hz), 129.6 (d,J C-P = 11.2 Hz), 128.7, 128.6, 128.5 (d, J C-P = 5.4 Hz), 128.1, 127.3, 126.8,126.2, 121.7 (d, J C-P = 9.8 Hz), 120.0 (d, J C-P = 9.4 Hz); 31 P NMR (162 MHz, CDCl3) δ 32.3; HRMS (ESI) Calcd for C 26 H 17 OPNa [M +Na] + 399.0909, found 409.0973.

[0062] Example 8

[0063] The bicyclic olefin compound was 1,4-epoxy-1,4-dihydronaphthalene, used in an amount of 0.4 mmol; the secondary phosphine oxide compound was bis([1,1'-biphenyl]-4-yl)phosphine oxide, used in an amount of 0.2 mmol; the catalyst Co(dmgH)2pyCl was used in an amount of 10 mol% of the molar amount of 1,4-epoxy-1,4-dihydronaphthalene; and the organic base 4-dimethylaminopyridine was used in an amount of 30 mol% of the molar amount of 1,4-epoxy-1,4-dihydronaphthalene. The final product was: 5-([1,1'-biphenyl]-4-yl)-2-phenyldibenzo[ b,f Phosphanin-5-oxide, chemical formula as follows:

[0064] Yield: Method A: 72%; Method B: 82%.

[0065] Yellow solid, mp 253.0-254.8 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.35-8.27 (m, 2H), 8.20 (s, 1H), 7.94 (d, J= 8.2 Hz, 1H), 7.86 (t, J = 8.2 Hz, 2H), 7.80 (d, J = 8.0 Hz, 1H), 7.77 (d, J= 8.0 Hz, 1H), 7.71 (d, J = 7.6 Hz, 2H), 7.63 (t, J = 9.1 Hz, 4H), 7.54 (d, J= 8.8 Hz, 4H), 7.51 (s, 1H), 7.47-7.42 (m, 3H), 7.37 (d, J = 7.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 146.7 (d, J C-P = 2.2 Hz), 145.1 (d, J C-P =2.9 Hz), 142.8 (d, J C-P = 20.6 Hz), 140.0 (d, J C-P = 15.9 Hz), 137.2 (d, J C-P =22.3 Hz), 135.8, 133.6 (d, J C-P = 12.2 Hz), 131.9 (d, J C-P = 9.7 Hz), 131.9 (d,J C-P = 109.3 Hz), 131.7 (d, J C-P = 11.3 Hz), 130.4 (d, J C-P = 9.6 Hz), 130.1 (d,J C-P = 109.7 Hz), 129.5 (d, J C-P = 98.3 Hz), 129.3, 128.9 (d, J C-P = 12.2 Hz),128.9, 128.7, 128.6, 128.4, 128.1, 127.5, 127.43, 127.38, 127.33, 127.26,127.2; 31P NMR (162 MHz, CDCl3) δ 32.4; HRMS (ESI) Calcd for C 34 H 24 OP [M + H] + 479.1559, found 479.1563.

[0066] Example 9

[0067] The bicyclic olefin compound was 1,4-epoxy-1,4-dihydroanthracene, used in an amount of 0.4 mmol; the secondary phosphine oxide compound was bis(4-methoxyphenyl)phosphine oxide, used in an amount of 0.2 mmol; the catalyst Co(dmgH)₂pyCl was used in an amount of 10 mol% of the molar amount of 1,4-epoxy-1,4-dihydroanthracene; and the organic base 4-dimethylaminopyridine was used in an amount of 30 mol% of the molar amount of 1,4-epoxy-1,4-dihydroanthracene. The final product was: 2-methoxy-5-(4-methoxyphenyl)benzo[ b Naphtho[2,3-] f Phosphanin-5-oxide, chemical formula as follows:

[0068] Yield: Method B: 71%.

[0069] Yellow solid, mp 239.8-240.4 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.46 (s, 1H), 8.38 (s, 1H), 8.37 (d, J =10.8 Hz, 1H), 8.32 (s, 1H), 7.99 (t, J = 10.1 Hz, 2H), 7.71-7.58 (m, 3H),7.56-7.45 (m, 3H), 6.96 (d, J = 8.5 Hz, 1H), 6.91 (dd, J = 8.3, 3.3 Hz, 2H),3.98 (s, 3H), 3.80 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 164.1 (d, J = 2.3 Hz), 162.6 (d, J = 3.0Hz), 144.5 (d, J = 21.3 Hz), 135.6 (d, J = 22.2 Hz), 133.1, 133.0 (d, J =12.4 Hz), 132.6 (d, J = 1.1 Hz), 132.4 (d, J = 9.2 Hz), 132.2, 132.1 (d, J =107.4 Hz), 131.3, 131.2 131.0, 128.4 (d, J = 10.5 Hz), 128.1, 127.2, 126.7,126.1, 125.3 (d, J = 112.6 Hz), 122.8 (d, J = 112.8 Hz), 119.9 (d, J = 9.2Hz), 116.0 (d, J = 12.1 Hz), 114.3 (d, J = 13.8 Hz), 106.4 (d, J = 10.7 Hz),55.6, 55.3; 31 P NMR (162 MHz, CDCl3) δ 31.1; HRMS (ESI) Calcd for C 28 H 21 OP [M + H] + 437.1301, found 437.1310.

[0070] Example 10

[0071] The bicyclic olefin compound was 1,4-epoxy-1,4-dihydroanthracene, used in an amount of 0.4 mmol; the secondary phosphine oxide compound was bis(4-tert-butylphenyl)phosphine oxide, used in an amount of 0.2 mmol; the catalyst Co(dmgH)₂pyCl was used in an amount of 10 mol% of the molar amount of 1,4-epoxy-1,4-dihydroanthracene; and the organic base 4-dimethylaminopyridine was used in an amount of 30 mol% of the molar amount of 1,4-epoxy-1,4-dihydroanthracene. The final product was: 2-(tert-butyl)-5-(4-(tert-butyl)phenyl)benzo[ b Naphthalene[2,3- f Phosphanin-5-oxide, chemical formula as follows:

[0072] Yield: Method B: 72%.

[0073] Yellow solid, mp 290.1-290.9 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.47 (s, 1H), 8.40 (t, J = 10.4 Hz, 3H), 8.07 (d, J = 2.7 Hz, 1H), 7.97 (dd, J = 14.5, 8.1 Hz, 2H), 7.72 (t, J = 8.7Hz, 1H), 7.65 (dd, J = 12.9, 8.0 Hz, 2H), 7.56-7.42 (m, 3H), 7.41 (dd, J =8.4, 2.8 Hz, 2H), 1.45 (d, J = 1.9 Hz, 9H), 1.27 (s, 9H); 13 C NMR (100 MHz, CDCl3) δ 157.2 (d, J = 2.2 Hz), 155.5 (d, J = 3.0Hz), 142.2 (d, J = 19.7 Hz), 136.3 (d, J = 22.5 Hz), 133.2, 132.8 (d, J =11.2 Hz), 132.8, 132.2, 131.8 (d, J = 95.1 Hz), 131.1 (d, J = 12.8 Hz), 131.1(d, J = 11.3 Hz), 129.7 (d, J = 110.8 Hz), 129.6 (d, J = 9.6 Hz), 128.4 (d, J= 4.7 Hz), 128.1, 128.0, 127.2 (d, J = 11.3 Hz), 127.1, 126. 7, 126.1, 125.7 (d, J = 12.8 Hz), 119.5 (d, J = 9.4 Hz), 118.3 (d, J = 10.0 Hz), 35.4, 34.9,31.2, 31.0; 31 P NMR (162 MHz, CDCl3) δ 31.8; HRMS (ESI) Calcd for C 34 H 33 OP [M + H] + 489.2342, found 489.2350. Application Example 1: Photophysical Property Testing Photophysical property tests were performed on some embodiments of this application. The results showed that the compound of the present invention (taking Example 5 as an example) exhibits clear fluorescence activity in dichloromethane solution, with a fluorescence quantum yield of 39.8%. Combined with its high fluorescence quantum yield of 11688 cm⁻¹... -1 With its extremely large Stokes shift, this compound exhibits unique advantages: although its absolute quantum yield still has room for improvement, the large Stokes shift can effectively avoid the concentration quenching and self-absorption effects common in solid-state thin films, thus ensuring that the final device has high light output efficiency. Therefore, this compound still has important application value in the field of OLEDs.

[0074] The compounds of this invention (as shown in Examples 6, 9, and 10) exhibit characteristic fluorescence emission in dichloromethane solution. Their most representative characteristic is fluorescence emission above 10,000 cm⁻¹. -1 The molecule exhibits a large Stokes shift. This characteristic indicates that the molecule undergoes significant structural relaxation or intramolecular charge transfer after excitation. For OLED applications, such a large Stokes shift is an extremely valuable property, ensuring that the emitted light and absorption spectra of the device are almost completely separated, fundamentally eliminating self-absorption and thus potentially achieving extremely high color purity and device efficiency.

[0075] Application Example 2: Preparation and Application of Trivalent Phosphine Compounds Under an argon atmosphere, 5-phenyldibenzo[3-]O-2-methyl[2-ethylhexyl ... b,f Phosphanin-5-oxide (130.4 mg, 0.4 mmol) and toluene (10 mL) were added sequentially. HSi(OEt)3 (265.9 mg, 1.6 mmol) and Ti(O) were then added. i Pr)4 (34.1 mg, 0.12 mmol). The reaction system was stirred at 120 °C for half an hour. After removing volatiles under reduced pressure, the crude product was purified by silica gel column chromatography (PE / DCM = 10 / 1).

[0076] The final product obtained is: 5-Phenylacetyl-5H-dibenzo[ b,f Phosphorus Indene

[0077] White solid (115.3 mg, 93% yield); mp 109.8–111.6 °C; 1H NMR (400 MHz, CDCl3) δ 8.38 (s, 1H), 8.18 (d, J = 5.7 Hz, 1H), 8.10 (d, J = 7.8 Hz, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.72(t, J = 6.4 Hz, 1H), 7.54-7.44 (m, 3H), 7.40-7.30 (m, 3H), 7.22 (q, J = 7.2,5.4 Hz, 3H); 13 C NMR (100 MHz, CDCl3) δ 143.4 (d, J = 2.1 Hz), 142.8 (d, J = 3.5Hz), 141.5 (d, J = 1.9 Hz), 140.5 (d, J = 3.4 Hz), 137.3 (d, J = 20.3 Hz), 133.7, 133.2 (d, J = 8.0 Hz), 132.6 (d, J = 20.1 Hz), 130.8 (d, J = 1.6 Hz), 130.6 (d, J = 2.9 Hz), 129.2, 128.9, 128.6 (d, J = 7.5 Hz), 128.3, 128.2 (d,J = 7.5 Hz), 128.0, 126.5, 126.0, 121.8, 119.7; 31 P NMR (162 MHz, CDCl3) δ -11.9; HRMS (ESI) Calcd for C 22 H 16 P [M + H] + 311.0984, found 311.0990. Add [Au(SMe2)Cl] (0.2 mmol) and 5-phenyl-5H-dibenzo[] to a solution in 5 mL of dichloromethane. b,f Phosphadinium (0.24 mmol). The reaction mixture was stirred at room temperature for 3 hours. The mixture was then concentrated to a minimum, the product precipitated, and washed three times with 10 mL of pentane.

[0078] The final product obtained is:

[0079] Orange solid (81.3 mg, 75% yield); 1 H NMR (400 MHz, CDCl3) δ 8.34 (d, J = 2.2 Hz, 1H), 8.21 (d, J = 11.9Hz, 1H), 8.08 (dd, J = 7.8, 2.3 Hz, 1H), 7.96 (d, J = 8.2 Hz, 1H), 7.82 (d, J= 8.1 Hz, 1H), 7.70 (dd, J = 10.3, 7.6 Hz, 1H), 7.65 (t, J = 7.6 Hz, 1H),7.61-7.50 (m, 4H), 7.50-7.40 (m, 2H), 7.40-7.31 (m, 2H); 13 C NMR (101 MHz, CDCl3) δ 143.1 (d, J = 11.3 Hz), 138.9 (d, J = 13.1Hz), 135.1 (d, J = 1.7 Hz), 133.7 (d, J = 15.2 Hz), 133.2 (d, J = 9.6 Hz),133.1 (d, J = 14.4 Hz), 132.9 (d, J = 86.5 Hz), 132.7 (d, J = 2.1 Hz), 132.5(d, J = 3.0 Hz), 131.4 (d, J = 14.4 Hz), 130.1 (d, J = 99.9 Hz), 129.6, 129.5(d, J = 91.7 Hz), 129.4, 129.3, 128.7, 128.6 (d, J = 10.3 Hz), 127.3, 122.2(d, J = 7.1 Hz), 120.9 (d, J = 7.0 Hz); 31 P NMR (162 MHz, CDCl3) δ 23.74; HRMS (ESI) Calcd for C 22 H 15 AuClP [M -Cl] + 507.0577, found 507.0585。

Claims

1. A method for preparing a large π-conjugated phosphorus heterocyclic compound, characterized in that, Includes the following steps: S1, under an inert atmosphere, using a cobalt oxime complex as a catalyst, in the presence of an organic base and under visible light irradiation, a dicyclic olefin compound and a secondary phosphine oxide compound undergo a dehydrophosphine radical addition / cyclization reaction in an organic solvent to generate a phosphorus heterocyclic intermediate; S2, the phosphorus heterocyclic intermediate obtained in S1 is heated under reflux in acid to carry out deoxyaromatization reaction. After the reaction is completed, it is cooled to room temperature, separated by dichloromethane extraction, dried with magnesium sulfate, and separated by silica gel column chromatography to obtain the large π-conjugated phosphorus heterocyclic compound.

2. The method for preparing a large π-conjugated phosphorus heterocyclic compound according to claim 1, characterized in that, Step S2 can be replaced by: separating the phosphorus heterocyclic intermediate obtained in S1 by silica gel column chromatography, heating the separated product under reflux in acid for deoxyaromatization, cooling to room temperature after the reaction is completed, separating by dichloromethane extraction, drying with magnesium sulfate, and separating by silica gel column chromatography to obtain the large π-conjugated phosphorus heterocyclic compound.

3. The method for preparing a large π-conjugated phosphorus heterocyclic compound according to claim 1 or 2, characterized in that, The bicyclic olefin compound in step S1 is 1,4-epoxy-1,4-dihydronaphthalene or a derivative thereof; the secondary phosphine oxide compound is diphenylphosphine oxide or a derivative thereof with electron-donating or electron-withdrawing substituents on its benzene ring; The molar ratio of the bicyclic olefin compound to the secondary phosphine oxide compound is 2:

1.

4. The method for preparing a large π-conjugated phosphorus heterocyclic compound according to claim 3, characterized in that, The derivatives of the 1,4-epoxy-1,4-dihydronaphthalene are 6,7-dimethyl-1,4-epoxy-1,4-dihydronaphthalene, 6,7-dimethoxy-1,4-epoxy-1,4-dihydronaphthalene, 6,7-difluoro-1,4-epoxy-1,4-dihydronaphthalene, 5,8-dimethoxy-1,4-epoxy-1,4-dihydronaphthalene, and 5,8-dihydro-5,8-epoxynaphthalene[2,3- d [1,3]dioxolane, 1,4-epoxy-1,4-dihydroanthracene; The diphenylphosphine oxide derivatives with electron-donating or electron-withdrawing substituents on their benzene rings are one of bis([1,1'-biphenyl]-4-yl)phosphine oxide, bis(4-methoxyphenyl)phosphine oxide, and bis(4-tert-butylphenyl)phosphine oxide.

5. A method for preparing a large π-conjugated phosphorus heterocyclic compound according to claim 1 or 2, characterized in that, The cobalt oxime complex mentioned in step S1 is Co(dmgH)2PyCl, and its amount is 1-10 mol% of the molar amount of the bicyclic olefin compound. The organic base is 4-dimethylaminopyridine, and its amount is 10-50 mol% of the molar amount of the bicyclic olefin compound. The organic solvent is dichloroethane, and the molar ratio of the bicyclic olefin compound to the volume of dichloroethane is 0.4 mmol: 4 mL; The visible light wavelength is 450 nm; the reaction temperature is 25 °C, and the time is 24-72 h.

6. A method for preparing a large π-conjugated phosphorus heterocyclic compound according to claim 1 or 2, characterized in that, The acid mentioned in step S2 is concentrated hydrochloric acid with a concentration of 12N; the volume ratio of the concentrated hydrochloric acid to the organic solvent is 1:

1. The reflux temperature is 80-100℃, and the reaction time is 4-12h.

7. A large π-conjugated phosphorus heterocyclic compound prepared by the method according to any one of claims 1 or 2, characterized in that, The general structural formula of the large π-conjugated phosphorus heterocyclic compound is as follows: ； in: R is monosubstituted or polysubstituted, selected from one of H, F, Cl, Br, C1-C6 straight-chain or branched alkyl, C1-C6 straight-chain or branched alkenyl, C1-C6 straight-chain or branched alkoxy, and when R is polysubstituted, different substituents can form a ring. R 1 It can be monosubstituted or polysubstituted, and is selected from H, phenyl, C1-C6 straight-chain or branched alkyl, and C1-C6 straight-chain or branched alkoxy. Ar is a phenyl or substituted phenyl, wherein the substitution is a phenyl, a C1-C6 straight-chain or branched alkyl, or a C1-C6 straight-chain or branched alkoxy.

8. The application of the large π-conjugated phosphorus heterocyclic compound as described in claim 7 in organic optoelectronic devices, characterized in that, The organic optoelectronic devices include organic light-emitting diodes, fluorescent sensors, and organic solar cells.

9. The use of the large π-conjugated phosphorus heterocyclic compound as described in claim 7 in the preparation of trivalent phosphine compounds.

10. The application according to claim 9, characterized in that, The prepared trivalent phosphine compounds are used to prepare organometallic complexes.

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