CN104628756A - 2,2-fluoro-4,6-bis(N-ethylcarbazole-3)-2H-1,3,2-dioxin borane compound as well as preparation method and application thereof - Google Patents
2,2-fluoro-4,6-bis(N-ethylcarbazole-3)-2H-1,3,2-dioxin borane compound as well as preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses fluoro- 4,6- bis- (N- ethyl carbazole-the 3) -2H-1 of 2,2- of one kind bis-, 3,2- dioxa glutinous rehmannia borane compounds and its preparation method and application. Shown in the structural formula of compound such as formula (I):
The present invention passed through in aqueous solution using it weak interaction force be assembled into nanosphere,Nanometer rods or the property of nanotube prepare the corresponding organic nano material with special appearance,The photophysical property of two aromatic radical formoxyl methane compound of fluoroboration at the nanoscale is in depth understood to more comprehensive,And it explores such nano material and has great significance in the application of bio-imaging and field of photovoltaic materials; The acceptor molecule of different proportion can be adulterated simultaneously into nanometer rods,The luminescent behavior of regulation nanometer rods as needed,It is set also to have good application value in terms of manual simulation's light capture system.
Description
Technical field
The present invention relates to organic nano material and preparation field thereof, more specifically, a kind of fluoroboric dye 2,2-bis-fluoro-4 is related to, 6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound and synthetic method thereof, also relate to and utilize 2,2-bis-fluoro-4, organic nano material of 6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine assembling and preparation method thereof and application.
Background technology
Fluorine boronation diaryl formyl methane compound (BF
2dbm) be the fluorescence dye of a class excellent performance, there is abundant photophysical property, such as photoluminescence quantum yield and molar extinction coefficient are high, luminous position is easy to regulate, stoke shift is comparatively large, room temperature phosphorimetry, and solid luminescence is strong, the advantages such as good light stability, have important using value in fields such as imaging biological cells, fluorescent mark and fluorescent optical sensors.Mainly concentrate in solution or crystalline phase to the research of fluorine boronation diaryl formyl methane compounds photophysical property at present, research object is free small molecules or the molecule of solid state shape.After making nano material, many fluorescence molecules can show and photophysical properties significantly different under solution and solid state shape.And utilize fluorine boronation two aromatic base formyl methane compounds very rare to the report preparing organic fluorescence nano material.Therefore present stage needs a kind of fluorine boronation two aromatic base formyl methane compound of development badly; and the organic nano material of different-shape can be prepared by this compounds; for in depth understanding the photophysical property of fluorine boronation two aromatic base formyl radical methane compound under nanoscale more comprehensively, and explore such nano material and have great significance in the application of bio-imaging and field of photovoltaic materials.
Summary of the invention
First object of the present invention is to provide a kind of novel fluorine boronation two aromatic base formyl methane compounds 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine.
Second object of the present invention is the synthetic method providing a kind of novel fluorine boronation two aromatic base formyl methane compounds 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine.
3rd object of the present invention is to provide a kind of compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine preparing the application in organic nano material.
4th object of the present invention is to provide a kind of organic nano rod prepared based on compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine solely to catch application in system manual simulation.
The present invention synthesizes 2 first, 2-bis-fluoro-4, 6-bis-(N-ethyl carbazole-3)-2H-1, 3, 2-dioxa glutinous rehmannia borane compound, and utilize it can be assembled into nanometer ball by weak interaction force in aqueous, the character of nanometer rod or nanotube prepares the organic nano material accordingly with special appearance, preparation method is simply effective, reproducible, for in depth understanding the photophysical property of fluorine boronation two aromatic base formyl radical methane compound under nanoscale more comprehensively, and explore such nano material and have great significance in the application of bio-imaging and field of photovoltaic materials, can adulterate the acceptor molecule of different ratios in nanometer rod, and regulate and control the luminescent behavior of nanometer rod as required, making it solely catch in system manual simulation also has good using value simultaneously.
For reaching above-mentioned first object, the present invention adopts following technical proposals:
A kind of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound, has following structure formula I:
For reaching above-mentioned second object, the present invention adopts following technical proposals:
The preparation method of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound, comprises the steps:
1) there is the synthesis of the N-ethyl-3-ethanoyl carbazole of formula II structure
2) there is the synthesis of the N-ethyl carbazole-3-formic acid of formula III structure
3) there is the synthesis of the N-ethyl carbazole-3-methyl-formiate of formula IV structure
4) there is the synthesis of 1,3-bis-(N-ethyl carbazole-3)-propanedione of formula (V) structure
5) there is the synthesis of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound of formula I structure.
Preferably, step 1) synthesis step of described compound N-ethyl-3-ethanoyl carbazole is as follows:
Taking N-ethyl carbazole joins in reaction flask; add anhydrous 1; 2-ethylene dichloride; add aluminum trichloride (anhydrous), slowly instill acetyl bromide, under nitrogen protection, after room temperature reaction, obtain reaction solution; reaction solution is poured in dilute hydrochloric acid; isolate organic phase, solvent in evaporated under reduced pressure organic phase, after chromatography column is separated, obtains compound N-ethyl-3-ethanoyl carbazole.
Preferably, step 2) synthesis step of described compound N-ethyl carbazole-3-formic acid is as follows:
Taking N-ethyl carbazole-3-formaldehyde joins in reaction flask, add the mixed solvent of acetone and water, potassium permanganate is added under ice bath, filter after back flow reaction, filtrate can separate out precipitation after being adjusted to pH=3 with hydrochloric acid, by the sedimentation and filtration of separating out, be placed in baking oven drying and obtain compound N-ethyl carbazole-3-formic acid.
Preferably, step 3) synthesis step of described compound N-ethyl carbazole-3-methyl-formiate is as follows:
Taking N-ethyl carbazole-3-formic acid adds in reaction flask, add anhydrous methanol, add 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride and DMAP, evaporated under reduced pressure solvent after back flow reaction, be dissolved in methylene dichloride, washing, obtains filtrate by filtering after organic phase drying again, solvent in evaporated under reduced pressure filtrate, obtains compound N-ethyl carbazole-3-methyl-formiate after chromatography column is separated.
Preferably, step 4) synthesis step of described compound 1,3-bis-(N-ethyl carbazole-3)-propanedione is as follows:
Taking N-ethyl-3-ethanoyl carbazole joins in reaction flask; add anhydrous tetrahydro furan; then excessive sodium hydride is added; return stirring for some time under nitrogen protection; add N-ethyl carbazole-3-methyl-formiate, filter after back flow reaction under nitrogen protection and obtain filtrate, the solvent in evaporated under reduced pressure filtrate; compound 1,3-bis-(N-ethyl carbazole-3)-propanedione is obtained after chromatography column is separated.
Preferably, step 5) synthesis step of described compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine is as follows:
Take 1,3-bis-(N-ethyl carbazole-3)-propanedione adds in reaction flask, add triethylamine, stirring at room temperature, add boron trifluoride diethyl etherate, again after stirring at room temperature, add shrend and to go out reaction, isolate organic phase, organic phase saturated sodium-chloride water solution is washed three times, obtaining filtrate, the solvent in evaporated under reduced pressure filtrate by filtering after organic phase drying again, being separated through chromatography column and obtaining compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine.
For reaching above-mentioned 3rd object, the present invention proposes a kind of compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine and is preparing the application in organic nano material.
Preferably, described organic nano material is organic nano ball, organic nanotube or organic nano rod.
Preferably, the preparation process of described organic nano ball, organic nanotube and organic nano rod is as follows respectively:
1) preparation of organic nano ball
Take 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine is dissolved in tetrahydrofuran (THF) and obtains organic phase, organic phase is injected in pure water, at the uniform velocity stir and obtain dispersed microemulsion, after standing aging, organic nano ball can be obtained;
2) preparation of organic nanotube
Take 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine is dissolved in tetrahydrofuran (THF) and obtains organic phase, organic phase is injected in the water containing tensio-active agent, at the uniform velocity stirs and obtain homodisperse microemulsion, after standing aging, can organic nanotube be obtained; Described tensio-active agent is selected from cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate; The volume ratio of described aqueous phase and organic phase is 1:0.3-0.6;
3) preparation of organic nano rod
Take 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine is dissolved in tetrahydrofuran (THF) and obtains organic phase, organic phase is injected in the water containing tensio-active agent, at the uniform velocity stirs and obtain homodisperse microemulsion, after standing aging, organic nano rod can be obtained; Described tensio-active agent is selected from cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate; The volume ratio of described aqueous phase and organic phase is 1:0.1-0.3.
Compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3, the 2-dioxa glutinous rehmannia borine of the present invention's synthesis can be dissolved completely in tetrahydrofuran (THF), but is undissolved in water.The tetrahydrofuran solution being dissolved with this compound is injected into after in water, forms microemulsion.Residing for compound, environment becomes poor environment from benign environment, causes this compound to be separated out gradually, and then spontaneous assembling forms the organic nano material of different-shape.Wherein, nanometer rod and the difference of nanotube formation condition are that the condition forming microemulsion is different, and the organic phase being namely dissolved with this compound is different from the volume ratio of the aqueous phase being dissolved with tensio-active agent.
For reaching above-mentioned 4th object, the present invention proposes a kind of organic nano rod prepared based on 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine and solely catches application in system manual simulation.
Preferably, specific application process is at compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3, energy acceptor molecule is added while 2-dioxa glutinous rehmannia borine joins tetrahydrofuran (THF), energy acceptor molecule accounts for compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1, the molar ratio of 3,2-dioxa glutinous rehmannia borine is 0.0001%, 0.0005%, 0.001%, 0.005%, 0.01%, 0.05% or 0.1%, the organic nano rod of the energy acceptor molecule of the different molar weight that can obtain adulterating.
Preferably, described energy acceptor molecule is the fluoro-4-of compound 2,2-bis-(N-ethyl carbazole-3)-6-(2-diethylin naphthalene-6)-2H-1,3, the 2-dioxa glutinous rehmannia borine with formula VI structure
Or the compound 2,2-bis-of formula (VII) structure fluoro-4,6-bis-(2-diethylin naphthalene-6)-2H-1,3,2-dioxa glutinous rehmannia borine
Preferably, the described preparation method with the compound of formula VI structure is: carry out Claisen condensation reaction by the ketone with formula II structure and the ester with formula (Ⅸ) structure and obtain, or the ketone with formula (VIII) structure and the ester with formula IV structure carry out Claisen condensation reaction and obtain;
Preferably, the preparation method described in the compound of formula (VII) structure is: carry out Claisen condensation reaction by the ketone with formula (VIII) structure with the ester with formula (Ⅸ) structure and obtain;
Beneficial effect of the present invention is as follows:
The present invention achieves compound 2 first, 2-bis-fluoro-4, 6-bis-(N-ethyl carbazole-3)-2H-1, 3, the synthesis preparation of 2-dioxa glutinous rehmannia borine, and make use of this compound and be assembled into nanometer ball by weak interaction force in aqueous, the character of nanometer rod or nanotube prepares the organic nano material accordingly with special appearance, constructed based on 2 simultaneously, 2-bis-fluoro-4, 6-bis-(N-ethyl carbazole-3)-2H-1, 3, the efficient light of 2-dioxa glutinous rehmannia borine nanometer rod catches system, lay a good foundation in the application of bio-imaging and field of photovoltaic materials for exploring such material.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates the absorption spectrum of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound in the opposed polarity solvent chosen in the embodiment of the present invention 1.
Fig. 2 illustrates the fluorescence emission spectrum of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound in the opposed polarity solvent chosen in the embodiment of the present invention 1.
Fig. 3 illustrates the stereoscan photograph of the organic nano ball prepared based on 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound in the embodiment of the present invention 1.
Fig. 4 illustrates the stereoscan photograph of the organic nano rod prepared based on 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound in the embodiment of the present invention 1.
Fig. 5 illustrates the stereoscan photograph of the organic nanotube prepared based on 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound in the embodiment of the present invention 1.
Fig. 6 illustrates the absorption spectrum of organic nano ball and the nanometer rod prepared based on 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound in the embodiment of the present invention 1.
Fig. 7 illustrates the fluorescence emission spectrum of organic nano ball and the nanometer rod prepared based on 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound in the embodiment of the present invention 1.
Fig. 8 a illustrates in the embodiment of the present invention 1 based on 2,2-bis-fluoro-4, stereoscan photograph after the energy acceptor molecule (VI) of organic nano rod doping different ratios prepared by 6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound.
Fig. 8 b illustrates in the embodiment of the present invention 1 based on 2,2-bis-fluoro-4, stereoscan photograph after the energy acceptor molecule (VII) of organic nano rod doping different ratios prepared by 6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound.
Fig. 9 a illustrates in the embodiment of the present invention 1 based on 2,2-bis-fluoro-4, fluorescence spectrum change after the energy acceptor molecule (VI) of organic nano rod doping different ratios prepared by 6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound.
Fig. 9 b illustrates in the embodiment of the present invention 1 based on 2,2-bis-fluoro-4, fluorescence spectrum change after the energy acceptor molecule (VII) of organic nano rod doping different ratios prepared by 6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Embodiment 1
The synthesis of (1) 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound:
1. the N-ethyl carbazole taking 5mmol is placed in the bottle with two necks of 100mL, then in bottle, 20mL anhydrous 1 is added, 2-ethylene dichloride, add the aluminum trichloride (anhydrous) of 10mmol, slowly the acetyl bromide solution of instillation 5.5mmol, obtains reaction solution after room temperature reaction 10h under nitrogen protection, reaction solution is poured in dilute hydrochloric acid, separate organic phase, solvent in evaporated under reduced pressure organic phase, after chromatography column is separated, obtains compound N-ethyl-3-ethanoyl carbazole;
2. the N-ethyl carbazole-3-formaldehyde taking 5mmol joins in the single port bottle of 200mL, then in bottle, add the mixed solvent of 80ml acetone and water, the potassium permanganate of 10mmol is added under ice bath, filter after back flow reaction 6h, filtrate is adjusted to pH=3 with hydrochloric acid, the sedimentation and filtration of separating out, is placed in baking oven drying and obtains N-ethyl carbazole-3-formic acid;
3. the N-ethyl carbazole-3-formic acid taking 4mmol is placed in the single port bottle of 100mL, add anhydrous methanol, add 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride of 10mmol and the DMAP of 4mmol, evaporated under reduced pressure solvent after back flow reaction 12h, be dissolved in again in methylene dichloride, wash with water, filter after organic phase drying and obtain filtrate, solvent in evaporated under reduced pressure filtrate, obtains N-ethyl carbazole-3-methyl-formiate after chromatography column is separated;
4. the N-ethyl-3-ethanoyl carbazole taking 2mmol joins in the there-necked flask of 100mL, add 10mL anhydrous tetrahydro furan, add the sodium hydride of 10mmol, return stirring 30 minutes under nitrogen protection, add the N-ethyl carbazole-3-methyl-formiate of 2.2mmol, under nitrogen protection, back flow reaction is filtered after 24 hours and is obtained filtrate, solvent in evaporated under reduced pressure filtrate, 1,3-bis-(N-ethyl carbazole-3)-1,3-propanedione is obtained after chromatography column is separated;
5. 1 of 1mmol is taken, 3-bis-(N-ethyl carbazole-3)-1,3-propanedione adds in the single port bottle of 100mL, add the triethylamine of 2.5mmol, stirring at room temperature 30 minutes, adds the boron trifluoride diethyl etherate of 2.5mmol, after stirring at room temperature reacts 4 hours, add shrend to go out reaction, separate organic phase, organic phase saturated sodium-chloride water solution is washed three times, filter after organic phase drying, solvent in evaporated under reduced pressure filtrate, 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1 is obtained after chromatography column is separated, 3,2-dioxa glutinous rehmannia borane compound.
The compound 2 of the present invention's synthesis, 2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3, as shown in Figure 1, its fluorescence emission spectrum in the solvent of opposed polarity as shown in Figure 2 for the absorption spectrum of 2-dioxa glutinous rehmannia borine in the solvent of opposed polarity.Test result shows: the spectral quality of compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine changes along with the difference of solvent polarity, and presents green fluorescence in organic solvent.
(2) based on the preparation of the organic nano material of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound:
1. the preparation of organic nano ball
Be 2 of 1mM by concentration, 2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3, the tetrahydrofuran solution 1mL of 2-dioxa glutinous rehmannia borine is injected in 5mL deionized water, stirring at room temperature obtains homodisperse microemulsion in 3 minutes, leave standstill aging 24 hours, obtain based on 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1, the organic nano ball of 3,2-dioxa glutinous rehmannia borane compound, pattern is as shown in Figure 3, as shown in Figure 6, fluorescence emission spectrum as shown in Figure 7 for absorption spectrum.This characterization result illustrates: nanometer ball has homogeneous pattern and size, and diameter is approximately 120 nanometers, and has the character of red fluorescence.
2. the preparation of organic nano rod
Be 2 of 1mM by concentration, 2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3, the tetrahydrofuran solution 1mL of 2-dioxa glutinous rehmannia borine is injected into 5mL and contains in the deionized water of Surfactant SDS 8mM, stirring at room temperature 3min, leaves standstill aging 24h, and after centrifugal solid, redispersion is in water, recentrifuge obtains based on 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3, the organic nano rod of 2-dioxa glutinous rehmannia borane compound, as shown in Figure 4, as shown in Figure 6, fluorescence emission spectrum as shown in Figure 7 for absorption spectrum for pattern.This characterization result illustrates: nanometer rod has homogeneous pattern and size, is about long 7 microns, diameter 500 nanometer, and has the character of yellow fluorescence.
3. the preparation of organic nanotube
Be 2 of 1mM by concentration, 2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3, the tetrahydrofuran solution 3mL of 2-dioxa glutinous rehmannia borine is injected into 5mL and contains in the deionized water of Surfactant SDS 8mM, stirring at room temperature 3min, leave standstill aging 24h, after centrifugal solid, redispersion is in water, and recentrifuge obtains based on 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1, the organic nanotube of 3,2-dioxa glutinous rehmannia borane compound, pattern as shown in Figure 5.
(3) solely to catch the application in system manual simulation based on the organic nano rod of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound:
1. energy acceptor molecule (VI) 2, the fluoro-4-of 2-bis-(N-ethyl carbazole-3)-6-(2-diethylin naphthalene-6)-2H-1,3,2-dioxa glutinous rehmannia borine and (VII) 2,2-bis-fluoro-4, the synthesis of 6-bis-(2-diethylin naphthalene-6)-2H-1,3,2-dioxa glutinous rehmannia borine:
(VI) synthetic method obtains compound 2 by N-ethyl-3-ethanoyl carbazole and 6-(diethylin)-2-2-methyl naphthoate or N-ethyl-3-carbazole methyl-formiate and 6-(diethylin)-2 acetyl naphthalene by Claisen condensation reaction, the fluoro-4-of 2-bis-(N-ethyl carbazole-3)-6-(2-diethylin naphthalene-6)-2H-1,3,2-dioxa glutinous rehmannia borine;
(VII) synthetic method obtains compound 2 by 6-(diethylin)-2 acetyl naphthalene and 6-(diethylin)-2-2-methyl naphthoate by Claisen condensation reaction; 2-bis-fluoro-4; 6-bis-(2-diethylin naphthalene-6)-2H-1; 3,2-dioxa glutinous rehmannia borine.
2. manual simulation solely catches the preparation process of system as the preparation of above-mentioned organic nano rod: at 2 of preparation 1mM, 2-bis-fluoro-4, 6-bis-(N-ethyl carbazole-3)-2H-1, 3, while the tetrahydrofuran solution of 2-dioxa glutinous rehmannia borane compound, add and energy acceptor molecule (VI) 2, the fluoro-4-of 2-bis-(N-ethyl carbazole-3)-6-(2-diethylin naphthalene-6)-2H-1, 3, 2-dioxa glutinous rehmannia borine or (VII) 2, 2-bis-fluoro-4, 6-bis-(2-diethylin naphthalene-6)-2H-1, 3, 2-dioxa glutinous rehmannia borine, energy acceptor molecule accounts for 2, 2-bis-fluoro-4, 6-bis-(N-ethyl carbazole-3)-2H-1, 3, the molar ratio of 2-dioxa glutinous rehmannia borine is 0.0001%, 0.0005%, 0.001%, 0.005%, 0.01%, 0.05% or 0.1%, finally obtain adulterating the organic nano rod of different molar weight acceptor molecule, the impact that the pattern of this nanometer rod and size are not all adulterated, as Fig. 8 a (the organic nano rod stereoscan photograph of different molar weight acceptor molecule (VI) of adulterating), shown in Fig. 8 b (the organic nano rod stereoscan photograph of different molar weight acceptor molecule (VII) of adulterating).
The nanometer rod of the different molar weight acceptor molecule of the doping 3. prepared, test its fluorescence emission spectrum, as Fig. 9 a be doping different ratios energy acceptor molecule (VI) after fluorescence spectrum change spectrogram, Fig. 9 b is the fluorescence spectrum change spectrogram after the energy acceptor molecule (VII) of doping different ratios, proportional concentration in figure refers to acceptor molecule and accounts for donor molecule 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1, the molar ratio of 3,2-dioxa glutinous rehmannia borine.Reduce gradually to the luminescence of body (≈ 567nm), and acceptor (VI) (2, the fluoro-4-of 2-bis-(N-ethyl carbazole-3)-6-(2-diethylin naphthalene-6)-2H-1, 3, 2-dioxa glutinous rehmannia borine or (VII) 2, 2-bis-fluoro-4, 6-bis-(2-diethylin naphthalene-6)-2H-1, 3, the luminescence of 2-dioxa glutinous rehmannia borine strengthens gradually, and give/acceptor ratio reach 1000 time, to the luminescence of body substantially by complete cancellation, show based on 2, 2-bis-fluoro-4, 6-bis-(N-ethyl carbazole-3)-2H-1, 3, the organic nano rod of 2-dioxa glutinous rehmannia borine has excellent light acquisition performance.
Embodiment 2
The synthesis of (1) 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound:
1. the N-ethyl carbazole taking 20mmol is placed in the bottle with two necks of 250mL, then in bottle, 100mL anhydrous 1 is added, 2-ethylene dichloride, add the aluminum trichloride (anhydrous) of 40mmol, slowly the acetyl bromide solution of instillation 22mmol, under nitrogen protection after room temperature reaction 10h, pour in dilute hydrochloric acid, separate organic phase, solvent in evaporated under reduced pressure organic phase, after chromatography column is separated, obtains compound N-ethyl-3-ethanoyl carbazole;
2. the N-ethyl-3-ethanoyl carbazole taking 15mmol joins in the single port bottle of 200mL, then in bottle, add the mixed solvent of 100ml acetone and water, the potassium permanganate of 45mmol is added under ice bath, filter after back flow reaction 6h, filtrate is adjusted to pH=3 with hydrochloric acid, the sedimentation and filtration of separating out, is placed in baking oven drying and obtains N-ethyl carbazole-3-formic acid;
3. the N-ethyl carbazole-3-formic acid taking 10mmol is placed in the single port bottle of 200mL, add anhydrous methanol, add 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride of 20mmol and the DMAP of 10mmol, evaporated under reduced pressure solvent after back flow reaction 12h, be dissolved in again in methylene dichloride, wash with water, after filtering after organic phase drying, obtain filtrate, solvent in evaporated under reduced pressure filtrate, obtains N-ethyl carbazole-3-methyl-formiate after chromatography column is separated;
4. the N-ethyl-3-ethanoyl carbazole taking 8mmol joins in the there-necked flask of 100mL, add 15mL anhydrous tetrahydro furan, add the sodium hydride of 50mmol, return stirring 30 minutes under nitrogen protection, add the N-ethyl carbazole-3-methyl-formiate of 9mmol, under nitrogen protection, back flow reaction filtered to get filtrate after 24 hours, solvent in evaporated under reduced pressure filtrate, 1,3-bis-(N-ethyl carbazole-3)-1,3-propanedione is obtained after chromatography column is separated;
5. 1 of 5mmol is taken, 3-bis-(N-ethyl carbazole-3)-1,3-propanedione adds in the single port bottle of 100mL, add the triethylamine of 15mmol, stirring at room temperature 30 minutes, adds the boron trifluoride diethyl etherate of 15mmol, after stirring at room temperature reacts 4 hours, add shrend to go out reaction, separate organic phase, wash three times with saturated sodium-chloride water solution, filter to get filtrate after organic phase drying, solvent in evaporated under reduced pressure filtrate, 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1 is obtained after chromatography column is separated, 3,2-dioxa glutinous rehmannia borane compound.
(2) based on the preparation of the organic nano material of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound:
Repeat embodiment 1, difference is: the concentration of Surfactant SDS used increases to 20mM, identical preparation method, and can obtain organic nano ball, nanometer rod and nanotube that pattern is homogeneous, test result is similar to embodiment 1.
Embodiment 3
Repeat embodiment 1, difference is: the cetyl trimethylammonium bromide taking 5mg is dissolved in 5mL deionized water, identical preparation method, and can obtain organic nano ball, nanometer rod and nanotube that pattern is homogeneous, test result is similar to embodiment 1.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of amplifying out or variation be still in the row of protection scope of the present invention.
Claims (10)
1.2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound, is characterized in that having following structure formula I:
2. the preparation method of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound as claimed in claim 1, is characterized in that, comprise the steps:
1) there is the synthesis of the N-ethyl-3-ethanoyl carbazole of formula II structure
2) there is the synthesis of the N-ethyl carbazole-3-formic acid of formula III structure
3) there is the synthesis of the N-ethyl carbazole-3-methyl-formiate of formula IV structure
4) there is the synthesis of 1,3-bis-(N-ethyl carbazole-3)-propanedione of formula (V) structure
5) there is the synthesis of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borane compound of formula I structure.
3. 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1 according to claim 2; 3; the preparation method of 2-dioxa glutinous rehmannia borane compound, is characterized in that, step 1) synthesis step of described compound N-ethyl-3-ethanoyl carbazole is as follows:
Taking N-ethyl carbazole joins in reaction flask; add anhydrous 1; 2-ethylene dichloride; add aluminum trichloride (anhydrous), instillation acetyl bromide, obtains reaction solution after room temperature reaction under nitrogen protection; reaction solution is poured in dilute hydrochloric acid; isolate organic phase, solvent in evaporated under reduced pressure organic phase, after chromatography column is separated, obtains compound N-ethyl-3-ethanoyl carbazole.
4. the preparation method of 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine according to claim 2, is characterized in that, step 2) synthesis step of described compound N-ethyl carbazole-3-formic acid is as follows:
Taking N-ethyl carbazole-3-formaldehyde joins in reaction flask, add the mixed solvent of acetone and water, potassium permanganate is added under ice bath, filter after back flow reaction, filtrate can separate out precipitation after being adjusted to pH=3 with hydrochloric acid, by the sedimentation and filtration of separating out, be placed in baking oven drying and obtain compound N-ethyl carbazole-3-formic acid.
5. 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1 according to claim 2,3, the preparation method of 2-dioxa glutinous rehmannia borine, is characterized in that, step 3) synthesis step of described compound N-ethyl carbazole-3-methyl-formiate is as follows:
Taking N-ethyl carbazole-3-formic acid adds in reaction flask, add anhydrous methanol, add 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride and DMAP, evaporated under reduced pressure solvent after back flow reaction, be dissolved in methylene dichloride, washing, obtains filtrate by filtering after organic phase drying again, solvent in evaporated under reduced pressure filtrate, obtains compound N-ethyl carbazole-3-methyl-formiate after chromatography column is separated.
6. 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1 according to claim 2, the preparation method of 3,2-dioxa glutinous rehmannia borine, is characterized in that, step 4) synthesis step of described compound 1,3-bis-(N-ethyl carbazole-3)-propanedione is as follows:
Taking N-ethyl-3-ethanoyl carbazole joins in reaction flask; add anhydrous tetrahydro furan; then excessive sodium hydride is added; return stirring under nitrogen protection; add N-ethyl carbazole-3-methyl-formiate, filter after back flow reaction under nitrogen protection and obtain filtrate, the solvent in evaporated under reduced pressure filtrate; compound 1,3-bis-(N-ethyl carbazole-3)-propanedione is obtained after chromatography column is separated.
7. according to claim 22,2-bis-fluoro-4, the preparation method of 6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine, it is characterized in that, step 5) described compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1, the synthesis step of 3,2-dioxa glutinous rehmannia borine is as follows:
Take 1,3-bis-(N-ethyl carbazole-3)-propanedione adds in reaction flask, add triethylamine, stirring at room temperature, add boron trifluoride diethyl etherate, again after stirring at room temperature, add shrend and to go out reaction, isolate organic phase, organic phase saturated sodium-chloride water solution is washed three times, obtaining filtrate, the solvent in evaporated under reduced pressure filtrate by filtering after organic phase drying again, being separated through chromatography column and obtaining compound 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine.
8.2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine is preparing the application in organic nano material, it is characterized in that: described organic nano material is organic nano ball, organic nanotube or organic nano rod.
9. the application in system solely caught by the organic nano rod prepared based on 2,2-bis-fluoro-4,6-bis-(N-ethyl carbazole-3)-2H-1,3,2-dioxa glutinous rehmannia borine manual simulation.
10. one according to claim 9 is based on 2, 2-bis-fluoro-4, 6-bis-(N-ethyl carbazole-3)-2H-1, 3, the application in system solely caught by organic nano rod prepared by 2-dioxa glutinous rehmannia borine manual simulation, it is characterized in that: compound 2, 2-bis-fluoro-4, 6-bis-(N-ethyl carbazole-3)-2H-1, 3, energy acceptor molecule is added while 2-dioxa glutinous rehmannia borine joins tetrahydrofuran (THF), energy acceptor molecule accounts for compound 2, 2-bis-fluoro-4, 6-bis-(N-ethyl carbazole-3)-2H-1, 3, the molar ratio of 2-dioxa glutinous rehmannia borine is 0.0001%, 0.0005%, 0.001%, 0.005%, 0.01%, 0.05% or 0.1%, can be obtained adulterating the organic nano rod of energy acceptor molecule of different molar weight, described energy acceptor molecule is the fluoro-4-of compound 2,2-bis-(N-ethyl carbazole-3)-6-(2-diethylin naphthalene-6)-2H-1,3, the 2-dioxa glutinous rehmannia borine with formula VI structure
Or the compound 2,2-bis-of formula (VII) structure fluoro-4,6-bis-(2-diethylin naphthalene-6)-2H-1,3,2-dioxa glutinous rehmannia borine
The described preparation method with the compound of formula VI structure is: carry out Claisen condensation reaction by the ketone with formula II structure and the ester with formula (Ⅸ) structure and obtain, or the ketone with formula (VIII) structure and the ester with formula IV structure carry out Claisen condensation reaction and obtain;
The described preparation method with the compound of formula (VII) structure is: carry out Claisen condensation reaction by the ketone with formula (VIII) structure with the ester with formula (Ⅸ) structure and obtain;
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