CN111349109B - Synthetic method of seven-element boron dipyrromethene fluorescent dye - Google Patents
Synthetic method of seven-element boron dipyrromethene fluorescent dye Download PDFInfo
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- CN111349109B CN111349109B CN202010255597.XA CN202010255597A CN111349109B CN 111349109 B CN111349109 B CN 111349109B CN 202010255597 A CN202010255597 A CN 202010255597A CN 111349109 B CN111349109 B CN 111349109B
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- C—CHEMISTRY; METALLURGY
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- 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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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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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- 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
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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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
Abstract
The invention discloses a novel seven-element boron dipyrromethene fluorescenceThe structure of the compound is as follows:
the synthesis method is that 2-acetyl pyrrole is taken as raw material, triethylamine and boron trifluoride ethyl ether are added in sequence, and then the product is obtained through self-condensation. The seven-element boron dipyrromethene fluorescent dye is synthesized by one step by adopting a one-pot method, has the advantages of extremely simple operation, mild reaction conditions, easy control, higher yield and convenient separation and purification, and can be applied to industrial mass production.
Description
Technical Field
The invention discloses a seven-element boron dipyrromethene fluorescent dye and a synthesis method thereof, wherein the dye can be widely applied to the fields of environment, analysis, material science and the like.
Background
The fluoroboric fluorescent dye (BODIPY) is a fluorescent compound with excellent photophysical and chemical properties which is developed in the last twenty years and is widely regarded. BODIPY has excellent physicochemical properties, such as higher fluorescence quantum yield and molar extinction coefficient; good light stability and chemical stability; the absorption emission wavelength can be regulated; easy to chemically modify, etc. At present, the fluorescent dye is widely applied to the fields of biological labeling, organelle fluorescence imaging, up-conversion materials and the like.
However, most of the synthesis of the fluoroboric fluorescent dye so far requires at least two steps, namely condensation with aromatic aldehyde and then fluoroboric, so that the operation process is complicated and the comprehensive yield is not high. Therefore, the preparation of the fluorine-boron fluorescent dye with high efficiency and mass production through a simple synthetic route from raw materials is a difficult problem to be solved.
The invention designs and synthesizes the seven-element boron dipyrromethene dye with a novel structure, has the greatest advantages of one-step synthesis through easily obtained raw materials, extremely simple operation, mild reaction conditions, easy control and high yield of about 60 percent, and can be applied to industrial mass production. In addition, the material is easy to modify, and can be used as a raw material to obtain more materials with different excellent properties.
Disclosure of Invention
The invention mainly aims to provide a seven-element boron dipyrromethene fluorescent dye and a synthetic method thereof.
The technical scheme of the invention is as follows:
a seven-membered boron-dipyrromethene fluorescent dye, wherein the chemical structural formula of the compound is as follows:
the synthesis method for synthesizing the seven-membered BODIPY fluorescent dye comprises the following synthesis paths:
the method comprises the following steps:
(1) adding 2-acetylpyrrole and toluene into a reaction bottle at room temperature, stirring for dissolving, then adding triethylamine and boron trifluoride diethyl etherate, heating and stirring to obtain a reaction solution;
(2) and (2) washing, extracting, drying and concentrating the reaction solution in the step (1), and then separating by silica gel column chromatography to obtain a red solid product I, namely the heptatomic BODIPY fluorescent dye.
In the step (1), the feeding ratio of the 2-acetyl pyrrole, the triethylamine and the boron trifluoride diethyl etherate is 1: 1-10.
The feeding sequence of the step (1) is 2-acetyl pyrrole, toluene, triethylamine and boron trifluoride ethyl ether. When the feeding sequence is 2-acetyl pyrrole, toluene, boron trifluoride diethyl etherate and triethylamine, the reaction does not occur.
The heating temperature of the step (1) is 50-100 ℃, and the heating time is 2-18 hours. The reaction time is not determined according to the amount of raw materials. The compound structure is damaged and the yield is reduced due to the overhigh temperature; too low a temperature can result in too long a reaction time.
The invention has the following beneficial effects:
the synthesis of the invention is one-step synthesis, the raw materials are easy to obtain, the operation is simple, the reaction condition is mild and easy to control.
The synthesis yield of the invention is higher by about 60 percent, and the invention is easy to separate and purify.
Drawings
FIG. 1 is a single crystal diffractogram of Compound I obtained in example 1.
FIG. 2 is a hydrogen spectrum of Compound I obtained in example 1.
FIG. 3 is a carbon spectrum of Compound I obtained in example 1.
FIG. 4 is an absorption spectrum of Compound I obtained in example 1.
FIG. 5 is a graph showing the emission spectrum of Compound I obtained in example 1.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Example 1
Weighing 2-acetylpyrrole (218mg, 2.00mmol), taking 30.00ml of toluene solution, mixing and dissolving, adding triethylamine (1.5ml, 10.79mmol) and boron trifluoride diethyl etherate (1.8ml, 14.27mmol) in sequence while heating and stirring, heating and stirring at 80 ℃ for 4 hours, washing the reactant with water, extracting, drying, carrying out rotary evaporation, and purifying by column chromatography to obtain a red solid I141mg with the yield of 56.8%.
Fig. 1 is a single crystal diffractogram of compound I obtained in example 1, showing that its structure is correct and its absolute configuration can be visualized. FIG. 2 is a hydrogen spectrum of Compound I obtained in example 1, with a total of 11 hydrogens. 1H NMR (400MHz, DMSO) δ 12.59(s,1H),7.56(d, J ═ 43.9Hz,3H),7.25(d, J ═ 3.3Hz,1H),6.87(s,1H),6.49(ddd, J ═ 8.6,3.9,2.2Hz,2H),2.56(s, 3H). FIG. 3 is a carbon spectrum diagram of Compound I obtained in example 1, for a total of 12 carbons. 13C NMR (101MHz, DMSO). delta. 169.07,155.54,135.12,133.97,132.99,130.19,123.98,123.51,114.56,114.38,108.84, 24.87. FIG. 4 is an absorption spectrum of compound I obtained in example 1, which shows that the compound can absorb visible light at 430-540nm, wherein the maximum absorption wavelength is 515 nm. FIG. 5 is an emission spectrum of compound I obtained in example 1, which shows that the compound can emit light of 525-675nm through radiation relaxation after photoexcitation, and the maximum emission wavelength is 544 nm.
Example 2
Weighing 2-acetylpyrrole (218mg, 2.00mmol), taking 30.00ml of toluene solution, mixing and dissolving, adding triethylamine (1.5ml, 10.79mmol) and boron trifluoride diethyl etherate (1.8ml, 14.27mmol) in sequence while heating and stirring, heating and stirring at 100 ℃ for 4 hours, washing the reactant with water, extracting, drying, carrying out rotary evaporation, and purifying by column chromatography to obtain a red solid I123mg with the yield of 49.6%. When the reaction temperature was increased by 20 ℃ relative to example 1, the yield decreased by 7.2%.
Example 3
Weighing 2-acetylpyrrole (218mg, 2.00mmol), taking 30.00ml of toluene solution, mixing and dissolving, adding triethylamine (1.5ml, 10.79mmol) and boron trifluoride diethyl etherate (1.8ml, 14.27mmol) in sequence while heating and stirring, heating and stirring at 80 ℃ for 8 hours, washing the reactant with water, extracting, drying, carrying out rotary evaporation, and purifying by column chromatography to obtain a red solid I143mg with the yield of 57.6%. When the reaction time was increased by 4 hours relative to example 1, there was no significant increase in yield.
Example 4
Weighing 2-acetylpyrrole (218mg, 2.00mmol), taking 30.00ml of toluene solution, mixing and dissolving, adding triethylamine (1.5ml, 10.79mmol) and boron trifluoride diethyl etherate (1.8ml, 14.27mmol) in sequence while heating and stirring, heating and stirring at 60 ℃ for 8 hours, washing the reactant with water, extracting, drying, carrying out rotary evaporation, and purifying by column chromatography to obtain a red solid I154mg with the yield of 62.1%. When the reaction temperature was decreased by 20 ℃ relative to example 2, the yield increased by 4.5%.
Example 5
Weighing 2-acetylpyrrole (218mg, 2.00mmol), taking 30.00ml of toluene solution, mixing and dissolving, adding triethylamine (2.0ml, 14.39mmol) and boron trifluoride diethyl etherate (1.8ml, 14.27mmol) in sequence while heating and stirring, heating and stirring at 80 ℃ for 4 hours, washing the reactant with water, extracting, drying, carrying out rotary evaporation, and purifying by column chromatography to obtain a red solid I140mg with the yield of 56.4%. When the amount of added triethylamine was increased by 1/3 relative to example 1, the yield did not change significantly.
Example 6
Weighing 2-acetylpyrrole (218mg, 2.00mmol), taking 30.00ml of toluene solution, mixing and dissolving, adding triethylamine (2.0ml, 14.39mmol) and boron trifluoride diethyl etherate (2.4ml, 19.03mmol) in sequence while heating and stirring, heating and stirring at 80 ℃ for 4 hours, washing the reactant with water, extracting, drying, carrying out rotary evaporation, and purifying by column chromatography to obtain a red solid I151mg with the yield of 60.9%. When the amount of added triethylamine and boron trifluoride were increased by 1/3 relative to example 1, the yield was increased by 4.1%.
Example 7
Weighing 2-acetylpyrrole (436mg, 4.00mmol), taking 60.00ml of toluene solution, mixing and dissolving, adding triethylamine (3ml, 21.58mmol) and boron trifluoride diethyl etherate (3.6ml, 28.54mmol) while heating and stirring, heating and stirring at 80 ℃ for 4 hours, washing the reactant with water, extracting, drying, rotary steaming, and purifying by column chromatography to obtain a red solid I273 mg, wherein the yield is 55.0%. When the amount of the material of the whole reaction was increased by two times with respect to example 1, the reaction temperature and time were not changed, and the yield was decreased by 1.8%.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (4)
1. A synthetic method of a seven-element boron dipyrromethene fluorescent dye is characterized in that the chemical structural formula of the dye is as follows:
(1) adding 2-acetylpyrrole and toluene into a reaction bottle at room temperature, stirring for dissolving, then adding triethylamine and boron trifluoride diethyl etherate, heating and stirring for reacting to obtain a reaction solution;
(2) and (2) washing, extracting, drying and concentrating the reaction solution in the step (1), and then separating by silica gel column chromatography to obtain a red solid product I, namely the heptatomic BODIPY fluorescent dye.
2. The method for synthesizing a hepta-boron-dipyrromethene fluorescent dye according to claim 1, wherein in the step (1), the feeding molar ratio of 2-acetyl pyrrole, triethylamine and boron trifluoride diethyl etherate is 1: 1-10.
3. The method for synthesizing a heptatomic BODIPY fluorescent dye according to claim 2, wherein the feeding sequence of the step (1) is 2-acetylpyrrole, toluene, triethylamine and boron trifluoride diethyl etherate.
4. The method for synthesizing the heptatomic BODIPY fluorescent dye according to claim 3, wherein the heating reaction temperature in the step (1) is 50-100 ℃, and the heating reaction time is 2-18 hours.
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