CN117865968A - Preparation method and application of benzo [ kl ] indole [3,2,1-de ] acridine - Google Patents
Preparation method and application of benzo [ kl ] indole [3,2,1-de ] acridine Download PDFInfo
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- CN117865968A CN117865968A CN202311604556.7A CN202311604556A CN117865968A CN 117865968 A CN117865968 A CN 117865968A CN 202311604556 A CN202311604556 A CN 202311604556A CN 117865968 A CN117865968 A CN 117865968A
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- benzo
- indole
- acridine
- naphthalene
- amine
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- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 title claims abstract description 42
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 title claims abstract description 40
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 title claims abstract description 21
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 125000005605 benzo group Chemical group 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 8- (9H-carbazole-9-yl) naphthalene-1-amine Chemical compound 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000003208 petroleum Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 7
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000004440 column chromatography Methods 0.000 claims abstract description 4
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims abstract description 4
- 239000000741 silica gel Substances 0.000 claims abstract description 4
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 3
- 238000006862 quantum yield reaction Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 15
- 238000007363 ring formation reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Indole Compounds (AREA)
Abstract
Benzo [ kl]Indole [3,2,1-de ]]A preparation method and application of acridine. 1, 8-diamine naphthalene and 5H-5 lambda are added into a dry reaction tube 3 Dibenzo [ b, d ]]Iodine-5-yl trifluoro methanesulfonate, copper acetate monohydrate, and sodium carbonate were dissolved in N, N-dimethylformamide, and reacted at 120 ℃ under air conditions for 24 hours. After the reaction is completed, a petroleum ether and ethyl acetate system is used for carrying out a rapid column chromatography to obtain 8- (9H-carbazole-9-yl) naphthalene-1-amine. The obtained 8- (9H-carbazole-9-yl) naphthalene-1-amine is dissolved in acetic acid solution, and is dripped into sodium nitrite aqueous solution. The mixture was kept at a temperature below 0 ℃ for 30 minutes, then stirred at 40 ℃ for 2 hours, cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and filtered. Vacuum distilling, purifying the crude product with silica gel column, eluting with petroleum ether to obtain yellowish green solid, i.e. benzo [ kl ]]Indole [3,2,1-de ]]Acridine. The invention has the following advantages ofSimple process, low cost, good repeatability and the like, and the synthesized product is applied to luminescent materials.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a preparation method and application of benzo [ kl ] indole [3,2,1-de ] acridine.
Background
mono-N-cyclization in aryl diamines has been disclosed as having the advantage of being able to build N-aminoaryl carbazole in good yield, high selectivity and narrow half-peak width [ see: D. zhu, Q.Liu, B.Luo, M.Chen, R.Pi, P.Huang and S.Wen, adv. Synth. Catal., 2013, 355, 2172–2178]. By reacting residual NH 2 Diazotization is carried out, and then intramolecular electrophilic cyclization is carried out, so that the obtained N-aminoaryl carbazole can be easily converted into an N-condensed/spiral carbazole bracket. The type and size of the second ring is determined by the two NH's in the diamine 2 The distance of the groups is determined. To date, many methods for constructing C-fused benzocarbazole by a cyclic pi-expansion strategy have been documented [ see: (a) Y, hiraga, R, kuwahara and T, hatta, tetrahedron, 2021, 94, 132317, (b) A, narita, X.—Y, wang, X, feng and K, muellen, chem, soc, rev, 2015, 44, 6616-6643;]. And nitrogen fused indole [3,2,1-jk ]]Carbazole is receiving increasing attention due to its unified emitter with multiple resonance effects and full width at half maximum [ see: X.F. Luo, S.Q. Song, H.X. Ni, H.Ma, D.Yang, D.Ma, Y. -X.Zheng and J. -L.Zuo, angew.chem., int. Ed., 2022, 61, e202209984, (b) H.L. Lee, W.J. Chung, J.Y. Lee, small, 2020, 16, 1907569)]. N-aminoaryl carbazole as a potential C-N axial chiral diaryl can provide a modular approach to pi-extended carbazole, five/six membered ring fusion, helices, and cationic helices by diazotisation/cyclization [ see: S.—S..Li, Y.—Q..Xia, F.—Z..Hu, C.—F..Liu, F..Su and L..Dong, chem.—Asian J..2016, 11, 3165-3168]. There are few general, inexpensive and modular tools for assembling six-membered ring fused carbazole at the N-site, and therefore it is very interesting and necessary to develop a modular approach that can achieve pi-expansion of carbazole by diazotisation/cyclization. In addition, fluorescence spectra and quantum yields of the novel scaffolds were also measured, six-membered ring carbazole showed high quantum yields, with a narrow half-peak width (43 nm) and a small HOMO/LUMO energy gap, showing the potential of OLED devices.
Disclosure of Invention
The invention aims to provide a preparation method and application of benzo [ kl ] indole [3,2,1-de ] acridine.
The invention has the following thought: with 1, 8-diamine naphthalene and 5H-5 lambda 3 Dibenzo [ b, d ]]The benzo [ kl ] is obtained by diazotizing iodine-5-base trifluoro methanesulfonate as a raw material]Indole [3,2,1-de ]]Acridine.
The specific steps for preparing benzo [ kl ] indole [3,2,1-de ] acridine are as follows:
(1) Weighing 0.1-0.3 millimole of 1, 8-diamine naphthalene and 1-3 equivalent of 5H-5 lambda 3 Dibenzo [ b, d ]]Iodine-5-base trifluoro methanesulfonate, 10-20 mole percent copper acetate monohydrate and 1-2 equivalents of sodium carbonate are dissolved in 3 ml of N, N-dimethylformamide to prepare a solution, and the solution is transferred into a reaction tube. Reacting for 24 hours at 120 ℃ under the air condition, and carrying out a rapid column chromatography by using a petroleum ether and ethyl acetate system after the reaction is finished to obtain the product benzo 8- (9H-carbazole-9-yl) naphthalene-1-amine.
(2) 0.3-0.6 mmol of benzo 8- (9H-carbazole-9-yl) naphthalene-1-amine is dissolved in 3-8 ml of acetic acid solution, and sodium nitrite aqueous solution (2-5 equivalent sodium nitrite and 3.0 ml of distilled water) is dripped. The mixture was kept at a temperature below 0℃for 30 minutes, then stirred at 40℃for 2 hours, and cooled to room temperature. The mixture was extracted with dichloromethane. The organic phase was dried over sodium sulfate solid and filtered. After volatile components are removed from the filtrate, the crude product is purified on a silica gel (300-400 mesh) column, and eluted with petroleum ether to obtain a yellowish green solid, namely benzo [ kl ] indole [3,2,1-de ] acridine.
The benzo [ kl ] indole [3,2,1-de ] acridine disclosed by the invention is applied to luminescent materials and OLED devices.
Drawings
FIG. 1 is a synthetic reaction equation for benzo [ kl ] indole [3,2,1-de ] acridine.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of benzo [ kl ] indole [3,2,1-de ] acridine.
FIG. 3 is a fluorescence excitation spectrum and an emission spectrum of benzo [ kl ] indole [3,2,1-de ] acridine.
FIG. 4 is the quantum yield of benzo [ kl ] indole [3,2,1-de ] acridine.
Detailed Description
Examples:
(1) Weigh 0.2 mmole (31.6 mg) of 1, 8-diamine naphthalene, 1.5 equivalents (128.5 mg) of 5H-5 lambda 3 Dibenzo [ b, d ]]Iodine-5-yl triflate, 20 mole percent (8 mg) copper acetate monohydrate, and 2.5 equivalents (53 mg) sodium carbonate were dissolved in 1 ml of N, N-dimethylformamideThe amine produced a solution which was transferred into a reaction tube. Reacting for 24 hours at 120 ℃ under the air condition, and carrying out a rapid column chromatography by using a petroleum ether and ethyl acetate system after the reaction is finished to obtain the product benzo 8- (9H-carbazole-9-yl) naphthalene-1-amine.
(2) 0.8 mmol (246.8 mg) of benzo 8- (9H-carbazol-9-yl) naphthalen-1-amine was dissolved in 5 ml of acetic acid solution, and an aqueous solution of sodium nitrite (3.5 equivalents total of 120.8 mg of sodium nitrite and 3.0 ml of distilled water) was added dropwise. The mixture was kept at a temperature below 0℃for 30 minutes, then stirred at 40℃for 2 hours, and cooled to room temperature. The mixture was extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and filtered. After volatile components are removed from the filtrate, the crude product is purified on a silica gel (300-400 mesh) column, and eluted with petroleum ether to obtain a yellowish green solid, namely benzo [ kl ] indole [3,2,1-de ] acridine.
The organic benzo [ kl ] indole [3,2,1-de ] acridine was subjected to liquid fluorescence test at room temperature with a slit width of 1.0/2.5nm. As can be seen from FIG. 2, the organic benzo [ kl ] indole [3,2,1-de ] acridine itself possesses a strong fluorescence. The excitation wavelength is 310 and nm, the emission wavelengths are 452 and 482 and nm, and the quantum yield is 62%.
Claims (2)
1. A preparation method of benzo [ kl ] indole [3,2,1-de ] acridine is characterized by comprising the following specific steps:
(1) Weigh 0.2 mmole of 1, 8-diaminonaphthalene, 1.25 equivalents of 5H-5 lambda 3 Dibenzo [ b, d ]]Iodine-5-base trifluoro methanesulfonate, 20 mole percent copper acetate monohydrate and 2 equivalent sodium carbonate are dissolved in 1 ml of N, N-dimethylformamide to prepare a solution, and the solution is transferred into a reaction tube; reacting for 24 hours at 120 ℃ under the air condition, and performing a rapid column chromatography by using a petroleum ether and ethyl acetate system after the reaction is finished to obtain a product benzo 8- (9H-carbazole-9-yl) naphthalene-1-amine;
(2) 0.5 mmol of benzo 8- (9H-carbazol-9-yl) naphthalene-1-amine was dissolved in 5 ml of acetic acid solution, and an aqueous solution of sodium nitrite (3.5 equivalents of sodium nitrite and 3.0 ml of distilled water) was added dropwise; maintaining the temperature of the mixture below 0deg.C for 30 min, stirring at 40deg.C for 2 hr, and cooling to room temperature; extracting the mixture with dichloromethane; the organic phase was dried over anhydrous sodium sulfate and filtered; vacuum distilling, purifying the crude product on silica gel (300-400 mesh) column, eluting with petroleum ether to obtain yellow green solid, which is benzo [ kl ] indole [3,2,1-de ] acridine.
2. A benzo [ kl ] indole [3,2,1-de ] acridine prepared by the method as claimed in claim 1, which has the advantages of narrow half-width, high quantum yield and excellent yield, and can be applied to luminescent materials.
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|---|---|---|---|
| CN202311604556.7A CN117865968A (en) | 2023-11-28 | 2023-11-28 | Preparation method and application of benzo [ kl ] indole [3,2,1-de ] acridine |
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| CN202311604556.7A CN117865968A (en) | 2023-11-28 | 2023-11-28 | Preparation method and application of benzo [ kl ] indole [3,2,1-de ] acridine |
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