An eight-membered spirocyclic silylfluorene derivative, preparation method and application thereof

Abstract

The invention discloses an octa-membered spirocyclic silanol derivative, the structural formula of which is: wherein, in general formula I, Ar is any one or more of 4-methoxyphenyl, 4-(9H-9-carbazole)phenyl, triphenylamine, trifluoromethylphenyl, tetraphenylethylene, 1,2,3-tri(dodecyloxy)phenyl, and in general formula II, R is any one or more of p-methylphenyl, triphenylamine, 4-methoxyphenyl, trans-4-n-pentylcyclohexylphenyl, 3-thienyl, and 3-furanyl. The octa-membered spirocyclic silanol derivative of the invention is a class of organic fluorescent materials with simple preparation method, high quantum yield, high fluorescence brightness, and good photothermal stability. Such compounds have potential application value in the fields of optical functional organic materials such as organic light emitting diodes (OLEDs), organic field effect transistors (OFETs), bioimaging, fluorescence sensing, latent fingerprint detection and identification.

Description

Technical Field

[0001] The invention belongs to the field of chemical technology and optoelectronic materials, and specifically relates to an octa-membered spirocyclic silylfluorene derivative, a preparation method and an application thereof. Background Art

[0002] In recent years, fluorene-based compounds with silicon bridges at the 9-position of the fluorene structure have attracted increasing attention from researchers due to their unique electronic structure and optoelectronic properties. These compounds have broad application prospects in optoelectronic functional materials such as organic light-emitting diodes (OLEDs), organic solar cells (OSCs), and organic field effect transistors (OFETs). In addition, as organic optoelectronic functional materials, fluorene-based compounds have shown great application prospects in many high-tech fields such as organic electroluminescence, organic solid lasers, photoelectric sensors, bioimaging, and photodynamic therapy due to their unique electronic structure and properties, and have become an emerging multidisciplinary cross-cutting frontier research field. With the deepening of research work, fluorene-based derivatives have been proven to be superior to traditional fluorescent dyes in bioimaging and fluorescence imaging technology. Therefore, in recent years, many simple, efficient and innovative fluorene-based compound synthesis technologies have been developed to obtain fluorene-based derivatives with new structures and functions.

[0003] Fluorescent materials are used as fluorescent dyes in applications such as fluorescence visualization sensing and bio-imaging. They must have the advantages of large emission wavelength, high color purity, sufficient brightness, and good photothermal stability. In many fingerprint imaging technologies, fluorescent dye staining is a very popular high-sensitivity fingerprint detection method. However, organic small molecules will undergo fluorescence quenching due to the ACQ effect in the solid state, which limits their application in fingerprint recognition.

[0004] Therefore, through a simple synthetic strategy, the design and synthesis of silane derivatives with long-wavelength emission, high color purity, high solid-state quantum yield, sufficient brightness, high photothermal stability and potential for visualization of fingerprints are of great value and significance as alternatives to traditional fluorescent dyes. Summary of the invention

[0005] The present invention is made to solve the above problems, and aims to provide an octa-membered spirocyclic silylfluorene derivative, a preparation method and an application thereof.

[0006] The present invention provides an eight-membered spirocyclic silylfluorene derivative having the following characteristics and a structural formula:

[0007]

[0008] or

[0009]

[0010] Wherein, in the general formula I, Ar is any one or more of 4-methoxyphenyl, 4-(9H-9-carbazole)phenyl, triphenylamine, trifluoromethylphenyl, tetraphenylethylene, 1,2,3-tri(dodecyloxy)phenyl, and in the general formula II, R is any one or more of p-methylphenyl, triphenylamine, 4-methoxyphenyl, trans-4-n-pentylcyclohexylphenyl, 3-thienyl and 3-furanyl.

[0011] The present invention provides a method for preparing an eight-membered spirocyclic silylfluorene derivative, which is used for preparing the eight-membered spirocyclic silylfluorene derivative and has the following characteristics, comprising the following steps: step S1, adding tetrahydrofuran and a lithium reagent to a compound shown in the following structural formula III, stirring for 2 hours under ultra-low temperature conditions, adding 1,1-dichlorosilylcyclobutane, stirring overnight, quenching the reaction mixture with a saturated aqueous ammonium chloride solution after the reaction is completed, and extracting with dichloromethane, washing the organic layer with brine three times, drying with anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and purifying the crude product by column chromatography to obtain the desired product IV;

[0012]

[0013] Step S2, add platinum catalyst and toluene to the product IV shown in the following structural formula IV, quench the reaction mixture with saturated aqueous ammonium chloride solution after the reaction is completed, and extract with dichloromethane, wash the organic layer three times with brine, dry with anhydrous magnesium sulfate, filter, and concentrate under reduced pressure. Purify the crude product by column chromatography to obtain the desired product V;

[0014]

[0015] Step S3, piperidine, palladium catalyst, cuprous iodide and arylacetylene are added to the product V shown in the following structural formula V, and after the reaction is completed, the reaction mixture is quenched with a saturated aqueous ammonium chloride solution, and extracted with dichloromethane, the organic layer is washed three times with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure, and the crude product is purified by column chromatography to obtain the desired product, to obtain the following 1-6 described in formula I, a total of 6 octa-membered spirocyclic silylene derivatives,

[0016]

[0017]

[0018] The preparation method of the octa-membered spirocyclic silafluorene derivative provided by the present invention may also have the following characteristics: wherein the molar ratio of the product IV to the platinum catalyst is 20:1, the reaction temperature is 85°C, the reaction time is 24 hours, the reaction atmosphere is nitrogen or argon atmosphere, and the solvent for column chromatography purification is dichloromethane or petroleum ether.

[0019] The present invention provides a method for preparing an eight-membered spirocyclic silanol derivative, which is used for preparing the eight-membered spirocyclic silanol derivative, and has the following characteristics: anhydrous sodium carbonate, a palladium catalyst, anhydrous ethanol, deionized water, toluene and boric acid are added to a compound as shown in structural formula V, and after the reaction is completed, the reaction mixture is quenched with a saturated aqueous ammonium chloride solution, extracted with dichloromethane, the organic layer is washed three times with brine, dried with anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and the crude product is purified by column chromatography to obtain the desired product, thereby obtaining the following 7-12 eight-membered spirocyclic silanol derivatives described by formula II, a total of 6:

[0020]

[0021] The present invention provides a method for preparing an eight-membered spirocyclic silanol derivative, which is used for preparing the eight-membered spirocyclic silanol derivative and has the following characteristics, comprising the following steps: step S1', adding anhydrous sodium carbonate, a palladium catalyst, anhydrous ethanol, deionized water, toluene and an aryl boronic acid to a product VII shown in the following structural formula VI, quenching the reaction mixture with a saturated aqueous ammonium chloride solution after the reaction is completed, and extracting with dichloromethane, washing the organic layer with brine three times, drying with anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and purifying the crude product by column chromatography to obtain the desired product VII;

[0022]

[0023] Step S2', adding liquid bromine and dichloromethane to the product VII shown in the following structural formula VII, quenching the reaction mixture with a saturated sodium thiosulfate aqueous solution after the reaction is completed, and extracting with dichloromethane, washing the organic layer three times with brine, drying over anhydrous magnesium sulfate, filtering, and concentrating under reduced pressure, and purifying the crude product by column chromatography to obtain the desired product VIII;

[0024]

[0025] Step S3', tetrahydrofuran and lithium reagent are added to the product VIII shown in the following structural formula VIII, and 1,1-dichlorosilylcyclobutane is added thereto under ultra-low temperature conditions for 2 hours, and the mixture is stirred overnight. After the reaction is completed, the reaction mixture is quenched with a saturated aqueous solution of ammonium chloride, and extracted with dichloromethane. The organic layer is washed three times with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by column chromatography to obtain the desired product IX;

[0026]

[0027] Step S4', adding a platinum catalyst to the product IX shown in the following structural formula IX, quenching the reaction mixture with a saturated aqueous solution of ammonium chloride after the reaction is completed, and extracting with dichloromethane, washing the organic layer three times with brine, drying over anhydrous magnesium sulfate, filtering, and concentrating under reduced pressure, purifying the crude product by column chromatography to obtain the desired product, and obtaining 7-10 described by the general formula II, a total of 4 octa-membered spirocyclic silanol derivatives,

[0028]

[0029] The preparation method of the octa-membered spirocyclic silanol derivative provided by the present invention may also have the following characteristics: wherein, in step S1', Ar in formula VII is any one or more of p-methylphenyl, triphenylamine, 4-methoxyphenyl, and trans-4-n-pentylcyclohexylphenyl; in step S2', Ar in formula VII is any one or more of p-methylphenyl, triphenylamine, 4-methoxyphenyl, and trans-4-n-pentylcyclohexylphenyl; in step S3', Ar in formula VIII is any one or more of p-methylphenyl, triphenylamine, 4-methoxyphenyl, and trans-4-n-pentylcyclohexylphenyl.

[0030] The invention provides an application of an eight-membered spirocyclic silicon fluorene derivative, which has the following characteristics: the eight-membered spirocyclic silicon fluorene derivative is applied to fluorescence visualization.

[0031] In the application of the eight-membered spirocyclic silicon fluorene derivative provided by the present invention, the eight-membered spirocyclic silicon fluorene derivative can also have the following characteristics: the eight-membered spirocyclic silicon fluorene derivative is used as a fluorescent visualization material for fingerprint detection and identification.

[0032] Functions and Effects of the Invention

[0033] The octa-membered spirocyclic silylfluorene derivative of the present invention has high quantum yield, high brightness and high photothermal stability, and possesses the characteristics that a substitute for traditional fluorescent dyes should possess, and can be used in applications such as latent fingerprint detection and identification, and other aspects of fluorescence visualization.

[0034] In addition, the preparation method of the octa-membered spirocyclic silanol derivative provided by the present invention is a simple metal catalyst ring expansion method. By connecting two silanols together in a ring-opening dimerization mode, the substitution sites of the molecule are increased, thereby introducing more substitution groups, and preparing a series of novel silanol derivatives with high quantum yield and brightness. It is a simple and efficient method strategy. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a schematic diagram of the preparation route of the octa-membered spirocyclic silanol derivative in Example 1 of the present invention.

[0036] Figure 2 is the H NMR spectrum of compound IV in Example 1 of the present invention;

[0037] Figure 3 is the NMR carbon spectrum of compound IV in Example 1 of the present invention;

[0038] Figure 4 is the H NMR spectrum of compound V in Example 1 of the present invention;

[0039] Figure 5 is the NMR carbon spectrum of compound V in Example 1 of the present invention;

[0040] Figure 6 is the H NMR spectrum of compound 3 in Example 1 of the present invention;

[0041] Figure 7 is the NMR carbon spectrum of compound 3 in Example 1 of the present invention;

[0042] Figure 8 It is a schematic diagram of the preparation route of the octa-membered spirocyclic silanol derivative in Example 2 of the present invention.

[0043] Fig. 9 is the H NMR spectrum of compound 7 in Example 2 of the present invention;

[0044] Fig.10 is the NMR carbon spectrum of compound 7 in Example 2 of the present invention;

[0045] Fig.11 is the crystal structure of compound 7 in Example 2 of the present invention;

[0046] Fig.12 It is a schematic diagram of the preparation route of the octa-membered spirocyclic silanol derivative in Example 3 of the present invention.

[0047] Fig.13 is the H NMR spectrum of compound VII (Ar is p-methylphenyl) in Example 3 of the present invention;

[0048] Fig.14 is the C NMR spectrum of compound VII (Ar is p-methylphenyl) in Example 3 of the present invention;

[0049] Fig.15 is the H NMR spectrum of compound VIII (Ar is p-methylphenyl) in Example 3 of the present invention;

[0050] Fig.16 is the C NMR spectrum of compound VIII (Ar is p-methylphenyl) in Example 3 of the present invention;

[0051] Fig.17 is the H NMR spectrum of compound IX (Ar is p-methylphenyl) in Example 3 of the present invention;

[0052] Fig.18is the NMR carbon spectrum of compound IX (Ar is p-methylphenyl) in Example 3 of the present invention;

[0053] Fig.19 The UV-visible absorption spectra, fluorescence emission spectra and fluorescence photographs of some compounds in Example 4 of the present invention in dichloromethane and the fluorescence photographs of compound 3 in different solvents are shown in FIG. Fig.19 (a) is the UV-visible absorption spectrum; Fig.19 (b) is the fluorescence emission spectrum; Fig.19 (c) is a fluorescent photograph; Fig.19 (d) is the fluorescence photograph of compound 3 in different solvents;

[0054] Fig. 20 are solid fluorescence spectra and fluorescence photographs of some compounds in Example 4 of the present invention, wherein Fig. 20 (a) is the fluorescence spectrum; Fig. 20 (b) is a fluorescent photograph;

[0055] Fig.21 Compound 3 in Example 5 of the present invention is used as a detection and identification photo of latent fingerprints;

[0056] Fig. 22 This is a photo of compound 5 in Example 5 of the present invention used for detection and identification of latent fingerprints. DETAILED DESCRIPTION

[0057] In order to make the technical means, creative features, objectives and effects achieved by the present invention easier to understand, the present invention is described in detail below in conjunction with embodiments.

[0058] <Example 1>

[0059] This embodiment provides a method for preparing an octa-membered spirocyclic silanol derivative 1-6.

[0060] Figure 1 It is a schematic diagram of the preparation route of the octa-membered spirocyclic silanol derivative in Example 1 of the present invention.

[0061] like Figure 1 As shown, the preparation method of the octa-membered spirocyclic silylfluorene derivative 1-6 comprises the following steps:

[0062] Step S1, preparation of a quaternary spirocyclic silylfluorene derivative (IV): the compound shown in the following structural formula III (6.24 g, 10.00 mmol) is placed in a 250 mL double-necked flask equipped with a stirring rod, anhydrous tetrahydrofuran (200 mL) and n-butyl lithium reagent (2.5 equivalents, 2.4 mol / L n-hexane solution, 10.41 mL) are added, the mixture is stirred at -78 ° C for 2 hours, 1,1-dichlorosilylcyclobutane (1.5 equivalents, 1.78 ml) is added, and stirred at room temperature for 18 hours. After the reaction is completed, the reaction mixture is quenched with a saturated NH4Cl aqueous solution and extracted with dichloromethane. The organic layer is washed three times with brine, dried with MgSO4 and concentrated. The crude product is separated and purified by column chromatography on silica gel 200-300 mesh, and the eluent is V 乙酸乙酯 :V 石油醚 =1:10, and obtain white powder.

[0063]

[0064] The reaction formula is as follows:

[0065]

[0066] Figure 2 It is the H NMR spectrum of compound IV in Example 1 of the present invention.

[0067] Figure 3 It is the NMR carbon spectrum of compound IV in Example 1 of the present invention.

[0068] like Figure 2 , 3 As shown, the following compound IV (2.80 g, yield: 63.6%) was obtained: 1 H NMR (600MHz, CDCl3) δ7.89 (s, 2H), 7.23 (s, 2H), 4.04 (s, 6H), 2.37 (m, J1 = 8.4Hz, J2 = 7.8Hz, 2H), 1.59 (t, J = 8.4Hz, 4H). 13 C NMR (151MHz, CDCl3) δ158.25(s),148.03(s),137.84(s),129.58(s),112.32(s),104.63(s),56.35(s),19.09(s),15.38(s). 29 Si NMR (119MHz, CDCl3) δ11.24ppm.

[0069]

[0070] Step S2, preparation of octa-spirocyclic silanol derivative (V): IV (3 g, 6.82 mmol) in step S1 was placed in a 500 mL double-necked flask equipped with a stirring bar, toluene (200 mL) and Pt catalyst (0.1 equivalent. 0.85 g, 0.682 mmol) were added, and the mixture was stirred at 85°C for 24 hours. After the reaction was completed, the reaction mixture was quenched with saturated NH4Cl aqueous solution and extracted with dichloromethane. The organic layer was washed three times with brine, dried over MgSO4 and concentrated. The crude product was separated and purified by column chromatography on silica gel 200-300 mesh, and the eluent was V 乙酸乙酯 :V 石油醚 =1:10, a white powder is obtained, and the reaction formula is as follows.

[0071]

[0072] Figure 4 is the H NMR spectrum of compound V in Example 1 of the present invention;

[0073] Figure 5 It is the C NMR spectrum of compound V in Example 1 of the present invention.

[0074] like Figure 4 , 5 As shown, the prepared compound V (1.60 g, yield: 53.3%): 1 H NMR (600MHz, CDCl3) δ7.82 (s, 4H), 7.31 (s, 4H), 4.05 (s, 12H), 2.21 (m, J1 = 7.2Hz, J2 = 6Hz, 4H), 1.34 (t, J = 6.6Hz, 8H). 13 C NMR (151MHz, CDCl3) δ157.84(s),148.00(s),137.37(s),131.64(s),112.19(s),105.08(s),56.36(s),18.94(s),16.33(s). 29 Si NMR (119MHz, CDCl3) δ1.83ppm.

[0075] Step S3, preparation of octa-membered spirocyclic silanol derivative (3): V (0.18 g, 0.20 mmol) prepared in step S2 was placed in a 10 mL double-necked flask equipped with a stirring bar, and palladium catalyst (0.05 equivalent, 11.5 mg), cuprous iodide (0.1 equivalent, 3.8 mg), 4-ethynyltriphenylamine (6 equivalent, 323.2 mg) and piperidine (6 mL) were added, and the mixture was stirred at 85° C. for 24 hours. After the reaction was completed, the reaction mixture was quenched with saturated NH4Cl aqueous solution and extracted with dichloromethane. The organic layer was washed three times with brine, dried over MgSO4 and concentrated. The crude product was separated and purified by column chromatography on silica gel 200-300 mesh, and the eluent was V 二氯甲烷 :V 石油醚 =1:5, to obtain a yellow solid, the reaction formula is as follows.

[0076]

[0077] Figure 6 It is the H NMR spectrum of compound 3 in Example 1 of the present invention.

[0078] Figure 7 It is the NMR carbon spectrum of compound 3 in Example 1 of the present invention.

[0079] like Figure 6 , 7 As shown, the obtained eight-membered spirocyclic silylene derivative 3 (143.7 mg, yield: 43.0%): 1 HNMR (600MHz, CDCl3) δ7.82 (s, 4H), 7.44 (d, J = 9Hz, 8H), 7.33 (s, 4H), 7.26 (t, J1 = 8.4Hz, J2 = 7.8Hz, 16H), 7.10 (d ,J=7.8Hz,16H),7.05(t,J=7.2Hz,8H),7.00(d,J=8.4Hz,16H),4.07(s,12H),2.28(m,4H),1.41(t,J=6.6Hz,8H). 13 C NMR(151MHz, CDCl3)δ162.09(s),148.88(s),147.76(s),147.26(s),137.78(s),132.65(s),130.62(s),129.37(s),124 .90(s),123.43(s),122.42(s),116.56(s),112.66(s),103.84(s),94.91(s),85.57(s),56.05(s),19.17(s),16.57(s). 29Si NMR (119MHz, CDCl3) δ1.55ppm.HRMS (ESI, m / z): [M+Na] + calculated for C 114 H 88 N4O4Si2,1634.1520; found 1656.6265.

[0080] The synthesis steps of the eight-membered spirocyclic silylfluorene derivatives 1-6 are the same.

[0081] The obtained eight-membered spirocyclic silylfluorene derivative 4 (113.8 mg, yield: 45.0%): 1 H NMR (600MHz, CDCl3) δ7.86 (s, 4H), 7.68 (d, J = 8.4Hz, 8H), 7.59 (d, J = 9.0Hz, 8H), 7 .37(s,4H),4.10(s,12H),2.30(J1=6.6Hz,J2=5.4Hz,4H),1.44(t,J=6.6Hz,8H). 13 C NMR(151MHz, CDCl3)δ162.69(s),149.72(s),138.17(s),131.98(s),130.86(s),127.53(s),12 5.32-125.42(m),112.09(s),104.19(s),93.41(s),88.88(s),56.22(s),19.27(s),16.69(s). 29 Si NMR (119MHz, CDCl3) δ1.64ppm.[2M+Na] + calculated for C 70 H 48 F 12 O4Si2,1237.3008; found 2496.5722.

[0082] The obtained eight-membered spirocyclic silylfluorene derivative 5 (166.3 mg, yield: 41.0%): 1 H NMR (600MHz, CDCl3) δ7.78(d,J=1.8Hz,4H),7.33(t,J=9Hz,12H),7.09(d,J=3Hz,3 6H),7.00-7.04(m,32H),4.05(s,12H),2.24(m,J=6.0Hz,4H),1.38(t,J=6Hz,8H). 13C NMR(151MHz, CDCl3)δ162.37(s),149.20(s),143.99(s),143.72(s),143.63(s),143.52( s),141.76(s),140.56(s),138.03(s),131.54(s),131.46(s),131.20(s),130.79(s),129 .18(s),128.38(s),127.97(s),127.87(s),127.80(s),126.80(s),126.72(s),126.68(s) ,121.57(s),112.65(s),104.05(s),94.98(s),86.71(s),56.17(s),19.28(s),16.71(s). 29 Si NMR (119MHz, CDCl3) δ1.57ppm.[M+Na] + calculated for C 146 H 108 O4Si2,1982.6360; found 2004.7740.

[0083] The obtained eight-membered spirocyclic silylfluorene derivative 6 (311.9 mg, yield: 48.0%): 1 H NMR(600MHz, CDCl3)δ7.82(s,4H),7.34(s,4H),6.78(s,8H),4.08(s,12H),3.94-3.97(m,24H ),2.32(m,4H),1.71-1.80(m,32H),1.45(m,36H),1.25(d,J=6Hz,180H),0.86-0.89(m,36H). 13 C NMR(151MHz, CDCl3)δ162.28(s),153.14(s),149.13(s),139.35(s),137.93(s) ),132.22(s),130.72(s),128.70(s),118.05(s),112.70(s),110.53(s),104. 04(s),95.22(s),85.00(s),73.68(s),69.35(s),56.19(s),32.08(s),29.91( s),29.85(s),29.80(s),29.58(s),29.52(s),26.28(s),22.84(s),14.24(s). 29 Si NMR (119MHz, CDCl3) δ1.45ppm.[M+H]+ calculated for C 146 H 108 O4Si2,3177.1840; found3178.4226.

[0084] <Example 2>

[0085] This embodiment provides a method for preparing an eight-membered spirocyclic silanol derivative 7-12.

[0086] Figure 8 It is a schematic diagram of the preparation route of the octa-membered spirocyclic silanol derivative in Example 2 of the present invention.

[0087] like Figure 8 As shown, the preparation method of the octa-membered spirocyclic silylfluorene derivative 7-12 comprises the following steps:

[0088] Synthesis of eight-membered spirocyclic silylfluorene derivative (7):

[0089] Compound V (0.18 g, 0.20 mmol) in Example 1 was placed in a 10 mL double-necked flask equipped with a stirring bar, and palladium catalyst (0.05 equivalent, 11.5 mg), anhydrous sodium carbonate (6 equivalent, 127.2 mg), p-methylphenylboronic acid (6 equivalent, 163.2 mg), anhydrous ethanol (0.6 mL), toluene (6 mL) and deionized water (0.6 mL) were added, and the mixture was stirred at 105 ° C for 24 hours. After the reaction was completed, the reaction mixture was quenched with a saturated NH4Cl aqueous solution and extracted with dichloromethane. The organic layer was washed three times with brine, dried with MgSO4 and concentrated. The crude product was separated and purified by column chromatography on silica gel 200-300 mesh, and the eluent was V 二氯甲烷 :V 石油醚 =1:6, a white powder solid was obtained. The reaction formula is as follows.

[0090]

[0091] Fig. 9 is the H NMR spectrum of compound 7 in Example 2 of the present invention;

[0092] Fig.10 It is the NMR carbon spectrum of compound 7 in Example 2 of the present invention.

[0093] like Fig. 9 , 10 As shown, the obtained eight-membered spirocyclic silylene derivative 7 (102.6 mg, yield: 57.0%): 1HNMR (600MHz, CDCl3) δ7.68 (s, 4H), 7.55 (d, J = 7.8Hz, 8H), 7.48 (s, 4H), 7.29 (d, J = 7. 8Hz,8H),4.00(s,12H),2.44(s,12H),2.28(m,4H),1.44(t,J1=6.0Hz,J2=7.2Hz,8H). 13 C NMR(151MHz, CDCl3)δ158.87(s),148.70(s),136.80(s),135.81(s),135.37(s),130.68(s) ,130.19(s),129.57(s),128.94(s),104.18(s),55.79(s),21.38(s),19.42(s),16.88(s). 29 Si NMR (119MHz, CDCl3) δ1.55ppm.[M+Na] + calculated for C 62 H 60 O4Si2,925.3280; found948.3967.

[0094] Fig.11 It is the crystal structure of compound 7 in Example 2 of the present invention.

[0095] The synthesis steps of the eight-membered spirocyclic silylfluorene derivatives 7-12 are all the same.

[0096] <Example 3>

[0097] This embodiment provides a method for preparing an eight-membered spirocyclic silylfluorene derivative 7-10:

[0098] Fig.12 It is a schematic diagram of the preparation route of the octa-membered spirocyclic silanol derivative in Example 3 of the present invention.

[0099] like Fig.12 As shown, the preparation method of the octa-membered spirocyclic silylfluorene derivative 7-10 comprises the following steps:

[0100] Step S1', preparing compound (VII) (wherein Ar is p-methylphenyl):

[0101] The compound shown in the following structural formula VI (3 g, 8.06 mmol) was placed in a 1000 mL double-necked flask equipped with a stirring bar, and palladium catalyst (0.05 equivalent, 465.7 mg), anhydrous sodium carbonate (9 equivalent, 7.63 g), p-methylphenylboronic acid (2.5 equivalent, 2.74 g), anhydrous ethanol (36 mL), toluene (360 mL) and deionized water (36 mL) were added. The mixture was stirred at 105°C for 24 hours. After the reaction was completed, the reaction mixture was quenched with a saturated NH4Cl aqueous solution and extracted with dichloromethane. The organic layer was washed three times with brine, dried with MgSO4 and concentrated. The crude product was separated and purified by column chromatography on silica gel 200-300 mesh, and the eluent was V 二氯甲烷 :V 石油醚 =1:8, to obtain a white powder solid.

[0102]

[0103] The reaction formula is as follows:

[0104]

[0105] Fig.13 This is the H NMR spectrum of compound VII (Ar is p-methylphenyl) in Example 3 of the present invention.

[0106] Fig.14 This is the carbon NMR spectrum of compound VII (Ar is p-methylphenyl) in Example 3 of the present invention.

[0107] like Fig.13 , 14 As shown, the obtained compound VII (2.29 g, yield: 72.0%): 1 HNMR (600MHz, CDCl3) δ7.52(d,J=7.8Hz,4H),7.44(d,J=7.7Hz,2H),7.32(d,J =7.8Hz,2H),7.28(d,J=7.7Hz,4H),7.25(s,2H),3.92(s,6H),2.44(s,6H).13C NMR(151MHz, CDCl3)δ156.93(s),144.17(s),136.89(s),135.35(s),131.21(s),13 0.02(s),129.51(s),128.96(s),119.83(s),110.37(s),55.85(s),21.37(s).[M+H] + calculated for C 28 H 26 O2,394.5140; found395.2006.

[0108] Step S2', synthesis of compound (VIII) (wherein Ar is p-methylphenyl):

[0109] The compound shown in the structural formula VII obtained in step S1' was placed in a 100mL double-necked flask equipped with a stirring rod, and liquid bromine (2.1 equivalents, 0.58ml) and dichloromethane (60mL) were added. The mixture was stirred at room temperature for 4 hours. After the reaction was completed, the reaction mixture was quenched with a saturated aqueous sodium thiosulfate solution and extracted with dichloromethane. The organic layer was washed three times with brine, dried over MgSO4 and concentrated. The crude product was separated and purified by column chromatography on silica gel 200-300 mesh, and the eluent was V 二氯甲烷 :V 石油醚 =1:8, a white powder solid was obtained. The reaction formula is as follows.

[0110]

[0111] Fig.15 This is the H NMR spectrum of Compound VIII (Ar is p-methylphenyl) in Example 3 of the present invention.

[0112] Fig.16 This is the carbon NMR spectrum of compound VIII (Ar is p-methylphenyl) in Example 3 of the present invention.

[0113] like Fig.15 , 16 As shown, the obtained compound VIII (2.42 g, yield: 86.5%): 1 HNMR (600MHz, CDCl3) δ7.64(s,2H),7.51(d,J=7.7Hz,4H),7.29(d,J=7.7Hz,4H),6.96(s,2H),3.84(s,6H),2.44(s,6H). 13 C NMR(151MHz, CDCl3)δ155.61(s),144.41(s),137.50(s),134.25(s),133.96(s), 132.29(s),129.47(s),129.04(s),114.19(s),114.01(s),56.08(s),21.39(s).

[0114] Step S3', synthesis of a quaternary spirocyclic silanol derivative (IX): (wherein Ar is p-methylphenyl):

[0115] The compound (2.1 g, 3.8 mmol) of the structural formula VIII obtained in step S2' was placed in a 250 mL double-necked flask equipped with a stirring rod, and anhydrous tetrahydrofuran (100 mL) and n-butyl lithium reagent (2.5 equivalents, 2.4 mol / L n-hexane solution, 3.96 mL) were added. The mixture was stirred at -78 ° C for 2 hours, and 1,1-dichlorosilylcyclobutane (2.1 equivalents, 0.95 ml) was added and stirred at room temperature for 18 hours. After the reaction was completed, the reaction mixture was quenched with a saturated NH4Cl aqueous solution and extracted with dichloromethane. The organic layer was washed three times with brine, dried with MgSO4 and concentrated. The crude product was separated and purified by column chromatography on silica gel 200-300 mesh, and the eluent was V 乙酸乙酯 :V 石油醚 =1:10, a white powder is obtained, and the reaction formula is as follows.

[0116]

[0117] Fig.17 This is the H NMR spectrum of Compound IX (Ar is p-methylphenyl) in Example 3 of the present invention.

[0118] Fig.18 This is the carbon NMR spectrum of compound IX (Ar is p-methylphenyl) in Example 3 of the present invention.

[0119] like Fig.17 , 18 As shown, the obtained compound IX (1.1 g, yield: 62.9%): 1 H NMR (600MHz, CDCl3) δ7.71 (s, 2H), 7.50 (d, J = 8.4Hz, 4H), 7.38 (s, 2H), 7.26 (d, J =

[0120] 7.8Hz, 4H), 3.96 (s, 6H), 2.42 (s, 6H), 2.36 (m, J = 8.4Hz, 2H), 1.60 (t, J = 8.4Hz, 4H). 13 C NMR(151MHz, CDCl3)δ159.44(s),148.78(s),136.87(s),135.78(s),135.70(s),130.61(s) ,129.50(s),128.95(s),128.41(s),103.96(s),55.86(s),21.39(s),19.26(s),15.66(s). 29 Si NMR (119MHz, CDCl3) δ11.27ppm.[M+H] + calculated for C 31 H 30O2Si,462.6640; found463.2088.

[0121] Step S4', synthesis of eight-membered spirocyclic silylfluorene derivative (7):

[0122] The compound represented by the structural formula IX obtained in step S3' (1 g, 2.16 mmol) was placed in a 100 mL double-necked flask equipped with a stirring bar, and toluene (70 mL) and Pt catalyst (0.1 equivalent, 268.7 mg) were added, and the mixture was stirred at 85°C for 24 hours. After the reaction was completed, the reaction mixture was quenched with a saturated NH4Cl aqueous solution and extracted with dichloromethane. The organic layer was washed three times with brine, dried over MgSO4 and concentrated. The crude product was separated and purified by column chromatography on silica gel 200-300 mesh, and the eluent was V 乙酸乙酯 :V 石油醚 =1:10, a white powder was obtained, and the NMR characterization was shown Fig. 9 , 10 , the reaction equation is as follows.

[0123]

[0124] The obtained eight-membered spirocyclic silylfluorene derivative 7 (0.57 g, yield: 57.0%): 1 H NMR (600MHz, CDCl3) δ7.68(s,4H),7.55(d,J=7.8Hz,8H),7.48(s,4H),7.29(d,J=7.8 Hz, 8H), 4.00 (s, 12H), 2.44 (s, 12H), 2.28 (m, 4H), 1.44 (t, J1=6.0Hz, J2=7.2Hz, 8H). 13 CNMR(151MHz, CDCl3)δ158.87(s),148.70(s),136.80(s),135.81(s),135.37(s),130.68(s) ),130.19(s),129.57(s),128.94(s),104.18(s),55.79(s),21.38(s),19.42(s),16.88(s). 29 Si NMR (119MHz, CDCl3) δ1.55ppm.[M+Na] + calculated for C 62 H 60 O4Si2,925.3280; found 948.3967.

[0125] <Example 4>

[0126] This example provides characterization and performance testing of the products prepared in Examples 1 to 3.

[0127] The eight-membered spirocyclic silylfluorene derivatives prepared in Examples 1, 2, and 3 were characterized by single crystal X-ray diffraction, high-resolution mass spectrometry, H NMR, and C NMR. The crystal structure of compound 7 is shown in Fig.11 .

[0128] Fig.19 The UV-visible absorption spectra, fluorescence emission spectra and fluorescence photographs of some compounds in Example 4 of the present invention in dichloromethane and the fluorescence photographs of compound 3 in different solvents are shown in FIG. Fig.19 (a) is the UV-visible absorption spectrum; Fig.19 (b) is the fluorescence emission spectrum; Fig.19 (c) is a fluorescent photograph; Fig.19 (d) is the fluorescence photograph of compound 3 in different solvents.

[0129] Fig. 20 are solid fluorescence spectra and fluorescence photographs of some compounds in Example 4 of the present invention, wherein Fig. 20 (a) is the fluorescence spectrum; Fig. 20 (b) is a fluorescence photograph.

[0130] The photophysical data of some of the compounds synthesized in Examples 1, 2, and 3 are listed in Table 1. Their UV-visible absorption spectra, fluorescence emission spectra, and corresponding fluorescence photos in dichloromethane are shown in Table 1. Fig.19 As shown in Table 1, compound 6 has the highest quantum yield of 96% in dichloromethane, the maximum emission wavelength of the solution is 464 nanometers, and the luminescent color ranges from sky blue to dark blue. The solid fluorescence spectra and photos of related compounds are shown in Fig. 20 ,Depend on Fig. 20 As shown in Table 1, solid compound 5 has the highest quantum yield of 34%, the maximum emission wavelength of the solid is 497 nanometers, and the luminescent color ranges from sky blue to yellow-green.

[0131] Table 1 Photophysical data of compounds 3-7 in different solvents

[0132]

[0133] <Example 5>

[0134] This example provides the application of the eight-membered spirocyclic silylfluorene derivative prepared in Example 1 in fluorescence visualization:

[0135] Fig.21 This is a photo of compound 3 in Example 5 of the present invention used for detection and identification of latent fingerprints.

[0136] The eight-membered spirocyclic silanol derivative 3 prepared in Example 1 can be double-checked with diatomaceous earth treated with hydrochloric acid and high temperature at a content of 0.1‰ to form a phosphor 3@diatomaceous earth diatomaceous earth material. It can also be used for the detection and identification of latent fingerprints on the surfaces of objects such as copper plates, zinc plates, plastic bags, glass, wood, and leather, and only requires ultraviolet light irradiation and camera photography, without the need for a fluorescent microscope, and has certain application significance in the field of criminal investigation. The test results are as follows: Fig.21 shown.

[0137] Fig. 22 This is a photo of compound 5 in Example 5 of the present invention used for detection and identification of latent fingerprints.

[0138] The octa-spirocyclic silanol derivative 5 prepared in Example 1 can be dissolved in a mixed solution of tetrahydrofuran and deionized water to form a fluorescent agent 5@tetrahydrofuran & water. It can also be used for the detection and identification of latent fingerprints on the surfaces of objects such as glass slides, zinc plates, copper plates, iron spoons and plastic films, and only requires ultraviolet light irradiation and camera photography, without the need for a fluorescence microscope, and has certain application significance in the field of criminal investigation. The detection results are as follows: Fig. 22 shown.

[0139] Functions and Effects of the Embodiments

[0140] The octa-membered spirocyclic silylfluorene derivatives involved in the above embodiments have high quantum yield, high brightness and high photothermal stability, and possess the characteristics that should be possessed as a substitute for traditional fluorescent dyes. They can be used in applications such as latent fingerprint detection and recognition in terms of fluorescence visualization.

[0141] In addition, the preparation method of the octa-membered spirocyclic silanol derivative provided in the above embodiment is a simple metal catalyst ring expansion method. By connecting two silanols together in a ring-opening dimerization manner, the substitution sites of the molecule are increased, thereby introducing more substitution groups, and preparing a series of new silanol derivatives with high quantum yield and brightness. It is a simple and efficient method strategy.

[0142] The above-mentioned embodiments are preferred examples of the present invention and are not intended to limit the protection scope of the present invention.

Claims

1. An eight-membered spirocyclic silylfluorene derivative, characterized in that: The structural formula is: Wherein, in the general formula I, Ar is 4-methoxyphenyl, 4-(9H-9-carbazole)phenyl, triphenylamine, trifluoromethylphenyl, tetraphenylethylene or 1,2,3-tri(dodecyloxy)phenyl, In the general formula II, R is p-methylphenyl, triphenylamino, 4-methoxyphenyl, trans-4-n-pentylcyclohexylphenyl, 3-thienyl or 3-furyl.

2. The method for preparing the octa-membered spirocyclic silylfluorene derivative according to claim 1, characterized in that: The following steps are involved: Step S1, adding tetrahydrofuran and lithium reagent to the compound shown in the following structural formula III, stirring for 2 hours under ultra-low temperature conditions, then adding 1,1-dichlorosilylcyclobutane, stirring overnight, quenching the reaction mixture with saturated aqueous ammonium chloride solution after the reaction, and extracting with dichloromethane, washing the organic layer three times with brine, drying over anhydrous magnesium sulfate, filtering, and concentrating under reduced pressure, and purifying the crude product by column chromatography to obtain the desired product IV; Step S2, adding a platinum catalyst and toluene to the product IV shown in the following structural formula IV, quenching the reaction mixture with a saturated aqueous solution of ammonium chloride after the reaction is completed, and extracting with dichloromethane, washing the organic layer three times with brine, drying with anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and purifying the crude product by column chromatography to obtain the desired product V; Step S3, adding piperidine, palladium catalyst, cuprous iodide and arylacetylene to the product V shown in the following structural formula V, quenching the reaction mixture with a saturated aqueous ammonium chloride solution after the reaction is completed, and extracting with dichloromethane, washing the organic layer three times with brine, drying over anhydrous magnesium sulfate, filtering, and concentrating under reduced pressure, purifying the crude product by column chromatography to obtain the desired product, and obtaining the following 1-6 described in the formula I, a total of 6 eight-membered spirocyclic silanol derivatives, 3. The method for preparing the octa-membered spirocyclic silylfluorene derivative according to claim 2, characterized in that: in, The molar ratio of the product IV to the platinum catalyst is 20:1, In step S2 and step S3, the reaction temperature is 85°C and the reaction time is 24 hours. In steps S1 to S3, the solvent for column chromatography purification is dichloromethane or petroleum ether.

4. The method for preparing the octa-membered spirocyclic silylfluorene derivative according to claim 2, characterized in that: Anhydrous sodium carbonate, palladium catalyst, anhydrous ethanol, deionized water, toluene and arylboronic acid are added to the compound shown in structural formula V. After the reaction is completed, the reaction mixture is quenched with a saturated aqueous ammonium chloride solution and extracted with dichloromethane. The organic layer is washed three times with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by column chromatography to obtain the desired product, and the following 7-12 described in formula II, a total of 6 of the octa-membered spirocyclic silanol derivatives are obtained:

5. The method for preparing the octa-membered spirocyclic silylfluorene derivative according to claim 4, characterized in that: The following steps are involved: Step S1', adding anhydrous sodium carbonate, palladium catalyst, anhydrous ethanol, deionized water, toluene and arylboronic acid to the compound VI shown in the following structural formula VI, quenching the reaction mixture with a saturated aqueous ammonium chloride solution after the reaction, and extracting with dichloromethane, washing the organic layer three times with brine, drying with anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and purifying the crude product by column chromatography to obtain the desired product VII; Step S2', adding liquid bromine and dichloromethane to the product VII shown in the following structural formula VII, quenching the reaction mixture with a saturated sodium thiosulfate aqueous solution after the reaction is completed, and extracting with dichloromethane, washing the organic layer three times with brine, drying over anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and purifying the crude product by column chromatography to obtain the desired product VIII; Step S3', tetrahydrofuran and lithium reagent are added to the product VIII shown in the following structural formula VIII, and 1,1-dichlorosilylcyclobutane is added after stirring for 2 hours under ultra-low temperature conditions, and the mixture is stirred overnight. After the reaction is completed, the reaction mixture is quenched with a saturated aqueous solution of ammonium chloride, and extracted with dichloromethane. The organic layer is washed three times with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by column chromatography to obtain the desired product IX; Step S4', adding a platinum catalyst to the product IX shown in the following structural formula IX, quenching the reaction mixture with a saturated aqueous solution of ammonium chloride after the reaction is completed, and extracting with dichloromethane, washing the organic layer three times with brine, drying with anhydrous magnesium sulfate, filtering, and concentrating under reduced pressure, purifying the crude product by column chromatography to obtain the desired product, and obtaining 7-10 4 octa-membered spirocyclic silanol derivatives described by the general formula II, 6. The use of the octa-membered spirocyclic silylfluorene derivative according to claim 1, characterized in that: The eight-membered spirocyclic silanol derivative is used in fluorescence visualization for the purpose of non-disease diagnosis and treatment.

7. The use of the octa-membered spirocyclic silylfluorene derivative according to claim 6, characterized in that: The eight-membered spirocyclic silylfluorene derivative is used as a fluorescent visualization material for fingerprint detection and identification.

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