CN106905213B - A kind of bipolar bidentate ligand and its synthetic method, application - Google Patents
A kind of bipolar bidentate ligand and its synthetic method, application Download PDFInfo
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- CN106905213B CN106905213B CN201710022692.3A CN201710022692A CN106905213B CN 106905213 B CN106905213 B CN 106905213B CN 201710022692 A CN201710022692 A CN 201710022692A CN 106905213 B CN106905213 B CN 106905213B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/47—Scattering, i.e. diffuse reflection
Abstract
A kind of bipolar bidentate ligand and its synthetic method, application.The present invention relates to a kind of Novel Bipolar bidentate ligand IPTP and its synthetic methods and the application in uranium analysis.The present invention is react with pyrrole using m-terephthal aldehyde prepares a kind of Novel Bipolar bidentate ligand IPTP, and carrying out coordination with uranyl causes system to generate strong resonance light scattering signal, to establish the new method of Resonance Light Scattering Method detection uranium.
Description
Technical field
The present invention relates to organic synthesis field, more particularly to a kind of novel bipolar bidentate ligand and preparation method thereof and
Application in uranium analysis.
Background technique
Uranium is a kind of very important energy resources and strategic resource, it has heavy metal toxicity and radioactivity, can be persistently
Ground damages human health, or even causes cancer.Therefore uranium detection to development of resources, health maintenance and environmental protection all
It is extremely important.The method of detection uranium mainly has x-ray fluorescence method, inductive coupling plasma emission spectrum method, radiometric analysis at present
Method etc., but these methods need the experimental cost of expensive instrument and great number, are not suitable for conventional analysis.Photometry testing cost
It is low but to generally require pretreatment to sample separation and concentration.Therefore it establishes a kind of advantage of lower cost, operate relatively easy, sensitivity
Preferably uranium detection method is of great significance higher, selectivity.
Resonance Light Scattering Method (RLS) has many advantages, such as that instrument is simple, quick, most of ion easy to operate does not interfere, mesh
Before have been used for the detection of plurality of target analyte.Compared with spectrophotometry and fluorescence analysis, RLS method linear relationship
Good, the range of linearity is wide, is a kind of new spectrum analysis detection method.But existing Resonance Light Scattering Method (RLS) detects uranium Shi Peihe
Object resonant light scattering signal is weaker, and testing result is unsatisfactory.In view of this, spy of the present invention propose it is a kind of new for resonance light
The ligand of scattering method (RLS) detection uranium.
Summary of the invention
There is a problem of that testing result is undesirable when the present invention is for existing Resonance Light Scattering Method analysis uranium, provides a kind of new
The bipolar bidentate ligand of type (IPTP).Using Novel Bipolar bidentate ligand of the present invention carry out RLS method analysis uranium when, uranyl from
Son can be in conjunction with bidentate ligand bipolar in molecule, and being formed by supermolecule polymer significantly increases the RLS of system.Using this
It invents the ligand and carries out RLS method analysis uranium, have the characteristics that sensitivity is higher, selectivity is more preferable.
The present invention, which adopts the following technical scheme that, to be attained in that
A kind of Novel Bipolar bidentate ligand (IPTP) has the structural formula such as Formulas I:
The bipolar bidentate ligand of Formulas I (IPTP) of the present invention is to be reacted under the action of catalyst by pyrroles with m-terephthal aldehyde
It obtains.The reaction mechanism mechanism of reaction is specific as follows:
The catalyst is selected from dilute hydrochloric acid or trifluoroacetic acid.
The molar ratio of the pyrroles and m-terephthal aldehyde is (12-25): 1.In the reaction, the part pyrroles having more can
Be conducive to reaction as solvent to carry out that other impurity will not be introduced again.
The reaction is carried out under the conditions of room temperature, being protected from light.TLC real-time monitoring is carried out to reaction system in reaction process,
After TLC detection reaction substrate m-terephthal aldehyde completely consumes, reaction was completed.
After reaction, reaction solution is neutralized to pH=8-9 using ammonium hydroxide, filtered, and rinse filter cake to filter with petroleum ether
Liquid is colourless, using ethyl acetate-light petrol recrystallization or column chromatography (silica, petroleum ether: ethyl acetate=100:1-1:
1) it purifies, is dried in vacuo up to bipolar bidentate ligand IPTP.
As one of preferred embodiment for the present invention, the preparation method of the bipolar bidentate ligand, which is characterized in that
Room temperature, under the conditions of being protected from light, pyrroles and m-terephthal aldehyde react under dilute hydrochloric acid or trifluoroacetic acid effect；After reaction, sharp
Reaction solution is neutralized to pH=8-9 with ammonium hydroxide, is filtered, it is colourless to filtrate with petroleum ether flushing filter cake, utilize ethyl acetate-pet
Ether recrystallization or column Chromatographic purification, vacuum drying to get.
The present invention also provides application of the IPTP ligand in uranium analysis.When analyzing uranium using Resonance Light Scattering Method, with this
The invention IPTP is ligand, and uranyl nitrate ion generates supramolecule in conjunction with IPTP.Specific cohesive process is as follows:
Technical solution of the present invention the utility model has the advantages that
When carrying out RLS method analysis uranium as ligand using IPTP of the present invention, uranyl nitrate ion can be with molecule
In bipolar bidentate ligand combine, being formed by supermolecule polymer makes the RLS of system significantly increase (as shown in Figure 2), to build
The new method of higher, the selective preferably Resonance Light Scattering Method detection uranium of sensitivity is found.
Detailed description of the invention
Fig. 1: the infrared spectrogram of bipolar bidentate ligand IPTP of the present invention.
Fig. 2: the ultraviolet spectrogram of bipolar bidentate ligand IPTP and Complexes of Uranyl of the present invention.A is that bipolar bidentate is matched
Body, b are the complex of bipolar bidentate ligand and uranyl.
Fig. 3: the hydrogen nuclear magnetic resonance spectrogram of bipolar bidentate ligand IPTP of the present invention.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
The synthesis of the bipolar bidentate ligand of embodiment 1
0.12mol/L dilute hydrochloric acid 100mL is added in 250mL round-bottomed flask, 60mmol pyrroles, 5mmol isophthalic diformazan is added
Aldehyde, magneton stir lower reacting at normal temperature without light, have carried out TLC real-time monitoring to reaction system.The suitable reaction time is controlled, when
After TLC monitoring reaction substrate m-terephthal aldehyde substantially completely consumes, reaction was completed；
Reaction solution is neutralized to pH=8-9 with ammonium hydroxide, is filtered, and it is colourless to filtrate constantly to rinse with petroleum ether filter cake.It will
Filter obtained solid send HPLC to monitor its each composition content a little, remaining solid can be recrystallized with ethyl acetate-light petrol or
Person's column chromatographs (silica, petroleum ether: ethyl acetate=100:1-1:1) purification, is dried in vacuo up to bipolar bidentate ligand.It produces
Amount is 1.31g, yield 71.3%.
The characterization result of the bipolar bidentate ligand of gained is shown in Fig. 1, Fig. 3.
Experimental example 1 is using 1 gained ligand of embodiment to uranium analysis detection
10mL colorimetric cylinder is taken, 10 μm of ol/L ligand solutions of 1mL is separately added into, adds Tris-HCl buffer (pH
7.0) 1.0mL, the uranyl standard solution of appropriate amount, is settled to 10mL with secondary distilled water, mixed liquor is shaken up, stand at room temperature
1 hour, scanning is synchronized with λ=0 △, Resonance light-scat-tering spectroscopy is recorded, with resonant light scattering intensity (IRLS) to the dense of uranyl
It spends (c) and draws standard curve；
Use this field routine uranium analysis method and ligand of the present invention for probe using RLS method to environmental water sample
In middle uranyl carry out quantitative analysis, the results are shown in Table 1.
Table 1 measures the comparison of uranium distinct methods in water
As shown in Table 1, dynamics phosphorimetry is that analyst coverage is most wide in all uranium analytic approach, and detection limits minimum analysis side
Method, but determination condition is harsh；Inductively coupled plasma-mass spectrometry need to be analyzed in dustfree environment, and testing cost is higher, and
Detect limit for height；Cathodic Stripping Voltammetry, arsenazo-III spectrophotometry the problem of there is also detection limits for height, and analyst coverage is not
It is analyzed suitable for uranium, is also not easy to be used more widely.And it as the RLS uranium analytic approach detection limit of ligand and is moved using IPTP of the present invention
Mechanics phosphorimetry is close, and analyst coverage is suitble to, and comprehensively considers the optimized analysis method that can be used as uranium analysis.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (7)
1. a kind of preparation method of bipolar bidentate ligand, which is characterized in that pyrroles is anti-under the action of catalyst with m-terephthal aldehyde
It should obtain；
The catalyst is selected from dilute hydrochloric acid or trifluoroacetic acid；
The molar ratio of the pyrroles and m-terephthal aldehyde is (12-25): 1；
The structural formula as I of the bipolar bidentate ligand:
2. the preparation method of bipolar bidentate ligand according to claim 1, which is characterized in that it is described reaction be room temperature,
It is carried out under the conditions of being protected from light.
3. the preparation method of bipolar bidentate ligand according to claim 1 or 2, which is characterized in that after reaction, utilize
Reaction solution is neutralized to pH=8-9 by ammonium hydroxide, filtering, colourless to filtrate with petroleum ether flushing filter cake, is purified, vacuum drying.
4. the preparation method of bipolar bidentate ligand according to claim 3, which is characterized in that the purification is to utilize acetic acid
Ethyl ester-petroleum ether recrystallization or column chromatography.
5. the preparation method of bipolar bidentate ligand according to claim 1, which is characterized in that under the conditions of room temperature, being protected from light,
Pyrroles reacts under dilute hydrochloric acid or trifluoroacetic acid effect with m-terephthal aldehyde；It after reaction, will be in reaction solution using ammonium hydroxide
With to pH=8-9, filtering is colourless to filtrate with petroleum ether flushing filter cake, utilizes ethyl acetate-light petrol recrystallization or column layer
Analysis purification, vacuum drying to get.
6. having application of the bipolar bidentate ligand of IPTP such as Formulas I structural formula in the analysis of Resonance Light Scattering Method uranium:
7. application according to claim 6, which is characterized in that using the IPTP as ligand, uranyl acetate ion and IPTP
In conjunction with generation supramolecule.
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| CN108558892A (en) * | 2018-03-26 | 2018-09-21 | 南华大学 | A kind of compound and preparation method thereof and its application in uranium analysis |
| CN108776113A (en) * | 2018-06-06 | 2018-11-09 | 南华大学 | A kind of application of double-core Complexes of Uranyl in ATP analyses |
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Non-Patent Citations (2)
| Title |
|---|
| Bridged bis-BODIPYs: their synthesis, structures and properties;Praseetha E. Kesavan，et al.;《Dalton Transactions》;20151231(第44期);第17209-17221页 |
| Triphenylamine substituted dipyrrinato metal complexes: Synthesis,optical and electrochemical studies;Sudipta Das，et al.;《Inorganic Chemistry Communications》;20151231(第60期);第54-60页 |
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