Preparation method of A3B type asymmetric porphyrin compounds

Abstract

The invention relates to a preparation method of A3B type asymmetric porphyrin compounds, which comprises the steps of mixing aldehyde A and pyrrole, adding into a solution containing C2-8 straight-chain fatty acid, xylene and water removal agent, reacting at 120-140 DEG C for 1-5 minutes, simultaneously adding aldehyde A and aldehyde B, and further reacting for 0.5-2 hours, thus obtaining the A3B type asymmetric porphyrin compounds. The yield of the method is 10-20%. According to the method, a small amount of trifluoroacetic acid and water removal agent are added, so that the reaction time is shortened, the preparation steps are simplified, the yield of an intermediate compound dipyrrolidine is increased, and the damage of the generated moisture to the intermediate compound is reduced, thereby increasing the product yield and further simplifying the separation and purification steps. Besides, low-toxicity xylene is used instead of nitrobenzene with high toxicity, thus reducing the environmental pollution. The method provided by the invention effectively utilizes the resources, reduces the environmental pollution and realizes energy saving and emission reduction in a true sense. Thus, compared with the existing synthesis method, the method provided by the invention has wider industrial application prospects.

Description

technical field [0001] The invention relates to a preparation method of an asymmetric porphyrin compound. Specifically, a 3 A preparation method of type B asymmetric porphyrin compounds. Background technique [0002] A 3 The B-type asymmetric porphyrin compound is different from the traditional symmetrical porphyrin compound structure. Due to its special structure, it has broad application prospects in many fields such as biomimetic catalysis, photodynamic therapy, and material science. [0003] Currently preparing A 3 The methods for B-type asymmetric porphyrin compounds mainly include the mixed aldehyde method and the dipyrrolidine method. The dipyrrolidine method is to synthesize and separate the dipyrrolidine in advance, then carry out the condensation reaction between the dipyrrolidine and two aldehydes, and finally separate and obtain the target product. [0004] Durantini et al. (J.Porphyrins Phthalocyanines4,233-242(2000)) reported a synthesis of A using dipyrr...

AI Technical Summary

Problems solved by technology

[0007] 1. The operation is cumbersome, and it is necessary to pre-synthesize dipyrrolidine, and then separate and purify it, resulting in high cost and high energy consumption;

[0008] 2. The reaction needs to be carried out under anhydrous and anaerobic conditions, and the reaction concentration is not allowed to be too high, resulting in a large consumption of solvent.

[0009] cause waste of resources

[0010] 3. The reaction requires the use of expensive and toxic strong oxidants, which not only causes environmental pollution, but also results in high synthesis costs

[0013] (1) The reaction time is long, usually 5 to 60 minutes, resulting in high energy consumption;

[0014] (2) The reaction needs to be synthesized in two steps, and the synthesis and separation operations are cumbersome

[0015] (3) The product yield is low, generally only 2-5%, the reaction efficiency is low, and the energy consumption is high

[0016] ①The reaction step is to mix B aldehyde and pyrrole first, and then add A aldehyde, resulting in an increase in by-products and a decrease in product yield

② Due to the insufficient reaction between B aldehyde and pyrrole, the yield of dipyrrolidine is low and there are many by-products, resulting in a decrease in product yield and difficulty in separation and purification

[0017] ③The water generated in the reaction inhibits the formation of the reaction intermediate porphyrinogen, reducing the product yield

[0018] (4) Due to the use of highly toxic nitrobenzene or nitrobenzene derivatives in the reaction, it will cause serious environmental pollution

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