CN108752383B - Pyrazole carboxylate manganese complex with SOD activity and preparation method thereof - Google Patents

Abstract

Pyrazole carboxylate manganese complex with SOD activity, and molecular formula thereof is [ Mn (ehpc) ]₂phen](wherein Hehpc is ethyl 5-hydroxy-4-pyrazolecarboxylate, phen is 1, 10-phenanthroline), and the synthesis method of the complex comprises the following steps: dissolving 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester, 1, 10-phenanthroline and manganese acetate tetrahydrate in a mixed solvent of ethanol and water, reacting in an oven at 80-100 ℃ for 12-48 hours, and cooling to obtain yellow blocky crystals. The preparation method is simple and low in cost. The complex is determined to be a monoclinic system, C2/C space group through a single crystal diffraction test, and the unit cell parameters are as follows:

β is 104.363(7) °. The synthesized manganese complex simulates Mn-SOD metalloenzyme, has certain biological activity, and provides basis for designing clinical medicines with better pharmacological activity.

Description

Pyrazole carboxylate manganese complex with SOD activity and preparation method thereof

Technical Field

The invention relates to the technical field of complexes, and particularly relates to a pyrazole carboxylic ester manganese complex with SOD activity and a preparation method thereof.

Background

The complex is a functional compound with different network structures formed by metal ions and organic ligands through coordination, and the design and synthesis of the complex relate to the fields of inorganic chemistry, organic chemistry, crystal engineering and the like. The functional compounds combine the performances of organic ligands and inorganic metal ions, and have potential application values in various fields such as catalysis, adsorption, ion exchange, fluorescent materials, biotechnology and the like.

Pyrazole is a nitrogen-containing five-membered heterocyclic azole compound, has rich coordination modes due to the fact that the pyrazole contains a plurality of coordination sites, and is an important organic ligand in coordination chemistry. The pyrazole compounds are mainly applied to two fields of medicines and pesticides, for example, pharmacological activities such as pain relieving, bacteriostasis, sterilization, hyperglycemia resistance, cancer resistance, anticoagulant and the like shown by the pyrazole compounds are widely applied to the field of medicines, and the pyrazole compounds have excellent characteristics in the aspects of sterilization, weeding, insect killing, plant growth regulation and the like and have wide application in the aspect of pesticides. In addition, the pyrazole derivatives have wide application in the aspects of energy storage material luminescent materials and dyes. Therefore, the pyrazole derivatives are nitrogen-containing heterocyclic compounds with good prospects, and the functional complex with a novel structure based on the pyrazole derivatives as organic ligands has wide application prospects.

Disclosure of Invention

The first object of the present invention is to provide a manganese pyrazole carboxylate complex having SOD activity;

the second purpose of the invention is to provide a preparation method of pyrazole carboxylic ester manganese complex with SOD activity.

The pyrazole carboxylic ester manganese complex with SOD activity is a novel compound, no related literature reports the substance through scifinider query, and the chemical formula of the complex is shown as the following diagram:

the manganese complex is a monoclinic system, C2/C space group, and the unit cell parameters are as follows:

β 104.363(7) °; the asymmetric structural unit of the compound consists of a central metal Mn (II), two 5-hydroxy-4-pyrazole ethyl formate ligand molecules and a 1, 10-phenanthroline molecule, wherein the central metal Mn (II) is in a six-coordination mode and is in a six-coordination deformed octahedral configuration.

The preparation method of the pyrazole carboxylic ester manganese complex with SOD activity comprises the following steps:

1) dissolving 1 part by weight of ethyl 5-hydroxy-4-pyrazolecarboxylate and 0.6-1.3 parts by weight of 1, 10-phenanthroline in 75-101 parts by weight of organic solvent to obtain a ligand solution; the organic solvent is one or more than two of methanol, ethanol, acetone and tetrahydrofuran;

2) dissolving 0.8-1.3 parts by weight of manganese acetate in 55-65 parts by weight of distilled water to obtain a manganese acetate solution;

3) mixing the ligand solution obtained in the step 1) and the manganese acetate solution 1 obtained in the step 2): 1, uniformly mixing, reacting at 80-100 ℃ for 12-48 hours, cooling to room temperature, filtering, washing and air-drying to obtain the pyrazole carboxylic ester manganese complex with SOD activity.

The pyrazole carboxylate manganese complex serving as a Mn-SOD model compound can be applied to clinic as a medicine.

Compared with the prior art, the invention has the following beneficial effects:

the pyrazole carboxylate manganese complex is a new compound, has SOD activity, is simple in synthesis method and low in cost, provides a certain basis for synthesizing a metal complex based on a pyrazole derivative organic ligand, and has important significance for development of clinical medicines.

Drawings

FIG. 1 is a crystal structure diagram of a complex of the present invention; wherein the symmetry is as in Table 2, and the hydrogen atoms on all carbon atoms are omitted.

FIG. 2 is an infrared spectrum of a complex of the present invention.

Detailed Description

In order that the invention may be readily understood, the following examples set forth more particular details.

Example 1: preparation of pyrazole carboxylate manganese complex with SOD activity

Dissolving 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester and 0.8 time of 1, 10-phenanthroline in weight of 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester in 80 times of 5-hydroxy-4-pyrazolesDissolving manganese acetate 1 time of the weight of 5-hydroxy-4-pyrazole ethyl formate in distilled water 60 times of the weight of 5-hydroxy-4-pyrazole ethyl formate to obtain a manganese acetate solution. Uniformly mixing the ligand solution and the manganese acetate solution to obtain a bright yellow solution, reacting in an oven at 100 ℃ for 48 hours, naturally cooling to room temperature after the reaction is finished, and filtering, washing and air-drying to obtain a bright yellow blocky manganese complex single crystal; yield: 82.5%, the infrared data of the obtained product are as follows: IR (KBr, cm)^-1)： 3218(w)，2975(w)，2935(w)，2368(w)，1654(s)，1627(s)，1558(m)，1517(m)， 1448(m)，1317(m)，1205(w)，1135(s)，1024(w)，917(m)，848(w)，786(m)，725(w)， 638(w)，597(w)。

Example 2: preparation of pyrazole carboxylate manganese complex with SOD activity

Dissolving 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester and 1, 10-phenanthroline in an amount which is 1.2 times the weight of 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester in an ethanol solvent in an amount which is 80 times the weight of 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester to obtain a ligand solution, and dissolving manganese acetate in an amount which is 1.0 times the weight of 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester in distilled water in an amount which is 60 times the weight of 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester to obtain a manganese acetate solution. Uniformly mixing the ligand solution and the manganese acetate solution to obtain a bright yellow solution, reacting in an oven at 80 ℃ for 24 hours, naturally cooling to room temperature after the reaction is finished, and filtering, washing and air-drying to obtain a bright yellow blocky manganese complex single crystal; yield: 70.5 percent.

Example 3: preparation of pyrazole carboxylate manganese complex with SOD activity

Dissolving 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester and 1, 10-phenanthroline 1.2 times the weight of 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester in an ethanol solvent 100 times the weight of 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester to obtain a ligand solution, and dissolving manganese acetate 1.2 times the weight of 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester in distilled water 60 times the weight of 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester to obtain a manganese acetate solution. Uniformly mixing the ligand solution and the manganese acetate solution to obtain a bright yellow solution, reacting in an oven at 100 ℃ for 36 hours, naturally cooling to room temperature after the reaction is finished, and filtering, washing and air-drying to obtain a bright yellow blocky manganese complex single crystal; yield: 78.5 percent.

TABLE 1 Main crystallographic data for manganese complexes of pyrazole carboxylates

^aR₁＝Σ||F_o|-|F_c||/Σ|F_o|,wR₂＝[Σw(F_o ²-F_c ²)²/Σw(F_o ²)²]^1/2

Table 2 crystal bond length of manganese pyrazole carboxylate complex (unit:

)

note: symmetrical operation: a 1-x, y,3/2-z

TABLE 3 Crystal bond angles (units:. degree.) of manganese pyrazolecarboxylate complexes

O1-Mn1-O1A	103.23(11)	O1-Mn1-N3	159.40(7)
				O1-Mn1-O2	88.93(6)	O1A-Mn1-N3A	159.40(7)
O1A-Mn1-O2A	88.93(6)	O2-Mn1-N3	81.72(7)
				O1-Mn1-O2A	87.21(6)	O2A-Mn1-N3A	81.72(7)
O1A-Mn1-O2	87.21(6)	O2-Mn1-N3A	103.40(6)
				O2A-Mn1-O2	173.79(9)	O2A-Mn1-N3	103.40(6)
O1A-Mn1-N3	93.92(8)	N3A-Mn1-N3	72.05(10)
				O1-Mn1-N3A	93.92(8)

Note: symmetric operation as in Table 2

Example 4: SOD activity detection of manganese complex

The superoxide radical inhibition activity of the synthesized manganese complex is measured by using a pyrogallol autoxidation method, and the IC of the manganese complex can be obtained by measuring and calculating₅₀The value:

TABLE 4 IC of manganese pyrazolecarboxylate complexes₅₀Value of

Complexes	IC50(μg/mL)
		MnC24H22N6O6	8.6

Claims (4)

1. A pyrazole carboxylic ester manganese complex with SOD activity is characterized by comprising the following structural formula:

。

2. the manganese complex of claim 1, having the structure of monoclinic, C2/C space group and unit cell parameters: a = 19.847(13) a, b = 10.488(7) a, c = 12.096(8) a, β =104.363(7) °; an asymmetric structural unit of the modified octahedral coordination compound consists of a central metal Mn (II), two 5-hydroxy-4-pyrazolecarboxylic acid ethyl ester ligands and a 1, 10-phenanthroline molecule, wherein the central metal Mn (II) adopts a six-coordination mode and is in a deformed octahedral configuration.

3. The method for preparing a manganese complex having SOD activity as claimed in claim 1 or 2, comprising the steps of:

1) dissolving 1 part by weight of ethyl 5-hydroxy-4-pyrazolecarboxylate and 0.6-1.3 parts by weight of 1, 10-phenanthroline in 75-101 parts by weight of organic solvent to obtain a ligand solution; the organic solvent is one or more than two of methanol, ethanol, acetone and tetrahydrofuran;

2) dissolving 0.8-1.3 parts by weight of manganese acetate in 55-65 parts by weight of distilled water to obtain a manganese acetate solution;

3) mixing the ligand solution obtained in the step 1) and the manganese acetate solution 1 obtained in the step 2): 1, uniformly mixing, reacting at 80-100 ℃ for 12-48 hours, cooling to room temperature, filtering, washing and air-drying to obtain the pyrazole carboxylic ester manganese complex with SOD activity.

4. The use of the pyrazole carboxylic acid ester manganese complex with SOD activity in the preparation of anti-aging drugs according to claim 1.

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