CN113308130B - Fluorodipyrrole fluorescent dye and preparation method and application thereof - Google Patents
Fluorodipyrrole fluorescent dye and preparation method and application thereof Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 144
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 30
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 30
- 238000004440 column chromatography Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 238000000605 extraction Methods 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 22
- 239000012074 organic phase Substances 0.000 claims description 19
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 18
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 238000006482 condensation reaction Methods 0.000 claims description 16
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 11
- 238000005893 bromination reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- QGLVEAGMVUQOJP-UHFFFAOYSA-N prop-2-enylboronic acid Chemical compound OB(O)CC=C QGLVEAGMVUQOJP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003504 photosensitizing agent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 8
- 238000000862 absorption spectrum Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 56
- 238000005406 washing Methods 0.000 description 20
- 238000001035 drying Methods 0.000 description 16
- 238000006862 quantum yield reaction Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ULUNQYODBKLBOE-UHFFFAOYSA-N 2-(1h-pyrrol-2-yl)-1h-pyrrole Chemical compound C1=CNC(C=2NC=CC=2)=C1 ULUNQYODBKLBOE-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- OVTCUIZCVUGJHS-UHFFFAOYSA-N dipyrrin Chemical compound C=1C=CNC=1C=C1C=CC=N1 OVTCUIZCVUGJHS-UHFFFAOYSA-N 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- CUHSDSLPLNSDHX-UHFFFAOYSA-N ClC=1C(C(=C(C(C1Cl)=O)C#N)C#N)=O.O1CCCC1 Chemical compound ClC=1C(C(=C(C(C1Cl)=O)C#N)C#N)=O.O1CCCC1 CUHSDSLPLNSDHX-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- RAFKCLFWELPONH-UHFFFAOYSA-N acetonitrile;dichloromethane Chemical compound CC#N.ClCCl RAFKCLFWELPONH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention provides a BODIPY fluorescent dye and a preparation method and application thereof, belonging to the field of fluorescent dyes. The invention provides a BODIPY fluorescent dye, which takes BODIPY as a center, toluene is introduced to the No. 8 position of the BODIPY fluorescent dye, a conjugated system is added, propylene is introduced to the No. 3 and No. 5 positions, the electron-withdrawing capability is improved, the ultraviolet absorption spectrum and the fluorescence emission spectrum of the obtained BODIPY fluorescent dye generate larger red shifts, a stronger absorption peak is arranged in a green light range, and a stronger emission peak is arranged in a green light range in the fluorescence emission spectrum.
Description
Technical Field
The invention relates to the field of fluorescent dyes, in particular to a boron dipyrromethene fluorescent dye and a preparation method and application thereof.
Background
Fluorescent dyes have been around the last century, attracting the attention of multidisciplinary scientists. Fluorescent dyes have been used as functional materials in many fields, such as light energy conversion, organic light emitting devices, bio-imaging, diagnostic treatment, and the like, and have been actively developed. Now, a plurality of high-fluorescence organic dyes are discovered, and the BODIPY fluorescent dye serving as one of a plurality of dyes has high fluorescence quantum yield and molar extinction coefficient, and also has strong light stability and chemical stability, thereby being paid attention by a plurality of researchers. But the existing BODIPY fluorescent dye has smaller red shift. As the prior art, benzene ring is introduced into the No. 8 position and methyl is introduced into the No. 3 and No. 5 positions of the BODIPY mother nucleus in the prior art of "Photophysical Properties of Borndipyrometric antibodies in Solution" (J.Phy.chem.A 2005, 109, 7371-.
Disclosure of Invention
The invention aims to provide a BODIPY fluorescent dye and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a boron dipyrromethene fluorescent dye, which has a structure shown in a formula I:
the invention also provides a preparation method of the BODIPY fluorescent dye, which comprises the following steps:
mixing pyrrole, p-tolualdehyde and trifluoroacetic acid, and carrying out condensation reaction under a protective atmosphere to obtain an intermediate shown in a formula II;
under the protective atmosphere, mixing a tetrahydrofuran solution of an intermediate shown as a formula II with N-bromosuccinimide at a temperature of between 80 ℃ below zero and 76 ℃ below zero, adding a tetrahydrofuran solution of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone after the N-bromosuccinimide is dissolved, and then carrying out bromination reaction at room temperature to obtain an intermediate shown as a formula III;
mixing the intermediate shown in the formula III with triethylamine, boron trifluoride diethyl etherate and dichloromethane, and carrying out a fluoroboration reaction to obtain an intermediate shown in a formula IV;
mixing the intermediate shown in the formula IV with allyl boronic acid pinacol ester, potassium carbonate, tetratriphenylphosphine palladium, ethanol and toluene, and carrying out Suzuki coupling reaction to obtain the fluorodipyrromethene fluorescent dye shown in the formula I;
preferably, the molar ratio of the pyrrole to the p-tolualdehyde is 18-22: 1; the molar ratio of the p-tolualdehyde to the trifluoroacetic acid is 1: 0.08-0.12; the condensation reaction time is 12-16 h; the temperature of the condensation reaction is room temperature.
Preferably, after the condensation reaction is completed, mixing the reaction solution obtained by the condensation reaction with dichloromethane and sodium hydroxide solution for first extraction, washing and drying the obtained organic phase in turn, distilling to remove pyrrole, and then performing first column chromatography on the obtained residue; the volume ratio of the dichloromethane to the sodium hydroxide solution is 1.8-2.2: 1; the eluent for the first column chromatography is a mixed solution obtained by mixing petroleum ether, ethyl acetate and triethylamine according to the volume ratio of 8:2: 1.
Preferably, the molar ratio of the intermediate shown in the formula II to the N-bromosuccinimide is 1: 2-2.2; the molar ratio of the intermediate shown in the formula II to 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is 1: 1-1.2; the bromination reaction time is 1.8-2.2 h.
Preferably, the molar ratio of the intermediate shown in the formula II to triethylamine is 1: 3.8-4.0; the molar ratio of the intermediate shown in the formula II to boron trifluoride diethyl etherate is 1: 5-5.4; the temperature of the fluoroboric reaction is room temperature, and the time is 1.8-2.2 h.
Preferably, after the fluoroboric reaction is completed, mixing the reaction liquid obtained by the fluoroboric reaction with dichloromethane and water for second extraction, washing and drying the obtained organic phase in turn, distilling to remove the solvent, and performing second column chromatography on the obtained residue; the volume ratio of the dichloromethane to the water is 1.8-2.2: 1; the eluent for the second column chromatography is a mixed solution obtained by mixing petroleum ether and dichloromethane according to the volume ratio of 3: 1.
Preferably, the molar ratio of the intermediate shown in the formula IV to the allylboronic acid pinacol ester is 1: 1.4-1.6; the molar ratio of the intermediate shown in the formula IV to potassium carbonate is 1: 5.8-6.2; the molar ratio of the intermediate shown in the formula IV to the palladium tetratriphenylphosphine is 1: 0.06-0.08; the volume ratio of the ethanol to the toluene is 1: 4.8-5.2; the temperature of the Suzuki coupling reaction is 95-105 ℃, and the time is 10-14 h.
Preferably, after the Suzuki coupling reaction is completed, mixing the reaction liquid obtained by the Suzuki coupling reaction with dichloromethane and water for third extraction, washing and drying the obtained organic phase, distilling to remove dichloromethane, and performing third column chromatography on the obtained residue; the volume ratio of the dichloromethane to the water is 1.8-2.2: 1; the eluent for the third column chromatography is a mixed solution obtained by mixing petroleum ether and dichloromethane according to the volume ratio of 4: 1.
The invention also provides the application of the BODIPY fluorescent dye in the technical scheme in the preparation of a photosensitizer or a fluorescent probe or a light-emitting layer of an organic light-emitting diode.
The invention provides a BODIPY fluorescent dye which has a structure shown in a formula I. The invention takes BODIPY as the center, introduces toluene on the 8 th position to improve the conjugation degree of the compound, introduces propylene on the 3 rd and 5 th positions to improve the electron-withdrawing ability, and enables the ultraviolet absorption spectrum and the fluorescence emission spectrum of the obtained BODIPY fluorescent dye to generate larger red shift, and the BODIPY fluorescent dye has stronger absorption peak in the green light range in the ultraviolet absorption spectrum so as to be used as a green light photosensitizer, and has stronger emission peak in the green light range in the fluorescence emission spectrum, so the BODIPY fluorescent dye has potential application in the light-emitting layers of green light fluorescent probes and green light organic light-emitting diodes. In addition, the BODIPY-AK provided by the invention has higher quantum yield in different solvents.
Drawings
FIG. 1 is a graph of the UV-VIS absorption spectrum of BODIPY-AK obtained in example 1;
FIG. 2 is a graph of fluorescence emission spectrum of BODIPY-AK obtained in example 1;
FIG. 3 normalized fluorescence emission spectra of BODIPY-AK obtained in example 1 in different solvents.
Detailed Description
The invention provides a boron dipyrromethene fluorescent dye, which has a structure shown in a formula I:
the invention also provides a preparation method of the BODIPY fluorescent dye, which comprises the following steps:
mixing pyrrole, p-tolualdehyde and trifluoroacetic acid, and carrying out condensation reaction under a protective atmosphere to obtain an intermediate shown in a formula II;
under the protective atmosphere, mixing a tetrahydrofuran solution of an intermediate shown in a formula II with N-bromosuccinimide at a temperature of between 80 ℃ below zero and 76 ℃ below zero, adding a tetrahydrofuran solution of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone after the N-bromosuccinimide is dissolved, and then carrying out bromination reaction at room temperature to obtain an intermediate shown in a formula III;
mixing the intermediate shown in the formula III with triethylamine, boron trifluoride diethyl etherate and dichloromethane, and carrying out a fluoroboration reaction to obtain an intermediate shown in a formula IV;
mixing the intermediate shown in the formula IV with allyl boronic acid pinacol ester, potassium carbonate, tetratriphenylphosphine palladium, ethanol and toluene, and carrying out Suzuki coupling reaction to obtain the fluorodipyrromethene fluorescent dye shown in the formula I;
in the present invention, all the organic solvents used are dried organic solvents unless otherwise specified.
Pyrrole, p-tolualdehyde and trifluoroacetic acid are mixed and subjected to condensation reaction under protective atmosphere to obtain an intermediate shown as a formula II.
In the present invention, the mixing of pyrrole, p-tolualdehyde and trifluoroacetic acid is preferably performed by mixing pyrrole and p-tolualdehyde, stirring them uniformly in a protective atmosphere, and then adding trifluoroacetic acid.
In the present invention, the protective atmosphere is preferably nitrogen or an inert gas atmosphere unless otherwise specified.
In the invention, the molar ratio of pyrrole to p-tolualdehyde is preferably 18-22: 1, and more preferably 20: 1; the molar ratio of the p-tolualdehyde to the trifluoroacetic acid is preferably 1: 0.08-0.12, and more preferably 1: 0.1; the mixing and stirring time of the pyrrole and the p-tolualdehyde is preferably 13-17 min, and more preferably 15 min; the time of the condensation reaction is preferably 12-16 h; the temperature of the condensation reaction is preferably room temperature, i.e. no additional heating or cooling is required.
After the condensation reaction is finished, preferably, the reaction liquid obtained by the condensation reaction is mixed with dichloromethane and sodium hydroxide solution for first extraction, the obtained organic phase is washed and dried in turn, pyrrole is removed by distillation, and then the obtained residue is subjected to first column chromatography; the volume ratio of the dichloromethane to the sodium hydroxide solution is preferably 1.8-2.2: 1, more preferably 2:1, the concentration of the sodium hydroxide solution is preferably 0.1M, the sodium hydroxide solution acts as trifluoroacetic acid in a neutralization reaction, the dosage of the first extraction dichloromethane and the sodium hydroxide solution is not particularly limited, in the embodiment of the invention, the dosage ratio of the p-tolualdehyde to the first extraction dichloromethane and the sodium hydroxide solution is 20mmol:100mL:50 mL; the method for washing and drying the organic phase obtained by the first extraction is not particularly limited, and the conventional organic phase washing method (such as water washing) and drying method (such as drying by a drying agent) can be adopted; the eluent for the first column chromatography is preferably a mixed solution obtained by mixing petroleum ether, ethyl acetate and triethylamine according to the volume ratio of 8:2: 1.
After the first column chromatography is finished, the invention preferably performs vacuum drying on the obtained fraction containing the intermediate shown in the formula II to obtain the intermediate shown in the formula II. The invention has no special limitation on the specific parameters of the vacuum drying, and can obtain a product with constant weight.
After the intermediate shown in the formula II is obtained, the tetrahydrofuran solution of the intermediate shown in the formula II and N-bromosuccinimide are mixed at-80 to-76 ℃ under a protective atmosphere, after the N-bromosuccinimide is dissolved, the tetrahydrofuran solution of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is added, and then bromination reaction is carried out at room temperature to obtain the intermediate shown in the formula III. In the present invention, the product of the bromination reaction is highly unstable, and therefore, the bromination reaction is carried out at a low temperature.
In the invention, the molar ratio of the intermediate shown in the formula II to the N-bromosuccinimide is preferably 1: 2-2.2, and more preferably 1: 2.1; the molar ratio of the intermediate shown in the formula II to the 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is preferably 1: 1-1.2; the time of the bromination reaction is preferably 1.8-2.2 h, and more preferably 2 h.
In the present invention, the tetrahydrofuran solution of the intermediate represented by the formula II and the N-bromosuccinimide are mixed at-80 to-76 ℃, preferably the N-bromosuccinimide is added to the tetrahydrofuran solution of the intermediate represented by the formula II, preferably in portions, more preferably in two portions within 1 h.
The concentration of the tetrahydrofuran solution of the intermediate represented by the formula ii and the tetrahydrofuran solution of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is not particularly limited, and it is sufficient to ensure that the reaction proceeds smoothly, and in the embodiment of the present invention, the concentration of the tetrahydrofuran solution of the intermediate represented by the formula ii is preferably 0.0564mmol/mL, and the concentration of the tetrahydrofuran solution of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is preferably 0.215 mmol/mL.
After the bromination reaction is completed, the tetrahydrofuran in the obtained reaction liquid is preferably removed in the invention, so that the intermediate shown in the formula III is obtained. In the present invention, the removal method of tetrahydrofuran is not particularly limited, and in the examples of the present invention, tetrahydrofuran is preferably removed by vacuum distillation.
After obtaining the intermediate shown in the formula III, the intermediate shown in the formula III is mixed with triethylamine, boron trifluoride diethyl etherate and dichloromethane to carry out fluoroboric reaction, and the intermediate shown in the formula IV is obtained. In the invention, the triethylamine is an acid-binding agent which can promote the fluoroboric reaction.
In the invention, the molar ratio of the intermediate shown in the formula II to triethylamine is preferably 1: 3.8-4.0, and more preferably 1: 3.9; the molar ratio of the intermediate shown in the formula II to boron trifluoride diethyl etherate is 1: 5-5.4; the temperature of the fluoroboric reaction is preferably room temperature, and the time is preferably 1.8-2.2 h.
In the present invention, the amount of dichloromethane used for the fluoroboration reaction is not particularly limited, and it is sufficient to ensure that the reaction proceeds smoothly, and in the present embodiment, the ratio of the amount of boron trifluoride diethyl etherate to the amount of dichloromethane is preferably 22.1mmol:20 mL.
After the fluoroboration reaction is finished, the reaction liquid obtained by the fluoroboration reaction is preferably mixed with dichloromethane and water for second extraction, the obtained organic phase is washed and dried in turn, the solvent is removed by distillation, and the obtained residue is subjected to second column chromatography; the volume ratio of the dichloromethane to the water is 1.8-2.2: 1, more preferably 2:1, the dosage of the dichloromethane and the water for the second extraction is not particularly limited, in the embodiment of the invention, the dosage ratio of the intermediate shown in the formula II to the dichloromethane and the water for the second extraction is preferably 4.23mmol:100mL:50 mL; the method for washing and drying the organic phase obtained by the second extraction is not particularly limited, and the conventional organic phase washing method (such as water washing) and drying method (such as drying by a drying agent) can be adopted; the eluent for the second column chromatography is preferably a mixed solution obtained by mixing petroleum ether and dichloromethane according to the volume ratio of 3: 1.
After the second column chromatography is completed, the solvent is preferably removed from the obtained fraction containing the intermediate shown in the formula IV to obtain the intermediate shown in the formula IV. The specific method for removing the solvent is not particularly limited in the present invention, and a product with constant weight can be obtained, and in the embodiment of the present invention, the method for removing the solvent is preferably reduced pressure distillation, and the temperature of the reduced pressure distillation is preferably 40 ℃.
After the intermediate shown in the formula IV is obtained, the intermediate shown in the formula IV is mixed with allyl boronic acid pinacol ester, potassium carbonate, tetratriphenylphosphine palladium, ethanol and toluene, and subjected to Suzuki coupling reaction to obtain the fluoroboric dipyrrole fluorescent dye shown in the formula I. In the invention, the potassium carbonate provides an alkaline environment for the reaction, the palladium tetratriphenylphosphine is used as a catalyst, and the ethanol and the toluene are used as a mixed solvent to provide a proper polar environment for the reaction.
In the invention, the molar ratio of the intermediate shown in the formula IV to the allylboronic acid pinacol ester is preferably 1: 1.4-1.6, and more preferably 1: 1.5; the molar ratio of the intermediate shown in the formula IV to potassium carbonate is preferably 1: 5.8-6.2, and more preferably 1: 6; the molar ratio of the intermediate shown in the formula IV to the palladium tetratriphenylphosphine is preferably 1: 0.06-0.08, and more preferably 1: 0.07; the volume ratio of the ethanol to the toluene is preferably 1: 4.8-5.2, more preferably 1:5, the total amount of the ethanol and the toluene is not particularly limited, and the smooth reaction can be ensured, in the embodiment of the invention, the ratio of the total amount of the ethanol and the toluene to the amount of the intermediate shown in the formula IV is 20 mL: 0.68 mmol; the temperature of the Suzuki coupling reaction is preferably 95-105 ℃, more preferably 100 ℃, the time is preferably 10-14 h, more preferably 12h, and the Suzuki coupling reaction is preferably carried out in a protective atmosphere.
After the Suzuki coupling reaction is finished, preferably mixing reaction liquid obtained by the Suzuki coupling reaction with dichloromethane and water for third extraction, washing and drying the obtained organic phase, distilling to remove dichloromethane, and performing third column chromatography on the obtained residue; in the third extraction, the volume ratio of dichloromethane to water is preferably 1.8-2.2: 1, more preferably 2:1, the use amount of dichloromethane and water for the third extraction is not particularly limited, in the embodiment of the invention, the use amount ratio of the intermediate represented by the formula IV to dichloromethane and water for the third extraction is preferably 0.68mmol:100mL:50mL, the method for washing and drying the organic phase obtained by the third extraction is not particularly limited, and a conventional organic phase washing method (such as water washing and saturated brine washing) and a drying method (such as drying by a drying agent) are adopted; the eluent for the third column chromatography is a mixed solution obtained by mixing petroleum ether and dichloromethane according to the volume ratio of 4: 1.
After the third column chromatography is completed, the fraction containing the fluoroboric dipyrrole fluorescent dye shown in the formula I is preferably subjected to vacuum drying to obtain the fluoroboric dipyrrole fluorescent dye shown in the formula I. The invention has no special limitation on the specific parameters of the vacuum drying, and can obtain a product with constant weight.
The invention also provides the application of the BODIPY fluorescent dye in the technical scheme in the preparation of a photosensitizer or a fluorescent probe or a light-emitting layer of an organic light-emitting diode.
The present invention provides a BODIPY fluorescent dye, a preparation method and applications thereof, which are described in detail below with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Preparation of intermediates of formula II
Pyrrole (27.8mL, 400mmol) and p-tolualdehyde (2.36mL, 20mmol) were mixed, stirred under nitrogen atmosphere for 15min, then trifluoroacetic acid (0.15mL, 2mmol) is added, the reaction is stirred for 14h, then the obtained reaction solution is mixed with 50mL of 0.1M sodium hydroxide solution and 100mL of dichloromethane for first extraction, the obtained organic phase is washed twice with 50mL of water each time, then, sequentially carrying out saturated saline solution washing and anhydrous magnesium sulfate drying, then carrying out vacuum distillation to remove unreacted pyrrole, carrying out first column chromatography on the obtained residue, wherein an eluent is a mixed solution obtained by mixing petroleum ether, ethyl acetate and triethylamine according to a volume ratio of 8:2:1, and carrying out vacuum drying on the obtained fraction containing the target product to obtain an intermediate shown as a red brown solid, wherein the calculated yield is 85%;
the product was characterized by nuclear magnetism and the results were as follows:
1HNMR(chloroform-d)δ7.92(br,2H),7.12(s,4H),6.69(m,2H),6.16(m,2H),5.93(s,2H),2.35(s,3H)；
according to the characterization data, the product obtained in the step has a structure shown in a formula II;
(2) preparation of intermediates of formula IV
Mixing an intermediate (1.0g and 4.23mmol) shown in the formula II with 75mL of tetrahydrofuran, cooling to-78 ℃ under nitrogen, adding N-bromosuccinimide (1.6g and 9.0mmol) into the reaction solution twice within 1 hour, dropwise adding 20mL of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone tetrahydrofuran solution with the concentration of 0.215mmol/mL by using a constant-pressure dropping funnel after the N-bromosuccinimide is completely dissolved, and stirring the obtained reaction solution at room temperature for reaction for 2 hours; after the reaction is finished, carrying out vacuum distillation to remove tetrahydrofuran to obtain an intermediate shown in a formula III; triethylamine (2.14g, 16.57mmol), boron trifluoride diethyl etherate (3.14g, 22.1mmol), dichloromethane (20mL) and the intermediate shown in the formula III are mixed and stirred for reaction at room temperature for 2 h; then mixing the obtained reaction solution with 100mL of dichloromethane and 50mL of water for second extraction; washing the organic phase obtained by the second extraction twice with 50mL of water each time, then sequentially washing with brine and drying with anhydrous magnesium sulfate, then carrying out vacuum distillation to remove dichloromethane, carrying out second column chromatography on the obtained residue, wherein an eluent used in the second column chromatography is a mixed solution obtained by mixing petroleum ether and dichloromethane according to a volume ratio of 3:1, and evaporating the obtained solution containing the target product at 40 ℃ under reduced pressure to remove the solvent to obtain an intermediate shown in a formula IV, wherein the intermediate is a red solid, and the yield is 80%;
performing nuclear magnetic characterization on the product obtained in the step, wherein the result is as follows:
1H NMR(400MHz,CDCl3)δ7.39(d,J＝8.1Hz,2H),7.32(d,J＝7.9Hz,2H),6.81(d,J＝4.0Hz,2H),6.53(d,J＝4.3Hz,2H),2.47(s,3H)；
according to the analysis of the characterization data, the product obtained in the step has a structure shown in a formula IV;
(3) preparation of BODIPY fluorescent dye shown as formula I
Mixing an intermediate (0.30g, 0.68mmol) shown in the formula IV, allylboronic acid pinacol ester (0.17g, 1.03mmol), potassium carbonate (0.56g, 4.08mmol), palladium tetrakistriphenylphosphine (0.056mg, 0.05mmol), ethanol (4mL) and toluene (20mL), heating to 100 ℃ under a nitrogen atmosphere, and stirring for reaction for 12 hours; after the reaction is finished, cooling to room temperature, and then mixing the obtained reaction solution with 100mL of dichloromethane and water (50mL) for third extraction; washing the organic phase obtained by the third extraction twice with water, wherein the amount of water used for washing each time is 50mL, then sequentially washing the obtained organic phase with brine and drying over anhydrous magnesium sulfate, then carrying out vacuum distillation to remove dichloromethane, carrying out third column chromatography on the obtained residue, wherein an eluent used for the third column chromatography is a mixed solution obtained by mixing petroleum ether and dichloromethane according to the volume ratio of 4:1, and then carrying out vacuum drying on the obtained fraction containing the target product to obtain a black solid, wherein the calculated yield is 65%;
performing nuclear magnetic characterization on the black solid obtained in the step (3), wherein the result is as follows:
1H NMR(400MHz,CDCl3)δ7.38(d,J＝5.4Hz 2H),7.28(d,J＝6.6Hz,2H),7.06(d,J＝16.4Hz,2H),6.75(d,J＝4.4Hz,2H),6.69(s,2H),6.57(m,2H),2.45(s,3H),2.03(d,J＝1.7Hz,3H),2.01(d,J＝1.7Hz,3H)；
analysis of the data shows that the obtained black solid is BODIPY-AK which is a BODIPY fluorescent dye shown as a formula I.
Testing of ultraviolet-visible absorption spectrum:
under the condition of room temperature, an Agilent 8453 type ultraviolet-visible spectrophotometer is used for carrying out ultraviolet absorption spectrum scanning at the wave band of 200-800 nm, the ultraviolet-visible absorption spectrum of the BODIPY-AK in a tetrahydrofuran solution is measured, and the test result is shown in figure 1. As can be seen from FIG. 1, BODIPY-AK shows strong absorption peaks at about 250-375 nm and 500-600 nm.
Fluorescence emission spectroscopy test:
fluorescence emission spectra were obtained under room temperature conditions using a SPEX fluorolog-3 fluorometer/phorometer fluorometer with excitation at 333 nm. The results are shown in FIG. 2. As can be seen from FIG. 2, the BODIPY-AK shows a large emission peak at about 550-700 nm.
Solvation effect and quantum yield test:
fluorescence emission spectra were obtained at room temperature using a SPEX fluorology-3 fluorometer/phorometer fluorometer with n-hexane, toluene, tetrahydrofuran, dichloromethane and acetonitrile as solvents at 530nm wavelength. The results are shown in FIG. 3. Relative quantum yields (lambda) of BODIPY-AK in different solvents were obtained using rhodamine 6G as a standard sampleem/nm(Фem a) Wherein λ isemPernm is the emission wavelength, [ phi ]em aQuantum yield), the results are shown in table 1. As can be seen from FIG. 3, BODIPY-AK has strong fluorescence emission in different solvents, and no obvious solvatochromic effect is observed, indicating that the excited state can be mainly attributed to pi-pi*And (4) transition. As shown in Table 1, the BODIPY-AK provided by the invention has higher quantum yield in different solvents.
TABLE 1 relative quantum yields of BODIPY-AK in different solvents
| Solvent(s) | N-hexane | Toluene | Tetrahydrofuran (THF) | Methylene dichloride | Acetonitrile |
| λem/nm(Фem a) | 580(0.92) | 587(0.64) | 584(0.85) | 584(0.53) | 581(0.69) |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A BODIPY fluorescent dye is characterized by having a structure shown in a formula I:
2. the method for preparing a fluorodipyrromethene fluorescent dye according to claim 1, comprising the steps of:
mixing pyrrole, p-tolualdehyde and trifluoroacetic acid, and carrying out condensation reaction under a protective atmosphere to obtain an intermediate shown in a formula II;
under the protective atmosphere, mixing a tetrahydrofuran solution of an intermediate shown as a formula II with N-bromosuccinimide at a temperature of between 80 ℃ below zero and 76 ℃ below zero, adding a tetrahydrofuran solution of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone after the N-bromosuccinimide is dissolved, and then carrying out bromination reaction at room temperature to obtain an intermediate shown as a formula III;
mixing the intermediate shown in the formula III with triethylamine, boron trifluoride diethyl etherate and dichloromethane, and carrying out a fluoroboration reaction to obtain an intermediate shown in a formula IV;
mixing the intermediate shown in the formula IV with allyl boronic acid pinacol ester, potassium carbonate, tetratriphenylphosphine palladium, ethanol and toluene, and carrying out Suzuki coupling reaction to obtain the fluorodipyrromethene fluorescent dye shown in the formula I;
3. the preparation method according to claim 2, wherein the molar ratio of pyrrole to p-tolualdehyde is 18-22: 1; the molar ratio of the p-tolualdehyde to the trifluoroacetic acid is 1: 0.08-0.12; the condensation reaction time is 12-16 h; the temperature of the condensation reaction is room temperature.
4. The preparation method according to claim 2 or 3, characterized in that after the condensation reaction is completed, the reaction solution obtained by the condensation reaction is mixed with dichloromethane and sodium hydroxide solution for first extraction, the obtained organic phase is washed and dried in turn, pyrrole is removed by distillation, and then the obtained residue is subjected to first column chromatography; the volume ratio of the dichloromethane to the sodium hydroxide solution is 1.8-2.2: 1; the eluent for the first column chromatography is a mixed solution obtained by mixing petroleum ether, ethyl acetate and triethylamine according to the volume ratio of 8:2: 1.
5. The preparation method of claim 2, wherein the molar ratio of the intermediate represented by the formula II to the N-bromosuccinimide is 1: 2-2.2; the molar ratio of the intermediate shown in the formula II to 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is 1: 1-1.2; the bromination reaction time is 1.8-2.2 h.
6. The preparation method of claim 2, wherein the molar ratio of the intermediate represented by the formula II to triethylamine is 1: 3.8-4.0; the molar ratio of the intermediate shown in the formula II to boron trifluoride diethyl etherate is 1: 5-5.4; the temperature of the fluoroboric reaction is room temperature, and the time is 1.8-2.2 h.
7. The production method according to claim 2 or 6, wherein after the fluoroboration reaction is completed, the reaction liquid obtained by the fluoroboration reaction is mixed with methylene chloride and water to carry out a second extraction, the obtained organic phase is washed and dried in turn, the solvent is distilled off, and the obtained residue is subjected to a second column chromatography; the volume ratio of the dichloromethane to the water is 1.8-2.2: 1; the eluent for the second column chromatography is a mixed solution obtained by mixing petroleum ether and dichloromethane according to the volume ratio of 3: 1.
8. The preparation method according to claim 2, wherein the molar ratio of the intermediate shown in the formula IV to the allylboronic acid pinacol ester is 1: 1.4-1.6; the molar ratio of the intermediate shown in the formula IV to potassium carbonate is 1: 5.8-6.2; the molar ratio of the intermediate shown in the formula IV to the palladium tetratriphenylphosphine is 1: 0.06-0.08; the volume ratio of the ethanol to the toluene is 1: 4.8-5.2; the temperature of the Suzuki coupling reaction is 95-105 ℃, and the time is 10-14 h.
9. The preparation method according to claim 2 or 8, characterized in that after the Suzuki coupling reaction is completed, the reaction solution obtained by the Suzuki coupling reaction is mixed with dichloromethane and water for third extraction, the obtained organic phase is washed and dried in turn, dichloromethane is removed by distillation, and the obtained residue is subjected to third column chromatography; the volume ratio of the dichloromethane to the water is 1.8-2.2: 1; the eluent for the third column chromatography is a mixed solution obtained by mixing petroleum ether and dichloromethane according to the volume ratio of 4: 1.
10. Use of the fluorodipyrromethene fluorescent dye according to claim 1 in the preparation of a photosensitizer or a fluorescent probe or a light emitting layer of an organic light emitting diode.
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