CN109232590B

CN109232590B - Method for microwave solid-phase synthesis of tetrabenzoporphyrin zinc (II)

Info

Publication number: CN109232590B
Application number: CN201811310878.XA
Authority: CN
Inventors: 杨水彬; 周庆; 张玉洁; 张雪梅
Original assignee: Huanggang Normal University
Current assignee: Huanggang Normal University
Priority date: 2018-11-06
Filing date: 2018-11-06
Publication date: 2021-07-06
Anticipated expiration: 2038-11-06
Also published as: CN109232590A

Abstract

The invention discloses a method for microwave solid-phase synthesis of tetrabenzoporphyrin zinc (II), which comprises the following preparation steps: (1) weighing malonic acid, potassium phthalimide and zinc acetate, mixing and grinding to obtain mixed powder; (2) irradiating the mixed powder by using microwave until the reaction is completed to obtain a reactant; (3) cooling the reactant away from light, and performing column chromatography separation to obtain the product. The invention has the beneficial effects that: (1) the reaction is carried out in a solid phase, the reaction environment is loose, the reaction condition limitation is small, and the applicability is strong; (2) the microwave three-dimensional heating reaction is adopted, so that the reaction time is effectively shortened, the reaction energy barrier is reduced, the heat sublimation phenomenon is avoided, and the yield is improved; (3) the reaction does not need a solvent, so that the use and the recovery of the solvent can be avoided, and the cost is reduced; (4) no solvent participates in the reaction, which is beneficial to purification.

Description

Method for microwave solid-phase synthesis of tetrabenzoporphyrin zinc (II)

Technical Field

The invention belongs to the field of organic synthesis, and particularly relates to a synthetic method of zinc tetraphenylporphyrin (II).

Background

The metal porphyrin compound and the derivatives thereof are macrocyclic aromatic compounds containing 18r electronic structures, have wide application, can be applied to the fields of cancer diagnosis and identification, catalysis, photocell, molecular identification, photosensitive materials and the like, and can also simulate the physiological process in organisms and treat NO in automobile exhaust_xAnd the like.

The existing methods for synthesizing metalloporphyrin compounds include an Alder synthesis method, a Lindesy synthesis method, a Guoshan new synthesis method and a novel method for improving the Goodpasture. These conventional synthetic methods have many operation steps, long reaction time and low yield. The solid direct heating method has the defects of complex operation, long reaction time and difficult separation and purification due to serious sublimation and low yield (up to 15 percent).

Disclosure of Invention

In order to solve the technical problem, the invention provides a method for microwave solid-phase synthesis of tetrabenzoporphyrin zinc (II). The method ensures that reactants directly react in a solid phase, and has the characteristics of high heating speed, high energy utilization rate and easy purification and separation.

The microwave synthesis has the action principle that a direct current power supply is used for providing direct current power required by a magnetron of a microwave generator, then the microwave generator generates an alternating electric field, the alternating electric field acts on an object placed in the microwave field, and molecules can quickly absorb electromagnetic waves generated by the microwave generator due to the uneven charge distribution of the molecules, so that the polar molecules rotate and collide with each other very quickly, and then the polar molecules can swing along with the change of an external electric field, and the heat effect is generated. The principle of the molecules oscillating with the variation of the electric field due to their own thermal motion and the interaction between the molecules is hindered by the fact that the molecules oscillate with the variation of the electric field, which produces an effect similar to friction, converting a part of the energy into molecular thermal energy, directly aggravating the thermal motion of the molecules, which are in a metastable state due to the high speed rotation and vibration of the molecules, which are very helpful for further ionization of the molecules or for the molecules in a state of readiness for reaction, i.e. for which the temperature of the heated substance can rise linearly in a relatively short time.

The heating method of the microwave by the inventor enables the reaction to be carried out in a short time and the reaction to be directly carried out in a solid phase, probably because the microwave reduces the reaction energy barrier so that the reaction can be carried out under a milder condition, and on the other hand, partial molecules are probably in a metastable state to be more beneficial to the reaction. Besides, the yield is improved due to no thermal sublimation phenomenon because of milder reaction conditions.

The scheme provided by the invention is as follows:

a method for microwave solid phase synthesis of tetrabenzoporphyrin zinc (II) comprises the following preparation steps:

(1) weighing malonic acid, potassium phthalimide and zinc acetate, mixing and grinding to obtain mixed powder;

(2) irradiating the mixed powder by using microwave until the reaction is completed to obtain a reactant;

(3) cooling the reactant away from light, and performing column chromatography separation to obtain the product.

The molar ratio of malonic acid, potassium phthalimide and zinc acetate in the step (1) is 4.8:4.8: 1.

The grinding time in the step (1) is 5 min.

The power of the microwave radiation in the step (2) is 800w, and the radiation time is 5 min.

The invention has the beneficial effects that:

(1) the reaction is carried out in a solid phase, the reaction environment is loose, the reaction condition limitation is small, and the applicability is strong;

(2) the microwave three-dimensional heating reaction is adopted, so that the reaction time is effectively shortened, the reaction energy barrier is reduced, the heat sublimation phenomenon is avoided, and the yield is improved;

(3) the reaction does not need a solvent, so that the use and the recovery of the solvent can be avoided, and the cost is reduced;

(4) no solvent participates in the reaction, which is beneficial to purification.

Drawings

FIG. 1 is an infrared spectrum of the product prepared in example 1;

FIG. 2 is a UV spectrum of the product prepared in example 1;

FIG. 3 is a nuclear magnetic hydrogen spectrum of the product prepared in example 1.

Detailed Description

The invention will be further illustrated with reference to specific examples, to which the present invention is not at all restricted.

Example 1

Microwave synthesis of tetrabenzoporphyrin zinc (II)

Weighing 0.19g (18mmol) of malonic acid, 0.33g (18mmol) of potassium phthalimide and 0.75g (3.75mmol) of zinc acetate in a mortar, mixing and grinding for 5min, transferring the mixed powder into a 150mL round-bottom flask, reacting for 5min under the radiation of 800W under the microwave power, taking out after the reaction is finished, and cooling away from light to obtain a crude product. And (4) carrying out column chromatography separation on the crude product to obtain a refined product. The yield was 30%.

The synthesis by the method has the advantages of high reaction speed, short reaction time and no sublimation phenomenon. The conventional method comprises the steps of fully grinding the raw materials, uniformly mixing, putting the powder on a quartz boat, putting the quartz boat into a quartz tube, and reacting for 60min at 400 ℃ under the protection of argon, wherein the yield is 15%. The comparison shows that the method can effectively avoid the problem of sublimation, and the yield is almost doubled.

Example 2

Product map verification

And (3) infrared spectrum verification: FIG. 1 shows the infrared spectrum of zinc tetraphenylporphyrin (II) prepared in example 1, and it can be seen from the analysis that 1400cm^-1～1600cm^-1The strong absorption peak can be assigned to the characteristic absorption peak of C ═ C, C ═ N in porphyrin molecule, 1340cm^-1Is the C-N stretching vibration absorption peak.

Ultraviolet spectrum verification: FIG. 2 shows the UV spectrum of zinc (II) tetraphenylporphyrin prepared in example 1, and from the analysis, it is found that the absorption is strong at both 424nm and 623nm, wherein the strong absorption peak at 424nm is the characteristic peak of the Soret band of porphyrin, and the absorption peak at 623nm is the absorption peak of the Q band.

Nuclear magnetic hydrogen spectrum verification:¹H NMR:7.89(m,2H)，7.78(m,4H)，7.71(d,2H)，7.57(m,4H)，7.35(m,3H)， 7.19(m,4H)，7.02(d,1H)。

from the above-mentioned spectrum analysis, the product synthesized in example 1 was confirmed to be zinc tetrabenzoporphyrin (ii).

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.

Claims

1. A method for microwave solid phase synthesis of tetrabenzoporphyrin zinc (II) is characterized by comprising the following preparation steps:

the molar ratio of the malonic acid to the potassium phthalimide to the zinc acetate in the step (1) is 4.8:4.8: 1;

(2) irradiating the mixed powder by using microwave until the reaction is completed to obtain a reactant; the power of the microwave radiation is 800w, and the radiation time is 5 min;