Diazaspiro[4.4]non-1,3,8-triene nitrile compounds, preparation method and application thereof

Abstract

The application discloses diazasprio[4.4] non-1,3,8-triazine compound and a preparation method and application thereof. The compound structural formula is shown as formula (I), wherein R1 is selected from 3-chloro, 4-hydrogen, 4-chloro, 4-fluoro, 4-bromo, 3-trifluoromethyl, 2-methoxy, 4-methyl or N-carbazole phenyl, and R2 is selected from 4-hydrogen, 4-methyl, 4-methoxy, 4-isopropyl, 4-chloro, 4-fluoro, 4-bromo, β-naphthalene, 1-phenyl naphthalene or 10-phenothiazine phenyl. The diazasprio[4.4] non-1,3,8-triazine compound has strong solid fluorescence and wide solid ultraviolet absorption function, good thermal stability, and is expected to have certain application in organic photoelectric devices, solar cells, chemical sensors and biological probes and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fluorescent materials, in particular to diazaspiro[4.4]non-1,3,8-triene nitrile compounds and a preparation method and application thereof. BACKGROUND

[0002] Organic luminescent molecules have been widely used in electronics, photonics, optoelectronics, chemical sensors and biological probes for many years. The design and synthesis of new organic luminescent molecules have attracted great attention from industry and academia. In particular, the design and synthesis of highly efficient fluorescent molecules have important scientific significance and application value for in-depth exploration of the luminescence mechanism of fluorescent molecules and the application of fluorescent molecules in various fields, especially in complex biological assay systems (Scientific reports 2015, 5, 9335).

[0003] At present, compounds with spiro skeleton are widely used in OLED materials, biological imaging, fluorescent labeling, solar cells, drug delivery and other fields, which benefits from their adjustable rigid spatial structure and small enough singlet-triplet splitting energy. The introduction of spiro skeleton provides researchers with a new idea for designing and synthesizing the third generation (thermally activated delayed fluorescence type) OLED materials. Literature reports that the spiro skeleton applied to OLED design includes: spirobifluorene (J. Mater. Chem. C, 2022, 10, 1357-1364), spirofluorene xanthene (Chemical Engineering Journal, 2023, 452, 139387), spiroacridine (J. Mater. Chem. C, 2022, 10, 17550-17556) (Adv. Funct. Mater. 2023, 33, 2211), spiro naphthalene (Angew. Chem. Int. Ed. 2021, 60, 3493-3497) and the like. They have achieved remarkable results in the construction of light response systems and materials. It is urgent to study new compounds with spiro skeleton structure with solid-state fluorescence function.

[0004] The present application is the research under the support of the National Natural Science Foundation (21702239). SUMMARY

[0005] The purpose of the present application is to provide diazaspiro[4.4]non-1,3,8-triene nitrile compounds and a preparation method and application thereof.

[0006] The present application is realized by the following technical solutions:

[0007] The application relates to a diazaspironon-1,3,8-triene nitrile compound, in particular 8-amine-6-imine-2,7-diazaspironon-1,3,8-triene-4-nitrile compound, and a preparation method thereof.

[0008]

[0009] In the formula, R1 is selected from 3-chloro, 4-hydrogen, 4-chloro, 4-fluoro, 4-bromo, 3-trifluoromethyl, 2-methoxy, 4-methyl or N-carbazole phenyl, and R2 is selected from 4-hydrogen, 4-methyl, 4-methoxy, 4-isopropyl, 4-chloro, 4-fluoro, 4-bromo, beta-naphthalene, 1-phenyl naphthalene or 10-phenothiazine phenyl.

[0010] Preferably, when the substituent R1 is 3-chloro, R2 is 4-hydrogen, 4-methyl, 4-methoxy, 4-isopropyl, 4-chloro, 4-fluoro, 4-bromo, beta-naphthalene, 1-phenyl naphthalene or 10-phenothiazine phenyl; and when the substituent R2 is 4-hydrogen, R1 is 4-hydrogen, 4-chloro, 4-fluoro, 4-bromo, 3-trifluoromethyl, 2-methoxy, 4-methyl or N-carbazole phenyl.

[0011] The 8-amine-6-imine-2,7-diazaspironon-1,3,8-triene-4-nitrile compound is shown in the following table.

[0012] Table 1

[0013]

[0014]

[0015] The application further protects a preparation method of the diazaspironon-1,3,8-triene nitrile compound, which comprises the following steps: taking compound 1 and an aniline compound as raw materials, taking an organic solvent as a reaction solvent, and reacting to obtain a target compound (8-amine-6-imine-2,7-diazaspironon-1,3,8-triene-4-nitrile compound); and a reaction formula is as follows:

[0016]

[0017] Preferably, the organic solvent is one of N,N-dimethylamide, dimethyl sulfoxide, acetonitrile, toluene, tetrahydrofuran, acetone, chloroform and dichloromethane.

[0018] Preferably, the aniline compound is selected from one of aniline, p-methylaniline, p-methoxyaniline, p-isopropylaniline, p-chloroaniline, p-fluoroaniline, beta-naphthylamine, p-bromoaniline, 4-naphthalen-1-yl aniline and 4-(10H-phenothiazin-10-yl)aniline.

[0019] Preferably, the molar ratio of the compound 1 and the aniline compound is 1:2-50, and the concentration of the compound 1 is 0.01-0.40 mol / L.

[0020] Preferably, the reaction temperature is 0-120 DEG C, and the reaction time is 1-24 hours.

[0021] The application also protects the application of the diazasprio[4.4]non-1,3,8-triene nitrile compound as an organic small molecule with solid-state function in the preparation of a fluorescent material.

[0022] Preferably, the fluorescent material is an organic optoelectronic device, a solar cell, a chemical sensor or a biological probe.

[0023] Compared with the prior art, the 8-amine-6-imine-2,7-diazaspiro[4.4]non-1,3,8-triene-4-nitrile compound has strong solid fluorescence and extensive solid ultraviolet absorption function, and good thermal stability, and is expected to have certain application in organic optoelectronic devices, solar cells, chemical sensors and biological probes. DETAILED DESCRIPTION

[0024] The application will be further described in detail below in combination with examples. The examples are only used to illustrate the application and not used to limit the scope of the application. The experimental methods not specified in the following examples are generally according to the conventional conditions in the art or according to the conditions suggested by the manufacturers; the raw materials, reagents and the like used are, if not specifically stated, raw materials and reagents that can be obtained through conventional market or commercial channels.

[0025] The nuclear magnetic spectrum (NMR) of the application is measured by an AVANCE 600 instrument produced by Bruker Company in Germany, and the solvent peak is used as an internal standard; the mass spectrum of the application is measured by an Ultimate 3000ISQ EC (ESI source) produced by Thermo Fisher Company; the chemical reagents are purchased from Shanghai Bide Pharmaceutical Technology Co., Ltd., Guangzhou Mingwang Biological Technology Co., Ltd., Beijing Inokai Technology Co., Ltd., Shaoyuan Technology (Shanghai) Co., Ltd., Aladdin Reagent (Shanghai) Co., Ltd. and the like; the silica gel for column chromatography is purchased from Qingdao Marine Chemical Plant.

[0026] Example 1:

[0027]

[0028] Synthesis of compound 2a: 6a-amino-2,5-bis(3-chlorophenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (42 mg, 0.1 mmol), aniline (28 mg, 0.3 mmol), acetonitrile (0.5 mL), at 70 °C for 4 h; after the reaction was completed, the yellow solid (2a) 53 mg was isolated by flash column chromatography in 90% yield.

[0029] MS (ESI): m / z = 587 [M-H] - . 1 H NMR (600 MHz, DMSO-d6) δ 10.45 (s, 1H), 9.44 (s, 1H), 8.36 (s, 1H), 8.05 (s, 1H), 7.83 - 7.76 (m, 4H), 7.73 - 7.31 (m, 10H), 7.15 - 7.08 (m, 2H), 7.03 (t, J = 7.7 Hz, 1H), 6.99 - 6.88 (m, 2H).

[0030] Example 2: Synthesis of compound 2b

[0031]

[0032] Synthesis of compound 2b: 6a-amino-2,5-bis(3-chlorophenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (42 mg, 0.1 mmol), p-toluidine (214 mg, 2 mmol), N,N-dimethylformamide (2 mL), at 120 °C for 1 h; after the reaction was completed, the yellow solid (2b) 28 mg was isolated by flash column chromatography in 45% yield.

[0033] MS (ESI): m / z = 615 [M-H] - . 1 H NMR (600 MHz, DMSO-d6) δ 10.41 (s, 1H), 9.41 (s, 1H), 8.32 (s, 1H), 8.03 (s, 1H), 7.77 (dd, J = 11.7, 4.9 Hz, 2H), 7.68 (d, J = 8.0 Hz, 2H), 7.59 - 7.51 (m, 2H), 7.46 (d, J = 7.9 Hz, 2H), 7.34 (s, 2H), 7.22 (d, J = 8.2 Hz, 2H), 7.12 (dd, J = 8.0, 2.1 Hz, 1H), 7.05 (t, J = 7.7 Hz, 1H), 7.01 - 6.87 (m, 2H), 2.42 (s, 3H), 2.30 (s, 3H)..

[0034] Example 3:

[0035]

[0036] Synthesis of compound 2c: 6a-amino-2,5-bis(3-chlorophenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (84 mg, 0.2 mmol), p- methoxyaniline (125 mg, 1 mmol), dimethyl sulfoxide (0.5 mL), at 100 °C for 2 h; after the reaction was completed, fast column chromatography was used to isolate to obtain yellow solid (2c) 19 mg, yield 29%. MS (ESI): m / z = 647 [M-H] - . 1 H NMR (600 MHz, DMSO-d6) δ 10.38 (s, 1H), 9.40 (s, 1H), 8.34 (s, 1H), 8.03 (s, 1H), 7.80-7.75 (m, 2H), 7.74-7.70 (m, 2H), 7.57 (dt, J = 8.1, 1.7 Hz, 1H), 7.53 (t, J = 7.8 Hz, 1H), 7.37 (s, 2H), 7.23-7.17 (m, 2H), 7.14-7.11 (m, 1H), 7.06 (t, J = 7.7 Hz, 1H), 7.01-6.94 (m, 4H), 3.85 (s, 3H), 3.77 (s, 3H).

[0037] Example 4:

[0038]

[0039] Synthesis of compound 2d: 6a-amino-2,5-bis(3-chlorophenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (42 mg, 0.1 mmol), p- isopropylaniline (544 mg, 4 mmol), chloroform (5 mL), at 50 °C for 8 h; after the reaction was completed, fast column chromatography was used to isolate to obtain yellow solid (2d) 34 mg, yield 58%. MS (ESI): m / z = 671 [M-H] - . 1H NMR (600 MHz, Chloroform-d) δ 9.52 (s, 1H), 8.13 - 7.83 (m, 3H), 7.58 (s, 2H), 7.47 - 7.41 (m, 1H), 7.40 - 7.33 (m, 3H), 7.32 - 7.21 (m, 4H), 7.13 (s, 1H), 7.07 - 7.00 (m, 2H), 6.94 (t, J = 7.8 Hz, 1H), 2.93 (dhept, J = 27.7, 6.9 Hz, 2H), 1.25 (dd, J = 6.9, 3.1 Hz, 12H).

[0040] Example 5:

[0041]

[0042] Synthesis of compound 2e: 6a-amino-2,5-bis(3-chlorophenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (42 mg, 0.1 mmol), p-chloroaniline (128 mg, 1 mmol), toluene (8 mL), at 80 °C for 6 h; after the reaction was completed, the yellow solid (2e) 50 mg was isolated by flash column chromatography in 75% yield. MS (ESI): m / z = 655 [M-H] - . 1 H NMR (600 MHz, DMSO-d6) δ 10.57 (s, 1H), 9.56 - 9.34 (m, 1H), 8.54 (s, 1H), 8.25 (s, 1H), 7.88 - 7.65 (m, 8H), 7.60 - 7.43 (m, 8H), 7.12 (d, J = 8.0 Hz, 1H), 7.05 (t, J = 7.7 Hz, 1H), 6.98 - 6.89 (m, 3H).

[0043] Example 6:

[0044]

[0045] Synthesis of compound 2f: 6a-amino-2,5-bis(3-chlorophenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (42 mg, 0.1 mmol), p-fluoroaniline (555 mg, 5 mmol), tetrahydrofuran (10 mL), at 50 °C for 16 h; after the reaction was completed, the yellow solid (2f) 36 mg was isolated by flash column chromatography in 50% yield. MS (ESI): m / z = 623 [M-H] - . 1H NMR (600 MHz, Chloroform-d and DMSO-d6) δ 10.16 (d, J = 70.2 Hz, 1H), 9.51 (s, 1H), 7.95 - 7.75 (m, 3H), 7.59 (d, J = 27.0 Hz, 2H), 7.39 (dtd, J = 55.7, 20.0, 8.9 Hz, 5H), 7.16 - 6.92 (m, 5H).

[0046] Example 7:

[0047]

[0048] Synthesis of compound 2g: 6a-amino-2,5-bis(3-chlorophenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (42 mg, 0.1 mmol), β-naphthylamine (29 mg, 0.2 mmol), acetone (3 mL), at 60 °C for 8 h; after the reaction was completed, the yellow solid (2g) 22 mg was isolated by flash column chromatography with a yield of 32%. MS (ESI): m / z = 687 [M-H] - . 1 H NMR (600 MHz, Chloroform-d) δ 9.47 (s, 1H), 8.26 (s, 2H), 8.08 - 7.67 (m, 8H), 7.66 - 7.30 (m, 8H), 7.19 - 6.91 (m, 3H), 6.83 (t, J = 8.0 Hz, 1H), 5.71 (s, 1H), 1.88 (s, 2H).

[0049] Example 8:

[0050]

[0051] Synthesis of compound 2h: 6a-amino-2,5-bis(3-chlorophenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (84 mg, 0.2 mmol), p-bromoaniline (86 mg, 0.5 mmol), dichloromethane (3 mL), at 25 °C for 24 h; after the reaction was completed, the yellow solid (2h) 68 mg was isolated by flash column chromatography with a yield of 46%. MS (ESI): m / z = 743 [M-H] - . 1H NMR (600 MHz, DMSO-d6) δ 10.53 (s, 1H), 9.43 (s, 1H), 8.55 (s, 1H), 8.25 (s, 1H), 7.96 (d, J = 7.7 Hz, 1H), 7.90 - 7.73 (m, 8H), 7.66 - 7.47 (m, 8H), 7.47 - 7.33 (m, 3H), 7.12 (d, J = 8.1 Hz, 1H), 7.05 (t, J = 7.8 Hz, 1H), 6.96 - 6.88 (m, 3H).

[0052] Example 9:

[0053]

[0054] Synthesis of compound 2i: 6a-amino-2,5-bis(4-methylphenyl)-3a,6a- dihydrofuranyl[2,3-b]furan-3,3a,4-tricarbonitrile (38 mg, 0.1 mmol), aniline (46 mg, 0.5 mmol), chloroform (1 mL), at 60 °C for 8 h; after the reaction was completed, the yellow solid (2i) 28 mg was isolated by flash column chromatography in 51% yield. MS (ESI): m / z = 547 [M-H] - . 1 H NMR (600 MHz, DMSO-d6) δ 10.27 (d, J = 24.1 Hz, 1H), 9.55 (s, 1H), 7.99 (s, 1H), 7.83 (d, J = 8.0 Hz, 3H), 7.76 - 7.35 (m, 9H), 7.30 (d, J = 8.0 Hz, 2H), 7.12 (t, J = 7.4 Hz, 1H), 6.89 (d, J = 7.5 Hz, 2H), 6.76 (d, J = 7.5 Hz, 2H), 2.37 (s, 3H), 2.04 (s, 3H).

[0055] Example 10:

[0056]

[0057] Synthesis of compound 2j: 6a-amino-2,5-bisphenyl-3a,6a-dihydrofuranyl[2,3- b]furan-3,3a,4-tricarbonitrile (35 mg, 0.1 mmol), aniline (37 mg, 0.4 mmol), tetrahydrofuran (0.5 mL), at 70 °C for 5 h; after the reaction was completed, the yellow solid (2j) 43 mg was isolated by flash column chromatography in 82% yield. MS (ESI): m / z = 519 [M-H] - . 1H NMR (600 MHz, DMSO-d6) δ 10.37 (s, 1H), 9.55 (s, 1H), 8.23 (s, 1H), 7.96 (s, 1H), 7.82 (d, J = 8.1 Hz, 4H), 7.66 (t, J = 7.7 Hz, 2H), 7.59 (t, J = 7.6 Hz, 1H), 7.54 - 7.35 (m, 7H), 7.13 (t, J = 7.4 Hz, 1H), 7.09 - 6.93 (m, 5H).

[0058] Example 11:

[0059]

[0060] Synthesis of compound 2k: 6a-amino-2,5-bis(4-chlorophenyl)-3a,6a- dihydrofuranyl[2,3-b]furan-3,3a,4-tricarbonitrile (42 mg, 0.1 mmol), aniline (46 mg, 0.5 mmol), acetonitrile (1 mL), at 70 °C for 4 h; after the reaction was completed, the yellow solid (2k) 51 mg was isolated by flash column chromatography in 85% yield. MS (ESI): m / z = 587 [M-H] - . 1 H NMR (600 MHz, DMSO-d6) δ 10.44 (s, 1H), 9.46 (s, 1H), 8.36 (s, 1H), 8.04 (s, 1H), 7.82 (t, J = 7.3 Hz, 4H), 7.62 (dd, J = 30.2, 8.0 Hz, 5H), 7.52 - 7.35 (m, 4H), 7.15 (t, J = 7.3 Hz, 1H), 7.00 (q, J = 8.0 Hz, 4H).

[0061] Example 12:

[0062]

[0063] Synthesis of compound 2l: 6a-amino-2,5-bis(4-fluorophenyl)-3a,6a- dihydrofuranyl[2,3-b]furan-3,3a,4-tricarbonitrile (39 mg, 0.1 mmol), aniline (93 mg, 1 mmol), toluene (2 mL), at 80 °C for 3 h; after the reaction was completed, the yellow solid (2l) 37 mg was isolated by flash column chromatography in 66% yield. MS (ESI): m / z = 555 [M-H] - . 1H NMR (600 MHz, DMSO-d6) δ 10.40 (d, J = 22.7 Hz, 1H), 9.48 (d, J = 32.2 Hz, 1H), 8.21 (s, 1H), 8.03 - 7.78 (m, 5H), 7.76 - 7.26 (m, 10H), 7.15 (t, J = 7.2 Hz, 1H), 7.04 (q, J = 6.9, 6.1 Hz, 2H), 6.79 (t, J = 8.4 Hz, 2H).

[0064] Example 13:

[0065]

[0066] Synthesis of compound 2m: 6a-amino-2,5-bis(2-methoxyphenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (40 mg, 0.1 mmol), aniline (74 mg, 0.8 mmol), acetonitrile (2 mL), at 80 °C for 3 h; after the reaction was completed, the yellow solid (2m) 42 mg was isolated by flash column chromatography in 73% yield. MS (ESI): m / z = 579 [M-H] - . 1 H NMR (600 MHz, DMSO-d6) δ 10.16 (s, 1H), 9.40 (s, 1H), 7.92 - 7.74 (m, 3H), 7.72 - 7.54 (m, 3H), 7.54 - 7.41 (m, 3H), 7.39 - 7.29 (m, 3H), 7.08 (dd, J = 19.4, 7.8 Hz, 3H), 6.99 (td, J = 7.5, 1.0 Hz, 1H), 6.85 (s, 1H), 6.57 (d, J = 8.3 Hz, 1H), 6.47 (t, J = 7.4 Hz, 1H), 3.87 (s, 3H), 3.08 (s, 3H).

[0067] Example 14:

[0068]

[0069] Synthesis of compound 2n: 6a-amino-2,5-bis(4-bromophenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (51 mg, 0.1 mmol), aniline (28 mg, 0.3 mmol), dimethyl sulfoxide (1 mL), at 100 °C for 2 h; after the reaction was completed, the yellow solid (2n) 28 mg was isolated by flash column chromatography in 48% yield. MS (ESI): m / z = 675 [M-H] - . 1H NMR (600 MHz, DMSO-d6) δ 10.40 (d, J = 14.1 Hz, 1H), 9.45 (d, J = 25.3 Hz, 1H), 8.32 (s, 1H), 8.03 (s, 1H), 7.82 (d, J = 8.0 Hz, 2H), 7.77 - 7.36 (m, 11H), 7.14 (t, J = 7.3 Hz, 3H), 6.91 (d, J = 7.9 Hz, 2H).

[0070] Example 15: Synthesis of compound 2o

[0071]

[0072] Synthesis of compound 2o: 6a-amino-2,5-bis(N-carbazolylphenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (42 mg, 0.1 mmol), aniline (140 mg, 1.5 mmol), chloroform (2 mL), at 100 °C for 2 h; after the reaction was completed, the yellow solid (2o) 34 mg was isolated by flash column chromatography in 40% yield. MS (ESI): m / z = 849 [M-H] - . 1 H NMR (600 MHz, DMSO-d6) δ 10.53 (d, J = 21.4 Hz, 1H), 9.56 (d, J = 37.5 Hz, 1H), 8.35 (s, 1H), 8.31 - 8.15 (m, 6H), 8.14 - 7.96 (m, 3H), 7.75 (q, J = 5.8, 4.1 Hz, 1H), 7.66 (t, J = 7.9 Hz, 2H), 7.62 - 7.47 (m, 5H), 7.45 - 7.08 (m, 18H), 6.98 (d, J = 7.8 Hz, 2H).

[0073] Example 16:

[0074]

[0075] Synthesis of compound 2p: 6a-amino-2,5-bis(3-trifluoromethylphenyl)-3a,6a- dihydrofuro[2,3-b]furan-3,3a,4-tricarbonitrile (49 mg, 0.1 mmol), aniline (28 mg, 0.3 mmol), acetone (5 mL), at 60 °C for 16 h; after the reaction was completed, the yellow solid (2p) 33 mg was isolated by flash column chromatography in 50% yield. MS (ESI): m / z = 655 [M-H] - . 1H NMR (600 MHz, DMSO-d6) δ 10.53 (d, J = 8.8 Hz, 1H), 9.47 (d, J = 31.5 Hz, 1H), 8.48 (s, 1H), 8.16 (d, J = 18.5 Hz, 1H), 8.05 (d, J = 20.7 Hz, 2H), 7.85 (dd, J = 19.6, 7.9 Hz, 3H), 7.73 (td, J = 15.5, 12.4, 8.8 Hz, 2H), 7.68 - 7.45 (m, 4H), 7.40 (dt, J = 13.6, 7.6 Hz, 3H), 7.34 - 7.22 (m, 3H), 7.15 (t, J = 7.5 Hz, 1H).

[0076] Example 17:

[0077]

[0078] Synthesis of compound 2q: 6a-amino-2,5-bis(3-chlorophenyl)-3a,6a-dihydrofuranyl[2,3- b]furan-3,3a,4-tricarbonitrile (42 mg, 0.1 mmol), β-naphthylaniline (66 mg, 0.3 mmol), acetonitrile (2 mL), at 70 °C for 5 h; after the reaction was completed, flash column chromatography was used to isolate a yellow solid (2q) 67 mg, yield 79%. MS (ESI): m / z = 839 [M-H] - . 1 H NMR (600 MHz, Chloroform-d) δ 9.67 (s, 1H), 8.53 (s, 1H), 7.97 (s, 1H), 7.86 (dtt, J = 37.2, 14.6, 7.2 Hz, 9H), 7.59 (d, J = 7.9 Hz, 2H), 7.55 - 7.41 (m, 8H), 7.37 (dt, J = 14.6, 6.9 Hz, 4H), 7.32 - 7.27 (m, 2H), 7.26 - 7.17 (m, 2H), 7.11 (d, J = 7.5 Hz, 1H), 7.02 (d, J = 8.0 Hz, 1H), 6.92 (t, J = 7.8 Hz, 1H), 6.15 (s, 1H).

[0079] Example 18:

[0080]

[0081] Synthesis of compound 2r: 6a-amino-2,5-bis(3-chlorophenyl)-3a,6a- dihydrofuran[2,3-b]furan-3,3a,4-tricarbonitrile (42 mg, 0.1 mmol), 10- phenothiazine aniline (116 mg, 0.4 mmol), chloroform (2 mL), at 80 °C for 4 h; after the reaction was completed, the yellow solid (2r) 86 mg was separated by flash column chromatography with a yield of 88%. MS (ESI): m / z = 981 [M-H] - . 1 H NMR (600 MHz, DMSO-d6) δ 10.70 (s, 1H), 9.55 (d, J = 39.0 Hz, 1H), 8.60 (s, 1H), 8.46 - 8.20 (m, 2H), 8.14 (d, J = 8.2 Hz, 2H), 7.85 (d, J = 14.8 Hz, 2H), 7.78 - 7.42 (m, 8H), 7.25 - 6.78 (m, 16H), 6.74 - 6.46 (m, 2H), 6.26 (d, J = 8.3 Hz, 2H).

[0082] Experimental Example 1

[0083] The spectroscopic properties of the 8-amino-6-imino-2,7-diazaspiro[4.4]nona-1,3,8- triene-4-carbonitrile compounds obtained in Test Examples 1 to 18 were tested, and the spectroscopic results of each compound are shown in Table 2 below.

[0084] Table 2

[0085]

[0086] As shown in Table 2, the results show that the 8-amino-6-imino-2,7-diazaspiro[4.4]nona-1,3,8-triene-4-carbonitrile compounds have strong solid fluorescence properties. By introducing electron-withdrawing groups into the molecular skeleton, the compounds obtain higher quantum yields in the solid state, which can be used as an improved approach for this type of molecular skeleton compound in solid-state fluorescent materials.

[0087] Experimental Example 2

[0088] The thermal stability properties of some of the 8-amino-6-imino-2,7-diazaspiro[4.4]nona-1,3,8-triene-4-carbonitrile compounds obtained in Test Examples 1 to 18 were tested, and the thermal stability results of each compound are shown in Table 3 below.

[0089] Table 3

[0090]

[0091] As shown in Table 2, the compound of the type proposed in the application has good thermal stability, and the thermal decomposition temperature is greater than 230°C.

[0092] As can be seen from the above results, the 8-amine-6-imine-2,7-diazaspiro[4.4]non-1,3,8-triene-4-nitrile compound proposed in the application has strong solid fluorescence function and good thermal stability, and is expected to have certain application in organic optoelectronic devices, solar cells, chemical sensors and biological probes, etc.

[0093] The above examples are only used to help understand the technical solutions of the application and its core idea. It should be pointed out that for those skilled in the art, without departing from the principles of the application, the application can be improved and modified in several ways, and these improvements and modifications also fall within the protection scope of the claims of the application.

Claims

1. Diazaspiro[4.4]nona-1,3,8-triene carbonitriles characterized in that, The diazaspiro[4.4]non-1,3,8-triene nitrile compound is specifically 8-amino-6-imino-2,7-diazaspiro[4.4]non-1,3,8-triene-4-nitrile, and its structural formula is shown as formula (I). Formula I R1 is selected from 3-chloro, 4-hydrogen, 4-chloro, 4-fluoro, 4-bromo, 3-trifluoromethyl, 2-methoxy, 4-methyl or N-carbazole phenyl, and R2 is selected from 4-hydrogen, 4-methyl, 4-methoxy, 4-isopropyl, 4-chloro, 4-fluoro, 4-bromo, β-naphthyl, 1-naphthyl or 10-phenothiazine.

2. The diazaspiro[4.4]non-1,3,8-triene nitrile compound according to claim 1, characterized in that, When the substituent R1 is 3-chloro, R2 is 4-hydrogen, 4-methyl, 4-methoxy, 4-isopropyl, 4-chloro, 4-fluoro, 4-bromo, β-naphthyl, 1-naphthyl or 10-phenothiazine; when the substituent R2 is 4-hydrogen, R1 is 4-hydrogen, 4-chloro, 4-fluoro, 4-bromo, 3-trifluoromethyl, 2-methoxy, 4-methyl or N-carbazole phenyl.

3. The method of producing diazaspiro[4.4]non-1,3,8-triene carbonitrile compounds according to claim 1, characterized by, The method comprises the following steps: taking compound 1 and an aniline compound as raw materials, and taking an organic solvent as a reaction solvent to obtain a target compound; and a reaction formula is as follows: 。 4. The production method according to claim 3, characterized by, The organic solvent is selected from one of N,N-dimethylamide, dimethyl sulfoxide, acetonitrile, toluene, tetrahydrofuran, acetone, chloroform and dichloromethane.

5. The preparation method according to claim 3, characterized in that The aniline compound is selected from one of aniline, p-methylaniline, p-methoxyaniline, p-isopropylaniline, p-chloroaniline, p-fluoroaniline, β-naphthylamine, 4-naphth-1-ylaniline and 4-(10H-phenothiazine-10-yl)aniline.

6. The preparation method according to claim 3, characterized in that The molar ratio of the compound 1 and the aniline compound is 1:2-50, and the concentration of the compound 1 is 0.01-0.40 mol / L.

7. The preparation method according to claim 3, characterized in that The reaction temperature is 0-120°C, and the reaction time is 1-24 hours.

8. Application of the diazaspiro[4.4]non-1,3,8-triene nitrile compound in claim 1 or the diazaspiro[4.4]non-1,3,8-triene nitrile compound obtained by the preparation method in any one of claims 3-7 as an organic small molecule with solid-state function to prepare a fluorescent material.

9. Use according to claim 8, characterized in that, The fluorescent material is an organic optoelectronic device, a solar cell, a chemical sensor or a biological probe.

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