CN111100154A - Benzoic acid substituted BODIPY derivative dye ligand and preparation method thereof - Google Patents

Benzoic acid substituted BODIPY derivative dye ligand and preparation method thereof Download PDF

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CN111100154A
CN111100154A CN201911411168.0A CN201911411168A CN111100154A CN 111100154 A CN111100154 A CN 111100154A CN 201911411168 A CN201911411168 A CN 201911411168A CN 111100154 A CN111100154 A CN 111100154A
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戴劲草
谢浩然
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Abstract

The invention discloses a benzoic acid substituted BODIPY derivative dye ligand, which takes 1,3,5, 7-tetramethyl BODIPY as a core skeleton, and carboxyl and benzoic acid are grafted on 2, 6-position and 8-position respectively, so as to form a novel BODIPY derivative dye ligand, namely 8- [ 4-benzoic acid ] -4, 4-difluoro-1, 3,5, 7-tetramethyl-2, 6-dicarboxy-4-bora-3 a,4 a-diaza-s-indacene, which not only has excellent optical activity in a visible light region, but also has better water solubility, metal coordination capacity and fluorescence sensitivity to metal ions. The invention also discloses a preparation method of the benzoic acid substituted BODIPY derivative dye ligand, the method is simple and easy to control, the raw materials are easy to obtain, the general adaptability is realized, and the intermediate C generated in the preparation process also has high sensitivity to metal ions.

Description

Benzoic acid substituted BODIPY derivative dye ligand and preparation method thereof
Technical Field
The invention relates to the field of organic dye ligand compounds, in particular to a benzoic acid substituted BODIPY derivative dye ligand and a preparation method thereof.
Background
Photofunctional molecular materials have attracted much attention in recent decades and have many interesting applications in the fields of information storage, optoelectronic devices, chemical sensors, solar cells, life sciences, and the like. BODIPY (BODIPY for short) is a very interesting fluorescent functional dye molecule, has a high molar extinction coefficient, a narrow spectral peak and high photosensitivity, and the photoactive organic dye micromolecules are widely applied to the fields of analysis, sensing, information storage, photoelectric devices, biological image marking technology and the like in nearly two decades, and particularly are used as photoactive ligands to construct metal complex skeleton optical functional molecular materials in recent years, so that the photoactive organic dye micromolecules gradually become research hotspots in the field of material chemistry. In order to construct a metal complex framework photofunctional molecular material, the BODIPY must be modified, and a functional group with a specific function is introduced into a core framework of the BODIPY by a chemical method, so that the photoactivity and the physicochemical property of the BODIPY are changed, and the coordination capacity to metal ions is improved.
Usually, functional groups with different functions are introduced into the BODIPY skeleton, so that the photophysical properties of the BODIPY skeleton can be regulated, for example, a methyl functional group for electricity supply is introduced into the 1,3,5, 7-position to form 1,3,5, 7-tetramethyl boron dipyrromethene, so that the photophysical properties of dye molecules can be regulated, and the fluorescence quantum yield can be obviously improved; the introduction of the electron pulling functional group on the 2, 6-position is beneficial to the blue shift phenomenon of dye molecules, and the introduction of the electron pulling functional group on the 8-position is beneficial to the generation of a fluorescent antenna effect, and not only can the fluorescent emission be enhanced and the quantum yield be improved. Carboxyl and benzoic acid both belong to electron withdrawing functional groups, have better aqueous solution compatibility, and generally present various coordination modes to metals. By combining the BODIPY with two functional groups of carboxyl and benzoic acid, the photophysical properties of the BODIPY dye can be hopefully regulated, the sensing to metal ions and the coordination capacity to the metal ions are improved, and a good foundation is laid for the dye ligand molecules in the construction of a metal complex framework optical functional material with optical activity.
Disclosure of Invention
The invention aims to provide a benzoic acid substituted BODIPY derivative dye ligand which not only has optical activity in a visible light region, but also has better water solubility, metal coordination capacity and fluorescence sensitivity to metal ions.
The invention also aims to provide a preparation method of the benzoic acid substituted BODIPY derivative dye ligand, which is simple and easy to control and has universal adaptability.
In order to achieve the above purpose, the solution of the invention is:
a benzoic acid substituted BODIPY derivative dye ligand, the chemical structural formula of which is shown in formula I,
Figure BDA0002349997870000021
is named 8- [ 4-benzoic acid ] -4, 4-difluoro-1, 3,5, 7-tetramethyl-2, 6-dicarboxy-4-bora-3 a,4 a-diaza-s-indacene.
A preparation method of a benzoic acid substituted BODIPY derivative dye ligand comprises the following steps:
step 1, dissolving 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl and p-formylbenzoic acid in a reaction medium under stirring, then dropwise adding trifluoroacetic acid in the atmosphere of protective gas, and reacting for 1-48H at 20-35 ℃ in a dark place to obtain a reaction solution A;
step 2, dropwise adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone into the reaction solution A obtained in the step 1 under stirring for oxidation reaction, and reacting at 20-35 ℃ for 1-24 hours to obtain a reaction solution B;
step 3, slowly adding N, N-diisopropylethylamine into the reaction solution B obtained in the step 2, dropwise adding boron trifluoride-diethyl ether solution at 0-25 ℃ for reaction, stirring for 1-48 h, stopping the reaction when the thin-layer chromatography detects that the reactants are completely consumed, washing and filtering the reaction product by using saturated saline solution, washing the obtained filter residue by using dichloromethane for multiple times until no obvious product residue exists, separating an organic phase from the filtrate obtained by filtering by using a separating funnel, combining the organic phase obtained by washing the dichloromethane and the organic phase obtained by separating, drying and filtering by using anhydrous sodium sulfate, carrying out rotary evaporation and concentration on the organic phase, and finally separating and purifying by using a silica gel chromatographic column to obtain an intermediate C;
step 4, dissolving the intermediate C obtained in the step 3 in a reaction medium to obtain a reaction solution, and adding a small amount of palladiumIntroducing H under the action of carbon catalyst2And (3) reducing, reacting for 3-9 hours under stirring, stopping the reaction after the thin-layer chromatography detects that the intermediate C is completely consumed, filtering, respectively collecting filtrate and filter residue, adding a washing solvent into the filter residue to wash the reaction product for multiple times until no product is left, obtaining a washing liquid with the palladium-carbon catalyst filtered out, combining the filtrate and the washing liquid, drying in vacuum, and collecting to obtain the target compound, namely the benzoic acid substituted BODIPY derivative dye ligand.
In the step 1 and the step 4, the reaction medium is one or more of dichloromethane, trichloromethane, tetrahydrofuran, dioxane, acetonitrile, toluene, ethyl acetate, n-hexane, petroleum ether, methanol, ethanol and isopropanol; in step 1, the protective gas is one of nitrogen, helium and argon.
In the step 1, the reaction medium is dichloromethane, the amount of the reaction medium is 50-200 mL, in the step 4, the reaction medium is a dichloromethane-methanol mixed solvent with a volume ratio of 2:1, and the amount of the reaction medium is 20-30 mL.
In the step 1, the reaction temperature is 25 ℃, the reaction time is 24 hours, in the step 2, the reaction temperature is 25 ℃, the reaction time is 4 hours, in the step 3, the reaction temperature is 0 ℃, the stirring time is 4-8 hours, and in the step 4, the reaction temperature is room temperature.
In step 3, the eluent used for separation and purification is a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1.2:1, or a mixed solvent of ethyl acetate and n-hexane in a volume ratio of 1.2: 1.
In the step 4, the concentration of the intermediate C in the reaction solution is 4.5-6.0 g/L, the palladium content of the palladium-carbon catalyst is 2-10 wt%, and the washing solvent is one of methanol and dimethylformamide.
The molar ratio of the 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl, p-formylbenzoic acid, trifluoroacetic acid, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, N-diisopropylethylamine and boron trifluoride-diethyl ether solution is 2.60-3.80: 1.50-2.50: 1.00-1.50: 1.50-2.00: 18.0-40.0: 24.0-80.0.
The molar ratio of the 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl, p-formylbenzoic acid, trifluoroacetic acid, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, N-diisopropylethylamine and boron trifluoride-diethyl ether solution is 3.50:2.00:1.08:1.67:36.3: 71.0.
The chemical structural formula of the intermediate C is shown as formula II:
Figure BDA0002349997870000041
is named 8- [ 4-benzoic acid ] -4, 4-difluoro-1, 3,5, 7-tetramethyl-2, 6-dimethyl-benzyl-4-bora-3 a,4 a-diaza-s-indacene.
The synthetic route of the benzoic acid substituted BODIPY derivative dye ligand is as follows:
Figure BDA0002349997870000051
the starting material 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl ester in the present invention can be synthesized by reference to the literature (Toru Komatsu, Yasuter Urano, Yuuta Fujikawa, Tomonio Kobayashi, Hirotatsu Kojima, TakuyaTerai, Kenjiro Hanaoka, Tetsu Nagano, Development of 2, 6-carboxy-substuttute dborne dipyrromethene (BODIPY) as a novel scaffold of ratio metric phenol resins for live cell l imaging, chem. Commun, 2009,7015 Ack 7017), which is roughly: under the conditions of ice bath and protective gas atmosphere, 2, 4-dimethyl-pyrrole-3-formic acid is dissolved in N, N-dimethylformamide solvent containing cesium carbonate to form solution, then benzyl bromide is dripped to carry out esterification reaction, and the product is extracted by dichloromethane, washed, dried, filtered, rotary evaporated and subjected to silica gel column chromatography to obtain pure colorless solid raw material 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl with the yield of 68%.
After the technical scheme is adopted, the benzoic acid substituted BODIPY derivative dye ligand is characterized in that 1,3,5, 7-tetramethyl BODIPY is used as a core skeleton, carboxyl is grafted on the 2, 6-position of the core skeleton, and benzoic acid is grafted on the 8-position of the core skeleton, so that a novel BODIPY derivative dye ligand is formed, namely 8- [ 4-benzoic acid ] -4, 4-difluoro-1, 3,5, 7-tetramethyl-2, 6-dicarboxyl-4-bora-3 a,4 a-diaza-s-indacene not only has excellent optical activity in a visible light region, but also has good water solubility, metal coordination capacity and fluorescence sensitivity to metal ions.
The preparation method of the benzoic acid substituted BODIPY derivative dye ligand is simple and easy to control, raw materials are easy to obtain, and the benzoic acid substituted BODIPY derivative dye ligand has universal adaptability, and an intermediate C generated in the preparation process also has high sensitivity to metal ions.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of intermediate C;
FIG. 2 is an ESI-MS plot of intermediate C;
FIG. 3 is an infrared spectrum of intermediate C;
FIG. 4 is a nuclear magnetic hydrogen spectrum of a target compound;
FIG. 5 is an ESI-MS diagram of a target compound;
FIG. 6 is a chart of an infrared spectrum of a target compound;
FIG. 7 shows UV-VIS absorption spectra and fluorescence emission spectra of intermediate C in different solvent systems;
FIG. 8 shows UV-visible absorption spectra and fluorescence emission spectra of a target compound in different solvent systems;
FIG. 9 shows fluorescence emission spectra of intermediate C in the presence of various metal ions;
FIG. 10 shows fluorescence emission spectra of target compounds in the presence of various metal ions;
FIG. 11 shows [ Zn ] formed by the target compound and metallic zinc2(target Compound) (OH). 2H2O]nCrystal structure diagram of the complex.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Preparation of target compound
Example 1
A preparation method of a benzoic acid substituted BODIPY derivative dye ligand comprises the following steps:
step 1, under magnetic stirring, sequentially adding 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl (800mg, 3.5mmol), p-formylbenzoic acid (295mg, 2.0mmol) and dried dichloromethane (200mL) prepared according to a reference document into a 500mL three-neck flask, introducing helium for 10-20 min, dropwise adding 200 muL of trifluoroacetic acid (1.08mmol), wherein the 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl in the three-neck flask can be observed to be completely dissolved, the p-formylbenzoic acid is slightly dissolved in a white suspension state, reacting at 25 ℃ for about 1H, gradually disappearing the white suspension, changing the reaction solution from light yellow to pink, and continuing stirring for reacting for 23H until the white suspension completely disappears to obtain a dark red reaction solution A;
step 2, dropwise adding 380mg of 2, 3-dichloro-5, 6-dicyan p-benzoquinone (1.67mmol) into the reaction solution A obtained in the step 1 under stirring, supplementing and introducing helium for 10min, carrying out oxidation reaction at 25 ℃, and stirring for reaction for 4h to obtain a dark purple reaction solution B;
step 3, slowly adding 6mL of N, N-diisopropylethylamine (36.3mmol) into the reaction solution B obtained in the step 2, supplementing helium for 10min, dropwise adding 9mL of boron trifluoride-diethyl ether solution (71mmol) at 0 ℃ for reaction, supplementing helium for 10min for the last time, naturally heating to 25 ℃, continuing stirring for reaction for 8H, stopping the reaction after the thin-layer chromatography detects that the reactant 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl is completely consumed, washing the reaction product with equal volume of saturated saline solution, performing suction filtration, washing the obtained filter residue with 10-20 mL of dichloromethane for multiple times until no chromatographic spot of the reaction product appears in the filter residue, combining organic phases obtained by washing with dichloromethane, separating the organic phase from the filtrate obtained by suction filtration by using a separating funnel, combining the two obtained organic phases, drying by using anhydrous sodium sulfate, filtering, carrying out rotary evaporation to concentrate the organic phases, and finally separating and purifying the organic phases by using a silica gel chromatographic column (200-300 meshes), wherein an eluent is an ethyl acetate-petroleum ether mixed solvent with a volume ratio of 1.2:1 to obtain an orange intermediate C530 mg with a yield of 48%, and the orange intermediate C is obtained by adopting dichloromethane for recrystallization, wherein the chemical structural formula of the orange single crystal of the intermediate C is shown as a formula II:
Figure BDA0002349997870000081
step 4, dissolving 100mg of intermediate C (0.16mmol) obtained in step 3 in 20mL of dichloromethane-methanol mixed solvent with the volume ratio of 2:1 by magnetic stirring in a 100mL three-neck flask under the protection of helium to obtain a reaction solution, and introducing H under the action of 12-13 mg of 10 wt% Pd palladium-carbon catalyst2Reducing, stirring and reacting for 3 hours at room temperature, separating out a greenish fluorescent solid, continuing to react for 6 hours, stopping the reaction after the thin-layer chromatography detects that the intermediate C is completely consumed, filtering, respectively collecting filter residue and filtrate, adding 20mL of dimethylformamide into the filter residue to wash the reaction product for multiple times until no chromatographic spot of the reaction product appears in the filter residue, obtaining a washing solution with the palladium-carbon catalyst filtered out, combining the filtrate and the washing solution, placing the filter residue and the washing solution in a vacuum drying oven, performing vacuum drying at 85 ℃, collecting orange-red powder 68mg, namely the target compound benzoic acid substituted boron dipyrromethene derivative dye ligand, wherein the yield is 95%, and the chemical structural formula is shown as formula I:
Figure BDA0002349997870000082
the target compound is insoluble in n-hexane and dichloromethane, slightly soluble in chloroform and acetonitrile, and easily soluble in tetrahydrofuran, ethyl acetate, methanol and DMF.
Example 2
A preparation method of a benzoic acid substituted BODIPY derivative dye ligand comprises the following steps:
step 1, under magnetic stirring, sequentially adding 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl (800mg, 3.5mmol), p-formylbenzoic acid (295mg, 2.0mmol) and dried dichloromethane (100mL) prepared according to a reference document into a 500mL three-neck flask, introducing helium for 10-20 min, dropwise adding 200 muL of trifluoroacetic acid (1.08mmol), wherein the 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl in the three-neck flask can be observed to be completely dissolved, the p-formylbenzoic acid is slightly dissolved in a white suspension state, reacting at 25 ℃ for about 1H, gradually disappearing the white suspension, changing the reaction solution from light yellow to pink, and continuing stirring for reacting for 47H until the white suspension completely disappears to obtain a dark red reaction solution A;
step 2, dropwise adding 380mg of 2, 3-dichloro-5, 6-dicyan p-benzoquinone (1.67mmol) into the reaction solution A obtained in the step 1 under stirring, carrying out oxidation reaction at 25 ℃, and stirring for reaction for 20 hours to obtain a dark purple reaction solution B;
step 3, slowly adding 6mL of N, N-diisopropylethylamine (36.3mmol) into the reaction solution B obtained in the step 2, dropwise adding 9mL of boron trifluoride-diethyl ether solution (71mmol) at 25 ℃ for reaction, continuously stirring for reaction for 8 hours, stopping the reaction when the consumption of the reactant 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl is completely monitored by thin-layer chromatography, washing the reaction product with equal volume of saturated saline solution, performing suction filtration, washing the obtained filter residue with 10-20 mL of dichloromethane for multiple times until no chromatographic spot of the reaction product appears in the filter residue, combining the organic phases obtained by washing with dichloromethane, separating the organic phases from the filtrate obtained by suction filtration by using a separating funnel, combining the two organic phases, drying and filtering by using anhydrous sodium sulfate, performing rotary evaporation to concentrate the organic phases, and finally separating and purifying the organic phases by using a silica gel chromatographic column (200 meshes and 300 meshes), the eluent is an ethyl acetate-n-hexane mixed solvent with the volume ratio of 1.2:1 to obtain an orange intermediate C480 mg with the yield of 43%, and the orange single crystal of the intermediate C can be obtained by adopting dichloromethane for recrystallization, wherein the chemical structural formula is shown as a formula II:
Figure BDA0002349997870000101
step 4, dissolving 100mg of intermediate C (0.16mmol) obtained in step 3 in 20mL of dichloromethane-methanol mixed solvent with a volume ratio of 2:1 in a 100mL three-neck flask under magnetic stirring to obtain a reaction solution, and introducing H under the action of 12-13 mg of 10 wt% Pd palladium-carbon catalyst2Reducing, stirring at room temperature for 3h, precipitating green fluorescent solid, and reacting for 6hWhen the thin-layer chromatography detects that the intermediate C is completely consumed, stopping the reaction, filtering, respectively collecting filter residue and filtrate, adding 250mL of methanol into the filter residue to wash a reaction product for multiple times until no chromatographic spot of the reaction product appears in the filter residue, obtaining a washing liquid with the palladium-carbon catalyst filtered out, combining the filtrate and the washing liquid, placing the filtrate and the washing liquid in a vacuum drying oven for vacuum drying at 40 ℃, and collecting orange red powder 61mg, namely target compound benzoic acid substituted BODIPY derivative dye ligand, wherein the yield is 85%, and the chemical structural formula is shown as formula I:
Figure BDA0002349997870000102
the target compound is insoluble in n-hexane and dichloromethane, slightly soluble in chloroform and acetonitrile, and easily soluble in tetrahydrofuran, ethyl acetate, methanol and DMF.
II, structural characterization
1. The structural characterization of intermediate C is shown in fig. 1-3, and the characterization data is as follows:1H NMR(DMSO-d6,500MHz)：δ＝13.33(br,1H)、8.13(d,2H)、7.60(d,2H)、7.38(m,10H)、5.26(s,4H)、2.73(s,6H)、1.58(s,6H)；ESI-MS m/z：[M-H]-calcd.for C36H31B F2N2O6：635.2164，found.635.2161；IR(KBrpellet,cm-1): 3300(br), 3066(w), 3032(w), 2929(w), 1704(s), 1606(w), 1557(w), 1498(m), 1429(s), 1375(m), 1253(s), 1086(s), 1027(w), 949(w), 905(w), 782(m), 744(s) and 694(s), and the characterized nuclear magnetic chemical shift peaks, mass spectrum peaks and infrared absorption peaks are all identical with those of the chemical structural formula II of the intermediate C.
2. The structural characterization of the target compound is shown in fig. 4-6, and the characterization data is as follows:1H NMR(DMSO-d6,500MHz)：δ＝13.00(br,3H)、8.14(d,J＝8.2Hz,2H)、7.61(d,J＝8.20Hz,2H)、2.74(s,6H)、1.60(s,6H)；ESI-MS m/z：[M-H]-calcd.for C22H18B F2N2O6：455.1225，found.455.1230；IR(KBr pellet，cm-1)：v＝3439(br)、2968(vw), 2927(w), 2851(w), 2635(vw), 2547(vw), 1675(s), 1503(s), 1425(m), 1307(s), 1180(s), 1121(s), 1018(s), 935(w), 861(w), 797(vw), 768(w), 745(m), 616(m), 577 (w); the characterized nuclear magnetic chemical shift peak, mass spectrum peak and infrared absorption peak are identical with the chemical structural formula I of the target compound.
Triple, photoactive and coordinative ability
1. The ultraviolet-visible absorption spectrum and the fluorescence emission spectrum of the intermediate C in four different solvents are shown in FIG. 7, the detailed data are shown in Table 1, and the intermediate C shows the characteristic photophysical characteristics of the BODIPY dye: a sharp absorption peak and a fluorescence emission peak, wherein the intrinsic transition absorption peak appears around 493-501nm, and the intrinsic transition emission peak appears in the range of 521-526nm, the former is attributed to the pi → pi transition of the molecule, and the latter is attributed to the pi → pi transition of the intermediate C, compared with the common BODIPY dye which usually appears at the absorption peak of 500nm and the emission peak of 550nm, the introduction of the electron-withdrawing functional group benzoic acid obviously generates a blue shift phenomenon.
TABLE 1 spectral Properties of intermediate C in different solvents
Figure BDA0002349997870000121
Note:aabsorbing light wavelengths;ba wavelength of the emitted light;cmolar extinction coefficient;dquantum yield of light
2. The ultraviolet visible absorption spectrum and the fluorescence emission spectrum of the target compound in three different solvents are shown in fig. 8, the detailed data are shown in table 2, the intrinsic transition ultraviolet visible absorption spectrum and the intrinsic transition fluorescence emission spectrum of the target compound respectively appear around 498nm and within 518-524nm, and the characteristics of the absorption spectrum and the emission spectrum of the target compound and the benzyl ester derivative intermediate C are reflected that: the introduction of the electron-withdrawing functional groups benzoic acid and carboxyl groups generates a remarkable blue shift phenomenon.
TABLE 2 spectral properties of the target compounds in different solvents
Figure BDA0002349997870000122
Note:aabsorbing light wavelengths;ba wavelength of the emitted light;cmolar extinction coefficient;dquantum yield of light
3. Fluorescence emission spectra of the intermediate C and the target compound in the presence of various metal ions are shown in FIGS. 9 and 10, and it can be seen that the intermediate C has excellent fluorescence sensing properties for metal ions such as zinc, cadmium, copper, aluminum, and lead ions, and the target compound also has good fluorescence sensing properties for metal copper ions.
4. The target compound has excellent coordination ability and forms [ Zn ] with metallic zinc ions2(target Compound) (OH). 2H2O]nThe complex structure is shown in FIG. 11.
The above embodiments and drawings are not intended to limit the form and style of the present invention, and any suitable changes or modifications thereof by those skilled in the art should be considered as not departing from the scope of the present invention.

Claims (10)

1. A benzoic acid substituted BODIPY derivative dye ligand is characterized in that: the chemical structural formula is shown as formula I,
Figure FDA0002349997860000011
is named 8- [ 4-benzoic acid ] -4, 4-difluoro-1, 3,5, 7-tetramethyl-2, 6-dicarboxy-4-bora-3 a,4 a-diaza-s-indacene.
2. The preparation method of the benzoic acid substituted BODIPY derivative dye ligand according to claim 1, which is characterized by comprising the following steps: the method comprises the following steps:
step 1, dissolving 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl and p-formylbenzoic acid in a reaction medium under stirring, then dropwise adding trifluoroacetic acid in the atmosphere of protective gas, and reacting for 1-48H at 20-35 ℃ in a dark place to obtain a reaction solution A;
step 2, dropwise adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone into the reaction solution A obtained in the step 1 under stirring for oxidation reaction, and reacting for 1-24 hours at 20-35 ℃ to obtain a reaction solution B;
step 3, slowly adding N, N-diisopropylethylamine into the reaction solution B obtained in the step 2, dropwise adding boron trifluoride-diethyl ether solution at 0-25 ℃ for reaction, stirring for 1-48 h, stopping the reaction when the thin-layer chromatography detects that the reactants are completely consumed, washing and filtering the reaction product by using saturated saline solution, washing the obtained filter residue by using dichloromethane for multiple times until no obvious product residue exists, separating an organic phase from the filtrate obtained by filtering by using a separating funnel, combining the organic phase obtained by washing the dichloromethane and the organic phase obtained by separating, drying and filtering by using anhydrous sodium sulfate, carrying out rotary evaporation and concentration on the organic phase, and finally separating and purifying by using a silica gel chromatographic column to obtain an intermediate C;
step 4, dissolving the intermediate C obtained in the step 3 in a reaction medium to obtain a reaction solution, and introducing H under the action of a small amount of palladium-carbon catalyst2And (3) reducing, reacting for 3-9 hours under stirring, stopping the reaction after the thin-layer chromatography detects that the intermediate C is completely consumed, filtering, respectively collecting filtrate and filter residue, adding a washing solvent into the filter residue to wash the reaction product for multiple times until no product is left, obtaining a washing liquid with the palladium-carbon catalyst filtered out, combining the filtrate and the washing liquid, drying in vacuum, and collecting to obtain the target compound, namely the benzoic acid substituted BODIPY derivative dye ligand.
3. The method for preparing a benzoic acid substituted BODIPY derivative dye ligand according to claim 2, wherein the method comprises the following steps: in the step 1 and the step 4, the reaction medium is one or more of dichloromethane, trichloromethane, tetrahydrofuran, dioxane, acetonitrile, toluene, ethyl acetate, n-hexane, petroleum ether, methanol, ethanol and isopropanol; in step 1, the protective gas is one of nitrogen, helium and argon.
4. The method for preparing a benzoic acid substituted BODIPY derivative dye ligand according to claim 3, wherein the method comprises the following steps: in the step 1, the reaction medium is dichloromethane, the amount of the reaction medium is 50-200 mL, in the step 4, the reaction medium is a dichloromethane-methanol mixed solvent with a volume ratio of 2:1, and the amount of the reaction medium is 20-30 mL.
5. The method for preparing a benzoic acid substituted BODIPY derivative dye ligand according to claim 2, wherein the method comprises the following steps: in the step 1, the reaction temperature is 25 ℃, the reaction time is 24 hours, in the step 2, the reaction temperature is 25 ℃, the reaction time is 4 hours, in the step 3, the reaction temperature is 0 ℃, the stirring time is 4-8 hours, and in the step 4, the reaction temperature is room temperature.
6. The method for preparing a benzoic acid substituted BODIPY derivative dye ligand according to claim 2, wherein the method comprises the following steps: in step 3, the eluent used for separation and purification is a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1.2:1, or a mixed solvent of ethyl acetate and n-hexane in a volume ratio of 1.2: 1.
7. The method for preparing a benzoic acid substituted BODIPY derivative dye ligand according to claim 2, wherein the method comprises the following steps: in the step 4, the concentration of the intermediate C in the reaction solution is 4.5-6.0 g/L, the palladium content of the palladium-carbon catalyst is 2-10 wt%, and the washing solvent is one of methanol and dimethylformamide.
8. The method for preparing a benzoic acid substituted BODIPY derivative dye ligand according to claim 2, wherein the method comprises the following steps: the molar ratio of the 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl, p-formylbenzoic acid, trifluoroacetic acid, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, N-diisopropylethylamine and boron trifluoride-diethyl ether solution is 2.60-3.80: 1.50-2.50: 1.00-1.50: 1.50-2.00: 18.0-40.0: 24.0-80.0.
9. The method for preparing a benzoic acid substituted BODIPY derivative dye ligand according to claim 8, wherein the method comprises the following steps: the molar ratio of the 2, 4-dimethyl-1H-pyrrole-3-methyl benzyl, p-formylbenzoic acid, trifluoroacetic acid, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, N-diisopropylethylamine and boron trifluoride-diethyl ether solution is 3.50:2.00:1.08:1.67:36.3: 71.0.
10. The method for preparing a benzoic acid substituted BODIPY derivative dye ligand according to claim 2, wherein the method comprises the following steps: the chemical structural formula of the intermediate C is shown as formula II:
Figure FDA0002349997860000031
is named 8- [ 4-benzoic acid ] -4, 4-difluoro-1, 3,5, 7-tetramethyl-2, 6-dimethyl-benzyl-4-bora-3 a,4 a-diaza-s-indacene.
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