Spirofluorene compound and preparation method thereof

Abstract

The invention relates to the technical field of organic synthesis, in particular to a spirofluorene compound and a preparation method thereof. The structural formula of the spirofluorene compound is as shown in formula I in the specification. Wherein R is selected from hydrogen, alkyl, alkoxy, halogen, nitryl and aryl; r'is alkyl; ar is selected from aromatic hydrocarbon and heteroaromatic hydrocarbon. The problems that an existing spirofluorene compound skeleton is poor in modifiability, and a preparation method of the spirofluorene compound is tedious in step, harsh in condition and limited in raw materials are solved.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a spirofluorene compound and its preparation method. Background Technology

[0002] In related technologies, spirofluorene compounds are a class of aromatic molecules with a rigid three-dimensional spirocyclic skeleton. Their structure contains a sp³ hybridized spirocarbon atom connecting two approximately orthogonal aromatic ring planes. This unique structure endows them with excellent morphological stability, high thermal stability, and good photoelectric properties, making them of significant application value in optoelectronic functional materials such as organic light-emitting diodes, perovskite solar cells, and organic field-effect transistors.

[0003] Currently, common spirofluorene compounds include spirodifluorene (SBF), spirofluorene-naphthalene (SFN), spirofluorene-oxanthracene (SFX), and spiroacridine (SAF). However, existing spirofluorene compounds have limited structural diversity, few functional groups available for further modification, and their synthesis methods are usually cumbersome, require harsh reaction conditions, and have unavailable starting materials, thus limiting their expanded applications in optoelectronic materials. Summary of the Invention

[0004] In view of the above problems, the present invention is proposed to provide a spirofluorene compound and its preparation method that overcome or at least partially solve the above problems, aiming to solve the problems of poor modifiability of existing spirofluorene compound skeletons and the problems of cumbersome steps, harsh conditions and limited raw materials in their preparation methods.

[0005] On the one hand, the present invention provides spirofluorene compounds with the structural formula shown in Formula I: Where R, R′, and Ar are each independent; R is selected from hydrogen, alkyl, alkoxy, halogen, nitro, and aryl; R′ is an alkyl group; Ar is selected from aromatic hydrocarbons and heteroaromatic hydrocarbons.

[0006] Optionally, the Ar is an aromatic hydrocarbon selected from benzene, substituted benzene, naphthalene, or anthracene; or The Ar is a heteroaromatic hydrocarbon selected from thiophene, benzothiophene, or benzofuran.

[0007] On the other hand, the present invention also provides a method for preparing the spirofluorene compound, comprising: Compounds II and III were mixed with a catalyst and a solvent under an inert gas atmosphere and then synthesized under light conditions. After the reaction was completed, the spirofluorene compounds were obtained through post-processing. The synthetic route is shown below: .

[0008] Optionally, the molar ratio of compound II to compound III is 1:1.0 to 2.0.

[0009] Optionally, during the reaction, the reaction temperature is 15–80°C and the reaction time is 5–12 hours.

[0010] Optionally, the catalyst is selected from any one of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate), tripyridine ruthenium chloride, and tris[4,4'-bis(tert-butyl)-2,2'-bipyridine]ruthenium hexafluorophosphate(II).

[0011] Optionally, the molar ratio of the catalyst to compound II is 0.010 to 0.025:1.

[0012] Optionally, the solvent is selected from one or more of acetonitrile, dichloromethane, and 1,4-dioxane.

[0013] Optionally, the illumination conditions include: a light source wavelength of 440–460 nm and a light source power of 3–30 W.

[0014] Optionally, the post-processing includes filtration, concentration, and column chromatography purification steps.

[0015] In the spirofluorene compounds and their preparation methods of the present invention, the spirofluorene compounds exhibit novel structures and strong modifiability. Specifically, in the structure of the spirofluorene compounds, various substituents can be attached to the R position, and Ar can be an aromatic or heteroaromatic hydrocarbon. Furthermore, the ester groups attached to the structure can be further modified and transformed, greatly enriching the structural diversity and functional tunability of the spirofluorene compounds. The spirofluorene compounds of the present invention have promising application prospects in the field of organic optoelectronic materials and are suitable as key frameworks for developing novel organic light-emitting diodes (OLEDs), perovskite solar cells, and materials with specific charge transport or photoelectric response functions.

[0016] Furthermore, in the preparation method of spirofluorene compounds of the present invention, a photocatalytic "single-carbon insertion-skeletal recombination" strategy is applied for the first time to the construction of such a skeleton. The synthetic principle of spirofluorene compounds is as follows: under light irradiation, a photocatalyst can be activated to generate excited-state species, which in turn promotes the generation of diazomethyl radicals in compound III. These radicals then undergo radical addition with the olefin moiety in compound II. After cyclopropanization, ring opening, and single-electron transfer, an allyl cation intermediate is obtained, realizing the single-carbon insertion process into the olefin. This allyl cation intermediate further undergoes electrophilic substitution with its own aryl moiety to complete spirocyclization, ultimately realizing the synthesis of spirofluorene compound I.

[0017] The above method has outstanding advantages such as mild reaction conditions, readily available and simple raw materials, wide substrate applicability, high reaction efficiency, and simple operation and post-processing. Specifically, the method is carried out under light irradiation and does not require the use of strong acids or bases; it has good compatibility with various aromatic rings, heteroaromatic rings, and various functional groups; the yield of the target product can reach up to 85%. This provides a general and reliable new route for the efficient and green synthesis of structurally diverse spirofluorene compounds.

[0018] Therefore, those skilled in the art will more readily understand the above and other objects, advantages and features of the present invention from the following detailed description of specific embodiments of the invention in conjunction with the accompanying drawings. Attached Figure Description

[0019] The following sections will describe some specific embodiments of the invention in a detailed manner, by way of example and not limitation, with reference to the accompanying drawings. In the drawings: Figure 1 This is a schematic flowchart illustrating a method for preparing spirofluorene compounds according to an embodiment of the present invention. Detailed Implementation

[0020] This invention provides a spirofluorene compound with the structural formula shown in Formula I: Wherein: R, R′ and Ar are independent; R is selected from hydrogen, alkyl, alkoxy, halogen, nitro, aryl; R′ is alkyl; Ar is selected from aromatic hydrocarbons and heteroaromatic hydrocarbons.

[0021] In this embodiment, the R position can be connected to various substituents, Ar can be an aromatic hydrocarbon or a heteroaromatic hydrocarbon, and the ester groups attached to the structure can be further modified and transformed, expanding and enriching the existing structural frameworks of spirofluorene compounds. The spirofluorene compounds of this invention have promising application prospects in the field of organic optoelectronic materials and are suitable as key frameworks for developing novel organic light-emitting diodes (OLEDs), perovskite solar cells, and materials with specific charge transport or photoelectric response functions.

[0022] In some embodiments of the present invention, Ar is an aromatic hydrocarbon selected from benzene, substituted benzene, naphthalene, or anthracene; or, Ar is a heteroaromatic hydrocarbon selected from thiophene, benzothiophene, or benzofuran. That is, Ar can be a variety of substituted benzene, naphthalene, anthracene, or other aromatic hydrocarbons, or thiophene, benzothiophene, or other heteroaromatic hydrocarbons.

[0023] Among them, aromatic hydrocarbons such as benzene, naphthalene, and anthracene can effectively regulate the degree of conjugation and energy level of molecules, while the introduction of heteroaromatic hydrocarbons such as thiophene and benzofuran can regulate charge transport characteristics and enrich luminescence behavior, thereby broadening the application potential of this compound in optoelectronic devices such as OLEDs and solar cells.

[0024] This invention also provides a method for preparing spirofluorene compounds, the method comprising: mixing compound II and compound III with a catalyst and a solvent under an inert gas atmosphere, and then carrying out a synthesis reaction under light irradiation conditions; after the reaction is completed, post-processing is performed to obtain the spirofluorene compounds.

[0025] The synthetic route is shown below: .

[0026] In this embodiment, the photocatalytic "single-carbon insertion-skeletal recombination" strategy is applied for the first time to the construction of such a skeleton. The synthesis principle of spirofluorene compounds is as follows: under light irradiation, a photocatalyst can be activated to generate excited-state species, which in turn promotes the generation of diazomethyl radicals in compound III. These radicals then undergo radical addition with the olefin moiety in compound II. After cyclopropanation, ring opening, and single-electron transfer, an allyl cation intermediate is obtained, realizing the single-carbon insertion process into the olefin. This allyl cation intermediate further undergoes electrophilic substitution with its own aryl moiety to complete spirocyclization, ultimately achieving the synthesis of spirofluorene compound I.

[0027] The above method has significant advantages, including mild reaction conditions, readily available and simple raw materials, a wide range of applicable substrates, high reaction efficiency, and convenient operation and post-processing. Specifically, this method is carried out under light irradiation and does not require strong acids or bases; it exhibits good compatibility with various aromatic rings, heteroaromatic rings, and functional groups; and the yield of the target product (spirofluorene compounds) can reach up to 85%. This provides a general and reliable new route for the efficient and green synthesis of structurally diverse spirofluorene compounds.

[0028] In some optional embodiments of the present invention, the molar ratio of compound II to compound III is 1:1.0 to 2.0. This ratio range can effectively promote the forward shift of the reaction equilibrium, ensuring high conversion while avoiding waste of raw materials.

[0029] In some optional embodiments of the present invention, the reaction temperature is 15–80°C and the reaction time is 5–12 hours during the synthesis reaction. These mild reaction conditions are easy to implement and control, reducing energy consumption and operational risks.

[0030] In some alternative embodiments of the present invention, the catalyst is selected from any one of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate), ruthenium tripyridine chloride, and tris[4,4'-bis(tert-butyl)-2,2'-bipyridine]ruthenium hexafluorophosphate(II). The selected ruthenium-based complexes exhibit excellent photosensitivity and can efficiently initiate and advance the photocatalytic cycle.

[0031] In some optional embodiments of the present invention, the molar ratio of catalyst to compound II is 0.010 to 0.025:1. This low catalyst loading can significantly reduce production costs while ensuring high catalytic activity.

[0032] In some optional embodiments of the present invention, the solvent is selected from one or more of acetonitrile, dichloromethane, and 1,4-dioxane. The amount of solvent used is sufficient to fully dissolve the raw materials. The selected solvent can fully dissolve the reactants and catalyst, and has good light transmittance and chemical inertness, thereby forming a homogeneous and stable reaction system, ensuring the efficient transfer and utilization of light energy, and creating ideal conditions for the smooth progress of homogeneous photocatalytic reactions.

[0033] In some optional embodiments of the present invention, the illumination conditions include: a light source wavelength of 440–460 nm and a light source power of 3–30 W. This specific range of blue light can precisely excite the catalyst, ensuring the efficient and selective initiation of the free radical reaction.

[0034] In some optional embodiments of the present invention, the post-processing includes filtration, concentration, and column chromatography purification steps. In this embodiment, the post-processing procedure is simple to operate and can efficiently separate and obtain high-purity products (spirofluorene compounds) in high yield.

[0035] In some alternative embodiments of the invention, diatomaceous earth is used for filtration. Using diatomaceous earth filtration allows for the rapid and thorough removal of solid impurities and catalyst residues, simplifying the initial purification steps.

[0036] In some alternative embodiments of the present invention, such as Figure 1 As shown, a method for preparing a spirofluorene compound includes: Step S100: Compound II and Compound III are mixed with the catalyst and solvent under an inert gas atmosphere to obtain a mixed solution; Step S200 involves subjecting the mixed solution to a synthesis reaction under light irradiation. Step S300: Post-processing is performed to obtain spirofluorene compounds.

[0037] Specifically, in step S100, the molar ratio of compound II to compound III is 1:1.0 to 2.0. The catalyst is selected from any one of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate), ruthenium tripyridine chloride, and tris[4,4'-bis(tert-butyl)-2,2'-bipyridine]ruthenium hexafluorophosphate (II). The molar ratio of the catalyst to compound II is 0.010 to 0.025:1. The solvent is selected from one or more of acetonitrile, dichloromethane, and 1,4-dioxane.

[0038] In step S200, the reaction temperature is 15–80°C, and the reaction time is 5–12 hours. The wavelength of the light source is 440–460 nm, and the power of the light source is 3–30 W.

[0039] In step S300, the post-processing sequentially includes filtration, concentration, and column chromatography purification steps.

[0040] In this embodiment, a novel photocatalytic "single-carbon insertion-skeleton recombination" strategy is employed. The reaction involves processes such as radical generation, cyclopropanation, ring opening / insertion, and electrophilic spirocyclization to construct a novel spirofluorene compound skeleton. The preparation method features mild and easily controllable reaction conditions, readily available raw materials, a wide range of applicable substrates, high reaction conversion, and high selectivity and yield in a short time. Furthermore, the post-processing is simple, providing a valuable reference for subsequent research in the field of organic optoelectronic materials.

[0041] The preparation method of this application will be described in detail below with reference to specific embodiments.

[0042] The structural formulas of the spirofluorene compounds in Examples 1 to 9 are shown in Formula I-1: .

[0043] Example 1 The preparation method of the spirofluorene compound shown in Formula I-1 includes the following steps: 0.15 mmol of 9-benzylmethylfluorene, 0.15 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of terpyridine ruthenium chloride are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 15W blue light at 440-460 nm at room temperature. The reaction is stopped after 12 hours. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 18.3 mg of the target product, with a yield of 36%.

[0044] The structural characterization of the spirofluorene compounds shown in Formula I-1 is as follows: mp: 170.5-171.3 ℃ 1 H NMR (400MHz, CDCl3) δ 8.04 (s, 1H), 7.81 (d, J = 7.6 Hz, 2H), 7.57 (d, J = 7.5 Hz, 1H), 7.35 (d, J = 13.9 Hz, 2H), 7.29 (t, J = 7.5 Hz, 1H), 7.12 (t, J = 7.5 Hz, 3H), 6.80(d, J = 7.6 Hz, 2H), 6.63 (d,J = 7.6 Hz, 1H), 3.83 (q, J = 7.1 Hz, 2H), 0.83 (t, J =7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 163.0, 151.1, 144.9, 143.2, 142.7,141.9, 141.5, 128.9, 127.8, 127.7, 127.4, 123.6, 123.1, 122.7, 120.2, 67.3,59.9, 13.6 ppm; HRMS (ESI): m / z calcd for C 24 H 18 NaO2 + [M+Na] + , 361.1199. Found:m / z 361.1199. Example 2 The preparation method of the spirofluorene compound shown in Formula I-1 includes the following steps: 0.15 mmol of 9-benzylmethylene fluorene, 0.15 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 15W blue light at 440–460 nm at room temperature. After 12 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 23.8 mg of the target product, with a yield of 47%. (The structural characterization of this compound is the same as in Example 1.)

[0045] Example 3 The preparation method of the spirofluorene compound shown in Formula I-1 includes the following steps: 0.15 mmol of 9-benzylmethylene fluorene, 0.15 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris[4,4'-bis(tert-butyl)-2,2'-bipyridine]ruthenium(II) hexafluorophosphate are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 15W blue light at 440-460 nm at room temperature. After 12 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 20.3 mg of the target product, with a yield of 40%. (The structural characterization of this compound is the same as in Example 1.)

[0046] Example 4 The preparation method of the spirofluorene compound shown in Formula I-1 includes the following steps: 0.15 mmol of 9-benzylmethylene fluorene, 0.15 mmol of diazoethyl ethyl iodonium salt, and 0.0075 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 15W blue light at 440–460 nm at room temperature. The reaction is stopped after 12 hours. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 24.8 mg of the target product, with a yield of 49%. (The structural characterization of this compound is the same as in Example 1.)

[0047] Example 5 The preparation method of the spirofluorene compound shown in Formula I-1 includes the following steps: 0.15 mmol of 9-benzylmethylene fluorene, 0.15 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of dichloromethane solvent is added, and the mixture is irradiated with 15W blue light at 440–460 nm at room temperature. After 12 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 5.6 mg of the target product, with a yield of 11%. (The structural characterization of this compound is the same as in Example 1.)

[0048] Example 6 The preparation method of the spirofluorene compound shown in Formula I-1 includes the following steps: 0.15 mmol of 9-benzylmethylene fluorene, 0.15 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of 1,4-dioxane solvent is added, and the mixture is irradiated with 15W blue light at 440–460 nm at room temperature. After 12 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 7.6 mg of the target product, with a yield of 15%. (The structural characterization of this compound is the same as in Example 1.)

[0049] Example 7 The preparation method of the spirofluorene compound shown in Formula I-1 includes the following steps: 0.15 mmol of 9-benzylmethylene fluorene, 0.15 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 3W blue light at 440–460 nm at room temperature. After 12 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 15.6 mg of the target product, with a yield of 41%. (The structural characterization of this compound is the same as in Example 1.)

[0050] Example 8 The preparation method of the spirofluorene compound shown in Formula I-1 includes the following steps: 0.15 mmol of 9-benzylmethylfluorene, 0.15 mmol of diazoiodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440–460 nm blue light at room temperature. After 12 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 21.3 mg of the target product, with a yield of 56%. (The structural characterization of this compound is the same as in Example 1.)

[0051] Example 9 The preparation method of the spirofluorene compound shown in Formula I-1 includes the following steps: 0.15 mmol of 9-benzylmethylene fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440–460 nm blue light at room temperature. The reaction is stopped after 5 hours. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 26.7 mg of the target product, with a yield of 70%. (The structural characterization of this compound is the same as in Example 1.)

[0052] Example 10 The structural formulas of spirofluorene compounds are shown in Formula I-2: .

[0053] The preparation method of the spirofluorene compound shown in Formula I-2 includes the following steps: 0.15 mmol of 9-(4-methylenebenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and column chromatography is used to purify 44.9 mg of the target product, with a yield of 85%.

[0054] The structural characterization of the spirofluorene compounds shown in Formula I-2 is as follows: mp: 154.3-155.8 ℃; 1 H NMR (400MHz, CDCl3) δ 8.01 (s, 1H), 7.82 (d, J = 7.6 Hz, 2H), 7.45 (d, J = 7.7 Hz, 1H), 7.35 (t, J = 7.5 Hz, 2H), 7.12 (q, J= 7.3 Hz, 3H), 6.80 (d, J = 7.5 Hz, 2H), 6.44(s, 1H), 3.81 (q, J = 7.1 Hz, 2H), 2.16 (s, 3H), 0.82 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 163.1, 151.3, 145.3, 143.3, 142.6, 140.9, 139.3, 138.9,128.5, 127.7, 127.4, 123.7, 123.3, 122.8, 120.1, 67.0, 59.8, 21.6, 13.6. ppm; HRMS (ESI): m / z calcd for C 25 H 20 NaO2 + [M+Na] + , 375.1356. Found: m / z 375.1356. Example 11 The structural formulas of spirofluorene compounds are shown in Formula I-3: .

[0055] The preparation method of the spirofluorene compound shown in Formula I-3 includes the following steps: 0.15 mmol of 9-(4-tert-butylbenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 49.1 mg of the target product, with a yield of 83%.

[0056] The structural characterization of the spirofluorene compounds shown in Formula I-3 is as follows: mp: 158.3-159.7 ℃; 1 H NMR (400MHz, CDCl3) δ 8.00 (s, 1H), 7.81 (d, J = 7.6 Hz, 2H), 7.49 (d, J = 8.0 Hz, 1H),7.38-7.30 (m, 3H), 7.15-7.07 (m, 2H), 6.80 (d, J= 7.6 Hz, 2H), 6.61 (s, 1H), 3.80 (q, J = 7.1 Hz, 2H), 1.12 (s, 9H), 0.81 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 163.1, 152.6, 151.1, 145.3, 142.9, 142.7, 141.5, 139.0, 127.6,127.3, 124.8, 122.9, 122.8, 120.0, 119.9, 67.3, 59.8, 35.0, 31.3, 13.6 ppm; HRMS (ESI): m / z calcd for C 28 H 26 NaO2 + [M+Na] + , 417.1825. Found: m / z 417.1820. Example 12 The structural formulas of spirofluorene compounds are shown in Formula I-4: .

[0057] The preparation method of the spirofluorene compound shown in Formula I-4 includes the following steps: 0.15 mmol of 9-(4-isopropylbenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. The reaction is stopped after 5 hours. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 45.7 mg of the target product, with a yield of 80%.

[0058] The structural characterization of the spirofluorene compounds shown in Formula I-4 is as follows: mp: 160.4-161.3 ℃; 1 H NMR (400MHz, CDCl3) δ 8.01 (s, 1H), 7.82 (d, J = 7.6 Hz, 2H), 7.49 (d, J = 7.8 Hz, 1H), 7.35 (td, J = 7.5, 1.1 Hz, 2H), 7.18 (dd, J = 7.9, 1.7 Hz, 1H), 7.12 (td, J= 7.5,1.2 Hz, 2H), 6.84-6.77 (m, 2H), 6.47 (d, J = 1.6 Hz, 1H), 3.80 (q, J = 7.1 Hz, 2H), 2.70 (p, J = 6.9 Hz, 1H), 1.07 (d, J = 6.9 Hz, 6H), 0.81 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 163.1, 151.3, 150.4, 145.3, 143.1, 142.7, 141.2,139.4, 127.6, 127.4, 125.6, 123.3, 122.9, 121.5, 120.0, 67.2, 59.8, 34.3,23.9, 13.6. HRMS (ESI): m / z calcd for C 27 H 24 NaO2 + [M+Na] + , 403.1669. Found: m / z403.1669. Example 13 The structural formulas of spirofluorene compounds are shown in Formula I-5: .

[0059] The preparation method of the spirofluorene compound shown in Formula I-5 includes the following steps: 0.15 mmol of 9-(4-ethylbenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and column chromatography is used to purify 46.7 mg of the target product, with a yield of 85%.

[0060] The structural characterization of the spirofluorene compounds shown in Formula I-5 is as follows: mp: 108.5-110.8 ℃; 1 H NMR (400MHz, CDCl3) δ 8.01 (s, 1H), 7.82 (d, J = 7.6 Hz, 2H), 7.48 (d, J= 7.8 Hz, 1H), 7.35 (td, J = 7.5, 1.1 Hz, 2H), 7.17-7.08 (m, 3H), 6.81 (d, J = 7.5 Hz, 2H), 6.45(s, 1H), 3.81 (q, J = 7.1 Hz, 2H), 2.46 (q, J = 7.6 Hz, 2H), 1.05 (t, J = 7.6 Hz, 3H), 0.82 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 163.1, 151.3, 145.7,145.3, 143.2, 142.6, 141.1, 139.2, 127.6, 127.4, 127.3, 123.4, 122.8, 122.7,120.0, 67.1, 59.8, 28.9, 15.4, 13.6 ppm; HRMS (ESI): m / z calcd for C 26 H 22 NaO2 + [M+Na] + , 417.1825. Found: m / z 417.1820. Example 14 The structural formulas of spirofluorene compounds are shown in Formula I-6: .

[0061] The preparation method of the spirofluorene compound shown in Formula I-6 includes the following steps: 0.15 mmol of 9-(4-methoxybenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and column chromatography is used to purify 39.8 mg of the target product, with a yield of 72%.

[0062] The structural characterization of the spirofluorene compounds shown in Formula I-6 is as follows: mp: 132.2-134.1 ℃; 1 H NMR (400MHz, CDCl3) δ 7.99 (s, 1H), 7.81 (d, J= 7.6 Hz, 2H), 7.48 (d, J = 8.3 Hz, 1H), 7.35 (t, J = 7.5 Hz, 2H), 7.17-7.09 (m, 2H), 6.86-6.77 (m, 3H), 6.15 (d, J = 2.3Hz, 1H), 3.81 (q, J = 7.1 Hz, 2H), 3.60 (s, 3H), 0.82 (t, J = 7.1 Hz, 3H); 13 C NMR(101 MHz, CDCl3) δ 163.1, 160.9, 153.4, 145.3, 143.1, 142.6, 139.8, 134.3,127.7, 127.4, 124.4, 122.8, 120.1, 113.7, 108.8, 67.2, 59.7, 55.4, 13.6 ppm; HRMS (ESI): m / z calcd for C 25 H 20 NaO3 + [M+Na] + , 391.1305. Found: m / z 391.1307. Example 15 The structural formulas of spirofluorene compounds are shown in Formula I-7: .

[0063] The preparation method of the spirofluorene compound shown in Formula I-7 includes the following steps: 0.15 mmol of 9-(4-trifluoromethylbenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and column chromatography is used to purify 33.5 mg of the target product, with a yield of 55%.

[0064] The structural characterization of the spirofluorene compounds shown in Formula I-7 is as follows: mp: 92.1-93.2 ℃; 1 H NMR (400MHz, CDCl3): δ 8.02 (s, 1H), 7.84 (d, J = 7.6 Hz, 2H), 7.68 (d,J = 7.9 Hz, 1H), 7.58 (d, J = 8.1 Hz, 1H), 7.39 (td, J = 7.5, 1.1 Hz, 2H), 7.15 (td, J = 7.5, 1.1Hz, 2H), 6.87 (s, 1H), 6.78 (d, J = 7.6 Hz, 2H), 3.84 (q, J = 7.1 Hz, 2H), 0.83(t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3): δ 162.5, 151.4, 144.9, 144.9,143.4, 142.8, 141.4, 130.6 (q, J = 32.3 Hz), 128.2, 127.6, 125.1 (q, J = 4.0 Hz), 124.0 (d, J = 273.7 Hz), 123.6, 122.7, 120.4, 120.0 (q, J = 4.0 Hz), 67.38,60.25, 13.54; 19 F NMR (376 MHz, CDCl3): δ -61.95 (s) ppm; HRMS (ESI): m / z calcdfor C 25 H 17 F3NaO2 + [M+Na] + , 429.1073. Found: m / z 429.1074. Example 16 The structural formulas of spirofluorene compounds are shown in Formula I-8: .

[0065] The preparation method of the spirofluorene compound shown in Formula I-8 includes the following steps: 0.15 mmol of 9-(4-fluorobenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and column chromatography is used to purify 31.0 mg of the target product, with a yield of 58%.

[0066] The structural characterization of the spirofluorene compounds shown in Formula I-8 is as follows: mp: 121.3-122.5 ℃; 1 H NMR (400MHz, CDCl3) δ 7.99 (s, 1H), 7.82 (d, J = 7.6 Hz, 2H), 7.52 (dd, J = 8.3, 5.0 Hz, 1H), 7.37 (td, J = 7.5, 1.1 Hz, 2H), 7.14 (td, J = 7.4, 1.1 Hz, 2H), 6.99 (td, J =9.2, 2.4 Hz, 1H), 6.84-6.77 (m, 2H), 6.34 (dd, J = 8.4, 2.4 Hz, 1H), 3.82 (q, J =7.1 Hz, 2H), 0.82 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 163.5 (d, J =249.9 Hz), 162.7, 153.6 (d, J = 8.4 Hz), 144.3, 142.6, 142.1, 141.9 (d, J = 4.4Hz), 137.3 (d, J = 2.6 Hz), 127.9, 127.5, 124.6 (d, J = 9.1 Hz), 122.67, 120.3,114.9 (d, J = 23.4 Hz), 110.9 (d, J = 23.8 Hz), 67.3, 59.9, 13.6 ppm;19 F NMR (376MHz, CDCl3) δ -111.14. HRMS (ESI): m / z calcd for C 24 H 17 FNaO2 + [M+Na] + , 379.1105.Found: m / z 379.1101. Example 17 The structural formulas of spirofluorene compounds are shown in Formula I-9: .

[0067] The preparation method of the spirofluorene compound shown in Formula I-9 includes the following steps: 0.15 mmol of 9-(4-chlorobenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 36.3 mg of the target product, with a yield of 65%.

[0068] The structural characterization of the spirofluorene compounds shown in Formula I-9 is as follows: mp: 142.1-144.0 ℃; 1 H NMR (400MHz, CDCl3) δ 7.98 (s, 1H), 7.82 (dt, J = 7.7, 1.0 Hz, 2H), 7.49 (d, J = 8.1 Hz, 1H), 7.37 (td, J = 7.5, 1.1 Hz, 2H), 7.27 (dd, J = 8.1, 1.9 Hz, 1H), 7.14 (td, J =7.5, 1.1 Hz, 2H), 6.80 (d, J = 7.6 Hz, 2H), 6.61 (d, J = 1.9 Hz, 1H), 3.82 (q, J =7.1 Hz, 2H), 0.82 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3): δ 162.7, 152.7,144.0, 142.6, 142.4, 141.9, 139.9, 134.9, 128.1, 128.0, 127.6, 124.4, 123.6,122.7, 120.3, 67.2, 60.1, 13.6 ppm; HRMS (ESI): m / z calcd for C 24 H 17 ClNaO2 + [M+Na] + , 395.0809. Found: m / z 395.0811. Example 18 The structural formulas of spirofluorene compounds are shown in Formula I-10: .

[0069] The preparation method of the spirofluorene compound shown in Formula I-10 includes the following steps: 0.15 mmol of 9-(4-bromobenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and column chromatography is used to purify 41.9 mg of the target product, with a yield of 67%.

[0070] The structural characterization of the spirofluorene compounds shown in Formula I-10 is as follows: mp: 146.8-147.5 ℃; 1 H NMR (400MHz, CDCl3) δ 7.97 (s, 1H), 7.82 (d, J = 7.6 Hz, 2H), 7.43 (d, J = 1.2 Hz, 2H), 7.36 (dd, J = 7.6, 1.1 Hz, 2H), 7.14 (td, J = 7.5, 1.1 Hz, 2H), 6.80 (d, J = 7.6Hz, 2H), 6.76 (s, 1H), 3.82 (q, J = 7.1 Hz, 2H), 0.82 (t, J = 7.1 Hz, 3H); 13C NMR(101 MHz, CDCl3) δ 162.66, 152.90, 143.93, 142.61, 142.40, 142.03, 140.39,130.93, 128.06, 127.59, 126.48, 124.72, 123.10, 122.75, 120.33, 67.22, 60.08,13.58 ppm; HRMS (ESI): m / z calcd for C 24 H 17 BrNaO2 + [M+Na] + , 439.0304. Found: m / z439.0308.

[0071] Example 19 The structural formula of spirofluorene compounds is shown in Formula I-11: .

[0072] The preparation method of the spirofluorene compound shown in Formula I-11 includes the following steps: 0.15 mmol of 1-(4-((9H-fluorene-9-ylidene)methyl)phenyl)-1H-pyrazole, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21W, 440-460nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 28.5 mg of the target product, with a yield of 47%.

[0073] The structural characterization of the spirofluorene compounds shown in Formula I-11 is as follows: mp: 146.8-147.5 ℃; 1 H NMR (400MHz, DMSO) δ 8.42 (d, J = 2.6 Hz, 1H), 8.19 (s, 1H), 8.00 (d, J = 7.6 Hz, 2H),7.85 (s, 2H), 7.58 (d, J = 1.7 Hz, 1H), 7.42-7.38 (m, 2H), 7.18-7.14 (m, 2H), 6.95 (s, 1H), 6.80 (d, J = 7.5 Hz, 2H), 6.47-6.40 (m, 1H), 3.80 (q, J= 7.1 Hz, 2H), 0.86 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, DMSO) δ 162.2, 152.9, 144.8,143.4, 142.6, 141.6, 141.2, 140.5, 139.5, 128.4, 128.4, 128.2, 125.7, 122.7,121.2, 118.0, 112.9, 108.6, 67.4, 60.1, 14.1; HRMS (ESI): m / z calcd forC 27 H 20 N2NaO2 + [M+Na] + , 427.1417. Found: m / z 427.1419. Example 20 The structural formula of spirofluorene compounds is shown in Formula I-12: .

[0074] The preparation method of the spirofluorene compound shown in Formula I-12 includes the following steps: 0.15 mmol of 9-([1,1'-biphenyl]-4-methylene)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 31.1 mg of the target product, with a yield of 50%.

[0075] The structure of the compound represented by Formula I-12 is characterized as follows: mp: 152.5-154.5 ℃; 1 H NMR (400 MHz, DMSO) δ 8.20 (s, 1H), 7.98 (d, J = 7.6 Hz, 2H), 7.83 (d, J = 8.1 Hz, 1H), 7.66(d, J = 7.9 Hz, 1H), 7.38 (t, J = 8.1 Hz, 2H), 7.34 (d, J = 8.2 Hz, 2H), 7.29 (t, J =7.2 Hz, 2H), 7.24 (t,J = 7.0 Hz, 1H), 7.14 (t, J = 7.5 Hz, 2H), 6.78 (d, J = 7.5Hz, 2H), 6.64 (s, 1H), 3.79 (q, J = 7.1 Hz, 2H), 0.86 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, DMSO) δ 162.3, 152.1, 145.0, 143.7, 142.6, 141.5, 141.4, 141.1,139.9, 129.4, 128.3, 128.1, 127.0, 125.3, 122.8, 121.1, 120.5, 67.3, 60.0,14.1 ppm; HRMS (ESI): m / z calcd for C 30 H 22 NaO2 + [M+Na] + , 437.1512. Found: m / z437.1514. Example 21 The structural formula of spirofluorene compounds is shown in Formula I-13: .

[0076] The preparation method of the spirofluorene compound shown in Formula I-13 includes the following steps: 0.15 mmol of 9-(3-methylbenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. The reaction is stopped after 5 hours. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 22.2 mg of the target product, with a yield of 42%.

[0077] The structure of the compound shown in Formula I-13 is characterized as follows: mp: 90.2-91.1 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.17 (s, 1H), 7.81 (d, J = 7.6 Hz, 2H), 7.34 (td, J = 7.5, 1.2 Hz, 2H),7.15-7.07 (m, 3H), 7.02 (t,J = 7.5 Hz, 1H), 6.80 (d, J = 7.6 Hz, 2H), 6.44 (d, J =7.4 Hz, 1H), 3.83 (q, J = 7.1 Hz, 2H), 2.59 (s, 3H), 0.82 (t, J = 7.1 Hz, 3H); 13 CNMR (101 MHz, CDCl3) δ 163.2, 151.1, 145.0, 142.6, 141.6, 141.1, 140.5,133.2, 129.1, 128.7, 127.7, 127.4, 122.7, 120.5, 120.1, 67.4, 59.9, 18.6,13.6 ppm; HRMS (ESI): m / z calcd for C 25 H 20 NaO2 + [M+Na] + , 375.1356. Found: m / z375.1358. Example 22 The structural formula of spirofluorene compounds is shown in Formula I-14: .

[0078] The preparation method of the spirofluorene compound shown in Formula I-14 includes the following steps: 0.15 mmol of 9-(3-methoxybenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 27.6 mg of the target product, with a yield of 50%.

[0079] The structure of the compound shown in Formula I-14 is characterized as follows: mp: 208.1-210.1 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.20 (s, 1H), 7.80 (d, J = 7.6 Hz, 2H), 7.34 (td, J = 7.6, 1.2 Hz, 2H),7.16-7.05 (m, 3H), 6.79 (dd, J= 15.0, 7.9 Hz, 3H), 6.23 (d, J = 7.5 Hz, 1H), 3.96 (s, 3H), 3.83 (q, J = 7.1 Hz, 2H), 0.85 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 162.9, 154.6, 153.0, 144.9, 142.6, 139.9, 139.8, 130.6, 130.1,127.7, 127.4, 122.7, 120.2, 115.6, 109.4, 67.6, 59.8, 55.6, 13.6. ppm; HRMS(ESI): m / z calcd for C 25 H 20 NaO3 + [M+Na] + , 391.1305. Found: m / z 395.1308. Example 23 The structural formulas of spirofluorene compounds are shown in Formula I-15: .

[0080] The preparation method of the spirofluorene compound shown in Formula I-15 includes the following steps: 0.15 mmol of 9-(3-fluorobenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 18.7 mg of the target product, with a yield of 35%.

[0081] The structure of the compound shown in Formula I-15 is characterized as follows: mp: 221.8-223.1 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.13 (s, 1H), 7.82 (d, J = 7.6 Hz, 2H), 7.37 (td, J = 7.5, 1.1 Hz, 2H),7.18-7.06 (m, 3H), 6.98 (t, J = 8.7 Hz, 1H), 6.81 (d, J= 7.6 Hz, 2H), 6.42 (d, J =7.5 Hz, 1H), 3.84 (q, J = 7.1 Hz, 2H), 0.86 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3): δ 162.6, 157.1 (d, J = 254.5 Hz), 153.6 (d, J = 4.0 Hz), 144.2, 142.6,141.9, 137.4 (d, J = 1.0 Hz), 130.7 (d, J = 7.0 Hz), 128.7 (d, J = 17.2 Hz), 127.9,127.6, 122.7, 120.3, 119.0 (d, J = 3.0 Hz), 114.3 (d, J = 19.2 Hz), 67.6, 60.1,13.6 ppm; 19 F NMR (376 MHz, CDCl3) δ -118.59; HRMS (ESI): m / z calcd forC 24 H 17 FNaO2 + [M+Na] + , 379.1105. Found: m / z 379.1107. Example 24 The structural formula of spirofluorene compounds is shown in Formula I-16: .

[0082] The preparation method of the spirofluorene compound shown in Formula I-16 includes the following steps: 0.15 mmol of 9-(3-bromobenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 25.2 mg of the target product, with a yield of 40%.

[0083] The structure of the compound shown in Formula I-16 is characterized as follows: mp: 118.4-119.9 ℃;1 H NMR (400 MHz, CDCl3) δ 8.08 (s, 1H), 7.81 (d, J = 7.7 Hz, 2H), 7.42 (dd, J = 8.0, 0.9 Hz, 1H), 7.36 (td, J = 7.5, 1.1 Hz, 2H), 7.14 (td, J = 7.5, 1.1 Hz, 2H), 6.97 (t, J = 7.8Hz, 1H), 6.82 (d, J = 7.6 Hz, 2H), 6.55 (d, J = 7.6 Hz, 1H), 3.85 (q, J = 7.1 Hz, 2H), 0.86 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 162.5, 152.6, 143.9,142.7, 142.6, 141.9, 141.9, 130.9, 130.3, 128.0, 127.6, 122.7, 122.0, 120.3,117.4, 68.3, 60.2, 13.6 ppm; HRMS (ESI): m / z calcd for C 24 H 17 BrNaO2 + [M+Na] + ,439.0304. Found: m / z 439.0305. Example 25 The structural formula of spirofluorene compounds is shown in Formula I-17: .

[0084] The preparation method of the spirofluorene compound shown in Formula I-17 includes the following steps: 0.15 mmol of 9-(3,5-dimethylbenzyl)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 35.2 mg of the target product, with a yield of 64%.

[0085] The structure of the compound shown in Formula I-17 is characterized as follows: mp: 110.6-111.3 ℃; 1 H NMR (400 MHz, CDCl3) δ 7.94 (s, 1H), 7.80 (d, J = 7.6 Hz, 2H), 7.34 (t, J = 7.5 Hz, 2H), 7.24(s, 1H), 7.12 (t, J = 6.9 Hz, 2H), 6.82 (d, J = 7.6 Hz, 2H), 6.75 (s, 1H), 3.79(q, J = 7.1 Hz, 2H), 2.36 (s, 3H), 1.25 (s, 4H), 0.83 (t, J = 7.1 Hz, 3H); 13 C NMR(101 MHz, CDCl3) δ 162.9, 145.4, 143.3, 143.2, 143.1, 142.3, 142.2, 137.7,133.9, 131.7, 127.6, 127.3, 122.7, 121.8, 119.9, 67.0, 59.8, 21.2, 16.4, 13.6ppm; HRMS (ESI): m / z calcd for C 26 H 22 NaO2 + [M+Na] + , 389.1512. Found: m / z389.1513. Example 26 The structural formula of spirofluorene compounds is shown in Formula I-18: .

[0086] The preparation method of the spirofluorene compound shown in Formula I-18 includes the following steps: 0.15 mmol of 9-(naphthyl-1-methylene)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 28.0 mg of the target product, with a yield of 48%.

[0087] The structure of the compound shown in Formula I-18 is characterized as follows: mp: 165.3-166.3 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.63 (s, 1H), 8.27 (d, J = 8.3 Hz, 1H), 7.85 (d, J = 7.8 Hz, 3H), 7.65(t, J = 8.3 Hz, 2H), 7.56-7.51 (m, 1H), 7.37 (t, J = 7.5 Hz, 2H), 7.11 (t, J = 7.5Hz, 2H), 6.76 (dd, J = 14.2, 8.0 Hz, 3H), 3.88 (q, J = 7.1 Hz, 2H), 0.87 (t, J =7.1 Hz, 4H); 13 C NMR (101 MHz, CDCl3) δ 162.9, 149.8, 143.8, 142.9, 141.7,140.8, 133.2, 129.7, 128.8, 128.6, 127.8, 127.5, 126.9, 125.9, 123.6, 122.7,121.1, 120.3, 59.9, 13.7 ppm; HRMS (ESI): m / z calcd for C 28 H 20 NaO2 + [M+Na] + ,411.1356. Found: m / z 411.1357. Example 27 The structural formula of spirofluorene compounds is shown in Formula I-19: .

[0088] The preparation method of the spirofluorene compound shown in Formula I-19 includes the following steps: 0.15 mmol of 9-(naphthyl-2-methylene)-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and column chromatography is used to purify 35.0 mg of the target product, with a yield of 60%.

[0089] The structure of the compound shown in Formula I-19 is characterized as follows: mp: 148.6-149.1 ℃; 1 H NMR (400 MHz, DMSO) δ 8.27 (s, 1H), 8.10 (d, J = 7.6 Hz, 2H), 8.01 (d, J = 8.4 Hz, 1H), 7.97-7.89 (m, 2H), 7.41 (t, J = 7.5 Hz, 2H), 7.31 (t, J = 7.6 Hz, 1H), 7.07 (dt, J =15.3, 7.5 Hz, 3H), 6.65 (d, J = 7.6 Hz, 2H), 6.58 (d, J = 8.5 Hz, 1H), 3.77 (q, J =7.1 Hz, 2H), 0.86 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, DMSO) δ 162.1, 145.5,145.1, 144.0, 143.0, 142.7, 140.2, 134.0, 129.8, 129.5, 128.4, 128.2, 127.9,127.2, 126.3, 122.8, 122.5, 122.4, 121.5, 67.9, 59.9, 14.1 ppm; HRMS (ESI):m / z calcd for C 28 H 20 NaO2 + [M+Na] + , 411.1356. Found: m / z 411.1357. Example 28 The structural formulas of spirofluorene compounds are shown in Formula I-20: .

[0090] The preparation method of the spirofluorene compound shown in Formula I-20 includes the following steps: 0.15 mmol of 9-((9H-fluorene-9-ylidene)methyl)phenanthrene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 32.9 mg of the target product, with a yield of 50%.

[0091] The structure of the compound shown in Formula I-20 is characterized as follows: mp: 223.2-224.1 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.75 (d, J = 7.9 Hz, 1H), 8.65 (d, J = 7.8 Hz, 2H), 8.43-8.34 (m, 1H), 7.96 (d, J = 7.6 Hz, 2H), 7.80-7.72 (m, 2H), 7.48-7.36 (m, 3H), 7.12-7.05 (m,3H), 6.76 (t, J = 7.6 Hz, 3H), 3.86 (q, J = 7.1 Hz, 2H), 0.89 (t, J = 7.1 Hz, 4H); 13 C NMR (101 MHz, CDCl3) δ 162.7, 144.8, 144.8, 143.5, 142.9, 140.3, 137.6,131.1, 131.0, 127.9, 127.6, 127.4, 127.4, 127.2, 127.1, 126.9, 126.5, 124.5,124.1, 123.4, 123.2, 123.0, 120.7, 69.1, 59.9, 13.7 ppm; HRMS (ESI): m / zcalcd for C 32 H 22 NaO2 + [M+Na] + , 461.1512. Found: m / z 461.1513. Example 29 The structural formula of spirofluorene compounds is shown in Formula I-21: .

[0092] The preparation method of the spirofluorene compound shown in Formula I-21 includes the following steps: 0.15 mmol of 3-((9H-fluorene-9-ylidene)methyl)thiophene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 19.1 mg of the target product, with a yield of 37%.

[0093] The structure of the compound shown in Formula I-21 is characterized as follows: mp: 153.4-154.5 ℃; 1 H NMR (400 MHz, CDCl3) δ 7.97 (s, 1H), 7.79 (dt, J = 7.5, 0.9 Hz, 2H), 7.39-7.33 (m, 3H), 7.18-7.11 (m, 3H), 6.85 (d, J = 7.6 Hz, 2H), 3.79 (q, J = 7.1 Hz, 2H), 0.81 (t, J = 7.1Hz, 3H); 13 C NMR (101 MHz, CDCl3): δ 162.2, 154.5, 145.9, 144.5, 144.4, 142.3,138.8, 130.0, 128.0, 127.5, 122.7, 120.3, 120.1, 65.3, 59.7, 13.6 ppm; HRMS(ESI): m / z calcd for C 22 H 16 NaO2S + [M+Na] + , 367.0763. Found: m / z 367.0765. Example 30 The structural formula of spirofluorene compounds is shown in Formula I-22: .

[0094] The preparation method of the spirofluorene compound shown in Formula I-22 includes the following steps: 0.15 mmol of 3-((9H-fluorene-9-ylidene)methyl)benzo[b]thiophene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21W, 440-460nm blue light at room temperature. The reaction is stopped after 5 hours. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 30.7 mg of the target product, with a yield of 52%.

[0095] The structure of the compound shown in Formula I-22 is characterized as follows: mp: 144.8-146.0 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.23 ​​(s, 1H), 7.96 (d, J = 7.9 Hz, 1H), 7.82 (d, J = 7.6 Hz, 2H), 7.75 (d, J = 8.1 Hz, 1H), 7.47 (t, J = 7.6 Hz, 1H), 7.41-7.30 (m, 3H), 7.17-7.13 (m,2H), 6.88 (d, J = 7.6 Hz, 2H), 3.83 (q, J = 7.1 Hz, 2H), 0.84 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 162.1, 156.6, 145.1, 143.9, 143.7, 142.5, 140.9,137.5, 132.3, 128.3, 127.7, 125.1, 124.4, 123.9, 122.8, 121.7, 120.4, 66.3,59.8, 13.7 ppm; HRMS (ESI): m / z calcd for C 26 H 18 NaO2S + [M+Na] + , 417.0920. Found:m / z 417.0924. Example 31 The structural formula of spirofluorene compounds is shown in Formula I-23: .

[0096] The preparation method of the spirofluorene compound shown in Formula I-23 includes the following steps: 0.15 mmol of 9-benzyl-2-bromo-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. The reaction is stopped after 5 hours. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and column chromatography is used to purify 53.2 mg of the target product, with a yield of 85%.

[0097] The structure of the compound shown in Formula I-23 is characterized as follows: mp: 131.2-132.6 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.04 (s, 1H), 7.78 (d, J = 7.6 Hz, 1H), 7.67 (d, J = 8.1 Hz, 1H), 7.58 (d, J = 7.6 Hz, 1H), 7.47 (dd, J = 8.1, 1.8 Hz, 1H), 7.38-7.30 (m, 2H), 7.19-7.11(m, 2H), 6.92 (d, J = 1.8 Hz, 1H), 6.78 (d, J = 7.6 Hz, 1H), 6.63 (d, J = 7.6 Hz, 1H), 3.86 (q, J = 7.1 Hz, 2H), 0.88 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ162.7, 150.2, 147.1, 144.7, 143.5, 141.6, 141.5, 141.4, 141.3, 130.9, 129.1,127.9, 127.9, 127.9, 126.0, 123.7, 123.1, 122.8, 121.4, 121.0, 120.3, 66.9,60.1, 13.6 ppm; HRMS (ESI): m / z calcd for C 24 H 18 BrO2 + [M+H] +, 417.0485. Found:m / z 417.0487. Example 32 The structural formula of spirofluorene compounds is shown in Formula I-24: .

[0098] The preparation method of the spirofluorene compound shown in Formula I-24 includes the following steps: 0.15 mmol of 9-benzyl-2-nitro-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. The reaction is stopped after 5 hours. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 32.8 mg of the target product, with a yield of 57%.

[0099] The structure of the compound represented by Formula I-24 is characterized as follows: mp: 115.5-117.2 ℃; 1 H NMR (400 MHz, DMSO) δ 8.35-8.26 (m, 2H), 8.24 (s, 1H), 8.18 (d, J = 7.6 Hz, 1H), 7.78 (d, J =7.6 Hz, 1H), 7.52-7.45 (m, 2H), 7.40 (t, J = 8.1 Hz, 1H), 7.30 (t, J = 7.5 Hz, 1H), 7.19 (t, J = 7.0 Hz, 1H), 6.83 (d, J = 7.6 Hz, 1H), 6.55 (d, J = 7.6 Hz, 1H), 3.80 (q, J = 7.1 Hz, 2H), 0.86 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, DMSO) δ166.9, 154.1, 152.0, 151.5, 149.9, 149.9, 146.6, 145.1, 144.5, 135.1, 134.6,133.7, 133.6, 129.9, 129.4, 127.8, 127.7, 127.6, 126.6, 122.3, 71.7, 65.0,18.8 ppm; HRMS (ESI): m / z calcd for C 24 H 17 NNaO4 + [M+Na] + , 406.1050. Found: m / z406.1056. Example 33 The structural formulas of spirofluorene compounds are shown in Formula I-25: .

[0100] The preparation method of the spirofluorene compound shown in Formula I-25 includes the following steps: 0.15 mmol of 9-benzyl-2,7-dichloro-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 47.7 mg of the target product, with a yield of 78%.

[0101] The structure of the compound shown in Formula I-25 is characterized as follows: mp: 122.5-123.2 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.04 (s, 1H), 7.69 (d, J = 8.2 Hz, 2H), 7.59 (d, J = 7.6 Hz, 1H), 7.38-7.30 (m, 3H), 7.18 (td, J = 7.6, 1.1 Hz, 1H), 6.76 (d, J = 1.9 Hz, 2H), 6.63 (d, J = 8.4 Hz, 1H), 3.90 (q, J = 7.1 Hz, 2H), 0.93 (t, J = 7.1 Hz, 3H);13 C NMR (101MHz, CDCl3) δ 162.5, 149.5, 146.7, 143.8, 141.4, 140.7, 140.1, 133.4, 129.3,128.3, 128.2, 123.9, 123.2, 123.1, 121.1, 66.7, 60.3, 13.7 ppm; HRMS (ESI):m / z calcd for C 24 H 16 Cl2NaO4 + [M+Na] + , 429.0420. Found: m / z 429.0421. Example 34 The structural formula of spirofluorene compounds is shown in Formula I-26: .

[0102] The preparation method of the spirofluorene compound shown in Formula I-26 includes the following steps: 0.15 mmol of 9-benzyl-2,7-dibromo-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21W blue light at 440-460 nm at room temperature. The reaction is stopped after 5 hours. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 59.5 mg of the target product, with a yield of 80%.

[0103] The structure of the compound shown in Formula I-26 is characterized as follows: mp: 268.1-270.2 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.04 (s, 1H), 7.65 (d, J = 8.1 Hz, 2H), 7.59 (d, J = 7.6 Hz, 1H), 7.48 (dd, J = 8.1, 1.8 Hz, 2H), 7.35 (t, J = 7.6 Hz, 1H), 7.18 (t, J = 7.6 Hz, 1H), 6.91(d, J = 1.8 Hz, 2H), 6.63 (d, J = 7.6 Hz, 1H), 3.90 (q, J = 7.1 Hz, 2H), 0.93 (t,J =7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 162.5, 149.4, 146.8, 143.9, 141.4,140.7, 140.5, 131.1, 129.3, 128.3, 126.1, 123.9, 123.2, 121.5, 66.7, 60.3,13.7 ppm; HRMS (ESI): m / z calcd for C 24 H 16 Br2NaO4 + [M+Na] + , 516.9409. Found: m / z516.9414. Example 35 The structural formula of spirofluorene compounds is shown in Formula I-27: .

[0104] The preparation method of the spirofluorene compound shown in Formula I-27 includes the following steps: 0.15 mmol of 9-benzyl-2,7-diiodo-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21W, 440-460nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 53.0 mg of the target product, with a yield of 60%.

[0105] The structure of the compound shown in Formula I-27 is characterized as follows: mp: 108.5-109.2 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.03 (s, 1H), 7.68 (dd, J = 8.0, 1.6 Hz, 2H), 7.59 (d, J = 7.6 Hz, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.35 (td, J = 7.5, 1.1 Hz, 1H), 7.18 (td, J = 7.5, 1.1Hz, 1H), 7.09 (d, J = 1.6 Hz, 2H), 6.63 (d, J = 7.6 Hz, 1H), 3.90 (q,J = 7.1 Hz, 2H), 0.93 (t, J = 7.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 162.5, 149.4, 146.7,143.8, 141.4, 141.3, 140.6, 136.9, 131.8, 129.3, 128.3, 123.9, 123.2, 121.9,93.1, 66.5, 60.3, 13.7 ppm; HRMS (ESI): m / z calcd for C 24 H 17 I₂O₄ + [M+H] + ,590.9312. Found: m / z 590.9310. Example 36 The structural formula of spirofluorene compounds is shown in Formula I-28: .

[0106] The preparation method of the spirofluorene compound shown in Formula I-28 includes the following steps: 0.15 mmol of 9-benzyl-2,7-di-tert-butyl-9H-fluorene, 0.20 mmol of diazoethyl ethyl iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 52.7 mg of the target product, with a yield of 78%.

[0107] The structure of the compound shown in Formula I-28 is characterized as follows: mp: 168.2-169.2 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.05 (s, 1H), 7.67 (d, J = 8.0 Hz, 2H), 7.58 (d, J = 7.5 Hz, 1H), 7.35(d, J = 8.1 Hz, 2H), 7.29 (t, J = 7.5 Hz, 1H), 7.11 (t, J = 7.0 Hz, 1H), 6.72 (s,2H), 6.64 (d, J = 7.6 Hz, 1H), 3.79 (q,J = 7.1 Hz, 2H), 1.19 (s, 18H), 0.73 (t, J = 7.0 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 163.3, 151.8, 150.3, 144.9, 143.2,142.6, 141.4, 140.1, 128.7, 127.3, 124.7, 123.4, 123.3, 119.3, 119.2, 67.5,59.6, 34.8, 31.5, 13.6 ppm; HRMS (ESI): m / z calcd for C 32 H 34 NaO2 + [M+Na] + ,473.2451. Found: m / z 473.2450. Example 37 The structural formula of spirofluorene compounds is shown in Formula I-29: .

[0108] The preparation method of the spirofluorene compound shown in Formula I-29 includes the following steps: 0.15 mmol of 9-benzyl-9H-fluorene, 0.20 mmol of methyl diazoacetate iodonium salt, and 0.003 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of acetonitrile solvent is added, and the mixture is irradiated with 21 W, 440-460 nm blue light at room temperature. After 5 hours, the reaction is stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and column chromatography is used to purify 35.0 mg of the target product, with a yield of 72%.

[0109] The structure of the compound shown in Formula I-29 is characterized as follows: mp: 158.3-159.2 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.02 (s, 1H), 7.83 (d, J = 7.6 Hz, 2H), 7.57 (d, J = 7.6 Hz, 1H), 7.36(td, J = 7.5, 1.1 Hz, 2H), 7.29 (td, J = 7.5, 1.1 Hz, 1H), 7.14-7.10 (m, 3H), 6.79 (d, J = 7.6 Hz, 2H), 6.61 (d,J = 7.6 Hz, 1H), 3.46 (s, 3H).; 13 C NMR (101MHz, CDCl3) δ 163.2, 151.2, 144.7, 143.3, 142.5, 141.4, 141.3, 128.9, 127.8,127.6, 127.5, 123.6, 123.1, 122.6, 120.3, 67.3, 51.3 ppm; HRMS (ESI): m / zcalcd for C 23 H 16 NaO2 + [M+Na] + , 347.1043. Found: m / z 347.1045. Example 38 The structural formulas of spirofluorene compounds are shown in Formula I-30: .

[0110] The preparation method of the spirofluorene compound shown in Formula I-30 includes the following steps: 0.15 mmol of 1,4-bis((9H-fluorene-9-ylidene)methyl)benzene, 0.30 mmol of diazoethyl ethyl iodonium salt, and 0.005 mmol of tris(2,2'-bipyridine)ruthenium di(hexafluorophosphate) salt are added to a reaction tube. Under a nitrogen atmosphere, an appropriate amount of mixed solvent (acetonitrile:dichloromethane = 1:1) is added. The mixture is irradiated with 30W, 440-460nm blue light at room temperature for 12 hours and then stopped. The reaction solution is filtered through diatomaceous earth, the filtrate is concentrated, and purified by column chromatography to obtain 41.3 mg of the target product, with a yield of 46%.

[0111] The structure of the compound shown in Formula I-30 is characterized as follows: mp: 309.7-311.2 ℃; 1 H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 7.6 Hz, 4H), 7.75 (s, 2H), 7.39 (t, J = 7.5 Hz, 4H), 7.16(t, J = 7.5 Hz, 4H), 6.86-6.74 (m, 6H), 3.77 (q, J = 7.1 Hz, 4H), 0.77 (t, J = 7.1Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 162.7, 151.0, 144.7, 142.9, 142.6, 142.5,142.4, 127.9, 127.5, 122.8, 120.3, 118.2, 66.9, 59.9, 13.5 ppm; HRMS (ESI):m / z calcd for C 42 H 31 O4 + [M+H] + , 599.2217; Found: m / z 599.2211. As shown in Examples 1 to 38, the method of the present invention is applicable to substrates containing different substituents, such as aromatic rings, heteroaromatic rings, and fluorene rings with different substituents, and can obtain the target spirofluorene compound in good to excellent yields.

[0112] While this invention provides several exemplary embodiments, many other variations or modifications consistent with the principles of this invention can be directly determined or derived from the disclosure of this invention without departing from its spirit and scope. Therefore, the scope of this invention should be understood and recognized as covering all such other variations or modifications.

Claims

1. A spirofluorene compound, characterized by, The structural formula is shown as formula I: Wherein: R, R' and Ar are each independently; R is selected from hydrogen, alkyl, alkoxy, halogen, nitro, aryl; R' is alkyl; Ar is selected from aromatic hydrocarbon, heteroaromatic hydrocarbon.

2. The spirofluorene compound according to claim 1, characterized in that, The Ar is aromatic hydrocarbon, selected from benzene, substituted benzene, naphthalene or anthracene; or The Ar is heteroaromatic hydrocarbon, selected from thiophene, benzothiophene or benzofuran.

3. A method of preparing the spirofluorene compound according to claim 1, characterized by, Comprising: After mixing compound II, compound III, catalyst and solvent under inert gas atmosphere, the synthesis reaction is carried out under light condition, and after reaction, the spirofluorene compound is obtained through post-treatment; Wherein, the synthesis route is as follows: 。 4. The preparation method according to claim 3, characterized in that, The molar ratio of the compound II to the compound III is 1:1.0-2.

0.

5. The preparation method according to claim 3, characterized in that, During the reaction, the reaction temperature is 15-80℃, and the reaction time is 5-12 hours.

6. The preparation method according to claim 3, characterized in that, The catalyst is selected from any one of tris(2,2'-bipyridyl)ruthenium dichloride, trispyridine ruthenium chloride, tris[4,4'-bis(tert-butyl)-2,2'-bipyridine]ruthenium (II) hexafluorophosphate.

7. The preparation method according to claim 3, characterized in that, The molar ratio of the catalyst to the compound II is 0.010-0.025:

1.

8. The preparation method according to claim 3, characterized in that, The solvent is selected from one or more of acetonitrile, dichloromethane, 1,4-dioxane.

9. The preparation method according to claim 3, characterized in that, The light condition includes: the wavelength of light source is 440-460nm, and the power of light source is 3-30W.

10. The preparation method according to claim 3, characterized in that, The post-treatment includes the steps of filtration, concentration and column chromatography purification.

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