CN104974090B - Naphthalimide derivative, preparation method and its usage - Google Patents
Naphthalimide derivative, preparation method and its usage Download PDFInfo
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- CN104974090B CN104974090B CN201510367288.0A CN201510367288A CN104974090B CN 104974090 B CN104974090 B CN 104974090B CN 201510367288 A CN201510367288 A CN 201510367288A CN 104974090 B CN104974090 B CN 104974090B
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- naphthalimide
- naphthalimide derivative
- derivative
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- hydrazino
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- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 19
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 27
- 239000000523 sample Substances 0.000 claims description 16
- 238000001514 detection method Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000005104 Neeliglow 4-amino-1,8-naphthalimide Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- SMQUZDBALVYZAC-UHFFFAOYSA-N ortho-hydroxybenzaldehyde Natural products OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- -1 salicylaldehyde Schiff base Chemical class 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 5
- DTUOTSLAFJCQHN-UHFFFAOYSA-N 4-bromo-1,8-naphthalic anhydride Chemical compound O=C1OC(=O)C2=CC=CC3=C2C1=CC=C3Br DTUOTSLAFJCQHN-UHFFFAOYSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000003068 molecular probe Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002466 imines Chemical group 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- BYVCTYDTPSKPRM-UHFFFAOYSA-N naphthalene-1-carbonyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(OC(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 BYVCTYDTPSKPRM-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910017108 Fe—Fe Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The present invention relates to a kind of naphthalimide derivatives, preparation method and its usage, belong to technical field of organic synthesis.The naphthalimide derivative, structural formula are as follows:Naphthalimide derivative of the invention not only has good ion selectivity, can identify Fe with the form relay of fluorescence " On-Off-On "3+With
Description
Technical Field
The invention relates to a naphthalimide derivative, a preparation method and application thereof, belonging to the technical field of organic synthesis.
Background
The naphthalimide derivative has high luminous efficiency, moderate fluorescence emission wavelength, large Stokes shift and good thermal stability, and is particularly suitable for being used as a fluorescent group of a fluorescent 'on-off' type molecular probe. In the prior art, the research focuses on introducing different substituents as recognition groups on a naphthalene ring of naphthalimide, and using the substituents as ion recognition probes; the imine position is used for connecting long-chain aliphatic amine, so that the flexibility and the solubility of the molecule are improved, and the research on the imine position connecting recognition group is not deep enough.
The invention takes 1, 8-naphthalimide as a fluorescent group, introduces salicylaldehyde Schiff base at the imine position, and synthesizes a potential fluorescent molecular probe.
Disclosure of Invention
The invention aims to provide a naphthalimide derivative, a preparation method and application thereof, wherein the naphthalimide derivative has good ion selectivity and can be used for a fluorescent 'on-off' type molecular probe.
The structural formula of the naphthalimide derivative is as follows:
the preparation method of the naphthalimide derivative comprises the following steps:
(1) preparation of N-hydrazino-4-amino-1, 8-naphthalimide:
adding 4-bromo-1, 8-naphthalene anhydride and 80% hydrazine hydrate into the mixed solution of ethylene glycol butyl ether and ethanol, and adding N2Heating to reflux under protection, tracking the reaction by TLC, cooling to room temperature after 4-bromo-1, 8-naphthalic anhydride completely participates in the reaction, pouring the reaction liquid into distilled water under vigorous stirring, filtering, and drying a filter cake under vacuum to obtain N-hydrazino-4-amino-1, 8-naphthalimide;
(2) preparation of 1, 8-naphthalimide derivative:
adding N-hydrazino-4-amino-1, 8-naphthalimide, salicylaldehyde and glacial acetic acid into ethanol, heating to reflux, tracking reaction by TLC, cooling to room temperature after N-hydrazino-4-amino-1, 8-naphthalimide completely participates in the reaction, and filtering to obtain a crude product of N-hydrazino-4-amino-1, 8-naphthalimide; recrystallizing with mixed solution of N, N-dimethylformamide and acetonitrile to obtain the 1, 8-naphthalimide derivative.
The synthetic route is as follows:
wherein,
the molar ratio of the 4-bromo-1, 8-naphthalic anhydride to 80% hydrazine hydrate is: 1:3.7-1:7.0.
In the step (1), the volume ratio of the ethylene glycol butyl ether to the ethanol is 1:1-2: 1. The drying temperature is 60 ℃, and the drying time is as follows: 8-12 hours.
In the step (2), the molar ratio of the N-hydrazino-4-amino-1, 8-naphthalimide to the salicylaldehyde to the glacial acetic acid is as follows: 1:4:0.05-1:8: 0.05; the volume ratio of the N, N-dimethylformamide to the acetonitrile is 1: 1.
The application of the naphthalimide derivative in detecting Fe3+Andthe probe of (4) was used.
In conclusion, the beneficial effects of the invention are as follows:
the naphthalimide derivative has good ion selectivity, and can relay-identify Fe in a fluorescent 'on-off-on' form3+Andand the preparation method is simple and easy to operate.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of N-hydrazino-4-amino-1, 8-naphthalimide prepared by the embodiment of the invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a 1, 8-naphthalimide derivative prepared by an example of the present invention;
FIG. 3 is a diagram of the 1, 8-naphthalimide derivative probe of the present invention against Fe3+The selective identification schematic of (1);
FIG. 4 shows the detection of Fe by 1, 8-naphthalimide derivative ion probe3+The interference immunity identification schematic diagram of (1);
FIG. 5 shows the 1, 8-naphthalimide derivative solution with Fe3+A graph of change in concentration-increasing fluorescence spectra;
FIG. 6 shows 1, 8-naphthalimide derivatives with Fe3+Complex pairThe selective identification schematic of (1);
FIG. 7 shows 1, 8-naphthalimide derivatives with Fe3+Intensity of complex fluorescence withA graph of change in concentration-increasing fluorescence spectra;
FIG. 8 shows 1, 8-naphthalimide derivatives, 1, 8-naphthalimide derivatives and Fe3+Complex and 1, 8-naphthalimide derivative and Fe3+Complexes andcombined ESI mass spectra.
Detailed Description
The present invention is further described below with reference to examples.
The chemical structural formula of the 1, 8-naphthalimide derivative in examples 1 to 3 is shown below:
example 1
The preparation method of the naphthalimide derivative described in this example is as follows:
(1) preparation of N-hydrazino-4-amino-1, 8-naphthalimide:
4-bromo-1, 8-naphthalenic anhydride (1.39g,13.5mmol) and 80% hydrazine hydrate (0.6g,50mmol) were added to 50mL of a mixture of butyl cellosolve and ethanol (v/v ═ 1:1), and N was added2Heating to reflux under protection, tracking reaction by TLC, cooling to room temperature after 4-bromo-1, 8-naphthalic anhydride completely participates in reaction, and violently coolingPouring the reaction solution into distilled water under stirring, filtering, and drying a filter cake for 8 hours at 60 ℃ under vacuum to obtain 1.11g of N-hydrazino-4-amino-1, 8-naphthalimide with the yield of 92%;
(2) preparation of 1, 8-naphthalimide derivative:
adding N-hydrazino-4-amino-1, 8-naphthalimide (1.20g,5mmol), salicylaldehyde (0.24g,20mmol) and glacial acetic acid (2 drops) into 150mL ethanol, heating to reflux, tracking reaction by TLC, cooling to room temperature after N-hydrazino-4-amino-1, 8-naphthalimide completely participates in reaction, and filtering to obtain a crude product of N-hydrazino-4-amino-1, 8-naphthalimide; recrystallization from a mixture of N, N-dimethylformamide and acetonitrile (v/v ═ 1:1) gave 1.89g of the 1, 8-naphthalimide derivative in 85% yield.
Example 2
The preparation method of the naphthalimide derivative described in this example is as follows:
(1) preparation of N-hydrazino-4-amino-1, 8-naphthalimide:
4-bromo-1, 8-naphthalenic anhydride (1.39g,13.5mmol) and 80% hydrazine hydrate (0.81g,67.5mmol) were added to 50mL of a mixture of butyl cellosolve and ethanol (v/v ═ 1:1), and N was added2Heating to reflux under protection, tracking the reaction by TLC, cooling to room temperature after 4-bromo-1, 8-naphthalic anhydride completely participates in the reaction, pouring the reaction solution into distilled water under vigorous stirring, filtering, and drying a filter cake at 60 ℃ for 10 hours under vacuum to obtain 1.13g of N-hydrazino-4-amino-1, 8-naphthalimide with the yield of 93%;
(2) preparation of 1, 8-naphthalimide derivative:
adding N-hydrazino-4-amino-1, 8-naphthalimide (1.20g,5mmol), salicylaldehyde (0.36g,30mmol) and glacial acetic acid (2 drops) into 150mL ethanol, heating to reflux, tracking reaction by TLC, cooling to room temperature after N-hydrazino-4-amino-1, 8-naphthalimide completely participates in reaction, and filtering to obtain a crude product of N-hydrazino-4-amino-1, 8-naphthalimide; recrystallization from a mixture of N, N-dimethylformamide and acetonitrile (v/v ═ 1:1) gave 1.88g of the 1, 8-naphthalimide derivative in 84% yield.
Example 3
The preparation method of the naphthalimide derivative described in this example is as follows:
(1) preparation of N-hydrazino-4-amino-1, 8-naphthalimide:
4-bromo-1, 8-naphthalenic anhydride (1.39g,13.5mmol) and 80% hydrazine hydrate (1.13g,94.5mmol) were added to 50mL of a mixture of butyl cellosolve and ethanol (v/v ═ 1:1), and N was added2Heating to reflux under protection, tracking the reaction by TLC, cooling to room temperature after 4-bromo-1, 8-naphthalic anhydride completely participates in the reaction, pouring the reaction solution into distilled water under vigorous stirring, filtering, and drying the filter cake at 60 ℃ for 12 hours under vacuum to obtain 1.08g of N-hydrazino-4-amino-1, 8-naphthalimide with the yield of 90%;
(2) preparation of 1, 8-naphthalimide derivative:
adding N-hydrazino-4-amino-1, 8-naphthalimide (1.20g,5mmol), salicylaldehyde (0.48g,40mmol) and glacial acetic acid (2 drops) into 150mL ethanol, heating to reflux, tracking reaction by TLC, cooling to room temperature after N-hydrazino-4-amino-1, 8-naphthalimide completely participates in reaction, and filtering to obtain a crude product of N-hydrazino-4-amino-1, 8-naphthalimide; recrystallization from a mixture of N, N-dimethylformamide and acetonitrile (v/v ═ 1:1) gave 1.94g of the 1, 8-naphthalimide derivative in 87% yield.
Carrying out structural characterization on the products prepared in the examples 1-3, and determining the structures of the products; and the performance of the ion probe is tested:
1. the structure of the material is researched by adopting a nuclear magnetic resonance hydrogen spectrum:
1.1 NMR Hydrogen Spectroscopy of N-hydrazino-4-amino-1, 8-naphthalimide
The structure of the product prepared in the step (1) is characterized by adopting a nuclear magnetic resonance hydrogen spectrum, the characterization result is shown in figure 1,1HNMR(DMSO,400MHz,TMS)δ(ppm)9.19(s,1H),8.63(d,J＝8.4Hz,1H),8.43(d,J＝7.2Hz,1H),8.29(d,J＝8.4Hz,1H),7.65(dd,J1＝7.6Hz,J2＝8.0Hz,1H),7.25(d,J＝8.4Hz,1H),5.73(s,2H),4.70(s,2H)。
nuclear magnetic resonance hydrogen spectrum of 1.21, 8-naphthalimide derivative
The structure of the product prepared in the step (2) is characterized by adopting a nuclear magnetic resonance hydrogen spectrum, the characterization result is shown in figure 2,1HNMR(DMSO,400MHz,TMS)δ(ppm)11.55(s,1H),11.16(s,1H),10.25(s,1H),9.00(s,1H),8.87(d,J＝8.4Hz,1H),8.82(s,1H),8.53(d,J＝6.8Hz,1H),8.42(d,J＝8.8Hz,1H),7.86(d,J＝7.6Hz,1H),7.83(dd,J1＝8.0Hz,J2＝8.0Hz,1H),7.68(d,J＝8.8Hz,1H),7.51(dd,J1＝8.4Hz,J2＝7.2Hz,1H),7.28(dd,J1＝7.2Hz,J2＝7.2Hz 1H),7.05(dd,J1＝8.0Hz,J2＝7.2Hz,2H),6.96(dd,J1＝8.0Hz,J2＝7.2Hz,2H)。
2. selective analysis of 1, 8-naphthalimide derivative cationic probes
1, 8-naphthalimide derivative is prepared to have a concentration of 1.0X 10-4mol/L THF/H2O (95/5, v/v) solution, then adding 5.0X 10-3metal ion (Fe) in mol/L3+、Cu2+、Ag+、Ca2+、Cd2+、Fe2+、Ba2+、Ni2+、Mg2+、Mn2 +、Pb2+、Zn2+And Co2+) And the change in fluorescence spectrum was measured (see FIG. 3), in which P1 represents a 1, 8-naphthalimide derivative. The metal ions are respectively from FeCl3·6H2O、CuCl2·2H2O、AgNO3、CaCl2、CdCl2·2.5H2O、FeCl2·4H2O、BaCl2·2H2O、NiCl2·6H2O、MgCl2·6H2O、PbCl2、MnCl2·4H2O、ZnCl2And CoCl2·6H2O。
As can be seen from FIG. 3, Mg2+And Ca2+And the abundant cations in the water body hardly have any influence on the luminescence of the probe; other transition metals and heavy metal ions also have limited luminescence for the probe. Cu2+Luminescence of the probe can be reduced only, but Fe3+The emission of the probe can be completely quenched. This indicates that the 1, 8-naphthalimide derivative ion probe is directed against Fe3+Has good selective recognition effect and is potential Fe3+Fluorescent molecular probes.
3. Anti-interference recognition of 1, 8-naphthalimide derivative ion probe
1, 8-naphthalimide derivative is prepared to have a concentration of 1.0X 10-4mol/L THF/H2O (95/5, v/v) solution, followed by the addition of 5.0X 10, respectively-3mol/L of Fe3+、Ag+、Ca2+、Cd2+、Cu2+、Fe2+、Co2+、Ni2+、Mg2+、Mn2+、Pb2+And Zn2+And All represents except Fe3+Besides, all the cations are added into the same solution; then adding equal amount of Fe3 +And the change in fluorescence spectrum was measured (see FIG. 4), in which P1 represents a 1, 8-naphthalimide derivative.
In FIG. 4, the left diagonal bar shows the fluorescence emission spectrum of the solution after the addition of metal ions; the black bars on the right indicate the addition of equal amounts of Fe3+Thereafter, the fluorescence emission spectrum of the solution. As can be seen from the figure, the same amount of Fe was added3+After that, the fluorescence of each group of solutions was completely quenched, indicating Fe3+The process of quenching the luminescence of the 1, 8-naphthalimide derivative is not influenced by other interfering ions and has good anti-interference performance.
4. 1, 8-naphthalimide derivative ion probe pair Fe3+Linear identification of
1, 8-naphthalimide derivative is prepared to have a concentration of 1.0X 10-4mol/L THF/H2O (95/5, v/v) solution,adding Fe with different concentrations in sequence3+(0-2.0 fold), the change of fluorescence emission spectrum was analyzed (see FIG. 5), in which P1 represents a 1, 8-naphthalimide derivative. As can be seen from FIG. 5, when the concentration of the 1, 8-naphthalimide derivative is 1.0X 10-4mol/L THF/H2Linearly dropwise adding Fe into O (95/5, v/v) solution3+(0-2 times) after the fluorescent material is used, the fluorescence emission intensity is reduced regularly; when Fe is in the system3+The concentration also reaches 1.0 multiplied by 10-4Continuing to dropwise add Fe after mol/L3+The fluorescence intensity does not change any more. From this, P1 and Fe can be preliminarily inferred3+Combined in a stoichiometric ratio of 1: 1. The insert shows the change in fluorescence with Fe3+Linear variation of concentration. The linear relationship is Fe3+The concentration of the Fe-Fe alloy shows a good linear relation between 0 and 1 times, and the Fe can be treated3+Linear identification of (2).
5. 1, 8-naphthalimide derivative and Fe3+Selective analysis of complexes as anion probes
First, a 1, 8-naphthalimide derivative was formulated to have a concentration of 1.0X 10-4mol/L THF/H2O (95/5, v/v) solution, adding equal amount of Fe3+Forming a complex solution, adding 1.25 × 10 of the complex solution-3mol/L of a common anion: ( F–、Cl–、Br–、I–、HPO4 2-、H2PO4 -、Ac–、NO3 –、) The fluorescence intensity of each set of solutions was measured (see FIG. 6), in which P1 represents a 1, 8-naphthalimide derivativeAnd (4) living things. The anions are respectively from Na3PO4、NaF、NaCl、NaBr、KI、Na2HPO4、NaH2PO4、CH3COONa、Na2SO4、NaNO3、Na2CO3And NaHCO3。
As can be seen from FIG. 6, when the above anion is added to the system, onlyThe luminescence of the solution can be obviously enhanced, and the solution has no obvious response to other anions;can also enhance the luminescence of the system, but withIn contrast, the fluorescence enhancement is very limited and not sufficient forThe effect of the enhancement of (b) is produced,the fluorescence emission of the system can be almost completely restored.
6. 1, 8-naphthalimide derivative and Fe3+Complex pairLinear identification of
FIG. 7 shows the reaction between a 1, 8-naphthalimide derivative and Fe3+The complex concentration is 1.0X 10-4mol/L THF/H2O (95/5v/v) solution is added with different concentrations in sequence(0～2.2×10-3mol/L), and P1 represents 1, 8-naphthalimide derivative. As shown in the figureShown in the figure: in a system withThe increase of the concentration shows the regular enhancement of the fluorescence of the solution. When in useAt a concentration 16 times the concentration of the complex, the tendency of the system to increase fluorescence disappears, and after 16 timesThe addition does not result in the enhancement of the fluorescence intensity of the system, the luminescence of the solution tends to be flat, and the fluorescence quantum yield of the solution is also restored to 0.60, which also proves thatCompetitive complexing of Fe3+Correctness of the effect. The illustration is to/[ Complex Compound]A titration curve with the fluorescence intensity of the solution as ordinate plotted on the abscissaThe concentration is 0-16 times of the concentration of the complex, and a good linear relation is presented, so that the pair can be realizedLinear identification of (2).
7. Mechanism research of selective recognition of 1, 8-naphthalimide derivative
1, 8-naphthalimide derivative ion probe pair Fe3+The linear identification experiment preliminarily proves that the 1, 8-naphthalimide derivative and the Fe3+The ESI mass spectrum results provide more direct evidence for this inference, complexed at a stoichiometric ratio of 1: 1. As shown in FIG. 8(a), ESI mass spectrum of 1, 8-naphthalimide derivative has only one peak of 451.1 m/z, and Fe was added3+Thereafter, the ESI mass spectrum result showed the main result as shown in FIG. 8(b)The peak was m/z 505.6, and the peak component was analyzed to be [1, 8-naphthalimide derivative +1Fe3+]This directly demonstrates the 1, 8-naphthalimide derivative in combination with Fe3+Are combined in a chemical combination ratio of 1: 1. FIG. 8(c) is additionThe subsequent ESI mass spectrum showed that the main peak was changed to 451.1 m/z again, which is the same as the ESI mass spectrum of FIG. 8(a), indicating additionThen, Fe3+QuiltAfter competitive complexation, the free 1, 8-naphthalimide derivative molecules are released.
Claims (1)
1. Use of a naphthalimide derivative, characterized in that: as detection of Fe3+Andthe use of a probe capable of relaying recognition of Fe in the form of fluorescent "on-off-on3+And
the structural formula of the naphthalimide derivative is as follows:
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