CN108117871A - A kind of green light excitation fluorescent dye and preparation method and application - Google Patents
A kind of green light excitation fluorescent dye and preparation method and application Download PDFInfo
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- CN108117871A CN108117871A CN201611085685.XA CN201611085685A CN108117871A CN 108117871 A CN108117871 A CN 108117871A CN 201611085685 A CN201611085685 A CN 201611085685A CN 108117871 A CN108117871 A CN 108117871A
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 230000005284 excitation Effects 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000003287 optical effect Effects 0.000 claims abstract description 5
- 238000003384 imaging method Methods 0.000 claims abstract description 4
- 239000000990 laser dye Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 84
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 36
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 239000012074 organic phase Substances 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 14
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical class [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 claims description 9
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- -1 cyano, phenyl Chemical group 0.000 claims description 3
- 150000003232 pyrogallols Chemical class 0.000 claims description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N trihydroxybenzene Natural products OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 3
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 9
- 238000000295 emission spectrum Methods 0.000 abstract description 3
- 238000000695 excitation spectrum Methods 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 43
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000006862 quantum yield reaction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 230000008033 biological extinction Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- AKYHKWQPZHDOBW-UHFFFAOYSA-N (5-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol Chemical compound OS(O)(=O)=O.C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 AKYHKWQPZHDOBW-UHFFFAOYSA-N 0.000 description 1
- NEPSIUNPMILOFF-UHFFFAOYSA-N 1,3-diethoxy-2-methoxybenzene Chemical compound COC1=C(C=CC=C1OCC)OCC NEPSIUNPMILOFF-UHFFFAOYSA-N 0.000 description 1
- AOAKLPMKCNKYEF-UHFFFAOYSA-N 1-ethoxy-3-methoxy-2-phenoxybenzene Chemical compound CCOC1=CC=CC(=C1OC2=CC=CC=C2)OC AOAKLPMKCNKYEF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000001576 FEMA 2977 Substances 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000684 flow cytometry Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229960003110 quinine sulfate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention relates to field of optical functional material, and in particular to and green light excites fluorescent dye, has the structure as shown in formula (I), wherein, R1、R2、R3Selected from C1‑C10One kind in alkyl, cyano, aromatic radical or heterocycle.The fluorescent dye has higher emissive porwer and quantum efficiency, emission spectrum main peak is between 560nm~585nm, with very wide excitation spectrum, and good light stability, trace detection, sensitivity is high, available for the different applications such as cell imaging, fluorescence probe, laser dye, fluorescent optical sensor field, shows good practicability.Preparation method cost of material provided by the invention is low, pollution-free, simple for process, yield is high, fluorescent dye structure novel, the function admirable of preparation, suitable in the extensive use in the fields such as biology, environment.
Description
Technical Field
The invention relates to the field of optical functional materials, in particular to a green light excited fluorescent dye and a preparation method and application thereof.
Background
Dyes that absorb strongly and emit fluorescence in the visible range are called fluorochromes, each molecule has a series of strictly discrete energy levels, and most of the molecules of substances are in the "ground state" at room temperature, and when these substances absorb light energy under irradiation of light, they enter a new state, called the "excited state", and the molecular weight in the "excited state" is unstable and can pass through 10 th of the dye-9～10-7The emitted light quanta return to the ground state within a very short time of seconds, a process which fluoresces. Fluorescent dyes have been widely used in various industries such as textile, plastic dyeing, printing pigments, etc. since the 20 th century. In recent years, fluorescent dyes have been widely used to label, detect, and/or quantify components in samples, and various methods for such detection and/or quantification include fluorescence microscopy, fluorescence immunoassay, flow cytometric analysis of cells, and a variety of other applications.
In particular, there is a need for a fluorescent dye that: which can be efficiently excited by a green laser in a multicolor flow cytometer. The target dyes used in these applications should have essentially the following characteristics: (1) the excitation spectrum has a maximum value; (2) (ii) has a strong spectrally resolvable emission maximum; (3) has the ability to couple to biomolecules via reactive groups. To date, there has been a lack of a green-excited fluorophore that can be conjugated to different ligands to provide dye-labeled reagents with fluorescence spectral characteristics that can be separated optically and electronically.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to provide a fluorescent dye that can be effectively excited by green light by overcoming the defect of difficulty in preparing the green light excited fluorescent dye in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the green light excited fluorescent dye has a structure shown as a formula (I):
wherein,
R1、R2r3 is selected from C1-C10One of alkyl, cyano, aryl or heterocyclic aromatic hydrocarbon.
Optionally, the R is1、R2、R3One selected from methyl, ethyl, cyano, phenyl and 2-thienyl.
Alternatively, the structural formula is shown in (II), (III), (IV), (V), (VI):
optionally, the method comprises the following steps:
(1) preparation of intermediate 1-I
Adding anhydrous aluminum chloride and dichloromethane into an eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to 0-minus 3 ℃, adding 2, 4-dimethylpyrrole, continuously cooling to-3-minus 10 ℃, beginning to dropwise add chloroacetyl chloride, controlling the temperature not to exceed 0-minus 7 ℃, and reacting for 10-12 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding deionized water, adjusting the pH value to 7.0-8.0 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and evaporating the organic solvent to obtain a yellow solid, namely an intermediate 1-I.
(2) Preparation of intermediate 2-I
Adding anhydrous aluminum chloride and dichloromethane into an eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to 0-minus 3 ℃, and adding R1，R2，R3Continuously cooling the substituted 1, 2, 3-benzenetriol to-3 to-10 ℃, beginning to dropwise add a dichloromethane solution of the intermediate 1-I, controlling the temperature not to exceed 0 to-7 ℃, and reacting for 10 to 12 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding deionized water, adjusting the pH value to 7.0-8.0 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and evaporating the organic solvent to obtain a yellow solid, namely an intermediate 2-I.
(3) Preparation of intermediate I
Slowly dropwise adding boron trifluoride diethyl etherate and triethylamine into the dichloromethane solution of the intermediate 2-I obtained in the step (2), continuously stirring, controlling the temperature to be 15-20 ℃, reacting for 2-3 hours, directly evaporating the solvent to obtain an oily substance, and recrystallizing by using isopropanol and petroleum ether (the volume ratio is 2: 8-4: 6) to obtain a white-like solid, namely the compound (I).
Optionally, in the step (1), the 2, 4-dimethylpyrrole, the chloroacetyl chloride and the anhydrous aluminum chloride are added in the ratio of 1: 1.5-2.0: 3-4.
Optionally, in the step (2), R is added1，R2，R3Substituted 1, 2, 3-benzenetriols, intermediates 1The mass ratio of the anhydrous aluminum chloride substances is 1: 1.5-2.0: 3-4.
Optionally, in the step (3), boron trifluoride diethyl etherate and triethylamine are added in a volume ratio of (1.5-2.0) to 1.
The invention also provides application of the method for exciting the fluorescent dye by the green light in cell imaging, fluorescent probes, laser dyes, organic nonlinear optical materials and photoelectric functional devices.
The technical scheme of the invention has the following advantages:
1. the green light excitation fluorescent dye provided by the embodiment of the invention contains benzene ring or heterocycle and has conjugated double bond, and non-bonding electrons of O or N atoms can be excited to pi when in an excited state*The bond is expressed as a large pi bond which enlarges the organic fluorescent molecule, so that the conjugated system of the whole organic fluorescent molecule is enlarged, and the function of enhancing the fluorescence of the organic molecule is achieved.
2. The green light excited fluorescent dye provided by the embodiment of the invention has a simple synthesis process, adopts palladium as a catalyst, does not need to add a phosphine ligand, has high selectivity, is not easy to polymerize, has high fluorescence quantum yield and good light stability, can greatly reduce the interference of self-absorption and autofluorescence of substances in organisms when being used for detecting the substances in the organisms, improves the sensitivity and selectivity of detection, and can reduce the damage to the life.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an excitation and emission spectrum of green excited fluorescent dye in ethanol according to examples 1-5 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The basic chemical raw materials such as the reagent used in the embodiment of the invention can be purchased in the domestic chemical product market or customized in the relevant intermediate preparation plant.
Example 1
The preparation method of the green light excitation fluorescent dye (II) provided in this example:
has the structure of formula (II):
the preparation method comprises the following steps:
(1) preparation of intermediates 1 to II
Adding 0.6mol of anhydrous aluminum chloride and 200mL of dichloromethane into a 500mL eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to-1 ℃, adding 0.2mol of 2, 4-dimethylpyrrole, continuously cooling to-10 ℃, starting to dropwise add chloroacetyl chloride, controlling the temperature not to exceed-7 ℃, dropwise adding 0.3mol of chloroacetyl chloride altogether, and reacting for 10 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding 200ml of deionized water, adjusting the pH value to 7.0 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and distilling out the organic solvent to obtain a yellow solid, namely the intermediate 1-II, wherein the yield is 96.2%, and the purity is 99.8%.
(2) Preparation of intermediates 2 to II
Adding 0.3mol of anhydrous aluminum chloride and 100ml of dichloromethane into a 500ml eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to 0 ℃, adding 0.1mol of 1, 2, 3-trimethoxybenzene, continuously cooling to-6 ℃, beginning to dropwise add a dichloromethane solution (50ml) of the intermediate 1-II, controlling the temperature not to exceed-3 ℃, and dropwise adding 0.15mol of the intermediate 1-II together for reacting for 10 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding 100ml of deionized water, adjusting the pH value to 7.0 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and distilling out the organic solvent to obtain a yellow solid, namely the intermediate 2-II, wherein the yield is 89.2%, and the purity is 96.7%.
(3) Preparation of Compound (II)
Slowly dripping 45ml of boron trifluoride ethyl ether and 30ml of triethylamine into dichloromethane solution (100ml) of the intermediate 2-II obtained in the step (2), continuously stirring, controlling the temperature to be between 15 and 16 ℃, reacting for 2 hours, directly distilling out the solvent to obtain an oily substance, and recrystallizing by using isopropanol and petroleum ether (the volume ratio is 2: 8) to obtain a white-like solid, namely the compound (II), wherein the yield is 86.1 percent, and the purity is 99.4 percent.
In this example, the detection and characterization data for the green-excited fluorescent dye (II) of the present invention are as follows:
calculated elemental analysis (CHBFNO): c22H25BF2N2O3
Mass spectrum (MS +): 414.25(M +)
m/z：414.19(100.0％)，415.20(25.0％)，413.20(24.8％)，414.20(6.0％)，416.20(3.5％)
Elemental analysis: c, 63.79; h, 6.08; b, 2.61; f, 9.17; n, 6.76; and O, 11.59.
Example 2
The preparation method of the green light excitation fluorescent dye (III) provided in this example:
has the structure of formula (III):
the preparation method comprises the following steps:
(1) preparation of intermediates 1 to III
Adding 1.6mol of anhydrous aluminum chloride and 500mL of dichloromethane into a 1000mL eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to-3 ℃, adding 0.4mol of 2, 4-dimethylpyrrole, continuously cooling to-10 ℃, beginning to dropwise add chloroacetyl chloride, controlling the temperature not to exceed-7 ℃, dropwise adding 0.6mol of chloroacetyl chloride together, and reacting for 12 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding 500ml of deionized water, adjusting the pH value to 8.0 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and distilling out the organic solvent to obtain yellow solids, namely the intermediates 1-III, wherein the yield is 97.8%, and the purity is 96.4%.
(2) Preparation of intermediates 2 to III
Adding 0.9mol of anhydrous aluminum chloride and 250ml of dichloromethane into a 500ml eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to-2 ℃, adding 0.3mol of 1, 3-diethoxy-2-methoxybenzene, continuously cooling to-8 ℃, beginning to dropwise add dichloromethane solution (80ml) of the intermediates 1-III, controlling the temperature not to exceed-5 ℃, jointly dropping 0.6mol of the intermediates 1-III, and reacting for 11 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding 150ml of deionized water, adjusting the pH value to 7.2 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and distilling out the organic solvent to obtain a yellow solid, namely the intermediate 2-III, wherein the yield is 90.7%, and the purity is 94.1%.
(3) Preparation of Compound (III)
Slowly dropwise adding 150ml of boron trifluoride diethyl etherate and 100ml of triethylamine into a dichloromethane solution (150ml) of the intermediate 2-III obtained in the step (2), continuously stirring, controlling the temperature to be between 18 and 19 ℃, reacting for 2.5 hours, directly distilling out the solvent to obtain an oily substance, and recrystallizing by using isopropanol and petroleum ether (the volume ratio is 3: 7) to obtain a white-like solid, namely the compound (III), wherein the yield is 79.7 percent, and the purity is 97.9 percent.
In this example, the detection and characterization data for the green-excited fluorescent dye (III) of the present invention are as follows:
calculated elemental analysis (CHBFNO): c23H29BF2N2O3
Mass spectrum (MS +): 430.22(M +)
m/z：430.22(100.0％)，431.23(26.2％)，429.23(24.8％)，430.23(6.3％)，432.23(3.7％)
Elemental analysis: c, 64.20; h, 6.79; b, 2.51; f, 8.83; n, 6.51; and O, 11.15.
Example 3
The preparation method of the green light excitation fluorescent dye (IV) provided in this example:
has the structure of formula (IV):
the preparation method comprises the following steps:
(1) preparation of intermediates 1 to IV
Adding 0.18mol of anhydrous aluminum chloride and 50mL of dichloromethane into a 250mL eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to-1 ℃, adding 0.05mol of 2, 4-dimethylpyrrole, continuously cooling to-5 ℃, beginning to dropwise add chloroacetyl chloride, controlling the temperature not to exceed-2 ℃, dropwise adding 0.1mol of chloroacetyl chloride together, and reacting for 10 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding 50ml of deionized water, adjusting the pH value to 7.8 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and distilling out the organic solvent to obtain a yellow solid, namely the intermediate 1-IV, wherein the yield is 92.7%, and the purity is 95.3%.
(2) Preparation of intermediates 2 to IV
Adding 0.08mol of anhydrous aluminum chloride and 30ml of dichloromethane into a 100ml eggplant-shaped bottle, placing the bottle in a cold salt bath, stirring, cooling to 0 ℃, adding 0.02mol of 1-cyanoxy-2-ethoxy-3-methoxybenzene, continuously cooling to-3 ℃, beginning to dropwise add a dichloromethane solution (20ml) of the intermediate 1-IV, controlling the temperature to be not more than 0 ℃, and dropwise adding 0.03mol of the intermediate 1-IV for reaction for 12 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding 50ml of deionized water, adjusting the pH value to 8.0 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and distilling out the organic solvent to obtain a yellow solid, namely the intermediate 2-IV, wherein the yield is 90.2%, and the purity is 97.9%.
(3) Preparation of Compound (IV)
Slowly dripping 10ml of boron trifluoride ethyl ether and 5ml of triethylamine into dichloromethane solution (20ml) of the intermediate 2-IV obtained in the step (2), continuously stirring, controlling the temperature to be between 19 and 20 ℃, reacting for 3 hours, directly distilling out the solvent to obtain an oily substance, and recrystallizing by using isopropanol and petroleum ether (the volume ratio is 4: 6) to obtain a white-like solid, namely the compound (IV), wherein the yield is 88.9 percent, and the purity is 97.0 percent.
In this example, the detection and characterization data for the green-excited fluorescent dye (IV) of the present invention are as follows:
calculated elemental analysis (CHBFNO): c23H24BF2N3O3
Mass spectrum (MS +): 439.19(M +)
m/z：439.19(100.0％)，440.19(23.8％)，438.19(23.3％)，441.19(3.6％)，440.18(1.0％)
Elemental analysis: c, 62.89; h, 5.51; b, 2.46; f, 8.65; n, 9.57; o, 10.93.
Example 4
The preparation method of the green light excitation fluorescent dye (V) provided in this example:
has a structure of formula (V):
the preparation method comprises the following steps:
(1) preparation of intermediates 1-V
Adding 0.3mol of anhydrous aluminum chloride and 150mL of dichloromethane into a 250mL eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to-2 ℃, adding 0.1mol of 2, 4-dimethylpyrrole, continuously cooling to-9 ℃, beginning to dropwise add chloroacetyl chloride, controlling the temperature not to exceed-6 ℃, dropwise adding 0.15mol of chloroacetyl chloride together, and reacting for 11 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding 150ml of deionized water, adjusting the pH value to 7.0 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and distilling out the organic solvent to obtain a yellow solid, namely an intermediate 1-V, wherein the yield is 97.8%, and the purity is 99.9%.
(2) Preparation of intermediate 2-V
Adding 0.15mol of anhydrous aluminum chloride and 60ml of dichloromethane into a 250ml eggplant-shaped bottle, placing the bottle in a cold salt bath, stirring, cooling to-2 ℃, adding 0.05mol of 1-ethoxy-3-methoxy-2-phenoxybenzene, continuously cooling to-7 ℃, beginning to dropwise add a dichloromethane solution (30ml) of an intermediate 1-V, controlling the temperature not to exceed-4 ℃, and dropwise adding 0.075mol of the intermediate 1-V together for reacting for 12 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding 50ml of deionized water, adjusting the pH value to 7.9 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and distilling out the organic solvent to obtain a yellow solid, namely an intermediate 2-V, wherein the yield is 93.7%, and the purity is 97.0%.
(3) Preparation of Compound (V)
Slowly dripping 25ml of boron trifluoride ethyl ether and 20ml of triethylamine into dichloromethane solution (60ml) of intermediate 2-V obtained in the step (2), continuously stirring, controlling the temperature to be between 15 and 17 ℃, reacting for 2 hours, directly distilling out the solvent to obtain an oily substance, and recrystallizing by using isopropanol and petroleum ether (the volume ratio is 3: 7) to obtain a white-like solid, namely the compound (V), wherein the yield is 89.9 percent, and the purity is 99.6 percent.
In this example, the detection and characterization data for the green-excited fluorescent dye (V) of the present invention are as follows:
elemental analysisCalculated (CHBFNO): c27H26BF2N2O3
Mass spectrum (MS +): 475.31(M +)
m/z：475.20(100.0％)，476.20(30.1％)，474.20(24.8％)，475.21(7.3％)，477.21(4.4％)，476.21(1.5％)
Elemental analysis: c, 68.23; h, 5.51; b, 2.27; f, 7.99; n, 5.89; o, 10.10.
Example 5
The preparation method of the green light excitation fluorescent dye (VI) provided in this example:
has the structure of formula (VI):
the preparation method comprises the following steps:
(1) preparation of intermediates 1 to VI
Adding 0.7mol of anhydrous aluminum chloride and 200mL of dichloromethane into a 500mL eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to-2 ℃, adding 0.2mol of 2, 4-dimethylpyrrole, continuously cooling to-6 ℃, starting to dropwise add chloroacetyl chloride, controlling the temperature not to exceed-3 ℃, dropwise adding 0.35mol of chloroacetyl chloride together, and reacting for 12 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding 200ml of deionized water, adjusting the pH value to 8.0 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and distilling out the organic solvent to obtain a yellow solid, namely the intermediate 1-VI, wherein the yield is 98.9%, and the purity is 99.3%.
(2) Preparation of intermediates 2 to VI
Adding 0.35mol of anhydrous aluminum chloride and 100ml of dichloromethane into a 500ml eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to-1 ℃, adding 0.1mol of (2, 6-diethoxybenzyl) thiophene, continuing to cool to-5 ℃, beginning to dropwise add a dichloromethane solution (50ml) of the intermediate 1-VI, controlling the temperature not to exceed-2 ℃, jointly dropping 0.2mol of the intermediate 1-VI, and reacting for 10 hours; slowly pouring the reaction liquid into a saturated carbon sodium hydrogen solution, adding 100ml of deionized water, adjusting the pH value to 7.5 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and distilling out the organic solvent to obtain a yellow solid, namely the intermediate 2-VI, wherein the yield is 90.7%, and the purity is 95.9%.
(3) Preparation of Compound (VI)
Slowly dripping 50ml of boron trifluoride ethyl ether and 30ml of triethylamine into dichloromethane solution (100ml) of intermediate 2-VI obtained in the step (2), continuously stirring, controlling the temperature to be between 16 and 18 ℃, reacting for 3 hours, directly distilling out the solvent to obtain an oily substance, and recrystallizing by using isopropanol and petroleum ether (the volume ratio is 3: 7) to obtain a white-like solid, namely the compound (VI), wherein the yield is 90.7 percent, and the purity is 99.6 percent.
In this example, the detection and characterization data for the green-excited fluorescent dye (VI) of the present invention are as follows:
calculated elemental analysis (CHBFNOS): c27H29BF2N2O3S
Mass spectrum (MS +): 510.40(M +)
m/z：510.20(100.0％)，511.20(29.6％)，509.20(23.1％)，512.20(5.2％)，512.19(4.2％)，513.20(1.5％)
Elemental analysis: c, 63.54; h, 5.74; b, 2.11; f, 7.44; n, 5.48; o, 9.40; s, 6.29.
Examples of the experiments
In order to verify the fluorescence property of the green light excited fluorescent dye, the fluorescence spectrum, the molar extinction coefficient and the fluorescence quantum yield of the green light excited fluorescent dye are measured, and the specific measurement method of each parameter is as follows:
experimental example 1 measurement of absorption Spectroscopy of Green light-excited fluorescent dye
Accurately weighing the compound to be measured to prepare the compound with the concentration of 1.0 multiplied by 10-5The absorption spectrum of the solution in mol/L was measured, as shown in FIG. 1.
Experimental example 2 measurement of fluorescence Spectroscopy of Green light-excited fluorescent dye
The fluorescence spectrum was measured using the maximum absorption wavelength in the measured green spectrum as the excitation wavelength of the fluorescence spectrum. The test compound was weighed to a concentration of 1.0X 10-6mol/L ethanol: the emission spectrum of the aqueous (50: 50, v/v) solution was measured, as shown in FIG. 1.
EXAMPLE 3 determination of molar extinction coefficient of Green light-excited fluorescent dye
The molar extinction coefficient of the compound was determined by uv-vis absorption spectroscopy. The calculation formula is shown as formula (1):
a ═ ε cl formula (1)
Wherein A represents the absorption intensity,. epsilon.is the molar absorption coefficient, c is the concentration of the compound, and l is the thickness of the quartz cell for detection.
EXPERIMENTAL EXAMPLE 4 measurement of fluorescence Quantum yield of Green-excited fluorescent dye
The fluorescence quantum yield of the green-excited fluorescent dye was measured at 20 ℃ with quinine sulfate (0.1M H as solvent)2SO4Quantum yield of 0.56) as a reference, and the fluorescence quantum yield was calculated by measuring the integrated intensity of fluorescence obtained under the same excitation conditions and the ultraviolet absorption value at the excitation wavelength of a dilute solution of the green-excited fluorescent dye and the reference. The product was dissolved in absolute ethanol.
The calculation formula is shown in formula (2):
wherein phi is the quantum yield of the object to be detected, subscript R represents reference substance, I is fluorescence integral intensity, A is ultraviolet absorption value, η is solvent refractive index, and the general requirement absorbance A, ARAre all less than 0.1.
TABLE 1 spectroscopic Properties of the Green excited fluorescent dyes described in examples 1-5
As shown in table 1, the green-excited fluorescent dye (VI) described in example 5 has the maximum absorption wavelength, and corresponds to the maximum emission wavelength of 583nm, the maximum molar absorption coefficient of 9.3 and the maximum fluorescence quantum yield of 93.09%, indicating that the compound has advantages for cell imaging, fluorescent probes, laser dyes and fluorescent sensors.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. A green-excited fluorescent dye, which has a structure represented by formula (I):
wherein,
R1、R2、R3is selected from C1-C10One of alkyl, cyano, aryl or heterocycle.
2. The green-excited fluorescent dye according to claim 1, wherein R is1、R2、R3One selected from methyl, ethyl, cyano, phenyl and 2-thienyl.
3. The green-excited fluorescent dye according to claim 1 or 2, which has a structural formula shown in the following formula:
4. a method of preparing a green-excited fluorescent dye according to any one of claims 1 to 3, comprising the steps of:
(1) preparation of intermediate 1-I
Adding anhydrous aluminum chloride and dichloromethane into an eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to 0-minus 3 ℃, adding 2, 4-dimethylpyrrole, continuously cooling to-3-minus 10 ℃, beginning to dropwise add chloroacetyl chloride, controlling the temperature not to exceed 0-minus 7 ℃, and reacting for 10-12 hours; slowly pouring the reaction solution into a saturated carbon sodium hydrogen solution, adding deionized water, adjusting the pH value to 7.0-8.0 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and evaporating the organic solvent to obtain an intermediate 1-I.
(2) Preparation of intermediate 2-I
Adding anhydrous aluminum chloride and dichloromethane into an eggplant-shaped bottle, placing the eggplant-shaped bottle in a cold salt bath, stirring, cooling to 0-minus 3 ℃, and adding R1，R2，R3Continuously cooling the substituted 1, 2, 3-benzenetriol to-3 to-10 ℃, beginning to dropwise add a dichloromethane solution of the intermediate 1-I, controlling the temperature not to exceed 0 to-7 ℃, and reacting for 10 to 12 hours; will be reversedSlowly pouring the reaction solution into a saturated carbon sodium hydrogen solution, adding deionized water, adjusting the pH value to 7.0-8.0 by using sodium carbonate, extracting the chloroform for three times, collecting an organic phase, drying the organic phase for 3 hours by using anhydrous magnesium sulfate, performing suction filtration, and evaporating the organic solvent to obtain an intermediate 2-I.
(3) Preparation of Compound I
Slowly dropwise adding boron trifluoride diethyl etherate and triethylamine into the dichloromethane solution of the intermediate 2-I obtained in the step (2), continuously stirring, controlling the temperature to be 15-20 ℃, reacting for 2-3 hours, directly evaporating the solvent to obtain an oily substance, and recrystallizing by using isopropanol and petroleum ether (the volume ratio is 2: 8-4: 6) to obtain a white-like solid, namely the compound (I).
5. The method for preparing the green-light excited fluorescent dye according to any one of claims 1 to 4, wherein the 2, 4-dimethylpyrrole, the chloroacetyl chloride and the anhydrous aluminum chloride are added in the step (1) in a ratio of 1: 1.5-2.0: 3-4.
6. The method for preparing a green-excited fluorescent dye according to any one of claims 1 to 5, wherein in the step (2), R is added1，R2，R3The mass ratio of the substituted 1, 2, 3-benzenetrisol, the intermediate 1-I and the anhydrous aluminum chloride is 1: 1.5-2.0: 3-4.
7. The method for preparing a green-excited fluorescent dye according to any one of claims 1 to 6, wherein in the step (3), boron trifluoride diethyl etherate and triethylamine are added in a volume ratio of (1.5-2.0) to 1.
8. Use of the method of any one of claims 1 to 7 for green excitation of fluorescent dyes in cell imaging, fluorescent probes, laser dyes, organic nonlinear optical materials, and optoelectronic functional devices.
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