CN116891494A - Preparation method and application of viscosity-sensitive heterocyclic compound - Google Patents

Preparation method and application of viscosity-sensitive heterocyclic compound Download PDF

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CN116891494A
CN116891494A CN202310634781.9A CN202310634781A CN116891494A CN 116891494 A CN116891494 A CN 116891494A CN 202310634781 A CN202310634781 A CN 202310634781A CN 116891494 A CN116891494 A CN 116891494A
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glycerol
compound
viscosity
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fluorescence
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晏佳莹
王璇
张诺诺
张驰
王龙
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China Three Gorges University CTGU
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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    • C07F5/022—Boron compounds without C-boron linkages
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • C09K2211/1044—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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
    • G01N2011/006—Determining flow properties indirectly by measuring other parameters of the system
    • G01N2011/008—Determining flow properties indirectly by measuring other parameters of the system optical properties

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Abstract

The application discloses a preparation method and application of a viscosity-sensitive heterocyclic compound, wherein the fluorescent dye has the following structural formula:

Description

Preparation method and application of viscosity-sensitive heterocyclic compound
Technical Field
The application relates to a heterocyclic compound, in particular to a preparation method and application of a viscosity-sensitive heterocyclic compound, which has certain response to viscosity, and has weaker fluorescence when the viscosity is low, and the fluorescence is enhanced along with the increase of the viscosity.
Background
The viscosity of body fluids is a defining biomarker for pathological conditions. When the cells are subjected to external pressure, abnormalities in cell viscosity occur. The bopylin probe has the advantages of high sensitivity, small biological light damage, good biocompatibility, real-time detection and the like as a small molecular fluorescent probe responding to the viscosity, so that the bopylin probe can be used for detecting the abnormal change of the intracellular microenvironment with high sensitivity. For example, the increased viscosity exhibited by mitochondrial swelling is associated with a number of diseases, such as the neurodegenerative diseases Parkinson's disease, alzheimer's disease and atherosclerosis. Meanwhile, as a probe with a large conjugated system, the probe has the advantages of low fluorescence background signal, large photon penetration depth and the like, has great significance for biological living body analysis, and has great potential in the clinical medical application direction.
Fluorescent probes are of great interest due to their potential convenience and high spatial-temporal resolution of microbiological sample microscopic monitoring. It is highly desirable to find small molecule probes that monitor viscosity for disease diagnosis and basic research. Dyes with rotatable substituents exhibit a responsive fluorescence enhancement to viscosity and have large conjugated systems that make probes more penetrating. Typically log (viscosity) is a linear response to log (fluorescence intensity). Under the liquid environment with lower viscosity, the intramolecular rotary bond of the probe can rotate at high speed, so that a very low background fluorescence signal is generated; in a liquid environment with higher viscosity, the rotation of the molecules is blocked, and the molecules emit strong fluorescent signals. As the viscosity increases, the luminescence of the probe can be enhanced up to 7.5 times.
The probe provided by the application is a preparation method and application of a viscosity-sensitive heterocyclic compound, and has weak fluorescence, but the fluorescence is gradually enhanced along with the increase of viscosity. The viscosity sensitivity coefficient is 3.76-4.70, and the maximum fluorescence enhancement to the viscosity is 2.7-7.5 times of the original fluorescence intensity.
Disclosure of Invention
The application mainly aims to provide a preparation method and application of a viscosity-sensitive heterocyclic compound.
The technical scheme of the application is as follows:
a preparation method and application of a viscosity-sensitive heterocyclic compound are provided, wherein the chemical structural formula of the compound is as follows:
wherein, the substituent R is any one selected from N, N-diphenylamino and cyano, and as a preferable scheme,
the chemical structural formula of the viscosity-sensitive heterocyclic compound is as follows:
any one of the following.
The preparation method and application of synthesizing the viscosity-sensitive heterocyclic compound comprise the following synthesis routes:
the method comprises the following steps:
(1) Adding a compound 1 and toluene into a reaction bottle at room temperature, stirring and dissolving, then adding a compound 2, piperidine and acetic acid, and heating and refluxing to obtain a reaction solution;
(2) And (3) performing rotary evaporation on the reaction liquid in the step (1), and separating by silica gel column chromatography to obtain a product I, namely the heptayuan boron dipyrate derivative.
The compound 1 is a seven-membered boron dipyrrole compound, and the compound 2 is a para-position derivative of benzaldehyde; the feeding mole ratio of the compound 1 to the compound 2 is 1:1-10. The feeding sequence of the step (1) is compound 1, toluene, compound 2, piperidine and acetic acid.
The acetic acid deprotonates the methylene compound to form an imine ion from the amine in the resonance stable enolate, carbonyl compound and piperidine, the enolate and the imine ion form a tetrahedral intermediate, which is 1, 2-eliminated to give the desired α, β -unsaturated dicarbonyl or related compound. Acetic acid and piperidine all play a role in activating reactants, and the last addition is needed. The molar feed ratio of the compound 1 to the piperidine is 1:1-10, and the molar feed ratio of the compound 1 to the acetic acid is 1:1-10.
The heating temperature of the step (1) is 30-150 ℃ and the heating time is 2-18 hours. The reaction temperature and time are variable depending on the reactants. When the temperature is raised to above 120 ℃, the yield is reduced; the temperature is reduced to 60 c and it will be difficult to start the reaction, resulting in an increase in the reaction time.
The application discloses application of a seven-membered fluorine boron dipyrrole heterocyclic compound in detecting liquid viscosity.
The liquid is selected from one or more of DMF, DME, DMSO, glycol, ethanol, n-butanol, isopropanol and PBS.
The viscosity of the liquid is in the range of 0.1-400 mpa.s; further preferably 0.1 to 320 mPas; further preferably 0.1 to 300 mPas; further preferably 0.1 to 280 mPas; further preferably 0.1 to 270 mPas; further preferably 0.1 to 250 mPas; further preferably 0.1 to 200 mPas; further preferably 0.1 to 150 mPas.
The heterocyclic compounds of the present application fluoresce less under low viscosity conditions because the free-spinning non-radiative pathways consume energy. At high viscosity, free rotation is blocked and strong fluorescence is turned on in a negligible non-radiative path. With the increase of the viscosity, the fluorescence intensity is continuously increased, and when the viscosity is increased to be more than 400 mpa.s, the free rotation is limited to the maximum, and the fluorescence intensity is not increased any more.
The application has the following beneficial effects:
(1) The compound has certain response to the viscosity, the fluorescence of the compound is weak, the fluorescence is gradually enhanced along with the increase of the viscosity, and the maximum fluorescence to the viscosity is enhanced by 7.5 times.
(2) The synthesis reaction condition of the application is easy to control, the product is simple to purify, and the application has universal applicability.
(3) The synthesis method has simple synthesis steps and mild reaction conditions.
Drawings
FIG. 1 is a graph showing fluorescence spectra of the compound I-1 obtained in example 1 in DMF-glycerol mixtures of different proportions.
FIG. 2 shows the fluorescence intensity log I of the compound I-1 obtained in example 1 729nm Linear relationship to log η.
FIG. 3 is a graph showing fluorescence spectra of the compound I-2 obtained in example 8 in DMF-glycerol mixtures of different proportions.
FIG. 4 shows the fluorescence intensity log I of the compound I-2 obtained in example 8 586nm Linear relationship to log η.
Detailed Description
The present application will be further illustrated by the following examples, but the scope of the application is not limited to the examples.
Example 1
Seven-membered boron dipyrrole compound (399 mg,1 mmol) of compound 1 is weighed, 30.00mL of toluene is taken and mixed for dissolution, 4-diphenyl aminobenzaldehyde (279 mg,1 mmol) and piperidine (0.09 mL,1 mmol) are sequentially added, acetic acid (0.06 mL,1 mmol) is heated and stirred at 90 ℃ for 8 hours for complete reaction, the reactant is distilled in a rotary manner, and the purple solid I-1 (196.9 mg) is obtained after column chromatography purification, and the yield is 30.1%.
Example 2
Seven-membered boron dipyrrole compound (399 mg,1 mmol) of compound 1 is weighed, 30.00mL of toluene is taken and mixed for dissolution, 4-diphenyl aminobenzaldehyde (546 mg,1 mmol) and piperidine (0.09 mL,1 mmol) are sequentially added, acetic acid (0.06 mL,1 mmol) is heated and stirred at 90 ℃ for 8 hours for complete reaction, the reactant is distilled in a rotary manner, and the purple solid I-1 (306.1 mg) is obtained after column chromatography purification, and the yield is 46.8%. When the amount of 4-cyanobenzaldehyde was increased 1-fold relative to example 1, the yield was increased by 16.7%.
Example 3
Seven-membered boron dipyrrole compound (399 mg,1 mmol) of compound 1 is weighed, 30.00mL of toluene is taken and mixed for dissolution, 4-diphenyl aminobenzaldehyde (279 mg,1 mmol) and piperidine (0.18 mL,2 mmol) are sequentially added, acetic acid (0.12 mL,2 mmol) is heated and stirred at 90 ℃ for 8 hours for complete reaction, the reactant is distilled in a rotary manner, and the purple solid I-1 (175.9 mg) is obtained after column chromatography purification, and the yield is 26.9%. When the amounts of piperidine and acetic acid were increased 1-fold relative to example 1, the yields were not significantly changed.
Example 4
Seven-membered boron dipyrrole compound (399 mg,1 mmol) of compound 1 is weighed, 30.00mL of toluene is taken and mixed for dissolution, 4-diphenyl aminobenzaldehyde (279 mg,1 mmol) and piperidine (0.09 mL,1 mmol) are sequentially added, acetic acid (0.06 mL,1 mmol) is heated and stirred at 120 ℃ for 6 hours for complete reaction, the reactant is distilled in a rotary manner, and a purple solid I-1 (428.4 mg) is obtained after column chromatography purification, and the yield is 65.5%. When the reaction temperature was increased by 30℃relative to example 1, the reaction time was reduced by 2 hours, and the yield was increased by 35.4%.
Example 5
Seven-membered boron dipyrrole compound (399 mg,1 mmol) of compound 1 is weighed, 30.00mL of toluene is taken and mixed for dissolution, 4-diphenyl aminobenzaldehyde (279 mg,1 mmol) and piperidine (0.09 mL,1 mmol) are sequentially added, acetic acid (0.06 mL,1 mmol) is heated and stirred at 140 ℃ for 6 hours for complete reaction, the reactant is distilled in a rotary manner, and the purple solid I-1 (106.6 mg) is obtained after column chromatography purification, and the yield is 16.3%. When the reaction temperature was increased by 50℃relative to example 1, the reaction time was reduced by 2 hours, and the yield was reduced by 13.8%.
Example 6
Seven-membered boron dipyrrole compound (399 mg,1 mmol) of compound 1 is weighed, 30.00mL of toluene is taken and mixed for dissolution, 4-diphenyl aminobenzaldehyde (279 mg,1 mmol) and piperidine (0.09 mL,1 mmol) are sequentially added, acetic acid (0.06 mL,1 mmol) is heated and stirred at 60 ℃ for 12 hours for complete reaction, the reactant is distilled in a rotary manner, and the purple solid I-1 (123.6 mg) is obtained after column chromatography purification, and the yield is 18.9%. When the reaction temperature was reduced by 30℃relative to example 1, the reaction time was increased by 4 hours, and the yield was reduced by 11.2%.
Example 7
Seven-membered fluoroborodipyrrole compound (399 mg,1 mmol) of compound 1 was weighed, 60.00mL of toluene was mixed and dissolved, then 4-diphenylaminobenzaldehyde (279 mg,1 mmol), piperidine (0.09 mL,1 mmol) and acetic acid (0.06 mL,1 mmol) were sequentially added, the reaction was stirred at 90℃for 8 hours and completed, the reaction was distilled off soon, and after column chromatography purification, purple solid I-1 (179.2 mg) was obtained in 27.4% yield. When the volume of toluene was doubled with respect to example 1, the yield was lowered by 2.7%.
Example 8
Seven-membered fluoroborodipyrrole compound (399 mg,1 mmol) of compound 1 was weighed, 30mL of toluene was taken and mixed to dissolve, 4-cyanobenzaldehyde (131 mg,1 mmol), piperidine (0.09 mL,1 mmol) and acetic acid (0.06 mL,1 mmol) were sequentially added, the reaction was stirred for 8 hours at 90℃and completed, the reaction was distilled off soon, and after column chromatography purification, purple solid I-2 (228.2 mg) was obtained in 34.9% yield.
Example 9 response of Compounds I-1, I-2 to viscosity
Weighing compound I-1 (6.54 mg,0.01 mmol) and dissolving 1mL DMF to obtain 0.01mol/L mother liquorThen, 10. Mu.L of each mother liquor was dissolved in 3ml of a mixture of DMF and glycerol of different viscosities to prepare 33.3. Mu. Mol/L of a solution to be measured (DMF: glycerol=10:0, e.g. 3ml DMF with a viscosity of 0.77mpa·s), (DMF: glycerol=9:1, such as a compound of 2.7ml DMF and 0.3ml glycerol, with a viscosity of 1.5mpa·s), (DMF: glycerol=8:2, such as a compound of 2.4ml DMF and 0.6ml glycerol, with a viscosity of 2.41mpa·s), (DMF: glycerol=7:3, such as a compound of 2.1ml DMF and 0.9ml glycerol, with a viscosity of 4.22mpa·s), (DMF: glycerol=6:4, such as a compound of 1.8ml DMF and 1.2ml glycerol, with a viscosity of 7.36mpa·s) (DMF: glycerol=5, such as a compound of 1.5ml DMF and 1.5ml glycerol, with a viscosity of 14.2mpa·s), (DMF: glycerol=4:6, such as a compound of 1.2ml DMF and 1.8ml glycerol, with a viscosity of 19.9mpa·s), (DMF: glycerol=3:7, such as a compound of 0.9ml DMF and 2.1ml glycerol, with a viscosity of 64.6mpa·s), respectively, and obtaining their respective fluorescent intensities, and fitting them to the spectrum of fig. 1 g, i 729nm Linear relationship with log η, resulting in fig. 2.I-1 itself is weak in fluorescence, but gradually increases in fluorescence as viscosity increases. The viscosity coefficient was 4.7 and the maximum fluorescence enhancement to viscosity was 2.7 times.
Weighing compound I-1 (6.54 mg,0.01 mmol), dissolving 1mL of DME to prepare 0.01mol/L mother solution, then dissolving 10 mu L of mother solution into 3mL of a mixture of DME and glycerol with different viscosities respectively to prepare 33.3 mu mol/L solution to be tested, wherein (DME: glycerol=10:0), (DME: glycerol=9:1), (DME: glycerol=8:2), (DME: glycerol=7:3), (DME: glycerol=6:4) (DME: glycerol=5:5) and (DME: glycerol=4:6), respectively detecting fluorescence spectra of the mother solutions, and the fluorescence gradually increases with the increase of the viscosity. The viscosity can be detected in the range of 0.1-260 mPas.
Weighing compound I-1 (6.54 mg,0.01 mmol), dissolving 1mL of DMSO to prepare 0.01mol/L mother solution, then dissolving 10 mu L of mother solution into 3mL of mixture of DMSO and glycerol with different viscosities respectively to prepare 33.3 mu mol/L to-be-tested solution, wherein (DMSO: glycerol=10:0), (DMSO: glycerol=9:1), (DMSO: glycerol=8:2), (DMSO: glycerol=7:3), (DMSO: glycerol=6:4) (DMSO: glycerol=5:5), (DMSO: glycerol=4:6), (DMSO: glycerol=3:7), (DMSO: glycerol=2:8) and (DMSO: glycerol=1:9), respectively detecting fluorescence spectra of the two solutions, and gradually increasing fluorescence with the increase of viscosity. The viscosity can be detected in the range of 0.1 to 300 mPas.
Weighing a compound I-1 (6.54 mg,0.01 mmol), dissolving 1mL of ethylene glycol to prepare 0.01mol/L mother solution, then respectively dissolving 10 mu L of mother solution into 3mL of mixture of ethylene glycol and glycerin with different viscosities to prepare 33.3 mu mol/L solution to be tested, wherein (ethylene glycol: glycerin=10:0), (ethylene glycol: glycerin=9:1), (ethylene glycol: glycerin=8:2), (ethylene glycol: glycerin=7:3), (ethylene glycol: glycerin=6:4), (ethylene glycol: glycerin=5:5), (ethylene glycol: glycerin=4:6), (ethylene glycol: glycerin=3:7) and (ethylene glycol: glycerin=2:8), and the fluorescence spectra of the mother solutions are detected respectively, and the fluorescence gradually increases with the increase of the viscosity. The viscosity can be detected in the range of 0.1 to 270 mPas.
Weighing a compound I-1 (6.54 mg,0.01 mmol), dissolving 1mL of ethanol to prepare 0.01mol/L mother solution, then respectively dissolving 10 mu L of mother solution into 3mL of mixture of ethanol and glycerol with different viscosities to prepare 33.3 mu mol/L solution to be tested, wherein (ethanol: glycerol=10:0), (ethanol: glycerol=9:1), (ethanol: glycerol=8:2), (ethanol: glycerol=7:3), (ethanol: glycerol=6:4), (ethanol: glycerol=5:5), (ethanol: glycerol=4:6) and (ethanol: glycerol=3:7), respectively detecting fluorescence spectra of the mother solution, and gradually increasing fluorescence with the increase of the viscosity. The viscosity can be detected in the range of 0.1-200 mPas.
Weighing a compound I-1 (6.54 mg,0.01 mmol), dissolving 1mL of n-butanol to prepare 0.01mol/L mother solution, then respectively dissolving 10 mu L of mother solution into 3mL of mixture of n-butanol and glycerin with different viscosities to prepare 33.3 mu mol/L solution to be tested, wherein (n-butanol: glycerin=10:0), (n-butanol: glycerin=9:1), (n-butanol: glycerin=8:2), (n-butanol: glycerin=7:3), (n-butanol: glycerin=6:4), (n-butanol: glycerin=5:5) and (n-butanol: glycerin=4:6), respectively detecting fluorescence spectra of the n-butanol and glycerin, and gradually increasing fluorescence with increasing viscosity. The viscosity can be detected in the range of 0.1-200 mPas.
Weighing a compound I-1 (6.54 mg,0.01 mmol), dissolving 1mL of isopropanol to prepare 0.01mol/L mother solution, then respectively dissolving 10 mu L of mother solution into 3mL of a mixture of isopropanol and glycerol with different viscosities to prepare 33.3 mu mol/L solution to be tested, wherein (isopropanol: glycerol=10:0), (isopropanol: glycerol=9:1), (isopropanol: glycerol=8:2), (isopropanol: glycerol=7:3), (isopropanol: glycerol=6:4), (isopropanol: glycerol=5:5), (isopropanol: glycerol=4:6), (isopropanol: glycerol=3:7) and (isopropanol: glycerol=2:8), and respectively detecting fluorescence spectra of the mother solutions, wherein fluorescence gradually increases with the increase of the viscosity. The viscosity can be detected in the range of 0.1 to 250 mPas.
Compound I-1 (6.54 mg,0.01 mmol) was weighed and 1ml of lpbs was dissolved to prepare 0.01mol/L of mother liquor, then 10 μl of each mother liquor was dissolved into 3ml of a mixture of PBS and glycerol of different viscosities, respectively, to prepare 33.3 μl of solutions to be tested, wherein (PBS: glycerol=10:0), (PBS: glycerol=9:1), (PBS: glycerol=8:2), (PBS: glycerol=7:3), (PBS: glycerol=6:4), (PBS: glycerol=5:5), (PBS: glycerol=4:6), (PBS: glycerol=3:7), (PBS: glycerol=2:8), respectively, their fluorescence spectra were measured, and the fluorescence gradually increased with increasing viscosity. The viscosity can be detected in the range of 0.1 to 250 mPas.
Weighing compound I-2 (5.12 mg,0.01 mmol), dissolving 1mL of DMF to prepare 0.01mol/L mother liquor, and then dissolving 10 mu L of mother liquor into 3mL of mixture of DMF and glycerol with different viscosities respectively to prepare 33.3 mu mol/L of solution to be tested (DMF: glycerol=10:0, such as 3mL of DMF, with a viscosity of 0.77 mPa-s), (DMF: glycerol=9:1, such as a compound of 2.7mL of DMF with 0.3mL of glycerol, a viscosity of 1.5 mPa-s), (DMF: glycerol=8:2, such as a compound of 2.4mL of DMF with 0.6mL of glycerol, a viscosity of 2.41 mPa-s), (DMF: glycerol=7:3, such as a compound of 2.1mL of DMF with 0.9mL of glycerol, a viscosity of 4.22 mPa-s), (DMF: glycerol=6:4, such as a compound of 1.8mL of DMF with 1.2mL of glycerol, a viscosity of 7.36 mPa-s) (DMF: glycerol=5:5, such as a compound of 1.5mL of DMF with 1.5mL of glycerol, a viscosity of 14.2 mPa-s), their fluorescence spectra were detected, respectively, to give fig. 3, and the fluorescence intensities log I were fitted 586nm Linear relationship with log η, resulting in fig. 4. Fluorescence of I-2 itselfWeaker, but with increasing viscosity, fluorescence gradually increases. The viscosity coefficient was 3.76 and the maximum fluorescence enhancement to viscosity was 7.5 times.
Weighing compound I-2 (5.12 mg,0.01 mmol), dissolving 1mL of DME to prepare 0.01mol/L mother solution, dissolving 10 mu L of mother solution into 3mL of a mixture of DME and glycerol with different viscosities respectively to prepare 33.3 mu mol/L solution to be tested, wherein (DME: glycerol=10:0), (DME: glycerol=9:1), (DME: glycerol=8:2), (DME: glycerol=7:3), (DME: glycerol=6:4) (DME: glycerol=5:5), (DME: glycerol=4:6), (DME: glycerol=3:7) and (DME: glycerol=2:8), and respectively detecting fluorescence spectra of the mother solutions, wherein fluorescence gradually increases with the increase of the viscosity. The viscosity can be detected in the range of 0.1 to 320 mPas.
Weighing compound I-2 (5.12 mg,0.01 mmol), dissolving 1mL of DMSO to prepare 0.01mol/L mother solution, and dissolving 10 mu L of mother solution into 3mL of mixture of DMSO and glycerol with different viscosities to prepare 33.3 mu mol/L solution to be tested, wherein (DMSO: glycerol=10:0), (DMSO: glycerol=9:1), (DMSO: glycerol=8:2), (DMSO: glycerol=7:3), (DMSO: glycerol=6:4) (DMSO: glycerol=5:5), (DMSO: glycerol=4:6), (DMSO: glycerol=3:7), and DMSO: glycerol = 2: 8) Their fluorescence spectra were separately measured, with the fluorescence gradually increasing as the viscosity increased. The viscosity can be detected in the range of 0.1 to 280 mPas.
Weighing a compound I-2 (5.12 mg,0.01 mmol), dissolving 1mL of ethylene glycol to prepare 0.01mol/L mother solution, then respectively dissolving 10 mu L of mother solution into 3mL of mixture of ethylene glycol and glycerol with different viscosities to prepare 33.3 mu mol/L solution to be tested, wherein (ethylene glycol: glycerol=10:0), (ethylene glycol: glycerol=9:1), (ethylene glycol: glycerol=8:2), (ethylene glycol: glycerol=7:3), (ethylene glycol: glycerol=6:4), (ethylene glycol: glycerol=5:5), (ethylene glycol: glycerol=4:6), (ethylene glycol: glycerol=3:7), (ethylene glycol: glycerol=2:8) and (ethylene glycol: glycerol=1:9), and the fluorescence spectrum is detected respectively, and the fluorescence gradually increases with the increase of the viscosity. The viscosity can be detected in the range of 0.1 to 300 mPas.
Weighing compound I-2 (5.12 mg,0.01 mmol), dissolving 1mL of ethanol to prepare 0.01mol/L mother solution, then respectively dissolving 10 mu L of mother solution into 3mL of mixture of ethanol and glycerol with different viscosities to prepare 33.3 mu mol/L solution to be tested, wherein (ethanol: glycerol=10:0), (ethanol: glycerol=9:1), (ethanol: glycerol=8:2), (ethanol: glycerol=7:3), (ethanol: glycerol=6:4), (ethanol: glycerol=5:5) and (ethanol: glycerol=4:6), respectively detecting fluorescence spectra of the compounds, and gradually increasing fluorescence with the increase of viscosity. The viscosity can be detected in the range of 0.1-230 mPas.
Weighing compound I-2 (5.12 mg,0.01 mmol), dissolving 1mL of n-butanol to prepare 0.01mol/L mother solution, then respectively dissolving 10 mu L of mother solution into 3mL of mixture of n-butanol and glycerin with different viscosities to prepare 33.3 mu mol/L solution to be tested, wherein (n-butanol: glycerin=10:0), (n-butanol: glycerin=9:1), (n-butanol: glycerin=8:2), (n-butanol: glycerin=7:3), (n-butanol: glycerin=6:4), (n-butanol: glycerin=5:5), (n-butanol: glycerin=4:6) and (n-butanol: glycerin=3:7), respectively detecting fluorescence spectra of the compounds, and gradually increasing fluorescence with the increase of viscosity. The viscosity can be detected in the range of 0.1 to 180 mPas.
Weighing compound I-2 (5.12 mg,0.01 mmol), dissolving 1mL of isopropanol to prepare 0.01mol/L mother solution, then respectively dissolving 10 mu L of mother solution into 3mL of mixture of isopropanol and glycerol with different viscosities to prepare 33.3 mu mol/L solution to be tested, wherein (isopropanol: glycerol=10:0), (isopropanol: glycerol=9:1), (isopropanol: glycerol=8:2), (isopropanol: glycerol=7:3), (isopropanol: glycerol=6:4), (isopropanol: glycerol=5:5), (isopropanol: glycerol=4:6), (isopropanol: glycerol=3:7) and (isopropanol: glycerol=2:8), respectively detecting fluorescence spectra of the mother solution, and fluorescence gradually increases with the increase of viscosity. The viscosity can be detected in the range of 0.1 to 250 mPas.
Weighing compound I-2 (5.12 mg,0.01 mmol), dissolving 1mLPBS to prepare 0.01mol/L mother solution, then respectively dissolving 10 mu L mother solution into 3ml of mixture of PBS with different viscosities and glycerol to prepare 33.3 mu mol/L solution to be tested, wherein (PBS: glycerol=10:0), (PBS: glycerol=9:1), (PBS: glycerol=8:2), (PBS: glycerol=7:3), (PBS: glycerol=6:4) and (PBS: glycerol=5:5) respectively detecting fluorescence spectra of the two solutions, and the fluorescence gradually increases with the increase of the viscosity. The viscosity can be detected in the range of 0.1 to 150 mPas.
The above embodiments are merely preferred embodiments of the present application, and should not be construed as limiting the present application, and the embodiments and features of the embodiments of the present application may be arbitrarily combined with each other without collision. The protection scope of the present application is defined by the claims, and the protection scope includes equivalent alternatives to the technical features of the claims. I.e., equivalent replacement modifications within the scope of this application are also within the scope of the application.

Claims (6)

1. A seven-membered fluoroborodipyrrole heterocyclic compound, characterized in that the heterocyclic compound has the structural formula:
wherein the substituent R is any one selected from N, N-diphenylamino and cyano.
2. A process for the preparation of a seven-membered borofluoride heterocyclic compound according to claim 1, comprising the following synthetic routes:
wherein, the substituent R is any one selected from N, N-diphenylamino and cyano,
(1) Adding a compound 1 and toluene into a reaction bottle at room temperature, stirring and dissolving, adding a compound 2, piperidine and acetic acid, and heating and refluxing to obtain a reaction solution;
(2) And (3) performing rotary evaporation on the reaction liquid in the step (1), and separating by silica gel column chromatography to obtain a product I, namely the heptayuan boron dipyrrole heterocyclic compound.
3. The method according to claim 2, wherein in the step (1), the compound 2 is a para-position derivative of benzaldehyde, and the molar ratio of the compound 1 to the para-position derivative of benzaldehyde is 1:1-10.
4. The method of claim 2, wherein the heating temperature in step (1) is 30 to 150 ℃ and the heating time is 2 to 18 hours.
5. Use of a seven-membered borofluoride heterocyclic compound according to claim 1 for detecting liquid viscosity.
6. The use according to claim 5, wherein the liquid is selected from any one or more of DMF, DME, DMSO, ethylene glycol, ethanol, n-butanol, isopropanol, PBS.
CN202310634781.9A 2023-05-31 2023-05-31 Preparation method and application of viscosity-sensitive heterocyclic compound Pending CN116891494A (en)

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