CN113004313A - Double-thiophene-double-coumarin-based BODIPY near-infrared fluorescent dye and preparation method thereof - Google Patents
Double-thiophene-double-coumarin-based BODIPY near-infrared fluorescent dye and preparation method thereof Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229960000956 coumarin Drugs 0.000 title description 4
- 229960001912 dicoumarol Drugs 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- -1 N, N-diethylamino Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 206010028980 Neoplasm Diseases 0.000 abstract description 4
- 238000000862 absorption spectrum Methods 0.000 abstract description 4
- 238000003745 diagnosis Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000012634 optical imaging Methods 0.000 abstract description 4
- 230000008033 biological extinction Effects 0.000 abstract description 2
- 238000013086 organic photovoltaic Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
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- 235000001671 coumarin Nutrition 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- LWISLHRIEATKTM-UHFFFAOYSA-N 2-Ethynylthiophene Chemical compound C#CC1=CC=CS1 LWISLHRIEATKTM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DOBMPNYZJYQDGZ-UHFFFAOYSA-N dicoumarol Chemical compound C1=CC=CC2=C1OC(=O)C(CC=1C(OC3=CC=CC=C3C=1O)=O)=C2O DOBMPNYZJYQDGZ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 239000012847 fine chemical Substances 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
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- 230000001766 physiological effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
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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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- 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
- C09B57/02—Coumarine dyes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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Abstract
The invention relates to a bithiophene-dicoumarin BODIPY near-infrared fluorescent dye and a preparation method thereof, which are realized by the following steps: carrying out Knoevenagel condensation reaction on the diiodo BODIPY derivative (I) and 7- (N, N diethylamino) coumarin-3-formaldehyde to obtain a 3, 5-dicoumarinyl BODIPY derivative (II), and carrying out Sonogashira coupling reaction on the 3, 5-dicoumarinyl BODIPY derivative (II) and 2-ethinylthiophene to obtain a bithiophene-dicoumarinyl BODIPY derivative (III). The preparation method has the advantages of simple reaction steps, mild reaction conditions and good selectivity. The fluorescent dye has high molar extinction coefficient (more than 3.0 multiplied by 10)5cm‑1mol‑ 1L), large stokes shift, and good photo-physical properties such as light stability. Its strongest electronThe absorption spectrum is red-shifted to 770nm, the maximum fluorescence emission wavelength is 818nm, and the method has good application prospects in the fields of optical imaging, fluorescence identification, tumor diagnosis, military reconnaissance, infrared camouflage, organic photovoltaic materials and the like.
Description
Technical Field
The invention belongs to the technical fields of organic compound synthesis, functional fluorescent dyes and fine chemical engineering, and particularly relates to a bithiophene-dicoumarin BODIPY near-infrared fluorescent dye and a preparation method thereof.
Background
The near infrared light has the advantages of small interference in the transmission process, good permeability to substances, especially minimum absorption and fluorescence of biological molecules in the spectral region, avoidance of bias influence of organism scattered light and autofluorescence on detection results along with increase of wavelength, great reduction of scattering interference, strong permeability to tissue cells and the like. In recent years, near-infrared dye molecules play a significant role in a plurality of fields such as optical imaging, tumor diagnosis, military reconnaissance, infrared camouflage, nonlinear optical materials, fluorescent identification and the like. Therefore, research on BODIPY dyes tends to synthesize near-infrared dyes of long wavelengths.
In order to adjust the absorption wavelength and the emission wavelength of the BODIPY compounds, near-infrared fluorescent dyes with different excitation and emission wavelengths are synthesized by introducing different substituents at the peripheral positions of the BODIPY core, so that the near-infrared fluorescent dyes have attracted extensive attention of researchers at home and abroad. When the 2 and 6 positions of the BODIPY parent body have substituents, the spectrum of the BODIPY compound is greatly influenced, and the maximum absorption and emission wavelengths of the dye can be obviously increased by substituting the alkynyl groups on the two positions; the methyl groups at 3 and 5 sites of the parent nucleus of the BODIPY molecule also have certain chemical activity and can perform Knoevenagel condensation reaction with aromatic aldehyde. Therefore, different types of conjugated groups are introduced into 2, 3, 5 and 6 positions of the BODIPY molecule, a larger conjugated system is formed with the BODIPY main body, not only can the rigidity of the BODIPY be kept, but also the pi conjugated system can be expanded, the flatness of the molecule can be increased, the absorption spectrum and the emission spectrum are shifted to longer wavelengths, and a theoretical basis is provided for synthesizing the BODIPY near-infrared fluorescent dye.
The coumarin dyes are cinnamic acid lactone compounds with suppressed double-bond rotation, have the characteristics of high fluorescence quantum yield, large Stokes displacement, bright color light, strong fluorescence intensity and the like, and are widely regarded due to the fact that the coumarin dyes have a plurality of physiological activities. Thiophene is an aromatic compound with a five-membered heterocyclic structure, has good environmental stability and good optical and electrical properties, and the highest occupied orbital (HOMO) energy level can be reduced due to the higher electron cloud density.
Based on the easy modification property of the BODIPY fluorescent dye matrix, the excellent photophysical property of coumarin derivatives and the excellent photoelectric property of thiophene, the bithiophene-dicumaryl BODIPY near-infrared fluorescent dye is synthesized through Knoevenagel condensation and Sonogashira coupling reaction, and the problems of multiple synthesis steps, immature reaction, low selectivity and the like of most near-infrared BODIPY dyes are solved. In addition, in view of the important functions of the near-infrared fluorescent dye in the fields of optical imaging, tumor diagnosis, military reconnaissance, infrared camouflage, nonlinear optical materials, fluorescent identification and the like, the synthesis of the novel near-infrared fluorescent organic dye molecule has important scientific significance and application value.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention aims to provide a bithiophene-dicoumarin BODIPY near-infrared fluorescent dye and a preparation method thereof.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the invention relates to a bithiophene-dicoumarin BODIPY near-infrared fluorescent dye and a preparation method thereof, which are characterized in that the near-infrared fluorescent dye has a structural formula shown as the following formula (III):
a bithiophene-dicoumarin BODIPY near-infrared fluorescent dye and a preparation method thereof comprise the following steps:
step 1: under the anhydrous condition, adding the diiodo BODIPY derivative (I) and 7- (N, N diethylamino) coumarin-3-formaldehyde into dry toluene according to the molar ratio of 1: 3.0, adding p-toluenesulfonic acid and piperidine, stirring and heating, controlling the temperature at 125 ℃ and reacting for 6 hours to finish the reaction, and performing separation and purification by extraction, drying and silica gel column chromatography to obtain the 3, 5-bis-coumarinyl BODIPY derivative (II).
Step 2: under argonUnder the protection of gas, 3, 5-dicoumarin BODIPY derivative (II) and Pd (PPh)3)4And dissolving the CuI in tetrahydrofuran and triethylamine, and adding 2-acetylene thiophene. The mixture was slowly heated to 60 ℃ and stirred overnight. Cooling to room temperature, extracting with dichloromethane, washing with water, drying, evaporating the solvent under reduced pressure, and separating and purifying by silica gel column chromatography to obtain the bithiophene-bishydroxycoumarin BODIPY derivative (III).
The specific chemical reaction formula is as follows:
in the above step 1, the molar ratio of the bis-iodo BODIPY derivative (I), p-toluenesulfonic acid and 7- (N, N-diethylamino) coumarin-3-carbaldehyde is 1: 0.5: 3.0, and the volume to amount of the substance ratio of toluene, piperidine and bis-iodo BODIPY derivative (I) is 25 mL: 2 mL: 1 mmol.
In step 1, the eluent for silica gel column chromatography was 100% dichloromethane.
In the step 2, 3, 5-dicoumarin BODIPY derivative (II) and Pd (PPh)3)4The molar ratio of CuI to 2-acetylene thiophene is 1: 0.1: 3. The ratio of the volume of tetrahydrofuran, triethylamine and the amount of the substance of the bishydroxycoumarin BODIPY derivative (II) is 3 mL: 1 mL: 0.05 mmol.
In step 2, the eluent for silica gel column chromatography was 100% dichloromethane.
The invention has the advantages of
Compared with the prior art, the bithiophene-dicoumarin BODIPY near-infrared fluorescent dye and the preparation method thereof have the advantages that: (1) the preparation method is simple and easy to implement, the synthetic method is mature, and the selectivity is high; (2) has high molar extinction coefficient (greater than 3.0 × 10)5cm-1mol-1L), large stokes shift and good photo-thermal stability; (3) the fluorescent dye has the strongest electron absorption wavelength of 770nm and the largest fluorescence emission wavelength of 818nm, so that the fluorescent dye can be used as a nonlinear optical material for optical imaging, tumor diagnosis, military reconnaissance, infrared camouflage and the likeAnd fluorescent identification and the like.
Drawings
FIG. 1 is a diagram of an ultraviolet-visible absorption spectrum of a bithiophene-dicumarol BODIPY near-infrared fluorescent dye (III);
FIG. 2 is a fluorescence emission spectrum of a bithiophene-dicoumarin BODIPY near-infrared fluorescent dye (III);
FIG. 3 is an electrospray high-resolution mass spectrum of a bisthiophene-dicumaryl BODIPY near-infrared fluorescent dye (III).
Detailed Description
The invention is further described below with reference to the specific drawings.
By using1H-NMR, HRMS and UV-Vis spectrums characterize and confirm the structure of the near-infrared BODIPY fluorescent dye. The detection instrument is as follows: bruker ARX600 NMR Spectrometer (deuterated chloroform as solvent), Shimadzu UV-3100 UV-visible spectrophotometer (scanning range 300-900 nm, optical path slit 2nm), fluorescence spectrum was measured with American Amico Bowman Series 2 Luminescence Spectrometer.
Example 1 preparation of bis-coumarinyl BODIPY derivatives (II)
A dry round bottom flask was equipped with a Dean-Stark apparatus under anhydrous conditions, and bis-iodo BODIPY derivative (I) (618mg, 1mmol), 7- (N, N diethylamino) coumarin-3-carbaldehyde (735mg, 3mmol) and p-toluenesulfonic acid (86mg, 0.5mmol) were dissolved in 25mL of toluene and 2mL of piperidine, heated to 125 deg.C under reflux, and reacted for 6 hours. Cooled to room temperature, extracted with dichloromethane, washed with water, the organic layers were combined, the organic solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography eluting with 100% dichloromethane to give the 3, 5-biscoumarinyl BODIPY derivative (II) as a pale brown solid (375mg, 35%).1H NMR(600MHz，CDCl3)：δ8.38-8.03(m，2H)，8.00-7.86(m，2H)，7.85-7.50(m，2H)，7.41(t，J＝8.4Hz，2H)，6.99(d，J＝9.0Hz，2H)，6.69(d，J＝55.8Hz，2H)，6.54(dd，J＝19.8，2.4Hz，2H)，3.46(s，8H)，2.37(d，J＝6.0Hz，3H)，2.14-2.08(m，6H)，1.48(d，J＝3.6Hz，3H)，1.46(d，J＝24.6Hz，3H)，1.24(t，J＝6.0Hz，12H)。
Example 2 preparation of Bithien-Bicoumarinyl BODIPY derivative (III)
Under the protection of argon, 3, 5-dicoumarinyl BODIPY derivative (II) (536mg, 0.50mmol), Pd (PPh)3)4(58mg, 0.05mmol), CuI (10mg, 0.05mmol) were dissolved in 30mL of tetrahydrofuran and 10mL of triethylamine, and 2-ethynylthiophene (0.15mL, 1.5mmol) was added. The mixture was slowly heated to 60 ℃ and stirred overnight. Cooling to room temperature, extracting with dichloromethane, washing with water, drying, evaporating under reduced pressure to remove organic solvent, separating and purifying the residue by silica gel column chromatography with 100% dichloromethane as eluent to obtain bithiophene-dicumaryl BODIPY derivative (III) (232mg, 45%) as a gray solid product.1H NMR(600MHz，CDCl3): δ 8.63(s, 2H), 8.05(s, 2H), 7.86-7.84(d, J ═ 15.0Hz, 2H), 7.54(s, 2H), 7.43-7.42(d, J ═ 6.0Hz, 2H), 7.29(s, 2H), 7.03(s, 2H), 7.00(s, 2H), 6.61(s, 2H), 6.49(s, 2H), 3.47(s, 8H), 2.38(s, 3H), 2.13(s, 6H), 1.58(s, 6H), 1.25-1.24(d, J ═ 6.0Hz, 12H). UV-vis: 511nm, 770nm (FIG. 1); emission wavelet: 818nm (FIG. 2).
Example 3 UV-VIS absorption Spectroscopy of a solution of a Bithien-Bicoumarinyl BODIPY derivative (III)
Dissolving bithiophene-dicoumarinyl BODIPY derivative (III) in dichloromethane to obtain solution with concentration of 1 × 10- 5The ultraviolet-visible absorption spectrum of the methylene chloride solution was measured. FIG. 1 shows the UV-VIS absorption spectrum of the near-IR fluorescent dye (III) solution prepared in example 2 of the present invention.
Example 4 fluorescence Spectroscopy of solution of Bithien-Bicoumarinyl BODIPY derivative (III)
Dissolving bithiophene-dicoumarinyl BODIPY derivative (III) in dichloromethane to obtain solution with concentration of 1 × 10- 5And measuring the fluorescence emission spectrum of the dichloromethane solution with mol/L. FIG. 2 shows the fluorescence spectrum of a fluorescent dye (III) solution prepared in example 2 of the present invention.
Claims (6)
1. A bithiophene-dicoumarin BODIPY near-infrared fluorescent dye is characterized in that the structural formula is shown as the formula (III):
2. the preparation method of the bithiophene-dicoumarin BODIPY near-infrared fluorescent dye (III) according to claim 1, which is characterized in that the preparation method comprises the following steps: firstly, carrying out Knoevenagel condensation reaction on a diiodo BODIPY derivative (I) and 7- (N, N diethylamino) coumarin-3-formaldehyde to obtain a 3, 5-dicoumarinyl BODIPY derivative (II), and then carrying out Sonogashira coupling reaction on the 3, 5-dicoumarinyl BODIPY derivative (II) and 2-ethinylthiophene to synthesize the dithiophene-dicoumarinyl BODIPY near-infrared fluorescent dye (III), wherein the reaction formula in the synthesis process is as follows:
3. the preparation method of the bithiophene-dicoumarin BODIPY near-infrared fluorescent dye according to claim 2, which is characterized by comprising the following steps:
step 1: under the anhydrous condition, adding the diiodo BODIPY derivative (I) and 7- (N, N diethylamino) coumarin-3-formaldehyde into dry toluene according to the molar ratio of 1: 3.0, adding p-toluenesulfonic acid and piperidine, stirring and heating, controlling the temperature at 125 ℃, reacting for 6 hours, finishing the reaction, and performing separation and purification by extraction, drying and silica gel column chromatography to obtain a 3, 5-bis-coumarinyl BODIPY derivative (II);
step 2: under the protection of argon, 3, 5-dicoumarin BODIPY derivative (II) and Pd (PPh)3)4Dissolving CuI in tetrahydrofuran and triethylamine, adding 2-acetylene thiophene, slowly heating the mixture to 60 ℃, stirring overnight, cooling to room temperature, extracting with dichloromethane, washing with water, drying, evaporating the solvent under reduced pressure, and passing through a silica gel column layerSeparating, separating and purifying to obtain the bithiophene-dicoumarin BODIPY derivative (III).
4. The method for preparing a bithiophene-dicoumarin BODIPY near-infrared fluorescent dye according to claim 3, wherein in the step 1, the molar ratio of the diiodo BODIPY derivative (I), p-toluenesulfonic acid and 7- (N, N-diethylamino) coumarin-3-carbaldehyde is 1: 0.5: 3.0, and the volume ratio of toluene, piperidine and compound (I) to the amount of substance is 25 mL: 2 mL: 1 mmol.
5. The method for preparing the bis-thiophene-bis-coumarinyl BODIPY near-infrared fluorescent dye according to claim 3, wherein in the step 2, the bis-coumarinyl BODIPY derivative (II) and Pd (PPh)3)4The mol ratio of CuI and 2-acetylene thiophene is 1: 0.1: 3, and the ratio of the volume of tetrahydrofuran and triethylamine to the amount of the dicoumaryl BODIPY derivative (II) substance is 3 mL: 1 mL: 0.05 mmol.
6. The bisthiophene-biscoumarin BODIPY near-infrared fluorescent dye as claimed in claim 2, wherein the maximum absorption wavelength is 770nm, and the molar absorption coefficient is greater than 3.0 x 105cm-1mol-1L, maximum fluorescence emission wavelength of 818 nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113444118A (en) * | 2021-07-28 | 2021-09-28 | 南京林业大学 | Coumarin group BODIPY HSO3-Near-infrared fluorescent probe and preparation method and application thereof |
| CN113461722A (en) * | 2021-08-06 | 2021-10-01 | 南京林业大学 | double-BODIPY near-infrared fluorescent dye with AIE effect and preparation method thereof |
| CN115925728A (en) * | 2021-10-09 | 2023-04-07 | 南京林业大学 | Preparation method and application of near-infrared probe for kidney injury diagnosis |
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| CN110156821A (en) * | 2019-04-24 | 2019-08-23 | 南京林业大学 | A kind of near infrared fluorescent probe and preparation method thereof of BODIPY class acid pH response |
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| CN110156821A (en) * | 2019-04-24 | 2019-08-23 | 南京林业大学 | A kind of near infrared fluorescent probe and preparation method thereof of BODIPY class acid pH response |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113444118A (en) * | 2021-07-28 | 2021-09-28 | 南京林业大学 | Coumarin group BODIPY HSO3-Near-infrared fluorescent probe and preparation method and application thereof |
| CN113444118B (en) * | 2021-07-28 | 2022-03-15 | 南京林业大学 | Preparation and detection of coumarin-based BODIPY near-infrared fluorescent probe for HSO3-Application in probes |
| CN113461722A (en) * | 2021-08-06 | 2021-10-01 | 南京林业大学 | double-BODIPY near-infrared fluorescent dye with AIE effect and preparation method thereof |
| CN113461722B (en) * | 2021-08-06 | 2022-04-19 | 南京林业大学 | double-BODIPY near-infrared fluorescent dye with AIE effect and preparation method thereof |
| CN115925728A (en) * | 2021-10-09 | 2023-04-07 | 南京林业大学 | Preparation method and application of near-infrared probe for kidney injury diagnosis |
| CN115925728B (en) * | 2021-10-09 | 2024-06-28 | 南京林业大学 | Preparation method and application of near infrared probe for kidney injury diagnosis |
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