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.
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.