A Fluorescent Probe Based on Thiophene-Benzene Conjugated Macrocycle and Its Preparation and Application
A fluorescent probe and conjugated macrocycle technology, applied in the field of fluorescent probes, can solve the problems of complicated operation, expensive instruments, long time-consuming, etc., and achieve the effects of good selectivity, low cost and simple detection method.
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[0028] The present invention also provides a method for preparing a fluorescent probe based on a thiophene-benzene conjugated macrocycle as described above, which includes the steps of:
[0029] A. Under the protection of inert gas, the Trimethylsilylacetylene, CuI, Pd(PPh 3 ) 4 、PPh 3 1. The organic amine is dissolved in the first organic solvent, heated to reflux for stirring reaction, cooled to room temperature after the reaction is complete, the reaction solution is concentrated and separated by column chromatography to obtain the first intermediate; the structural formula of the first intermediate is
[0030] B. Under the protection of an inert gas, dissolve the first intermediate and tetrabutylammonium fluoride in the second organic solvent, and carry out a stirring reaction at room temperature. After the reaction is complete, add deionized water to quench the reaction, and extract and concentrate the organic solvent. Phase, column chromatography separation obtains...
Embodiment 1
[0044] With R=n-C 6 h 13 As an example, the preparation route is shown in the following formula (1) to obtain the substrate 3 for preparing a fluorescent probe based on a thiophene-benzene conjugated macrocycle.
[0045]
[0046] (1) In a 250mL round bottom flask, add compound 1 (3.00g, 5.45mmol), biboronic acid pinacol ester (8.31g, 32.71mmol), potassium acetate (3.21g, 32.71mmol); [1,1'- Bis(diphenylphosphino)ferrocene]palladium dichloride (Pd(PPh 3 ) 2 Cl 2 , 398.90mg, 0.545mmol) and 1,1'-bis(diphenylphosphino)ferrocene (302.24mg, 0.545mmol), added dry 1,4-dioxane 100mL under nitrogen protection, heated to 100 Reflux at ℃, stir overnight, and monitor the reaction progress by TLC. After the reaction, extract with water and ethyl acetate, combine the organic phases, and spin dry with a vacuum device to obtain the first crude product.
[0047] The first crude product was added to a 250mL two-necked flask containing potassium carbonate (3.73g, 27.0mmol), m-bromoiodobenz...
Embodiment 2
[0051] With R=n-C 6 h 13 As an example, the preparation route is shown in the following formula (2) to prepare the first intermediate 4 of the fluorescent probe based on a thiophene-benzene conjugated macrocycle.
[0052]
[0053] Add compound 3 (4.50g, 5.37mmol), trimethylsilylacetylene (1.58g, 16.11mmol), cuprous iodide (CuI, 102.2mg, 0.536mmol), tetrakis(triphenylphosphine) in a 250mL two-necked flask ) Palladium (Pd(PPh 3 ) 4 , 620mg, 0.536mmol), triphenylphosphine (PPh 3 , 281.45mg, 1.07mmol) and diisopropylamine (1mL, 7.13mmol), under nitrogen protection, add toluene (80mL), heat to reflux, stir overnight, monitor the reaction process with TLC, after the reaction is over, remove the reaction solution under reduced pressure solvent in , using dichloromethane / petroleum ether (v / v=1 / 5) as eluent to carry out silica gel column chromatography to obtain 3.60g of the first intermediate 4 as a yellow oil with a yield of 76.8% . The structural characterization data of th...
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