CN106749095B - A kind of benzothiazole derivant and its preparation and application with spectral signal amplification performance - Google Patents
A kind of benzothiazole derivant and its preparation and application with spectral signal amplification performance Download PDFInfo
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- CN106749095B CN106749095B CN201710032406.1A CN201710032406A CN106749095B CN 106749095 B CN106749095 B CN 106749095B CN 201710032406 A CN201710032406 A CN 201710032406A CN 106749095 B CN106749095 B CN 106749095B
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- signal amplification
- spectral signal
- amplification performance
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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
- C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
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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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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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
- 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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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
The present invention relates to a kind of benzothiazole derivants with spectral signal amplification performance and its preparation and application, structural formula to be：
Description
Technical field
The invention belongs to spectral signal amplification performance material and its preparation and application fields, more particularly to a kind of to have spectrum
The benzothiazole derivant of signal amplification performance and its preparation and application.
Background technology
Function organic dyestuff is because with answering Light harvest antenna molecule, light-sensitive device and luminescent material etc. are important in recent years
It is concerned with foreground.It can be needed in the process first in manual simulation's photosynthesis conversion solar by aggregation luminous energy can be absorbed
Organic dyestuff antenna carries out catching light, and in the novel organic electronic device that Organic Light Emitting Diode (OLED) is representative,
The organic fluorescent dye of high efficiency light-emitting is then critical material.Therefore there is high efficiency extinction to have engine dyeing with what is shone for design synthesis
Material molecule is the hot spot of current functional organic material research.Benzothiazole derivant is that a kind of good light stability and luminous efficiency are high
Fluorescent chemicals, be common efficiently one of luminous organic material, but its absorptivity is smaller, and fluorescence quantum yield is still
There is very big room for promotion.It can be seen that by rational MOLECULE DESIGN, synthesizes the benzothiazole with spectral signal amplification performance and derive
Object is undoubtedly to promoting its application in Light harvest antenna molecule and luminous organic material to be of great significance.
Invention content
Technical problem to be solved by the invention is to provide a kind of, and the benzothiazole with spectral signal amplification performance derives
Object and its preparation and application, benzothiazole derivant preparation process of the present invention is simple, gained compound molar absorptivity
Coefficient is big, fluorescence quantum yield is high, has in developing Light harvest antenna molecule and luminescent material with spectral signal amplification performance
There are important application foreground, present invention design to synthesize a kind of novel benzothiazole derivant with spectral signal amplification performance,
Its molar absorption coefficient is up to 3 × 104L/molcm, fluorescence quantum yield is up to 60%.
A kind of benzothiazole derivant with spectral signal amplification performance of the present invention, the benzothiazole derivant
For：
bis-2,6-HBT
A kind of preparation method of benzothiazole derivant with spectral signal amplification performance of the present invention, including：
(1) after 105-115 DEG C of back flow reaction 48-72h, hydrochloric acid is added in trifluoroacetic acid with hexamethylenetetramine in bisphenol-A
Solution is further continued for reaction 0.5-1h, is cooled to room temperature, filters to obtain solid crude product, further purifies, obtain intermediate product bis-phenol
Tetra- aldehyde of A；Wherein bisphenol-A, hexamethylenetetramine, trifluoroacetic acid proportioning be 1g:4g:6-8ml；
(2) four aldehyde of bisphenol-A and 2- aminothiophenols are dissolved in solvent, stir 48-72h at ambient temperature, filters, washes
It washs to get to the benzothiazole derivant with spectral signal amplification performance；Wherein four aldehyde of bisphenol-A, 2- aminothiophenols, solvent
Ratio be 1g:2g:60-70mL.
A concentration of 2M of hydrochloric acid in the step (1)；The wherein ratio of hydrochloric acid, four aldehyde of bisphenol-A, 2- aminothiophenols, solvent
Example is 80-100mL:1g:2g:60-70mL.
Purification is silica gel column chromatography separating-purifying in the step (1), and eluant, eluent is absolute dichloromethane.
It is 1 that solvent, which is volume ratio, in the step (2):1 dichloromethane, alcohol mixed solution.
Washing is that dichloromethane washs in the step (2).
The step (2) obtains having the absorbing wavelength of the benzothiazole derivant of spectral signal amplification performance ranging from
350-400nm, molar absorption coefficient is up to 3 × 104L/molcm, fluorescence emission wavelengths ranging from 500-750nm, fluorescent quantum
Yield is up to 60%.
For the ultraviolet absorption spectrum instrument used for PerkinElmer Lambda 35, Fluorescence Spectrometer is Edinburgh FS5
Test the chloroformic solution of benzothiazole derivant or the spectral quality of solid powder.
A kind of application of benzothiazole derivant with spectral signal amplification performance of the present invention, benzothiazole derivant
In the Light harvest antenna molecule with spectral signal amplification performance, light-sensitive device, the application in luminous organic material.
Advantageous effect
In a kind of benzothiazole derivant with spectral signal amplification performance of the present invention and its preparation method and application
The organic compound being related to is 2,6-2 ', 6 '-four benzothiazolyl bisphenol-As (bis-2,6-HBT), and reaction condition stirs for room temperature
Mix, processing procedure be simple filtration washing, products therefrom molar absorption coefficient is big, fluorescence quantum yield is high, caught in Development of Novel
There is important application foreground in optical antenna molecule and luminescent material.
Description of the drawings
Fig. 1 is the synthetic route schematic diagram of organic compound bis-2,6-HBT according to the present invention；
Fig. 2 is absorption light of the organic compound bis-2,6-HBT and 2,6-HBT according to the present invention in chloroformic solution
Compose the comparison diagram (B) of (A) and corresponding molar absorption coefficient；
Fig. 3 is fluorescence spectrums of the organic compound bis-2,6-HBT and 2,6-HBT of the present invention in chloroformic solution
(A) and its comparison diagram (B) of chloroformic solution and solid powder fluorescence quantum yield.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
The control compounds being related to are 2,6-HBT, synthesis according to document complete (X.Zhang, J.-Y.Liu,
Dyes and Pigments,2016,125,80-88).Control compounds 2,6-HBT structures are
Embodiment 1
The synthesis of benzothiazole derivant.The synthetic route of bis-2,6-HBT is as shown in Figure 1.
(1) under nitrogen protection, by bisphenol-A (4.5g) and hexamethylenetetramine (18g) in 30ml trifluoroacetic acids and 105-
Under conditions of 115 DEG C after back flow reaction 72h, the hydrochloric acid solution (2M) of 90ml is added, is further continued for reaction 1h, is cooled to room temperature.It crosses
Solid crude product is filtered to obtain, further column chromatography purifying, eluant, eluent is dichloromethane.Rotary evaporation removes solvent, obtains solid production
Object 4.0g, yield 59%.
1H NMR(400MHz,DMSO),δ(ppm):11.52(s,2H),10.22(s,4H),7.94(s,4H),1.72(s,
6H)；13C NMR(100MHz,DMSO),δ(ppm):30.37,41.99,123.67,135.50,141.51,159.34,
160.99,192.90.
(2) under nitrogen protection, by four aldehyde of products therefrom bisphenol-A (0.3g) in step (1) and 2- aminothiophenols (0.6g)
It is dissolved in 10ml dichloromethane and 10ml alcohol mixed solvents, 72h is stirred at room temperature.Light yellow solid is obtained by filtration, with less
It measures dichloromethane to wash 3 times, drying obtains 0.4g target products bis-2,6-HTB, yield 50%.
1H NMR(400MHz,CDCl3),δ(ppm):8.44 (s, 4H), 8.17 (d, J=8.0Hz, 4H), 7.94 (d, J=
8.0Hz, 4H), 7.55 (t, J=8.0Hz, 4H), 7.44 (t, J=8.0Hz, 4H), 2.09 (s, 6H ,-CH3).MALDI-TOF-
MS:m/z calcd for C43H28N4O2S4,760.97；found 761.58(M+H)+.
Embodiment 2
Spectral signal parameter measurement and comparison.
The benzothiazole derivant bis-2,6-HTB and control compounds 2,6-HBT of gained in embodiment 1 are used respectively
Chloroform dissolves, and is configured to the solution of 10 μM/l.It pipettes the above-mentioned chloroformic solutions of 3ml to be placed in quartz colorimetric utensil, in PerkinElmer
Absorption spectrum is tested on 35 spectrometers of Lambda, molar absorption coefficient (Fig. 2) is calculated according to absorbance.Pipette the above-mentioned chlorine of 3ml
Imitative solution is placed in fluorescence cuvette, and fluorescence spectrum (Fig. 3 A) is tested on Edinburgh FS5 spectrometers.Chloroformic solution and solid
The fluorescence quantum yield of body powder sample is directly to measure absolute value institute using the integrating sphere accessory that Edinburgh FS5 are configured
, Comparative result is as shown in Figure 3B.By the light of the visible benzothiazole derivant bis-2,6-HTB of the present invention of test result
Spectrum and compound 2,6-HTB's is closely similar, but the former spectral signal is significantly stronger than the latter, molar absorption coefficient and fluorescence volume
Sub- yield has respectively reached 3 × 104L/molcm and 60%, the analog value compared with 2,6-HTB have been respectively increased about 2.5 and 1.5 times
(Fig. 2 and Fig. 3) shows that bis-2,6-HTB are a kind of benzothiazole derivants with spectral signal amplification performance.
Claims (7)
1. a kind of benzothiazole derivant with spectral signal amplification performance, it is characterised in that：The benzothiazole derivant
For：
2. a kind of preparation method of the benzothiazole derivant as described in claim 1 with spectral signal amplification performance, packet
It includes：
(1) under nitrogen protection, by bisphenol-A and hexamethylenetetramine in trifluoroacetic acid after 105-115 DEG C of back flow reaction 48-72h,
Hydrochloric acid solution is added, is further continued for reaction 0.5-1h, is cooled to room temperature, filter, purification obtains four aldehyde of bisphenol-A；Wherein bisphenol-A, six
Methine tetramine, trifluoroacetic acid proportioning be 1g:4g:6-8ml；
(2) under nitrogen protection, four aldehyde of bisphenol-A and 2- aminothiophenols is dissolved in solvent, stir 48-72h at ambient temperature,
It is filtered, washed to get to the benzothiazole derivant with spectral signal amplification performance.
3. a kind of preparation method of benzothiazole derivant with spectral signal amplification performance according to claim 2,
It is characterized in that：A concentration of 2M of hydrochloric acid in the step (1)；Wherein hydrochloric acid, bisphenol-A four aldehyde, 2- aminothiophenols, solvent
Ratio is 80-100mL:1g:2g:60-70mL.
4. a kind of preparation method of benzothiazole derivant with spectral signal amplification performance according to claim 2,
It is characterized in that：Purification is silica gel column chromatography separating-purifying in the step (1), and eluant, eluent is absolute dichloromethane.
5. a kind of preparation method of benzothiazole derivant with spectral signal amplification performance according to claim 2,
It is characterized in that：It is 1 that solvent, which is volume ratio, in the step (2):1 dichloromethane, alcohol mixed solution.
6. a kind of preparation method of benzothiazole derivant with spectral signal amplification performance according to claim 2,
It is characterized in that：Washing is that dichloromethane washs in the step (2).
7. a kind of application of the benzothiazole derivant as described in claim 1 with spectral signal amplification performance, feature
It is：Benzothiazole derivant is in Light harvest antenna molecule, light-sensitive device, luminous organic material with spectral signal amplification performance
In application.
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| WO2023036868A1 (en) * | 2021-09-10 | 2023-03-16 | Reuter Chemische Apparatebau E.K. | (het)aryl substituted bisphenol compounds and thermoplastic resins |
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| CN111440129B (en) * | 2020-03-06 | 2023-01-31 | 齐鲁工业大学 | 2- (2-hydroxyphenyl) benzothiazole derivative HTPA, preparation method thereof and application thereof in fluorescence anti-counterfeiting |
| WO2023038156A1 (en) * | 2021-09-10 | 2023-03-16 | Mitsubishi Gas Chemical Company, Inc. | (het)aryl substituted bisphenol compounds and thermoplastic resins |
| WO2024010302A1 (en) * | 2022-07-05 | 2024-01-11 | 주식회사 엘지화학 | Resin and preparation method therefor |
| WO2024010277A1 (en) * | 2022-07-05 | 2024-01-11 | 주식회사 엘지화학 | Resin and method for manufacturing same |
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