CN108822141B - Nitrogen heterocyclic ring transition metal copper complex containing benzotriazole ring, and preparation method and application thereof - Google Patents
Nitrogen heterocyclic ring transition metal copper complex containing benzotriazole ring, and preparation method and application thereof Download PDFInfo
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- -1 Nitrogen heterocyclic ring transition metal copper complex Chemical class 0.000 title claims abstract description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 38
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 37
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 32
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000003814 drug Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000013078 crystal Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 150000001879 copper Chemical class 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002329 infrared spectrum Methods 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 abstract description 13
- 230000003078 antioxidant effect Effects 0.000 abstract description 10
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 abstract description 10
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003963 antioxidant agent Substances 0.000 abstract description 8
- 235000006708 antioxidants Nutrition 0.000 abstract description 7
- 229930003427 Vitamin E Natural products 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 4
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002000 scavenging effect Effects 0.000 abstract description 4
- 235000019165 vitamin E Nutrition 0.000 abstract description 4
- 229940046009 vitamin E Drugs 0.000 abstract description 4
- 239000011709 vitamin E Substances 0.000 abstract description 4
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229930182555 Penicillin Natural products 0.000 description 5
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 5
- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 229940049954 penicillin Drugs 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229940123457 Free radical scavenger Drugs 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 208000035240 Disease Resistance Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 206010020718 hyperplasia Diseases 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P39/00—General protective or antinoxious agents
- A61P39/06—Free radical scavengers or antioxidants
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a nitrogen heterocyclic ring transition metal copper complex containing a benzotriazole ring, a preparation method and application thereof, wherein the nitrogen heterocyclic ringThe transition metal copper complex is 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) copper complex with a molecular formula of [ Cu (C)15H13N5)2Cl2](ii) a Wherein, C15H13N5Is ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole). The invention takes 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) as a ligand to react with copper chloride to prepare the nitrogen heterocyclic transition metal copper complex, the complex has stronger scavenging action on DPPH free radicals, which is far higher than that of 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) used alone to scavenge DPPH free radicals, and is stronger than common antioxidant vitamin E under certain low concentration. The result shows that the nitrogen heterocyclic ring transition metal copper complex has good antioxidation and is an innovation on antioxidant medicines.
Description
Technical Field
The invention relates to a nitrogen heterocyclic ring transition metal copper complex containing a benzotriazole ring, and a preparation method and application thereof, and belongs to the technical field of medicines.
Background
In recent years, with the rapid development of medicine from basic biology and free radicals, research shows that free radicals in organisms gradually increase and accumulate with the increase of human age and the reduction of antioxidant enzyme activity, so that a series of effects are caused, the organisms finally accelerate aging, and meanwhile, active oxygen radicals can induce various diseases and canceration by attacking various substances in cell tissues. Therefore, maintaining the balance of free radical generation and elimination in the organism is the key for keeping health, and developing safe, low-toxicity and green antioxidants is also more and more valued by scientific researchers.
DPPH radical is a synthetic, one-electron, stable, nitrogen-centered paramagnetic compound. When the free radical scavenger exists, the DPPH free radical accepts one electron or hydrogen atom to form a stable DPPH-H compound, so that the alcoholic solution of the DPPH-H compound changes from purple to yellow, the absorbance at the wavelength of 517nm is reduced, and the change degree and the free radical scavenging degree are in a linear relation, namely, the stronger the scavenging capacity of the free radical scavenger is, the smaller the absorbance is. Since DPPH free radical has simple structure and easy control of reaction, it has been widely used in the evaluation of antioxidant properties of animal and plant extracts or single compounds.
Benzotriazole compounds have strong biological activity, and benzotriazole derivatives have obvious effects on the aspects of anti-inflammation, rheumatoid disease resistance, anti-hyperplasia, tuberculosis resistance, tumor resistance and the like. The nitrogen atom on the nitrogen 1 position in the benzotriazole is very active, and hydroxylation, alkylation, alkoxylation, amination, methyl amination and other reactions can be carried out on the nitrogen 1 position, so that various derivatives can be synthesized. The coordination capability of imidazole functional groups in the benzimidazole compound is strong, and the benzimidazole compound can be coordinated with metal ions to form a metal complex.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a nitrogen heterocyclic ring transition metal copper complex containing a benzotriazole ring, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a nitrogen heterocyclic transition metal copper complex containing benzotriazole ring is a 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) copper complex with a molecular formula of [ Cu (C)15H13N5)2Cl2](ii) a Wherein, C15H13N5Is ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and the molecular structural formula is as follows:
a preparation method of a nitrogen heterocyclic ring transition metal copper complex containing a benzotriazole ring comprises the following steps:
(1) accurately weighing 0.02-0.04mmol of copper chloride, and dissolving in 4-6mL of solvent to obtain copper salt solution;
(2) accurately weighing 0.02-0.04mmol of ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and dissolving in 4-6mL of solvent to obtain a ligand solution;
(3) adding the ligand solution into the copper salt solution, uniformly mixing, filtering, adding a solvent into the filtrate to 14-18mL, and standing at room temperature until a green rectangular crystal is precipitated, thus obtaining the ligand.
The solvent in the steps (1), (2) and (3) is one or a mixture of two of water, methanol, ethanol, acetonitrile and dimethyl sulfoxide.
An application of a nitrogen heterocyclic ring transition metal copper complex containing a benzotriazole ring in inhibiting DPPH free radicals.
An application of a nitrogen heterocyclic transition metal copper complex containing a benzotriazole ring in preparing an antioxidant drug.
The preparation method of the ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) can be seen in the invention name: a nitrogen heterocyclic ring transition metal copper complex containing a plurality of coordination sites, a preparation method and application thereof (application number: CN 2016105551014).
The invention has the beneficial effects that:
1. the invention takes 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) as a ligand to react with copper chloride to prepare the nitrogen heterocyclic transition metal copper complex, the complex is a mononuclear complex, copper ions are four-coordinated and are respectively coordinated with two nitrogen atoms and two chlorine ions on two ligands 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and the problem of combination of an asymmetric nitrogen heterocyclic compound serving as a ligand and transition metal copper ions is effectively solved.
2. The nitrogen heterocyclic transition metal copper complex prepared by the invention, namely the 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) copper complex has stronger scavenging action on DPPH free radicals, which is far higher than that of the 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) used alone on DPPH free radicals, and is stronger than that of common antioxidant vitamin E under certain low concentration. The result shows that the nitrogen heterocyclic ring transition metal copper complex has good antioxidation and is an innovation on antioxidant medicines.
3. The preparation method is simple, convenient to operate, low in production cost, easy to popularize technologically and good in social and economic benefits.
Drawings
FIG. 1 shows a complex [ Cu (C) ]15H13N5)2Cl2]Structural unit diagram (2).
FIG. 2 shows a complex [ Cu (C) ]15H13N5)2Cl2]The stacked graph of (1).
Detailed Description
The following examples further illustrate the embodiments of the present invention in detail.
Example 1
A nitrogen heterocyclic ring transition metal copper complex containing a benzotriazole ring comprises the following steps:
(1) accurately weighing 0.02mmol of copper chloride, and dissolving in 4mL of methanol to obtain a copper salt solution;
(2) accurately weighing 0.02mmol of ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and dissolving in 4mL of methanol to obtain a ligand solution;
(3) adding the ligand solution into the copper salt solution, uniformly mixing, filtering, adding methanol into the filtrate to 14mL, and standing at room temperature until a green rectangular crystal is precipitated, thus obtaining the ligand.
The experimental conditions and results of the X-ray single crystal diffraction structure of the complex of the invention are as follows:
selecting a single crystal sample with better crystal form, carrying out an X-ray diffraction experiment on an Xcaliibur, Gemini CCD single crystal diffractometer, and adopting Mo-k α ray position monochromized by a graphite monochromator
As a diffraction light source, diffraction points were collected in an omega-2 theta scanning manner. The crystal structure is solved by a direct method, the crystal structure is expanded by a Fourier technology, correction is carried out according to anisotropy, finally a full matrix least square method is adopted for correction to obtain unit cell parameters, and single crystal data are solved by a difference Fourier electron density map by a SHELX-97 direct method.
The single crystal structure of the prepared nitrogen heterocyclic transition metal copper complex is shown in figures 1 and 2, the complex belongs to a triclinic system, P-1 space group and unit cell parameter a is
b is
c is
α is 107.817(7) ° β is 98.259(6) ° gamma is 92.472(6) ° and volume V is
Z is 1 and the density is 1.231Mg m-3Theta is 3.8900to 25.8290 DEG, the limiting factors are-11-h 11, -12-k 8, -12-l 13, F (000) 339, R1＝0.0439，wR20.1277. The element content is according to C30H26N10Cl2Cu (%), theoretical value (%): c50.45; h3.67; n23.54; experimental values (%): c50.20; h3.69; and N23.63.
Infrared Spectrum (cm)-1，KBr)：3420(s)，2408(m),2072(w),1910(w),1673(s),1603(w),1586(w),1508(m),1485(w),1452(m),1398(s),1320(s),1291(s),1162(w),1100(w)，1074(w)，934(w),800(w),779(w),769(w),751(m),716(s),686(w),665(w),618(w),593(w)，528(s),419(w)。
Example 2
A nitrogen heterocyclic ring transition metal copper complex containing a benzotriazole ring comprises the following steps:
(1) accurately weighing 0.03mmol of copper chloride, and dissolving in 4mL of water to obtain a copper salt solution;
(2) accurately weighing 0.03mmol of ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and dissolving in 6mL of methanol to obtain a ligand solution;
(3) adding the ligand solution into the copper salt solution, uniformly mixing, filtering, adding ethanol into the filtrate to 16mL, and standing at room temperature until a green rectangular crystal is precipitated, thus obtaining the ligand.
The single crystal structure of the prepared nitrogen heterocyclic transition metal copper complex is shown in figures 1 and 2, the complex belongs to a triclinic system, P-1 space group and unit cell parameter a is
b is
c is
α is 107.817(7) ° β is 98.259(6) ° gamma is 92.472(6) ° and volume V is
Z is 1 and the density is 1.231Mg m-3Theta is 3.8900to 25.8290 DEG, the limiting factors are-11-h 11, -12-k 8, -12-l 13, F (000) 339, R1＝0.0439，wR20.1277. The element content is according to C30H26N10Cl2Cu (%), theoretical value (%): c50.45; h3.67; n23.54; experimental values (%): c50.20; h3.69; and N23.63.
Infrared Spectrum (cm)-1，KBr)：3420(s)，2408(m),2072(w),1910(w),1673(s),1603(w),1586(w),1508(m),1485(w),1452(m),1398(s),1320(s),1291(s),1162(w),1100(w)，1074(w)，934(w),800(w),779(w),769(w),751(m),716(s),686(w),665(w),618(w),593(w)，528(s),419(w)。
Example 3
A nitrogen heterocyclic ring transition metal copper complex containing a benzotriazole ring comprises the following steps:
(1) accurately weighing 0.04mmol of copper chloride, and dissolving the copper chloride in a mixed solution of 4mL of methanol and 2mL of water to obtain a copper salt solution;
(2) accurately weighing 0.04mmol of ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and dissolving the ligand in a mixed solution of 4mL of methanol and 2mL of acetonitrile to obtain a ligand solution;
(3) adding the ligand solution into the copper salt solution, uniformly mixing, filtering, adding dimethyl sulfoxide into the filtrate to 18mL, standing at room temperature until a green rectangular crystal is precipitated, and thus obtaining the product.
The single crystal structure of the prepared nitrogen heterocyclic transition metal copper complex is shown in figures 1 and 2, the complex belongs to a triclinic system, P-1 space group and unit cell parameter a is
b is
c is
α is 107.817(7) ° β is 98.259(6) ° gamma is 92.472(6) ° and volume V is
Z is 1 and the density is 1.231Mg m-3Theta is 3.8900to 25.8290 DEG, the limiting factors are-11-h 11, -12-k 8, -12-l 13, F (000) 339, R1＝0.0439，wR20.1277. The element content is according to C30H26N10Cl2Cu (%), theoretical value (%): c50.45; h3.67; n23.54; experimental values (%): c50.20; h3.69; and N23.63.
Infrared Spectrum (cm)-1，KBr)：3420(s)，2408(m),2072(w),1910(w),1673(s),1603(w),1586(w),1508(m),1485(w),1452(m),1398(s),1320(s),1291(s),1162(w),1100(w)，1074(w)，934(w),800(w),779(w),769(w),751(m),716(s),686(w),665(w),618(w),593(w)，528(s),419(w)。
Examples of the experiments
The nitrogen heterocyclic transition metal copper complex is used for inhibiting DPPH free radicals, and the inhibition rate determination method comprises the following steps:
1. reagent preparation
Preparation of DPPH radical solution: the DPPH radical was precisely weighed to 0.0039g by a balance, and then 100mL was made by absolute ethanol to prepare a DPPH radical solution having a concentration of 0.1 mmol/L.
2. Taking 12 penicillin bottles, adding 2mL of 0.1mmol/L DPPH free radical solution, and adding 2mL of the following reagents according to the setting:
penicillin bottles 1, 2 and 3: 0.05mg/mL, 0.5mg/mL and 5mg/mL vitamin E2 mL
Penicillin bottles 4, 5 and 6: 0.05mg/mL, 0.5mg/mL, and 5mg/mL of the azacyclo transition metal copper complex of the present invention 2mL
Penicillin bottles 7, 8 and 9: 0.05mg/mL, 0.5mg/mL, and 5mg/mL CuCl22mL
Penicillin bottles 10, 11, 12: 0.05mg/mL, 0.5mg/mL, and 5mg/mL of 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) 2 mL;
mixing, standing at room temperature in dark for 0.5h, measuring absorbance at 517nm with ultraviolet spectrophotometer, measuring absorbance values for 3 times, and taking average value as Ai(the absorbance was corrected for a blank before the absorbance was measured).
The clearance was calculated according to the following formula:
P＝[1-(Ai-Aj)/Ac]×100％
note: a. thecReplacing the sample with a solvent (DMF: water volume ratio 1:9)
AjReplacement of DPPH radical solution by absolute ethanol
The DPPH free radical inhibitory activity of the complexes of the invention is shown in the following table:
inhibition of DPPH free radical by compounds of different concentrations
Note: a. thec＝0.564
From the determination result of the in vitro antioxidant activity experiment, CuCl2Has certain inhibition effect on DPPH free radicals and is almost the same as the nitrogen heterocyclic ring transition metal copper complex, but the experiment measures the mass concentration of CuCl under the same mass concentration in terms of the mass concentration of the substance alone2The quantity concentration of the substance is far greater than that of the nitrogen heterocyclic transition metal copper complex, so that the scavenging effect of the nitrogen heterocyclic transition metal copper complex with the same quantity concentration on DPPH free radicals is greater than that of CuCl2In (1). The nitrogen heterocyclic ring transition metal copper complex has stronger inhibition effect on DPPH free radicals and is stronger than common antioxidant vitamin E under certain low concentration. And the test solution only containing 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) has obviously weaker inhibition effect on DPPH free radicals, and is lower than not only nitrogen heterocyclic transition metal copper complexes but also vitamin E. This shows that the nitrogen heterocyclic ring transition metal copper complex synthesized by the invention has great superiority only in view of in vitro antioxidant activity. Based on the complex, the complex can be further researched for pharmacological and physiological activities.
Claims (5)
1. The application of the nitrogen heterocyclic transition metal copper complex containing the benzotriazole ring in the preparation of the DPPH free radical inhibiting medicine is characterized in that the nitrogen heterocyclic transition metal copper complex is a 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole) copper complex, and the molecular formula is [ Cu (C)15H13N5)2Cl2](ii) a Wherein, C15H13N5Is ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and the molecular structural formula is as follows:
the nitrogen heterocyclic ring transition metal copper complex belongs to a triclinic crystal systemP-1 space group, unit cell parameters a of 9.0231(6) Å, b of 9.6883(8) Å, C of 10.8754(7) Å of 107.817(7) ° C of β of 98.259(6) ° C of 92.472(6) ° C, and element content as C30H26N10Cl2Cu (%), theoretical value (%): c50.45; h3.67; n23.54; experimental values (%): c50.20; h3.69; and N23.63.
2. The use according to claim 1, wherein said azacyclo transition metal copper complex has an infrared spectrum (cm)-1，KBr）：3420（s），2408（m）,2072（w）,1910（w）,1673（s）,1603（w）,1586（w）,1508（m）,1485（w）,1452（m）,1398（s）,1320（s）,1291（s）,1162（w）,1100（w），1074（w），934（w）,800（w）,779（w）,769（w）,751（m）,716（s）,686（w）,665（w）,618（w）,593（w），528（s）,419（w）。
3. The use according to claim 1, wherein the preparation method of the nitrogen heterocyclic transition metal copper complex comprises the following steps:
(1) accurately weighing 0.02-0.04mmol of copper chloride, and dissolving in 4-6mL of solvent to obtain copper salt solution;
(2) accurately weighing 0.02-0.04mmol of ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and dissolving in 4-6mL of solvent to obtain a ligand solution;
(3) adding the ligand solution into the copper salt solution, uniformly mixing, filtering, adding a solvent into the filtrate to 14-18mL, and standing at room temperature until a green rectangular crystal is precipitated, thus obtaining the ligand.
4. The use according to claim 3, wherein the solvent of steps (1), (2) and (3) is one or a mixture of two of water, methanol, ethanol, acetonitrile and dimethyl sulfoxide.
5. The use according to claim 4, wherein the preparation method of the nitrogen heterocyclic transition metal copper complex comprises the following steps:
(1) accurately weighing 0.02mmol of copper chloride, and dissolving in 4mL of methanol to obtain a copper salt solution;
(2) accurately weighing 0.02mmol of ligand 1- (benzotriazole-1-methyl) -1- (2-methylbenzimidazole), and dissolving in 4mL of methanol to obtain a ligand solution;
(3) adding the ligand solution into the copper salt solution, uniformly mixing, filtering, adding methanol into the filtrate to 14mL, and standing at room temperature until a green rectangular crystal is precipitated, thus obtaining the ligand.
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