A boron-nitrogen doped fused ring expanded purazine derivative, a synthetic method and application thereof
Patent Information
- Application Number
- CN202610651388.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-05-12
- Publication Date
- 2026-08-21
AI Technical Summary
但受合成路线有限、分子本征稳定性欠佳等问题制约，目前含B-N键的多环芳烃体系仍缺乏系统、深入的研究
1、本发明合成了一类硼氮掺杂稠环拓展呜拉嗪衍生物并探究其光电性质，为获得更加高效的有机光电材料提供更多的方案。本发明采用改进的合成方法使得反应原料价低易得，反应过程避免使用有毒试剂，合成方法简单易行，硼氮掺杂稠环拓展呜拉嗪衍生物在有机发光二极管、有机太阳能电池、有机场效应晶体管、有机激光器、有机传感器、分子开关以及医药中间体等领域具有广泛的应用。
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Abstract
Description
Technical Field
[0001] This invention relates to the fields of organic synthesis and organic functional molecules, and in particular to a boron-nitrogen-doped fused-ring extended uracil derivative, its synthesis method, and its applications. Background Technology
[0002] Urazine is a nitrogen-containing heterocyclic polycyclic aromatic hydrocarbon with a 16π electron structure, and is isoelectronic with pyrene. The in-plane nitrogen atoms in its framework allow for the controllability of the system's electron cloud distribution, forming a positively charged delocalized π-electron resonance structure, giving urazine excellent electron donor properties and structural stability. Related tests and theoretical calculations show that, compared to the all-carbon polycyclic aromatic hydrocarbon pyrene, urazine exhibits stronger anion and cation structural stability, making it a superior parent framework for preparing high-performance organic optoelectronic conjugated materials with broad prospects for optoelectronic applications.
[0003] With breakthroughs and maturation in the synthesis process of urazine, the design, synthesis, and performance research of its derivatives have developed rapidly, and they have now been successfully applied in optoelectronic fields such as photosensitive materials for organic solar cells, organic semiconductors, functional dyes, and organic light-emitting devices. This material system has a large modification space and outstanding application potential, and still needs further development and exploration.
[0004] Heteroatom doping is a core technique for functionalizing and modifying polycyclic aromatic hydrocarbons (PAHs) and controlling their photoelectric and carrier transport properties. Currently, modification methods have evolved from single heteroatom doping to dual-heteroatom and multi-heteroatom co-doping, allowing for precise customization of various properties of organic conjugated materials. In particular, replacing traditional C=C bonds with isoelectronic BN bonds allows for precise control of the electron cloud distribution and energy level structure of the conjugated system while preserving the original spatial configuration and planar structure of the molecule, optimizing intrinsic photoelectric performance and overcoming the shortcomings of traditional modification techniques. BN-co-doped PAHs, with their unique electronic structure and photoelectric advantages, have significant application value in the field of organic optoelectronic devices. However, due to limitations in synthetic routes and poor intrinsic molecular stability, systematic and in-depth research on BN-bonded PAH systems remains lacking. Summary of the Invention
[0005] The purpose of this invention is to address the technical deficiencies in the prior art by providing a boron-nitrogen-doped fused-ring extended uracil derivative, its synthesis method, and its applications.
[0006] The technical solution adopted to achieve the purpose of this invention is: A boron-nitrogen-doped fused-ring extended uracil derivative has the following general structural formula:
[0007] Wherein, R1, R2, and R3 are independent substituted or unsubstituted groups, and R1 to R3 are aryl, heteroaryl, alkyl, alkenyl, alkynyl, hydrogen, or halogen atom X; Preferably, the alkyl group is a C1-C4 alkyl group; the alkenyl group is a C1-C4 alkenyl group; the alkynyl group is a C1-C4 alkynyl group; the aryl group is a C6-C15 aryl group; the heteroaryl group is a C6-C15 heteroaryl group; the halogen atom X is F, Cl, Br or I; the aryl or heteroaryl group may or may not have substituents; the substituents on the aryl or heteroaryl group are C1-C4 alkyl, C1-C4 alkoxy, halogen atom X, amino, cyano, phenyl, or trifluoromethaneyl.
[0008] In the above technical solution, the structural formula of the boron-nitrogen-doped fused-ring extended uracil derivative is as follows:
[0009] Another aspect of the present invention includes a method for synthesizing the boron-nitrogen-doped fused-ring extended uracil derivative, the method comprising the following steps: Step 1: Add raw material I and 2,5-dimethoxytetrahydrofuran to a solvent and react them via a Clauson-Kaas reaction to obtain intermediate II after separation and purification; Step 2: Intermediate II, 3-butenamine hydrochloride and Buchwald-Hartwig reagent are added to a solvent and subjected to Buchwald-Hartwig coupling reaction to separate and purify intermediate III. Step 3: Intermediate III, potassium vinyltrifluoroborate, silicon tetrachloride and triethylamine are added to a solvent and subjected to an electrophilic borylation reaction, followed by separation and purification to obtain intermediate IV; Step 4: Intermediate IV and Grubbs catalyst are added to a solvent and subjected to an olefin cyclization metathesis reaction to obtain intermediate V after separation and purification. Step 5: Intermediate V and oxidant are added to a solvent and subjected to oxidative dehydrogenation reaction to obtain compound VI after separation and purification; Step 6: Compound VI and N-bromosuccinimide are added to a solvent for bromination reaction, and compound VII is obtained by separation and purification. Step 7: Compound VII, raw material VIII and Suzuki reagent are added to a solvent to carry out a coupling reaction. Raw material VIII is an organoboronic acid compound with substituent groups R1 and R2. The boron nitrogen doped fused ring extended uracil compound is obtained by separation and purification, i.e. product I. The synthesis route is shown below: .
[0010] In the above scheme, in step 1, the solvent is a mixture of dichloroethane and glacial acetic acid. 1.0 equivalent of raw material I and 2.0~3.0 equivalents of 2,5-dimethoxytetrahydrofuran are mixed in the mixed solvent and reacted at 125~135℃ for 10~15h. After the reaction is complete, the reaction solution is dissolved in a dissolving solution, washed, the organic layer is collected, dried, and purified to obtain intermediate II; the dissolving solution is preferably dichloromethane.
[0011] In the above scheme, in step 2, under the protection of a protective gas, 1.0 equivalent of intermediate II, 2.5~3.0 equivalents of 3-butenamine hydrochloride, 0.1~0.5 equivalents of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride and 5.0~10.0 equivalents of sodium tert-butoxide are added to a solvent and mixed. The mixture is reacted at 80~100℃ for 8~14h. After the reaction is complete, the reaction solution is dissolved in a dissolving solution, washed, and the organic layer is collected, dried, and purified to obtain intermediate III. The solvent is preferably toluene or xylene, and the dissolving solution is preferably dichloromethane.
[0012] In the above scheme, in step 3, under the protection of a protective gas, 2.5-3.5 equivalents of potassium vinyltrifluoroborate and 2.5-3.0 equivalents of silicon tetrachloride are mixed in a solvent and reacted for 0.5-3 hours. Then, 5.0-7.0 equivalents of triethylamine are added and the reaction continues for another 0.5-3 hours. Subsequently, 1.0 equivalent of intermediate III is added, and the reaction is carried out at 80-100°C for 8-14 hours. After the reaction is complete, the reaction solution is dissolved in a solvent, washed, and the organic layer is collected, dried, and purified to obtain intermediate IV. The solvent is preferably toluene and cyclopentane-hexyl ether, with a volume ratio of toluene to cyclopentane-hexyl ether of 1:1 to 5:1. The solvent is preferably dichloromethane.
[0013] In the above scheme, in step 4, under the protection of a protective gas, 1.0 equivalent of intermediate IV and Grubbs catalyst are added to a solvent and mixed. The mixture is reacted at 20~35℃ for 12~24h. After the reaction is complete, the reaction solution is dissolved in a dissolving solution, washed, and the organic layer is collected, dried, and purified to obtain intermediate V. The solvent is preferably dichloromethane, and the dissolving solution is preferably dichloromethane.
[0014] In the above scheme, in step 5, under the protection of a protective gas, 1.0 equivalent of intermediate V and 1.0~3.0 equivalent of oxidant are mixed in a solvent and reacted at 150~160℃ for 7~12h. After the reaction is complete, the reaction solution is dissolved in a dissolving solution, washed, the organic layer is collected, dried and purified to obtain compound VI; the oxidant is preferably palladium on carbon, the solvent is preferably decane, and the dissolving solution is preferably dichloromethane.
[0015] In the above scheme, in step 6, under the protection of a protective gas, 1.0 equivalent of compound VI and 1.0~5.0 equivalent of N-bromosuccinimide are mixed in a solvent and reacted at 20~35°C for 12~24h. After the reaction is complete, the reaction solution is dissolved in a dissolving solution, washed, the organic layer is collected, dried, and purified to obtain compound VII. The solvent is preferably THF or DMF, and the dissolving solution is preferably dichloromethane.
[0016] In the above scheme, in step 7, under the protection of a protective gas, 1.0 equivalent of compound VII, 1.0~3.0 equivalent of raw material VIII, 0.1~0.5 equivalent of tetra-triphenylphosphine palladium and 4.0~6.0 equivalent of potassium carbonate are added to a solvent and mixed. The mixture is reacted at 80~90℃ for 8~14h. After the reaction is complete, the reaction solution is dissolved in a solvent, washed, the organic layer is collected, dried and purified to obtain product I. The solvent is preferably toluene, ethanol and water, with a volume ratio of toluene, ethanol and water of (2~6):1:1. The solvent is preferably dichloromethane.
[0017] Another aspect of the present invention includes the application of the boron-nitrogen-doped fused-ring extended uracil derivative in the preparation of optical or optoelectronic devices.
[0018] In the above technical solutions, the optical or optoelectronic device includes organic light-emitting diodes, organic solar cells, organic field-effect transistors, organic lasers, or organic sensors.
[0019] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention synthesizes a class of boron-nitrogen-doped fused-ring extended urazine derivatives and explores their photoelectric properties, providing more solutions for obtaining more efficient organic optoelectronic materials. The improved synthesis method employed in this invention makes the reactants inexpensive and readily available, avoids the use of toxic reagents, and is simple and easy to implement. These boron-nitrogen-doped fused-ring extended urazine derivatives have wide applications in organic light-emitting diodes, organic solar cells, organic field-effect transistors, organic lasers, organic sensors, molecular switches, and pharmaceutical intermediates.
[0020] 2. This invention provides more solutions for obtaining more efficient organic optoelectronic materials. The synthesis method of the target product is simple to operate, has a high yield, and exhibits a high fluorescence quantum yield (fluorescence quantum yield of 0.65-0.78). Therefore, this type of boron-nitrogen-doped fused-ring extended uracil derivative has broad potential application prospects in the field of organic optoelectronic materials, such as in the fabrication of optoelectronic materials, solar cells, electroluminescent devices, and sensors.
[0021] 3. The synthesis methods of this invention include Clauson-Kaas reaction, Buchwald-Hartwig coupling reaction, electrophilic borylation reaction, olefin cyclization metathesis reaction, oxidative dehydrogenation reaction, Suzuki coupling reaction, substitution reaction, etc.; the boron-oxygen doped fused-ring extended uracil derivatives prepared can be used in the fabrication of optoelectronic materials, solar cells, electroluminescent devices, and sensors.
[0022] 4. The boron-nitrogen-doped fused-ring extended urazine derivatives of this invention have broad application prospects in organic chemistry, such as in hydrogen storage materials, organic synthesis, catalysis, optoelectronic materials, sensors, probes, and bioactive molecules. By constructing boron-nitrogen-doped fused-ring extended urazine derivatives, their photoelectric physical properties were tested, and their potential application areas were explored. Attached Figure Description
[0023] Figure 1 The following is a description of the compound of formula (1). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0024] Figure 2 The figure shown is of compound (2). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0025] Figure 3 The figure shown is of compound (3). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0026] Figure 4 The following is a description of the compound of formula (25). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0027] Figure 5 The figure shown is of compound (26). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0028] Figure 6 The following is a description of the compound of formula (27). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0029] Figure 7 The following is a description of the compound of formula (96). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0030] Figure 8 The following is a description of the compound of formula (120). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0031] Figure 9 The following is a description of the compound of formula (144). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0032] Figure 10 The following is a description of the compound of formula (148). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0033] Figure 11 The following is a description of the compound of formula (162). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0034] Figure 12 The following is a description of the compound of formula (180). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0035] Figure 13 The following is a description of the compound of formula (198). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0036] Figure 14 The diagram shows the compound of formula (201). 1 1H NMR spectrum (400 MHz, CD3Cl).
[0037] Figure 15 The fluorescence absorption and emission spectra of compounds of formulas (25), (26), (27), and (96) are shown.
[0038] Figure 16 The fluorescence spectra of compounds of formulas (162), (180), (198), and (201) are shown.
[0039] Figure 17 The diagram shows the single-crystal structures of compounds of formulas (25), (26), (27), (96), (162), and (180). Detailed Implementation
[0040] The present invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0041] Example 1 The compounds of formulas (1), (2), and (3) are synthesized, and their structural formulas are as follows:
[0042] The synthesis method includes the following steps: Step 1, synthesize compound formula (1)-1:
[0043] Compound 2,6-dibromoaniline (500 mg, 1.63 mmol, 1.00 equiv.), glacial acetic acid (15 mL), and 2,5-dimethoxytetrahydrofuran (538 mg, 4.07 mmol, 2.50 equiv.) were reacted in an oil bath at 135 °C for 12 hours after being refluxed. The reaction was quenched with water after completion. Extraction was performed using dichloromethane and water, the organic phase was collected, dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (1)-1.
[0044] Step 2, synthesize compound formula (1)-2:
[0045] Compound (1)-1 (500 mg, 1.66 mmol, 1.00 equiv) and Pd(dppf)Cl were added to a 250 mL dry reaction tube. (425 mg, 0.58 mmol, 0.35 equiv) and t-BuOK (1490 mg, 13.28 mmol, 8.00 equiv) were purged with nitrogen three times, followed by the addition of anhydrous toluene (15 mL) and 2,6-dibromoaniline (1250 mg, 4.98 mmol, 3.00 equiv). The reaction was stirred in an oil bath at 100 °C for 12 hours until complete. After the reaction was complete, water was added to quench the reaction, and the mixture was extracted with dichloromethane and water. The organic phase was collected, dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (1)-2.
[0046] Step 3, synthesize compound formula (1)-3:
[0047] In a 150 mL reaction tube, potassium vinyltrifluoroborate (430 mg, 3.21 mmol, 3.00 equiv) was added. After three evacuations in a glove box, a mixed solvent of toluene / cyclopentyl methyl ether (15 mL each) and silicon tetrachloride (545 mg, 3.21 mmol, 3.00 equiv) was added under nitrogen protection, and the mixture was stirred at room temperature for 10 minutes. Subsequently, triethylamine (540 mg, 5.35 mmol, 5.00 equiv) and compound (1)-2 (300 mg, 1.07 mmol, 1.00 equiv) were added sequentially, and the mixture was reacted in an oil bath at 90 °C for 8 hours. After the reaction was completed, the mixture was quenched with water, extracted with dichloromethane and water, and the organic phase was collected. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (1)-3.
[0048] Step 4, synthesize compound formula (1)-4:
[0049] Compound (1)-3 (850 mg, 2.40 mmol, 1.00 equiv) was added to a 100 mL round-bottom flask. After three evacuations in a glove box, Grubbs-1 catalyst (210 mg, 0.24 mmol, 0.10 equiv) and dichloromethane solvent were added under nitrogen protection. The mixture was stirred at room temperature for 12 hours, and the reaction was monitored by TLC to indicate completion. After the reaction was complete, water was added to quench the reaction, and the mixture was extracted with dichloromethane and water. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (1)-4.
[0050] Step 5, synthesize compounds of formula (1) / formula (2) / formula (3):
[0051] Compound (1)-4 (1900 mg, 6.39 mmol, 1.00 equiv) and Pd / C (1700 mg, 15.97 mmol, 2.50 equiv) were added to a 250 mL reaction tube. After three evacuations in a glove box, decane (30 mL) was added under nitrogen protection. The reaction was stirred at room temperature for 20 hours, and TLC was used to monitor the completion of the reaction. After the reaction was complete, water was added to quench the reaction, and the mixture was extracted with dichloromethane and water. The organic phase was collected, dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (1). 1 H NMR spectrum as shown Figure 1 As shown, compound formula (2) 1H NMR spectrum as shown Figure 2 As shown and compound formula (3) 1 H NMR spectrum as shown Figure 3 As shown.
[0052] Example 2 The compounds of formulas (25), (26) and (27) are synthesized, and their structural formulas are as follows:
[0053] The synthesis principle is the same as in Example 1, except that in step 1, 2,6-dibromoaniline in Example 1 is replaced with an equal amount of 2,6-dibromo-4-tert-butylaniline, and compound formula (25)-1 is synthesized:
[0054] Then, replace compound formula (1)-1 with compound formula (25)-1, and proceed with steps 2, 3, 4, and 5 to obtain compound formula (25). 1 H NMR spectrum as shown Figure 4 As shown, compound formula (26) 1 H NMR spectrum as shown Figure 5 As shown and compound formula (27) 1 H NMR spectrum as shown Figure 6 As shown.
[0055] Example 3 The compounds of formulas (28), (29) and (30) are synthesized, and their structural formulas are as follows:
[0056] The synthesis principle is the same as in Example 1, except that in step 1, 2,6-dibromoaniline in Example 1 is replaced with an equal amount of formula (28)-1 to synthesize compound formula (28)-2:
[0057] Then, replace compound formula (1)-1 with compound formula (28)-2, and proceed with steps 2, 3, 4 and 5 to obtain compound formula (28), compound formula (29) and compound formula (30).
[0058] Example 4 The compounds of formulas (85), (86), and (87) are synthesized, and their structural formulas are as follows:
[0059] The synthesis principle is the same as in Example 1, except that in step 1, 2,6-dibromoaniline in Example 1 is replaced with an equal amount of compound formula (85)-1 to synthesize compound formula (85)-2:
[0060] Then, replace compound formula (1)-1 with compound formula (85)-2, and proceed with steps 2, 3, 4 and 5 to obtain compound formula (85), compound formula (86) and compound formula (87).
[0061] Example 5 The synthetic compound (96) has the following structural formula:
[0062] The first five steps of the synthesis are based on the same principle as in Example 2, except that there is one more reaction step, 6.
[0063] Step 6, synthesize compound formula (96):
[0064] In a 500 mL round-bottom flask, the starting compound (25) (450 mg, 1.29 mmol, 1.0 equiv) and a magnetic stir bar were added. 100 mL of tetrahydrofuran was added to the reaction flask, and 0.5 equiv of NBS (345 mg, 1.93 mmol, 1.5 equiv) was added every 30 min. The mixture was stirred at room temperature until the reaction was complete. The mixture was then quenched with water, extracted with dichloromethane and water, and the organic phase was collected. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (96). 1 H NMR spectrum as shown Figure 7 As shown.
[0065] Example 6 The synthetic formulas of compounds (97) and (98) are as follows:
[0066] The synthesis principle is the same as in Example 5, except that in step 6, compound formula (25) in Example 6 is replaced with an equal amount of compound formula (26) to synthesize compound formulas (97) and (98):
[0067] Example 7 The synthetic compound (99) has the following structural formula:
[0068] The synthesis principle is the same as in Example 5, except that in step 6, the compound formula (25) in Example 6 is replaced with an equal amount of compound formula (27) to synthesize compound formula (99):
[0069] Example 8 The synthetic compound (120) has the following structural formula:
[0070] The synthesis principle of the first 6 steps is the same as in Example 5, except that there is an additional reaction step 7.
[0071] Step 7, synthesize compound formula (120):
[0072] Take 50 mL of Shrek tube and add compound (96) (200 mg, 0.39 mmol, 1.0 equiv), compound phenylboronic acid (75 mg, 0.78 mmol, 1.5 equiv), potassium carbonate (218 mg, 1.57 mmol, 4.0 equiv), and a magnetic ball, respectively, and place them in a glove box. After evacuating the gas three times, add catalyst Pd(PPh3)4 (56 mg, 0.08 mmol, 0.2 equiv), seal the reaction flask, and remove it. Add an N2 balloon to equalize the system pressure. Then add 8 mL of mixed solvent (Tol / EtOH / H2O = 2 / 1 / 1) to the system and transfer the system to 70 °C to continue the reaction. After the reaction is complete, quench with water, extract with dichloromethane and water, collect the organic phase, dry with anhydrous magnesium sulfate, filter, and remove the solvent by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (120). 1 H NMR spectrum as shown Figure 8 As shown.
[0073] Example 9 The synthetic compound (123) has the following structural formula:
[0074] The synthesis principle is the same as in Example 8, except that in step 7, the compound formula (96) in Example 8 is replaced with an equal amount of compound formula (99) to synthesize compound formula (123):
[0075] Example 10 The synthetic compound (148) has the following structural formula:
[0076] The synthesis principle is the same as in Example 8, except that in step 7, the compound phenylboronic acid in Example 8 is replaced with an equal amount of the compound p-methoxyphenylboronic acid, and the compound formula (148) is synthesized:
[0077] Example 11 The synthetic compound (151) has the following structural formula:
[0078] The synthesis principle is the same as in Example 10, except that in step 7, the compound formula (96) in Example 10 is replaced with an equal amount of compound formula (99) to synthesize compound formula (151):
[0079] Example 12 The synthetic compound (152) has the following structural formula:
[0080] The synthesis principle is the same as in Example 8, except that in step 7, the compound phenylboronic acid in Example 8 is replaced with an equal amount of the compound 2,4,6-trimethylphenylboronic acid, resulting in compound formula (152):
[0081] Example 13 The synthetic compound (155) has the following structural formula:
[0082] The synthesis principle is the same as in Example 12, except that in step 7, the compound formula (96) in Example 10 is replaced with an equal amount of the compound 2,4,6-trimethylphenylboronic acid, to synthesize compound formula (155):
[0083] Example 14 The synthetic compound (162) has the following structural formula:
[0084] The synthesis principle of the first five steps is the same as in Example 2, except that there is an additional reaction step 6.
[0085] Step 6, synthesize compound formula (162):
[0086] In a 500 mL round-bottom flask, the starting compound (25) (450 mg, 1.29 mmol, 1.0 equiv) and a magnetic stir bar were added. 100 mL of tetrahydrofuran was added to the reaction flask, and 1.2 equiv of NBS (825 mg, 4.64 mmol, 3.6 equiv) was added every 30 min. The mixture was stirred at room temperature until the reaction was complete. The mixture was then quenched with water, extracted with dichloromethane and water, and the organic phase was collected. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (162). 1 H NMR spectrum as shown Figure 9 As shown.
[0087] Example 15 The synthetic compound (163) has the following structural formula:
[0088] The synthesis principle is the same as in Example 14, except that in step 6, the compound formula (25) in Example 6 is replaced with an equal amount of compound formula (26) to synthesize compound formula (163):
[0089] Example 16 The synthetic compound (164) has the following structural formula:
[0090] The synthesis principle is the same as in Example 14, except that in step 6, the compound formula (25) in Example 6 is replaced with an equal amount of compound formula (27) to synthesize compound formula (164):
[0091] Example 17 The synthetic compound (180) has the following structural formula:
[0092] The synthesis principle of the first 6 steps is the same as in Example 14, except that there is an additional reaction step 7.
[0093] Step 7, synthesize compound formula (180):
[0094] Take 50 mL of Shrek tubes and add compound (162) (200 mg, 0.39 mmol, 1.0 equiv), compound phenylboronic acid (144 mg, 1.18 mmol, 3.0 equiv), potassium carbonate (325 mg, 2.34 mmol, 6.0 equiv), and a magnetic flask, respectively, and place them in a glove box. After evacuating the gas three times, add catalyst Pd(PPh3)4 (28 mg, 0.04 mmol, 0.1 equiv), seal the reaction flask, and remove it. Add an N2 balloon to equalize the system pressure. Then add 8 mL of mixed solvent (Tol / EtOH / H2O = 2 / 1 / 1) to the system and transfer the system to 75 °C to continue the reaction. After the reaction is complete, quench with water, extract with dichloromethane and water, collect the organic phase, dry with anhydrous magnesium sulfate, filter, and remove the solvent by rotary evaporation. The crude product was purified by silica gel column chromatography to obtain compound (180). 1 H NMR spectrum as shown Figure 10 As shown, its fluorescence quantum yield is 0.78.
[0095] Example 18 The synthetic compound (181) has the following structural formula:
[0096] The synthesis principle is the same as in Example 17, except that in step 7, the compound formula (162) in Example 17 is replaced with an equal amount of compound formula (163) to synthesize compound formula (181):
[0097] Example 19 The synthetic compound (182) has the following structural formula:
[0098] The synthesis principle is the same as in Example 17, except that in step 7, the compound formula (162) in Example 17 is replaced with an equal amount of compound formula (164) to synthesize compound formula (182):
[0099] Example 20 The synthetic compound (201) has the following structural formula:
[0100] The synthesis principle is the same as in Example 17, except that in step 7, the compound phenylboronic acid in Example 17 is replaced with an equal amount of p-methoxyphenylboronic acid to synthesize compound (201), which has a fluorescence quantum yield of 0.65.
[0101] Example 21 The synthetic compound (202) has the following structural formula:
[0102] The synthesis principle is the same as in Example 20, except that in step 7, the compound formula (162) in Example 29 is replaced with an equal amount of compound formula (163) to synthesize compound formula (202):
[0103] Example 22 The synthetic compound (259) has the following structural formula:
[0104] The synthesis principle is the same as in Example 20, except that in step 7, the compound formula (162) in Example 20 is replaced with an equal amount of compound formula (164) to synthesize compound formula (203):
[0105] The structural characteristics and photophysical properties of these compounds were further investigated, including single-crystal structure analysis and ultraviolet fluorescence spectroscopy. Figures 1 to 17 The proton NMR spectra, ultraviolet absorption, and fluorescence emission of some compounds were characterized. Figures 1 to 14 The 1H NMR spectrum can prove the correctness of the compound's structure; through Figures 15 to 16 The UV absorption and fluorescence emission spectra of the compounds show that they exhibit good absorption around 300 nm and relatively pure emission in the 400-450 nm range, thus demonstrating their potential applications in optoelectronic materials. Meanwhile, through... Figure 17 The single-crystal structure diagram of compound (25) / (26) / (27) / (96) / (162) / (180) shows that the urazine skeleton of compound (25) / (26) / (27) / (96) / (162) / (180) exhibits a good planar structure, proving that this type of compound has potential charge transport properties.
[0106] The compounds of this invention expand the skeletal framework of uracil by introducing BN polar covalent bonds into the uracil framework. Novel organic light-emitting materials are constructed by doping the uracil framework with BN covalent bonds. The insertion of BN bonds maintains the planar structure of the uracil framework while acquiring unique photophysical properties. The material structure is optimized through the use of the parent core, peripheral substituents, and fused ring parallel arrangements.
[0107] The above description is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A boron-nitrogen-doped fused-ring extended uracil derivative, characterized in that, Its general structural formula is as follows: Wherein, R1, R2, and R3 are independent substituted or unsubstituted groups, and R1 to R3 are aryl, heteroaryl, alkyl, alkenyl, alkynyl, hydrogen, or halogen atom X; Preferably, the alkyl group is a C1-C4 alkyl group; the alkenyl group is a C1-C4 alkenyl group; the alkynyl group is a C1-C4 alkynyl group; the aryl group is a C6-C15 aryl group; the heteroaryl group is a C6-C15 heteroaryl group; the halogen atom X is F, Cl, Br or I; the aryl or heteroaryl group may or may not have substituents; the substituents on the aryl or heteroaryl group are C1-C4 alkyl, C1-C4 alkoxy, halogen atom X, amino, cyano, phenyl, or trifluoromethaneyl.
2. The boron-nitrogen-doped fused-ring extended uracil derivative as described in claim 1, characterized in that, The structural formula is:
3. The method for synthesizing boron-nitrogen-doped fused-ring extended uracil derivatives as described in claim 1 or 2, characterized in that, Includes the following steps: Step 1: Add raw material I and 2,5-dimethoxytetrahydrofuran to a solvent and react them via a Clauson-Kaas reaction to obtain intermediate II after separation and purification; Step 2: Intermediate II, 3-butenamine hydrochloride and Buchwald-Hartwig reagent are added to a solvent and subjected to Buchwald-Hartwig coupling reaction to obtain intermediate III after separation and purification. Step 3: Intermediate III, potassium vinyltrifluoroborate, silicon tetrachloride and triethylamine are added to a solvent and subjected to an electrophilic borylation reaction, followed by separation and purification to obtain intermediate IV; Step 4: Intermediate IV and Grubbs catalyst are added to a solvent and subjected to an olefin cyclization metathesis reaction to obtain intermediate V after separation and purification. Step 5: Intermediate V and oxidant are added to a solvent and subjected to oxidative dehydrogenation reaction to obtain compound VI after separation and purification; Step 6: Compound VI and N-bromosuccinimide are added to a solvent for bromination reaction, and compound VII is obtained by separation and purification. Step 7: Compound VII, raw material VIII and Suzuki reagent are added to a solvent to carry out a coupling reaction. Raw material VIII is an organoboronic acid compound with substituent groups R1 and R2. The boron nitrogen doped fused ring extended uracil compound is obtained by separation and purification, i.e. product I. The synthesis route is shown below: 。 4. The synthesis method as described in claim 3, characterized in that, In step 1, the solvent is a mixture of dichloroethane and glacial acetic acid. 1.0 equivalent of raw material I and 2.0-3.0 equivalents of 2,5-dimethoxytetrahydrofuran are mixed in the mixed solvent and reacted at 125-135°C for 10-15 hours. After the reaction is complete, the reaction solution is dissolved in a solvent, washed, and the organic layer is collected, dried, and purified to obtain intermediate II. The solvent is preferably dichloromethane. Preferably, in step 2, under the protection of a protective gas, 1.0 equivalent of intermediate II, 2.5-3.0 equivalents of 3-butenamine hydrochloride, 0.1-0.5 equivalents of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride and 5.0-10.0 equivalents of sodium tert-butoxide are added to a solvent and mixed. The mixture is reacted at 80-100°C for 8-14 hours. After the reaction is complete, the reaction solution is dissolved in a dissolving solution, washed, and the organic layer is collected, dried, and purified to obtain intermediate III. The solvent is preferably toluene or xylene, and the dissolving solution is preferably dichloromethane.
5. The synthesis method as described in claim 3, characterized in that, In step 3, under the protection of a protective gas, 2.5-3.5 equivalents of potassium vinyltrifluoroborate and 2.5-3.0 equivalents of silicon tetrachloride are mixed in a solvent and reacted for 0.5-3 hours. Then, 5.0-7.0 equivalents of triethylamine are added and the reaction continues for another 0.5-3 hours. Subsequently, 1.0 equivalent of intermediate III is added, and the reaction is carried out at 80-100°C for 8-14 hours. After the reaction is complete, the reaction solution is dissolved in a solvent, washed, and the organic layer is collected, dried, and purified to obtain intermediate IV. The solvent is preferably toluene and cyclopentane-hexane methyl ether, with a volume ratio of toluene to cyclopentane-hexane methyl ether of 1:1 to 5:
1. The solvent is preferably dichloromethane.
6. The synthesis method according to claim 3, characterized in that, In step 4, under the protection of a protective gas, 1.0 equivalent of intermediate IV and Grubbs catalyst are added to a solvent and mixed. The mixture is reacted at 20-35°C for 12-24 hours. After the reaction is complete, the reaction solution is dissolved in a dissolving solution, washed, and the organic layer is collected, dried, and purified to obtain intermediate V. The solvent is preferably dichloromethane, and the dissolving solution is preferably dichloromethane.
7. The synthesis method according to claim 3, characterized in that, In step 5, under the protection of a protective gas, 1.0 equivalent of intermediate V and 1.0~3.0 equivalent of oxidant are mixed in a solvent and reacted at 150~160℃ for 7~12h. After the reaction is complete, the reaction solution is dissolved in a dissolving solution, washed, the organic layer is collected, dried and purified to obtain compound VI. The oxidant is preferably palladium on carbon, the solvent is preferably decane, and the dissolving solution is preferably dichloromethane.
8. The synthesis method as described in claim 3, characterized in that, In step 6, under the protection of a protective gas, 1.0 equivalent of compound VI and 1.0~5.0 equivalent of N-bromosuccinimide are mixed in a solvent and reacted at 20~35°C for 12~24h. After the reaction is complete, the reaction solution is dissolved in a dissolving solution, washed, the organic layer is collected, dried, and purified to obtain compound VII. The solvent is preferably THF or DMF, and the dissolving solution is preferably dichloromethane.
9. The synthesis method according to claim 3, characterized in that, In step 7, under the protection of a protective gas, 1.0 equivalent of compound VII, 1.0~3.0 equivalent of raw material VIII, 0.1~0.5 equivalent of tetra-triphenylphosphine palladium, and 4.0~6.0 equivalent of potassium carbonate are added to a solvent and mixed. The mixture is reacted at 80~90℃ for 8~14h. After the reaction is complete, the reaction solution is dissolved in a solvent, washed, the organic layer is collected, dried, and purified to obtain product I. The solvent is preferably toluene, ethanol, and water, with a volume ratio of toluene, ethanol, and water of (2~6):1:
1. The solvent is preferably dichloromethane.
10. The application of the boron-nitrogen-doped fused-ring extended uracil derivative as described in claim 1 or 2 in the fabrication of optical or optoelectronic devices, characterized in that, The optical or optoelectronic device includes organic light-emitting diodes, organic solar cells, organic field-effect transistors, organic lasers, or organic sensors.