CN108610349B - Preparation and application of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide - Google Patents
Preparation and application of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide Download PDFInfo
- Publication number
- CN108610349B CN108610349B CN201810355117.XA CN201810355117A CN108610349B CN 108610349 B CN108610349 B CN 108610349B CN 201810355117 A CN201810355117 A CN 201810355117A CN 108610349 B CN108610349 B CN 108610349B
- Authority
- CN
- China
- Prior art keywords
- rhodamine
- hydrazide
- chlorobenzene
- hydroxy
- zinc ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention provides preparation and application of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide, and belongs to the technical field of organic material synthesis and application. The method adopts a liquid phase synthesis method, firstly, adding excessive hydrazine hydrate into rhodamine B ethanol solution, heating and refluxing for reaction to obtain an initial product, and then respectively adopting concentrated hydrochloric acid and sodium hydroxide solution to adjust a reaction system to be neutral to obtain a reduced intermediate product rhodamine B hydrazide; and then, the rhodamine B hydrazide and 5-chlorosalicylaldehyde are further reacted in methanol and recrystallized to prepare the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide which can be used for quickly, sensitively and highly selectively identifying zinc ions and even detecting trace amounts of zinc ions. The compound has the advantages of simple synthesis process, mild reaction conditions, less reagent consumption, low manufacturing cost, less environmental pollution, better optical characteristics and biocompatibility, and can be developed to be used as a brand-new fluorescent probe for identifying zinc ions in organisms.
Description
Technical Field
The invention belongs to the technical field of organic material synthesis and application, and particularly relates to a synthesis method for simply and conveniently preparing a rhodamine B derivative fluorescent sensing material and application thereof.
Background
Zinc ion is one of the essential trace elements in the organism, is mainly present in brain, pancreas and sperm cells in the human body, and plays a very important physiological role in the aspects of gene expression, apoptosis, enzyme regulation, neurotransmission and the like. The lack of zinc ions can cause many diseases including nerve injury, epilepsy, transient global ischemia, senile dementia and the like, meanwhile, the zinc ions are heavy metal ions, and the industries such as zinc ore mining, smelting processing, mechanical manufacturing, zinc plating and the like can cause great pollution to the environment, so that the search for a method and a technology capable of rapidly and non-invasively identifying and evaluating the concentration of the zinc ions in organisms or in the environment has great research significance. There are many methods for measuring zinc ions, such as atomic absorption method, high performance liquid chromatography, inductively coupled plasma mass spectrometry, chemiluminescence method, and electrochemical method. In comparison, the fluorescence sensing analysis method is not only simple to operate, but also has outstanding advantages in the aspects of sensitivity, selectivity, response time, real-time online measurement, remote detection, no damage to samples and the like. In recent years, molecular probes based on quinoline, bipyridine, pyrene and other groups are used as optical sensors to identify or detect zinc ions in trace organisms and in environments, and a great deal of documents are reported, but the molecular probes are complex in structure, expensive in synthesis raw materials, complex in synthesis steps and low in identification sensitivity.
The rhodamine-based fluorescent dye is a basic dye taking xanthene as a matrix, and has higher fluorescence quantum yield, long-wave absorption, short-wave emission, excellent water solubility and biocompatibility, so the rhodamine-based fluorescent dye is concerned by vast analysis and scientific research workers. Rhodamine derivatives contain an on-off balanced lactone spiro structure inside, and can realize quinoid and lactone tautomerism under different environments, so that the rhodamine derivatives have recently been developed into fluorescent molecular switches with application potential.
Disclosure of Invention
The invention aims to overcome the defects of complex zinc ion identification and detection method, expensive instrument, complex process, low identification response sensitivity, poor selectivity and the like in the existing organism or environment, and synthesizes the rhodamine B derivative with good optical performance and novel structure by utilizing the basic principle of fluorescence sensing through two-step reaction, mild reaction conditions, cheap and easily-obtained raw material function-oriented design and adopts a fluorescence analysis method with simple equipment to identify and detect zinc ions with high sensitivity and specificity.
The invention relates to a preparation method of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide for zinc ion fluorescence identification and detection, which specifically comprises the following steps: firstly, dissolving rhodamine B in a proper amount of ethanol, adding hydrazine hydrate after stirring, carrying out heating reflux reduction reaction for a certain time, concentrating the solvent to obtain a yellow crude product, adjusting the acidity of a reaction medium to be nearly neutral by respectively adopting concentrated hydrochloric acid and sodium hydroxide with a certain concentration, then precipitating a large amount of precipitates, filtering and drying to obtain light pink rhodamine B hydrazide intermediate product powder; and then dissolving the rhodamine B hydrazide and 5-chlorosalicylaldehyde together in a proper amount of methanol, heating and refluxing for reaction, separating out a white solid, cooling to room temperature, carrying out suction filtration, washing and vacuum drying, and finally recrystallizing twice by using absolute ethyl alcohol to obtain the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide light skin color product (the synthetic route of which is shown as the following formula).
The rhodamine B derivative can be used as a fluorescent molecular probe to be applied to zinc ion fluorescent recognition.
The rhodamine B derivative used in the invention is prepared by a solution synthesis method, and the reference related material (Zeng X, Wu C, Dong L, Mu L, Xue S F, Tao Z.A new tripodal rhodomine B derivative a highlyselective and sensitive fluorescence sensor for copper (II) Sci China Ser B-chem.2009,52(4):523-528.)
The scientific principle of the invention is as follows:
the rhodamine B compound with good switching effect, high quantum yield, long-wave absorption, short-wave emission, good water solubility and low biological toxicity is adopted to carry out condensation reaction with an amino derivative connecting unit containing salicyl low-toxicity biological ligand to prepare the Schiff base rhodamine derivative fluorescent molecular probe with novel structure, strong coordination capacity, good stability, excellent water solubility and excellent photoelectric property, and the fluorescence response of the Schiff base rhodamine derivative fluorescent molecular probe to zinc ions is researched.
Compared with other synthesis methods and applications of zinc ion fluorescent sensing molecular probe materials, the invention has the following technical effects:
1. the synthesis process is simple, the raw material consumption is less, the reaction condition is mild, the reaction time is short, and the energy is saved and the consumption is reduced;
2. the synthetic product has strong stability and higher optical activity;
3. the molecular probe has good water solubility and biocompatibility;
4. the molecular probe has high sensitive response (within 5 s) to zinc ions;
5. the molecular probe has good zinc ion recognition selectivity and is not interfered by other metal ions;
6. can be used for the trace determination of zinc ions (the detection limit reaches 3.6 mu m).
Drawings
FIG. 1 is a Benesi-Hildebrand diagram of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide prepared in example 3 of the present invention after a dimethylformamide solution is reacted with zinc ions (L in the figure is N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide).
FIG. 2 is a Job's diagram of N- (2-hydroxy-5-chlorobenzene) rhodamine B hydrazide prepared in example 3 of the present invention after a dimethylformamide solution is reacted with zinc ions (in the figure, HCPRH is an abbreviated name of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide).
FIG. 3 is a bar graph of fluorescence spectra of a solution of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide dimethylformamide prepared in example 3 of the present invention, after zinc ions are added, and other ions are added.
FIG. 4 is a fluorescence titration spectrum of the N- (2-hydroxy-5-chlorobenzene) rhodamine B hydrazide dimethylformamide solution prepared in example 3 of the present invention after gradually adding different amounts of zinc ions.
FIG. 5 is a linear calibration chart showing the difference in fluorescence intensity and the concentration of zinc ions (10-250. mu.M) after different amounts of zinc ions are gradually added to the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide dimethylformamide solution prepared in example 3 of the present invention.
Detailed Description
The essential features and the remarkable effects of the present invention can be obtained from the following examples, which are not intended to limit the present invention in any way, and those skilled in the art who have the benefit of this disclosure will be able to make numerous insubstantial modifications and adaptations to the present invention without departing from the scope of the present invention. The invention is further illustrated by the following specific embodiments, wherein the nuclear magnetic data test of the reaction products in the examples is characterized by using a 400MHz nuclear magnetic resonance apparatus (TMS is internal standard) of AVANCE-III from Bruker, Germany; the infrared spectrum test characterization adopts an American Nicolet/Nexus-870FT-IR type infrared spectrometer (KBr tablet); fluorescence and UV-visible absorption spectra were measured using a Perkin Elmer LS55 model U.S. fluorescence spectrometer and a WinASPECT PLUS2000 model U.S.A..
Firstly, the synthesis of rhodamine B derivatives
Example 1
(1) Dissolving 1.2g (2.5mmol) of rhodamine B in an ethanol solvent, adding 2mL of 80% hydrazine hydrate, heating and refluxing for 3 hours at 80 ℃, concentrating the solvent, separating out a yellow product, performing suction filtration and drying, then placing in a small beaker, continuously dropwise adding concentrated hydrochloric acid to completely dissolve the product into a mauve solution, adjusting the pH value of the system to about 7.0 by using a 40% sodium hydroxide aqueous solution, separating out a large amount of light pink solid, and performing suction filtration and drying to obtain light pink rhodamine B hydrazide intermediate product powder;
(2) dissolving 0.456g (1mmol) of the intermediate product obtained in the step (1) in methanol, adding 0.133g (0.8mmol) of 5-chlorosalicylaldehyde, refluxing at 50 ℃ for 28 hours, separating out a white solid, cooling to room temperature, carrying out suction filtration and washing, carrying out vacuum drying at 40 ℃ for 12 hours, and finally recrystallizing twice with absolute ethyl alcohol to obtain the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide with light skin color.
Example 2
(1) Dissolving 1.2g (2.5mmol) of rhodamine B in an ethanol solvent, adding 4mL of 80% hydrazine hydrate, heating and refluxing for 1 hour at 90 ℃, concentrating the solvent, separating out a yellow product, performing suction filtration and drying, then placing in a small beaker, continuously dropwise adding concentrated hydrochloric acid to completely dissolve the product into a mauve solution, adjusting the pH value of the system to about 7.0 by using a 40% sodium hydroxide aqueous solution, separating out a large amount of light pink solid, and performing suction filtration and drying to obtain light pink rhodamine B hydrazide intermediate product powder;
(2) dissolving 0.456g (1mmol) of the intermediate product obtained in the step (1) in methanol, adding 0.199g (1.2mmol) of 5-chlorosalicylaldehyde, refluxing at 70 ℃ for 20 hours, separating out a white solid, cooling to room temperature, carrying out suction filtration and washing, carrying out vacuum drying at 50 ℃ for 8 hours, and finally recrystallizing twice with absolute ethyl alcohol to obtain the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide with light skin color.
Example 3
(1) Dissolving 1.2g (2.5mmol) of rhodamine B in an ethanol solvent, adding 3mL of 80% hydrazine hydrate, heating and refluxing for 2 hours at 85 ℃, concentrating the solvent, separating out a yellow product, performing suction filtration and drying, then placing in a small beaker, continuously dropwise adding concentrated hydrochloric acid to completely dissolve the product into a mauve solution, adjusting the pH value of the system to about 7.0 by using a 40% sodium hydroxide aqueous solution, separating out a large amount of light pink solid, and performing suction filtration and drying to obtain light pink rhodamine B hydrazide intermediate product powder;
(2) dissolving 0.456g (1mmol) of the intermediate product obtained in the step (1) in methanol, adding 0.166g (1.0mmol) of 5-chlorosalicylaldehyde, refluxing at 60 ℃ for 24 hours, separating out a white solid, cooling to room temperature, carrying out suction filtration and washing, carrying out vacuum drying at 45 ℃ for 10 hours, and finally recrystallizing twice with absolute ethyl alcohol to obtain the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide with light skin color.
Example 4
(1) Dissolving 1.2g (2.5mmol) of rhodamine B in an ethanol solvent, adding 2.5mL of 80% hydrazine hydrate, heating and refluxing for 3 hours at 80 ℃, concentrating the solvent, separating out a yellow product, performing suction filtration and drying, then placing in a small beaker, continuously dropwise adding concentrated hydrochloric acid to completely dissolve the product into a mauve solution, adjusting the pH value of the system to about 7.0 by using a 40% sodium hydroxide aqueous solution, separating out a large amount of pale pink solid, and performing suction filtration and drying to obtain pale pink rhodamine B hydrazide intermediate product powder;
(2) dissolving 0.456g (1mmol) of the intermediate product obtained in the step (1) in methanol, adding 0.149g (0.9mmol) of 5-chlorosalicylaldehyde, refluxing at 65 ℃ for 22 hours, separating out a white solid, cooling to room temperature, performing suction filtration and washing, performing vacuum drying at 40 ℃ for 12 hours, and finally recrystallizing twice with absolute ethyl alcohol to obtain the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide with light skin color.
Example 5
(1) Dissolving 1.2g (2.5mmol) of rhodamine B in an ethanol solvent, adding 3.5mL of 80% hydrazine hydrate, heating and refluxing for 3 hours at 85 ℃, concentrating the solvent, separating out a yellow product, performing suction filtration and drying, then placing in a small beaker, continuously dropwise adding concentrated hydrochloric acid to completely dissolve the product into a mauve solution, adjusting the pH value of the system to about 7.0 by using a 40% sodium hydroxide aqueous solution, separating out a large amount of pale pink solid, and performing suction filtration and drying to obtain pale pink rhodamine B hydrazide intermediate product powder;
(2) dissolving 0.456g (1mmol) of the intermediate product obtained in the step (1) in methanol, adding 0.166g (1mmol) of 5-chlorosalicylaldehyde, refluxing at 70 ℃ for 20 hours, separating out a white solid, cooling to room temperature, performing suction filtration, washing, performing vacuum drying at 50 ℃ for 8 hours, and finally recrystallizing twice with absolute ethyl alcohol to obtain the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide with light skin color.
And (3) characterization of a target product: the yield was 55%.1H NMR(400MHz，DMSO-d6):10.48(s，1H)， 9.05(s，1H)，7.92-7.90(d，J＝8Hz，1H)，7.65-7.56(m，J＝36Hz，2H)，7.39-7.38 (d，J＝4Hz，1H)，7.24-7.20(m，J＝24Hz，1H)，7.13-7.11(d，J＝8Hz,1H)， 6.81-6.79(d,J＝8Hz,1H),6.43-6.32(m,J＝44Hz,6H),3.33-3.28(m,J＝20Hz,8H),1.08-1.05 (m,J＝12Hz,12H)；IR(KBr,cm-1) 3498(-OH), 1700(-C ═ O), 1590(C ═ N), 1592(C ═ C). Secondly, the fluorescence recognition and detection effect evaluation of the rhodamine B derivative on zinc ions
The N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide prepared in the best example 3 is taken as a molecular probe to research the fluorescence sensing response effect on zinc ions.
(1) The research finds that zinc ions are added into the dimethylformamide solution of the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide, and the dark N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide is observed under a 365nm ultraviolet lamp to be rapidly enhanced into bright yellow fluorescence within 5s of the dimethylformamide solution of the dark N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide. The reason why the fluorescence intensity is obviously enhanced is probably because C ═ N isomerization of the original molecular probe is hindered or intramolecular charge transfer is promoted after the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide reacts with zinc ions.
(2) From the fluorescence spectra data in combination with the modified Benesi-Hildebrand equation (Singh T S, Paul P C, Pramanik H A R. fluorescent chemical sensor based on sensitive Schiff base for selective detection of Zn2+Spectrochim. acta A.2014,121:520-526.) ((as shown in FIG. 1, ordinate 1/F-F in the figure)0Representing the reciprocal of the difference in fluorescence intensity) was calculated to have a coordination binding constant of 6.90X 10 between the molecular probe and the zinc ion3M-1The result shows that the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide has strong binding capacity to zinc ions. Further use Job's curve (Li Z, Zhou Y, Yin K, Yu Z, Li Y.J.ren. A new fluoro sequence "turn-on" type chemosensor for Fe3+based on naphthalene derivatives and gold amines, dyes Pigments,2014,105:7-11) analyzed the binding ratio between N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide and zinc ions, as shown in FIG. 2, when the mole fraction of zinc ions reaches 0.5, the fluorescence intensity change value reaches the maximum, which proves that N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide coordinates with zinc ions in a molar ratio of 1: 1.
(3) The influence of other possibly coexisting ions on the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide dimethyl formamide solution is further researched by adopting a fluorescence spectrometer, and is shown in figure 3. After various ions except zinc ions such as chromium ions, copper ions, ferric ions, sodium ions, potassium ions, cadmium ions, aluminum ions, ferrous ions, nickel ions and cobalt ions are added into the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide dimethylformamide solution, the fluorescence intensity of the compound is hardly changed remarkably, and the fluorescence color is not changed, which shows that the molecular probe has high recognition selectivity on the zinc ions. In addition, the influence of the mixed system of the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide and the zinc ion after the metal ion is added is tested, and the result shows that other ions have no obvious interference (not shown) on the process of identifying the zinc ion by the fluorescent probe.
(4) Through a fluorescence titration method, zinc ions are continuously added into the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide dimethylformamide solution, the fluorescence intensity of the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide is continuously enhanced, and after 300 mu mol of zinc ions are added, the fluorescence intensity reaches the maximum and hardly changes (as shown in figure 4). After calculation, the zinc ion concentration is 10-250 mu m, a good linear relation is formed between the zinc ion concentration and the fluorescence intensity change value of the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide (as shown in figure 5), the correlation coefficient is 0.9970, the detection limit is 3.6 mu m, and trace measurement of zinc ions can be realized.
Claims (1)
1. An application of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide as a molecular probe in zinc ion fluorescence recognition and detection in the environment;
the preparation method of the N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide comprises the following steps:
(1) dissolving 1.2g of rhodamine B in an ethanol solvent, adding 2-4 mL of 80% hydrazine hydrate, heating and refluxing for 1-3 hours at 80-90 ℃, concentrating the solvent, separating out a yellow product, performing suction filtration and drying, then placing in a small beaker, continuously dropwise adding concentrated hydrochloric acid to completely dissolve the product into a mauve solution, adjusting the pH value of the system to about 7.0 by using a 40% sodium hydroxide aqueous solution, separating out a large amount of light pink solid, and performing suction filtration and drying to obtain light pink rhodamine B hydrazide intermediate product powder;
(2) dissolving the intermediate product obtained in the step (1) in methanol, adding 5-chlorosalicylaldehyde, refluxing for 20-28 hours at 50-70 ℃, separating out a white solid, cooling to room temperature, performing suction filtration, washing, performing vacuum drying for 8-12 hours at 40-50 ℃, and finally recrystallizing twice with absolute ethyl alcohol to obtain an N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide light skin color product; the molar ratio of the rhodamine B hydrazide to the 5-chlorosalicylaldehyde is 1: 0.8-1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810355117.XA CN108610349B (en) | 2018-04-19 | 2018-04-19 | Preparation and application of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810355117.XA CN108610349B (en) | 2018-04-19 | 2018-04-19 | Preparation and application of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108610349A CN108610349A (en) | 2018-10-02 |
| CN108610349B true CN108610349B (en) | 2021-02-19 |
Family
ID=63660443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810355117.XA Active CN108610349B (en) | 2018-04-19 | 2018-04-19 | Preparation and application of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108610349B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970750A (en) * | 2019-04-03 | 2019-07-05 | 东华大学 | A kind of detection various metals ion rhodamine probe and its preparation and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105400233A (en) * | 2015-12-31 | 2016-03-16 | 东华大学 | Functional reactive dye for zinc ion probe, and preparation method and application thereof |
-
2018
- 2018-04-19 CN CN201810355117.XA patent/CN108610349B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105400233A (en) * | 2015-12-31 | 2016-03-16 | 东华大学 | Functional reactive dye for zinc ion probe, and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| A rhodamine-based dual chemosensor for the visual detection of copper and the ratiometric fluorescent detection of vanadium;Fang-Jun Huo et al.;《Dyes and Pigments》;20091224;第86卷;第50-55页 * |
| Fluorescent salicylaldehyde hydrazine as selective chemosensor for Zn2+ in aqueous ethanol;Na Li et al.;《Luminescence》;20091013;第25卷;第445-451页 * |
| Recognition of Mg2+ and Zn2+ based on a naphthalene-based fluorescent probe by regulating solvents;Jing-can Qin et al.;《Inorganica Chimica Acta》;20150702;第433卷;第194-199页 * |
| 一种高灵敏度高选择性的荧光素基比色荧光锌传感器;郭敏等;《无机化学学报》;20090630;第25卷(第6期);第956-961页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108610349A (en) | 2018-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | A highly selective “turn-on” fluorescent sensor for zinc ion based on a cinnamyl pyrazoline derivative and its imaging in live cells | |
| CN104962278B (en) | Palladium ion fluorescent probe, and preparation method and applications thereof | |
| CN104017568B (en) | -Application of fluorescent probe containing rhodamine in detecting Hg2+ | |
| CN113501822B (en) | Purine-vanillin-based palladium and copper ion detection fluorescent probe and preparation method and application thereof | |
| CN110156806B (en) | Copper ion ratio type fluorescent probe based on rhodamine derivatives, and preparation method and application thereof | |
| CN109593078B (en) | N-butyl-4-hydroxy-1, 8-naphthalimide-3-formaldehyde- (2-pyridine) hydrazone and application thereof | |
| CN108892672B (en) | Preparation method of rhodamine 6G Schiff base derivative for pH fluorescence sensing | |
| Prabakaran et al. | Bis naphthalene derived dual functional chemosensor: Specific signalling for Al3+ and Fe3+ ions with on-the-spot detection, bio-imaging, and logic gate applications | |
| CN106800548B (en) | 8- benzimidazole quinoline Ratio-type pH probe and its preparation method and application | |
| CN107434801B (en) | 4 '-pyridyl-pyrimidine class compounds of one kind and its synthetic method and application | |
| CN103275697A (en) | Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof | |
| CN108610349B (en) | Preparation and application of N- (2-hydroxy-5-chlorobenzene) based rhodamine B hydrazide | |
| CN107698557B (en) | Pyridine bipyrazole acylhydrazone derivative-based fluorescent probe and preparation method and application thereof | |
| CN110028515B (en) | Preparation and application of aminoacyl methyl- (2-methylamino furan) rhodamine amide derivative | |
| CN108586382A (en) | A kind of schiff base compound and its preparation and the application in copper ion detection | |
| CN106967025B (en) | A kind of preparation and its application of the chloro- 3- of 6- [(2- hydroxyl -4- diethylin benzylidene) amino] cumarin | |
| CN113912612B (en) | Alkaline pH fluorescent probe pyridazino [4,5-b ] quinoxaline-1, 4-diamine Schiff base and preparation method and application thereof | |
| CN107098852B (en) | Di (2-methylpyridine) amine modified pyrene derivative fluorescent probe and synthetic method and application thereof | |
| CN113307763B (en) | Amino acid derivative, preparation method thereof and application of amino acid derivative as acid-base indicator and fluorescent probe | |
| CN105017270A (en) | Fluorescein-benzoyl thiourea difunctional fluorescence probe and preparation method and application thereof | |
| CN109721592B (en) | Fluorescent probe containing aminopyrazine acylhydrazone derivatives of coumarin as well as preparation method and application of fluorescent probe | |
| CN110563609B (en) | Preparation method and application of near-infrared fluorescent probe for detecting selenious acid roots | |
| CN108276423B (en) | Calcium ion and zinc ion dual-channel rhodamine fluorescent probe and preparation method and application thereof | |
| CN111635412A (en) | Multifunctional fluorescent probe for detecting cadmium ions and mercury ions, and preparation method and application thereof | |
| CN115304614B (en) | Fluorescent probe for detecting aluminum ions and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |