CN111019646A - Preparation and application of naphthalimide pyrrolo [2,1-b ] [1,3] benzoxazine derivative CN-probe - Google Patents
Preparation and application of naphthalimide pyrrolo [2,1-b ] [1,3] benzoxazine derivative CN-probe Download PDFInfo
- Publication number
- CN111019646A CN111019646A CN201911334308.9A CN201911334308A CN111019646A CN 111019646 A CN111019646 A CN 111019646A CN 201911334308 A CN201911334308 A CN 201911334308A CN 111019646 A CN111019646 A CN 111019646A
- Authority
- CN
- China
- Prior art keywords
- naphthalimide
- probe
- pyrrolo
- benzoxazine derivative
- yellow solid
- 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.)
- Granted
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D498/16—Peri-condensed systems
-
- 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"
- 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
-
- 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
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the technical field of organic photoelectric or fluorescent probe synthesis, and discloses a naphthalimide pyrrolo [2,1-b ]][1,3]Benzoxazine derivative CN-probe and application thereof, wherein the probe is N-butyl-3, 4- (2 ' -phenyl-3 ', 3 ' -dimethyl indole) -1, 8-naphthalimido [2,1-b ]][1,3]Benzoxazines, probes not subject to F‑，Cl‑，Br‑，I‑，CH3COO‑，ClO4 ‑，NO2 ‑，NO3 ‑，SCN‑，SO4 2‑，Fe3+，Fe2+，Cu+，Sn2+，Cd2+，Ca2+，Mg2+，Li+，Ba2+，Na+The interference of ions shows good anti-interference capability even if the ion concentration of the anions and cations is as high as 1 mM. The probe has high sensitivity, and the lowest detectable cyanide ion concentration is 5.0 multiplied by 10‑8mol·L‑1。
Description
Technical Field
The invention belongs to the technical field of organic photoelectric or fluorescent probe synthesis, and relates to naphthalimide pyrrolo [2,1-b ]][1,3]Benzoxazine derivative CN-Probes and uses thereof.
Background
Various countries have very strict inspection standards for cyanide ions in industrial wastewater, domestic sewage, drinking water, etc., and the environmental protection agency in the united states of america stipulates that the maximum safe concentration in drinking water is 0.2 mg/L.
The 1, 8-naphthalimide has the chemical structure characteristic of a large-pi-bond conjugated system, is commonly used as a chromophore and a fluorescent functional group, and has the characteristic color of yellow green. After different substituents are introduced on N and C-4 positions of 1, 8-naphthalic anhydride or 1, 8-naphthalimide, one end of a molecule is introduced with a strong electron-donating group, and the other end of the molecule has a strong electron-withdrawing group to form a strong push-pull electron system, electrons in the system are easy to be irradiated by light to generate transition so as to generate fluorescence, and fluorescence with different colors can be obtained to meet different actual requirements. The 1, 8-naphthalimide derivative has bright color, high fluorescence intensity and good photo-thermal stability and is widely applied to the fields of fluorescent dyes, fluorescent whitening agents, fluorescent sensors and the like. However, the currently reported 1, 8-naphthalimide derivatives are generally detected in a neutral environment, have weak anti-interference capability, high detectability and insufficient sensitivity in practical application, and simultaneously cannot well control CN-Identification of (1).
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides naphthalimide-pyrrolo [2,1-b ]][1,3]Benzoxazine derivative CN-Probes and uses thereof.
The invention is realized by the technical proposal that the invention is a naphthalimide pyrrolo [2,1-b ]][1,3]Benzoxazine derivative CN-A probe, said N-butyl-1, 8-naphthalimido-pyrrolo [2,1-b][1,3]Benzoxazine derivative CN-The probe is (N-butyl-3, 4- (2 ' -phenyl-3 ', 3 ' -dimethyl indole) -1, 8-naphthalimido [2, 1-b)][1,3]Benzoxazine) of the formula
The probe synthesizes an oxazine compound with a photoswitch and fluorescence performance by taking a 1, 8-naphthalimide fragment as a fluorophore, an oxazine fragment as a photoswitch and a cyanogen ion recognition group, and the oxazine compound is used as a signal output for cyanogen ion recognition through the change of ultraviolet absorption and fluorescence spectrum. The 1, 8-naphthalimide segment is introduced not only as a fluorescent group of the oxazine compound, but also the 1, 8-naphthalimide has double functions of a larger conjugated system and electron withdrawing in the ring-opening structure of the oxazine compound, thereby being beneficial to stabilizing the ring-opening structure of the oxazine compound and improving CN-The stability of the probe can be kept unchanged for 50 min.
Another object of the present invention is to provide a method for synthesizing the naphtho-imidazopyrrolo [2,1-b ] [1,3] benzoxazine derivative CN-probe, comprising:
s01, dissolving 4-hydrazino-N-butyl-1, 8-naphthalimide in absolute ethyl alcohol, heating to 80 ℃ for reflux, dropwise adding an ethanol solution of phenyl isopropyl ketone in 15 minutes, continuously reacting for 3.5 hours, dropwise adding concentrated flow acid in 10 minutes, heating for reflux for 3.5 hours, cooling overnight, filtering to obtain a precipitate, performing column chromatography by using ethyl acetate/petroleum ether as eluent to separate out a golden yellow solid, wherein the molar ratio of the 4-hydrazino-N-butyl-1, 8-naphthalimide to the phenyl isopropyl ketone is not more than 1: 1.1;
s02, taking the yellow solid obtained in the step 1 and 5-nitro-2-chloromethyl phenol according to the mass ratio of 1.85:1 respectively, adding the yellow solid and the 5-nitro-2-chloromethyl phenol into acetonitrile to dissolve, heating and refluxing for 48 hours under the protection of Ar gas, cooling to room temperature, removing the acetonitrile under reduced pressure, dissolving with dichloromethane as little as possible, sequentially washing with 10% KOH solution and water respectively, drying an organic phase with anhydrous magnesium sulfate overnight, performing suction filtration, concentrating, and performing column chromatography separation on a concentrated residue by using ethyl acetate/petroleum ether as eluent to obtain a yellow solid. The aqueous solution of KOH was added to remove the acid generated during the reaction, water was added to wash to remove excess KOH,
further, the synthetic route of the golden solid is as follows:
further, the synthetic route of the yellow solid is as follows:
another object of the present invention is to provide the naphtho-imido-pyrrolo [2,1-b ]][1,3]Benzoxazine derivative CN-The cation concentration of the probe pair is 0.1 mol.L-1And the anion concentration is 2 mmol.L-1CN in salt solution-The use of detection.
In summary, the advantages and positive effects of the invention are: is not subject to F-，Cl-，Br-，I-， CH3COO-，ClO4 -，NO2 -，NO3 -，SCN-，SO4 2-，Fe3+，Fe2+，Cu+，Sn2+， Cd2+，Ca2+，Mg2+，Li+，Ba2+，Na+The interference of ions shows good anti-interference capability even if the ion concentration of the anions and cations is as high as 1 mM. The probe has high sensitivity, and the lowest detectable cyanide ion concentration is 5.0 multiplied by 10-8mol·L-1. The invention not only can eliminate the influence of the test environment on the stability of the probe, but also can effectively track the detection process in situ. The HCN limit value of the grain agricultural products of China, America and European Union is 185.19 mu mol.L-1The beverage limit value is 1.85-185.19 mu mol/L-1The limit value of the sugar for fruits, vegetables and vegetables is 185.19-1851.85 mu mol.L-1The international health organization for drinking water stipulates that HCN is less than 1.9 mu mol.L-1The limit value of HCN discharged by the water pollutants of the enterprise is 18.52 mu mol.L-1. Minimum detection concentration (0.05. mu. mol. L) of the probe of the present invention-1) All are lower than the limit value, therefore, the method can be used for residual CN in food, beverage, agricultural products, enterprise sewage and drinking water-The rapid detection and monitoring.
The naphthoimido [2,1-b ] of the present invention][1,3]The benzoxazine compound has strong anti-interference capability to anions and cations, even 1000 equivalents of anions, 20 equivalents of cations have no interference, the anti-interference effect of the benzoxazine compound is far better than that of a probe in a patent CN109053572A to 6 equivalents of interference anions, and the anti-interference effect of the benzoxazine compound is better than that of a probe in a patent CN104003935A to 2.1 equivalents of interference anions. The sensitivity is improved by one order of magnitude and is higher than the detection limit of CN106518763B (2.3 multiplied by 10)-7Mu mol/L, the probe of the invention far exceeds various inspection standards, the response time is within 30s, which is much longer than the response time of 10min of the probe of patent CN106518763B, and the stability is good, and the output signal is kept stable and unchanged within 50 min. Wide response range (5.0 × 10)-8mol/L to 1.0X 10-3In the mol/L range, the response range of the probe is 1.0 multiplied by 10 and is better than that of the probe in the patent CN106518763B-6～8×10-5mol/L. Therefore, the compound can be used as a real-time online detection means, and has a very high application prospect in the aspects of environmental protection, water body monitoring and the like.
Drawings
FIG. 1 is a naphthoquinopyrrolo [2,1-b ] diagram of example 1 of the present invention][1,3]Benzoxazine derivative CN-Probe needle1H NMR spectrum;
FIG. 2 is a naphthoquinopyrrolo [2,1-b ] diagram of example 2 of the present invention][1,3]Acetonitrile solution of benzoxazine derivative (1.0X 10)-4Absorption spectra before and after mol. L-1,298K) light irradiation;
FIG. 3 is a naphthoquinopyrrolo [2,1-b ] diagram of example 2 of the present invention][1,3]Acetonitrile solution of benzoxazine derivative (1.0X 10)-4mol·L-1298K) ultraviolet absorption spectrum after dripping different cyanide ions;
FIG. 4 is a naphthoquinopyrrolo [2,1-b ] diagram of example 3 of the present invention][1,3]Benzoxazine derivative (0.1 mmol. L)-1298K) in acetonitrile solutionAbsorption spectrum at 414nm after the same anion solution;
FIG. 5 is a naphthoquinopyrrolo [2,1-b ] diagram of example 4 of the present invention][1,3]Benzoxazine (0.1 mmol. L)-1298K) absorption spectrum at 414nm after dropping different metal cation solutions in acetonitrile solution;
FIG. 6 is an absorption spectrum at 414nm of naphthoquinopyrrolo [2,1-b ] [1,3] benzoxazine of example 6 of the present invention after dropping a solution of cyanide ion in acetonitrile.
Detailed description of the preferred embodiments
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples.
Example 1
Naphthalimide pyrrolo [2,1-b][1,3]Benzoxazine derivative CN-The structural formula of the probe is as follows:
the preparation method comprises the following specific steps:
in a 100mL round-bottomed flask, 4-bromo-1, 8-naphthalic anhydride (5g, 18mmol), glacial acetic acid (50mL), N-butylamine (1.7g, 23.3mmol) were added, the mixture was refluxed for 4 hours, naturally cooled to room temperature, and after cooling, 100mL of water was added to precipitate 5g of a white solid (N-butyl-4-bromo-1, 8-naphthalimide), the yield was 83%. Recrystallizing with absolute ethyl alcohol at m.p. of 109-110 ℃.
The synthetic route of the N-butyl-4-bromo-1, 8-naphthalimide is as follows:
adding N-butyl-4-bromo-1, 8-naphthalimide (5g, 18.0mmol), hydrazine hydrate (80%, 2mL) and 20mL of ethylene glycol monomethyl ether into a 50mL round-bottom flask, carrying out reflux reaction for 3h, naturally cooling to room temperature, carrying out suction filtration, and recrystallizing the crude product with absolute ethanol to obtain 3.6g of golden yellow needle-shaped crystals (4-hydrazino-N-butyl-1, 8-naphthalimide), wherein the yield is 84%. The melting point is 220-222 ℃.
The synthetic route of the 4-hydrazino-N-butyl-1, 8-naphthalimide is as follows:
4-hydrazino-N-butyl-1, 8-naphthalimide (2.88g, 0.01mol) is added into absolute ethyl alcohol (80mL), heated to 80 ℃ for reflux, added with a solution of phenyl isopropyl ketone (1.6 g, 0.011mol) in ethanol within 15 minutes, reacted for 3.5 hours, added with concentrated sulfuric acid (2.1g) within 10 minutes, heated for reflux for 3.5 hours, cooled overnight, precipitated with yellow crystals, and filtered. Column chromatography (mobile phase is ethyl acetate/petroleum ether, 1: 10) to obtain a golden yellow solid (0.67g) (N-butyl-3, 4- (2 ' -phenyl-3 ', 3 ' -dimethylindole) -1, 8-naphthalimide), yield is 17%, and m.p.184-185 ℃.
H spectrum detection is carried out on the golden yellow solid: 1H NMR (400MHz, CDCl)3，ppm)：δ9.07(dd，1H，Ar-H)，8.66-8.68(m，2H，Ar-H)，8.34-8.36(m， 2H，Ar-H)，7.86(dd，1H，Ar-H)，7.57-7.61(m，3H，Ar-H)，4.24 (t，2H，N-CH2)，1.72-1.80(m，8H，CH2，CH3)，1.44-1.51(m，2H， CH2)，1.01(t，3H，CH3)；
And C spectrum detection is carried out on the golden yellow solid:13C NMR(400MHz，CDCl3，ppm)：δ187.81，164.56，154.28，145.01，132.62，131.70，131.24，130.20， 128.96，126.82，125.33，124.53，122.82，119.95，55.12，40.29，30.30， 24.23，20.41，13.89；
ESI-MS(70eV):m/z＝397.19[M+1]+。
the synthetic route for the golden solid is:
dissolving N-butyl-3, 4- (2 ' -phenyl-3 ', 3 ' -dimethylindole) -1, 8-naphthalimide (0.1g, 0.25mmol) and 5-nitro-2-chloromethyl phenol (0.054g, 0.29mmol) in acetonitrile (5mL), and heating to reflux under Ar atmosphere for 4After 8 hours, the mixture was cooled to room temperature, the acetonitrile was removed under reduced pressure, the mixture was dissolved in a small amount of methylene chloride, and the mixture was washed with an aqueous solution of KOH (0.2M, 2mL) and water (5mL), separated, dried over anhydrous magnesium sulfate overnight, filtered with suction, and concentrated. The residue was separated by column chromatography (ethyl acetate/petroleum ether as mobile phase, 1: 10) to give the objective 4(36mg) (naphthoquinopyrrolo [2,1-b ] as a yellow solid][1,3]Benzoxazine derivative CN-Probe), yield 26%, m.p.: 205 to 207 ℃.
As in fig. 1, the yellow solid was subjected to H spectrum detection:1H NMR(400MHz，CDCl3， ppm)：δ8.57-8.62(m，2H，Ar-H)，8.45(s，1H，Ar-H)，7.95-7.98 (dd，1H，Ar-H)，7.91-7.92(d，1H，Ar-H)，7.69-7.73(dd，1H， Ar-H)，7.61-7.65(m，2H，Ar-H)，7.39-7.41(m，3H，Ar-H)，6.99-7.01(d， 1H，Ar-H)，5.60-5.64(d，1H，CH2)，5.08-5.12(d，1H，CH2)，4.16-4.19 (t，2H，N-CH2)，1.79(s，3H，CH3)，1.68-1.72(m，2H，CH2)，1.41-1.46(m，2H，CH2)，1.25(s，3H，CH3)，0.95-0.98(t，3H，CH3) (ii) a C spectrum detection is carried out on the yellow solid:13C NMR(400MHz，CDCl3，ppm)：δ13.87，19.38， 20.38，28.25，29.70，30.25，40.14，45.09，49.23，104.69，115.09， 118.47，118.52，120.52，122.40，123.81，124.12，125.12，126.37， 127.61，128.12，129.43，130.43，131.13，133.99，135.02，141.59， 148.48，158.14，163.97，164.37；
ESI-MS(70eV):m/z＝548.22[M+1]+，570.20[M+23]+， 1117.41[2M+23]+。
the yellow solid and the route are:
example 2
Naphthoimido pyrrolo [2,1-b ] [1,3] benzoxazine derivative photoswitch
Accurate weighing of naphthalimide-pyrrolo [2,1-b][1,3]Benzoxazine derivatives were formulated to 1.0 × 10- 4mol·L-1Acetonitrile solution of (1). The absorption spectra were measured on a Varian Cray 500 UV-Vis absorption spectrometer with a 10mm cell.
The naphthalimide-pyrrolo [2,1-b ] [1,3] benzoxazine derivative has ring-opening reaction under dark conditions, a new weak absorption peak appears at 561nm, and meanwhile, a colorless oxazine compound acetonitrile solution turns into red. As shown in fig. 2. This indicates that the spiro C-O bond is susceptible to cleavage and ring-opening reaction, forming an amphoteric merocyanine form, resulting in a color change in oxazines. Under the illumination of visible light, the new characteristic peak appearing at 561nm disappears, as does the UV absorption curve before ring opening. The reversible spectral change shows that the structure of the photochromic naphtho-imido pyrrolo [2,1-b ] [1,3] benzoxazine derivative is changed between a closed ring body a and an open ring body b as shown in the formula 1 under different external stimuli.
Example 3
Naphthylimidopyrrolo [2,1-b][1,3]Benzoxazine derivative CN-Probe application
Accurate weighing of naphthalimide-pyrrolo [2,1-b][1,3]Benzoxazine derivatives were formulated to 1.0 × 10- 4mol·L-1Acetonitrile solution of (1). The absorption spectra were measured on a Varian Cray 500 UV-Vis absorption spectrometer with a 10mm cell.
The naphthalimide pyrrolo [2,1-b ] [1,3] benzoxazine derivative in acetonitrile undergoes a ring-opening reaction under a dark condition to form an indole salt structure (formula 1, b), and the spiro carbon atom is enriched with partial positive charges and is easily attacked by nucleophilic groups. Due to the strong nucleophilicity of cyanide ions, when cyanide ions are added dropwise into an oxazine solution, an absorption peak at 561nm disappears, and a new absorption peak appears at 414nm (as shown in fig. 3), which is attributed to the nucleophilic addition reaction of cyanide ions to the oxazine ring-opening body (formula 1, c). The acetonitrile solution of oxazine also changed from red to light yellow. The change of color provides convenience for visual and intuitive observation.
The concentration of the oxazine compound acetonitrile solution in the ion interference experiment is 1.0 multiplied by 10-4mol·L-1The concentration of the cation (both sodium salts) was 0.1 mol. L-1The concentration of the anion (chloride, sulfate and acetate) is 2 mmol.L-1All diluted to 1.0X 10 in the test-4mol·L-1。
Naphthylimidopyrrolo [2,1-b][1,3]The colorimetric detection of the benzoxazine derivative is based on the response change of a characteristic absorption peak at 414nm, so that cyanide ions with different solubility are dripped into acetonitrile solution of a given oxazine compound, the characteristic ultraviolet absorption intensity of the benzoxazine derivative is correspondingly changed, and the solubility of the cyanide ions can be quantitatively determined. As shown in FIG. 3, at 5.0X 10-8mol·L-1To 1.0X 10-3mol·L-1In this range, the concentration of cyanide ion has a good correlation with the intensity of the absorption spectrum. When the concentration of the cyanogen ion is 5.0X 10-8mol·L-1When the method is used, a clear detectable absorption peak can be obtained on an ultraviolet detector relative to the time between the dropwise addition of the cyanide ions, so that the lowest detectable cyanide ion concentration is 5.0 x 10-8mol·L-1。
Example 4
Series of anion interference experiments of naphthalimide pyrrolo [2,1-b ] [1,3] benzoxazine derivative
Dissolving naphthalimide-pyrrolo [2,1-b ] with acetonitrile][1,3]The benzoxazine derivative is prepared into 0.1 mmol.L-1Solutions, aqueous solutions of different anions (sodium salts) were added dropwise and tested for uv-vis absorption spectra (fig. 4). The majority of the anions of the compound such as F can be seen-, Cl-,Br-,I-,NO2 -,NO3 -,SCN-,SO4 2-,HSO3 -,ClO4 -Etc. all have good anti-interference performance even if the ion concentration is as high as 1 mmol.L-1The oxazine compound still shows good anti-interference capability.
Example 5
Series of cation interference experiments of naphthalimide pyrrolo [2,1-b ] [1,3] benzoxazine derivative
Dissolving naphthalimide-pyrrolo [2,1-b ] with acetonitrile][1,3]The benzoxazine derivative is prepared into 0.1 mmol.L-1The solution was added dropwise with aqueous solutions of different cations and tested for uv-vis absorption spectra (fig. 5). The compound can be seen to have a relatively large portion of cations such as Fe3+，Fe2+， Cu+，Sn2+，Cd2+，Ca2+，Mg2+，Li+，Ba2+Etc. all have good anti-interference performance even if the ion concentration is as high as 1 mmol.L-1The oxazine compound still shows good anti-interference capability.
Example 6
Response time and stability of naphthalimide-pyrrolo [2,1-b ] [1,3] benzoxazine derivative
Dissolving naphthalimide-pyrrolo [2,1-b ] with acetonitrile][1,3]The benzoxazine derivative is prepared into 0.1 mmol.L-1The solution is added with cyanogen ions with equivalent weight. The UV-visible absorption spectrum was tested (FIG. 6). Within 30 seconds, the characteristic absorption intensity at 414nm changes significantly and can be kept substantially unchanged for 50 minutes. The oxazine compound has rapid response to cyanide ions and high stability.
Claims (5)
1. Naphthalimide pyrrolo [2,1-b][1,3]Benzoxazine derivative CN-The probe is characterized in that the N-butyl-1, 8-naphthalimido pyrrolo [2,1-b ] is][1,3]Benzoxazine derivative CN-The probe is N-butyl-3, 4- (2 ' -phenyl-3 ', 3 ' -dimethyl indole) -1, 8-naphthalimide [2,1-b][1,3]A benzoxazine of the formula
2. A method of synthesizing the naphthoimidyl pyrrolo [2,1-b ] [1,3] benzoxazine derivative CN-probe of claim 1, comprising the steps of:
s01, dissolving 4-hydrazino-N-butyl-1, 8-naphthalimide in absolute ethyl alcohol, heating to 80 ℃ for reflux, dropwise adding an ethanol solution of phenyl isopropyl ketone in 15 minutes, continuously reacting for 3.5 hours, dropwise adding concentrated flow acid in 10 minutes, heating for reflux for 3.5 hours, cooling overnight, filtering to obtain a precipitate, performing column chromatography by using ethyl acetate/petroleum ether as eluent to separate out a golden yellow solid, wherein the molar ratio of the 4-hydrazino-N-butyl-1, 8-naphthalimide to the phenyl isopropyl ketone is not more than 1: 1.1;
s02, respectively taking the yellow solid obtained in the step 1 and 5-nitro-2-chloromethyl phenol according to the mass ratio of 1.85:1, adding the yellow solid and the 5-nitro-2-chloromethyl phenol into acetonitrile to dissolve, heating and refluxing for 48 hours under the protection of Ar gas, cooling to room temperature, removing the acetonitrile under reduced pressure, dissolving with dichloromethane as little as possible, adding a KOH aqueous solution and water, carrying out liquid separation, drying over night by anhydrous magnesium sulfate, carrying out suction filtration, concentrating, and carrying out column chromatography separation on the concentrated residue by using ethyl acetate/petroleum ether as eluent to obtain a yellow solid.
3. The method for synthesizing the naphthalimide-pyrrolo [2,1-b ] [1,3] benzoxazine derivative CN-probe according to claim 2, wherein the synthetic route of the golden yellow solid is as follows:
4. the method for synthesizing the naphthalimide-pyrrolo [2,1-b ] [1,3] benzoxazine derivative CN-probe according to claim 2, wherein the synthetic route of the yellow solid is as follows:
5. a naphthoquinopyrrolo [2,1-b ] as defined in claim 1][1,3]Benzoxazine derivative CN-The cation concentration of the probe pair is 0.1 mol.L-1And the anion concentration is 2 mmol.L-1CN in salt solution-The use of detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911334308.9A CN111019646B (en) | 2019-12-23 | 2019-12-23 | Preparation and application of naphthalimide pyrrolo [2,1-b ] [1,3] benzoxazine derivative CN-probe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911334308.9A CN111019646B (en) | 2019-12-23 | 2019-12-23 | Preparation and application of naphthalimide pyrrolo [2,1-b ] [1,3] benzoxazine derivative CN-probe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111019646A true CN111019646A (en) | 2020-04-17 |
| CN111019646B CN111019646B (en) | 2023-03-31 |
Family
ID=70211529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911334308.9A Active CN111019646B (en) | 2019-12-23 | 2019-12-23 | Preparation and application of naphthalimide pyrrolo [2,1-b ] [1,3] benzoxazine derivative CN-probe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111019646B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003935A (en) * | 2014-05-16 | 2014-08-27 | 上海应用技术学院 | 4-aroyl-1,8-naphthalimide compound and preparation method and use thereof |
| CN104478855A (en) * | 2014-12-09 | 2015-04-01 | 上海应用技术学院 | 3-amino-4-((E)-pyridine-2(1-hydro)-alkenyl acetonitrile)-1,8-naphthalimide derivative |
| CN106518763A (en) * | 2016-11-03 | 2017-03-22 | 商丘师范学院 | High-selectivity fluorescence probe for detecting cyanide ions in ratio mode and synthesis method and application thereof |
| CN109053572A (en) * | 2018-09-27 | 2018-12-21 | 上海应用技术大学 | The bromo- 2- of 4- trifluoromethyl -6- replaces acetonitrile -1,8- naphthoyl imide compounds and its preparation method and application |
-
2019
- 2019-12-23 CN CN201911334308.9A patent/CN111019646B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003935A (en) * | 2014-05-16 | 2014-08-27 | 上海应用技术学院 | 4-aroyl-1,8-naphthalimide compound and preparation method and use thereof |
| CN104478855A (en) * | 2014-12-09 | 2015-04-01 | 上海应用技术学院 | 3-amino-4-((E)-pyridine-2(1-hydro)-alkenyl acetonitrile)-1,8-naphthalimide derivative |
| CN106518763A (en) * | 2016-11-03 | 2017-03-22 | 商丘师范学院 | High-selectivity fluorescence probe for detecting cyanide ions in ratio mode and synthesis method and application thereof |
| CN109053572A (en) * | 2018-09-27 | 2018-12-21 | 上海应用技术大学 | The bromo- 2- of 4- trifluoromethyl -6- replaces acetonitrile -1,8- naphthoyl imide compounds and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111019646B (en) | 2023-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Long et al. | A ratiometric fluorescent probe for iron (III) and its application for detection of iron (III) in human blood serum | |
| CN108409726B (en) | Coumarin 2-hydrazinobenzothiazole Schiff base Cd2+Preparation and application of fluorescent probe | |
| Tian et al. | A novel turn-on Schiff-base fluorescent sensor for aluminum (III) ions in living cells | |
| Zhang et al. | Substituent-dependent fluorescent sensors for zinc ions based on carboxamidoquinoline | |
| CN106632064B (en) | Reversible dihydroxy phenanthroimidazole Hg2+Fluorescent probe synthesis and methods of use | |
| Mabhai et al. | A novel chemosensor based on rhodamine and azobenzene moieties for selective detection of Al 3+ ions | |
| WO2019196022A1 (en) | 1,8-naphthalimide derivative, preparation method therefor and use thereof | |
| Guan et al. | A highly selective PET-based chemosensor for instant detecting of Zn 2+ | |
| CN113637004B (en) | Aluminum ion detection fluorescent probe based on bifunctional small organic molecule as matrix, and preparation method and application thereof | |
| CN110028471B (en) | Coumarin Schiff base Cu2+Fluorescent probe and preparation method and application thereof | |
| Wei et al. | Combining the PeT and ICT mechanisms into one chemosensor for the highly sensitive and selective detection of zinc | |
| Tachapermpon et al. | Near-infrared aza-BODIPY fluorescent probe for selective Cu 2+ detection and its potential in living cell imaging | |
| Kim et al. | An off-on fluorescent sensor for detecting a wide range of water content in organic solvents | |
| CN108658838B (en) | Heptamethine indocyanine-based formaldehyde fluorescent probe and preparation method and use method thereof | |
| Qin et al. | Ratiometric fluorescent probe for Al 3+ based on coumarin derivative in aqueous media | |
| KR101129574B1 (en) | Coumarin derivatives having CuII ion selectivity and luminescence sensor using the same | |
| CN109608382B (en) | Fluorescent probe for detecting cyanide ions and hypochlorous acid as well as preparation and application thereof | |
| Qu et al. | Fluorescent Probe Derived from 1, 8-Naphthalimide-Schiff Base for Copper (Ii) Ion: Synthesis, Characterization, and Application | |
| Wang et al. | Dimethyl yellow-based colorimetric chemosensors for “naked eye” detection of Cr 3+ in aqueous media via test papers | |
| Lee et al. | “Turn-on” fluorescent and colorimetric detection of Zn2+ ions by rhodamine-cinnamaldehyde derivative | |
| CN108250211B (en) | Fluorescent probe for detecting Zn2+ and preparation method thereof | |
| Gong et al. | Selective sensing of H 2 PO 4−(Pi) driven by the assembly of anthryl pyridinium ligands | |
| Esteban-Gómez et al. | A two-channel chemosensor for the optical detection of carboxylic acids, including cholic acid | |
| CN111019646B (en) | Preparation and application of naphthalimide pyrrolo [2,1-b ] [1,3] benzoxazine derivative CN-probe | |
| CN111393461B (en) | Palladium ion fluorescent probe compound based on BODIPY and synthetic method 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 |