Bicyclic [4.1. 1] octane azafluorene derivative as well as preparation method and application thereof

Abstract

The invention discloses a bicyclo [4.1. 1] octane azafluorene derivative with a structural formula shown as a formula I. A preparation method comprises the following steps: reacting a 2-(2-(2-hydroxybenzylidene)-2, 3-dihydro-1H-indenyl-1-methylene) malononitrile derivative for 0.5-6 hours in the presence of an organic or inorganic base catalyst and a DMF (Dimethyl Formamide) solvent at the temperature of 40-150 DEG C, adding distilled water after the reaction is finished, and reacting for 0.5-6 hours at the temperature of 40-150 DEG C to obtain the bicyclo [4.1. 1] octane azafluorene derivative with the structural formula shown as the formula I. The invention further discloses a preparation method of the bicyclo [4.1. 1] octane azafluorene derivative. Extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and carrying out column chromatography separation. The invention provides a simple, efficient and convenient preparation method of the bicyclo [4.1. 1] octane azafluorene derivative, and the preparation method has the advantages of high efficiency, convenience, low cost and the like, and has a good application prospect. The derivative can be applied as an organic catalyst or an organic photoelectric material, a fluorescent material and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of novel compound preparation, and particularly relates to a bicyclo【4.1.1】octane azafuorene derivative and a preparation method and application thereof. BACKGROUND

[0002] The three-dimensional saturated bridged ring skeleton with complex structure plays an important role in the fields of natural products, medicines, functional materials and the like as an important core skeleton in the field of organic chemistry; especially, with the successful application of the "escape from plane" strategy in the field of medicinal chemistry, the three-dimensional saturated bridged ring skeleton has become an important target in the research of benzene ring replacement due to its unique rigid conformation and excellent metabolic stability, and the compound with the three-dimensional saturated bridged ring structure is widely used in new drug development, organic optoelectronic functional materials and the like due to its excellent biological activity and good material performance. In view of the broad application prospect in drug development, it is of great significance to develop a new method for efficiently synthesizing the three-dimensional saturated bridged ring compound, which will strongly promote the application process of the compound in the fields of new drug development, organic optoelectronic functional materials and the like.

[0003] At present, organic chemists have developed various methods for synthesizing the bicyclo three-dimensional saturated bridged ring skeleton, however, these existing methods mainly focus on the construction of bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[3.1.1]heptane compounds, and there are relatively few reports on the efficient synthesis of bicyclo[4.1.1]octane compounds. As an important structural framework in natural products and drug molecules, this kind of bicyclo[4.1.1]octane skeleton can also be used as a meta-substituted arene and a bioisostere of 1,3-disubstituted cyclohexane in new drug development. Therefore, organic chemists are also committed to developing various effective methods for developing this kind of useful molecular skeleton, and the existing methods mainly include Wagner-Meerwein rearrangement reaction, intramolecular cyclization reaction of ultraviolet light excited enone compounds, transition metal catalysis (such as Pd, Ni) cycloaddition reaction and the like. However, these existing technical methods have technical defects such as high substrate dependence leading to limited substrate range and application, the need to use noble metals or special reaction equipment leading to harsh reaction conditions, and many synthesis steps leading to low reaction efficiency. Therefore, compared with bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[3.1.1]heptane compounds, the method for efficiently and practically constructing the structure of complex bicyclo[4.1.1]octane derivatives is still limited.

[0004] In view of the importance of bicyclo[4.1.1]octane derivatives skeleton in new drug development and the existing technical defects, it is urgent to solve these challenging technical problems and develop a mild and modular method to achieve the introduction of diversified substituents, a fast and precisely controllable method to synthesize these useful bicyclo[4.1.1]octane compounds.

[0005] Multi-step tandem reactions have been attracting much attention since their inception due to their significant advantages in building multiple chemical bonds or rings. Therefore, this application adopts tandem reactions to develop a variety of novel bicyclo[4.1.1]octane derivatives with high efficiency by using readily available starting materials under the catalysis of simple organic bases, which has important significance for the development of drug chemistry materials and organic catalysis field. SUMMARY

[0006] In view of the problems existing in the prior art, the present application aims to provide a bicyclo【4.1.1】octane azafuorene derivative which can be applied as an organic catalyst or an organic optoelectronic material, a fluorescent material and the like.

[0007] The present application also provides a preparation method and application of the above-mentioned bicyclo【4.1.1】octane azafuorene derivative, which has the advantages of high efficiency, convenience, strong operability and good application prospect.

[0008] To solve the above technical problems, the present application adopts the following technical scheme: A bicyclo【4.1.1】octane azafuorene derivative, the structure of the bicyclo【4.1.1】octane azafuorene derivative is shown in the following formula I: (I) Among them, R 1 is selected from at least one of hydrogen, halogen, alkyl, hydroxyl, trifluoromethyl, alkoxy, nitro, ester, amine, amide, alkanoyloxy, cyano, aryl, halobenzyloxy, halobenzylamine and halophenoxy and the like; Ar 2 is selected from ; R 1 is selected from at least one of hydrogen, halogen, alkyl, trifluoromethyl, hydroxyl, alkoxy, nitro, ester, amine, amide, alkanoyloxy, cyano, aryl, alkenyl, halobenzyloxy, halobenzylamine and halophenoxy and the like.

[0009] The alkyl group is a C1-C18 straight-chain or branched alkyl group, a carbocyclic or heterocyclic group (containing 1-3 oxygen, sulfur or nitrogen atoms), a substituted or unsubstituted alkyl group, wherein the substituent is a halogen, hydroxyl, carboxyl, nitro, cyano, substituted amino, amide, carboxyl, ester, alkoxy, alkylamino, alkanoyloxy, aryl, etc.

[0010] The aryl group is a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted aromatic heterocyclic ring.

[0011] The aromatic ring is a benzene ring or a pyridine ring; the substituents are halogen, methyl, trifluoromethyl, hydroxyl, nitro, amino, substituted amino, carboxyl, ester, alkoxy, alkyloxy or cyano, etc.

[0012] Further preferred, R 1 It is selected from at least one of hydrogen, methoxy, fluorine, chlorine, hydroxyl, methyl, tert-butyl, bromine, etc.; Ar 2 Selected from ; The R 1 'Selected from at least one of hydrogen, trifluoromethyl, fluorine, chlorine, hydroxyl, etc.

[0013] This invention provides a method for preparing the above-mentioned bicyclic [4.1.1] octane fluorene derivative, which includes the following steps: The 2-(2-(2-hydroxybenzyl)-2,3-dihydro-1H-indenyl-1-methylene)malonitrile derivative was reacted with a catalyst and solvent at 40-150℃ for 0.5-6 hours. After the reaction was completed, distilled water was added, and the mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The crude product was then separated by column chromatography to obtain the bicyclic [4.1.1] octane fluorene derivative. The reaction route is shown below: .

[0014] Specifically, the catalyst can be an organic base or an inorganic base, specifically selected from 1,4-diazabicyclo[2.2.2]octane (DABCO), 4-dimethylaminopyridine (DMAP), N,N-diisopropylethylamine (DIPEA), morpholine, triethylamine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tetramethylguanidine (TMG), sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate (Cs2CO3), potassium fluoride (KF), cesium fluoride (CsF), potassium phosphate (K3PO4), sodium hydroxide (NaOH), potassium hydroxide (KOH), potassium tert-butoxide ( t-at least one of potassium tert-butoxide (BuOK), sodium methoxide (MeONa), sodium ethoxide (EtONa), sodium hydride (NaH), and the like, wherein tetramethylguanidine (TMG) is preferred.

[0015] Further, the amount of the catalyst is 20%-200% of the molar amount of the 2-(2-(2-hydroxybenzylidene)-2,3-dihydro-1H-inden-1-ylmethyl)malononitrile derivative.

[0016] Specifically, the solvent is DMF. Further, 4-8 mL of the solvent is added per mmol of the 2-(2-(2-hydroxybenzylidene)-2,3-dihydro-1H-inden-1-ylmethyl)malononitrile derivative.

[0017] Further preferably, the reaction temperature is 60-100℃.

[0018] Specifically, the eluent used in the column chromatography separation is composed of a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 10:1-1:1.

[0019] The application also provides applications of the above-mentioned bicyclo【4.1.1】octane azafuorene derivative in organic catalysts (for example, can be used to catalyze Michael addition reaction of 3-benzofuranone and nitrostyrene, etc.), organic optoelectronic materials or fluorescent materials, etc.

[0020] Compared with the prior art, the application has the following advantages and beneficial effects: The application provides a simple, efficient and convenient preparation method of bicyclo【4.1.1】octane azafuorene derivative, which is prepared by using an organic base or an inorganic base as a catalyst and DMF as a solvent, has the advantages of high efficiency, convenience and low cost, and has a good application prospect. The compound is expected to be applied as an organic catalyst or an organic optoelectronic material, a fluorescent material, etc. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 It is a picture of the solid compound in application example 1 under sunlight and 365 nm ultraviolet lamp irradiation; Figure 2 It is a fluorescence emission spectrum of the compound in application example 1 in a mixed solution of petroleum ether and ethyl acetate in different proportions, and the inserted picture is a picture of the compound under 365 nm ultraviolet lamp irradiation in a mixed solution of petroleum ether and ethyl acetate in different proportions; Figure 3 It is a fluorescence emission intensity ratio of the compound in application example 1 in a mixed solution of petroleum ether and ethyl acetate in different proportions. DETAILED DESCRIPTION

[0022] The application will be further described in conjunction with specific examples. It should be understood that the following examples are only used to illustrate the application and not intended to limit the scope of the application. Those skilled in the art can make some non-essential improvements and adjustments according to the content of the above-mentioned application, which are all covered in the protection scope of the application.

[0023] Example 1 The structural formula of the bicyclo【4.1.1】octane azafuorene derivative of this embodiment is as follows: ; The preparation method of the bicyclo【4.1.1】octane azafuorene derivative of this embodiment is: 56.8 mg (0.20 mmol) of 2-(2-(2-hydroxybenzylidene)-2,3-dihydro-1H-inden-1-ylmethylene) propanedinitrile (the synthesis method can refer to the existing literature, for example, Chem. Lett .2008, 37 , 570, Org. Lett .,2022, 24 , 8277, Org. Biomol. Chem .2023, 21 , 6681, J. Am. Chem. Soc .2023, 145 , 14427, Org. Lett .,2024, 26 ,7999), 10.0 μL (40 mmol%) of TMG, 1.5 mL of DMF were added to the reaction tube, and the reaction was stirred at 90-100 ℃ for 0.5 hours. After the reaction was completed, 10 mL of distilled water was added, and the organic phase was extracted with 15 mL of ethyl acetate three times, dried with anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a crude product. The target product was obtained by column chromatography separation (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1). The product was a yellow solid with a melting point of 278-279 °C.

[0024] 1 H NMR (500 MHz, DMSO- d 6 ) δ 9.03 (s, 2H), 8.59 (d, J = 8.2 Hz, 1H), 8.29(d, J = 7.6 Hz, 1H), 8.18 (d, J= 7.5 Hz, 1H), 7.73 – 7.65 (m, 1H), 7.64 – 7.58(m, 1H), 7.58 – 7.50 (m, 2H), 7.44 – 7.33(m, 1H), 6.79 (s, 2H), 6.73 (t, J = 7.7 Hz, 2H), 6.47 (d, J = 8.0 Hz, 2H), 6.24 (t, J = 7.6 Hz, 2H), 5.87 (d, J = 7.7Hz, 2H), 4.55 (s, 2H), 4.10 (s, 2H). 13 C NMR (125 MHz, DMSO- d 6 ) δ 168.8, 159.0,155.7, 152.3, 151.3,150.63, 150.3, 139.0, 136.5, 132.5, 130.8, 128.8, 128.2,127.4, 127.2, 126.7, 125.1, 124.9, 124.5, 122.9, 122.1, 117.8, 117.4, 116.9,114.8, 104.6, 79.9,60.8, 56.4, 45.9, 43.0.

[0025] Example 2 The structure of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: ; The preparation method of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: 62.8 mg (0.20 mmol) of 2-(4-methoxy-2-(2-hydroxybenzylidene)-2,3-dihydro-1H-indenyl-1-methylene)propanedinitrile (the synthesis method can be carried out according to the existing literature, for example, Chem. Lett .2008, 37 , 570, Org. Lett .,2022, 24 , 8277, Org. Biomol. Chem .2023, 21 , 6681, J. Am. Chem. Soc .2023, 145 , 14427, Org. Lett .,2024, 26, 7999), 10.0 μL (40 mmol%) TMG, 1.5 mL of DMF were added into the reaction tube, and the reaction was stirred at 90-100 °C for 2 hours. After the reaction was completed, 10 mL of distilled water was added, and the mixture was extracted with 15 mL of ethyl acetate three times. The organic phase was combined, dried over anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a crude product. The target product was obtained by column chromatography separation (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1). The product was a yellow solid with a melting point of 292-293 °C.

[0026] 1 H NMR (500 MHz, DMSO- d 6 ) δ 8.98 (s, 2H), 8.18 (d, J = 8.1 Hz, 1H), 7.92(d, J = 7.7 Hz, 1H), 7.59 (t, J = 8.0 Hz, 1H), 7.36 (t, J = 8.1 Hz, 1H), 7.27 (d, J =8.2 Hz, 1H), 7.15 (d, J = 8.1 Hz, 1H), 6.76 – 6.70 (m, 4H), 6.47 (d, J = 8.0 Hz,2H), 6.24 (t, J = 7.5 Hz, 2H), 5.91 (d, J = 7.7 Hz, 2H), 5.00 (s, 2H), 4.01 (s,3H), 3.95 (s, 2H), 3.90 (s, 3H). 13 C NMR (125 MHz, DMSO- d 6 ) δ 168.9, 158.9,158.1, 155.7, 155.1,151.1, 150.5, 140.4, 140.0, 137.9, 135.4, 130.0, 129.1,128.3, 127.2, 127.2, 123.2, 117.76, 117.1, 116.9, 116.7, 114.8, 114.6, 113.6,113.5, 104.9, 80.0,61.2, 56.7, 55.8, 55.4, 43.7, 40.3。

[0027] Example 3 The structural formula of the bicyclo【4.1.1】octane azaf uroline derivative of the present embodiment is as follows: ; The preparation method of the bicyclo【4.1.1】octane azaf uroline derivative of the present embodiment is as follows: 60.4 mg (0.20 mmol) 2-(5-fluoro-2-(2-hydroxybenzylidene)-2,3-dihydro-1H-inden-1-ylmethyl)propanedinitrile (the synthesis method can refer to the existing literature, for example, Chem. Lett .2008, 37 , 570, Org. Lett .,2022, 24 , 8277, Org. Biomol. Chem .2023, 21 , 6681, J. Am. Chem. Soc .2023, 145 , 14427, Org. Lett .,2024, 26 , 7999) and 10.0 μL (40 mmol%) TMG, 1.5 mL of DMF were added to the reaction tube, and the reaction was stirred at 90-100 °C for 2 hours. After the reaction was completed, 10 mL of distilled water was added, and the organic phase was extracted with 15 mL of ethyl acetate three times, dried with anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a crude product. The target product was obtained by column chromatography separation (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1). The product was a yellow solid with a melting point of 287-288 °C.

[0028] 1 (500 MHz, DMSO- d 6 ) δ 9.02 (s, 2H), 8.60 (dd, J = 9.0, 5.2 Hz, 1H), 8.28(dd, J = 8.6, 5.0 Hz, 1H), 8.16 (dd, J = 9.1, 2.5 Hz, 1H), 7.47 (td, J = 8.9, 2.5Hz, 1H), 7.42 (dd, J = 8.7, 2.6 Hz, 1H), 7.25 (td, J = 9.0, 2.7 Hz, 1H), 6.80 (s,2H), 6.75 (t, J = 7.7 Hz, 2H), 6.47 (d, J= 8.0 Hz, 2H), 6.26 (t, J = 7.5 Hz, 2H),5.88 (d, J = 7.7 Hz, 2H), 4.56 (s, 2H), 4.05 (s, 2H). 13 C NMR (125 MHz, DMSO- d 6 ) δ167.3, 164.7 (d, J = 250.6 Hz), 164.1 (d, J = 245.6 Hz), 158.9, 155.6, 155.6 (d, J = 9.5 Hz), 153.7 (d, J = 9.6 Hz), 150.3, 150.2, 135.5 (d, J = 2.3 Hz), 132.8 (d, J = 1.6 Hz), 128.5, 127.5, 127.1, 127.0 (d, J = 10.2 Hz), 123.9 (d, J = 9.1 Hz),122.7, 117.8, 117.2, 116.7, 115.5 (d, J = 24.7 Hz), 114.8, 114.4 (d, J = 22.7Hz), 112.2 (d, J = 22.9 Hz), 111.8 (d, J = 22.2 Hz), 104.2 (d, J = 2.2 Hz), 79.7,60.7, 56.4 (d, J = 2.5 Hz), 45.7, 43.1。

[0029] Example 4 The structural formula of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: ; The preparation method of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: 63.7 mg (0.20 mmol) of 2-(5-chloro-2-(2-hydroxybenzylidene)-2,3-dihydro-1H-inden-1-ylmethylene)propanedinitrile (the synthesis method can refer to the existing literature, for example, Chem. Lett .2008,37 570 Org. Lett 2022 24 8277 Org. Biomol. Chem 2023, 21 , 6681, J. Am. Chem. Soc 2023, 145 14427 Org. Lett .,2024, 26 10.0 μL (40 mmol%) TMG and 1.5 mL DMF were added to the reaction tube and stirred at 90-100 °C for 3 hours. After the reaction was completed, 10 mL of distilled water was added, and the mixture was extracted three times with 15 mL of ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain the crude product. The crude product was separated by column chromatography (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1) to obtain the target product, which was a yellow solid with a melting point of 300-301 °C.

[0030] 1 (500 MHz, DMSO- d 6 ) δ 9.03 (s, 2H), 8.55 (d, J = 8.7 Hz, 1H), 8.40 (s,1H), 8.25 (d, J = 8.3 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.67 (s, 1H), 7.47 (d, J =8.7 Hz, 1H), 6.86 (s, 2H), 6.75 (t, J = 7.7 Hz, 2H), 6.47 (d, J = 8.0 Hz, 2H), 6.26 (t, J = 7.5 Hz, 2H), 5.84 (d, J = 7.7 Hz, 2H), 4.59 (s, 2H), 4.05 (s, 2H). 13 CNMR (125 MHz, DMSO- d 6) δ 167.4, 159.0, 155.6, 154.5, 152.7, 150.3, 150.3,138.0, 137.2, 135.7, 135.3,128.6, 128.4, 127.5, 127.1, 127.1, 126.2, 125.1,123.5, 122.7, 117.9, 117.0, 116.6, 114.8, 105.1, 80.0, 60.4, 56.4, 45.5,42.9.

[0031] Example 5 The structural formula of the bicyclo【4.1.1】octane azaf uorenoid derivatives of this example is as follows: The preparation method of the bicyclo【4.1.1】octane azaf uorenoid derivatives of this example is: 60.0 mg (0.20 mmol) 2-(6-hydroxy-2-(2-hydroxybenzylidene)-2,3-dihydro-1H-inden-1- ylmethyl)propanedinitrile (the synthesis method can refer to the existing literature, for example, Chem. Lett .2008, 37 , 570, Org. Lett .,2022, 24 , 8277, Org. Biomol. Chem .2023, 21 , 6681, J. Am. Chem. Soc .2023, 145 , 14427, Org. Lett .,2024, 26 , 7999), 10.0 μL (40 mmol%) TMG, 1.5 mL of DMF were added to the reaction tube, and stirred at 90-100 ℃ for 2 hours. After the reaction was completed, 10 mL of distilled water was added, and 15 mL of ethyl acetate was extracted three times, and the organic phase was combined and dried with anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a crude product. Column chromatography was used for separation (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1) to obtain the target product. The product was a yellow solid with a melting point of 319-320 °C.

[0032] 1 H NMR (500 MHz, DMSO- d 6 ) δ 9.91 (s, 1H), 9.56 (s, 1H), 8.99 (s, 2H),8.02 (d, J = 1.9 Hz, 1H), 7.90 (d, J= 8.3 Hz, 1H), 7.73 (d, J = 2.2 Hz, 1H), 7.28(d, J = 8.2 Hz, 1H), 7.05 (dd, J = 8.3, 2.3 Hz, 1H), 6.97 (dd, J = 8.2, 2.3 Hz,1H), 6.73 (t, J = 7.6 Hz, 2H), 6.66 (s, 2H), 6.48 (d, J = 8.0 Hz, 2H), 6.25 (t, J =7.5 Hz, 2H), 5.92 (d, J = 7.8 Hz, 2H), 4.44 (s, 2H), 3.94 (s, 2H). 13 C NMR (125 MHz, DMSO- d 6 ) δ 169.1, 158.9, 157.6, 156.0, 155.8,151.2, 150.6, 143.1, 141.1,140.1, 137.6, 129.6, 127.3, 127.3, 125.4, 125.1, 123.1, 120.9, 118.4, 117.8,117.3, 116.8, 114.8, 110.8, 108.6, 104.3, 79.7,61.6, 55.9, 45.2, 43.2.

[0033] Example 6 The structural formula of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: The preparation method of the bicyclo【4.1.1】octane azaf uorene derivative of this example is: 59.6 mg (0.20 mmol) 2-(6-methyl-2-(2-hydroxybenzylidene)-2,3-dihydro-1H-indenyl-1-methylene) propanedinitrile (the synthesis method can refer to the existing literature, for example, Chem. Lett .2008, 37 , 570, Org. Lett .,2022, 24 , 8277, Org. Biomol. Chem .2023, 21 , 6681, J. Am. Chem. Soc .2023,145 14427 Org. Lett .,2024, 26 10.0 μL (40 mmol%) TMG and 1.5 mL DMF were added to the reaction tube and stirred at 90-100 °C for 1 hour. After the reaction was completed, 10 mL of distilled water was added, and the mixture was extracted three times with 15 mL of ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain the crude product. The crude product was separated by column chromatography (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1) to obtain the target product, which was a yellow solid with a melting point of 293-294 °C.

[0034] 1 (500 MHz, DMSO- d 6 ) δ 9.01 (s, 2H), 8.41 (s, 1H), 8.08 (s, 1H), 8.05(d, J = 7.8 Hz, 1H), 7.48 (d, J = 7.8 Hz, 1H), 7.41 (d, J = 7.7 Hz, 1H), 7.36 (d, J =7.8 Hz, 1H), 6.77 (s, 2H), 6.72 (t, J = 7.6 Hz, 2H), 6.47 (d, J = 8.0 Hz, 2H), 6.24 (t, J = 7.5 Hz, 2H), 5.87 (d, J = 7.8 Hz, 2H), 4.50 (s, 2H), 4.02 (s, 2H), 2.49 (s, 3H), 2.35 (s, 3H). 13 C NMR (125 MHz, DMSO-) d 6 ) δ 168.7, 159.0, 155.7,151.1, 150.6, 149.7, 147.7, 139.2, 137.5, 136.7, 135.6, 133.6, 131.7, 129.1,127.3, 127.2, 125.0, 124.8, 124.2,122.9, 122.4, 117.8, 117.4, 116.9, 114.8,104.4, 79.8, 61.1, 56.1, 45.6, 43.0, 21.4, 21.4.

[0035] Example 7 The structural formula of the bicyclo【4.1.1】octane azaf uorenoid derivatives of this example is as follows: The preparation method of the bicyclo【4.1.1】octane azaf uorenoid derivatives of this example is: 68.0 mg (0.20 mmol) of 2-(6-tert-butyl-2-(2-hydroxybenzylidene)-2,3-dihydro-1H-inden-1-ylmethylene) propanedinitrile (the synthesis method can refer to the existing literature, for example, Chem. Lett .2008, 37 , 570, Org. Lett .,2022, 24 , 8277, Org. Biomol. Chem .2023, 21 , 6681, J. Am. Chem. Soc .2023, 145 , 14427, Org. Lett .,2024, 26 , 7999), 10.0 μL (40 mmol%) of TMG, 1.5 mL of DMF were added to the reaction tube, and stirred at 90-100 °C for 1 hour. After the reaction was completed, 10 mL of distilled water was added, and 15 mL of ethyl acetate was extracted three times, and the organic phase was combined and dried over anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a crude product. Column chromatography was used for separation (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1) to obtain the target product. The product was a yellow solid with a melting point of 301-303 °C.

[0036] 1 (500 MHz, DMSO- d 6 ) δ 9.01 (s, 2H), 8.50 (d, J = 8.6 Hz, 1H), 8.23 (s,1H), 8.17 (d, J = 8.2 Hz, 1H), 7.68 – 7.62 (m, 1H), 7.49 (s, 1H), 7.42 (d, J =8.6 Hz, 1H), 6.76 – 6.69 (m, 4H), 6.49 (d, J = 8.0 Hz, 2H), 6.24 (t, J = 7.5 Hz,2H), 5.89 (d, J= 7.7 Hz, 2H), 4.62 (s, 2H), 4.09 (s, 2H), 1.39 (s, 9H), 1.35(s, 9H). 13 C NMR (125 MHz, DMSO- d 6 ) δ 168.8, 158.9, 155.8, 155.6, 154.1,152.5,151.2, 150.7, 150.2, 136.6, 133.9, 128.7, 127.3, 127.3, 125.4, 124.6, 124.4,123.1, 121.6, 121.4, 121.4, 117.9, 117.6, 116.9, 114.8, 103.8, 79.5,61.4,56.6, 46.0, 42.7, 35.3, 35.0, 31.3, 31.0.。

[0037] Example 8 The structural formula of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: The preparation method of the bicyclo【4.1.1】octane azaf uorene derivative of this example is: 72.6 mg (0.20 mmol) 2-(6-bromo-2-(2-hydroxybenzylidene)-2,3-dihydro-1H-indenyl-1- methylene)propanedinitrile (the synthesis method can refer to the existing literature, for example, Chem. Lett .2008, 37 , 570, Org. Lett .,2022, 24 , 8277, Org. Biomol. Chem J. Am. Chem. Soc .2023, 21 , 6681, Org. Lett .2023, 145 , 14427, Chem. Lett .,2024, 26 , 7999) and 10.0 μL (40 mmol%) TMG, 1.5 mL of DMF were added to the reaction tube, and the reaction was stirred at 90-100 °C for 6 hours. After the reaction was completed, 10 mL of distilled water was added, and the organic phase was extracted with 15 mL of ethyl acetate three times, dried with anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a crude product. The target product was obtained by column chromatography separation (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1). The product was a yellow solid with a melting point of 319-320 °C.

[0038] 1 (500 MHz, DMSO- d 6 ) δ 9.00 (s, 2H), 8.74 (d, J = 1.8 Hz, 1H), 8.39 (d, J =1.8 Hz, 1H), 8.20 (d, J = 8.2 Hz, 1H), 7.88 (dd, J = 8.2, 1.9 Hz, 1H), 7.75 (dd, J = 8.1, 1.8 Hz, 1H), 7.53 (d, J = 8.1 Hz, 1H), 6.90 (s, 2H), 6.77 (td, J = 7.7,1.6 Hz, 2H), 6.49 (d, J = 8.0 Hz, 2H), 6.29 (t, J = 7.5 Hz, 2H), 5.86 (d, J = 7.8Hz, 2H), 4.57 (s, 2H), 4.03 (s, 2H). 13 C NMR(125 MHz, DMSO- d 6 ) δ 167.1, 158.9,155.5, 151.4, 150.2,149.8, 149.6, 141.3, 138.6, 134.8, 133.2, 129.1, 127.5,127.1, 127.0, 127.0, 126.6, 124.6, 122.5, 121.0, 119.7, 117.9, 116.7, 116.4,114.9, 105.7, 80.2,60.6, 56.2, 45.5, 42.8。

[0039] Example 9 The structural formula of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: The preparation method of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: 68.8 mg (0.20 mmol) of 2-(5,6-dimethoxy-2-(2-hydroxybenzylidene)-2,3-dihydro-1H-inden-1-ylmethylene)propanedinitrile (the synthesis method can be carried out according to the existing literature, for example, Org. Lett .2008,37 570 Org. 2022 24 8277 Biomol. Chem 2023, 21 , 6681, J. Am. Chem. Soc 2023, 145 14427 Org. Lett .,2024, 26 10.0 μL (40 mmol%) TMG and 1.5 mL DMF were added to the reaction tube and stirred at 90-100 °C for 1 hour. After the reaction was completed, 10 mL of distilled water was added, and the mixture was extracted three times with 15 mL of ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain the crude product. The crude product was separated by column chromatography (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1) to obtain the target product, which was a yellow solid with a melting point of 319-320 °C.

[0040] 1 (500 MHz, DMSO- d 6 ) δ 8.98 (s, 2H), 8.20 (s, 1H), 7.82 (d, J = 30.4 Hz,2H), 7.13 (s, 1H), 6.74 (t, J = 7.7 Hz, 2H), 6.60 (s, 2H), 6.49 (d, J = 8.0 Hz, 2H), 6.26 (t, J = 7.6 Hz, 2H), 5.94 (d, J = 7.7 Hz, 2H), 4.54 (s, 2H), 4.03 (s,2H), 3.95 (s, 3H), 3.90 (s, 3H), 3.89 (s, 3H), 3.76(s, 3H). 13 C NMR (125 MHz, DMSO- d 6) δ 168.8, 158.8, 155.8, 153.3, 151.9, 151.5, 150.2, 149.0, 147.7,147.6, 144.5, 131.1, 128.4, 128.2, 127.3, 123.4, 118.4, 117.8, 117.4,114.7,107.6, 107.1, 107.1, 104.3, 101.7, 78.5, 61.5, 56.3, 56.1, 55.9, 55.6, 55.4,45.8, 43.5.

[0041] Example 10 The structural formula of the bicyclo【4.1.1】octane azaf uorenoid derivatives of this example is as follows: The preparation method of the bicyclo【4.1.1】octane azaf uorenoid derivatives of this example is: 70.4 mg (0.20 mmol) 2-(5-trifluoromethyl-2-hydroxybenzylidene-2,3- dihydro-1H-inden-1-methylene) propanedinitrile (the synthesis method can refer to the existing literature, for example, Chem. Lett .2008, 37 , 570, Org. Lett .,2022, 24 , 8277, Org. Biomol. Chem .2023, 21 , 6681, J. Am. Chem. Soc .2023, 145 , 14427, Org. Lett .,2024, 26 , 7999), 10.0 μL (40 mmol%) TMG, 1.5 mL of DMF were added to the reaction tube, and stirred at 90-100 °C for 1 hour. After the reaction was completed, 10 mL of distilled water was added, and 15 mL of ethyl acetate was extracted three times, the organic phase was combined and dried with anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a crude product. The target product was obtained by column chromatography separation (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1). The product was a yellow solid with a melting point of 290-292 °C.

[0042] 1 (500 MHz, DMSO- d 6 ) δ 9.98 (s, 2H), 8.61 (d, J = 8.2 Hz, 1H), 8.34 (d, J= 7.6 Hz, 1H), 8.27 (d, J = 7.5 Hz, 1H), 7.73 (t, J = 7.4 Hz, 1H), 7.68 (t, J = 7.5Hz, 1H), 7.62 – 7.56 (m, 2H), 7.46 – 7.38 (m, 1H), 7.10 (dd, J = 8.6, 1.3 Hz,2H), 6.84 (s, 2H), 6.62 (d, J = 8.4 Hz, 2H), 6.13 (s, 2H), 4.63 (s, 2H), 4.14(s, 2H). 13 C NMR(125 MHz, DMSO- d 6 ) δ 168.1, 159.1, 158.9, 152.0, 151.7,150.4,149.8, 139.0, 136.3, 132.7, 131.2, 128.7, 127.5, 126.9, 125.0, 124.9 (d, J =3.8 Hz), 124.8 (d, J = 5.2 Hz), 124.2 (q, J = 269.2 Hz), 123.7, 122.2, 118.2 (q, J = 31.7 Hz), 116.9, 116.4, 115.2, 104.7, 79.9, 60.0, 56.0, 46.1, 42.6。

[0043] Example 11 The structural formula of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: The preparation method of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: 67.3 mg (0.20 mmol) of 2-(3-chloro-5-fluoro-2-hydroxybenzylidene-2,3-dihydro-1H-inden-1-ylmethyl)propanedinitrile (the synthesis method can be carried out according to the existing literature, for example, Chem. Lett .2008, 37 , 570, Org. Lett .,2022, 24 , 8277, Org. Biomol. Chem .2023,21 , 6681, J. Am. Chem. Soc 2023, 145 14427 Org. Lett .,2024, 26 10.0 μL (40 mmol%) TMG and 1.5 mL DMF were added to the reaction tube and stirred at 90-100 °C for 1 hour. After the reaction was completed, 10 mL of distilled water was added, and the mixture was extracted three times with 15 mL of ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain the crude product. The crude product was separated by column chromatography (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1) to obtain the target product, which was a yellow solid with a melting point of 217-218 °C.

[0044] 1 (500 MHz, DMSO- d 6 ) δ 8.94 (s, 2H), 8.58 (d, J = 8.2 Hz, 1H), 8.30 (d, J =7.6 Hz, 1H), 8.22 (d, J = 7.5 Hz, 1H), 7.70 (t, J = 7.4 Hz, 1H), 7.65 (t, J = 7.5Hz, 1H), 7.58 (t, J = 7.3 Hz, 1H), 7.53 (d, J = 7.6 Hz, 1H), 7.41 (t, J = 7.7 Hz,1H), 7.01 – 6.96 (m, 4H), 5.61 (dd, J = 10.0, 3.1 Hz, 2H), 4.72 (s, 2H), 4.09(s, 2H). 13 C NMR (125 MHz, DMSO-) d 6 ) δ 167.6, 159.3, 154.6, 152.7, 151.6,151.3,150.2, 148.9, 148.0 (d, J = 2.5 Hz), 138.2, 136.2, 133.0, 131.2, 128.7, 127.4(d, J= 7.5 Hz), 127.1, 126.9, 125.5, 124.7, 123.6 (d, J = 272.7 Hz), 121.0 (d, J =11.8 Hz), 116.8, 116.5, 114.8 (d, J = 25.6 Hz), 112.6 (d, J = 23.9 Hz), 104.7,80.3, 61.2, 56.5, 45.2, 42.4。

[0045] Example 12 The structural formula of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: The preparation method of the bicyclo【4.1.1】octane azaf uorene derivative of this example is: 57.0 mg (0.20 mmol) 2-(2-(3-hydroxypyridine)-4-benzylidene)-2,3-dihydro-1H-indenyl-1-methylene) malonitrile (the synthesis method can refer to the existing literature, for example, Figure 1 .2008, 37 , 570, Figure 2 .,2022, 24 , 8277, Figure 3 ​ .2023, 21 , 6681, ​ .2023, 145 , 14427, ​ .,2024, 26 , 7999), 10.0 μL (40 mmol%) TMG, 1.5 mL of DMF were added to the reaction tube, and the reaction was stirred at 90-100 °C for 0.5 hours. After the reaction was completed, 10 mL of distilled water was added, and the organic phase was extracted with 15 mL of ethyl acetate three times, dried with anhydrous sodium sulfate, filtered, and rotary evaporated to obtain a crude product. The target product was obtained by column chromatography separation (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1). The product was a yellow solid with a melting point of 312-313 °C.

[0046] 1 (500 MHz, DMSO- d 6 ) δ 9.55 (s, 2H), 8.59 (d, J = 8.2 Hz, 1H), 8.34 (d, J= 7.6 Hz, 1H), 8.27 (d, J = 7.4 Hz, 1H), 7.79 (s, 2H), 7.75 – 7.64 (m, 2H), 7.60– 7.55 (m, 2H), 7.50 (d, J = 5.0 Hz, 2H), 7.45 – 7.37 (m, 1H), 6.91 (s, 2H),5.76 (d, J = 5.1 Hz, 2H), 4.65 (s, 2H), 4.12 (s, 2H). 13 C NMR(125 MHz, DMSO- d 6 ) δ168.3, 159.6, 152.5, 152.4, 152.0, 150.5, 149.8, 139.9, 139.1, 137.7, 136.8,133.2, 131.5, 131.0, 129.1, 127.7, 127.4, 125.5, 125.3,125.3, 122.9, 122.0,117.4, 117.1, 105.0, 80.7, 60.4, 55.9, 46.2, 42.6。

[0047] Example 13 The structural formula of the bicyclo【4.1.1】octane azaf uorene derivative of this example is as follows: The preparation method of the bicyclo【4.1.1】octane azaf uorene derivative of this example is: 62.9 mg (0.20 mmol) 2-(5-methoxy-2-hydroxybenzylidene-2,3-dihydro-1H-inden-1-yl- methylene) propanedinitrile (the synthesis method can refer to the existing literature, for example, ​ .2008, 37 , 570, ​ .,2022, 24 , 8277, ​ ​ .2023, 21 , 6681, ​ .2023, 145 , 14427, ​ .,2024, 2610.0 μL (40 mmol%) TMG and 1.5 mL DMF were added to the reaction tube and stirred at 90-100 °C for 1 hour. After the reaction was completed, 10 mL of distilled water was added, and the mixture was extracted three times with 15 mL of ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain the crude product. The crude product was separated by column chromatography (eluent: petroleum ether and ethyl acetate in a volume ratio of 10:1 to 1:1) to obtain the target product, which was a yellow solid with a melting point of 264-266 °C.

[0048] 1 (500 MHz, DMSO- d 6 ) δ 8.62 (d, J = 8.2 Hz, 1H), 8.59 (s, 2H), 8.29 (d, J =7.7 Hz, 1H), 8.20 (d, J = 7.5 Hz, 1H), 7.69 (t, J = 7.4 Hz, 1H), 7.63 (t, J = 7.5Hz, 1H), 7.57 – 7.51 (m, 2H), 7.41 – 7.35 (m, 1H), 6.85 (s, 2H), 6.38 (d, J =8.7 Hz, 2H), 6.32 (dd, J = 8.7, 2.9 Hz, 2H), 5.45 (d, J = 2.9 Hz, 2H), 4.54 (s,2H), 4.10 (s, 2H), 3.12 (s, 6H). 13 C NMR (125 MHz, DMSO-) d 6 ) δ 168.9, 159.0,152.2, 151.4, 150.7, 150.7, 150.3, 149.5, 139.3, 136.4, 132.5,130.9, 128.6,128.3, 126.7, 125.1, 124.8, 124.6, 123.4, 121.9, 117.3, 116.7, 115.3, 112.8,112.6, 104.7, 79.7, 60.8, 56.4, 54.3, 46.0, 43.1.

[0049] Application Example 1 The structural formula of the bicyclic [4.1.1] octane fluorene derivative (Example 13) in this application example is as follows: .

[0050] In this application example, the concentration of the bicyclic [4.1.1] octaneazine derivative in ethyl acetate is 10. -4 At M, there is almost no fluorescence under excitation at a wavelength of 323 nm, but its solid exhibits green fluorescence under irradiation at a wavelength of 323 nm (e.g., ​ (As shown).

[0051] In this application example, the bicyclic [4.1.1] octane fluorene derivatives exhibited aggregation-induced emission (AIE) in different solvents, petroleum ether (a poor solvent) and ethyl acetate (a good solvent), in proportions ranging from 0% to 90%.

[0052] This invention further investigated the aggregation-induced emission (AIE) effect of the bicyclic [4.1.1] octaneazine derivative of this application example in different proportions (0% to 99%) of petroleum ether (a poor solvent) and ethyl acetate (a good solvent). The proportions of petroleum ether in the mixed solvents were 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 99%. Experimental results showed that as the proportion of petroleum ether increased, the fluorescence intensity gradually increased (e.g., ...). ​ (As shown). Furthermore, the experiment also found that the emission intensity in 90% petroleum ether (volume ratio) was approximately 5 times that in pure ethyl acetate (as shown). ​ (As shown). When the petroleum ether content was increased to 99%, a rapid decrease in emission intensity was observed due to the formation of large aggregates and solution inhomogeneity, a common phenomenon in aggregation-induced emission (AIE) polymers.

[0053] Application Example 2 The structural formula of the bicyclic [4.1.1] octane fluorene derivative (Example 12) in this application example is as follows: .

[0054] In this application example, the bicyclic [4.1.1] octane fluorene derivative exhibited good catalytic activity as an organic catalyst for the Michael addition reaction of 3-benzofuranone with nitrostyrene.

[0055] The application method of this example is as follows: 26.8 mg (0.20 mmol) of 3-benzofuranone, 35.8 mg (0.20 mmol) of 1-(2-methoxyphenyl)-2-nitroethylene, 22.8 mg (0.04 mmol) of the compound of Example 12, and 1.5 mL of dichloromethane were added to a reaction tube and reacted at 25 °C for 48 hours. After the reaction was completed, the mixture was concentrated and separated by column chromatography (eluent: petroleum ether and ethyl acetate, volume ratio of 10:1 to 1:1) to obtain the target product, which was a yellow solid (yield 25%).

[0056] 1 (500 MHz, CDCl3, a mixture of two isomers) δ 7.67 – 7.61 (m, 1H for isomer A and 1H for isomer B, overlapped), 7.61 – 7.55 (m, 1H for isomer A and1H for isomer B, overlapped), 7.34 – 7.29 (m, 1H, isomer A), 7.28 – 7.20 (m,1H for isomer A and 1H for isomer B, overlapped), 7.16 (dd, J = 7.6, 1.7 Hz,1H, isomer B), 7.16 – 7.08 (m, 1H for isomer A and 1H for isomer B, overlapped), 7.09 – 7.02 (m, 1H for isomer A and 1H for isomer B, overlapped), 6.99 – 6.94 (m, 1H, isomer A), 6.92 (d, J = 8.3 Hz, 1H, isomer A), 6.87 (d, J =8.4 Hz, 1H, isomer B), 6.85 – 6.80 (m, 1H, isomer B), 5.25 – 5.17 (m, 1H, isomer B), 5.05 (d, J= 7.2 Hz, , isomer B), 5.00 – 4.92 (m, 2H,isomer A), 4.90– 4.79 (m, 2H, 1H for isomer A and 1H for isomer B, overlapped), 4.51 – 4.42(m, 1H, isomer A), 4.38 (q, J = 7.2 Hz, 1H, isomer B), 3.86 (s, 3H, isomer A),3.86 (s, 3H, isomer B). 13 C NMR(125 MHz, CDCl3, a mixture of two isomers) δ199.8 (isomer B), 199.0 (isomer A), 172.5 (isomer B), 172.2 (isomer A), 157.3(isomer A and B, overlapped), 138.3 (isomer B), 130.1(isomer B), 129.8(isomer A), 129.7 (isomer A), 124.54 (isomer A), 124.47 (isomer B), 123.1(isomer A), 122.7 (isomer B), 122.6 (isomer A), 122.4 (isomerB), 121.23(isomer B), 121.15 (isomer A), 121.0 (isomer A), 120.9 (isomer B), 113.6(isomer A), 113.5 (isomer B), 111.3 (isomer B), 111.2 (isomer A), 84.0(isomerA), 83.1 (isomer B), 74.7 (isomer A), 74.6 (isomer B), 55.7 (isomer B), 55.6(isomer A), 40.9 (isomer A), 40.3 (isomer B)。

Claims

1. A bicyclic [4.1.1] octane-azafluorene derivative, characterized in that, The structural formula is shown in Equation I below: （Ⅰ） Among them, R 1 It is selected from at least one of hydrogen, halogen, alkyl, hydroxyl, trifluoromethyl, alkoxy, nitro, ester, amino, amide, alkylacyloxy, cyano, aryl, halobenzyloxy, halobenzylamine, and halophenoxy; Ar 2 Selected from ; The R 1 ' is selected from at least one of hydrogen, halogen, alkyl, trifluoromethyl, hydroxyl, alkoxy, nitro, ester, amino, amide, alkanoyloxy, cyano, aryl, alkenyl, halobenzyloxy, halobenzylamine, and halophenoxy.

2. The double ring as described in claim 1 4.1.1】A method for preparing octane-azafluorene derivatives, characterized in that, Includes the following steps: The 2-(2-(2-hydroxybenzyl)-2,3-dihydro-1H-indenyl-1-methylene)malononitrile derivative was reacted with a catalyst and solvent at 40-150℃ for 0.5-6 hours. After the reaction was complete, distilled water was added, and the mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The crude product was then separated by column chromatography to obtain the bicyclic […]. 4.1.1】Octane-azafluorene derivatives; The reaction route is shown below: 。 3. The double ring as described in claim 2 4.1.1】A method for preparing octane-azafluorene derivatives, characterized in that, The catalyst is selected from DABCO, DMAP, DIPEA, morpholine, Et3N, DBN, DBU, TMG, Na2CO3, K2CO3, Cs2CO3, KF, CsF, K3PO4, NaOH, and KOH. t- At least one of BuOK, MeONa, EtONa, and NaH.

4. The double ring as described in claim 3 4.1.1】A method for preparing octane-azafluorene derivatives, characterized in that, The catalyst is used at a rate of 20%-200% of the molar amount of the 2-(2-(2-hydroxybenzyl)-2,3-dihydro-1H-indenyl-1-methylene)malononitrile derivative.

5. The double-ring as described in claim 2 4.1.1】A method for preparing octane-azafluorene derivatives, characterized in that, The solvent is DMF.

6. The double ring as described in claim 5 4.1.1】A method for preparing octane-azafluorene derivatives, characterized in that, For every mmol of 2-(2-(2-hydroxybenzyl)-2,3-dihydro-1H-indenyl-1-methylene)malononitrile derivative, add 4-8 mL of solvent.

7. The double ring as described in claim 2 4.1.1】A method for preparing octane-azafluorene derivatives, characterized in that, The reaction temperature is 60-100℃.

8. The double-ring as described in claim 2 4.1.1】A method for preparing octane-azafluorene derivatives, characterized in that, The eluent used in column chromatography is a mixture of petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate is 10:1 to 1:

1.

9. The use of the bicyclic [4.1.1] octane fluorene derivative of claim 1 as an organic catalyst, organic optoelectronic material or fluorescent material.

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