CN103642489B - Quinaldine derivative a fluorescent reagent as well as preparation method and application thereof - Google Patents
Quinaldine derivative a fluorescent reagent as well as preparation method and application thereof Download PDFInfo
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- CN103642489B CN103642489B CN201310722745.4A CN201310722745A CN103642489B CN 103642489 B CN103642489 B CN 103642489B CN 201310722745 A CN201310722745 A CN 201310722745A CN 103642489 B CN103642489 B CN 103642489B
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- derivative
- fluorescent reagent
- fluorescent
- quinaldine red
- quinaldine
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Abstract
The invention discloses a quinaldine derivative a fluorescent reagent as well as a preparation method and an application thereof, and belongs to the fields of organic synthesis and analytical chemistry. The quinaldine derivative a fluorescent reagent is a quinaldine derivative a which is prepared from 8-hydroxy quinaldine as a raw material through Knoevenagel condensation reaction with 2,4-dihydroxy benzaldehyde, and has the name of (E)-2-(2,4-diacetoxyl phenyl) vinyl-8-acetoxyl quinoline. The reaction raw materials are easy to obtain, the synthesis method is simple, and a target product can be obtained through reaction at one step. In an acetonitrile solvent, the derivative a can be used as a fluorescent reagent for detecting Fe<3+>. The structural formula of the derivative is as shown in the specification.
Description
Technical field
The invention belongs to organic synthesis and analytical chemistry field, specifically a kind of quinaldine red derivative a fluorescent reagent and preparation method and application.
Background technology
The analyzing and testing of trace metal adopts atomic emissions, atomic absorption spectrum or traditional colorimetric spectrophotometry, polarography etc. mostly.Some sensitivity is lower, and some then needs relatively large analytical instrument or reagent consumption, it is comparatively large to pollute, complex operation etc.The fluorescent probe technique occurred in recent years, utilize the selective binding of probe to molecule, ion and the change of spectral response curve, molecular recognition information is expressed by fluorescent signal and colour-change, realize original position on a molecular scale to detect in real time, reach the special efficacy identification to bioprocess and environmental correclation metal, nonmetallic ion, molecule.This kind of fluorescent probe technique is widely used in fields such as life, environment, material and information sciences.Utilize the organic molecule of typical structure as platform, design, prepare highly sensitive, selectivity good, all kinds of fluorescent probe molecules of superb optical performance, from the novelty of molecular structure, the feasibility of synthesis route, correlative study is very challenging.
8-hydroxyl quinaldine red has another name called 2-methyl-oxine, it is a kind of derivative of oxine, for important Minute Organic Synthesis intermediate, be widely used as extraction agent and the fluorometric analysis reagent of metal ion, be also used as the divalence nonlinear optics material of preparation high strength and high stability.8-hydroxyl quinaldine red is bonded on resin, effectively absorbing copper and lead can waits metal ion; The title complex of oxine and metallic aluminium is used to the emissive material in organic electroluminescence device as a kind of luminophore, possess luminescence and electron transporting properties simultaneously.The molecular structure of the metal complexes of 8-hydroxyl quinaldine red has the characteristic of unique asymmetric and plane configuration and presents the superior characteristics of luminescence.8-hydroxyl quinaldine red gallium title complex launches strong blue-green fluorescent.On the other hand, itrated compound and the muriate of 8-hydroxyl quinaldine red still treat Digestive tract important drugs, and its derivative has different physiological roles.Based on molecular structure and the performance of 8-hydroxyl quinaldine red uniqueness, if simply modify in its structure, the conjugated structure of expansion molecule, strengthen molecular luminescence quantum yield, change its coordination ability, improve the selectivity that specific ion is coordinated, thus develop Novel ion probe reagent.
Summary of the invention
The object of the invention is to modify on the molecular structure, performance of 8-hydroxyl quinaldine red uniqueness, the conjugated structure of expansion molecule, strengthens molecular luminescence quantum yield, changes its coordination ability, improve the selectivity that specific ion is coordinated, thus greatly improve the sensitivity of ion detection.
A kind of quinaldine red derivative of the present invention
afluorescent reagent is for Knoevenagel(Borneo camphor Wen Gaier occurs for raw material and 2,4-Dihydroxy benzaldehyde with 8-hydroxyl quinaldine red) condensation reaction, introduce conjugated structure aromatic ring group in the 2-position of 8-hydroxyl quinaldine red, a kind of quinaldine red derivative obtained
a, be called for short derivative
a, chemical name is (E)-2-(2,4-diacetoxy phenyl) vinyl-8-acetoxyl group quinoline, and chemical structural formula is:
a
Derivative
a: (E)-2-(2,4-diacetoxy phenyl) vinyl-8-acetoxyl group quinoline
Molecular formula: C
23h
19nO
6
Molecular weight: 405.12
Fusing point: 131-133 DEG C
Solvability: be dissolved in chloroform, acetone, methyl-sulphoxide, DMF etc.
Spectral quality: the fluorescence exciting wavelength in acetonitrile solution is 350nm, emission wavelength is 415nm; Ultraviolet-ray visible absorbing maximum wavelength is 302nm, 350 nm.
A kind of quinaldine red derivative of the present invention
athe preparation method of fluorescent reagent is that 2,4-Dihydroxy benzaldehyde is raw material with 8-hydroxyl quinaldine red, take diacetyl oxide as solvent, and synthesis obtains derivative
a: (E)-2-(2,4-diacetoxy phenyl) vinyl-8-acetoxyl group quinoline, synthetic route is as follows:
Above-mentioned a kind of quinaldine red derivative
athe preparation method of fluorescent reagent, concrete technology condition is:
In there-necked flask; in the solution of acetic anhydride being dissolved with 8-hydroxyl quinaldine red, add 2,4-Dihydroxy benzaldehyde; 8-hydroxyl quinaldine red in molar ratio: 2; 4-Dihydroxy benzaldehyde equals 1:2, under nitrogen protection, and backflow; reaction terminates; concentrated removing solvent acetic acid acid anhydride, through silica gel column chromatography wash-out, obtains derivative
a:
Temperature of reaction: 139 DEG C (backflow)
Reaction times: 5h
Reaction solvent: diacetyl oxide
Eluent: chloroform: ethyl acetate=3:1, volume ratio
A kind of quinaldine red derivative of the present invention
athe application of fluorescent reagent is the analytical reagent being used as fluorescent spectrometry.Derivative
afor detecting micro Fe in fluorescent spectrometry
3+fluorescent reagent.Derivative
aacetonitrile solution when excitation wavelength is 350nm, launch the hyperfluorescenceZeng Yongminggaoyingguang of 415nm wavelength, Fe
3+add and make derivative
afluorescence significantly reduces, and other tests change derivative adding of metal ion hardly
afluorescence intensity, derivative
adetect Fe
3+fluorescence intensity not by the impact that other metal ions coexist.Detect Fe
3+concentration linearity range reach two orders of magnitude, detectability is low to moderate 10 most
-8mol
.l
-1.
The present invention utilizes the active methylene group that contains in 8-hydroxyl quinaldine red molecule and 2,4-Dihydroxy benzaldehyde that Knoevenagel(Borneo camphor Wen Gaier occurs in diacetyl oxide) condensation reaction, obtained derivative
a, reaction raw materials is easy to get, and synthetic method is simple, and with low cost, productive rate is higher.Single step reaction can prepare the fluorescent reagent that a kind of energy is highly sensitive, highly selective detects micro-ferric ion.The concentration linearity range detected is wide, detectability is low.Use fluorescent spectrometry, derivative
afe is detected as fluorescent reagent
3+time, the selection of excitation wavelength and solvent is key problem in technology.
The derivative of the present invention's synthesis
aproton nmr spectra data list in table 1, derivative
acarbon-13 nmr spectra data list in table 2, derivative
amass-spectrometric data list in table 3, derivative
ainfrared signature peak spectroscopic data list in table 4.
Table 1 derivative
ahydrogen nuclear magnetic resonance modal data
Table 2 derivative
acarbon-13 nmr spectra data
Accompanying drawing explanation
Fig. 1 concentration is 1.00 × 10
-5mol
.l
-1derivative
aacetonitrile solution, do not add metal ion respectively or add 2.00 × 10
-3mol
.l
-1metal cations Fe
3+, Li
+, Na
+, K
+, Mg
2+, Ca
2+, Ba
2+, Sr
2+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Cd
2+, Pb
2+, Ag
+, Zn
2+, Cr
3+, Al
3+after fluorescence spectrum.Fe
3+add and make derivative
afluorescence significantly reduces, and other above-mentioned adding of test metal ion change derivative hardly
afluorescence intensity.The excitation wavelength of test is 350nm, and emission wavelength is 415nm.
Fig. 2 coexistent metallic ion is to derivative
afluorometric assay Fe
3+impact
Be 1.00 × 10 in concentration
-5mol
.l
-1derivative
aacetonitrile solution in, add 2.00 × 10
-3molL
-1fe
3+rear derivative
afluorescence significantly reduces.Again respectively to
a-fe
3+other metal ions of isodose are added: Li in mixing solutions
+, Na
+, K
+, Mg
2+, Ca
2+, Ba
2+, Sr
2+, Zn
2+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Cd
2+, Pb
2+, Ag
+, Cr
3+, Al
3+after fluorescence intensity change.Black bar represents at derivative
ain add the fluorescence intensity of different metal ion.Grey bar represents
a-fe
3+mixing solutions adds the fluorescence intensity change after other coexistent metallic ions above-mentioned more respectively.Show derivative
adetect Fe
3+fluorescence intensity not by other impacts of coexisting of test metal ions above-mentioned.
Fig. 3 derivative
afluorescent spectrometry detect Fe
3+calibration curve.Excitation wavelength is 350nm, and emission wavelength is 415nm.Fe
3+concentration is 8.0 × 10
-7~ 1.2 × 10
-5mol
.l
-1its concentration and derivative in scope
afluorescence intensity linear.
Embodiment
embodiment one: derivative
athe i.e. synthesis of (E)-2-(2,4-diacetoxy phenyl) vinyl-8-acetoxyl group quinoline:
In the there-necked flask of the 100ml under nitrogen protection; add 8-hydroxyl quinaldine red 1.00g(6.29mmol), diacetyl oxide 20ml and 2; 4-Dihydroxy benzaldehyde 1.74g(12.58mmol); reflux 5h; concentrated removing solvent acetic acid acid anhydride; through column chromatography purification, eluent is: chloroform/ethyl acetate (
v:V=3:1) obtain 1.78g white object product
a, productive rate 70.0%.m.p. 131~133℃ ;
1H NMR(400MHz, CDCl
3)δ: 2.31(s, 3H, -COCH
3), 2.40(s, 3H, -COCH
3), 2.53(s, 3H, -COCH
3), 6.99(d, J=2.4Hz, 1H, ArH), 7.06-7.09(m, 1H, ArH), 7.30(s, 1H, ArH), 7.42-7.50(m, 2H, ArH), 7.58(d, J=8.4Hz, 1H, ArH), 7.67-7.78(m, 3H, ArH),8.14(d, J=8.4Hz, 1H, ArH); MS (ESI)
m/z: 406.1[M
+H]
+。
embodiment two:
In analytical procedure of the present invention, the compound method of all ingredients is:
(1) derivative
athe compound method of solution: the derivative taking 4.0 mg
a, dissolve with acetonitrile, be mixed with 100mL solution, concentration is 100 μm of olL
-1;
(2) Fe
3+standardized solution: take analytical pure Fe (NO
3)
39H
2o 80.8mg, uses second distillation water dissolution, and is mixed with 100mL solution, Fe
3+concentration is 2.00 × 10
-3molL
-1, use redistilled water stepwise dilution to suitable concentration as required;
(3) preparation of other coexistent metallic ion solution: nitrate or the hydrochloride of getting analytically pure various metal, uses second distillation water dissolution, and to be mixed with concentration be 2.00 × 10
-3molL
-1the second distillation aqueous solution.
The present invention's ultraviolet-visible spectrophotometer model used is UV-1800, and company of Japanese Shimadzu Corporation produces; Spectrophotofluorometer model is Cary Eclipse spectrophotofluorometer, and VARIAN company of the U.S. produces.
In the inventive method as detect the fluorescent reagent of micro-ferric ion have superb optical performance, detection selectivity high, detectability is extremely low, do not need the advantages such as discrete testing.May be used for the monitoring of specific ion in non-aqueous system.Operation and control method easy, unique properties, can be used as optical probe practical application.
embodiment three:
Derivative is added in 10.0 mL volumetric flasks
aacetonitrile storing solution (1.00 × 10
-4molL
-1, 1mL), metal cations Fe
3+(2.00 × 10
-3molL
-1, 1 mL), be diluted to scale with acetonitrile solution, shake up, the quartz colorimetric utensil moving into 1cm carries out fluorescence spectrum and uv-visible absorption spectra mensuration.Fluorescence spectrometry to excite with emission wavelength be 350/415 nm.
(1) to Fe
3+detect
Arranging fluorescence exciting wavelength is 350nm, adds about 3ml derivative in the cuvette of 1cm
a(concentration is 1.00 × 10
-5molL
-1) acetonitrile solution carry out spectral scan, derivative
afluorescent emission is had at 415 nm wavelength places.Add Fe
3+(concentration is 2.00 × 10
-4molL
-1) after, derivative
athe remarkable intensity of fluorescent emission intensity (quencher rate is 90.46%) of solution.Under the same terms, at derivative
ali is added respectively in solution
+, Na
+, K
+, Mg
2+, Ca
2+, Ba
2+, Sr
2+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Pb
2+, Cd
2+, Ag
+, Cr
3+, Al
3+after metal ion, change derivative hardly
afluorescence spectrum and intensity (as Fig. 1).Derivative
aonly to Fe
3+selective quenching of fluorescence detection perform.
Derivative
adetect Fe
3+fluorescence spectrometry by the impact (Fig. 2) of coexistent metallic ion.Other common coexistent metallic ions are at the Fe of concentration and test
3+ion Phase at that time, to detection Fe
3+fluorescence intensity impact relative deviation within 5%, not interference measurement.
In acetonitrile solution, with 350/415 nm for fluorescence exciting wavelength and emission wavelength, measure Fe
3+change in concentration and derivative
afluorescence intensity change calibration curve (as Fig. 3).By the slope of calibration curve and the standard deviation of mensuration 10 blank values, measure and calculate derivative
adetect Fe
3+concentration linearity range and detection limit list in table 5.
Claims (2)
1. a quinaldine red derivative
athe application of fluorescent reagent, is characterized in that with 8-hydroxyl quinaldine red for raw material, by there is Knoevenagel(Borneo camphor Wen Gaier with 2,4-Dihydroxy benzaldehyde) condensation reaction, obtain derivative
a, chemical name is (E)-2-(2,4-diacetoxy phenyl) vinyl-8-acetoxyl group quinoline, and chemical structural formula is:
a
Derivative
aas in fluorescent spectrometry for detecting specific micro Fe
3+fluorescent reagent.
2. a kind of quinaldine red derivative according to claim 1
athe application of fluorescent reagent, is characterized in that described derivative
afluorometric assay micro Fe is can be used as in acetonitrile solvent
3+fluorescent reagent, the concentration linearity range of detection reaches two orders of magnitude, and detectability is low to moderate 10 most
-8mol
.l
-1.
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| CN105424661B (en) * | 2015-11-13 | 2018-05-25 | 贵州大学 | A kind of ratio fluorescent, ratio absorbs or the micro F of visual detection-Detecting probe method |
| CN108329910B (en) * | 2018-01-23 | 2020-10-20 | 莆田学院 | Graphene oxide grafted 8-hydroxyquinoline fluorescent composite and intercalated layered double hydroxide fluorescent composite material thereof |
| CN117567370B (en) * | 2023-11-23 | 2024-05-10 | 山东大学 | PH value detection fluorescent probe and preparation method and application thereof |
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| CN102153570A (en) * | 2011-01-28 | 2011-08-17 | 太原理工大学 | Quick synthesis method of reverse-2-(2-hydroxy styryl)-8-oxyquinoline zinc |
| CN102533250A (en) * | 2010-12-17 | 2012-07-04 | 中国科学院生态环境研究中心 | Preparation of water-soluble fluorescence probe and rapid detection of iron ion by use of the same |
| CN102702096A (en) * | 2012-06-15 | 2012-10-03 | 华东理工大学 | Quinoline nitrile derivative with aggregation-induced emission performance |
| CN103436251A (en) * | 2013-07-16 | 2013-12-11 | 安徽大学 | Ratio meter type two-photon cadmium ion fluorescent probe and synthetic method thereof |
| CN103450887A (en) * | 2013-08-22 | 2013-12-18 | 贵州大学 | Conjugated phenanthroline-pyridine fluorescent reagents as well as preparation method and application thereof |
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| US7790896B2 (en) * | 2006-03-09 | 2010-09-07 | New York University | RNA-selective probes for live cell imaging of nuclear structure and function |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533250A (en) * | 2010-12-17 | 2012-07-04 | 中国科学院生态环境研究中心 | Preparation of water-soluble fluorescence probe and rapid detection of iron ion by use of the same |
| CN102153570A (en) * | 2011-01-28 | 2011-08-17 | 太原理工大学 | Quick synthesis method of reverse-2-(2-hydroxy styryl)-8-oxyquinoline zinc |
| CN102702096A (en) * | 2012-06-15 | 2012-10-03 | 华东理工大学 | Quinoline nitrile derivative with aggregation-induced emission performance |
| CN103436251A (en) * | 2013-07-16 | 2013-12-11 | 安徽大学 | Ratio meter type two-photon cadmium ion fluorescent probe and synthetic method thereof |
| CN103450887A (en) * | 2013-08-22 | 2013-12-18 | 贵州大学 | Conjugated phenanthroline-pyridine fluorescent reagents as well as preparation method and application thereof |
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