CN106220556B - A kind of melbine pyridinedicarboxylic acid closes Cr (III) complex and preparation method - Google Patents
A kind of melbine pyridinedicarboxylic acid closes Cr (III) complex and preparation method Download PDFInfo
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- CN106220556B CN106220556B CN201610580439.5A CN201610580439A CN106220556B CN 106220556 B CN106220556 B CN 106220556B CN 201610580439 A CN201610580439 A CN 201610580439A CN 106220556 B CN106220556 B CN 106220556B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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Abstract
The present invention provides a kind of melbine pyridinedicarboxylic acids to close Cr (III) complex and preparation method thereof.Specific steps include: by pyridinedicarboxylic acid, sodium hydroxide, Metformin hydrochloride is 2:5:1 ratio organic solvent stirring and dissolving in feed ratio, Cr (III) salting liquid is slowly added dropwise during low-grade fever, after being added dropwise, is heated to reflux 30-60min, stop reaction, 12h, filtering are stood, it is that melbine pyridinedicarboxylic acid closes Cr (III) complex that filtrate, which places a large amount of aubergine single crystal product articles of two weeks precipitation,.The present invention have it is easy to operate, product is easily separated, purity is high, it is at low cost the advantages that.
Description
Technical field
The invention belongs to metal complex and preparation method thereof technical fields, and in particular to a kind of melbine pyridine two
Formic acid closes Cr (III) complex and preparation method.
Background technique
Diabetes have been increasingly becoming global epidemic disease, and the lethality of disabling of superelevation makes global common pass
One of major disease of note, the World Health Organization are even more to be referred to as " disaster of 21 century ".Therefore, diabetes are prevented and treated
Have become the hot spot of researcher.According to related research, Cr (III) complex is during treating type-2 diabetes mellitus
Show important function, the metabolism that Cr (III) ion has enhancing insulin, promotes sugar, protein and lipid.To glycosuria
Patient, which supplements appropriate Cr (III), can enhance the effect of insulin, and the impaired glucose tolerance factor of sustained release human body reduces blood glucose water
Gentle serum cholesterol levels.Currently, although chromium supplementing agent available on the market has had compared with multiple types, there is it not
Same disadvantage, such as: chromium picolinate is current the most salable nutrition chromium supplementing agent, but related document report in the recent period, pyridine first
The disadvantages of sour chromium, which exists, may cause chromosome damage, and the mutation of DNA and induction cancer occur, its use gradually causes people
Query.Therefore synthesizing efficient, low toxicity, novel organic C r (III) complex easily absorbed are of great significance.
2,6- pyridinedicarboxylic acid is used as the competitive inhibitor of beef liver glutamte dehydrogenase.Melbine is anti-because of it
Blood glucose effect is obvious, side effect is smaller and is the effective medicine for treating diabetes B (T2D) without the features such as hypoglycemia acts on is generated
Object, also, this complex significantly reduces the electropositive of Cr (III) ion, played in complicated physiological environment stable chromium from
The effect of son increases absorption of the human body to chromium, while also improving 2, and the biology of 6- pyridinedicarboxylic acid and melbine itself is living
Sexuality enhances its hypoglycemic anti-obesity activity.This has research and development two generations agent containing chromium nutrition, popularization the chromium nutrition of practical application value
Growing number of obesity and diabetes cases have a very important significance at present for agent and containment.
Summary of the invention
Present invention aim to address existing organic C r (III) complex, there are inefficient, toxicity is big and is not easy to absorb
Technical problem provides a kind of melbine pyridinedicarboxylic acid and closes Cr (III) complex and preparation method.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of melbine pyridinedicarboxylic acid conjunction Cr (III) complex, structural formula are as follows:
A method of it preparing the melbine pyridinedicarboxylic acid and closes Cr (III) complex, include the following steps:
1) organic solvent is added in the ratio that pyridinedicarboxylic acid, sodium hydroxide, Metformin hydrochloride are 2:5:1 in molar ratio
In, in 35-40 DEG C of at a temperature of stirring and dissolving, the organic solvent is pyridinedicarboxylic acid, sodium hydroxide, Metformin hydrochloride are mixed
10-15 times for closing object product；
2) Cr (III) salt is dissolved in methanol according to Cr (III) salt, the ratio that methanol molar ratio is 1:5-10, and by Cr
(III) salting liquid is slowly added drop-wise in the solution in step 1), is heated to reflux 30-60min, stops reaction, stands 12h, is filtered,
Obtain red filtrate；
3) red filtrate is placed at room temperature, is protected from light, volatilized naturally two weeks, obtaining aubergine crystal is melbine
Change pyridinedicarboxylic acid and closes Cr (III) complex.
The organic solvent is the mixture of water and methanol, and the molar ratio of water and methanol is 1:1-2.
Cr (III) salt is any one in chromium chloride, chromic nitrate or chromium sulfate.
The invention adopts the above technical scheme, provides a kind of new Cr (III) complex, makes full use of the product of trivalent chromium
Pole effect, in combination with pyridinedicarboxylic acid and the distinctive pharmaceutical activity of Metformin hydrochloride itself, complex should be had concurrently such as drop
The multiple effects such as sugar, weight-reducing, antibacterial.It is expected that the complex can be used widely in hypoglycemic slimming medicine.
Detailed description of the invention
Fig. 1 is the crystal structure of Cr of the present invention (III) complex；
Fig. 2 is the uv-visible absorption spectra of pyridinedicarboxylic acid, melbine and complex.
Specific embodiment
Embodiment 1
One of the present embodiment melbine pyridinedicarboxylic acid closes Cr (III) complex, structural formula are as follows:
A method of it preparing melbine pyridinedicarboxylic acid described in the present embodiment and closes Cr (III) complex, including such as
Lower step:
1) organic solvent is added in the ratio that pyridinedicarboxylic acid, sodium hydroxide, Metformin hydrochloride are 2:5:1 in molar ratio
In, in 35 DEG C of at a temperature of stirring and dissolving, the organic solvent is the mixture of water and methanol with molar ratio for 1:1, Shui Hejia
Alcohol mixture is pyridinedicarboxylic acid, sodium hydroxide, 10 times of Metformin hydrochloride volume of mixture；
2) chromium chloride is dissolved in methanol according to chromium chloride, the ratio that methanol molar ratio is 1:5, and chromium chloride solution is slow
Slowly it is added drop-wise in the solution in step 1), is heated to reflux 30min, stop reaction, stand 12h, filtering obtains red filtrate；
3) red filtrate is placed at room temperature, is protected from light, volatilized naturally two weeks, obtaining aubergine crystal is melbine
Change pyridinedicarboxylic acid and closes Cr (III) complex.
Embodiment 2
Melbine pyridinedicarboxylic acid in the present embodiment closes in the structural formula and embodiment 1 of Cr (III) complex
It is identical.
A method of it preparing melbine pyridinedicarboxylic acid described in the present embodiment and closes Cr (III) complex, including such as
Lower step:
1) organic solvent is added in the ratio that pyridinedicarboxylic acid, sodium hydroxide, Metformin hydrochloride are 2:5:1 in molar ratio
In, in 40 DEG C of at a temperature of stirring and dissolving, the organic solvent is the mixture of water and methanol with molar ratio for 1:2, Shui Hejia
Alcohol mixture is pyridinedicarboxylic acid, sodium hydroxide, 15 times of Metformin hydrochloride volume of mixture；
2) chromium chloride is dissolved in methanol according to chromium chloride, the ratio that methanol molar ratio is 1:10, and by chromium chloride solution
It is slowly added drop-wise in the solution in step 1), is heated to reflux 60min, stop reaction, stand 12h, filtering obtains red filtrate；
3) red filtrate is placed at room temperature, is protected from light, volatilized naturally two weeks, obtaining aubergine crystal is melbine
Change pyridinedicarboxylic acid and closes Cr (III) complex.
Embodiment 3
Melbine pyridinedicarboxylic acid in the present embodiment closes in the structural formula and embodiment 1 of Cr (III) complex
It is identical.
A method of it preparing melbine pyridinedicarboxylic acid described in the present embodiment and closes Cr (III) complex, including such as
Lower step:
1) organic solvent is added in the ratio that pyridinedicarboxylic acid, sodium hydroxide, Metformin hydrochloride are 2:5:1 in molar ratio
In, in 38 DEG C of at a temperature of stirring and dissolving, the organic solvent is the mixture of water and methanol with molar ratio for 1:1.5, water and
Carbinol mixture is pyridinedicarboxylic acid, sodium hydroxide, 12 times of Metformin hydrochloride volume of mixture；
2) chromium chloride is dissolved in methanol according to chromium chloride, the ratio that methanol molar ratio is 1:7, and chromium chloride solution is slow
Slowly it is added drop-wise in the solution in step 1), is heated to reflux 50min, stop reaction, stand 12h, filtering obtains red filtrate；
3) red filtrate is placed at room temperature, is protected from light, volatilized naturally two weeks, obtaining aubergine crystal is melbine
Change pyridinedicarboxylic acid and closes Cr (III) complex.
Chromium chloride in above-described embodiment can also be replaced with the Cr such as chromic nitrate, chromium sulfate (III) salt.
Melbine pyridinedicarboxylic acid prepared in the above embodiments closes Cr (III) complex crystal measurement result (see attached
Fig. 1): complex molecule formula is C18H18Cr N7O8, molecular weight 512.39, crystal structure is monoclinic system, and space group is
P2(1)/n.Cell parameter: a=7.9044 (6), b=12.0899 (11), α=90.00, β=
90.7280 (10), γ=90.00 °,Z=4.Entire molecular structure by 2 pyridinedicarboxylic acid roots and
1 melbine molecule is constituted.
Determination of elemental analysis is as a result, by molecular formula C18H18Cr N7O8, theoretical value (%): C, 42.19；H,3.54；N:
19.14 experiment values (%): C, 42.55；H,3.45；N:19.08.
Uv-visible absorption spectra (see attached drawing 2): pyridinedicarboxylic acid have at 270nm characteristic absorption peak (curve a), with
Cr3+π-the π of its phenyl ring after coordination*To 262nm, (curve c) illustrates electron cloud in pi-conjugated system to Cr to absorption peak blue shift3+'s
Empty d track shifts；And melbine has characteristic absorption peak (curve b), as ion balance to entire cooperation at 238nm
The UV absorption of object influences little；Complex is attributed to Cr in complex in the absorption peak that 550nm occurs3+D-d transition peak it is (bent
Line d).
By analyzing above: the present invention has successfully obtained a kind of new melbine pyridinedicarboxylic acid conjunction Cr
(III) complex, it is raw materials used it is cheap and easy to get, preparation method is simple and product purity is higher.
Claims (3)
1. the preparation method that a kind of melbine pyridinedicarboxylic acid closes Cr (III) complex, it is characterised in that: the diformazan is double
The structural formula of guanidine pyridinedicarboxylic acid conjunction Cr (III) complex are as follows:
The melbine pyridinedicarboxylic acid closes the preparation method of Cr (III) complex, includes the following steps:
1) ratio that pyridinedicarboxylic acid, sodium hydroxide, Metformin hydrochloride are 2:5:1 in molar ratio is added in organic solvent,
In 35-40 DEG C of at a temperature of stirring and dissolving, the organic solvent is pyridinedicarboxylic acid, sodium hydroxide, Metformin hydrochloride mixing
10-15 times of object product；
2) Cr (III) salt is dissolved in methanol according to Cr (III) salt, the ratio that methanol molar ratio is 1:5-10, and by Cr (III)
Salting liquid is slowly added drop-wise in the solution in step 1), is heated to reflux 30-60min, stops reaction, stands 12h, and filtering obtains red
Color filtrate；
3) red filtrate is placed at room temperature, is protected from light, volatilized naturally two weeks, obtaining aubergine crystal is melbine pyrrole
Pyridine dioctyl phthalate closes Cr (III) complex.
2. a kind of method for preparing melbine pyridinedicarboxylic acid and closing Cr (III) complex according to claim 1,
It is characterized in that, the organic solvent is the mixture of water and methanol, and the molar ratio of water and methanol is 1:1-2.
3. a kind of side for preparing melbine pyridinedicarboxylic acid and closing Cr (III) complex according to claim 1 or 2
Method, which is characterized in that Cr (III) salt is any one in chromium chloride, chromic nitrate or chromium sulfate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104513279A (en) * | 2015-01-15 | 2015-04-15 | 山西大学 | Cr (III) chelate compound as well as preparation method and application thereof |
| CN105601670A (en) * | 2016-03-15 | 2016-05-25 | 山西大学 | Chromium (III) complex as well as preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104513279A (en) * | 2015-01-15 | 2015-04-15 | 山西大学 | Cr (III) chelate compound as well as preparation method and application thereof |
| CN105601670A (en) * | 2016-03-15 | 2016-05-25 | 山西大学 | Chromium (III) complex as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Pulmonary Immunotoxic Potentials of Metals Are Governed by Select Physicochemical Properties: Chromium Agents;Mitchell D.Cohen,et al;《Journal of Immunotoxicology》;20081009;第3卷;第69-81页，第71页Fig.1，第69页摘要 |
| Zakieh Yousefi, et al.Exploring the influence of crystal environment on the geometry of bis(pyridine-2,6-dicarboxylato) chromium(III) anionic complexes containing various cationic moieties: Synthesis, structures and Hirshfeld surface analysis.《 Journal of Molecular Structure》.2014,第1083卷第460-470页，第461页Scheme 1，第461页左栏第2段，第461页右栏第3段. |
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Effective date of registration: 20200927 Address after: 051530, Shijiazhuang, Hebei province Zhaoxian County new walled Industrial Zone Patentee after: SHIJIAZHUANG POLEE PHARMACEUTICAL Co.,Ltd. Address before: 030012 Shanxi city of Taiyuan province Huangling Road No. 19 Patentee before: TAIYUAN NORMAL University |