CN104311604A - Metal cobalt compound as well as preparation method and application thereof - Google Patents

Metal cobalt compound as well as preparation method and application thereof Download PDF

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Publication number
CN104311604A
CN104311604A CN201410520605.3A CN201410520605A CN104311604A CN 104311604 A CN104311604 A CN 104311604A CN 201410520605 A CN201410520605 A CN 201410520605A CN 104311604 A CN104311604 A CN 104311604A
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pyridyl
title complex
cobalt metal
metal title
reduced pressure
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CN104311604B (en
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霍丽妮
陈睿
黄富平
李培源
苏炜
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Jiaxing Zhuoshi Biotechnology Co ltd
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Guangxi University of Chinese Medicine
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/06Cobalt compounds
    • C07F15/065Cobalt compounds without a metal-carbon linkage

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  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a metal cobalt compound as well as a preparation method and an application thereof. The structural formula of the metal cobalt compound is as follows: the chemical name is di(3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazolyl) dihydroxy-benzoic cobalt (II), the molecular formula is C38H28CoN10O6, and the relative molecular weight is 779.63. The method for preparing the metal cobalt compound is high in synthesis rate; and moreover, the metal cobalt compound can be used for preparing antibacterial agents, and the prepared antibacterial agents are high in sterilization property and high in sterilization rate.

Description

A kind of cobalt metal title complex and its preparation method and application
Technical field
The present invention relates to technical field of medical chemistry, be specifically related to a kind of cobalt metal title complex and preparation method thereof, and it is preparing the application in medicine.
Background technology
Metal complexes is not only the important research object of inorganic chemistry, structural chemistry, also receives the concern of people because having the wide biological activitys such as anticancer, sterilization, anti-inflammatory.Cobalt is bioelement very important in life science, and cobalt complex all has potential using value at the numerous areas such as chemical, biological, medical.Experiment shows, cobalt complex is to Pseudomonas aeruginosa, and streptococcus aureus, sarcina and intestinal bacteria all have stronger bacteriostasis property.And in existing numerous heterogeneous ring compound, 1,2,4-triazole derivative due to the biological activity of its wide spectrum and wide application prospect always quite by the favor of people.This heterocyclic compounds mostly has sterilization, antimycotic isoreactivity.Therefore the present invention first with 3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazoles and P-hydroxybenzoic acid for part, synthesizing new cobalt metal title complex.
Summary of the invention
An object of the present invention is to provide a kind of cobalt metal title complex.Another object is to provide a kind of high method of synthetic ratio to prepare this cobalt metal title complex, and this cobalt metal title complex can be applied in preparation antibacterials, makes the antibacterials be prepared into have stronger bactericidal properties and higher sterilizing rate.
In order to solve the problems of the technologies described above, the invention provides a kind of cobalt metal title complex and its preparation method and application.
That the step preparing cobalt metal title complex comprises as follows:
1) by nicotinic acid in SOCl 2middle reflux stirs 4-5 hour, after solvent evaporated under reduced pressure, gained white solid is dissolved in chloroform, reflux after adding Isoniazid 5-6 hour, after solvent evaporated under reduced pressure, gained material ethyl alcohol recrystallization obtains 3-pyridyl-4-than pyridine base imines, and products therefrom is dissolved in ethanolic soln, last under Glacial acetic acid catalysis, with hydrazine hydrate ring closure reaction, backflow 8h, after solvent evaporated under reduced pressure, gained crude product chloroform or recrystallizing methanol obtain part two (3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole;
2) with two 3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole and P-hydroxybenzoic acid are that part and Cobaltous diacetate carry out capping at the temperature of 120-200 DEG C, reddish-orange crystals is had to be formed after 48-72h, be accredited as target product through X-single crystal diffraction, this target product is cobalt metal title complex of the present invention.
Preferably, described step 2) capping be heating and pressurizing sealed reaction in autoclave.
The structural formula of the cobalt metal title complex of the present invention be prepared into by aforesaid method is:
The chemical name of this cobalt metal title complex is: two (3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazolyls) resorcylic acid closes cobalt (II);
The molecular formula of this cobalt metal title complex is: C 38h 28coN 10o 6;
The relative molecular weight of this cobalt metal title complex is: 779.63.
This cobalt metal title complex can be applied in preparation antibacterials, such as makes one or more antimicrobials in injection, tablet, pill, capsule, suspension agent or emulsion.
Beneficial effect of the present invention: cobalt metal title complex of the present invention has more stable anti-microbial activity and using value, and preparation method's synthetic ratio of the present invention is high, byproduct is few, can effectively be applied in preparation antibacterials, and very high inhibition effect can be produced to intestinal bacteria, streptococcus aureus, subtilis, aerogenesis folder film bacillus, Pseudomonas aeruginosa etc., reach very high sterilizing rate.
Accompanying drawing explanation
Fig. 1 is the method route schematic diagram that the present invention prepares described cobalt metal title complex;
Fig. 2 is the x-ray crystal structure schematic diagram consistent with the crystalline structure of cobalt metal title complex of the present invention, and the atom do not marked in Fig. 2 is carbon atom C or hydrogen atom H.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, can implement according to this with reference to specification sheets word to make those skilled in the art.
Embodiment 1
Fig. 1 is the method route schematic diagram that the present invention prepares described cobalt metal title complex.Composition graphs 1, the preparation method of cobalt metal title complex of the present invention comprises following concrete steps:
1) 1.23g or 10mmol nicotinic acid is placed in 30ml SOCl2 reflux and stirs 5 hours, solvent evaporated under reduced pressure, obtain the nicotinoyl chlorine of white solid, product is dissolved in 30ml chloroform without separation, continue backflow after adding 1.22g or 10mmol Isoniazid 5 hours, after solvent evaporated under reduced pressure, gained material ethyl alcohol recrystallization obtains 0.72g3-pyridyl-4-than pyridine base imines; Products therefrom is dissolved in 30ml ethanolic soln, add 3-4 successively and drip Glacial acetic acid and 3ml hydrazine hydrate, under Glacial acetic acid catalysis, with hydrazine hydrate ring closure reaction, backflow 8h, after solvent evaporated under reduced pressure, gained crude product chloroform or recrystallizing methanol can obtain part two (3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole, the total recovery that this step obtains part can reach 32%;
2) by 0.11g or 0.5mmol3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole and 0.069g or 0.5mmol P-hydroxybenzoic acid are that part and 0.25g or 1mmol Cobaltous diacetate carry out capping at 160 DEG C, reddish-orange crystals is had to be formed after 72h, target product is accredited as through X-single crystal diffraction, this target product is cobalt metal title complex of the present invention, chemical name is two (3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazolyl) resorcylic acid conjunction cobalt (II), its molecular formula is C 38h 28coN 10o 6, its relative molecular weight is 779.63.
Below target product X ray crystal structure to be measured: choose monocrystalline that size is about 0.40mm × 0.20mm × 0.12mm and be placed on Brucker SMART 1000CCD X-ray single crystal diffractometer and carry out diffraction, with the Mo K alpha-ray through graphite monochromator monochromatization for incident wavelength, collect diffraction data 10129 with ω/2 scan mode in the scope of 3.01 ° to 25.24 °, wherein 3264 is independent point (R (int)=0.0892).All data all corrects through Lp Summing Factor empirical absorption.Adopt SHELXS-97 program to be solved by direct method, obtain its structure iron as shown in Figure 2, its structure is consistent with target product.
The above-mentioned cobalt metal title complex be prepared into is made antibacterial entry needle, and carries out bacteriostatic test according to GB15979-2002, antibacterial entry needle plays very strong bactericidal properties to intestinal bacteria, streptococcus aureus, subtilis, and sterilizing rate reaches more than 99%; Play certain bactericidal properties to aerogenesis folder film bacillus and Pseudomonas aeruginosa, sterilizing rate reaches 80-90%.
Embodiment 2
Fig. 1 is the method route schematic diagram that the present invention prepares described cobalt metal title complex.Composition graphs 1, the preparation method of cobalt metal title complex of the present invention comprises following concrete steps:
1) 2.46g nicotinic acid reflux in 60ml SOCl2 is stirred 4 hours, after solvent evaporated under reduced pressure, gained white solid is dissolved in 60ml chloroform, reflux 6 hours after adding 2.44g Isoniazid, after solvent evaporated under reduced pressure, gained material ethyl alcohol recrystallization obtains 1.41g3-pyridyl-4-than pyridine base imines, and by products therefrom in 60ml ethanolic soln, last under Glacial acetic acid catalysis, with 6ml hydrazine hydrate ring closure reaction, backflow 8h, after solvent evaporated under reduced pressure, gained crude product recrystallizing methanol obtains part two (3-(4-is than pyridine base)-5-(3-pyridyl)-1, 2, 4-triazole, the total recovery that this step obtains part can reach 31%,
2) with 0.22g bis-3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole and 0.138g P-hydroxybenzoic acid are that part and 0.5g Cobaltous diacetate carry out capping at the temperature of 120 DEG C, there is reddish-orange crystals to be formed after 48h, be accredited as target product through X-single crystal diffraction.This target product is cobalt metal title complex of the present invention, and its chemical name is that two (3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazolyls) resorcylic acid closes cobalt (II), and its molecular formula is C 38h 28coN 10o 6, its relative molecular weight is 779.63.
Below target product X ray crystal structure to be measured: choose monocrystalline that size is about 0.40mm × 0.20mm × 0.12mm and be placed on Brucker SMART 1000CCD X-ray single crystal diffractometer and carry out diffraction, with the Mo K alpha-ray through graphite monochromator monochromatization for incident wavelength, collect diffraction data 10129 with ω/2 scan mode in the scope of 3.01 ° to 25.24 °, wherein 3264 is independent point (R (int)=0.0892).All data all corrects through Lp Summing Factor empirical absorption.Adopt SHELXS-97 program to be solved by direct method, obtain its structure iron as shown in Figure 2, its structure is consistent with target product.
The above-mentioned cobalt metal title complex be prepared into is made the medicines such as antibacterial tablet, pill, capsule, suspension agent or emulsion, and carry out bacteriostatic test according to GB15979-2002, medicine plays very strong bactericidal properties to intestinal bacteria, streptococcus aureus, subtilis, and sterilizing rate reaches more than 95%; Play certain bactericidal properties to aerogenesis folder film bacillus and Pseudomonas aeruginosa, sterilizing rate reaches 75-88%.
Embodiment 3
Fig. 1 is the method route schematic diagram that the present invention prepares described cobalt metal title complex.Composition graphs 1, the preparation method of cobalt metal title complex of the present invention comprises following concrete steps:
1) 1.23g or 10mmol nicotinic acid is placed in 30mlSOCl 2middle reflux stirs 5 hours, solvent evaporated under reduced pressure, obtain the nicotinoyl chlorine of white solid, product is dissolved in 30ml chloroform without separation, continue backflow after adding 1.22g or 10mmol Isoniazid 6 hours, after solvent evaporated under reduced pressure, gained material ethyl alcohol recrystallization obtains 0.78g 3-pyridyl-4-than pyridine base imines; Products therefrom is dissolved in 30ml ethanolic soln, add 3-4 successively and drip Glacial acetic acid and 3ml hydrazine hydrate, under Glacial acetic acid catalysis, with hydrazine hydrate ring closure reaction, backflow 8h, after solvent evaporated under reduced pressure, gained crude product chloroform or recrystallizing methanol can obtain part two (3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole, the total recovery that this step obtains part can reach 35%;
2) by 0.15g or 0.55mmol3-(4-pyridyl)-5-(3-pyridyl)-1, 2, 4-triazole and 0.069g or 0.5mmol P-hydroxybenzoic acid are that part and 0.25g or 1mmol Cobaltous diacetate are placed in autoclave heating and pressurizing sealed reaction at 120 DEG C, reddish-orange crystals is had to be formed after 68h, target product is accredited as through X-single crystal diffraction, this target product is cobalt metal title complex of the present invention, chemical name is two (3-(4-is than pyridine base)-5-(3-pyridyl)-1, 2, 4-triazolyl) resorcylic acid conjunction cobalt (II), its molecular formula is C 38h 28coN 10o 6, its relative molecular weight is 779.63.
Below target product X ray crystal structure to be measured: choose monocrystalline that size is about 0.40mm × 0.20mm × 0.12mm and be placed on Brucker SMART 1000CCD X-ray single crystal diffractometer and carry out diffraction, with the Mo K alpha-ray through graphite monochromator monochromatization for incident wavelength, collect diffraction data 10129 with ω/2 scan mode in the scope of 3.01 ° to 25.24 °, wherein 3264 is independent point (R (int)=0.0892).All data all corrects through Lp Summing Factor empirical absorption.Adopt SHELXS-97 program to be solved by direct method, obtain its structure iron as shown in Figure 2, its structure is consistent with target product.
The above-mentioned cobalt metal title complex be prepared into is made antibacterial entry needle, and carry out bacteriostatic test according to GB 15979-2002, antibacterial entry needle plays very strong bactericidal properties to intestinal bacteria, streptococcus aureus, subtilis, and sterilizing rate reaches more than 99%; Play certain bactericidal properties to aerogenesis folder film bacillus and Pseudomonas aeruginosa, sterilizing rate reaches 80-90%.
Show from the above results, cobalt metal title complex of the present invention has very strong anti-microbial activity, all have very strong bactericidal properties with the antimicrobial that this cobalt metal complex preparation becomes to harmful bacterias such as intestinal bacteria, streptococcus aureus, subtilis, Pseudomonas aeruginosas, the present invention is that the new antibacterials of research and development provide new thinking.
Although embodiment of the present invention are open as above, but it is not restricted to listed in specification sheets and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details.

Claims (4)

1. a cobalt metal title complex, is characterized in that: the structural formula of described cobalt metal title complex is:
The chemical name of described cobalt metal title complex is: two (3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazolyls) resorcylic acid closes cobalt (II);
The molecular formula of described cobalt metal title complex is: C 38h 28coN 10o 6;
The relative molecular weight of described cobalt metal title complex is: 779.63.
2. prepare a method for cobalt metal title complex as claimed in claim 1, it is characterized in that, described method comprises the steps:
1) by nicotinic acid in SOCl 2middle reflux stirs 4-5 hour, after solvent evaporated under reduced pressure, gained white solid is dissolved in chloroform, reflux after adding Isoniazid 5-6 hour, after solvent evaporated under reduced pressure, gained material ethyl alcohol recrystallization obtains 3-pyridyl-4-pyridyl imines, and products therefrom is dissolved in ethanolic soln, last under Glacial acetic acid catalysis, with hydrazine hydrate ring closure reaction, backflow 8h, after solvent evaporated under reduced pressure, gained crude product chloroform or recrystallizing methanol obtain part two (3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole;
2) with two 3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole and P-hydroxybenzoic acid are that part and Cobaltous diacetate carry out capping at the temperature of 120-200 DEG C, have reddish-orange crystals to be formed, be accredited as target product through X-single crystal diffraction after 48-72h.
3. method according to claim 2, is characterized in that, described step 2) capping be heating and pressurizing sealed reaction in autoclave.
4. the application of cobalt metal title complex as claimed in claim 1 in preparation antibacterials.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108299515A (en) * 2018-03-15 2018-07-20 南阳师范学院 Cobalt complex and its preparation method and application with reversible thermochromic characteristic

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059011A (en) * 2013-01-22 2013-04-24 山东师范大学 Three metal organic frames based on Co(II) ion as well as synthesis method and application thereof
CN103724377A (en) * 2014-01-10 2014-04-16 中国科学院化学研究所 2,6-diene amine pyridine binuclear cobalt complex catalyst as well as preparation method and application thereof
CN103804419A (en) * 2014-03-13 2014-05-21 山东理工大学 2-(4-bromophenyl) quinoline-4-formic acid complex and preparation method and application thereof
CN103923126A (en) * 2014-03-26 2014-07-16 合肥学院 Dikaryotic cobalt complex and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059011A (en) * 2013-01-22 2013-04-24 山东师范大学 Three metal organic frames based on Co(II) ion as well as synthesis method and application thereof
CN103724377A (en) * 2014-01-10 2014-04-16 中国科学院化学研究所 2,6-diene amine pyridine binuclear cobalt complex catalyst as well as preparation method and application thereof
CN103804419A (en) * 2014-03-13 2014-05-21 山东理工大学 2-(4-bromophenyl) quinoline-4-formic acid complex and preparation method and application thereof
CN103923126A (en) * 2014-03-26 2014-07-16 合肥学院 Dikaryotic cobalt complex and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108299515A (en) * 2018-03-15 2018-07-20 南阳师范学院 Cobalt complex and its preparation method and application with reversible thermochromic characteristic
CN108299515B (en) * 2018-03-15 2020-04-17 南阳师范学院 Cobalt complex with reversible thermochromism characteristic and preparation method and application thereof

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