CN106749095A - 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 PDF

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Publication number
CN106749095A
CN106749095A CN201710032406.1A CN201710032406A CN106749095A CN 106749095 A CN106749095 A CN 106749095A CN 201710032406 A CN201710032406 A CN 201710032406A CN 106749095 A CN106749095 A CN 106749095A
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signal amplification
spectral signal
amplification performance
benzothiazole derivant
preparation
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CN106749095B (en
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张煊
马维维
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Donghua University
National Dong Hwa University
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Donghua University
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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
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • 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 derivant with spectral signal amplification performance and its preparation and application, structural formula is：Prepare：By the aldehyde of bisphenol-A four and 2 aminothiophenols in dichloromethane and alcohol mixed solvent room temperature reaction, after filtering and washing, obtain final product.Molar absorption coefficients and fluorescence quantum yield of the HBT of bis 2,6 in chloroformic solution are significantly increased, and show spectral signal amplification performance.Benzothiazole derivant preparation method in the present invention is simple, molar absorption coefficient is big, fluorescence quantum yield is high, has potential application prospect in development Light harvest antenna molecule, light-sensitive device and luminous organic material.

Description

A kind of benzothiazole derivant with spectral signal amplification performance and its prepare and Using
Technical field
It is more particularly to a kind of that there is spectrum the invention belongs to spectral signal amplification performance material and its preparation and application field The benzothiazole derivant of signal amplification performance and its preparation and application.
Background technology
In recent years function organic dyestuff because with the aspects such as Light harvest antenna molecule, light-sensitive device and luminescent material it is important answer Received much concern with prospect.Needed during manual simulation's photosynthesis conversion solar energy first by aggregation luminous energy can be absorbed Organic dyestuff antenna carries out catching light, and in the new 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 design synthesis has engine dyeing with high efficiency extinction with luminous Material molecule is the focus of current functional organic material research.Benzothiazole derivant is that a class good light stability and luminous efficiency are high Fluorescent chemicals, be one of conventional efficient 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, benzothiazole of the synthesis with spectral signal amplification performance derives Thing is undoubtedly significant to promoting its application in Light harvest antenna molecule and luminous organic material.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of benzothiazole with spectral signal amplification performance and derive Thing and its preparation and application, benzothiazole derivant preparation process of the present invention is simple, the molar absorptivity of gained compound Coefficient is big, fluorescence quantum yield is high, has in Light harvest antenna molecule and luminescent material with spectral signal amplification performance in development There is important application prospect, present invention design has synthesized a kind of new 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 invention, the benzothiazole derivant For：
bis-2,6-HBT
A kind of preparation method of benzothiazole derivant with spectral signal amplification performance of the invention, including：
(1) bisphenol-A adds hydrochloric acid with hexamethylenetetramine after 105-115 DEG C of back flow reaction 48-72h in trifluoroacetic acid Solution, is further continued for reacting 0.5-1h, is cooled to room temperature, filters to obtain solid crude product, and further purification, obtains intermediate product bis-phenol The aldehyde of A tetra-；Wherein bisphenol-A, hexamethylenetetramine, the proportioning of trifluoroacetic acid are 1g:4g:6-8ml；
(2) aldehyde of bisphenol-A four and 2- aminothiophenols are dissolved in solvent, 48-72h is stirred at ambient temperature, filtered, wash Wash, that is, obtain the benzothiazole derivant with spectral signal amplification performance；The wherein aldehyde of bisphenol-A four, 2- aminothiophenols, solvent Ratio be 1g:2g:60-70mL.
The concentration of hydrochloric acid is 2M in the step (1)；Wherein hydrochloric acid, the aldehyde of bisphenol-A four, 2- aminothiophenols, the ratio of 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.
Solvent is that volume ratio is 1 in the step (2):1 dichloromethane, alcohol mixed solution.
Washing is dichloromethane washing in the step (2).
The absorbing wavelength scope that the step (2) obtains the benzothiazole derivant with spectral signal amplification performance is 350-400nm, molar absorption coefficient is up to 3 × 104L/molcm, fluorescence emission wavelengths scope is 500-750nm, fluorescent quantum Yield is up to 60%.
The ultraviolet absorption spectrum instrument for using is PerkinElmer Lambda 35, and XRF 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 invention, benzothiazole derivant Application in Light harvest antenna molecule, light-sensitive device, luminous organic material with spectral signal amplification performance.
Beneficial effect
In a kind of benzothiazole derivant with spectral signal amplification performance of the 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 is stirred for room temperature Mix, processing procedure is that simple filtration is washed, products therefrom molar absorption coefficient is big, fluorescence quantum yield is high, caught in Development of Novel There is important application prospect in optical antenna molecule and luminescent material.
Brief description of the drawings
Fig. 1 is the synthetic route schematic diagram of organic compound bis-2,6-HBT involved in the present invention；
Fig. 2 is the absorption light of organic compound bis-2,6-HBT and 2,6-HBT involved in the present invention in chloroformic solution The comparison diagram (B) of spectrum (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 chloroformic solution and solid powder fluorescence quantum yield comparison diagram (B).
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
The control compounds being related to are 2,6-HBT, its 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, be further continued for reacting 1h, be cooled to room temperature.Cross Solid crude product is filtered to obtain, further column chromatography is purified, and eluant, eluent is dichloromethane.Rotary evaporation removes solvent, obtains solid product Thing 4.0g, yield is 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 the aldehyde of products therefrom bisphenol-A four (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 filtrated to get, with less Amount dichloromethane is washed 3 times, and 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 contrast.
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.Pipette the above-mentioned chloroformic solutions of 3ml to be placed in quartz colorimetric utensil, in PerkinElmer Absorption spectrum is tested on the spectrometers of Lambda 35, 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 the integrating sphere accessory direct measurement absolute value institute configured using Edinburgh FS5 , Comparative result is as shown in Figure 3 B.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 has 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 (8)

1. a kind of benzothiazole derivant with spectral signal amplification performance, it is characterised in that：The benzothiazole derivant For：bis-2,6-HBT
2. a kind of preparation method of the benzothiazole derivant with spectral signal amplification performance as claimed in claim 1, wraps Include：
(1) under nitrogen protection, by bisphenol-A and hexamethylenetetramine after 105-115 DEG C of back flow reaction 48-72h in trifluoroacetic acid, Hydrochloric acid solution is added, is further continued for reacting 0.5-1h, be cooled to room temperature, filtered, purification obtains the aldehyde of bisphenol-A four；Wherein bisphenol-A, six Methine tetramine, the proportioning of trifluoroacetic acid are 1g:4g:6-8ml；
(2) under nitrogen protection, the aldehyde of bisphenol-A four and 2- aminothiophenols are dissolved in solvent, 48-72h are stirred at ambient temperature, Filtering, washing, that is, obtain the benzothiazole derivant with spectral signal amplification performance.
3. the preparation method of a kind of benzothiazole derivant with spectral signal amplification performance according to claim 2, It is characterized in that：The concentration of hydrochloric acid is 2M in the step (1)；Wherein hydrochloric acid, bisphenol-A four aldehyde, 2- aminothiophenols, solvent Ratio is 80-100mL:1g:2g:60-70mL.
4. the preparation method of a kind 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. the preparation method of a kind of benzothiazole derivant with spectral signal amplification performance according to claim 2, It is characterized in that：Solvent is that volume ratio is 1 in the step (2):1 dichloromethane, alcohol mixed solution.
6. the preparation method of a kind of benzothiazole derivant with spectral signal amplification performance according to claim 2, It is characterized in that：Washing is dichloromethane washing in the step (2).
7. the preparation method of a kind of benzothiazole derivant with spectral signal amplification performance according to claim 2, It is characterized in that：The step (2) obtains the absorbing wavelength scope of the benzothiazole derivant with spectral signal amplification performance It is 350-400nm, molar absorption coefficient is up to 3 × 104L/molcm, fluorescence emission wavelengths scope is 500-750nm.
8. a kind of application of the benzothiazole derivant with spectral signal amplification performance as claimed in claim 1, its feature It is：Benzothiazole derivant is in Light harvest antenna molecule, light-sensitive device, luminous organic material with spectral signal amplification performance In application.
CN201710032406.1A 2017-01-16 2017-01-16 A kind of benzothiazole derivant and its preparation and application with spectral signal amplification performance Expired - Fee Related CN106749095B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111440129A (en) * 2020-03-06 2020-07-24 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
WO2024010277A1 (en) * 2022-07-05 2024-01-11 주식회사 엘지화학 Resin and method for manufacturing same
WO2024010302A1 (en) * 2022-07-05 2024-01-11 주식회사 엘지화학 Resin and preparation method therefor

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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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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111440129A (en) * 2020-03-06 2020-07-24 齐鲁工业大学 2- (2-hydroxyphenyl) benzothiazole derivative HTPA, preparation method thereof and application thereof in fluorescence anti-counterfeiting
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
WO2024010277A1 (en) * 2022-07-05 2024-01-11 주식회사 엘지화학 Resin and method for manufacturing same
WO2024010302A1 (en) * 2022-07-05 2024-01-11 주식회사 엘지화학 Resin and preparation method therefor

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