CN107141260A - A kind of difluorophenyl miazines solid-state green emission luminous organic material and preparation method thereof - Google Patents
A kind of difluorophenyl miazines solid-state green emission luminous organic material and preparation method thereof Download PDFInfo
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- CN107141260A CN107141260A CN201710417489.6A CN201710417489A CN107141260A CN 107141260 A CN107141260 A CN 107141260A CN 201710417489 A CN201710417489 A CN 201710417489A CN 107141260 A CN107141260 A CN 107141260A
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- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract
The invention discloses difluorophenyl miazines solid-state green emission luminous organic material shown in a kind of Formulas I and preparation method thereof.The fragrant propyl group of two kinds of functional structure units is replaced cyclic ketones and isopropyl methanesulfonamido difluorophenyl pyrimidine functional structure unit to be combined by polyenoid bridged bond by the present invention, forms the new difluorophenyl miazines solid-state green emission luminous organic material of a class.The luminous organic material that the present invention is provided shows solid broadband green emission characteristic in solid-state.The preparation method of the present invention, simple to operate, synthesis is convenient, and gained luminescent material stability is good, practical, available for fields such as luminescent device, laser dye, anti-counterfeiting technology, sensitive fluorescent, bio-medical analysis.The present invention has expanded research and the application field of difluorophenyl pyrimidines.Wherein X is C or N.
Description
Technical field：
The invention belongs to technical field of organic luminescence materials, and in particular to a kind of difluorophenyl miazines solid-state green emission
Luminous organic material and preparation method thereof.
Background technology：
Luminous organic material is widely used in organic electroluminescence device, organic solid laser, organic photovoltaic battery, life
The fields such as thing medical science fluorescence imaging, organic fluorescence sensor and anti-fake material.Design and develop with strong solid state fluorescence transmitting,
The luminous organic material of high fluorescence efficiency, various launch wavelengths, is a focus of current photoelectric material and technical field research,
With highly important theory significance and practical value.
Isopropyl methanesulfonamido difluorophenyl pyrimidine is a kind of important pharmacophoric group, is statins antilipemic of new generation
The auspicious effective efficiency construction unit for cutting down statin of medicine.Although isopropyl methanesulfonamido difluorophenyl pyrimidine derivatives are ground
Study carefully the attention of personnel, and carried out numerous studies, still, in the prior art to being limited to synthesis side the research of this kind of compound more
Method, technical study, and as medicine intermediate synthesize it is auspicious cut down statins in application, and be used for the preparation of luminescent material
Then it is rarely reported with research.
With 3- (4- (4- fluorophenyls) -6- isopropyls -2- (N- methyl-N- methane sulfonylaminos) pyrimidine -5- bases) methacrylaldehyde
For raw material, two isopropyl methanesulfonamido difluorophenyl pyrimidine function bases are connected by polyene ketone bridged bond, double fluorine are formd
For phenyl pyrimidine class compound, the compound has solid-state green emission characteristic, and involved in the present invention is operated in prior art
In there is not been reported.
The content of the invention：
An object of the present invention is to provide a kind of difluorophenyl miazines solid-state green emission luminous organic material.
The present invention is achieved by the following technical solutions：
A kind of structure of difluorophenyl miazines solid-state green emission luminous organic material is shown in formula I：
Wherein X is C or N.
It is a further object of the present invention to provide the system of above-mentioned difluorophenyl miazines solid-state green emission luminous organic material
Preparation Method this method comprises the following steps：It is 1 by mol ratio:Substitution cyclic ketones and 3- (4- (4- fluorobenzene shown in 2-2.3 formula II
Base) -6- isopropyls -2- (N- methyl-N- methane sulfonylaminos) pyrimidine -5- bases) methacrylaldehyde is dissolved in organic solvent, and stirring is lower to drip
Plus aqueous slkali, stirring reaction, after reaction completely, reaction solution is poured into water at room temperature, is stood, and the decompression of gained solid matter is taken out
Filter, is washed with water, drying at room temperature, is recrystallized with ethanol or ethanol-acetone, obtains target product；
Wherein X is C or N.
Described organic solvent is methanol or ethanol；Aqueous slkali for 15~20wt% potassium hydroxide aqueous solution or 15~
20wt% sodium hydrate aqueous solution.
As substitution cyclic ketones and 3- (4- (4- fluorophenyls) -6- isopropyls -2- (N- methyl-N- methane sulfonylaminos) pyrimidine -5-
Base) methacrylaldehyde mol ratio be 1：When 2, difluorophenyl miazines solid-state green emission luminous organic material of the present invention
Synthetic route is as follows：
Wherein X is C or N.
The present invention also protects the application of described difluorophenyl miazines solid-state green emission luminous organic material.
The difluorophenyl miazines solid-state green emission luminous organic material of the present invention, under 325nm laser excitations, is presented
Go out solid broadband green emission, its maximum emission wavelength is 529 or 551nm, luminescent spectrum almost covers whole visibility region, and
In Long wavelength region with acromion structure.Solid broadband green emission crystalline material provided by the present invention can be directly as green hair
Luminescent material, for fields such as luminescent device, laser dye, anti-counterfeiting technology, sensitive fluorescent, bio-medical analysis.
The present invention has the advantages that：
(1) present invention by propyl group by replacing cyclic ketones and isopropyl methanesulfonamido difluorophenyl pyrimidine functional structure list
Member is combined by polyenoid bridged bond, forms New Solid green emission difluorophenyl miazines luminous organic material；Provide
The new purposes of this kind of compound, develops new light emitting molecule skeleton.
(2) compound molecule provided by the present invention has conjugated system that is larger, more extending, this special point
Minor structure feature is conducive to strengthening the luminescent properties of organic material；Meanwhile, the presence of a variety of substituents in molecule, such as methyl, third
The groups such as base, isopropyl, methanesulfonamido, on the one hand can be effectively increased the steric hindrance of molecule, reduce being total to for whole molecule
Flatness, so that intermolecular interaction when effectively reducing solid-state, prevents fluorescent quenching；On the other hand, it can also increase
Plus the solubility of this kind of compound, improve processing characteristics and practicality.
(3) in molecule two have strong electronegativity fluorine atom introducing, largely change the thing of the compound
Physicochemical property and physiologically active in vivo, meanwhile, it can also change molecular energy level structure, aggregated structure or molecule
Stacked form, so as to cause the change of the luminescent properties and processability of organic photoelectrical material so that the application of compound
It can be greatly improved.In addition, because with groups such as pyrimidines in compound molecule, with good biocompatibility and biology
Active matter, has potential using value in fields such as bio-medical analysis, ion identification, medicine tracking, biosimulations.
(4) preparation method proposed by the present invention, technique is simple, and easy to operate, gained luminescent material stability is good.The present invention
There is provided a kind of new way for obtaining solid-state green-emitting material, the research and development available for new and effective green light luminescent material.Meanwhile,
Because selected raw material is medicine intermediate, therefore, one is provided again for the comprehensive development and utilization of related industry, industrial upgrading
New effective way.
Brief description of the drawings：
Fig. 1 is the solid luminescent spectrogram for the target product that Examples 1 and 2 are obtained；
Wherein, Ia, Ib represent the compound that embodiment 1, embodiment 2 are obtained respectively.
Embodiment：
With reference to embodiment, technical scheme is further illustrated, following embodiments are illustrative, are not
Limited, it is impossible to limit protection scope of the present invention with following embodiments.
Laboratory apparatus and model：Bruker AVANCE-300 nuclear magnetic resonance chemical analysers；Agilent LC/MSD Trap
XCT mass spectrographs；Horiba Jobin-Yvon LabRam HR800 laser Raman spectrometers.
Embodiment 1：(3- (4- (4- the fluorophenyls) -6- isopropyls -2- (N- methyl-N- mesyl ammonia of 4- propyl group -2,6- two
Base) pyrimidine -5- bases) acrol) and-cyclohexanone (compound Ia) preparation
In 250 milliliters of round-bottomed flasks, by 4- propylcyclohexanones (1mmol) and 3- (4- (4- fluorophenyls) -6- isopropyls -
2- (N- methyl-N- methane sulfonylaminos) pyrimidine -5- bases) methacrylaldehyde (2mmol) is dissolved in 100 milliliters of ethanol, quickly stirring
It is lower 20 milliliters of mass fractions are added dropwise into the solution to be 15~20% potassium hydroxide solution, and be stirred at room temperature reaction 10~
15 hours.Afterwards, reaction solution is poured into 150 milliliters of water, stood, gained solid matter decompression suction filtration is washed with water for several times, room
Temperature is dried.Recrystallized with ethanol-acetone mixed solvent, vacuum drying obtains yellow green acicular crystal, yield is 78%.
1H NMR(300MHz,CDCl3/TMS)δ:0.90 (t, J=6.6Hz, 3H), 1.19-1.22 (m, 4H), 1.30 (d, J
=6.6Hz, 12H), 1.62-1.1.64 (m, 1H), 1.92-2.01 (m, 2H), 2.42-2.48 (m, 2H), 3.35-3.39 (m,
2H), 3.53 (s, 6H), 3.58 (s, 6H), 6.28 (dd, J=15.9,11.7Hz, 2H), 6.97 (d, J=15.6Hz, 2H),
7.07-7.13 (m, 4H), 7.29 (d, J=11.7Hz, 2H), 7.59-7.65 (m, 4H)13HC NMR(75MHz,CDCl3/TMS)
δ:14.04,19.97,21.69,32.01,32.27,32.33,33.11,37.38,42.47,115.185,115.47,
121.15,131.75,131.95,132.06,133.58,134.42,134.46,135.24,135.38,157.38,161.81,
163.86,165.12,174.97,189.14.
Embodiment 2：(3- (4- (4- the fluorophenyls) -6- isopropyls -2- (N- methyl-N- mesyl ammonia of 1- propyl group -3,5- two
Base) pyrimidine -5- bases) acrol) and -4- piperidones (compound Ib) preparation：
In 250 milliliters of round-bottomed flasks, by 4- propylcyclohexanones (1mmol) and 3- (4- (4- fluorophenyls) -6- isopropyls -
2- (N- methyl-N- methane sulfonylaminos) pyrimidine -5- bases) methacrylaldehyde (2mmol) is dissolved in 100 ml methanols, quickly stirring
It is lower 20 milliliters of mass fractions are added dropwise into the solution to be 15~20% sodium hydroxide solution, and be stirred at room temperature reaction 10~
15 hours.Afterwards, reaction solution is poured into 150 milliliters of water, stood, gained solid matter decompression suction filtration is washed with water for several times, room
Temperature is dried.Recrystallized with ethanol-acetone mixed solvent, vacuum drying obtains yellow flat crystal, yield is 72%.
1H NMR(300MHz,CDCl3/TMS)δ:0.91 (t, J=7.5Hz, 3H), 1.26-1.39 (m, 14H), 2.32 (t,
J=7.5Hz, 2H), 3.22 (s, 4H), 3.33-3.38 (m, 2H), 3.53 (s, 6H), 3.58 (s, 6H), 6.18 (dd, J=
15.6,11.7Hz, 2H), 7.01 (d, J=15.6Hz, 2H), 7.08-7.14 (m, 4H), 7.28 (d, J=11.7Hz, 2H),
7.58-7.64(m,4H).ESI-MS m/z:860.4(M+H)+。
Embodiment 3：(3- (4- (4- the fluorophenyls) -6- isopropyls -2- (N- methyl-N- mesyl ammonia of 4- propyl group -2,6- two
Base) pyrimidine -5- bases) acrol) and-cyclohexanone (compound Ia) preparation
Obtain as described in Example 1, unlike, 4- propylcyclohexanones and 3- (4- (4- fluorophenyls) -6- isopropyls -
2- (N- methyl-N- methane sulfonylaminos) pyrimidine -5- bases) methacrylaldehyde mol ratio be 1:2.3, recrystallization solvent used is second
Alcohol.
Embodiment 4：Solid luminescent performance test
Solid-state photoluminescence spectra is determined with Horiba Jobin-Yvon LabRam HR800 laser Raman spectrometers, is swashed
Light emitting source is 325nm He-Cd lasers, as a result sees Fig. 1.
As shown in Figure 1, the crystalline material for the compound that embodiment 1 (compound Ia) and embodiment 2 (compound Ib) are obtained,
Under 325nm laser excitations, solid broadband green emission is showed, its maximum emission wavelength is respectively 529 and 551nm, hair
Light spectrum almost covers whole visibility region, and in Long wavelength region with acromion structure.It is real compared with the compound Ia of embodiment 1
The compound Ib of the example 2 obvious red shift of emission peak is applied, and there is stronger fluorescent emission intensity, broader emission band, become apparent from
Acromion structure.
The above results illustrate, the solid broadband green-emitting material in solid-state with good green emission characteristic, because
This, solid broadband green emission crystalline material provided by the present invention can directly as green luminescent material, for luminescent device,
The fields such as laser dye, anti-counterfeiting technology, sensitive fluorescent, bio-medical analysis.Solid-state green glow hair is obtained the invention provides one kind
The new way of material is penetrated, the research and development available for new and effective green light luminescent material.
Claims (5)
1. the difluorophenyl miazines solid-state green emission luminous organic material shown in a kind of formula I：
Wherein X is C or N.
2. a kind of preparation method of the difluorophenyl miazines solid-state green emission luminous organic material described in claim 1, its
It is characterised by, this method comprises the following steps：It is 1 by mol ratio:Substitution cyclic ketones and 3- (4- (4- fluorine shown in 2-2.3 formula II
Phenyl) -6- isopropyls -2- (N- methyl-N- methane sulfonylaminos) pyrimidine -5- bases) methacrylaldehyde is dissolved in organic solvent, under stirring
Aqueous slkali is added dropwise, stirring reaction, after the completion of reaction, reaction solution is poured into water at room temperature, stands, the decompression of gained solid matter is taken out
Filter, is washed with water, drying at room temperature, is recrystallized with ethanol or ethanol-acetone, obtains target product；
Wherein X is C or N.
3. the preparation method of difluorophenyl miazines solid-state green emission luminous organic material according to claim 2, its
It is characterised by, described organic solvent is methanol or ethanol；Aqueous slkali for 15~20wt% potassium hydroxide aqueous solution or 15~
20wt% sodium hydrate aqueous solution.
4. the application of the difluorophenyl miazines solid-state green emission luminous organic material described in claim 1.
5. the application of difluorophenyl miazines solid-state green emission luminous organic material according to claim 1, its feature
It is, is used for luminescent device, laser dye, anti-counterfeiting technology, sensitive fluorescent and biomedicine point as green luminous organic material
Analysis field.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744377A (en) * | 2015-02-12 | 2015-07-01 | 南京博优康远生物医药科技有限公司 | Preparation method of (E)-3-[4-(4-fluorophenyl)-6-isopropyl-2-(N-methyl-N-methanesulfonylamino) pyrimidine-5-yl] acrolein |
| CN105001141A (en) * | 2015-08-12 | 2015-10-28 | 中国广州分析测试中心 | Fluoro phenylindole compound, application of fluoro phenylindole compound as red organic luminescent material, and preparation method of fluoro phenylindole compound |
| CN105801562A (en) * | 2016-04-27 | 2016-07-27 | 中国广州分析测试中心 | Solid-state broadband red light emission organic light-emitting material and preparation method thereof |
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- 2017-06-06 CN CN201710417489.6A patent/CN107141260B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744377A (en) * | 2015-02-12 | 2015-07-01 | 南京博优康远生物医药科技有限公司 | Preparation method of (E)-3-[4-(4-fluorophenyl)-6-isopropyl-2-(N-methyl-N-methanesulfonylamino) pyrimidine-5-yl] acrolein |
| CN105001141A (en) * | 2015-08-12 | 2015-10-28 | 中国广州分析测试中心 | Fluoro phenylindole compound, application of fluoro phenylindole compound as red organic luminescent material, and preparation method of fluoro phenylindole compound |
| CN105801562A (en) * | 2016-04-27 | 2016-07-27 | 中国广州分析测试中心 | Solid-state broadband red light emission organic light-emitting material and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 付文娟等: "3种嘧啶类电子传输材料的合成及表征", 《化学试剂》 * |
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Address after: 510070 Guangzhou City, Guangzhou, Guangdong, No. 34 Patentee after: Institute of testing and analysis, Guangdong Academy of Sciences (Guangzhou analysis and testing center, China) Address before: 510070 Guangzhou City, Guangzhou, Guangdong, No. 34 Patentee before: GUANGDONG INSTITUTE OF ANALYSIS (CHINA NATIONAL ANALYTICAL CENTER, GUANGZHOU) |