Ph-sensitive axially substituted silicon phthalocyanine complexes and their preparation methods and applications in medicine
A technology of dichlorosilicon phthalocyanine and compound, which is applied in the field of medicine and can solve the problems of incapable of photodynamic damage, complex components, and weak targeting effect
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Embodiment 1
[0066] The synthesis of embodiment 1 compound 1
[0067]
[0068] step 1
[0069] In an ice-water bath, compound 1-1 (1.62g, 10mmol), cholesterol chloroformate (2.2g, 4.9mmol) and triethylamine (2g, 20mmol) were added into dichloromethane (30mL), and the stirring reaction was continued for 3 hours. Stop the reaction, add water (200mL) to the reaction solution, stir and let it stand, collect the organic phase, dry the organic phase with anhydrous sodium sulfate, and distill under reduced pressure. The crude product is separated and purified by silica gel chromatography column, and the eluent is trichloro Methane / methanol (9:1) afforded 1-2 as a white solid (1.45 g, 51%). MS(ESI):m / z=598[M+Na] + .
[0070] step 2
[0071] In an ice-water bath, add compound 1-2 (1.2g, 2.1mmol), compound 1-3 (0.52g, 1.5mmol), pyridine (1.1g, 14mmol) into dichloromethane (35mL), withdraw from the ice-water bath, The temperature was raised to room temperature and the stirring reaction was co...
Embodiment 2
[0074] The synthesis of embodiment 2 compound 2
[0075]
[0076] step 1
[0077] In an ice-water bath, add compound 2-1 (0.57g, 3.5mmol), cholesterol chloroformate (1.55g, 3.5mmol) and pyridine (0.8g, 10.1mmol) into dichloromethane (35mL), and the temperature was raised to room temperature, Continue to stir the reaction for 2 hours, stop the reaction, add water (100mL) to the reaction solution, stir and let it stand, collect the organic phase, dry the organic phase with anhydrous sodium sulfate, and distill under reduced pressure. The crude product is separated and purified by silica gel chromatography. The eluent was chloroform / methanol (15:1) to obtain white solid 2-2 (0.92 g, 46%). MS(ESI):m / z=599[M+Na] + .
[0078] step 2
[0079] In an ice-water bath, add compound 2-2 (0.9g, 1.6mmol), compound 2-3 (0.9g, 3.0mmol) into tetrahydrofuran (30mL), and slowly add sodium hydride (0.3g, 12.5mmol) into the reaction solution ), the ice-water bath was withdrawn, the temperat...
Embodiment 3
[0082] The synthesis of embodiment 3 compound 3
[0083]
[0084] step 1
[0085] In an ice-water bath, add compound 1-2 (1.2g, 2.1mmol), compound 3-1 (0.5g, 2.4mmol), pyridine (0.8g, 10.1mmol) into dichloromethane (25mL), and the temperature was raised to room temperature Continue to stir the reaction for 8 hours, stop the reaction, add water (100mL) to the reaction solution, stir and let it stand, collect the organic phase, dry the organic phase with anhydrous sodium sulfate, and distill under reduced pressure. The crude product is separated and purified by silica gel chromatography. The eluent was chloroform / methanol (9:1) to obtain pale yellow oil 3-2 (0.85g, 62%). MS(ESI):m / z=663[M] + . step 2
[0086] Dichlorosilicon phthalocyanine (0.21g, 0.34mmol), compound 1-4 (1.5g, 2.2mmol) and pyridine (1g, 12.7mmol) were added to toluene (30mL), and the temperature was raised to 120°C for 24 hours. Evaporate the solvent under pressure, add 100 ml of chloroform and 100 ml o...
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