CN104817504B - A kind of green fluorescence compound containing triphenylamine and bisbenzimidazole construction unit and its production and use - Google Patents
A kind of green fluorescence compound containing triphenylamine and bisbenzimidazole construction unit and its production and use Download PDFInfo
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- CN104817504B CN104817504B CN201510137419.6A CN201510137419A CN104817504B CN 104817504 B CN104817504 B CN 104817504B CN 201510137419 A CN201510137419 A CN 201510137419A CN 104817504 B CN104817504 B CN 104817504B
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- triphenylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/14—Radicals substituted by nitrogen atoms
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- 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
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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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Abstract
The present invention discloses a kind of green fluorescence compound 1 containing triphenylamine and bisbenzimidazole construction unit, 1 two (base of 1H benzimidazoles 2) 2 (base of triphenylamine 4) ethene and its preparation method and application, belongs to organic field of optical functional material.The compound under nitrogen protection and base catalysis, is prepared using double (base of 1H benzimidazoles 2) methane and 4 formoxyl triphenylamines as raw material by Knoevenagel condensation reactions, and crude product is purified through water and alcohol mixed solvent recrystallization.Product transmitting green fluorescence in solid-state and in DMF weak solutions, launches blue-green fluorescent in alcohol dilute solution.It is suitable as the fluorescent material of fluorescence labeling formulation product, household chemicals, papermaking, textile chemical fiber, plastics and OLED products.Present invention process is simple, safe operation, and product yield is high, it is easy to accomplish large-scale production.
Description
Technical field
The present invention relates to a kind of containing triphenylamine and the green fluorescence compound of bisbenzimidazole construction unit and its preparation side
Method and purposes.Specifically related to one kind 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene and preparation method thereof
And purposes, belong to organic field of optical functional material.The compound is suitable as fluorescence labeling formulation product, household chemicals, made
Paper, textile chemical fiber, the fluorescent material of plastics and photoelectron material derived product.
Background technology
With third generation Display Technique OLED fast development, the emitting layer material of its material foundation, electric transmission are used as
Layer material and hole transport layer material face great demand, and they are all often the fluorescences with good energy conversion efficiency
Matter.In recent years, organic molecule of the design synthesis with D- π-A structures (" push-and-pull electronics " structure), which turns into, seeks excellent performance OLED
One of maximum attention point of photoelectric material.Benzimidazole is the typical structure unit of Organic Electron Transport Material, and it is containing two
The rigid fused heterocyclic compound of individual nitrogen-atoms, with unique electronic structure, this causes its derivative to have good fluorescence
The physicochemical properties such as matter, electric conductivity and heat endurance, are widely used in organic electroluminescent light and electroluminescent material.And
Triphenylamine is then the typical structure unit of organic hole transport material.The two design is synthesized in same molecule by pi bond and held
Easily construct the organic photoelectrical material with D- π-A structures.Meanwhile, organic fluorescent substance is used as luminescence generated by light and electroluminescent
The main kind of material, the characteristics of molecular structure typically has following is just more beneficial for intramolecule generation electron transition and brought
Energy is converted：∏ conjugated systems are bigger, and delocalized electron is more easily excited, so that easier generation luminescence generated by light and electroluminescent hair
Light.General aroma system is bigger, and fluorescence is more moved to long wave direction, and intensity is also stronger；Molecular structure flatness and rigidity are stronger,
It is easier that there is more preferable fluorescence property, this result reduced mainly due to interior conversion probability caused by dissipation of vibrations.It is double
(1H- benzimidazolyl-2 radicals-yl) methane and 4- formoxyls triphenylamine are all that aroma system is larger, and rigidity and coplanarity are stronger
Big ∏ conjugated system molecules, the D- π-A that the two generation can be made to pass through carbon-to-carbon pi bond bridging by Knoevenagel condensation reactions
The organic fluorescent compounds of structure.As fluorescence labeling formulation product, household chemicals, papermaking, textile chemical fiber, plastics and photoelectricity
The fluorescent material of sub- product, with major application prospect.
The content of the invention
One of the object of the invention is to propose to contain triphenylamine and double benzos by the way that Knoevenagel condensation reactions synthesis is a kind of
The big ∏ of imidazole structure unit is conjugated the green fluorescence compound 1 of condensed hetero ring system, 1- bis- (1H- benzimidazolyl-2 radicals-yl) -2-
(triphenylamine -4- bases) ethene.The compound decomposition temperature height, Stability Analysis of Structures, fluorescence property are good, can be widely used for fluorescence labeling and match somebody with somebody
Square product, household chemicals, papermaking, textile chemical fiber, the fluorescent material field of plastics and photoelectron material derived product.
For achieving the above object, this invention takes following technical scheme：
The present invention provides the green fluorescence of one kind 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene
Compound, its molecular structural formula is as follows：
Another object of the present invention is to propose 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene
The preparation method of compound, technical scheme is as follows：
As described above, the preparation method of 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene, it is special
Levy and be：With double (1H- benzimidazolyl-2 radicals-yl) methane and structure 4- formyls as shown in formula (II) of the structure as shown in formula (I)
Base triphenylamine is raw material, under nitrogen protection and base catalysis, is prepared by Knoevenagel condensation reactions.
As described above, the preparation method of 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene, it is special
Levy and be：Reaction dissolvent used is ethanol, 1- propyl alcohol, ethylene glycol or cyclohexanol.
As described above, the preparation method of 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene, it is special
Levy and be：Alkali catalyst is diethylamine, triethylamine, hexahydropyridine and KOH.
As described above, the preparation method of 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene, it is special
Levy and be：Recrystallization mixed solvent is made up of water with ethanol, and the volume ratio of mixed solvent reclaimed water and ethanol is 1.0: 1.0~1.0:
3.0。
1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene of the present invention is amount yellow powder solid,
Its yield is 85%~92%, and fusing point is 308 ± 1 DEG C.Its synthesis technique principle is shown below：
Compared with prior art, the beneficial effects of the present invention are：
1. compound proposed by the present invention is the big ∏ conjugation organic micromolecule compounds of typical D- π-A structures, molecule
It is internal to contain most classical electron transport material benzimidazole unit and hole mobile material fluorine-triphenylamine structure unit simultaneously,
The two is connected by carbon-to-carbon double bond, and molecule coplanarity is good, the reduction of electron excitation energy, photosensitivity enhancing, fluorescence efficiency
It is high.
2. fluorescent chemicals proposed by the present invention contains two strong benzimidazole units of heat endurance, therefore the change
The heat-resistant stability of compound is greatly improved.It is advantageously used for the higher fluorescent material product of temperature in use.
3. fluorescent chemicals preparation method proposed by the present invention is simple, and raw material is cheap and easy to get, and cost is low, synthetic reaction it is molten
Agent can be recycled directly, it is easy to large-scale production, therefore have application, DEVELOPMENT PROSPECT well.
Brief description of the drawings
In order to which the structure and fluorescence property spy that further illustrate product provide drawings described below.
1st, Fig. 1 is synthesized 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene1H H NMR spectroscopies
Figure.
2nd, Fig. 2 is 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene 1 × 10-5mol/L DMF
Solution fluorescence under being excited with 365nm length ultraviolets light in ethanol.
3rd, Fig. 3 is 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene in 365nm length ultraviolet light
Solid film fluorescence under exciting.
Embodiment
Technical scheme is described further below in conjunction with specific embodiment, but claimed model
Enclose and be not limited thereto.The fusing point of final product is measured by SGW X-4 micro-meldometers obtained by embodiment；FT-IR by
Spectrum BX II types Fourier transformation infrared spectrometer is determined；UV-Vis spectrum are through TU-1901 type ultraviolet specrophotometers
(Beijing Pu Xi all purpose instruments Manufacturing Co., Ltd) measures；Fluorescence spectrum is through the LS55 type sepectrophotofluorometers (U.S.
PerkinElmer companies) measure；1H NMR magnetic resonance spectroscopies are through AVANCE type nuclear magnetic resonance chemical analysers (dmso-d6For solvent, TMS
For internal standard, Bruker companies of Switzerland) measure.The present invention raw materials used double (1H- benzimidazolyl-2 radicals-yl) is prepared according to literature method
(bibliography：Wang Luyao, Han Jie, Li Xiaojuan, etc..The simple synthesis [J] of double (2- benzimidazolyls) alkane.Chemistry examination
Agent, 2005,27 (5)：317-318；320.)；The stupid amine of raw materials used 4- formoxyls three prepares (bibliography according to literature method：
Grow into forest late, Ding Ruisong, Zhang Qichun, etc..The synthesis and its photoelectric properties research [J] of triphen amine formaldehyde diphenyl hydrazone.Photographic science with
Photochemistry, 2001,19 (1)：43-47).
Embodiment 1 is equipped with agitator, thermometer, reflux condensing tube and the tetra- mouthfuls of burnings of 100ml for connecting nitrogen protection device
Bottle in, add 10mmol (2.48g) double (1H- benzimidazolyl -2- bases) methane, 10mmol (2.73g) 4- formoxyls triphenylamine,
50ml ethanol and 1mL hexahydropyridines are stirred to dissolve as catalyst, after be warming up to 95 DEG C of temperature controls reaction 8h.Reaction solution is cooled down
Afterwards, precipitation generates, suction filtration while hot, product is washed repeatedly with ethanol, dry crude product.Crude product uses VWater∶VEthanol=1.0:
2.0 ethanol and water mixed solvent recrystallization, obtains 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene
Yellow powdery solid, yield is 87.2%, and fusing point is 308 ± 1 DEG C.
The sign and fluorescence property test result of product are as follows：
1H NMR(dmso-d6, TMS internal standards, 400MHz)：(s, 1H, carbon carbon are double by δ 12.45 (s, 2H, imidazole ring hydrogen), δ 6.69
Key hydrogen), δ 7.10-7.98 (m, 22H, Ar-H) meet target product molecular structure.
FT-IR (KBr tablettings)：3425cm-1For-NH stretching vibration peaks, 3077cm on imidazole ring-1Locate to stretch for phenyl ring C-H
Vibration peak, 1625cm-1Locate as carbon-carbon double bond stretching vibration peak, 1418~1594cm-1Locate the skeletal vibration for phenyl ring and imidazole ring
Peak, 765cm-1Locate to twist peak for the bending of c h bond in phenyl ring.
The UV-Vis of product：(1 × 10 in DMF and ethanol-5Mol/L have in) at 315nm and 385nm or so two compared with
Strong ultraviolet absorption peak.Absworption peak corresponds at the big conjugated system π-π * electron transitions of whole molecule, 315nm and absorbed at 385nm
Peak is probably to be caused by imidazole ring π-π * electron transitions.
The fluorometric investigation of product：Selection wavelength 365nm light is excited down, 1 × 10-5Maximum emission wavelength in mol/L ethanol
For 488nm, 1 × 10-5Maximum emission wavelength is 525.5nm in mol/L DMF.During using 360nm excitation wavelengths, product is consolidated
Body thin film fluorescence maximum emission wavelength is 528.5nm.
Embodiment 2 is equipped with agitator, thermometer, reflux condensing tube and tetra- mouthfuls of 100ml for connecting nitrogen protection device
In flask, 11mmol (2.73g) double (1H- benzimidazolyl -2- bases) methane, 10mmol (2.73g) 4- formoxyl triphens are added
Amine, 50ml ethylene glycol and 1mL hexahydropyridines are stirred to dissolve as catalyst, after be warming up to 100 DEG C of temperature controls reaction 8h.Reaction
After liquid cooling, there is precipitation to generate, suction filtration while hot, product is washed repeatedly with ethanol, dry crude product.Crude product uses VWater∶VEthanol
=1.0: 3.0 ethanol and water mixed solvent recrystallization, obtains 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4-
Base) ethene yellow solid, its yield is 88.2%, and fusing point is 308 ± 1 DEG C.
The sign and the performance test results be the same as Example 1 of product.
Embodiment 3 is equipped with agitator, thermometer, reflux condensing tube and the tetra- mouthfuls of burnings of 100ml for connecting nitrogen protection device
In bottle, 10.5mmol (2.61g) double (1H- benzimidazolyl -2- bases) methane, 10mmol (2.73g) 4- formoxyl triphens are added
Amine, 50ml ethanol and 1mL triethylamines are stirred to dissolve as catalyst, after be warming up to 100 DEG C of temperature controls reaction 7h.Reaction solution is cold
But after, precipitation generates, suction filtration while hot, product is washed repeatedly with ethanol, dry crude product.Crude product uses VWater∶VEthanol=
1.0: 1.0 ethanol and water mixed solvent recrystallization, obtains 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases)
Ethene yellow solid, its yield is 85.6%, and fusing point is 308 ± 1 DEG C.
The sign and the performance test results be the same as Example 1 of product.
Claims (2)
1. a kind of high temperature resistant green fluorescence compound 1 containing triphenylamine and bisbenzimidazole construction unit, (the 1H- benzo miaows of 1- bis-
Azoles -2- bases) -2- (triphenylamine -4- bases) ethene, it is characterised in that the molecular structural formula of the compound is：
2. the application of 1,1- bis- (1H- benzimidazolyl-2 radicals-yl) -2- (triphenylamine -4- bases) ethene as claimed in claim 1, it is special
Levy and be, the compound can launch 500~540nm green fluorescence under the exciting of 250~370nm wave band ultraviolet lights,
It is used for the glimmering of fluorescence labeling formulation product, household chemicals, papermaking, textile chemical fiber, plastics and photoelectron material derived product
Luminescent material.
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| CN107522848B (en) * | 2017-07-17 | 2020-10-30 | 浙江工业大学 | Polyquinacridone compound and preparation method and application thereof |
| CN115745965B (en) * | 2022-11-11 | 2024-01-30 | 华南师范大学 | Fluorescent molecule and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0444327A1 (en) * | 1990-03-01 | 1991-09-04 | Agfa-Gevaert N.V. | Dyes for use in thermal dye transfer |
| EP0982631A2 (en) * | 1998-08-27 | 2000-03-01 | Ricoh Company, Ltd. | Electrophotographic photoconductor and electrophotographic image forming apparatus using the photoconductor |
| CN103980255A (en) * | 2014-04-14 | 2014-08-13 | 苏州科技学院 | Dibenzimidazole derivative ultraviolet ray absorber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0731404B2 (en) * | 1986-04-09 | 1995-04-10 | ミノルタ株式会社 | Photoconductor |
| JPH0675206B2 (en) * | 1986-07-22 | 1994-09-21 | キヤノン株式会社 | Electrophotographic photoreceptor |
| TW524841B (en) * | 2001-05-08 | 2003-03-21 | Chi Mei Optoelectronics Corp | Organic electro-luminescent (OEL) compound |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0444327A1 (en) * | 1990-03-01 | 1991-09-04 | Agfa-Gevaert N.V. | Dyes for use in thermal dye transfer |
| EP0982631A2 (en) * | 1998-08-27 | 2000-03-01 | Ricoh Company, Ltd. | Electrophotographic photoconductor and electrophotographic image forming apparatus using the photoconductor |
| CN103980255A (en) * | 2014-04-14 | 2014-08-13 | 苏州科技学院 | Dibenzimidazole derivative ultraviolet ray absorber and preparation method thereof |
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