Application of non-surrounding displaced phthalocyanine zinc in preparing sonosensitizer
A zinc phthalocyanine, non-peripheral technology, applied in the application field of non-peripheral substituted zinc phthalocyanine in the preparation of sonosensitizers, which can solve the problems of sound sensitization ability to be improved, unstable composition and properties, and clinical application limitations , to achieve high stability, simple preparation and easy operation
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Embodiment 1
[0041] Tetrakis-a-(4-carboxyphenoxy)zinc phthalocyanine (also known as 1,8(11),15(18),22(25)-tetrakis(4-carboxyphenoxy)zinc phthalocyanine ( II) Synthesis of:
[0042] (1) Preparation of intermediate 3-(4-carboxyphenoxy)phthalonitrile:
[0043] Under the protection of nitrogen, dissolve 0.69g (5mmol) 4-hydroxybenzoic acid and 0.87g (5mmol) 3-nitrophthalonitrile in 20ml dimethyl sulfoxide (DMSO), stir at room temperature for 10 minutes, then add 1.5g (10.9mmol) anhydrous potassium carbonate, after 10min, add 1.0g potassium carbonate, continue to react for 12-24 hours (preferably 14 hours). Suction filter the reaction mixture, collect the filtrate, add 200ml ice-water mixture to the filtrate, adjust the pH value to 1~3 (preferably 2) with 2 mol / L HCl solution, the product is precipitated, filtered, washed with water until neutral, The filter cake was collected and dried under normal pressure at 70° C. to obtain 1.12 g of product with a yield of 87%.
[0044] The structural c...
Embodiment 2
[0058] Tetrakis-a-(3-carboxyphenoxy)zinc phthalocyanine (also known as 1,8(11),15(18),22(25)-tetrakis(3-carboxyphenoxy)zinc phthalocyanine ( II)) Synthesis
[0059] (1) Preparation of intermediate 3-(3-carboxyphenoxy)phthalonitrile:
[0060] Add 0.69g (5mmol) 3-hydroxybenzoic acid and 0.69-2.08g (4-6mmol) (preferably 0.87g, 5mmol) 3-nitrophthalonitrile into 35ml DMF, blow nitrogen, stir at room temperature, after 10 minutes Add 2.1g (15mmol) of potassium carbonate and react for 24 hours. Suction filter the reaction mixture, collect the filtrate, add 200ml ice-water mixture to the filtrate, adjust the pH value to 1~3 (preferably 2) with 2 mol / L HCl solution, the product is precipitated, filtered, washed with water until neutral, The filter cake was collected and dried under normal pressure at 70°C to obtain a crude product. The crude product was dissolved in a small amount of DMF, and then a large amount of water was added to precipitate a precipitate, which was filtered, wa...
Embodiment 3
[0076] Tetrakis-a-(2-methoxycarbonylphenoxy)zinc(II) phthalocyanine (also known as 1,8(11),15(18),22(25)-tetrakis(2-methoxycarbonylphenoxy base) phthalocyanine zinc (II)) synthesis
[0077] (1) Preparation of intermediate 3-(2-methoxycarbonylphenoxy)phthalonitrile
[0078] Add 0.3ml (2.3mmol) of methyl salicylate and 0.35g (2mmol) of 3-nitrophthalonitrile into 10ml of DMSO, blow nitrogen, stir and heat up to 60°C, add 0.7g (5mmol) of potassium carbonate after 10min , Reaction for 12-24 hours (preferably 18 hours). The reaction mixture was added to 200ml of ice-water mixture, stirred, and allowed to stand still, flocculent precipitates were precipitated, filtered with suction, washed with water until neutral, the filter cake was collected, and dried under normal pressure at 70°C to obtain a white crude product. Pass the crude product through CHCl 3 Purify by recrystallization, obtain 0.398g white product, productive rate 71.5%, Rf=0.58 (CH 2 CCl 2 ).
[0079] The structur...
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