CN110117253A - A kind of organic fluorescent dye with piezallochromy characteristic, preparation method and applications - Google Patents
A kind of organic fluorescent dye with piezallochromy characteristic, preparation method and applications Download PDFInfo
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- CN110117253A CN110117253A CN201810111537.3A CN201810111537A CN110117253A CN 110117253 A CN110117253 A CN 110117253A CN 201810111537 A CN201810111537 A CN 201810111537A CN 110117253 A CN110117253 A CN 110117253A
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- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
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- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
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- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- 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
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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
- 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
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- 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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- 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
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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Abstract
The invention discloses a kind of organic fluorescent dyes with piezallochromy characteristic, the dyestuff includes (E) -2- (4- (N, N- hexichol amido) styryl) benzothiazole hydrochloride, (E) -2- (4- (N, N- hexichol amido) styryl) any one in quinoline hydrochloride or (E) -2- (4- (N, N- hexichol amido) styryl) pyridine hydrochloride；This method designs the organic molecule with D- π-A structure first, and the rear structure optimization for carrying out ground state finally carries out the prediction of Polymorph using Materials Studio.The ten kinds of crystal structures obtained by analyzing prediction, can predict whether the molecule is capable of forming excimer and unimolecule state in the solid state.Molecule with excimer state and unimolecule state in the solid state can then become the power with high contrast and cause photochromic molecule.
Description
Technical field
The present invention relates to power mutagens color organic fluorescence materials, belong to functional fluorescent dyes, organic chemical industry and fine chemistry industry
Technical field.
Background technique
Anti-counterfeiting technology is widely used in the systems such as label, certificate, number field.Currently, being carried out with fluorescence signal anti-fake
Material be applied to the anti-fake of RMB, have the characteristics that high sensitivity, inexpensive；And fluorescence under stimulation being capable of reversible transition
Anti-fake material be then more difficult to copy, fluorescence emission wavelengths change great high contrast power mutagens especially under Pressure stimulation
Color material.
Currently, high contrast power causes off-color material few, and molecular weight is big, and synthesis is difficult.This method combination quantum chemical method,
MOLECULE DESIGN and synthesis can greatly be optimized.
Summary of the invention
Ground-state Structures optimization, Polymorph prediction of the present invention by binding molecule, propose a kind of high contrast power cause
The prediction new method of photochromic molecule.It is analyzed by calculating obtained crystal structure to Polymorph, is capable of forming sharp base
The molecule of states of matter of associating and unimolecule state, the molecular structure have push-and-pull electronic effect, then can become with high contrast
Power causes photochromic molecule.
First technical problem to be solved by this invention is that design structure is simple, and raw material is easy to get, and is had in the solid state certain
The organic fluorescent dye of luminous intensity.
Second technical problem to be solved by this invention is the form being likely to form to designed compound, is carried out more
Accurately prediction.
Third technical problem to be solved by this invention is to find effective stimulation power, so that organic dyestuff is glimmering
Light can issue the raw reversible transition for being greater than 100nm in external stimulus.
Based on above-mentioned technical problem, the present invention provides a kind of organic fluorescent dye with piezallochromy characteristic, the dyestuff
Including (E) -2- (4- (N, N- hexichol amido) styryl) benzothiazole hydrochloride, (E) -2- (4- (N, N- hexichol amido) benzene
Vinyl) any one in quinoline hydrochloride or (E) -2- (4- (N, N- hexichol amido) styryl) pyridine hydrochloride；
The compound structure such as Formulas I:
Formulas I.
Technical solution of the present invention is after designing the organic molecule with D- π-A structure using quantization software (such as Gamess
Or Gauss) carry out ground state structure optimization, method use density functional theory (DFT, b3lyp/6-31g+ (d, p)), will optimize
Structure import Materials Studio carry out Polymorph prediction, obtain crystal structure.Its technical solution describes such as
Under:
Further, described (the E) -2- (4- (N, N- hexichol amido) styryl) benzothiazole hydrochloride is through Ground-state Structures
Optimization, using density functional theory (DFT, b3lyp/6-31g+ (d, p)), by (E) -2- (4- (N, N- hexichol amido) styrene
Base) benzothiazole hydrochloride import Materials Studio carry out Polymorph prediction, obtain chemical structure and be capable of forming
The crystal structure compound of excimer state and unimolecule state, the crystal structure include
In appoint
It anticipates one kind.
Described (E) -2- (4- (N, the N- hexichol amido) styryl) quinoline hydrochloride optimizes through Ground-state Structures, and use is close
It spends Functional Theory (DFT, b3lyp/6-31g+ (d, p)), by (E) -2- (4- (N, N- hexichol amido) styryl) quinoline hydrochloric acid
Salt import Materials Studio carry out Polymorph prediction, obtain chemical structure be capable of forming excimer state and
The crystal structure compound of unimolecule state, the crystal structure include
In any one.
Described (E) -2- (4- (N, the N- hexichol amido) styryl) pyridine hydrochloride optimizes through Ground-state Structures, and use is close
It spends Functional Theory (DFT, b3lyp/6-31g+ (d, p)), by (E) -2- (4- (N, N- hexichol amido) styryl) pyridine hydrochloric acid
Salt import Materials Studio carry out Polymorph prediction, obtain chemical structure be capable of forming excimer state and
The crystal structure compound of unimolecule state, the crystal structure include
In any one.
Application of the organic fluorescent dye compound with piezallochromy characteristic on anti-fake mark: the material is applied to imitative puppet
In label, red pattern is shown under ultraviolet light irradiation；Bluish-green colored pattern is shown under scraping effect.
Under the action of being greater than 10MPa pressure, the variation for being greater than 100nm occurs the dyestuff for fluorescence, is changed by red green
Color or blue-green；And the fluorescence can restore under environmental stimulus to initial state.
The pressure is that temperature condition changes the lower grinding carried out or temperature condition changes the lower static pressure applied.
It include restoring under heating or solvent condition to initial state under the environmental stimulus.
The preparation method of the organic fluorescent dye compound with piezallochromy characteristic, which is characterized in that including
Following steps:
2- methylbenzothiazole, 2- methylquinoline or 2- picoline and 4- formoxyl triphenylamine are dissolved in ethyl alcohol, dripped
Adding mass concentration is 45-60%NaOH aqueous solution, is stirred overnight at room temperature, and rear filter obtains solid crude product, and chromatographs through column
Purification obtains neutral products, and gained compound is placed in concentrated hydrochloric acid environment and protonates 20-40min, obtains target compound (E)-
2- (4- (N, N- hexichol amido) styryl) benzothiazole hydrochloride, (E) -2- (4- (N, N- hexichol amido) styryl) quinoline
Quinoline hydrochloride or (E) -2- (4- (N, N- hexichol amido) styryl) pyridine hydrochloride；
2- methylbenzothiazole, 2- methylquinoline or the 2- picoline and 4- formoxyl triphenylamine and quality are dense
Degree is that the molar ratio of 45-60%NaOH aqueous solution is 1:0.8-1.5:3-6.
2- methylbenzothiazole, 2- methylquinoline or the 2- picoline and 4- formoxyl triphenylamine and quality are dense
Degree is that the molar ratio of 45-60%NaOH aqueous solution is 1:1:4.
Detailed description of the invention
Fig. 1 is the power mutagens color fluorescence pattern of the obtained QVP-H compound of embodiment 1.
Fig. 2 is the power mutagens color fluorescence pattern of the obtained BTVP-H compound of embodiment 2.
Fig. 3 is the power mutagens color fluorescence pattern of the obtained PVP-H compound of embodiment 3.
Specific embodiment
It is synthesized referring to molecular structure, final product is characterized.By obtained compound powder in not equality of temperature
(or applying static pressure) is ground under degree, significant change occurs for fluorescence emission wavelengths；Heating (or solvent processing) can be extensive
The multiple primary state in.
Embodiment 1
The 4- formoxyl triphenylamine of the 2- methylbenzothiazole of 10mmol and 10mmol are dissolved in 30mL ethyl alcohol, are added dropwise
The 50%NaOH aqueous solution of 3.2mL.Reaction is stirred at room temperature overnight, and rear filter obtains solid crude product, and is mentioned through column chromatography
It is pure to obtain neutral products, yield 50-80%.Gained compound is placed in concentrated hydrochloric acid environment and protonates half an hour, obtains targeted
Object (E) -2- (4- (N, N- hexichol amido) styryl) benzothiazole hydrochloride is closed, QVP-H is named as；
2- methylbenzothiazole, 4- formoxyl triphenylamine, NaOH molar ratio be 1:1:4.
(E) -2- (4- (N, N- hexichol amido) styryl) benzothiazole:1H NMR(400MHz,CDCl3)δ7.91(dd,
J=48.9,7.6Hz, 2H), 7.48-7.42 (m, 4H), 7.30 (t, J=7.9Hz, 5H), 7.14 (dd, J=8.6,1.1Hz,
4H),7.11-7.03(m,5H).
Embodiment 2
The 4- formoxyl triphenylamine of the 2- methylquinoline of 10mmol and 10mmol are dissolved in 30mL ethyl alcohol, 3.2mL is added dropwise
50%NaOH aqueous solution.Reaction is stirred at room temperature overnight, and rear filter obtains solid crude product, and obtains through column Chromatographic purification
Neutral products, yield 55-85%.Gained compound is placed in concentrated hydrochloric acid environment and protonates half an hour, obtains target compound
(E) -2- (4- (N, N- hexichol amido) styryl) quinoline hydrochloride, is named as BTVP-H；
2- methylquinoline, 4- formoxyl triphenylamine, NaOH molar ratio be 1:1:4.
(E) -2- (4- (N, N- hexichol amido) styryl) quinoline:1H NMR(400MHz,CDCl3): δ 8.10 (d, J=
8.6Hz, 1H), 8.06 (d, J=8.4Hz, 1H), 7.77 (d, J=8.1Hz, 1H), 7.67 (m, 3H), 7.53-7.45 (m, 3H),
7.29 (dd, J=12.9,4.5Hz, 5H), 7.18-7.11 (m, 4H), 7.10-7.02 (m, 4H)
Embodiment 3
The 4- formoxyl triphenylamine of the 2- picoline of 10mmol and 10mmol are dissolved in 30mL ethyl alcohol, 3.2mL is added dropwise
50%NaOH aqueous solution.Reaction is stirred at room temperature overnight, and rear filter obtains solid crude product, and obtains through column Chromatographic purification
Neutral products, yield 50-75%.Gained compound is placed in concentrated hydrochloric acid environment and protonates half an hour, obtains target compound
(E) -2- (4- (N, N- hexichol amido) styryl) pyridine hydrochloride, is named as PVP-H；
2- picoline, 4- formoxyl triphenylamine, NaOH molar ratio be 1:1:4.
(E) -2- (4- (N, N- hexichol amido) styryl) pyridine:1H NMR(400MHz,CDCl3): δ 8.58 (d, J=
3.9Hz, 1H), 7.65 (td, J=7.7,1.8Hz, 1H), 7.58 (d, J=16.1Hz, 1H), 7.45 (d, J=8.6Hz, 2H),
7.37 (d, J=7.9Hz, 1H), 7.30-7.23 (m, 4H), 7.15-7.10 (m, 5H), 7.09-7.02 (m, 5H)
Embodiment 4
Compound Q VP-H is dissolved in chloroform, and engraves on pattern on paper using it as ink；It is molten to be heated to 100 DEG C of volatilizations
Agent shows red pattern (emission wavelength 673nm) under ultraviolet light irradiation；Apply the pressure of 10Mpa under the conditions of 100 DEG C
Power, pattern transition are blue-green (emission wavelength 490nm)；Apply the pressure of 10MPa under conditions of 25 DEG C, pattern restores to red
Color.
Embodiment 5
Compound BTVP-H is dissolved in chloroform, and engraves on pattern on paper using it as ink；Equal solvent volatilizees dry naturally
Afterwards, red pattern (emission wavelength 650nm) is shown under ultraviolet light irradiation；Apply the pressure of 10Mpa under the conditions of 100 DEG C
Power, pattern transition are green (emission wavelength 495nm)；It is cooled to room temperature the pressure for applying 10Mpa again, pattern restores to red.
Embodiment 6
Compound PVP-H is dissolved in chloroform, and engraves on pattern on paper using it as ink；Equal solvent volatilizees dry naturally
Afterwards, red pattern (emission wavelength 600nm) is shown under ultraviolet light irradiation；Apply the pressure of 10Mpa under the conditions of 80 DEG C,
Pattern transition is blue-green (emission wavelength 476nm)；It is cooled to room temperature the pressure for applying 10Mpa again, pattern transition to red.
The above is the preferable specific embodiment of the present invention, and the scope of protection of the present invention is not limited to this, any to be familiar with
Those skilled in the art within the technical scope of the present invention, the simple change for the technical solution that can be become apparent to
Or equivalence replacement, it is within the scope of the invention.
Claims (10)
1. a kind of organic fluorescent dye with piezallochromy characteristic, which is characterized in that the dyestuff includes (E) -2- (4- (N, N-
Hexichol amido) styryl) benzothiazole hydrochloride, (E) -2- (4- (N, N- hexichol amido) styryl) quinoline hydrochloride,
Or any one in (E) -2- (4- (N, N- hexichol amido) styryl) pyridine hydrochloride；
The compound structure such as Formulas I:
2. the organic fluorescent dye described in claim 1 with piezallochromy characteristic, which is characterized in that described (the E) -2-
(4- (N, N- hexichol amido) styryl) benzothiazole hydrochloride optimizes through Ground-state Structures, using density functional theory (DFT,
B3lyp/6-31g+ (d, p)), (E) -2- (4- (N, N- hexichol amido) styryl) benzothiazole hydrochloride is imported
Materials Studio carries out the prediction of Polymorph, obtains chemical structure and is capable of forming excimer state and unimolecule
The crystal structure of state, the crystal structure include
In any one.
3. the organic fluorescent dye described in claim 1 with piezallochromy characteristic, which is characterized in that described (the E) -2-
(4- (N, N- hexichol amido) styryl) quinoline hydrochloride optimizes through Ground-state Structures, using density functional theory (DFT,
B3lyp/6-31g+ (d, p)), (E) -2- (4- (N, N- hexichol amido) styryl) quinoline hydrochloride is imported into Materials
Studio carries out the prediction of Polymorph, obtains the crystal that chemical structure is capable of forming excimer state and unimolecule state
Structural compounds, the crystal structure include
In any one.
4. the organic fluorescent dye described in claim 1 with piezallochromy characteristic, which is characterized in that described (the E) -2-
(4- (N, N- hexichol amido) styryl) pyridine hydrochloride optimizes through Ground-state Structures, using density functional theory (DFT,
B3lyp/6-31g+ (d, p)), (E) -2- (4- (N, N- hexichol amido) styryl) pyridine hydrochloride is imported into Materials
Studio carries out the prediction of Polymorph, obtains the crystal that chemical structure is capable of forming excimer state and unimolecule state
Structural compounds, the crystal structure include
In any one.
5. the described in any item organic fluorescent dye compounds with piezallochromy characteristic of claim 1-4 are on anti-fake mark
Application.
6. application described in claim 5, which is characterized in that under the action of ambient pressure, fluorescence occurs big the fluorescent dye
In the variation of 100nm；The fluorescent dye restores under environmental stimulus to initial state.
7. application as claimed in claim 6, which is characterized in that the ambient pressure environment includes that temperature condition changes lower carry out
Grinding or temperature condition change the lower static pressure applied or the pressure effect of at least 10MPa.
8. application as claimed in claim 6, which is characterized in that be included in heating under the environmental stimulus or in solvent condition
It is lower to restore to initial state.
9. the preparation method of the organic fluorescent dye compound described in claim 1 with piezallochromy characteristic, feature exist
In including the following steps:
2- methylbenzothiazole, 2- methylquinoline or 2- picoline and 4- formoxyl triphenylamine are dissolved in ethyl alcohol, matter is added dropwise
Amount concentration is 45-60%NaOH aqueous solution, is stirred overnight at room temperature, and rear filter obtains solid crude product, and through column Chromatographic purification
Obtain neutral products.Gained compound is placed in concentrated hydrochloric acid environment and protonates 20-40min, obtains target compound (E) -2- (4-
(N, N- hexichol amido) styryl) benzothiazole hydrochloride, (E) -2- (4- (N, N- hexichol amido) styryl) quinolinium
Hydrochlorate or (E) -2- (4- (N, N- hexichol amido) styryl) pyridine hydrochloride；
2- methylbenzothiazole, 2- methylquinoline or the 2- picoline and 4- formoxyl triphenylamine and mass concentration are
The molar ratio of 45-60%NaOH aqueous solution is 1:0.8-1.5:3-6.
10. the preparation method of the organic fluorescent dye compound as claimed in claim 9 with piezallochromy characteristic, feature exist
In the 2- methylbenzothiazole, 2- methylquinoline or 2- picoline and 4- formoxyl triphenylamine and mass concentration are
The molar ratio of 45-60%NaOH aqueous solution is 1:1:4.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111337465A (en) * | 2020-03-06 | 2020-06-26 | 齐鲁工业大学 | Solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam |
| CN114989081A (en) * | 2022-05-10 | 2022-09-02 | 南华大学 | Colorimetric probe and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102702090A (en) * | 2012-06-05 | 2012-10-03 | 上海师范大学 | Methyl pyridinium with organic two-photon absorption materia, and preparation method and application thereof |
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| CN114989081A (en) * | 2022-05-10 | 2022-09-02 | 南华大学 | Colorimetric probe and preparation method and application thereof |
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