CN114853783B - Imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound and preparation method and application thereof - Google Patents
Imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an imidazole [4,5-e ]]Thiophene [2,3-b ]]Pyridoindolone compounds, and preparation method and application thereof are provided. The structural formula of the compound is shown as a formula (I) or a formula (II), wherein a substituent R is halogeno, di (methoxy) or methyl. The invention provides imidazole [4,5-e ]]Thiophene [2,3-b ]]The pyridoindolone compound has strong solid fluorescence and liquid fluorescence functions, and good thermal stability, and is expected to be applied to organic photoelectric devices, chemical sensors, biological probes and the like.
Description
Technical Field
The invention relates to the technical field of fluorescent materials, in particular to an imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound, a preparation method and application thereof.
Background
Organic luminescent molecules have been widely used for many years in electronics, photonics, optoelectronics, chemical sensors and biological probes. The design and synthesis of novel organic luminescent molecules has received great attention from industry and academia. In particular to the design and synthesis of high-efficiency solid-liquid double fluorescent molecules, which has important scientific significance and application value for exploring the luminescence mechanism of fluorescent molecules in deep detail and the application of fluorescent molecules in various fields, in particular complex bioassay systems (Scientific reports 2015,5,9335).
At present, few types of organic light-emitting small molecules with solid-liquid double fluorescence function are reported in various documents, and the organic light-emitting small molecules mainly comprise: triphenylamine derivatives (Advanced materials 2015,27,4496-4501) with high-efficiency solid-liquid dual fluorescence luminescence properties designed by a conjugated-induced stiffness (CIR) strategy; p-dimethyl sulfonyl benzene compound (Angewandte Chemie 2015,54 (25), 7332-7335); low molecular weight gel organics containing naphthalenimine building blocks (Langmuir: the ACS journal of surfaces and colloids 2014,30 (39), 11753-11760); pyrene derivatives (RSC advance 2014,4 (60), 31594); carbazole derivatives (Dyes and Pigments 2016,124,82-92); thiazole [4,5-e ] thiophene [2,3-b ] pyridines reported in the subject group (Chemical Science 2016,7,4485-4491); imidazole [4,5-e ] thiophene [2,3-b ] pyridines (Dyes and Pigments 2019,160,839-847).
Therefore, a series of organic small molecules with solid-liquid double fluorescence functions and a novel framework structure are obtained by utilizing a rearrangement reaction and carrying out structural transformation on the organic small molecules, and the organic small molecule luminescent material of the type is not reported in the literature.
The invention is a research carried out with the fund of national science (21702239).
Disclosure of Invention
The invention provides an imidazole [4,5-e ] thiophene [2,3-b ] pyridoindolone compound, a preparation method and application thereof, wherein the imidazole [4,5-e ] thiophene [2,3-b ] pyridine compound is obtained by utilizing a rearrangement reaction, a novel imidazole [4,5-e ] thiophene [2,3-b ] pyridoindolone compound is developed by a dehydration condensation method, the structure of the novel imidazole [4,5-e ] thiophene [2,3-b ] pyridoindolone compound is improved, and the novel imidazole [4,5-e ] thiophene [2,3-b ] pyridoindolone compound is an organic small molecule with a novel framework structure and a solid-liquid double fluorescence function.
The invention aims to provide an imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound, the structural formula of which is shown as formula (I) or formula (II):
wherein the substituent R is halo, di (methoxy) or methyl.
Preferably, the substituent R is 4-hydrogen, 5-bromo, 4-fluoro, (4, 5) -di (methoxy) or 5-methyl.
Imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolones of formula (I) or formula (II) are shown in the following table:
the invention also provides a preparation method of the imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound, which comprises the following steps:
(1) In the form of the compound 5- (2-chlorophenyl) -7-isopropyl-3H-thieno [2,3-e][1,4]Diaza-type
2-imine (M6) and 2-formylbenzoic acid compounds are used as raw materials, a polar solvent is used as a reaction solvent in the presence of a catalyst, and the reaction is carried out for 10 to 14 hours at the temperature of 80 to 200 ℃ to obtain a target compound F (a); the reaction formula is:
(2) Using compound F (a) as raw material, using chloroform, dichloromethane, dichloroethane, tetrahydrofuran or toluene as solvent, adding dehydrating agent and activating agent to make dehydration condensation reaction, or using DIPEA (diisopropylethylamine) or Et 3 N (triethylamine) is used as alkali to carry out dehydration condensation reaction, and the reaction is carried out for 4 to 14 hours at the temperature of 0 to 80 ℃ to obtain compounds F (b) and F (c); the reaction formula is:
preferably, the catalyst in the step (1) is selected from one of zinc chloride, zinc triflate, silver triflate, scandium triflate and scandium acetate; the polar solvent is selected from one of DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide) and NMP (N-methylpyrrolidone).
Preferably, the 2-formylbenzoic acid compound in the step (1) is selected from one of 2-formylbenzoic acid, 5-bromo-2-formylbenzoic acid, 4-fluoro-2-formylbenzoic acid, 2-formyl- (4, 5) -dimethoxy-benzoic acid and 2-formyl-5-methyl-benzoic acid.
Preferably, the molar ratio of the compound M6, the 2-formylbenzoic acid compound and the catalyst in the step (1) is as follows: 1:1-5:0.01-1, and the concentration of the compound M6 is 0.1-1.0mol/L.
Preferably, the dehydrating agent in the step (2) is selected from DCC (dicyclohexylcarbodiimide), DIC (N, N' -diisopropylcarbodiimide) or EDCI (carbodiimide hydrochloride), and the activating agent is selected from HOBt (1-hydroxybenzotriazole), DMAP (p-dimethylaminopyridine) and NHS (N-hydroxysuccinimide), and the molar ratio of the compound F (a), the dehydrating agent and the activating agent is 1:1-10:1-10.
Preferably, the molar ratio of F (a) to the base in the step (2) is 1:2-10.
Further preferably, the concentration of compound F (a) in step (2) is 0.01 to 0.1mol/L.
The invention also protects the application of the imidazole [4,5-e ] thiophene [2,3-b ] pyridoindolone compound serving as an organic small molecule with solid-liquid double functions in the preparation of fluorescent materials. The fluorescent material is an organic photoelectric device, a chemical sensor or a biological probe.
Compared with the prior art, the invention has the beneficial effects that: the imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound provided by the invention has strong solid fluorescence and liquid fluorescence functions, and good thermal stability, and is expected to be applied to organic photoelectric devices, chemical sensors, biological probes and other aspects.
Detailed Description
The present invention will be described in further detail with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental methods without specific conditions noted in the examples below are generally in accordance with conventional conditions in the art or in accordance with manufacturer's recommendations; the raw materials, reagents and the like used, unless otherwise specified, are considered to be commercially available through conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
1. Instrument and medicine:
the nuclear magnetic resonance spectrum (NMR) of the invention is measured by AVANCE 400, AVANCE 500 and AVANCE 600 instruments manufactured by Bruker corporation, germany, and the solvent peak is used as an internal standard; the mass spectrum of the invention was determined by Ultimate 3000 ISQ EC (ESI source) manufactured by Siemens Fedder; chemical reagents are purchased from Shanghai Biget medical technologies Inc., guangzhou Ming Wang Biotechnology Inc., beijing InocKai technologies Inc., shaoshan technology (Shanghai) Inc., arraga Ding Shiji (Shanghai) Inc., etc.; column chromatography silica gel was purchased from Qingdao ocean chemical plant.
2. The structural formula of each compound in the following examples is shown as follows:
example 1
The preparation method of the imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound comprises the following steps:
(1) Synthesis of compound F11 a: compound M6 (318 mg,1 mmol), 2-formylbenzoic acid (150 mg,1 mmol), scandium triflate (5 mg,0.01 mmol), NMP (N-methylpyrrolidone) (5 mL) were reacted at 200℃for 10 hours; after the completion of the reaction, 120mL of ethyl acetate was added for extraction, the organic phase was dried over anhydrous sodium sulfate, and flash column chromatography was performed to obtain 192mg of a white solid (F11 a) in 43% yield. MS (ESI) m/z=446 [ M-H ]] - . 1 H NMR(600MHz,Chloroform-d)δ8.49–8.41(m,1H,ArH),8.28–8.23(m,1H,ArH),7.58–7.51(m,2H,ArH),7.44–7.33(m,4H,ArH),6.74(d,J＝1.1Hz,1H,ArH),3.22(heptd,J＝6.8,1.1Hz,1H,CH),1.39(dd,J＝6.9,1.1Hz,6H,CH 3 ).
(2) Synthesis of Compounds F11b and F11c: compound F11a (89 mg,0.2 mmol), NHS (N-hydroxysuccinimide) (230 mg,2 mmol), DCC (dicyclohexylcarbodiimide) (206 mg,2 mmol), chloroform (20 mL) were dehydrated and condensed at room temperature for 12 hours, and F11b and F11c were simultaneously obtained by flash column chromatography.
F11b: yellow solid, yield 42mg, yield 49%. MS (ESI) m/z=430 [ M+H ]] + . 1 H NMR(600MHz,Chloroform-d)δ7.98(d,J＝7.1Hz,1H,ArH),7.73–7.60(m,3H,ArH),7.59–7.49(m,2H,ArH),7.49–7.43(m,2H,ArH),6.69–6.63(m,1H,ArH),3.25–3.16(m,1H,CH),1.37(d,J＝6.8Hz,6H,CH 3 ).
F11c: yellow solid, yield 37mg, 43%. MS (ESI) m/z=430 [ M+H ]] + . 1 H NMR(600MHz,Chloroform-d)δ7.96–7.92(m,1H,ArH),7.91–7.87(m,1H,ArH),7.67–7.60(m,2H,ArH),7.58–7.54(m,1H,ArH),7.52–7.46(m,3H,ArH),6.66(d,J＝1.1Hz,1H,ArH),3.19(heptd,J＝6.9,1.1Hz,1H,CH),1.37(d,J＝6.8Hz,6H,CH 3 ).
Example 2
The preparation method of the imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound comprises the following steps:
(1) Synthesis of compound F12 a: compound M6 (318 mg,1 mmol), 5-bromo-2-formylbenzoic acid (458 mg,2 mmol), zinc chloride (136 mg,1 mmol), DMF (N, N-dimethylformamide) (10 mL) was reacted at 80℃for 14 hours; after the completion of the reaction, 120mL of ethyl acetate was added for extraction, the organic phase was dried over anhydrous sodium sulfate, and 242mg of pale yellow solid (F12 a) was obtained by flash column chromatography in 46% yield. MS (ESI) m/z=524 [ M-H ]] - . 1 H NMR(500MHz,Chloroform-d and CF 3 COOD)δ8.35(s,1H,ArH),7.92(s,2H,ArH),7.59(d,J＝8.1Hz,1H,ArH),7.56–7.51(m,1H,ArH),7.48–7.40(m,2H,ArH),6.85(s,1H,ArH),3.30(hept,J＝6.9Hz,1H,CH),1.42(d,J＝6.8Hz,6H,CH 3 ).
(2) Synthesis of Compounds F12b and F12c: compound F12a (105 mg,0.2 mmol), HOBt (1-hydroxybenzotriazole) (54 mg,0.4 mmol), DIC (N, N' -diisopropylcarbodiimide) (45 mg,0.4 mmol), tetrahydrofuran (2 mL) were subjected to dehydration-condensation reaction at 0℃to room temperature for 14 hours, and flash column chromatography gave F12b and F12c simultaneously.
F12b: yellow solid, yield 36mg, yield 38%. MS (ESI) m/z=508 [ M+H ]] + . 1 H NMR(600MHz,Chloroform-d)δ7.87–7.79(m,3H,ArH),7.65(d,J＝8.6Hz,1H,ArH),7.60–7.54(m,1H,ArH),7.51–7.44(m,2H,ArH),6.68(s,1H,ArH),3.22(hept,J＝6.8Hz,1H,CH),1.39(d,J＝6.9Hz,6H,CH 3 ).
F12c: yellow solid, yield 33mg, yield 34%. MS (ESI) m/z=508 [ M+H ]] + . 1 H NMR(600MHz,Chloroform-d)δ8.09(dd,J＝1.7,0.5Hz,1H),7.80(dd,J＝8.0,1.7Hz,1H),7.77(d,J＝8.0Hz,1H),7.66–7.64(m,1H),7.53–7.48(m,3H),6.68(d,J＝1.1Hz,1H),3.22(heptd,J＝6.8,1.1Hz,1H),1.39(d,J＝6.8Hz,6H).
Example 3
The preparation method of the imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound comprises the following steps:
(1) Synthesis of compound F14 a: compound M6 (318 mg,1 mmol), 4-fluoro-2-formylbenzoic acid (504 mg,3 mmol), zinc triflate (18 mg,0.05 mmol), DMSO (dimethyl sulfoxide) (1 mL) was reacted at 120℃for 12 hours; after the completion of the reaction, 120mL of ethyl acetate was added for extraction, the organic phase was dried over anhydrous sodium sulfate, and flash column chromatography was performed to obtain 279mg of a white solid (F14 a) with a yield of 60%. MS (ESI) m/z=464 [ M-H ]] - . 1 H NMR(600MHz,Chloroform-d and CF 3 COOD)δ8.32(dd,J＝8.8,5.1Hz,1H,ArH),7.69(dd,J＝8.0,2.5Hz,1H,ArH),7.61(d,J＝8.1Hz,1H,ArH),7.59–7.53(m,1H,ArH),7.52–7.45(m,3H,ArH),6.89(d,J＝1.1Hz,1H,ArH),3.37–3.26(m,1H,CH),1.44(d,J＝6.9Hz,6H,CH 3 ).
(2) Synthesis of Compounds F14b and F14c: compound F14a (100 mg,0.215 mmol), DIPEA (diisopropylethylamine) (277 mg,2.15 mmol), dichloromethane (8 mL) were reacted at 60℃for 4 h, flash column chromatography gave F14b and F14c simultaneously.
F14b: yellow solid, 51mg yield 53%. MS (ESI) m/z=448 [ M+H ]] + . 1 H NMR(600MHz,Chloroform-d)δ7.71(dd,J＝8.4,4.5Hz,1H,ArH),7.65(d,J＝8.0Hz,2H,ArH),7.60–7.54(m,1H,ArH),7.48(d,J＝6.9Hz,2H,ArH),7.20(td,J＝8.5,2.2Hz,1H,ArH),6.68(s,1H,ArH),3.22(hept,J＝7.0Hz,1H,CH),1.39(d,J＝6.9Hz,6H,CH 3 ).
F14c: yellow solid, 40mg yield 42%. MS (ESI) m/z=448 [ M+H ]] + . 1 H NMR(600MHz,Chloroform-d)δ7.95(dd,J＝8.3,4.6Hz,1H,ArH),7.67–7.63(m,1H,ArH),7.60(dd,J＝7.6,2.3Hz,1H,ArH),7.54–7.49(m,3H,ArH),7.24(td,J＝8.5,2.2Hz,1H,ArH),6.69(d,J＝1.1Hz,1H,ArH),3.22(heptd,J＝6.8,1.1Hz,1H,CH),1.39(d,J＝6.9Hz,6H,CH 3 ).
Example 4
The preparation method of the imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound comprises the following steps:
(1) Synthesis of compound F15 a: compound M6 (318 mg,1 mmol), 2-formyl- (4, 5) -dimethoxy-benzoic acid (420 mg,2 mmol), silver triflate (26 mg,0.1 mmol), DMF (N, N-dimethylformamide) (5 mL) was reacted at 100deg.C for 10 hours; after the completion of the reaction, 120mL of ethyl acetate was added for extraction, the organic phase was dried over anhydrous sodium sulfate and separated by flash column chromatography to obtain 238mg of pale yellow solid (F15 a) in 47% yield. MS (ESI) m/z=506 [ M-H ]] - . 1 H NMR(600MHz,Chloroform-d and CF 3 COOD)δ7.81(s,1H,ArH),7.64(d,J＝8.1Hz,1H,ArH),7.61–7.56(m,1H,ArH),7.56–7.47(m,2H,ArH),7.45(s,1H,ArH),6.89(d,J＝1.2Hz,1H,ArH),4.07(s,3H,CH 3 ),3.95(s,3H,CH 3 ),3.37–3.27(m,1H,CH),1.45(d,J＝6.9Hz,6H,CH 3 ).
(2) Synthesis of Compounds F15b and F15c: compound F15a (100 mg, 0.197mmol), triethylamine (40 mg, 0.390 mmol), toluene (5 mL) were reacted at 80℃for 4 hours, followed by flash column chromatography to give F15b and F15c simultaneously.
F15b: yellow solid, 40mg yield 42%. MS (ESI) m/z=490 [ M+H ]] + . 1 H NMR(600MHz,Chloroform-d)δ7.65–7.62(m,1H,ArH),7.57–7.52(m,1H,ArH),7.49–7.43(m,3H,ArH),7.20–7.17(m,1H,ArH)),6.66(s,1H,ArH),4.07–4.03(m,3H,CH 3 ),3.93–3.89(m,3H,CH 3 ),3.25–3.17(m,1H,CH),1.41–1.35(m,6H,CH 3 ).
F15c: yellow solid, yield 50mg, yield 52%. MS (ESI) m/z=490 [ M+H ]] + . 1 H NMR(600MHz,Chloroform-d)δ7.66–7.62(m,1H,ArH),7.53–7.47(m,3H,ArH),7.42(s,1H,ArH),7.39(s,1H,ArH),6.65(d,J＝1.1Hz,1H,ArH),4.00(s,3H,CH 3 ),3.97(s,3H,CH 3 ),3.20(heptd,J＝6.8,1.1Hz,1H,CH),1.38(d,J＝6.9Hz,6H,CH 3 ).
Example 5
The preparation method of the imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound comprises the following steps:
(1) Synthesis of compound F16 a: compound M6 (318 mg,1 mmol), 2-formyl-5-methyl-benzoic acid (820 mg,5 mmol), scandium acetate (33 mg,0.2 mmol), NMP (N-methylpyrrolidone) (10 mL) were reacted at 150℃for 12 hours; after the completion of the reaction, 120mL of ethyl acetate was added for extraction, the organic phase was dried over anhydrous sodium sulfate, and flash column chromatography was performed to obtain 263mg of a white solid (F16 a) in 57% yield. MS (ESI) m/z=460 [ M-H ]] - . 1 H NMR(600MHz,Chloroform-d and CF 3 COOD)δ8.16(d,J＝1.7Hz,1H,ArH),7.97(d,J＝8.0Hz,1H,ArH),7.66–7.59(m,2H,ArH),7.58–7.53(m,1H,ArH),7.51–7.46(m,2H,ArH),6.86(d,J＝1.1Hz,1H,ArH),3.34–3.26(m,1H,CH),2.55(s,3H,CH 3 ),1.43(d,J＝6.8Hz,6H,CH 3 ).
(2) Synthesis of Compounds F16b and F16c: compound F16a (100 mg,0.217 mmol), DMAP (p-dimethylaminopyridine) (27 mg,0.21 mmol), EDCI (carbodiimide hydrochloride) (42 mg,0.21 mmol), dichloroethane (3 mL) were reacted at 50℃for 8 hours and flash column chromatography gave F16b and F16c simultaneously.
F16b: yellow solid, 40mg yield 42%. MS (ESI) m/z=444 [ M+H ]] + . 1 H NMR(600MHz,Chloroform-d)δ7.85(d,J＝7.6Hz,1H,ArH),7.66–7.63(m,1H,ArH),7.58–7.53(m,1H,ArH),7.52–7.50(m,1H,ArH),7.49–7.46(m,3H,ArH),6.66(d,J＝1.1Hz,1H,ArH),3.22(heptd,J＝6.8,1.1Hz,1H,CH),2.45(s,3H,CH 3 ),1.39(d,J＝6.9Hz,6H,CH 3 ).
F16c: yellow solid, 40mg yield 42%. MS (ESI) m/z=444 [ M+H ]] + . 1 H NMR(600MHz,Chloroform-d)δ7.79–7.76(m,2H,ArH),7.65–7.62(m,1H,ArH),7.54–7.48(m,3H,ArH),7.46–7.44(m,1H,ArH),6.67(d,J＝1.2Hz,1H,ArH),3.21(heptd,J＝6.9,1.1Hz,1H,CH),2.48(s,3H,CH 3 ),1.39(d,J＝6.9Hz,6H,CH 3 ).
Experimental example 6
The spectral properties of all imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolones obtained in examples 1-5 were tested, and the spectral results of each compound are shown in Table 1 below:
TABLE 1
As shown in Table 1, the results show that the compounds of this type have strong solid fluorescence and liquid fluorescence properties. By constructing hydrogen bonds with smaller chemical bond substitution bond energy in the molecular skeleton, the compound obtains higher quantum yield and longer fluorescence lifetime in a solid state, also shows excellent luminescence performance in benzene solution, and can be used as a supplement of the molecular skeleton compound in the aspect of fluorescent materials in solid state and nonpolar solvents.
Experimental example 7
The thermal stability properties of all the imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compounds obtained in examples 1 to 5 were measured, and the thermal stability results of the respective compounds are shown in Table 2 below:
TABLE 2
| Compound | F11b | F11c | F12b | F12c | F14b | F14c | F15b | F15c | F16b | F16c |
| T 05 /℃ | 314 | 316 | 319 | 318 | 302 | 311 | 311 | 301 | 294 | 307 |
Table 2 shows that the compounds of the type provided by the invention have good thermal stability, and the thermal decomposition temperature is more than 290 ℃.
The results show that the imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound has strong solid fluorescence and liquid fluorescence functions and good thermal stability, and is expected to be applied to organic photoelectric devices, chemical sensors, biological probes and the like.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (9)
1. The imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound is characterized in that the structural formula is shown as formula (I) or formula (II):
（I） （II）
wherein the substituent R is halo, di (methoxy) or methyl.
2. The imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compound according to claim 1, wherein the substituent R is 4-hydrogen, 5-bromo, 4-fluoro, (4, 5) -di (methoxy) or 5-methyl.
3. The process for the preparation of imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolones according to claim 1 or 2, characterized by the following steps:
(1) The method comprises the steps of taking a compound 5- (2-chlorophenyl) -7-isopropyl-3H-thieno [2,3-e ] [1,4] diazepine-2-imine and a 2-formylbenzoic acid compound as raw materials, and reacting for 10-14 hours in the presence of a catalyst by taking a polar solvent as a reaction solvent at 80-200 ℃ to obtain a target compound F (a); the reaction formula is:
(2) Using compound F (a) as raw material, using chloroform, dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile, acetone, toluene or DMF as solvent, adding dehydrating agent and activating agent to make dehydration condensation reaction or using DIPEA and Et 3 N or pyridine is used as alkali to carry out dehydration condensation reaction, and the reaction is carried out for 4 to 14 hours at the temperature of 0 to 80 ℃ to obtain compounds of formula (I) and formula (II); the reaction formula is:
4. The method according to claim 3, wherein the 2-formylbenzoic acid compound of step (1) is selected from one of 2-formylbenzoic acid, 5-bromo-2-formylbenzoic acid, 4-fluoro-2-formylbenzoic acid, 2-formyl- (4, 5) -dimethoxy-benzoic acid and 2-formyl-5-methyl-benzoic acid.
5. The preparation method according to claim 3, wherein the molar ratio of the compound M6, the 2-formylbenzoic acid compound and the catalyst in the step (1) is 1:1-5:0.01-1, and the concentration of the compound M6 is 0.1-1.0mol/L.
6. A process according to claim 3, wherein the molar ratio of compound F (a), dehydrating agent and activator is from 1:1 to 10:1 to 10.
7. The process according to claim 3, wherein the molar ratio of F (a) to the base in the step (2) is 1:1 to 10 and the concentration of F (a) is 0.01 to 1mol/L.
8. The use of the imidazo [4,5-e ] thiophene [2,3-b ] pyridoindolone compounds according to claim 1 or 2 as small organic molecules with solid-liquid dual functions for preparing fluorescent materials.
9. The use according to claim 8, wherein the fluorescent material is an organic optoelectronic device, a chemical sensor or a biological probe.
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