CN102295601A - Arylpyrazoline luminescent compounds with 5-position substituted by polycyclic aromatic hydrocarbon - Google Patents
Arylpyrazoline luminescent compounds with 5-position substituted by polycyclic aromatic hydrocarbon Download PDFInfo
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Abstract
The invention relates to arylpyrazoline luminescent compounds with the 5-position substituted by polycyclic aromatic hydrocarbon. The general structure of the compounds is shown in the specification. In the general structure, R1 is a 4-nitrophenyl group, a 4-cyanphenyl group, a 4-ester phenyl group, a 2-nitrophenyl group, a 2-cyanphenyl group, a 2-ester phenyl group, a 2,4-dinitrophenyl group or hydrogen, R2 is a 4-nitro group, a 4-cyan group, a 4-ester group, a 2-nitro group, a 2-cyan group, a 2-ester group or a 2,4-dinitro group, and R3 is a 9-anthryl group, a 9-phenanthryl group or a 1-pyrenyl group. A preparation method of the compounds is that: a polycyclic aromatic aldehyde and an aromatic ketone substituted by an electron-withdrawing group at a phenyl ring are condensed to generate a chalcone intermediate which is condensed with an aromatic hydrazine substituted by the electron-withdrawing group at a phenyl ring to form a ring. So a generated pyrazoline molecule has two chromophores of "aryl pyrazoline" with enhanced intramolecular charge transfer and an anthracene ring at the 5-position, and the luminescent spectrum of the polycyclic aromatic hydrocarbon at the 5-position can overlap the absorption spectrum of the chromophore arylpyrazoline to generate an effective energy transfer, thereby the luminescence of the pyrazoline molecule and the two-photon fluorescence are improved.
Description
Technical field
The present invention relates to the arylpyrazole quinoline compounds that a kind of 5 condensed-nuclei aromaticss replace, this pyrazoline compounds can be used as fluorescence dye, laser dyes, electroluminescent organic material, fluorescence labeling material and fluorescence chemical sensitive material, organic non linear optical material etc.
Background technology
A lot of to the research of arylpyrazole quinoline compounds in recent decades, mainly concentrate on two aspects, the one, the potential drug research, found that the pyrazoline-substituting molecule has shown multiple biological activity, as antimicrobial, antibiotic, anti-inflammatory analgesic, antidepressant, [International Journal of Pharmaceutical Sciences and Drug Research 2010 such as antitumor; 2 (3): 165-175].The 2nd, as the research of organic light emission and nonlinear optical material, pyrazoline intramolecular " arylpyrazole quinoline " group has perfect rigidity conjugate planes, be the organic chromophore and the cavity transmission group of a quasi-representative, can be used as optical bleaching agent, electroluminescent material, fluorescent probe, two-photon fluorescence, nonlinear optical material etc.
Up to the present, the arylpyrazole quinoline compounds of being reported focuses on the design of 1 and 3 different substituents and the influence of and nonlinear optical properties luminous to it thereof more, because conjugation can not take place with " arylpyrazole quinoline group " in 5 bit substituents, few to its research, mostly be 5 do not have to replace, simple alkyl or simple aromatic group such as phenyl, naphthyl, substituted-phenyl etc., 5 bit substituents also only limit to charge transfer between itself and " arylpyrazole quinoline group " to the molecular optics Effect on Performance.
Summary of the invention
Technical problem: problem to be solved by this invention is to overcome existing disadvantages of background technology, the arylpyrazole quinoline class luminophor that provides a kind of 5 condensed-nuclei aromaticss that improve the optical properties such as luminous and two-photon fluorescence of pyrazoline molecule to replace, and make the pyrazoline compounds of preparation have high melt point and second-order transition temperature, make it can be applicable to above-mentioned field.
Technical scheme: the present invention is achieved through the following technical solutions, and promptly at first introduces different electron-withdrawing substituents at 1 of the pyrazoles ring with 3, with the intramolecular charge transferance that strengthens " arylpyrazole quinoline chromophoric group " and make its absorption and the emmission spectrum red shift.At the pyrazoles ring 5 introduce the aromatic condensed ring substituting group again, produce another near ultraviolet or the luminous chromophoric group of visible region, the luminescent spectrum that makes 5 aromatic condensed rings with " arylpyrazole quinoline chromophoric group " thus absorption spectrum overlap and produce effective energy and shift, improve the luminous and two-photon fluorescence of pyrazoline molecule.
The general structure of the arylpyrazole quinoline class luminophor that 5 condensed-nuclei aromaticss of the present invention replace is as follows:
Wherein, R
1=4-nitrophenyl, 4-cyano-phenyl, 4-ester group phenyl, 2-nitrophenyl, 2-cyano-phenyl, 2-ester group phenyl, 2,4-dinitrophenyl or hydrogen atom, R
2=4-nitro, 4-cyano group, 4-ester group, 2-nitro, 2-cyano group, 2-ester group or 2,4-dinitrobenzene, R
3=9-anthryl, 9-phenanthryl or 1-pyrenyl.
The preferred compound of this luminophor, its structural formula is as follows:
The preparation method of the arylpyrazole quinoline class luminophor that 5 condensed-nuclei aromaticss of the present invention replace is:
At first adopt to have the aromatic ketone condensation generation chalcone intermediate that electron-withdrawing group replaces on condensed ring aromatic aldehyde and the phenyl ring, have the aryl hydrazine cyclic condensation that electron-withdrawing group replaces then with on the phenyl ring; Make the pyrazoline molecule of generation have " arylpyrazole quinoline " and 5 anthracene nucleus two big chromophoric grouies that intramolecularly strengthens charge transfer, thereby the luminescent spectrum of 5 aromatic condensed rings and the chromophoric absorption spectrum of arylpyrazole quinoline are overlapped to produce effective energy transfer, improve the luminous and two-photon fluorescence of pyrazoline molecule.
Beneficial effect: exist energy to shift between two big chromophoric grouies in the arylpyrazole quinoline molecule that 5 aromatic condensed rings of the present invention replace, cause the fluorescence and the nonlinear reinforcing effect of compound, improved the luminous and two-photon fluorescence of pyrazoline molecule.And melting point compound height of the present invention, fusing point can reach 310 ℃, and Heat stability is good can be used as luminescent materials such as LED.
Description of drawings
Fig. 1 is normalization method absorption spectrum a and the fluorescence spectrum b of compd A in the toluene dilute solution, and excitation wavelength is 360nm.
Fig. 2 is normalization method absorption spectrum a and the fluorescence spectrum b of compd B in the toluene dilute solution, and excitation wavelength is 360nm.
Fig. 3 is normalization method absorption spectrum a and the fluorescence spectrum b of Compound C in the toluene dilute solution, and excitation wavelength is 360nm.
Embodiment
Following examples will help to understand the present invention, but be not limited to content of the present invention.
The present invention implements with reference to following route:
Embodiment 1
1.1 3-(9-anthryl)-1-hydrocinnamyl-2-alkene-1-ketone (intermediate) is synthetic
With methyl phenyl ketone 1.20g, 9-anthracene aldehyde 2.05g, 20ml ethanol adds in the 100ml there-necked flask, slowly drips the NaOH aqueous solution of 6ml 3mol/L under the room temperature magnetic agitation, and suction filtration behind the reaction 2h gets yellow needle-like crystal with the yellow solid that obtains with the acetate recrystallization.Yield: 85%, M.p.:128-130 ℃.
1.2 1-(4-nitrophenyl)-3-phenyl-5-(9-anthryl)-2-pyrazoline (compd A) is synthetic
With intermediate A 1.0g, paranitrophenylhydrazine 0.8g, dense HCl6ml, ethanol 60ml join in the 100ml there-necked flask, and the following 78 ℃ of reaction 6h postcooling of magnetic agitation have yellow solid to separate out to room temperature.Suction filtration with the solid re-crystallizing in ethyl acetate that obtains, gets yellow crystals.Yield: 74%, M.p.:288-291 ℃,
1HNMR (CDCl3): δ 8.54 (d, J=11.8Hz, 2H), 8.17 (d, J=7.2Hz, 1H), and 7.98-8.05 (t, 2H), 7.83-7.90 (m, 4H), and 7.69-7.72 (t, 1H), 7.61-7.69 (t, 1H), and 7.37-7.49 (m, 5H), 6.93 (d, J=8.7Hz, 2H), 6.75-6.83 (m, 1H), 4.14-4.24 (m, 1H), 3.63-3.73 (m, 1H)
1.3 optical performance test
1-(4-nitrophenyl)-3-phenyl-5-(9-anthryl)-2-pyrazoline is dissolved in toluene, be mixed with dilute solution, measure its ultra-violet absorption spectrum and fluorescence spectrum, absorption spectrum is at Shimadzu UV-2450/2550 spectrophotometric determination, and fluorescence spectrum is measured on Horiba FluoMax 4.
Solution absorption spectrum peak wavelength is 395nm, and the fluorescence spectrum emission peak wavelength is 531nm.
Embodiment 2:
2.1 3-(9-anthryl)-1-(4-oil of mirbane propyl group)-2-alkene-1-ketone (intermediate) is synthetic
With 4-nitro-acetophenone 1.65g, 9-anthracene aldehyde 2.06g, 20ml ethanol adds in the 100ml there-necked flask, the NaOH aqueous solution that slowly adds 6ml 3mol/L under the room temperature magnetic agitation, suction filtration behind the reaction 2h, (v: v=1: 1) recrystallization gets red needle-like crystal with ethyl acetate-acetate will to obtain red solid.Yield: 81%, M.p.:158-160 ℃.
2.2 1,3-two (4-nitrophenyl)-5-(9-anthryl)-2-pyrazoline (compd B) synthetic
With intermediate B 1.0g, paranitrophenylhydrazine 0.8g, dense HCl6ml, ethanol 60ml join in the 100ml there-necked flask, and the following 78 ℃ of reaction 6h postcooling of magnetic agitation have orange red solid to separate out to room temperature.Suction filtration, and, get orange red crystal with the solid re-crystallizing in ethyl acetate.Yield: 71%, M.p.:309-310 ℃,
1HNMR (CDCl3): δ 8.57 (s, 1H), 8.50 (d, J=9.4Hz, 1H), 8.34 (d, J-9.0Hz, 2H), 8.16 (d, J=9.3Hz, 1H), and 8.00-8.07 (t, 3H), 7.88 (d, J=7.5Hz, 3H), and 7.72-7.76 (t, 1H), 7.63-7.66 (t, 1H), 7.38-7.44 (m, 2H), 6.91-7.00 (m, 2H), 6.82-6.86 (m, 1H), and 4.16-4.26 (m, 1H), 3.66-3.75 (m, 1H)
2.3 optical performance test
With 1,3-two (4-nitrophenyl)-5-(9-anthryl)-2-pyrazoline is dissolved in toluene, is mixed with dilute solution, measures its ultra-violet absorption spectrum and fluorescence spectrum, absorption spectrum is at Shimadzu UV-2450/2550 spectrophotometric determination, and fluorescence spectrum is measured on Horiba FluoMax 4.
Solution absorption spectrum peak wavelength is 438nm, and the fluorescence spectrum emission peak wavelength is 539nm.
Embodiment 3:
3.1 3-(4-nitrophenyl)-5-(9-anthryl)-2-pyrazoline (Compound C) is synthetic
With intermediate 3-(9-anthryl)-1-(4-oil of mirbane propyl group)-2-alkene-1-ketone 1.0g, hydrazine hydrate 0.8g, dense HCl4ml, ethanol 40ml join in the 100ml there-necked flask, and the following 78 ℃ of reaction 6h postcooling of magnetic agitation have red solid to separate out to room temperature.Suction filtration with the solid ethyl alcohol recrystallization that obtains, gets red crystals.Yield: 70%, M.p.:192-193 ℃.
1HNMR(CDCl
3)：δ8.48(s，1H)，8.36-8.38(m，2H)，8.25-8.28(m，2H)，8.03-8.06(m，2H)，7.85-7.87(m，2H)，7.48-7.52(m，4H)，6.55-6.60(t，1H)，3.58-3.70(m，2H)
3.2 optical performance test
3-(4-nitrophenyl)-5-(9-anthryl)-2-pyrazoline is dissolved in toluene and is mixed with dilute solution, measure its ultra-violet absorption spectrum and fluorescence spectrum, absorption spectrum is at Shimadzu UV-3600 spectrophotometric determination, and fluorescence spectrum is measured on Horiba FluoroMax 4.
Solution absorption spectrum peak wavelength is 392nm, and the fluorescence spectrum emission peak wavelength is 502nm.
Claims (3)
1. the arylpyrazole quinoline class luminophor that replaces of 5 condensed-nuclei aromaticss is characterized in that the general structure of this luminophor is as follows:
Wherein, R
1Be 4-nitrophenyl, 4-cyano-phenyl, 4-ester group phenyl, 2-nitrophenyl, 2-cyano-phenyl, 2-ester group phenyl, 2,4-dinitrophenyl or hydrogen atom, R
2Be 4-nitro, 4-cyano group, 4-ester group, 2-nitro, 2-cyano group, 2-ester group or 2,4-dinitrobenzene, R
3Be 9-anthryl, 9-phenanthryl or 1-pyrenyl.
2. the arylpyrazole quinoline class luminophor that 5 condensed-nuclei aromaticss according to claim 1 replace is characterized in that the preferred compound of this luminophor, and its structural formula is as follows:
3. the preparation method of the arylpyrazole quinoline class luminophor that replaces of 5 condensed-nuclei aromaticss as claimed in claim 1 is characterized in that this preparation method is:
At first adopt to have the aromatic ketone condensation generation chalcone intermediate that electron-withdrawing group replaces on condensed ring aromatic aldehyde and the phenyl ring, have the aryl hydrazine cyclic condensation that electron-withdrawing group replaces then with on the phenyl ring; Make the pyrazoline molecule of generation have " arylpyrazole quinoline " and 5 anthracene nucleus two big chromophoric grouies that intramolecularly strengthens charge transfer, the luminescent spectrum and the chromophoric absorption spectrum of arylpyrazole quinoline of 5 aromatic condensed rings are overlapped to produce effective energy transfer, improve the luminous and two-photon fluorescence of pyrazoline molecule.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237520A (en) * | 2015-11-06 | 2016-01-13 | 江苏三月光电科技有限公司 | Compound material containing pyrazoline structure and application of compound material |
| CN113773254A (en) * | 2021-09-27 | 2021-12-10 | 上海兆维科技发展有限公司 | 1,3,4, 5-tetra-substituted pyrazole derivative and preparation method thereof |
| CN114057647A (en) * | 2021-11-26 | 2022-02-18 | 重庆工商大学 | Pyrazoline fluorescent molecule and preparation method thereof |
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| US6288232B2 (en) * | 1999-12-28 | 2001-09-11 | Emagin Corporation | Synthesis of pyrazolinylnaphthalic acid derivatives |
| WO2002011209A2 (en) * | 2000-08-01 | 2002-02-07 | Emagin Corporation | Method of patterning color changing media for organic light emitting diode display devices |
| JP2003109765A (en) * | 2001-09-28 | 2003-04-11 | Canon Inc | Organic light emitting element |
| WO2003078542A1 (en) * | 2002-03-19 | 2003-09-25 | Neoview Co., Ltd. | Red organic light-emitting compound and organic light-emitting device comprising the same |
| CN101429162A (en) * | 2008-12-11 | 2009-05-13 | 淮阴师范学院 | Method for producing 1-phenyl-3,5-di-substituted aryl-2-pyrazoline |
-
2011
- 2011-05-18 CN CN2011101307615A patent/CN102295601A/en active Pending
Patent Citations (5)
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| US6288232B2 (en) * | 1999-12-28 | 2001-09-11 | Emagin Corporation | Synthesis of pyrazolinylnaphthalic acid derivatives |
| WO2002011209A2 (en) * | 2000-08-01 | 2002-02-07 | Emagin Corporation | Method of patterning color changing media for organic light emitting diode display devices |
| JP2003109765A (en) * | 2001-09-28 | 2003-04-11 | Canon Inc | Organic light emitting element |
| WO2003078542A1 (en) * | 2002-03-19 | 2003-09-25 | Neoview Co., Ltd. | Red organic light-emitting compound and organic light-emitting device comprising the same |
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Non-Patent Citations (1)
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| WANG M. ET AL: "Intramolecular energy and charge transfer in 5-(9-anthryl)-3-(4-nitrophenyl)-1-phenyl-2-pyrazoline", 《JOURNAL OF LUMINESCENCE》, vol. 99, 31 December 2002 (2002-12-31), pages 79 - 83, XP004372185, DOI: doi:10.1016/S0022-2313(01)00204-6 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237520A (en) * | 2015-11-06 | 2016-01-13 | 江苏三月光电科技有限公司 | Compound material containing pyrazoline structure and application of compound material |
| CN105237520B (en) * | 2015-11-06 | 2018-01-30 | 江苏三月光电科技有限公司 | A kind of compound-material containing pyrazoline structure and its application |
| CN113773254A (en) * | 2021-09-27 | 2021-12-10 | 上海兆维科技发展有限公司 | 1,3,4, 5-tetra-substituted pyrazole derivative and preparation method thereof |
| CN114057647A (en) * | 2021-11-26 | 2022-02-18 | 重庆工商大学 | Pyrazoline fluorescent molecule and preparation method thereof |
| CN114057647B (en) * | 2021-11-26 | 2023-06-13 | 重庆工商大学 | Pyrazoline fluorescent molecule and preparation method thereof |
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Application publication date: 20111228 |