CN112707914B - Rhodamine compound based on phenol structure and synthetic method thereof - Google Patents
Rhodamine compound based on phenol structure and synthetic method thereof Download PDFInfo
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- 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
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
Abstract
The invention discloses a rhodamine compound based on a phenol structure and a synthesis method thereof, belonging to the field of chemical analysis and detection. The compound is obtained by reacting rhodamine B with 2-amino-4-nitrophenol, has mild synthesis conditions and simple and convenient operation, can be used as a fluorescent probe to detect simulation agent of diethyl chlorophosphate DCP of nerve toxicants, and has the advantages of high detection speed and high sensitivity, the response time is less than 30s, and the detection limit is 11 nM.
Description
Technical Field
The invention belongs to the field of chemical analysis and detection, and particularly relates to a rhodamine compound based on a phenol structure and a synthesis method thereof.
Background
The rhodamine dye is a fluorescent dye with a xanthene structure, has the advantages of good light stability, higher molar absorption coefficient, fluorescence quantum yield and the like, and particularly has interconversion between spirolactone or lactam and ring opening in the molecular structure of the rhodamine dye. When rhodamine exists in a spirolactone or lactam structure, an intramolecular conjugated system is destroyed, no absorption and fluorescence emission exist in visible light and near infrared regions, intramolecular conjugation can be formed after ring opening, and strong absorption and fluorescence emission phenomena can be generated in the visible light and near infrared regions. In view of the many excellent properties of rhodamine, it is widely used in the fields of biological and chemical analysis and detection.
The nerve toxicant is organic phosphonate ester derivative with high toxicity and easy volatility, and acts with acetylcholinesterase in human body to destroy nerve impulse conduction of human body, so that the nerve toxicant and the nerve toxicant cause poisoning and death of human body, and bring great threat to life safety and social stability of human. At present, many rhodamine dyes are used as fluorescent probes to detect nerve toxicants and simulation agents thereof, namely diethyl chlorophosphate (DCP for short), the probe structure is that different recognition groups are usually connected to nitrogen atoms of rhodamine lactam, and rhodamine ring opening is induced through intramolecular cyclization, substitution and other effects, so that strong fluorescent signal change is generated for detection, and the method has the advantages of high sensitivity, high detection speed, capability of realizing naked eye detection and the like.
The rhodamine-based fluorescent probe reported in the literature generally has a hydroxyl group, an amino group, etc. as a recognition group (Hee-Soo So, Satheshukrar Angugillai, Young-A. Son. Sensors and activators B: chemical.2016, 235, 447-456; Himadri Sekhar Sarkarr, Ayndria Ghos, Sujoy Das, et al. scientific reports.2018, 8, 3402; Xuanjun Wu, Zhisheng Wu and Shoufa Han. chem. Commun.2011, 47, 11468-11411411470). after the probe reacts with DCP in a solution, the probe usually changes from colorless to red and generates strong fluorescence of the structural formula, and the typical reaction is as follows:
therefore, it becomes important to design and synthesize a novel rhodamine dye, so that the rhodamine dye can be used for rapidly detecting the nerve agent simulator DCP.
Disclosure of Invention
The invention aims to provide a phenol structure-based rhodamine compound and a synthesis method thereof, the compound can be used for detecting nerve agent (DCP), and has the advantages of high detection speed, high sensitivity and the like.
The technical scheme adopted by the invention is as follows: the structural formula of the rhodamine compound RBNP based on the phenol structure is as follows:
the synthetic route of the phenol rhodamine compound is as follows:
the method for synthesizing the rhodamine compound based on the phenol structure comprises the following steps:
(1) dissolving 1mmol of rhodamine B in 10-30 mL of anhydrous 1, 2-dichloroethane, and then adding phosphorus oxychloride (POCl)3) Dropwise adding the mixture into a rhodamine B solution, reacting for 5-8 h under a reflux condition, and then performing rotary evaporation and concentration to obtain a deep red intermediate rhodamine acyl chloride RBCl;
(2) dissolving 1-1.5 mmol of 2-amino-4-nitrophenol in 10-30 mL of tetrahydrofuran, and adding triethylamine to form a solution of 2-amino-4-nitrophenol;
(3) dissolving an intermediate rhodamine acyl chloride RBCl in 30-50 mL of organic solvent, then dropwise adding the organic solvent into a solution of 2-amino-4-nitrophenol, reacting at 25-30 ℃ for 12-16 h, performing rotary evaporation and concentration after the reaction is finished, and separating and purifying through column chromatography to obtain phenol rhodamine.
Preferably, in the step (1), the molar ratio of the rhodamine B to the phosphorus oxychloride is 1: 2-5.
Preferably, in the step (2), the molar ratio of the 2-amino-4-nitrophenol to the triethylamine is 1: 1-3.
Preferably, in step (3), the eluent for column chromatography separation is dichloromethane/methanol-50/1.
The invention has the beneficial effects that: the rhodamine compound based on the phenol structure is obtained by the reaction of rhodamine B and 2-amino-4-nitrophenol, the synthesis condition is mild, and the operation is simple and convenient; the phenol rhodamine compound can be used as a fluorescent probe for detecting DCP, and has the advantages of high detection speed and high sensitivity, the response time is less than 30s, and the detection limit is 11 nM.
Drawings
FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum of phenol rhodamine RBNP
FIG. 2 nuclear magnetic resonance carbon spectrum of phenol rhodamine RBNP
FIG. 3 high resolution mass spectrogram of phenol rhodamine RBNP
FIG. 4 is a graph of UV absorption spectrum of phenol rhodamine RBNP solution after DCP is added
In the figure: the curves represent the DCP concentration, a is 0 and b is 1.0X 10-4mol/L, c is 2.0 × 10-4mol/L, d of 3.0X 10-4mol/L, e of 4.0X 10-4mol/L, f of 5.0X 10-4mol/L, g of 6.0X 10-4mol/L, h of 7.0X 10-4mol/L, i of 8.0X 10-4mol/L, j of 9.0X 10-4mol/L, k is 1.0X 10-3Ultraviolet absorption curve at mol/L; the abscissa is the absorption wavelength in nm and the ordinate is the absorption intensity.
FIG. 5 fluorescent spectrogram of phenol rhodamine RBNP solution added with DCP
In the figure: curves represent DCP concentrations, respectively, with a being 1.0X 10-4mol/L, b is 1.5X 10-4mol/L, c of 2.0X 10-4mol/L, d of 2.5X 10-4mol/L, e of 3.0X 10-4mol/L, f of 3.5X 10-4mol/L, g of 4.0X 10-4mol/L, h of 4.5X 10-4mol/L, j of 5.0X 10-4Fluorescence intensity curve at mol/L; the abscissa is the absorption wavelength in nm and the ordinate is the fluorescence intensity.
FIG. 6 fluorescent linear fitting graph of phenol rhodamine RBNP solution and DCP
In the figure: coefficient of correlation R20.9735, the abscissa is the concentration of DCP in 10-4mol/L, and the ordinate represents the fluorescence intensity.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1
Synthesis of phenol rhodamine RBNP
(1) Dissolving 1mmol of rhodamine B in 20mL of anhydrous 1, 2-dichloroethane, dropwise adding 0.36mL (2mmol) of phosphorus oxychloride into the rhodamine B solution, reacting for 8h under a reflux condition, and performing rotary evaporation and concentration to obtain a deep red intermediate rhodamine acyl chloride;
(2) 1.2mmol of 2-amino-4-nitrophenol was dissolved in 20mL of tetrahydrofuran, and 0.2mL (1.4mmol) of triethylamine was added thereto to form a solution of 2-amino-4-nitrophenol;
(3) dissolving rhodamine acyl chloride in 40mL of anhydrous tetrahydrofuran, then dropwise adding the rhodamine acyl chloride solution into a solution of 2-amino-4-nitrophenol, reacting at 25 ℃ for 12h, performing rotary evaporation concentration, and performing column chromatography separation and purification, wherein an eluent is dichloromethane/methanol-50/1, so as to obtain the red phenol rhodamine RBNP.
Nuclear magnetic and mass spectrometry characterization:
1H NMR(500MHz，CDCl3)，δ：8.02-8.03(d，1H)，7.91-7.94(dd，1H)，7.81(s，1H)，7.54-7.60(m，2H)，7.32-7.33(d，1H)，7.21-7.22(d，1H)，6.92-6.94(d，1H)，6.58-6.60(d，2H)，6.32-6.34(dd，2H)，6.30(d，2H)，3.30-3.35(m，8H)，1.14-1.17(m，12H)；13C NMR(126 MHz，CDCl3)，δ：168.34，154.30，153.24，149.96，148.97，133.14，130.09，129.77，129.11，128.44，128.37，126.10，124.75，124.12，123.40，119.15，108.38，105.89，97.87，68.98，44.39，20.56，12.25；ESI-MS：found，m/z579.2602(M+H+)，calculated for[C11H13N3+H+]：579.2601。
example 2
Detection and selectivity experiment of phenol rhodamine RBNP on DCP
5.8mg of RBNP synthesized in example 1 was put into a 100mL volumetric flask, dissolved and fixed to volume with DMF to give a concentration of 1.0X 10-4The mol/L solution is then transferred to a 100mL volumetric flask with 50mL solution, the volume is determined by DMF, and 5.0X 10 is prepared-5And (4) testing solution of mol/L. Preparing 7 sample bottles with the serial numbers of 1-7, and respectively adding 2mL of test solution into the 7 sample bottles, wherein the No. 1 sample bottle is used as a blank. Preparation 1.0X 10-1Taking DMF solutions of DCP (diethyl chlorophosphate), DMMP (dimethyl methylphosphonate), DCNP (diethyl cyanophosphonate), DMNP (methyl paraoxon), TEP (triethyl phosphate) and TPP (triphenyl phosphate) as analysis solutions, sequentially adding 20 mu L of DCP, DMMP, DCNP, DMNP, TEP and TPP solutions into No. 2-7 samples, shaking and shaking uniformly, and observing that the solution in the No. 2 sample bottle added with the DCP is rapidly changed into pink from yellow within 30s under the irradiation of sunlight; under 365nm ultraviolet light, the dissolution in the sample bottle No. 2 to which DCP was added was observedThe liquid fluoresced with a distinct pink color.
Example 3
Ultraviolet absorption and fluorescence spectrum experiments before and after adding DCP into phenol rhodamine RBNP
The concentration of RBNP is 1.0X 10-4mol/L of test solutions 1 and 5.0X 10-5mol/L of test solution 2 and 1.0X 10-1A DMF solution of mol/LDCP, then sequentially dropwise adding the solution with the concentration of 1.0 multiplied by 10 to 2mL of the test solution 1-4～1.0×10- 3measuring the ultraviolet absorption spectrum of the DCP solution in mol/L; to 2mL of test solution 2 was added dropwise in order at a concentration of 1.0X 10-4～5.0×10-4The fluorescence emission spectrum (excitation wavelength 540nm) of a mol/L DCP solution was measured. As shown in fig. 4, after the DCP solution is added, an ultraviolet absorption spectrum of the RBNP solution shows a distinct absorption peak near 563nm, and the absorption intensity increases with the increase of the concentration of the DCP solution; as shown in FIG. 5, after the DCP solution is added, the fluorescence spectrum of the RBNP solution has a distinct fluorescence emission peak at 586nm, which is the ring-opening fluorescence emission phenomenon after the reaction of RBNP and DCP, and the fluorescence intensity gradually increases with the increase of the concentration of the DCP solution. FIG. 6 shows RBNP at DCP concentration of 1.0X 10-4～3.0×10-4The linear relation is formed in the mol/L range, and the linear correlation coefficient is R20.9735, the limit of detection of DCP by RBNP is 1.1 × 10-8mol/L(11nM)。
Claims (3)
1. A rhodamine compound based on a phenol structure, characterized in that: the structural formula of the phenol rhodamine is as follows:
2. the rhodamine compound based on a phenol structure as recited in claim 1, wherein the synthesis method comprises the following steps:
(1) dissolving 1mmol of rhodamine B in 10-30 mL of anhydrous 1, 2-dichloroethane, and then adding phosphorus oxychloride POCl3Dropwise adding the mixture into a rhodamine B solution, reacting the rhodamine B and phosphorus oxychloride for 5-8 h under a reflux condition, and performing rotary evaporation and concentration to obtain a deep red intermediate rhodamine acyl chloride RBCl, wherein the molar ratio of the rhodamine B to the phosphorus oxychloride is 1: 2-5;
(2) dissolving 1-1.5 mmol of 2-amino-4-nitrophenol in 10-30 mL of tetrahydrofuran, and adding triethylamine to form a solution of 2-amino-4-nitrophenol, wherein the molar ratio of the 2-amino-4-nitrophenol to the triethylamine is 1: 1-3;
(3) dissolving an intermediate rhodamine acyl chloride RBCl in 30-50 mL of organic solvent, dropwise adding the intermediate rhodamine acyl chloride RBCl into a solution of 2-amino-4-nitrophenol, reacting at 25-30 ℃ for 12-16 h, performing rotary evaporation concentration after the reaction is finished, and performing column chromatography separation and purification to obtain phenol rhodamine.
3. A rhodamine compound based on a phenol structure according to claim 2, wherein: in the step (3), the eluent for column chromatography separation is dichloromethane/methanol-50/1.
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