CN110229137A - A kind of bis- thienyl anthracene compounds of symmetric form 9,10- and its preparation method and application - Google Patents
A kind of bis- thienyl anthracene compounds of symmetric form 9,10- and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to gathering induced luminescence material technical fields, more particularly to a kind of symmetric form 9, the bis- thienyl anthracene compounds of 10-, present invention thiophene xenyl replaces the styryl in traditional anthracene compound, obtained symmetric form 9, the bis- thienyl anthracene compound molecular structures of 10- are simple, have apparent AIE property, and its molecular end is easy to be modified by converting different groups, to regulate and control its characteristics of luminescence；The symmetric form 9 can be obtained by simple Suzuki coupling reaction in the present invention, and the bis- thienyl anthracene compounds of 10-, raw materials used cost is low, and synthesis is simple, is conducive to industrialized production, application prospect is big；Compound BMPTA, BPTA and BCPTA can be used as HeLa cell fluorescence marker, have potential application in cell dye field；Compound BMPTA and BPTA have the apparent mechanical feature that changes colour, and can be used for processing machinery power and regulate and control the original part etc. that shines.
Description
Technical field
The present invention relates to gathering induced luminescence material technical field more particularly to a kind of symmetric form 9, the bis- thienyl anthracenes of 10-
Compound and its preparation method and application.
Background technique
In recent years, luminous organic material is attracted wide attention in academia and industry.In most organic light emissions
In compound, their weak solution luminous efficiency usually with higher, and in coherent condition, the fluorescent quantum of compound produces
Rate and luminous efficiency significantly reduce, this characteristic is referred to as aggregation inducing quenching effect (Aggregation Caused
Quenching, ACQ), this defect greatly limits the practical ranges of luminous organic material.
2001, the Tang Benzhong professor team of Hong Kong University of Science and Thchnology reported the derivative of a Silole
(Luo,J.；Xie,Z.；Lam,J.W.；Cheng,L.；Chen,H.；Qiu,C.；Kwok,H.S.；Zhan,X.；Liu,Y.；Zhu,
D.；Tang,B.Z.Aggregation-induced emission of1-methyl-1,2,3,4,5-pentaphenylsil
Ole.Chem.Commun.2001,18,1740-1741.), the luminescent behavior of the compound and common ACQ type organic light emission
It is different to close object, does not shine under weak solution state, and when aggregation occurs or luminous efficiency sharply enhances in the solid state in it,
This phenomenon is referred to as aggregation-induced emission (Aggregation Induced Emission, AIE).This discovery, very great Cheng
It solves the drawbacks of conventional organic luminescence material on degree, causes the extensive concern of researcher.Hereafter, largely have AIE special
The compound of property is gradually found and is reported, such as tetraphenyl ethylene analog derivative and thiophene cough up analog derivative, they are organic light emissions
Popular molecular system in investigation of materials.Due to unique characteristics of luminescence of AIE material, make its biosensor, piezoelectric device,
The fields such as fluorescence probe and Organic Light Emitting Diode have broad application prospects.
With the development of Synthetic Organic Chemistry, develops novel organic luminescent material and be developing progressively current organic smooth function material
One big research hotspot of material, due to luminous organic material synthesis is mature, easily modification, easy processing, it is at low cost the advantages that, excite and grind
Study carefully the great interest of personnel.Organic luminescent compounds can be divided into luminescence generated by light, thermoluminescence, electroluminescent according to stimulation mode difference
Become and shines and mechanoluminescence etc..Wherein, mechanoluminescence phenomenon refers to when being stimulated by external force, and the optics behavior of substance is (such as
Absorption, reflection, fluorescence, phosphorescence etc.) it substantially change；It is stifling by heating or solvent after external force, which stimulates, to disappear, change
The optical property for closing object again can reversible the phenomenon that returning to original state.Compared with pH, light and temperature sensitive optical material, AIE
Power causes fluorescence off-color material to have important application potential in optical information storage, storage device and safety ink field.Currently,
Research around the AIE class material for causing fluorescence discoloration with power gradually causes the concern of researcher, due to lacking effectively solution
The mechanism of relationship between molecule assembling or filling variation and corresponding luminosity is released, so that current AIE power causes grinding for off-color material
Study carefully and still has certain defect.Therefore, pass through chemically synthesized method regulatory molecule state of aggregation and intermolecular interaction pair
It causes the development of off-color material to be of great significance in power, while developing with aggregation-induced emission and suppressing fluorescence color shifting properties
New A IE organic molecule skeleton is also a big hot spot of the current research field.
As a kind of important organic luminescent compounds, anthracene is widely used in dyestuff preparation, designs at present by parent nucleus of anthracene
The luminous organic material of synthesis is by wide coverage.Such as Prasad et al. (Kim, S.；Zheng,Q.；He,G.S.；Bharali,
D.J.；Pudavar,H.E.；Baev,A.；Prasad, P.N.Adv.Funct.Mater.2006,16,2317-2323.)
Reporting within 2006 anthracene ethylene compounds fluorescent emission intensity under state of aggregation has the phenomenon that substantially enhancing.Then, Tian Wen
Crystalline substance professor seminar successively reports diphenylethyllene anthracene (DSA) analog derivative that series has AIE property, has expanded such change
Close the application range in the fields such as optical sensing and photoelectric device of object.
However, the type of the anthracene derivative with AIE property is limited, it is derivative to develop the novel anthracene class with AIE property
Object still has great importance.
Summary of the invention
The purpose of the present invention is to provide bis- thienyl anthracene compounds of a kind of symmetric form 9,10- and preparation method thereof and answer
With the symmetric form 9, the bis- thienyl anthracene compounds of 10- have aggregation-induced emission property.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of symmetric form 9, the bis- thienyl anthracene compounds of 10- have structure shown in Formulas I:
Wherein, R be-Br,
The present invention provides symmetric form 9 described in above-mentioned technical proposal, the preparation method of the bis- thienyl anthracene compounds of 10- works as R
When for-Br, comprising the following steps:
2- methylthiophene, N-bromosuccinimide and tetrahydrofuran are mixed, substitution reaction is carried out, obtains 2- methyl-
3,5- dibromo thiophenes；
2- methyl -3,5- dibromo thiophene, ether, n-BuLi and butyl borate are mixed, it is anti-to carry out boration
It answers, obtains 5- boronate -2- methyl -3 bromo thiophene；
By the 5- boronate -2- methyl -3 bromo thiophene, tetrahydrofuran, triphenyl phosphorus palladium, sodium carbonate liquor and 9,10-
Dibromoanthracene mixing, carries out coupling reaction, obtains 9,10- bis- (4- bromine 5- methylthiophene -2- base) anthracenes, i.e. symmetric form 9, the bis- thiophenes of 10-
Pheno base anthracene compound.
Preferably, the molar ratio of the 2- methylthiophene and N-bromosuccinimide is (45~55): (90-110)；Institute
The amount ratio for stating 2- methylthiophene and tetrahydrofuran is (45~55) mmol:100mL；
The temperature of the substitution reaction is 0 DEG C, and the time of the substitution reaction is for 24 hours.
Preferably, the amount ratio of 2- methyl -3,5- dibromo thiophene, ether, n-BuLi and butyl borate is 15
~25mmol:80mL:10mL:8mL；
The temperature of the boration reaction is -78 DEG C, and the time of the boration reaction is 6h.
Preferably, the 5- boronate -2- methyl -3 bromo thiophene, tetrahydrofuran, triphenyl phosphorus palladium, sodium carbonate liquor and
The amount ratio of 9,10- dibromoanthracene is (5.0~7.0) mmol:150mL:(0.05~0.10) g:(40~50) mL:(2.5~3.5)
mmol；
The temperature of the coupling reaction is 80 DEG C, time 12h.
The present invention provides symmetric form 9 described in above-mentioned technical proposal, the preparation method of the bis- thienyl anthracene compounds of 10- works as R
ForWhen, comprising the following steps:
Bis- (the 4- bromine 5- methylthiophene -2- base) anthracenes of 9, the 10- that the preparation method is prepared by adopting the above technical scheme,
By the 9,10- bis- (4- bromine 5- methylthiophene -2- base) anthracene, phenyl boric acid compound, triphenyl phosphorus palladium, sodium carbonate liquor and tetrahydros
Furans mixing, carries out coupling reaction, obtains symmetric form 9, the bis- thienyl anthracene compounds of 10-；
The phenyl boric acid compound is phenyl boric acid, 4- methoxyphenylboronic acid or 4- first cyanophenylboronic acid.
Preferably, 9, the 10- bis- (4- bromine 5- methylthiophene -2- base) anthracenes, phenyl boric acid compound, triphenyl phosphorus palladium, carbon
The amount ratio of acid sodium solution and tetrahydrofuran is (1.5~2.5) mmol:(3~5) mmol:(0.05~1.0) g:(40~50)
mL:150mL；
Preferably, the temperature of the coupling reaction is 80 DEG C, time 12h.
The present invention provides the bis- thienyl anthracene compounds of symmetric form 9,10- described in above-mentioned technical proposal in biological cell fluorescence
Application in imaging technique, wherein R is
The present invention provides the bis- thienyl anthracene compounds of symmetric form 9,10- described in above-mentioned technical proposal as mechanical mutagens color
The application of material, wherein R is
The present invention provides a kind of symmetric form 9, the bis- thienyl anthracene compounds of 10-, the present invention is replaced with thiophene xenyl to be passed
Styryl in anthracene compound of uniting, obtained symmetric form 9, the bis- thienyl anthracene compound molecular structures of 10- are simple, have bright
Aobvious AIE property, and its molecular end is easy to be modified by converting different groups, to regulate and control its characteristics of luminescence；
The present invention provides the symmetric form 9, the preparation method of the bis- thienyl anthracene compounds of 10-, system provided by the invention
Preparation Method is with 2- methylthiophene, N-bromosuccinimide (NBS), butyl borate, 9,10- dibromoanthracene and phenyl boric acid compound
For raw material, the symmetric form 9, the bis- thienyl anthracene compounds of 10-, original used can be obtained by simple Suzuki coupling reaction
The cost of material is low, and synthesis is simple, is conducive to industrialized production, application prospect is big；
The present invention provides the symmetric forms 9, and 10- dipyrryl anthracene compound is in biological cell Imaging-PAM
It is using, wherein RCompound BMPTA, BPTA provided by the invention
It is able to enter HeLa cell with BCPTA, and shows good cell dyeing function.Therefore, such compound can be used as
HeLa cell fluorescence marker has potential application in cell dye field.
The present invention provides the bis- thienyl anthracene compounds of symmetric form 9,10- described in above-mentioned technical proposal as mechanical mutagens color
The application of material, wherein R isCompound BMPTA and BPTA have apparent mechanical discoloration
Feature can be used for processing machinery power and regulate and control the original part etc. that shines.
Detailed description of the invention
Fig. 1 is the bis- thienyl anthracenes of compound 9,10- of Examples 1 to 4 preparation respectively under THF solution and solid states
Uv absorption spectra: (C=2.0 × 10 in (A) THF solution-5mol/L)；(B) solid state powder state；
Fig. 2 is the bis- thienyl anthracenes of compound 9,10- of Examples 1 to 4 preparation respectively in THF solution and under solid states
Fluorescence emission spectrogram of compound: (C=2.0 × 10 in (A) THF solution-5mol/L)；(B) solid state powder state；
Fig. 3 is the bis- thienyl anthracenes of compound 9,10- of Examples 1 to 4 preparation in different proportion solvent (THF:H2O in)
Fluorescence spectra (C=2.0 × 10-5Mol/L): (A) compound BTA；(B) compound BMPTA；(C) compound BPTA；(D) change
Close object BCPTA；
Fig. 4 is the bis- thienyl anthracenes of compound 9,10- of Examples 1 to 4 preparation in different proportion solvent (THF:H2O in)
Fluorescence quantum yield variation diagram (C=2.0 × 10-5Mol/L): (A) compound BMPTA；(B) compound BPTA；(C) compound
BCPTA；
Fig. 5 be embodiment 2 prepare compound BMPTA under grinding condition fluorescence spectrum and color change；
Fig. 6 is fluorescence spectrum and color change of the compound BPTA of the preparation of embodiment 3 under grinding condition；
Fig. 7 is fluorescence spectrum and color change spectrogram of the compound BCPTA of the preparation of embodiment 4 under grinding condition；
Fig. 8 is stereoscan photograph of the bis- thienyl anthracenes of compound 9,10- of the preparation of embodiment 2~4 in state of aggregation:
(A) compound BMPTA；(B) compound BPTA；(C) compound BCPTA；
Fig. 9 is the HeLa cell fluorescence co-focusing imaging of compound BMPTA, BPTA and BCPTA prepared by embodiment 2~3
Scheme (A: fluorescent dark field；B: light field；C: superimposed field).
Specific embodiment
The present invention provides a kind of symmetric form 9, the bis- thienyl anthracene compounds of 10- have structure shown in Formulas I:
Wherein, R be-Br,
The present invention provides symmetric form 9 described in above-mentioned technical proposal, the preparation method of the bis- thienyl anthracene compounds of 10- works as R
When for-Br, comprising the following steps:
2- methylthiophene, N-bromosuccinimide and tetrahydrofuran are mixed, substitution reaction is carried out, obtains 2- methyl-
3,5- dibromo thiophenes；
2- methyl -3,5- dibromo thiophene, ether, n-BuLi and butyl borate are mixed, it is anti-to carry out boration
It answers, obtains 5- boronate -2- methyl -3 bromo thiophene；
By the 5- boronate -2- methyl -3 bromo thiophene, tetrahydrofuran, triphenyl phosphorus palladium, sodium carbonate liquor and 9,10-
Dibromoanthracene mixing, carries out coupling reaction, obtains 9,10- bis- (4- bromine 5- methylthiophene -2- base) anthracenes, i.e. symmetric form 9, the bis- thiophenes of 10-
Pheno base anthracene compound.
In the present invention, if without specified otherwise, the required raw material for preparing is commercial goods well known to those skilled in the art.
In the present invention, when R is-Br, the preparation process of the symmetric form 9, the bis- thienyl anthracene compounds of 10- is as follows
It is shown:
The present invention mixes 2- methylthiophene, N-bromosuccinimide and tetrahydrofuran, carries out substitution reaction, obtains 2-
Methyl -3,5- dibromo thiophene (compound 2).The present invention is preferably according to document (R.Lantz.A.B.Hornfeldt.Chem.Scr
Ipro.1972.2.9 2- methyl -3,5- dibromo thiophene) is prepared.In the present invention, the 2- methylthiophene and N- bromo amber
The imido molar ratio of amber is preferably (45~55): (90~110), more preferably 50:100；The 2- methylthiophene and tetrahydro
The amount ratio of furans is preferably (45~55) mmol:100mL, more preferably 50mmol:100mL.In the present invention, the mixing
2- methylthiophene is first preferably dissolved in tetrahydrofuran, then N-bromosuccinimide is added dropwise in gained mixed liquor.
In the present invention, the rate of the dropwise addition is preferably 20 drops/min.In the present invention, the temperature of the substitution reaction is preferably 0
DEG C (ice bath), the time of the substitution reaction, the present invention preferably carried out the substitution reaction under agitation preferably for 24 hours,
The rate of the stirring is preferably 600r/s.
After completing the substitution reaction, the present invention preferably by gained substitution product material successively carry out concentration be spin-dried for, extract,
Dry, suction filtration, revolving and separation, obtain 2- methyl -3,5- dibromo thiophene.The present invention is to the condition being spin-dried for that is concentrated without spy
Condition well known to those skilled in the art is selected in different restriction.The present invention is spin-dried for removing THF solvent by concentration.At this
In invention, the extraction agents useful for same is preferably the mixture of methylene chloride, saturated salt solution and water, and the methylene chloride is satisfied
Volume ratio with saline solution and water is preferably 100:150:250.In the present invention, the reagent of the drying is preferably anhydrous slufuric acid
Magnesium.The present invention does not have special restriction to the condition of the suction filtration, selects condition well known to those skilled in the art.This hair
It is bright to be removed the solvent in filtrate obtained by filtering as rotating.In the present invention, the isolated mode is preferably column chromatography point
From the eluent of the pillar layer separation is preferably petroleum ether.In the present invention, 2- methyl -3, the 5- dibromo thiophene being prepared
The characterize data of pheno is shown in document: R.Lantz.A.B.Hornfeldt.Chem.Scripro.1972.2.9.
After obtaining 2- methyl -3,5- dibromo thiophene, the present invention is by 2- methyl -3,5- dibromo thiophene, ether, normal-butyl
Lithium and butyl borate mixing, carry out boration reaction, obtain 5- boronate -2- methyl -3 bromo thiophene (compound 3).At this
In invention, the 5- boronate -2- methyl -3 bromo thiophene is preferably according to document (S.L.Gilat, S.H.Kawai, J.-
M.Lehn, Chem.Eur.J.11995.275-284.) the method preparation.In the present invention, 2- methyl -3,5- dibromo
Thiophene, ether, n-BuLi and butyl borate amount ratio be preferably 15~25mmol:80mL:10mL:8mL.In the present invention
In, the butyl borate uses as a solution, and the solvent of the butyl borate solution is preferably water, the boric acid three
The mass concentration of butyl acetate solution is preferably 4mmol.In the present invention, the ether is preferably anhydrous ether.In the present invention, institute
It states mixing preferably under nitrogen protection, 2- methyl -3,5- dibromo thiophene is first dissolved in ether, then keeping temperature is -78
DEG C, (1 drop/s) is added dropwise into gained mixed solution in n-BuLi, after 30min, then by boric acid three under the conditions of being kept for -78 DEG C
Butyl acetate solution is added dropwise in gained mixed solution.
In the present invention, the temperature of the boration reaction is preferably -78 DEG C, and the time is preferably 6h.The boration is anti-
Should completely after, the HCL solution of 10.0mL10% is added in the present invention preferably into gained reaction system, and reaction was completed.The present invention is preferred
The boration reaction is carried out under agitation, and the present invention does not have special restriction to the rate of the stirring, selects ability
Stirring rate known to field technique personnel.
After completing the boration reaction, gained reactant material is preferably successively extracted, neutralized and filtered by the present invention,
Obtain 5- boronate -2- methyl -3 bromo thiophene.In the present invention, it is 10% that the extraction agents useful for same, which is preferably mass concentration,
NaOH solution, the present invention preferably extracts ether layer to alkalinity.Extraction gained water phase mass concentration is preferably 5% by the present invention
HCL solution be neutralized to acidity.The present invention does not have special restriction to the mode of the filtering, selects those skilled in the art ripe
The mode known.In the present invention, the 5- boronate -2- methyl -3 bromo thiophene characterize data being prepared is shown in document:
S.L.Gilat,S.H.Kawai,J.-M.Lehn,Chem.Eur.J.11995.275-284。
After obtaining 5- boronate -2- methyl -3 bromo thiophene, the present invention by the 5- boronate -2- methyl -3 bromo thiophene,
Tetrahydrofuran, triphenyl phosphorus palladium, sodium carbonate liquor and 9,10- dibromoanthracene (compound 4) mixing, carry out coupling reaction, obtain 9,
10- bis- (4- bromine 5- methylthiophene -2- base) anthracenes (being denoted as BTA), i.e. symmetric form 9, the bis- thienyl anthracene compounds of 10-.In the present invention
In, the 5- boronate -2- methyl -3 bromo thiophene, tetrahydrofuran, triphenyl phosphorus palladium, sodium carbonate liquor and 9,10- dibromoanthracene
Amount ratio is preferably (5.0~7.0) mmol:150mL:(0.05~0.10) g:(40~50) mL:(2.5~3.5) mmol.At this
In invention, the concentration of the sodium carbonate liquor is preferably 2.0mol/L.In the present invention, the mixing is preferably first by triphenyl
Phosphorus palladium and 9,10- dibromoanthracene are dissolved in tetrahydrofuran, stir 20min, and 5- boronate -2- is then added into gained mixed liquor
Methyl -3 bromo thiophene and sodium carbonate liquor.
In the present invention, the temperature of the coupling reaction is preferably 80 DEG C, and the time is preferably 12h, and the present invention is preferably returning
The coupling reaction is carried out under the conditions of stream, the reflux ratio of the counterflow condition is preferably 1:3.
After completing the coupling reaction, products therefrom system is preferably successively cooled down, liquid separation, extraction, is done by the present invention
Dry, suction filtration, revolving and separation, obtain bis- (the 4- bromine 5- methylthiophene -2- base) anthracenes of 9,10-.In the present invention, the cooling is preferred
It is to be cooled to room temperature；The reagent of the extraction is preferably methylene chloride, after completing extraction, merges organic phase；The examination of the drying
Agent is preferably anhydrous magnesium sulfate；Solvent of the present invention in the filtrate as obtained by revolving removing suction filtration.In the present invention, the separation
Mode be preferably pillar layer separation, the isolated eluent is preferably petroleum ether.
The present invention provides symmetric form 9 described in above-mentioned technical proposal, the preparation method of the bis- thienyl anthracene compounds of 10- works as R
ForWhen, comprising the following steps:
Bis- (the 4- bromine 5- methylthiophene -2- base) anthracenes of 9, the 10- that the preparation method is prepared by adopting the above technical scheme,
By the 9,10- bis- (4- bromine 5- methylthiophene -2- base) anthracene, phenyl boric acid compound, triphenyl phosphorus palladium, sodium carbonate liquor and tetrahydros
Furans mixing, carries out coupling reaction, obtains symmetric form 9, the bis- thienyl anthracene compounds of 10-.
In the present invention, the phenyl boric acid compound is preferably phenyl boric acid, 4- methoxyphenylboronic acid or 4- first cyano benzene boron
Acid.In the present invention, 9, the 10- bis- (4- bromine 5- methylthiophene -2- base) anthracenes, phenyl boric acid compound, triphenyl phosphorus palladium, carbonic acid
The amount ratio of sodium solution and tetrahydrofuran is preferably (1.5~2.5) mmol:(3~5) mmol:(0.05~1.0) g:(40~50)
mL:150mL.In the present invention, the concentration of the sodium carbonate liquor is preferably 2.0mol/L.In the present invention, the mixing is excellent
Choosing is first by triphenyl phosphorus palladium and 9, and bis- (the 4- bromine 5- methylthiophene -2- base) anthracenes of 10- are dissolved in tetrahydrofuran, stirs 20min,
Then phenyl boric acid compound and sodium carbonate liquor are added into gained mixed liquor.
In the present invention, the temperature of the coupling reaction is preferably 80 DEG C, and the time is preferably 12h；The present invention is preferably returning
The coupling reaction is carried out under the conditions of stream, the reflux ratio of the counterflow condition is preferably 1:3.
After completing the coupling reaction, the present invention successively cools down products therefrom system, liquid separation, extraction, drying, pumping
Filter, revolving and separation, obtain bis- (the 4- bromine 5- methylthiophene -2- base) anthracenes of 9,10-.In the present invention, the cooling is preferably cold
But to room temperature；The reagent of the extraction is preferably methylene chloride, after completing extraction, merges organic phase；The reagent of the drying is excellent
It is selected as anhydrous magnesium sulfate；Solvent of the present invention in the filtrate as obtained by revolving removing suction filtration.In the present invention, the isolated side
Formula is preferably pillar layer separation, and the isolated eluent is preferably petroleum ether.
In the present invention, when R is p-methoxyphenyl, the symmetric form 9, the bis- thienyl anthracene compounds of 10- are denoted as
The preparation process of BMPTA, the BMPTA are as follows:
In the present invention, when R is phenyl, the symmetric form 9, the bis- thienyl anthracene compounds of 10- are denoted as BPTA, described
The preparation process of BPTA is as follows:
In the present invention, when R is to cyano-phenyl, the symmetric form 9, the bis- thienyl anthracene compounds of 10- are denoted as
The preparation process of BCPTA, the BCPTA are as follows:
The present invention provides the bis- thienyl anthracene compounds of symmetric form 9,10- described in above-mentioned technical proposal in imaging biological cells
Application in technology, wherein R is
Symmetric form 9 provided by the invention, the bis- thienyl anthracene compounds of 10- can be efficiently entering HeLa cell, in cell
It inside shows significantly to assemble the characteristics of luminescence, and intracellular fluorescence signal can be copolymerized focusing microscope detection, which makes
Symmetric form 9, the bis- thienyl anthracene compounds of 10- can be used as cell fluorescence marker, have the valence of applying in biological cell marker field
Value.
The present invention provides the bis- thienyl anthracene compounds of symmetric form 9,10- described in above-mentioned technical proposal as mechanical mutagens color
The application of material, wherein R is
Symmetric form 9 provided by the invention, the bis- thienyl anthracene compound BMPTA and BPTA of 10-, solid fluorescence launch wavelength
In 480nm or so, by solid by the universal red shift 20nm or more of fluorescence emission wavelengths after mortar grinder, by consolidating after grinding
Its fluorescence emission wavelengths restores reset condition again after the steam of body powder methylene chloride volatilization is stifling, therefore, compound BMPTA
There is the apparent mechanical feature that changes colour with BPTA, can be used for processing machinery power and regulate and control the original part etc. that shines.
Below with reference to embodiment to bis- thienyl anthracene compounds of symmetric form 9,10- provided by the invention and preparation method thereof and
Using being described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
2- methylthiophene (4.9g) is dissolved in 100.0mL THF, NBS (17.8g) is added with 20 drops/min rate
Enter in gained mixed solution, carries out substitution reaction for 24 hours under ice-water bath 600r/s stirring condition.Fully reacting to be replaced, by THF
Solution concentration is spin-dried for, with the mixture (volume of methylene chloride, saturated salt solution and water of methylene chloride, saturated salt solution and water
It is than being extracted for 100mL:150mL:250mL), gained extract is dry with anhydrous magnesium sulfate, it filters, filtrate revolving is gone molten
Agent carries out pillar layer separation by eluent of petroleum ether, obtains 2- methyl -3,5- dibromo thiophene (10g), yield: 78.4%.
Under nitrogen protection, 2- methyl -3,5- dibromo thiophene (5.1g) is dissolved in 80.0mL anhydrous ether, keep -
78 DEG C, 10.0mL n-BuLi is added dropwise in gained mixed solution with 1 drop/s rate, 0.5h is kept the temperature at -78 DEG C, is kept
Butyl borate solution is titrated in gained mixed solution by the reaction temperature, reaction 6h is then stirred at room temperature, to fully reacting
Backward gained system the HCL solution of 10.0mL10% is added reaction was completed；Then ether layer is extracted with 10% NaOH solution
To alkalinity, water phase is collected with 5% HCL solution and is neutralized to pH=5, filters, obtains the bromo- 5- boric acid thiophene of 2- methyl -3-
(3.0g), yield: 68.5%.
By 9,10- dibromoanthracene (1.0g) and Pd (PPh3)4(0.05g) is dissolved in 150.0mL THF, after stirring 20min, is added
Enter the bromo- 5- boric acid thiophene (1.3g) of 2- methyl -3- and concentration for the Na of 2.0mol/L2CO3Solution 50.0mL, 80 DEG C of reflux 12h into
Gained system is cooled to room temperature by row coupling reaction after the reaction was completed, and liquid separation is extracted with dichloromethane, and merges organic phase, nothing
Water magnesium sulfate is dry, filters, and filtrate revolving removes solvent, carries out pillar layer separation by eluent of petroleum ether, it is bis- to obtain 9,10-
(4- bromine 5- methylthiophene -2- base) anthracene (1.0g), is denoted as BTA, yield: 63.3%.
BTA is subjected to Structural Identification:1H NMR(400 MHz,CDCl3,ppm):δ2.56(s,6H),7.02(s,2H,
thiophene-H),7.45(q,4H,anthracene-H),7.94(q,4H,anthracene-H)。
Embodiment 2
Bis- (the 4- bromine 5- methylthiophene -2- base) anthracenes (BTA, 1.0g) of 9,10- prepared by embodiment 1 and Pd (PPh3)4
(0.05g) is dissolved in 150.0mLTHF, and 4- methoxyphenylboronic acid (0.58g) is added after stirring 20min and concentration is 2.0mol/
LNa2CO3Solution 50.0mL carries out coupling reaction and is after the reaction was completed cooled to room temperature gained system in 80 DEG C of reflux 12h,
Liquid separation is extracted with dichloromethane, and merges organic phase, and anhydrous magnesium sulfate is dry, filters, and filtrate revolving removes solvent, is with petroleum ether
Eluent carries out pillar layer separation, obtains bis- (4- (4- the methoxyphenyl) -5- methylthiophene -2- base) anthracenes of 9,10-, is denoted as
BMPTA, (0.2g), yield: 18.2%.
BMPTA is subjected to Structural Identification:1H NMR(400 MHz,CDCl3,ppm):δ2.68(s,6H),3.89(s,6H,
methoxy-H),7.03(d,4H,phenyl-H),7.17(s,2H,thiophene-H),7.48(m,8H,phenyl-H,
anthracene-H),8.12(t,4H,anthracene-H)。
Embodiment 3
Bis- (the 4- bromine 5- methylthiophene -2- base) anthracenes (BTA, 1.0g) of 9,10- prepared by embodiment 1 and Pd (PPh3)4
(0.05g) is dissolved in 150.0mLTHF, and phenyl boric acid (0.46g) is added after stirring 20min and concentration is 2.0mol/LNa2CO3Solution
50.0mL carries out coupling reaction and is after the reaction was completed cooled to room temperature gained system, dichloro is used in liquid separation in 80 DEG C of reflux 12h
Methane extraction merges organic phase, and anhydrous magnesium sulfate is dry, filters, and filtrate revolving removes solvent, carries out column by eluent of petroleum ether
Chromatographic isolation obtains bis- (the 5- methyl 4-phenyl thiophene -2- base) anthracenes of 9,10-, is denoted as BPTA, (0.1g), yield: 10.1%.
BPTA is subjected to Structural Identification:1H NMR(400 MHz,CDCl3,ppm):δ2.61(s,6H),7.11(s,2H,
thiophene-H),7.27(t,2H,phenyl-H),7.39(m,8H,phenyl-H),7.49(d,4H,anthracene-H),
7.49(q,4H,anthracene-H)。
Embodiment 4
Bis- (the 4- bromine 5- methylthiophene -2- base) anthracenes (BTA, 1.0g) of 9,10- prepared by embodiment 1 and Pd (PPh3)4
(0.05g) is dissolved in 150.0mLTHF, and 4- first cyanophenylboronic acid (0.56g) is added after stirring 20min and concentration is 2.0mol/
LNa2CO3Solution 50.0mL carries out coupling reaction and is after the reaction was completed cooled to room temperature gained system in 80 DEG C of reflux 12h,
Liquid separation is extracted with dichloromethane, and merges organic phase, and anhydrous magnesium sulfate is dry, filters, and filtrate revolving removes solvent, is with petroleum ether
Eluent carries out pillar layer separation, obtains bis- (4- (4- the cyano-phenyl) -5- methylthiophene -2- base) anthracenes of 9,10-, is denoted as BCPTA,
(0.2g), yield: 18.5%.
BCPTA is subjected to Structural Identification:1H NMR(400 MHz,CDCl3,ppm):δ2.72(s,6H),7.20(s,2H,
thiophene-H),7.50(q,4H,anthracene-H),7.70(d,4H,phenyl-H),7.80(d,4H,phenyl-H),
8.07(q,4H,anthracene-H)。
Characterize data:
Fig. 1 be Examples 1 to 4 preparation the bis- thienyl anthracenes of compound 9,10- respectively in THF with solid states under purple
Outer abosrption spectrogram: (C=2.0 × 10 in (A) THF-5mol/L)；(B) solid state powder state；As seen from the figure, Examples 1 to 4 system
Micro variation all has occurred in four kinds of standby compounds its UV absorption after introducing substituent group.
Fig. 2 is that the bis- thienyl anthracenes of compound 9,10- of Examples 1 to 4 preparation are glimmering in THF and under solid states respectively
Optical emission spectroscopy figure: (C=2.0 × 10 in (A) THF-5mol/L)；(B) solid state powder state；As seen from the figure, Examples 1 to 4 system
Micro variation all has occurred in four kinds of standby compounds its fluorescent emission after introducing substituent group.
Fig. 3 is the bis- thienyl anthracenes of compound 9,10- of Examples 1 to 4 preparation in different proportion solvent (THF:H2O in)
Fluorescence spectra (C=2.0 × 10-5Mol/L): (A) compound BTA；(B) compound BMPTA；(C) compound BPTA；(D) change
Close object BCPTA；As seen from the figure, four kinds of compounds of Examples 1 to 4 preparation show certain AIE property.
Fig. 4 is the bis- thienyl anthracenes of compound 9,10- of Examples 1 to 4 preparation in different proportion solvent (THF:H2O in)
Fluorescence quantum yield variation diagram (C=2.0 × 10-5Mol/L): (A) compound BTA；(B) compound BMPTA；(C) compound
BPTA；(D) compound BCPTA；As seen from the figure, the fluorescence quantum yield of four kinds of compounds increases with moisture than increasing,
Four kinds of compounds are demonstrated again all has AIE property.
Fig. 5 be embodiment 2 prepare compound BMPTA under the conditions of with mortar grinder fluorescence spectrum and color change；By
Figure it is found that compound BMPTA fluorescence emission wavelengths before not being ground are located at 484nm, when use mortar by solid abrasive it
Afterwards, launch wavelength red shift is to 508nm, and the color of solid fluorescence becomes blue-green from initial blue；After grinding
After solid is fumigated 5 minutes with methylene chloride steam, fluorescent emission and solid fluorescence color can be returned to original state, this
Show the property that there is compound BMPTA certain mechanical lapping to change colour.
Fig. 6 is fluorescence spectrum and color change of the compound BPTA of the preparation of embodiment 3 under grinding condition；It can by figure
To know, compound BPTA fluorescence emission wavelengths before not being ground are located at 477nm, after using mortar by solid abrasive,
Launch wavelength red shift is to 508nm, and the color of solid fluorescence becomes blue-green from initial blue；Solid after grinding is used
After methylene chloride steam is 5 minutes stifling, fluorescent emission and solid fluorescence color can be returned to original state；This showing
Close the property that there is object BPTA certain mechanical lapping to change colour.
Fig. 7 is fluorescence spectrum and color change spectrogram of the compound BCPTA of the preparation of embodiment 4 under grinding condition；By
Figure it is found that compound BCPTA fluorescence emission wavelengths before not being ground are located at 492nm, when use mortar by solid abrasive it
Afterwards, launch wavelength 492nm, fluorescence emission wavelengths show that substance B CPTA does not have mechanical lapping there is no significant change
Matter, the result also illustrate that substituent group of different nature has larger impact to machinery discoloration property.
Fig. 8 is stereoscan photograph of the bis- thienyl anthracenes of compound 9,10- of the preparation of embodiment 2~4 in state of aggregation:
(A) compound BMPTA；(B) compound BPTA；(C) compound BCPTA；By scanning electron microscope test substance in THF:
H2O=90% (THF and H2O volume ratio) under accumulation shape, as seen from the figure, compound BPTA and BMPTA are in state of aggregation
Nanosphere form is shown as, substance B CPTA then shows unformed shape.
Cell imaging experiment:
HeLa cell culture and dyeing:
1, it recovers
HeLa cell cryopreservation tube is removed from liquid nitrogen to come, is put into 37 DEG C of water-baths immediately, gentle agitation, until liquid melts
Change (general 1~1.5min), obtain cell suspension, sprinkling alcohol is placed on superclean bench on its surface；By the cell
Suspension is inhaled in the 15.0mL centrifuge tube equipped with 10.0mL culture solution, is centrifuged 5min under the conditions of 1000r/min；By gained supernatant
Liquid is absorbed, and is added 5.0mL culture medium to blow and beat cell uniformly, is allowed to be transferred in culture dish after mixing and all around gently shake
It is dynamic, it is uniformly distributed the cell in culture dish；Cell category and date etc. have been marked, culture dish is placed in CO2It is carried out in incubator
Culture, changes culture medium after cell is adherent；A subculture was changed every 2 days.
2, it passes on
It is passed on when the cell coverage rate in culture dish reaches 80~90%；Original culture medium is absorbed, is added
2.0mL trypsase, 1~2min of vitellophag.3.0mL culture solution is added after cell is rounded and terminates digestion；Use liquid-transfering gun
Cell is blown and beaten, the cell on culture dish wall is made to blow off wall surface.Cell is transferred in 15mL centrifuge tube, in 1000r/min condition
Lower centrifugation 5min；Supernatant is absorbed, 5.0mL culture medium is added, cell is all blown and beaten uniformly, cell is transferred in culture bottle, is put into
CO2It is cultivated in incubator.
3, cell dyeing
Cell containing 12.0mL culture medium is transferred to six orifice plates (every hole 2.0mL) culture 20.0h, to cell adherent growth
Completely.
Blank group and experimental group is respectively set.
Blank group: culture medium suction is washed with PBS buffer solution three times to wash off culture medium, and the training of 2.0mL cell is then added
Nutrient solution (DMEM culture solution) shoots cell state as blank group by total focussing mechanism using 405nm transmission channel.
Experimental group: it is 20 μM that Test Materials, which are made into concentration with cell culture fluid, and volume is that the Test Materials of 2.0mL are molten
Culture medium is sucked out and is washed with PBS buffer solution three times to wash off culture medium, culture dish is added in 2.0mL Test Materials solution by liquid
0.5h is cultivated, takes out and substance is sucked out, washed three times with PBS to wash off Test Materials；Be eventually adding 2.0mL cell culture fluid with
405nm transmission channel collects the fluorescence signal at intracellular 430~530nm by Laser Scanning Confocal Microscope.Wherein, the experiment object
Matter is compound BMPTA, BPTA and BCPTA prepared by embodiment 2~4.
Fig. 9 is the HeLa cell fluorescence co-focusing imaging of compound BMPTA, BPTA and BCPTA prepared by embodiment 2~4
Scheme (C=2.0 × 10-5mol/L)；Wherein A1For the fluorescent dark field image of compound BMPTA, B1For the bright of compound BMPTA
Field image, C1For the superimposed field image of compound BMPTA；A2For the fluorescent dark field image of compound BPTA, B2For chemical combination
The light field image of object BPTA, C2For the superimposed field image of compound BPTA；A3It is imaged for the fluorescent dark field of compound BCPTA
Figure, B3For the light field image of compound BCPTA, C3For the superimposed field image of compound BCPTA.As seen from the figure, compound
BMPTA, BPTA and BCPTA are used equally for HeLa cell dyeing, from cell fluorescence imaging picture, it is apparent that compound
BMPTA, BPTA and BCPTA are able to enter HeLa cell, and assemble in the cell, under 405nm laser excitation, issue
Apparent fluorescence signal can be simultaneously detected, and illustrate that such compound can be used for cell fluorescence imaging.
As seen from the above embodiment, the present invention provides a kind of symmetric form 9, the bis- thienyl anthracene compounds of 10-, the symmetric forms
9,10- bis- thienyl anthracene compound molecular structures are simple, have apparent AIE property, and its molecular end is easy to pass through transformation
Different groups are modified, to regulate and control its characteristics of luminescence；The present invention can be obtained by simple Suzuki coupling reaction
The symmetric form 9, the bis- thienyl anthracene compounds of 10-, raw materials used cost is low, and synthesis is simple, is conducive to industrialized production, answers
It is big with prospect；Compound BMPTA, BPTA and BCPTA can be used as HeLa cell fluorescence marker, have in cell dye field latent
Application value；Compound BMPTA and BPTA have the apparent mechanical feature that changes colour, and can be used for the regulation of processing machinery power and shine
Original part etc..
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of symmetric form 9, the bis- thienyl anthracene compounds of 10- have structure shown in Formulas I:
Wherein, R be-Br,
2. symmetric form 9 described in claim 1, the preparation method of the bis- thienyl anthracene compounds of 10-, when R is-Br, including it is following
Step:
2- methylthiophene, N-bromosuccinimide and tetrahydrofuran are mixed, substitution reaction is carried out, obtains 2- methyl -3,5-
Dibromo thiophene；
2- methyl -3,5- dibromo thiophene, ether, n-BuLi and butyl borate are mixed, boration reaction is carried out, obtains
To 5- boronate -2- methyl -3 bromo thiophene；
By the 5- boronate -2- methyl -3 bromo thiophene, tetrahydrofuran, triphenyl phosphorus palladium, sodium carbonate liquor and 9,10- dibromo
Anthracene mixing, carries out coupling reaction, obtains 9,10- bis- (4- bromine 5- methylthiophene -2- base) anthracenes, i.e. symmetric form 9, the bis- thienyls of 10-
Anthracene compound.
3. preparation method according to claim 2, which is characterized in that the 2- methylthiophene and N-bromosuccinimide
Molar ratio be (45~55): (90~110)；The amount ratio of the 2- methylthiophene and tetrahydrofuran is (45~55) mmol:
100mL；
The temperature of the substitution reaction is 0 DEG C, and the time of the substitution reaction is for 24 hours.
4. preparation method according to claim 2, which is characterized in that 2- methyl -3,5- dibromo thiophene, ether, just
The amount ratio of butyl lithium and butyl borate is 15~25mmol:80mL:10mL:8mL；
The temperature of the boration reaction is -78 DEG C, and the time of the boration reaction is 6h.
5. preparation method according to claim 2, which is characterized in that the 5- boronate -2- methyl -3 bromo thiophene, four
Hydrogen furans, triphenyl phosphorus palladium, sodium carbonate liquor and 9,10- dibromoanthracene amount ratio be (5.0~7.0) mmol:150mL:(0.05
~0.10) g:(40~50) mL:(2.5~3.5) mmol；
The temperature of the coupling reaction is 80 DEG C, time 12h.
6. symmetric form 9 described in claim 1, the preparation method of the bis- thienyl anthracene compounds of 10-, when R isWhen, comprising the following steps:
By 9,10- bis- (4- bromine 5- methylthiophene -2- base) anthracene, phenyl boric acid compound, triphenyl phosphorus palladium, sodium carbonate liquor and tetrahydros
Furans mixing, carries out coupling reaction, obtains symmetric form 9, the bis- thienyl anthracene compounds of 10-；Bis- (the 4- bromine 5- methyl of 9,10-
Thiophene -2- base) anthracene is prepared by any one of claim 2~5 preparation method；
The phenyl boric acid compound is phenyl boric acid, 4- methoxyphenylboronic acid or 4- first cyanophenylboronic acid.
7. preparation method according to claim 6, which is characterized in that 9, the 10- is bis- (4- bromine 5- methylthiophene -2- base)
Anthracene, phenyl boric acid compound, triphenyl phosphorus palladium, sodium carbonate liquor and tetrahydrofuran amount ratio be preferably (1.5~2.5) mmol:
(3~5) mmol:(0.05~1.0) g:(40~50) mL:150mL.
8. preparation method according to claim 6, which is characterized in that the temperature of the coupling reaction is 80 DEG C, and the time is
12h。
9. symmetric form 9 described in claim 1, application of the bis- thienyl anthracene compounds of 10- in biological cell Imaging-PAM,
Wherein, R is
10. symmetric form 9 described in claim 1, the bis- thienyl anthracene compounds of 10- are as the mechanical application for causing off-color material, wherein
R is
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| CN112851701A (en) * | 2021-01-11 | 2021-05-28 | 吉林大学 | Anthracene-based mechanoluminescence organic material and preparation method and application thereof |
| CN112851701B (en) * | 2021-01-11 | 2022-04-01 | 吉林大学 | Anthracene-based mechanoluminescence organic material and preparation method and application thereof |
| CN112939813A (en) * | 2021-02-22 | 2021-06-11 | 江西师范大学 | 9-aryl-10-aryloxy anthracene derivative, preparation method thereof and application thereof as luminescent material |
| CN112939813B (en) * | 2021-02-22 | 2022-06-17 | 江西师范大学 | 9-aryl-10-aryloxy anthracene derivative, preparation method thereof and application thereof as luminescent material |
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