CN118084785A - Naphthalimide Schiff base derivative and preparation method and application thereof - Google Patents
Naphthalimide Schiff base derivative and preparation method and application thereof Download PDFInfo
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- -1 Naphthalimide Schiff base Chemical class 0.000 title claims abstract description 63
- 239000002262 Schiff base Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 230000003068 static effect Effects 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 62
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 11
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 11
- 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 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004020 luminiscence type Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 11
- 230000005284 excitation Effects 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 150000002576 ketones Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 150000004753 Schiff bases Chemical class 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- SMQUZDBALVYZAC-UHFFFAOYSA-N ortho-hydroxybenzaldehyde Natural products OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 150000002085 enols Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002587 enol group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RQEUFEKYXDPUSK-SSDOTTSWSA-N (1R)-1-phenylethanamine Chemical compound C[C@@H](N)C1=CC=CC=C1 RQEUFEKYXDPUSK-SSDOTTSWSA-N 0.000 description 1
- RQEUFEKYXDPUSK-ZETCQYMHSA-N (1S)-1-phenylethanamine Chemical compound C[C@H](N)C1=CC=CC=C1 RQEUFEKYXDPUSK-ZETCQYMHSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance 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
-
- 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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a naphthalimide Schiff base derivative, and a preparation method and application thereof. The structural formula of the naphthalimide Schiff base derivative is as follows: Wherein R 1、R2、R3 and R 4 are each independently H or alkyl having 1 to 4 carbon atoms. The naphthalimide Schiff base derivative can improve the luminous intensity of the Schiff base ketone isomer, so that the naphthalimide Schiff base derivative is used as a static three-dimensional display medium, and the luminous intensity of voxel points generated by beam addressing can be improved.
Description
Technical Field
The invention belongs to the technical field of organic luminescent materials, and particularly relates to a naphthalimide Schiff base derivative, a preparation method and application thereof.
Background
Static volumetric three-dimensional display is a very important branch in three-dimensional display technology, and generally, voxel point luminescence is generated by addressing a light beam in a display medium, and a volumetric three-dimensional pattern is formed by a plurality of voxel point arrays.
In the currently reported methods, the rare earth materials are commonly used for up-converting luminescence or laser ionization of air to realize three-dimensional display of a static body, but the technologies need expensive high-energy light beams, and have great potential safety hazards. The photochromic material A can generate specific change under the action of light to generate isomers B with different properties, can recover under the action of the other beam of light or heat, does not need high-energy light beams, can realize light addressing to generate voxel point luminescence when the reaction speed is fast enough, wherein when salicylaldehyde primary amine Schiff base molecules are excited, the quick proton transfer in the molecules is generated to generate photochromic and thermochromic phenomena, and can be applied to the fields of information storage, optical switches, information display and the like. However, the ketone structure of salicylaldehyde primary Schiff base after photochromism has lower luminous intensity, which prevents the application of the salicylaldehyde primary Schiff base in a static three-dimensional display system.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, one object of the invention is to provide a naphthalimide Schiff base derivative, and a preparation method and application thereof. The naphthalimide Schiff base derivative can improve the luminous intensity of the Schiff base ketone isomer, so that the naphthalimide Schiff base derivative is used as a static three-dimensional display medium, and the luminous intensity of voxel points generated by beam addressing can be improved.
In a first aspect of the invention, the invention provides a naphthalimidyl schiff base derivative. According to the embodiment of the invention, the structural formula of the naphthalimide Schiff base derivative is as follows:
Wherein R 1、R2、R3 and R 4 are each independently H or alkyl having 1 to 4 carbon atoms.
According to the naphthalimide Schiff base derivative disclosed by the embodiment of the invention, the structure is enol type, the naphthalimide base derivative has the photochromic property, the naphthalimide base derivative can be rapidly isomerized into ketone type from enol type under the excitation of ultraviolet light based on an excitation state proton transfer principle, the absorption spectrum and the excitation wavelength are also changed, the ketone type isomer of the naphthalimide base derivative is of a metastable state structure, the naphthalimide base derivative can be rapidly restored into the enol type structure, when ultraviolet light and excitation light of the ketone type isomer are intersected, voxel point luminescence can be generated in a three-dimensional space, when the excitation light of the ultraviolet light or the ketone type isomer is closed, the voxel point is immediately disappeared, double-beam addressing in a medium space can be realized, meanwhile, a phenyl group connected with a nitrogen atom in the aldehyde group structure of the 1, 8-naphthalimide base is a rigid group, and the non-radiation transition of electrons can be reduced, so that the luminescence intensity of the Schiff base ketone type isomer can be improved, the Schiff base can be used as a three-dimensional display medium of a static body, the luminescence intensity of the point generated by the ultraviolet light can be improved, and the generated voxel point luminescence contrast is high, and the point luminescence is rapid, and stability is good.
In a second aspect of the present invention, the present invention provides a process for preparing the naphthalimidyl schiff base derivatives described above. According to an embodiment of the invention, the method comprises: carrying out a first reaction on a first compound and N- (3-formyl-4-hydroxy-1, 8-naphthaloyl) aniline in a first organic solvent so as to obtain the naphthalimidyl Schiff base derivative, wherein the structural formula of the first compound is as follows:
Wherein R 1、R2、R3 and R 4 are each independently H or alkyl having 1 to 4 carbon atoms.
Therefore, the naphthalimide Schiff base derivative prepared by the method can improve the luminous intensity of the Schiff base ketone isomer, so that the naphthalimide Schiff base derivative is used as a static three-dimensional display medium, the luminous intensity of voxel points generated by beam addressing can be improved, and the generated voxel points are high in contrast ratio, high in refreshing speed and good in stability. In addition, the method has high yield and low cost, and is suitable for industrial production.
In addition, the method for preparing the naphthalimide schiff base derivative according to the embodiment of the invention can also have the following additional technical characteristics:
In some embodiments of the invention, the molar ratio of N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline to the first compound is1 (0.9-1.1).
In some embodiments of the invention, the first organic solvent comprises at least one of methanol, ethanol, and dimethyl sulfoxide.
In some embodiments of the invention, N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline is prepared using the following steps: (1) Carrying out a second reaction of 4-bromo-1, 8-naphthalic anhydride and aniline in a first acidic solvent to obtain a second compound; (2) Carrying out a third reaction of the second compound with a methoxy reagent in a second organic solvent containing a catalyst to obtain a third compound; (3) Subjecting the third compound to a fourth reaction with a halogen acid to obtain a fourth compound; (4) And carrying out a fifth reaction on the fourth compound and urotropine in a second acidic solvent so as to obtain N- (3-formyl-4-hydroxy-1, 8-naphthaloyl) aniline.
In some embodiments of the invention, the first acidic solvent and the second acidic solvent each independently comprise glacial acetic acid and/or trifluoroacetic acid.
In some embodiments of the invention, in step (1), the molar ratio of 4-bromo-1, 8-naphthalic anhydride to aniline is 1 (1.5-3.5).
In some embodiments of the invention, in step (2), the molar ratio of the second compound, the methoxy reagent, and the catalyst is 1 (7-8): 0.1-0.3.
In some embodiments of the invention, the second organic solvent comprises at least one of methanol, N-dimethylformamide, and dimethyl sulfoxide.
In some embodiments of the invention, the methoxyl reagent comprises sodium methoxide and/or potassium methoxide.
In some embodiments of the invention, the catalyst comprises at least one of copper sulfate, copper phosphate, copper acetate, and copper nitrate.
In some embodiments of the invention, in step (3), the hydrohalic acid comprises HI and/or HBr.
In some embodiments of the invention, the concentration of the halogen acid is not less than 57wt%.
In some embodiments of the invention, the third compound comprises from 60mmol/L to 100mmol/L of the halogen acid.
In some embodiments of the invention, in step (4), the molar ratio of the fourth compound to urotropin is1 (1-3).
In a third aspect of the invention, the invention provides the application of the naphthalimide Schiff base derivative in a static three-dimensional display system. Therefore, the problem of the luminous intensity of the ketone isomer applied to the static three-dimensional display system of the Schiff base can be solved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow chart of a method for preparing N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline according to one embodiment of the present invention;
FIG. 2 is a flow chart of a process for preparing naphthalimide-based Schiff base derivatives according to example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of the target product obtained in example 1 according to the present invention;
FIG. 4 is an absorption spectrum of the objective product obtained in example 1 according to the present invention;
fig. 5 is a phenomenon that voxel points inside a solution prepared in accordance with example 3 of the present invention emit light.
Detailed Description
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect of the invention, the invention provides a naphthalimidyl schiff base derivative. According to the embodiment of the invention, the structural formula of the naphthalimide Schiff base derivative is as follows:
Wherein R 1、R2、R3 and R 4 are each independently H or alkyl having 1 to 4 carbon atoms.
According to the naphthalimide Schiff base derivative disclosed by the embodiment of the invention, the structure is enol type, the naphthalimide base derivative has the photochromic property, the naphthalimide base derivative can be rapidly isomerized into ketone type from enol type under the excitation of ultraviolet light based on an excitation state proton transfer principle, the absorption spectrum and the excitation wavelength are also changed, the ketone type isomer of the naphthalimide base derivative is of a metastable state structure, the naphthalimide base derivative can be rapidly restored into the enol type structure, when ultraviolet light and excitation light of the ketone type isomer are intersected, voxel point luminescence can be generated in a three-dimensional space, when the excitation light of the ultraviolet light or the ketone type isomer is closed, the voxel point is immediately disappeared, double-beam addressing in a medium space can be realized, meanwhile, a phenyl group connected with a nitrogen atom in the aldehyde group structure of the 1, 8-naphthalimide base is a rigid group, and the non-radiation transition of electrons can be reduced, so that the luminescence intensity of the Schiff base ketone type isomer can be improved, the Schiff base can be used as a three-dimensional display medium of a static body, the luminescence intensity of the point generated by the ultraviolet light can be improved, and the generated voxel point luminescence contrast is high, and the point luminescence is rapid, and stability is good.
In a second aspect of the present invention, the present invention provides a process for preparing the naphthalimidyl schiff base derivatives described above. According to an embodiment of the invention, the method comprises: carrying out a first reaction on a first compound and N- (3-formyl-4-hydroxy-1, 8-naphthaloyl) aniline in a first organic solvent so as to obtain naphthalimidyl Schiff base derivatives, wherein the structural formula of the N- (3-formyl-4-hydroxy-1, 8-naphthaloyl) aniline is as follows: The structural formula of the first compound is as follows: /(I) Wherein R 1、R2、R3 and R 4 are each independently H or alkyl having 1 to 4 carbon atoms. Therefore, the naphthalimide Schiff base derivative prepared by the method can improve the luminous intensity of the Schiff base ketone isomer, so that the naphthalimide Schiff base derivative is used as a static three-dimensional display medium, the luminous intensity of voxel points generated by beam addressing can be improved, and the generated voxel points are high in contrast ratio, high in refreshing speed and good in stability. In addition, the method has high yield and low cost, and is suitable for industrial production.
Specifically, the first compound and N- (3-formyl-4-hydroxy-1, 8-naphthaloyl) aniline can be mixed in a first organic solvent and refluxed for 2h-6h to obtain the naphthalimide Schiff base derivative. Thus, the first reaction is facilitated, and the utilization rate of the reaction raw materials is improved.
According to specific embodiments of the present invention, the molar ratio of N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline to the first compound may be 1 (0.9-1.1), for example, may be 1:0.9, 1:0.92, 1:0.94, 1:0.96, 1:0.98, 1:1, 1:1.02, 1:1.04, 1:1.06, 1:1.08, 1:1.1, etc. The inventors have found that too large or too small a molar ratio of N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline to the first compound reduces the yield of the first reaction. The present invention can improve the yield of the first reaction by controlling the molar ratio of N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline to the first compound within the above-mentioned range.
The specific composition of the first organic solvent is not particularly limited, and may be selected according to actual needs by those skilled in the art, and may include at least one of methanol, ethanol, and dimethyl sulfoxide, for example.
According to an embodiment of the present invention, referring to FIG. 1, N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline can be prepared by the following steps:
s100: the second reaction of 4-bromo-1, 8-naphthalene dicarboxylic anhydride and aniline in the first acid solvent
In the step, 4-bromo-1, 8-naphthalene dicarboxylic anhydride and aniline are subjected to a second reaction in a first acidic solvent to obtain a second compound. Wherein the structural formula of the second compound is as follows:
Specifically, 4-bromo-1, 8-naphthalic anhydride and aniline can be mixed in a first acidic solvent and refluxed for 4h to 8h under the protection of inert gas (such as nitrogen) to obtain a second compound. Thus, the second reaction is facilitated to be carried out, and the utilization rate of the reaction raw materials is improved.
According to specific embodiments of the present invention, the molar ratio of 4-bromo-1, 8-naphthalic anhydride to aniline may be 1 (1.5-3.5), for example, 1:1.5, 1:1.7, 1:2, 1:2.3, 1:2.5, 1:2.7, 1:3, 1:3.3, 1:3.5, etc. The present invention can improve the yield of the second reaction by controlling the molar ratio of 4-bromo-1, 8-naphthalic anhydride and aniline within the above range.
The specific composition of the first acidic solvent is not particularly limited, and one skilled in the art may select according to actual needs, and may include glacial acetic acid and/or trifluoroacetic acid (TFA), for example.
S200: the second compound and methoxy reagent are subjected to a third reaction in a second organic solvent containing a catalyst
In this step, the second compound and the methoxy reagent are subjected to a third reaction in a second organic solvent containing a catalyst to obtain a third compound. Wherein the structural formula of the third compound is as follows:
Specifically, the second compound and the methoxy reagent may be mixed in a second organic solvent, and refluxed for 6h to 10h under the protection of inert gas (such as nitrogen) to obtain a third compound. Thus, the third reaction is facilitated, and the utilization rate of the reaction raw material is improved.
According to specific embodiments of the present invention, the molar ratio of the second compound, methoxy reagent, and catalyst may be 1 (7-8): (0.1-0.3), for example, 1:7:0.1, 1:7:0.2, 1:7:0.3, 1:8:0.1, 1:8:0.2, 1:8:0.3, etc. The present invention can improve the yield of the third reaction by controlling the molar ratio of the second compound, the methoxy reagent and the catalyst within the above-mentioned range.
In particular, the methoxy reagent may include sodium methoxide and/or potassium methoxide; the second organic solvent may include at least one of methanol, N-dimethylformamide and dimethyl sulfoxide; the catalyst may include at least one of copper sulfate, copper phosphate, copper acetate, and copper nitrate.
S300: subjecting the third compound to a fourth reaction with a halogen acid
In this step, the third compound is subjected to a fourth reaction with a halogen acid to obtain a fourth compound. Wherein the hydrohalic acid may comprise HI and/or HBr; the structural formula of the fourth compound is as follows:
specifically, the third compound may be mixed with a halogen acid and refluxed under the protection of an inert gas (e.g., nitrogen) for 8 hours to 12 hours to obtain the fourth compound. This is advantageous in promoting the fourth reaction and improving the utilization ratio of the reaction raw materials.
According to an embodiment of the invention, the concentration of the halogen acid is not less than 57wt%. This facilitates the fourth reaction, and can improve the utilization ratio of the reaction raw materials.
According to the specific embodiment of the invention, the content of the third compound in the halogen acid can be 60mmol/L-100mmol/L, for example, 60mmol/L, 65mmol/L, 70mmol/L, 75mmol/L, 80mmol/L, 85mmol/L, 90mmol/L, 95mmol/L, 100mmol/L, etc. The present invention can improve the yield of the fourth reaction by controlling the content of the third compound in the halogen acid within the above-mentioned range.
S400: carrying out fifth reaction on the fourth compound and urotropine in the second acid solvent
In the step, a fifth reaction is carried out between the fourth compound and urotropine (HMTA) in a second acid solvent to obtain N- (3-formyl-4-hydroxy-1, 8-naphthaloyl) aniline. Wherein the second acidic solvent may comprise glacial acetic acid and/or trifluoroacetic acid.
Specifically, the mixture of the fourth compound and urotropine may be refluxed in glacial acetic acid and/or trifluoroacetic acid for 8h to 12h. This is advantageous in promoting the progress of the fifth reaction and improving the utilization ratio of the reaction raw materials.
According to embodiments of the present invention, the molar ratio of the fourth compound to urotropin may be 1 (1-3), for example, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, etc. The present invention can improve the yield of the fifth reaction by controlling the molar ratio of the fourth compound to urotropine within the above range.
In a third aspect of the invention, the invention provides the application of the naphthalimide Schiff base derivative in a static three-dimensional display system. Therefore, the problem of the luminous intensity of the ketone isomer applied to the static three-dimensional display system of the Schiff base can be solved.
Specifically, the naphthalimidyl schiff base derivative may be dispersed in an organic solvent or cured in a polymer material such as an epoxy resin, polymethyl methacrylate, or polydimethylsiloxane, to be used as a bulk three-dimensional display medium. The voxel point excitation light source adopts two light sources with different wavelengths, the two light sources are intersected in the display medium for addressing, and when the scanning speed of the light sources exceeds the human eye refreshing rate, a plurality of voxel point arrays can be formed, so that a three-dimensional stereoscopic image is displayed.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1
As shown in fig. 2, the preparation method of the naphthalimidyl schiff base derivative is as follows:
27.7g (0.1 mol) of 4-bromo-1, 8-naphthalenedicarboxylic anhydride and 18.6g (0.2 mol) of aniline are mixed in 300mL of glacial acetic acid, refluxed at 120℃for 6.5h under nitrogen protection, and after cooling, the mixture is poured into water to give a yellow precipitate. Filtering and recrystallizing to obtain light yellow crystals, namely a second compound;
17.6g (0.05 mol) of the second compound, 20.2g (0.375 mol) of sodium methoxide and 1.6g (0.01 mol) of copper sulfate were mixed and dispersed in 200mL of a dry methanol solution, refluxed at 65℃for 8 hours under nitrogen protection, and the obtained solution was cooled to room temperature and filtered to obtain a pale yellow solid. Then washed with 10wt% hydrochloric acid (30 ml x 3) and water (20 ml x 3) to give a third compound;
6.0g (0.02 mol) of the third compound and 200mL of 57wt% hydroiodic acid were mixed and refluxed under nitrogen for 12h, the resulting solution was cooled to room temperature, filtered, and the crude product was then washed with water (50 mL. Times.3) to give a yellowish green solid. Purifying the crude product by column chromatography to obtain a fourth compound;
A mixture of 2.9g (0.01 mol) of the fourth compound and 2.8g (0.02 mol) of urotropine was refluxed in trifluoroacetic acid for 8 hours, and then the resulting reaction mixture was cooled to room temperature. The reaction mixture was diluted with distilled water and the precipitate formed was filtered. The precipitate was washed with distilled water several times and dried. Then dissolving in dichloromethane and purifying by using a short silicon plug to obtain N- (3-formyl-4-hydroxy-1, 8-naphthaloyl) aniline;
0.63g (2 mmol) of N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline and 0.24g (2 mmol) of (S) -alpha-methylbenzylamine were mixed in 20mL of ethanol, refluxed for 4 hours, filtered and washed to obtain the target compound.
Example 2
The preparation method of the naphthalimide Schiff base derivative comprises the following steps:
0.63g (2 mmol) of N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline and 0.24g (2 mmol) of (R) -alpha-methylbenzylamine were mixed in 20mL of ethanol, refluxed for 4 hours, filtered and washed to obtain the target compound.
The target products obtained in examples 1-2 were subjected to nuclear magnetic resonance hydrogen spectrum and ultraviolet-visible absorption spectrum tests.
The nuclear magnetic resonance spectrum of the target product obtained in example 1 is shown in FIG. 3. 1 H NMR (400 MHz, DMSO-d 6) chemical shift (δ)：8.96(d,J＝12.7Hz,1H),8.60(d,J＝6.8Hz,1H),8.43(d,J＝6.8Hz,2H),7.69(d,J＝9.7Hz,1H),7.51(d,J＝7.2Hz,3H),7.48–7.43(m,5H),7.38(s,1H),7.31(t,J＝5.8Hz,2H),5.13(d,J＝9.6Hz,1H),1.24(s,4H). the number and position of H atoms in the nuclear magnetic resonance hydrogen spectrogram corresponds to the number and position of H atoms in the naphthalimide Schiff base derivative one by one, which shows that the naphthalimide Schiff base derivative with the structure meeting the requirement is prepared in example 1. The nuclear magnetic resonance hydrogen spectrum of the target product obtained in example 2 is similar to that of example 1, and it is explained that the naphthalimide Schiff base derivative with the structure meeting the requirements is prepared in example 2. The results of the ultraviolet-visible absorption spectrum test of the objective product obtained in example 1 are shown in fig. 4. The results of the ultraviolet-visible absorption spectrum test of the objective product obtained in example 2 were similar to those of example 1.
Example 3
The method for applying the naphthalimide Schiff base derivative in three dimensions comprises the following steps:
The naphthalimidyl schiff base derivative obtained in example 1 was sufficiently dissolved in cyclohexane to prepare a cyclohexane solution of 0.01mmol/L of the naphthalimidyl schiff base derivative, and the solution was placed in a quartz vessel. As shown in fig. 5, when a suitable light source such as 405nm laser and 488nm laser is selected to meet, the phenomenon that the voxel point emits light can be observed, the luminous intensity is high, and the reaction formula is as follows:
The addressing of the double-beam scanning in the solution is controlled, so that the three-dimensional display of the body can be completed. Thus, the naphthalimide Schiff base derivative obtained in example 1 can be applied to a beam-addressable static three-dimensional display system. Therefore, the naphthalimide Schiff base derivative can improve the luminous intensity of the Schiff base ketone isomer, so that the naphthalimide Schiff base derivative is used as a static three-dimensional display medium, and the luminous intensity of voxel points generated by beam addressing can be improved.
In the present invention, the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A naphthalimidyl schiff base derivative, characterized in that the naphthalimidyl schiff base derivative has the structural formula:
Wherein R 1、R2、R3 and R 4 are each independently H or alkyl having 1 to 4 carbon atoms.
2. A process for preparing the naphthalimidyl schiff base derivative according to claim 1, comprising: carrying out a first reaction on a first compound and N- (3-formyl-4-hydroxy-1, 8-naphthaloyl) aniline in a first organic solvent so as to obtain the naphthalimidyl Schiff base derivative, wherein the structural formula of the first compound is as follows:
Wherein R 1、R2、R3 and R 4 are each independently H or alkyl having 1 to 4 carbon atoms.
3. The method according to claim 2, wherein the molar ratio of N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline to the first compound is 1 (0.9-1.1);
optionally, the first organic solvent comprises at least one of methanol, ethanol, and dimethyl sulfoxide.
4. The method according to claim 2, wherein N- (3-formyl-4-hydroxy-1, 8-naphthalenedicarboxyl) aniline is prepared by:
(1) Carrying out a second reaction of 4-bromo-1, 8-naphthalic anhydride and aniline in a first acidic solvent to obtain a second compound;
(2) Carrying out a third reaction of the second compound with a methoxy reagent in a second organic solvent containing a catalyst to obtain a third compound;
(3) Subjecting the third compound to a fourth reaction with a halogen acid to obtain a fourth compound;
(4) And carrying out a fifth reaction on the fourth compound and urotropine in a second acidic solvent so as to obtain N- (3-formyl-4-hydroxy-1, 8-naphthaloyl) aniline.
5. The method of claim 4, wherein the first acidic solvent and the second acidic solvent each independently comprise glacial acetic acid and/or trifluoroacetic acid.
6. The process according to claim 4, wherein in step (1), the molar ratio of 4-bromo-1, 8-naphthalic anhydride to aniline is 1 (1.5-3.5).
7. The method of claim 4, wherein in step (2), the molar ratio of the second compound, the methoxy reagent, and the catalyst is 1 (7-8): 0.1-0.3;
optionally, the second organic solvent comprises at least one of methanol, N-dimethylformamide and dimethyl sulfoxide;
Optionally, the methoxy reagent comprises sodium methoxide and/or potassium methoxide;
Optionally, the catalyst comprises at least one of copper sulfate, copper phosphate, copper acetate, and copper nitrate.
8. The process according to claim 4, wherein in step (3), the hydrohalic acid comprises HI and/or HBr;
Optionally, the concentration of the halogen acid is not less than 57wt%;
optionally, the content of the third compound in the halogen acid is 60mmol/L-100mmol/L.
9. The method according to claim 4, wherein in the step (4), the molar ratio of the fourth compound to urotropin is 1 (1-3).
10. Use of the naphthalimidyl schiff base derivative according to claim 1 in a static three-dimensional display system.
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