CN1296949A - Process for synthesizing benzoporphyrin zinc complex - Google Patents

Abstract

The invention belongs to the field of carbocyclic compounds in organic chemistry, and relates to a method for preparing benzoporphyrin metal (zinc, cadmium) complexes. The benzoporphyrin metal complex is prepared by using phthalimide and zinc acetate (cadmium acetate) as raw materials. It is carried out under closed conditions in a reaction kettle, the temperature is controlled within the range of 340-380°C, and the time is 15 minutes. Minutes to 45 minutes. The total yield can reach 45% to 85%. After the reaction, the mixture was transferred into a hot anhydrous ethanol solvent, filtered hot, distilled water was added to the filtrate to re-precipitate benzoporphyrin, and then column chromatography was performed on a silica gel column. The invention is simple and easy to implement, and is suitable for mass production. Since the atmospheric pressure reaction is changed to a closed reaction, the yield is greatly improved, and the emission of exhaust gas is reduced at the same time.

Description

A new method for the synthesis of benzoporphyrin zinc complexes

The invention belongs to the field of organic chemistry, relates to carbocyclic compounds, and relates to a method for preparing benzoporphyrin metal (zinc, cadmium) complexes.

Metalloporphyrins have some important properties of photochemical and biochemical reactions, so they have a wide range of applications in organic semiconductors, organic superconductors, and drugs. In addition to the above-mentioned applications, benzoporphyrin metal has excellent characteristics in spectral hole burning related to high-density information storage and holographic information storage, so a new and simple method is sought to synthesize benzoporphyrin metal appears to be particularly important.

产率为20％(J.Chem.Soc.1940，1079)。缺点是产率较低，且需先制得反应原料(Ⅰ)。Benzoporphyrin was first synthesized by the complex PA Barrett et al. in 1940. The reaction formula is as follows:

The yield was 20% (J. Chem. Soc. 1940, 1079). The disadvantage is that the yield is low, and the reaction raw material (I) needs to be prepared first.

或其钾盐

与芳基乙酸 等为原料，在醋酸锌或醋酸镉存在下，N₂气保护，在烧瓶中于340～380℃条件下反应数小时，制得苯并卟啉化合物，反应装置如图1所示，结构式如下：

反应产率为17％。他们以3-BPI 代替邻苯二甲酰亚胺，可将产率提高到36％。产物的分离提纯如下：将上述在烧瓶中得到的固体研磨成粉末状，再分别用热水、石油醚和氯仿来提取，其中氯仿溶液中含有苯并卟啉。将氯仿溶液浓缩，之后在三氧化二铝色谱柱上层析，以1∶1的氯仿和石油醚的混合液作为淋洗液，得到纯的产品(Zh.Obshch.Kim.1981，51(11)，2513-17(Russ))。后一种改进虽然提高了产率，但需先制备出3-BPI，再合成卟啉，步骤较多，分离纯困难，不宜推广。The former Soviet Union VNKopranenkov et al. reported in 1981 that phthalimide

or its potassium salt

with aryl acetic acid etc. as raw materials, in the presence of zinc acetate or cadmium acetate, under the protection of _N2 gas, react in a flask at 340-380°C for several hours to obtain a benzoporphyrin compound. The reaction device is shown in Figure 1, and the structural formula is as follows :

The reaction yield was 17%. 3-BPI Replacing phthalimide increased the yield to 36%. The separation and purification of the product is as follows: the above-mentioned solid obtained in the flask is ground into powder, and then extracted with hot water, petroleum ether and chloroform respectively, wherein the chloroform solution contains benzoporphyrin. The chloroform solution is concentrated, then chromatographed on the aluminum oxide chromatographic column, with the mixed solution of 1:1 chloroform and sherwood oil as eluent, obtains pure product (Zh.Obshch.Kim.1981,51(11 ), 2513-17 (Russ)). Although the latter improvement improves the yield, it needs to prepare 3-BPI first, and then synthesize porphyrin, which has many steps and is difficult to separate and purify, so it is not suitable for promotion.

In 1983, American David.E.Remy realized the use of isoindole With benzaldehyde as the reaction raw material to prepare benzoporphyrin, the yield increased to 53% (Tetrahedron Lett. 1983, 24, 1451). Although this method has greatly improved the reaction yield, the price of the raw material isoindole is expensive, and the subsequent separation process is quite complicated, so this method is not suitable for large-scale preparation.

The invention provides a simple and feasible method for preparing benzoporphyrin metal complexes. The reaction rate is improved because the sublimation of the reaction raw materials is prevented, and the method is suitable for mass production.

The present invention is based on the synthetic method of former Soviet Union VNKopranenkov et al. One of the reaction raw materials is phthalimide, and the other is zinc acetate ((RC ₂ COO) ₂ Zn) or cadmium acetate ((RCll ₂ COO) ₂ Cd) with substituents in the β-position. _N2 protection is required, and the normal pressure reaction is changed to a closed high pressure reaction. This is because phthalimide has a sublimation property, and there is a relatively high pressure in the system at more than 300 degrees. The reaction temperature is still 340-380°C, but the reaction time is shortened to 15-45 minutes. The above-mentioned closed high-pressure reaction device can be a stainless steel reaction kettle.

The stainless steel reactor is shown in Figure 2. Among the figure, 1 is a stainless steel body, 2 is a polytetrafluoroethylene inner sleeve, 3 is a stainless steel nut, 4 is a polytetrafluoroethylene gasket, and 5 is a raw material for reaction. During synthesis, the reactants are ground and mixed into the reaction kettle, and the stainless steel nut 3 is tightened.

The reaction formula is as follows:

Product separation and purification.

The reaction mixture was added to hot absolute ethanol, filtered hot, and the insoluble matter was washed several times with hot absolute ethanol to separate out some impurities. Then the solution was transferred into a beaker, an appropriate amount of distilled water was added, heated and stirred, and the porphyrin was precipitated in solid form. Then pour out the solution and put the solid into a vacuum oven at 70°-90°C to dry for 1-3 hours to obtain a crude porphyrin product. Then use silica gel chromatography column to separate the above-mentioned crude product, and use 1,2-dioxane as developing solvent to obtain two main product bands, the first band is MR ₄ TBP (tetrasubstituted tetrabenzoporphyrin metal compound , the second band is MR ₃ TBP (three-substituted tetrabenzoporphyrin metal compound, the amount of the two is equivalent, the solvent is distilled off, and the pure product of the two is obtained by drying, and the total yield is between 45% and 85%. .

The invention can increase the reaction yield to more than 45%, and can simultaneously obtain four-substituted and three-substituted products; the raw materials are simple and easy to obtain; no _N2 protection is needed in the reaction, the emission of waste gas is reduced, and the impact on the environment is greatly reduced pollution; subsequent separation and purification are easy. In a word, the present invention is simple and easy to implement, is suitable for industrial production through transformation, and facilitates the development and application of these benzoporphyrins in the fields of semiconductors, medicine, and optoelectronics.

The implementation of the present invention will be described below in conjunction with the synthesis of ZnP ₄ TBP and ZnP ₃ TBP.

Weigh 0.1385 g (9.432×10 ^-4 mol) of phthalimide and 0.1628 g (4.860×10 ^-4 mol, slightly excess) of zinc phenylacetate, and carefully grind and mix them uniformly in an agate mortar. Put the mixture into a 10ml stainless steel reaction kettle with polytetrafluoroethylene lining, tighten the lid of the kettle, that is, the stainless steel nut, and place it in a Dover furnace at about 360°C for 25 minutes. Then remove and cool to room temperature. The product in the kettle was dark green, the yield was 0.1229 g, and the crude product yield was 60%.

Transfer the crude product into a 100ml beaker, add 20ml of absolute ethanol, heat and stir to dissolve the solid completely, suction filter it on a Buchner funnel while it is hot, and wash the insoluble matter twice with hot ethanol. Then filtrate is transferred in the beaker of 100ml clean, add 40ml water, heat and stir, porphyrin is separated out with solid form. Then the solution was poured out, and the porphyrin was put into a vacuum oven and dried at 80° C. for 2 hours to obtain the porphyrin from which impurities were removed.

The above treated porphyrin was chromatographed on a column equipped with silica gel H, and the developing solvent was 1,2-dichloroethane, and two main product bands were obtained, the first light green band was tetraphenyl tetraphenyl Benzoporphyrin (ZnP ₄ TBP), the second dark green band is triphenyltetrabenzoporphyrin (ZnP ₃ TBP), the amount of the two is equivalent, the solvent is removed by rotary evaporation, and the pure product of the two is obtained by drying , the total yield was 45%.

Claims (2)

1, the method for preparing benzoporphyrin metal (zinc, cadmium) title complex, with the phthalic imidine is raw material, in the presence of zinc acetate or cadmium acetate, carrying out crude product in 340 ℃～380 ℃ conditions synthesizes, then crude product is separated and purify, it is characterized in that the crude product building-up reactions carries out in a closed high-tension unit, the reaction times is 15 minutes～45 minutes; Described crude product separates purification process:

A. use the anhydrous alcohol solution of heat, filter, separating impurity,

B. add distilled water, heated and stirred makes product separate out with solid form,

C. with solid product in 70 ℃～90 ℃ vacuum drying oven dry 1～3 hour,

D. with 1,2-ethylene dichloride developping agent is used the silica gel column chromatography separated product, obtains two main product bands.

2, the method for preparing benzoporphyrin metal (zinc, cadmium) title complex according to claim 1 is characterized in that described closed device is a stainless steel cauldron.

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