CN109503632A - Pyrazoles -3- copper formate complexes and preparation method - Google Patents
Pyrazoles -3- copper formate complexes and preparation method Download PDFInfo
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- CN109503632A CN109503632A CN201811303816.6A CN201811303816A CN109503632A CN 109503632 A CN109503632 A CN 109503632A CN 201811303816 A CN201811303816 A CN 201811303816A CN 109503632 A CN109503632 A CN 109503632A
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- Prior art keywords
- pyrazoles
- copper
- formate
- dimethylaminopyridine
- copper formate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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 System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
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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
Abstract
The invention discloses a kind of pyrazoles -3- copper formate complexes and preparation methods.Pyrazoles -3- copper formate complexes belong to anorthic system, and space group isPī.In the complex, pyrazoles -3- formic acid is with bidentate bridging, the form and metal ion Cu (II) ion coordination of chelating, 4-dimethylaminopyridine in the form of monodentate with metal ion Cu (II) ion coordination.The present invention is ligand and Copper dichloride dihydrate by hydro-thermal method acquisition copper complex using pyrazoles -3- formic acid, 4-dimethylaminopyridine, has many advantages, such as simple process, low in cost, reproducible, the complex for synthesis transition metal provides certain foundation.
Description
Technical field
The invention belongs to complex preparation technical field, in particular to a kind of pyrazoles -3- copper formate complexes and preparation side
Method.
Background technique
Pyrazole carboxylic acid class organic ligand is a kind of heterocyclic compound with extensive bioactivity, therefore, pyrazole carboxylic acid class
Metal organic complex also has good bioactivity, this also becomes extensively the research heat of the chemical field of scholar at home and abroad
One of point, such as pyrazoles -3- formic acid.In addition, there is 4-dimethylaminopyridine intramolecular to be conjugated big pi bond, can be used as largely effective
Chromophore measure product, and there is good intramolecular electron transmission and energy transmission property, it is possible to as good
Good assistant ligand.There are rich and varied for the complex that transition metal Cu, pyrazoles -3- formic acid and 4-dimethylaminopyridine are formed
Structure gets a good eye meaning for the complex of design synthesis object construction.
Summary of the invention
The object of the present invention is to provide a kind of pyrazoles -3- copper formate complexes and preparation methods.
Thinking of the invention: being that ligand and Copper dichloride dihydrate pass through water using pyrazoles -3- formic acid, 4-dimethylaminopyridine
Thermal method obtains copper complex.
The molecular structure of pyrazoles -3- copper formate complexes of the present invention is shown in attached drawing 1.It is tiltedly brilliant that the complex belongs to three
System, space group arePī, central metallic ions are Cu (II) ion.In the complex, minimum structural unit is by two Cu
(II) ion, two pyrazoles -3- formate anions, four 4-dimethylaminopyridine neutral molecules and two free moisture subgroups
At.Center Cu1 ion respectively with the oxygen atom (N1, O2) on the nitrogen-atoms and carboxyl of a pyrazoles -3- formate anion with
The form coordination of bidentate chelating, is coordinated in the form of monodentate with the nitrogen-atoms (N2A) of another pyrazoles -3- formate anion,
It is coordinated in the form of monodentate with two nitrogen-atoms (N3, N5) of two 4-dimethylaminopyridine neutral molecules, forms pentacoordinate
Tetragonal pyramid configuration.The average bond length that the bond distance of Cu-O is 2.004, Cu-N is 2.055.
Pyrazoles -3- the copper formate complexes the preparation method comprises the following steps:
(1) it weighs 0.2 ~ 0.5 mM of Copper dichloride dihydrate to be dissolved in 3 ~ 5 milliliters of distilled water, it is molten that copper chloride is made
Liquid.
(2) it weighs 0.2 ~ 0.5 mM of pyrazoles -3- formic acid to be dissolved in 3 ~ 5 milliliters of distilled water, pyrazoles -3- is made
Formic acid solution.
(3) it weighs 0.2 ~ 0.5 mM of 4-dimethylaminopyridine to be dissolved in 2 ~ 4 milliliters of dehydrated alcohols, 4- is made
Dimethylamino naphthyridine solution.
(4) solution made from step (1), (2) and (3) is added in ptfe autoclave liner, dropwise addition 2 ~
3 drops analyze pure triethylamines, put on stainless steel cauldron housing and are put into 100 degrees Celsius and react 48 ~ 72 hours, after the reaction was completed with
10 degrees Celsius of gradients are down to room temperature per hour, open kettle after standing 12 ~ 24 hours, filter to obtain blue rhabdolith, as pyrazoles-
3- copper formate complexes.
The present invention has many advantages, such as simple process, low in cost, reproducible, has successfully synthesized pyrazoles -3- copper formate
Complex provides certain foundation to synthesize the complex of transition metal.
Detailed description of the invention
Fig. 1 is pyrazoles -3- copper formate complexes molecular structure of the invention.
Specific embodiment
Embodiment:
(1) it weighs 0.2 mM of (0.0341 gram) Copper dichloride dihydrate to be dissolved in 5 milliliters of distilled water, it is molten that copper chloride is made
Liquid.
(2) it weighs 0.2 mM of (0.0224 gram) pyrazoles -3- formic acid to be dissolved in 5 milliliters of distilled water, pyrazoles -3- is made
Formic acid solution.
(3) it weighs 0.5 mM of (0.0610 gram) 4-dimethylaminopyridine to be dissolved in 2 milliliters of dehydrated alcohols, 4- is made
Dimethylamino naphthyridine solution.
(4) solution made from step (1), (2) and (3) is added in ptfe autoclave liner, 2 drops is added dropwise
Pure triethylamine is analyzed, stainless steel cauldron housing is put on and is put into 100 degrees Celsius of reactions 72 hours, after the reaction was completed with per hour 10
Degree Celsius gradient is down to room temperature, opens kettle after standing 24 hours, filters to obtain blue rhabdolith, and as pyrazoles -3- copper formate cooperates
Object.
The complex belongs to anorthic system, and space group isPī, central metallic ions are Cu (II) ion.In the complex
In, minimum structural unit is by two Cu (II) ions, two pyrazoles -3- formate anions, four 4-dimethylaminopyridine
Neutral molecule and two dissociating water molecule compositions.The center Cu1 ion nitrogen-atoms with a pyrazoles -3- formate anion respectively
The form coordination chelated with the oxygen atom (N1, O2) on carboxyl with bidentate, it is former with the nitrogen of another pyrazoles -3- formate anion
Sub (N2A) is coordinated in the form of monodentate, and two nitrogen-atoms (N3, N5) with two 4-dimethylaminopyridine neutral molecules are with monodentate
Form coordination, form the tetragonal pyramid configuration of pentacoordinate.The bond distance of Cu-O is that the average bond length of 2.004, Cu-N is
2.055 Å。
Claims (2)
1. a kind of pyrazoles -3- copper formate complexes, it is characterised in that pyrazoles -3- copper formate complexes belong to anorthic system, space
Group bePī, central metallic ions are Cu (II) ion;In the complex, minimum structural unit by two Cu (II) ions,
Two pyrazoles -3- formate anions, four 4-dimethylaminopyridine neutral molecules and two dissociating water molecule compositions;Center
Cu1 ion is chelated respectively with oxygen atom, that is, N1, O2 on the nitrogen-atoms and carboxyl of a pyrazoles -3- formate anion with bidentate
Form coordination, be coordinated in the form of monodentate with nitrogen-atoms, that is, N2A of another pyrazoles -3- formate anion, with two 4-
Two nitrogen-atoms, that is, N3, N5 of dimethylamino naphthyridine neutral molecule are coordinated in the form of monodentate, form the tetragonal pyramid of pentacoordinate
Configuration;The average bond length that the bond distance of Cu-O is 2.004, Cu-N is 2.055.
2. the preparation method of pyrazoles -3- copper formate complexes according to claim 1, it is characterised in that specific steps are as follows:
(1) it weighs 0.2 ~ 0.5 mM of Copper dichloride dihydrate to be dissolved in 3 ~ 5 milliliters of distilled water, it is molten that copper chloride is made
Liquid；
(2) it weighs 0.2 ~ 0.5 mM of pyrazoles -3- formic acid to be dissolved in 3 ~ 5 milliliters of distilled water, pyrazoles -3- formic acid is made
Solution；
(3) it weighs 0.2 ~ 0.5 mM of 4-dimethylaminopyridine to be dissolved in 2 ~ 4 milliliters of dehydrated alcohols, 4- diformazan is made
Aminopyridine solution；
(4) solution made from step (1), (2) and (3) is added in ptfe autoclave liner, 2 ~ 3 drops is added dropwise
Pure triethylamine is analyzed, stainless steel cauldron housing is put on and is put into 100 degrees Celsius of reactions 48 ~ 72 hours, after the reaction was completed with every
Hour, 10 degrees Celsius of gradients were down to room temperature, opened kettle after standing 12 ~ 24 hours, filtered to obtain blue rhabdolith, as pyrazoles -3-
Copper formate complexes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114106019A (en) * | 2021-12-06 | 2022-03-01 | 桂林理工大学 | Crystal structure of pyrazole-3-copper formate complex and magnetic property thereof |
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2018
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114106019A (en) * | 2021-12-06 | 2022-03-01 | 桂林理工大学 | Crystal structure of pyrazole-3-copper formate complex and magnetic property thereof |
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