CN103102286B - Triphenylamine derivatives as well as preparation method and application thereof - Google Patents
Triphenylamine derivatives as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN103102286B CN103102286B CN201210533688.0A CN201210533688A CN103102286B CN 103102286 B CN103102286 B CN 103102286B CN 201210533688 A CN201210533688 A CN 201210533688A CN 103102286 B CN103102286 B CN 103102286B
- Authority
- CN
- China
- Prior art keywords
- organogel
- piezallochromy
- formula
- triphenylamine derivative
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 *c1ccc(C=C(c(cc2)ccc2-c(cc2)ccc2N(c2ccccc2)c2ccccc2)C#N)cc1 Chemical compound *c1ccc(C=C(c(cc2)ccc2-c(cc2)ccc2N(c2ccccc2)c2ccccc2)C#N)cc1 0.000 description 1
- MFHFWRBXPQDZSA-UHFFFAOYSA-N N#CCc(cc1)ccc1Br Chemical compound N#CCc(cc1)ccc1Br MFHFWRBXPQDZSA-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses triphenylamine derivatives represented by a formula (I) as well as a preparation method and an application thereof in piezochromic organogel. The preparation method comprises the following steps of: mixing an intermediate, para-hexadecyloxy benzaldehyde and sodium methoxide, dissolving with absolute ethyl alcohol, stirring and reacting for 3 hours at room temperature, and separating the reaction liquid after the reaction is complete so as to obtain the triphenylamine derivatives represented by formula (I). The piezochromic organogel is a micromolecule organogel material with multiple simulation responsiveness. The piezochromic organogel is simple in synthesis method, convenient in preparation, strong in simulation responsiveness, and can be applied to fields such as a sensor, anti-fake, store and display.
Description
(1) technical field
The present invention relates to the application in a kind of triphenylamine derivative and preparation method and preparation piezallochromy organogel.
(2) background technology
The phenomenon that fluorescence color changes in the time that material is applied in mechanical force is called piezallochromy phenomenon, and the material with piezallochromy phenomenon at least has stable state or the metastable state accumulation mode of two kinds of impacts that are stressed.After the power that is being subject to stimulates, intramolecular action power changes, and causes packing of molecules mode to change, make material from a kind of ordered structure become another kind of in order or partial order, disordered structure, the photophysical property of material changes thereupon.Then, after heating, solvent etc. are processed, it is original that the accumulation mode of molecule can revert to, and realizes the reversibility that fluorescence color changes.At present mainly concentrate on these several classes of small molecules, oligopolymer, liquid crystal and doped polymer to having the research of piezallochromy phenomenon, the Low-molecular weight organogel with piezallochromy performance have not been reported.
Gel, as the one of soft material, is subject to extensive concern in recent years.Low-molecular weight organogel is generally molecular by the small molecules gelifying agent of seldom measuring and a large amount of organic solvent, on rheological behavior with solid-phase seemingly, and on microcosmic, solvent molecule can move freely.The distinctive the Nomenclature Composition and Structure of Complexes of Low-molecular weight organogel makes it not only have stronger self-assembly ability and thermal reversibility, and has the feature of the strong response of weak impact, makes it be very suitable for preparing the material with external stimulus response performance.
But the reversible piezochromic phenomenon of report mainly concentrates on these several classes of small molecules, oligopolymer, liquid crystal and doped polymer at present, will limit greatly the application of this type of material like this.The discovery of gel is with a long history, and application is in daily life also very extensive, relates to the every aspects such as food, daily necessities, space flight and aviation science and technology, has using value widely so preparation has the functional gel of piezallochromy in actual life.
(3) summary of the invention
The object of the invention is to provide the application in a kind of triphenylamine derivative and preparation method and preparation piezallochromy organogel, prepared piezallochromy organogel small molecules, be a kind of Low-molecular weight organogel material with multiple stimulation responding ability, can be applicable to the sensor of fluorescence display.
The technical solution used in the present invention is:
The invention provides triphenylamine derivative shown in a kind of formula I,
The invention still further relates to one and prepare the method for described formula (I) triphenylamine derivative, described method is carried out as follows:
(1) by shown in formula (II), bromine nitrile benzyl and 4-boric acid triphenylamine being reacted to the intermediate of triphenylamine derivative shown in production (III) through Suzuki;
(2) intermediate of the triphenylamine derivative shown in formula (III) again with to n-Hexadecane oxygen benzaldehyde through the triphenylamine derivative shown in Knoevenagel condensation reaction production (I);
Further, described step (1) is carried out as follows: taking shown in 4-boric acid triphenylamine and formula II to bromine nitrile benzyl as raw material, taking tetrakis triphenylphosphine palladium as catalyzer, in organic solvent a and alkaline aqueous solution, under protection of inert gas, back flow reaction 16 ~ 48h, after reaction finishes, reaction solution a aftertreatment, obtains intermediate shown in formula III; Described alkaline aqueous solution is aqueous sodium carbonate or wet chemical; Described rare gas element is preferably nitrogen or argon gas; The mixed solution that described organic solvent a is toluene and tetrahydrofuran (THF) or the mixed solution of toluene and dehydrated alcohol.
Further, in described step (1), the method for reaction solution a aftertreatment is: after reaction finishes, after being cooled to room temperature, reaction solution a uses chloroform extraction, after taking off the water washing of layer extraction liquid saturated common salt, use anhydrous magnesium sulfate drying, filter, filtrate is dry through being evaporated to, get enriched material and carry out silica gel column chromatography taking the chloroform of volume ratio 1:150 and sherwood oil mixed solution as eluent, TLC follows the tracks of detection, the elutriant that collection contains target components, eluent is removed in distillation, obtains intermediate shown in formula III.
Further, described in the described intermediate preparation process of above-mentioned steps (1), be 1:1 ~ 1.2:0.01 ~ 0.1 to the feed intake ratio of amount of substance of bromine nitrile benzyl and 4-boric acid triphenylamine, tetrakis triphenylphosphine palladium; Described organic solvent a is toluene and mixed solution or toluene and the dehydrated alcohol mixed solution taking volume ratio as 5:3 of tetrahydrofuran (THF) taking volume ratio as 5:3, and the volumetric usage of described organic solvent a is to count 5 ~ 8ml/mmol to bromine nitrile benzyl amount of substance; The concentration of described alkaline aqueous solution is 2mol/L, and the volumetric usage of described alkaline aqueous solution is to count 0.3 ~ 0.5ml/mmol to bromine nitrile benzyl amount of substance.
Further, shown in above-mentioned formula I in the preparation method of triphenylamine derivative, described step (2) is carried out as follows: by intermediate shown in formula (III), to n-Hexadecane oxygen benzaldehyde and sodium methylate mixing, with anhydrous alcohol solution, at room temperature stirring reaction 3 ~ 9h, spends the night reaction solution b after reacting completely-20 DEG C of placements, filter, filter cake is dried for three times afterwards with dehydrated alcohol drip washing, obtains triphenylamine derivative shown in formula I.
Further, preparing intermediate shown in the method steps of triphenylamine derivative shown in formula I (2) Chinese style (III) is 1:1 ~ 1.2:0.1 ~ 1 with the ratio of amount of substance that n-Hexadecane oxygen benzaldehyde, sodium methylate are fed intake, and the volumetric usage of described dehydrated alcohol is counted 5 ~ 20ml/mmol with the amount of intermediate materials shown in formula (III).
The equation that the present invention prepares triphenylamine derivative shown in formula I is:
The present invention also provides a kind of piezallochromy organogel that contains triphenylamine derivative shown in formula I, and described piezallochromy organogel is the mixture that the final concentration that is mixed by triphenylamine derivative shown in formula I and organic solvent b is 5 ~ 10mg/ml; Described organic solvent b is the mixing of one or more arbitrary proportions in sherwood oil, normal hexane, hexanaphthene, benzene, toluene, ethanol, ethyl acetate, acetone, dimethyl sulfoxide (DMSO), polystyrene.
Further, described organic solvent b is preferably the one in sherwood oil, toluene, ethanol, ethyl acetate or dimethyl sulfoxide (DMSO).
Piezallochromy organogel of the present invention is prepared as follows: at 35 ~ 120 DEG C, triphenylamine derivative shown in formula (I) is dissolved with organic solvent b, be mixed with the mixed solution that final concentration is 5 ~ 10mg/ml, obtain described piezallochromy organogel after then mixed solution being cooled to room temperature.
The invention still further relates to a kind of described piezallochromy organogel stimulates the application of fluorescence transition material as reversible power, concrete described application is the mechanical force senser element of preparing fluorescence display with piezallochromy organogel.
Of the present invention can the multiple organic solvent of gelling containing triphenylamine derivative, the piezallochromy organogel of formation has very bright blue-greenish colour fluorescence, as reversible stimuli responsive fluorescent material application.For example, during as temperature sensor, under heating condition, organogel becomes solution, after cooling, again forms gel, and solution-gel reversible transition of this temperature adjusting can repeatedly circulate; During as outer force transducer, after mechanical force (pressure, shearing force or the grinding) effect of 2Mpa-10Mpa, fluorescence becomes yellow from blue-greenish colour, and the fluorescence color of this external force regulation and control changes and can repeatedly circulate.
The fluorescence color variation that piezallochromy organogel material of the present invention causes because accumulation mode changes presents reversible piezochromic phenomenon, under external force stimulates, be converted to yellow fluorescence from blue-greenish colour fluorescence, can return to the blue-greenish colour fluorescence state before not stressed through the post-stimulatory material of external force.It should be noted that, triphenylamine derivative small molecules provided by the invention (molecular weight is 689g/mol) is due to stronger intermolecular noncovalent interaction, approach the molecular conformation of plane and suitable solvability and there is gelling ability, can the multiple organic solvent of gelling, the gel forming has thermal stimulus responding ability, under heating or cooling conditions, can realize the reversible transition of gel-solution, and can repeatedly circulate.
Organic solvent a of the present invention, organic solvent b are organic solvent, name for ease of distinguishing different step organic solvent difference used, and described reaction solution a and reaction solution b are concentrated solution, name for ease of distinguishing the reaction solution difference of different step acquisition.
Compared with prior art, beneficial effect of the present invention is mainly reflected in:
A kind of new compound provided by the invention--triphenylamine derivative and preparation method and the application in preparation piezallochromy organogel, prepared piezallochromy organogel is the Low-molecular weight organogel material with multiple stimulation responding ability, described organogel synthetic method is simple, easy to prepare, stimulating responsive is strong, can be applicable to the fields such as sensor, false proof, storage and demonstration.
(4) brief description of the drawings
Fig. 1 is the photo of the organogel prepared of embodiment 5 under indoor natural light and ultraviolet light (365nm), and A is the gel photograph under natural light, and B is the gel photograph under ultraviolet lamp;
Fig. 2 is the stereoscan photograph of the organogel of preparation in embodiment 5,6,7 and 10, A is gel prepared by embodiment 3, B is gel prepared by embodiment 4, and C is gel prepared by embodiment 8, and D is that in embodiment 8, gel forms shaggy random pattern through External Force Acting;
Fig. 3 is gel photo under ultraviolet lamp before and after the application of force in embodiment 10, and a is the fluorescence that does not pass through external force excitor substance, and b is the fluorescence of material after External Force Acting, and c marks "+" shape on the material not stimulating through external force;
Fig. 4 is the fluorescence spectrum before and after the gel application of force in embodiment 10: the fluorescence spectrum that curve a is xerogel, and curve b is the xerogel fluorescence spectrum after pressurized;
Fig. 5 is that the power stimulation-solvent vapo(u)r of gel in embodiment 11 recovers cycle performance, and curve a group is xerogel after pressing, and curve b group is for recovering xerogel;
Fig. 6 is that in embodiment 12, organogel is subject to the photo of thermal stimulus front and back under ultraviolet lamp, and A is the photo without the organogel of heating, and B is the photo that organogel changes solution into after heating.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1: the preparation of intermediate
By 4-boric acid triphenylamine 3.47g(12mmol), to bromine nitrile benzyl 1.96g(10mmol), tetrakis triphenylphosphine palladium 0.11g(0.1mmol) be dissolved in the mixed solution of toluene 50mL/ tetrahydrofuran (THF) 30mL, add aqueous sodium carbonate (2.0M, 3mL).Under nitrogen protection, be warming up to 90 DEG C of reaction 36h, after reaction finishes, after being cooled to room temperature (25 DEG C), reaction solution uses chloroform extraction, after taking off the water washing of a layer extraction liquid (being trichloromethane layer) saturated common salt, use anhydrous magnesium sulfate drying, filter, filtrate is dry through being evaporated to, get enriched material and carry out silica gel column chromatography taking the chloroform of volume ratio 1:150 and sherwood oil mixed solution as eluent, TLC follows the tracks of detection, the elutriant that collection contains target product (III), distillation is except desolventizing, obtain yellow powder product (being intermediate shown in formula (III)) 2.76g, yield is 76.6%.The structural confirmation of material characterizes as follows:
1h NMR (500 MHz, CDCl
3) δ (ppm) 7.60 (d, J=8.5 Hz, 2H), 7.47 (d, J=8.5 Hz, 2H), 7.40 (d, J=8.0 Hz, 2H), 7.30 (t, J=7.5 Hz, 4H), 7.16 (d, J=8.5 Hz, 6H), 7.07 (t, J=7.5 Hz, 2H), 3.80 (s, 2H);
13c NMR (500 MHz, CDCl
3) δ 147.6,140.6,133.9,129.3,128.3,128.2,127.7,127.3,124.6,123.7,123.1,117.8,77.3,77.0,76.8.
The preparation of embodiment 2 intermediates
By 4-boric acid triphenylamine 3.47g(10mmol), to bromine nitrile benzyl 1.96g(10mmol), tetrakis triphenylphosphine palladium 0.55g(0.5mmol) be dissolved in the mixed solution of toluene 50mL/ dehydrated alcohol 30mL, add wet chemical (2.0M, 5mL).Under argon shield; be warming up to 90 DEG C of reaction 16h; after reaction finishes; after being cooled to room temperature (25 DEG C), reaction solution uses chloroform extraction; after taking off the water washing of layer extraction liquid saturated common salt, use anhydrous magnesium sulfate drying; filter; filtrate is dry through being evaporated to; get enriched material and carry out silica gel column chromatography taking the chloroform of volume ratio 1:150 and sherwood oil mixed solution as eluent; TLC follows the tracks of detection, collects the elutriant that contains target product (III), and distillation is except desolventizing; obtain yellow powder product (being intermediate shown in formula (III)) 2.70g, yield is 75%.
The preparation of triphenylamine derivative shown in embodiment 3 formula I
Get intermediate (III) 1.80g(5 mmol prepared by embodiment 1), to n-Hexadecane oxygen benzaldehyde 2.07g(6mmol) and sodium methylate 0.03g(0.5mmol) be dissolved in 30ml chromatographically pure ethanol, at the lower stirring reaction 3h of room temperature (25 DEG C), there are a large amount of solid particulate termination reactions, then after reaction solution being put into-20 DEG C of refrigerator overnight, filter, filter cake is dried for three times afterwards with dehydrated alcohol drip washing, obtain yellow-green colour powdered product (being triphenylamine derivative shown in formula I) 3.1g, yield is 90%.The structural confirmation of material characterizes as follows:
1h NMR (500 MHz, CDCl
3) δ (ppm) 7.89 (d, J=8.5 Hz, 2H), 7.70 (d, J=8.5 Hz, 2H), 7.63 (d, J=9.0 Hz, 2H), 7.50 (d, J=7.0 Hz, 2H), 7.49 (s, 1H), 7.28 (t, J=8.5 Hz, 4H), 7.14 (d, J=8.0 Hz, 6H), 7.05 (t, J=7.5 Hz, 2H), 6.97 (d, J=8.5 Hz, 2H), 4.02 (t, J=6.5 Hz, 2H), 1.82-1.78 (m, 2H), 1.48-1.44 (m, 2H), 1.36-1.26 (m, 24H), 0, 88 (t, J=7 Hz, 3H).
The preparation of triphenylamine derivative shown in embodiment 4 formula I
Get intermediate (III) 1.80g(5 mmol prepared by embodiment 1), to n-Hexadecane oxygen benzaldehyde 2.07g(5mmol) and sodium methylate 0.3g(5mmol) be dissolved in 100ml chromatographically pure ethanol, at the lower stirring reaction 9h of room temperature (25 DEG C), there are a large amount of solid particulate termination reactions, then after reaction solution being put into-20 DEG C of refrigerator overnight, filter, filter cake is dried for three times afterwards with dehydrated alcohol drip washing, obtain yellow-green colour powdered product (being triphenylamine derivative shown in formula I) 3.0g, yield is 87%.
Embodiment 5 piezallochromy organogels
Take triphenylamine derivative shown in formula I prepared by 8mg embodiment 2 and be placed in the vial with screw-cap, add 1mL dehydrated alcohol, be heated to 100
oc all dissolves solid, naturally cool to room temperature (25 DEG C), room temperature is placed and within 30 minutes, can be obtained yellow opaque gel, be the piezallochromy organogel containing triphenylamine derivative, organogel is compared under indoor natural light and ultraviolet light (365nm), as shown in Figure 1, in Fig. 1, A is the organogel photo under natural light to result, and B is ultraviolet light organogel photo.Organogel is carried out to electron-microscope scanning, the results are shown in Figure in 2 shown in A.Because solubleness declines, form orderly nanofiber three-dimensional network (in Fig. 2 shown in A) by self-assembly, thereby a large amount of solvents of gelling form immobilising gelling system at cooling process small molecular gelifying agent (being triphenylamine derivative).
Embodiment 6 piezallochromy organogels
Take triphenylamine derivative prepared by 5mg embodiment 2 and be placed in the vial with screw-cap, add 1mL sherwood oil, be heated to 50
oc all dissolves solid.Naturally cool to room temperature and place and within 3 minutes, can obtain yellow opaque gel, be the piezallochromy organogel containing triphenylamine derivative, electron-microscope scanning figure is shown in Fig. 2 shown in B.Because solubleness declines, form orderly willow leaf shape nanofiber three-dimensional network by self-assembly, thereby a large amount of solvents of gelling form immobilising gelling system at cooling process small molecular gelifying agent.
Embodiment 7 piezallochromy organogels
Take triphenylamine derivative prepared by 7mg embodiment 2 and be placed in the vial with screw-cap, add 1mL ethyl acetate, be heated to 70
oc all dissolves solid.Naturally cool to room temperature and place and within 5 minutes, can obtain yellow opaque gel, be the piezallochromy organogel containing triphenylamine derivative, electron-microscope scanning figure is shown in Fig. 2 shown in C.Because solubleness declines, form orderly banded nanofiber three-dimensional network by self-assembly, thereby a large amount of solvents of gelling form immobilising gelling system at cooling process small molecular gelifying agent.
Embodiment 8 piezallochromy organogels
Take triphenylamine derivative prepared by 6mg embodiment 2 and be placed in the vial with screw-cap, add 1mL dimethyl sulfoxide (DMSO), be heated to 90
oc all dissolves solid.Naturally cool to room temperature and place and can obtain opaque gel in 5 minutes, be the piezallochromy organogel containing triphenylamine derivative.
Embodiment 9 piezallochromy organogels
Take triphenylamine derivative prepared by 10mg embodiment 2 and be placed in the vial with screw-cap, add 1mL toluene, be heated to 90
oc all dissolves solid.Naturally cool to room temperature and place and can obtain opaque gel in 5 minutes, be the piezallochromy organogel containing triphenylamine derivative.
Variation before and after the embodiment 10 gel application of forces
Preparation in embodiment 5 shown to blue-greenish colour fluorescence (in Fig. 3 shown in a) containing the piezallochromy organogel of triphenylamine derivative under ultraviolet lamp, in Fig. 3, c represents that organogel marks "+" shape on the material not stimulating through external force, organogel fluorescence spectrum is (curve xerogel) as shown in Figure 4, gel is spread on quartz plate or be placed in mortar, scrape shearing force or pestle and do the used time and become green fluorescence (see in Fig. 3 shown in b) because orderly nanostructure and packing of molecules mode change when being subject to key, electron-microscope scanning is shown in Fig. 2 shown in D, fluorescence spectrum is (curve is pressed rear xerogel) as shown in Figure 4, remove external force, part of the force still keeps green fluorescence.Sample after using the stifling processing of ethyl acetate or alcohol vapour stressed, fluorescence returns to stressed front blue-greenish colour fluorescence state.
Power stimulation-the solvent vapo(u)r of embodiment 11 gels recovers cycle performance
Gel prepared by embodiment 6 spreads on quartz plate, under key is scraped shearing force, fluorescence spectrum generation red shift, maximum wavelength reaches 506nm, as shown in a suite line in Fig. 5, again through alcohol vapour is stifling process after, fluorescence spectrum generation blue shift, maximum wavelength reaches 481nm, as shown in b suite line in Fig. 5, this process can repeatedly circulate, and as shown in Figure 5, the material after 4 times that circulates still has good external force responding ability.
Embodiment 12 gels are subject to change before and after thermal stimulus
Gel prepared by embodiment 5 (photo see in Fig. 6 shown in A) is heated to dissolve completely, clear solution that immobilising gel conversion is flowable green fluorescence (photo see in Fig. 6 shown in B).Naturally cool to room temperature and form again immobilising blue-fluorescence gel.
Claims (9)
1. contain a piezallochromy organogel for triphenylamine derivative shown in formula I, it is characterized in that described piezallochromy organogel is the mixture that the final concentration that is mixed by triphenylamine derivative shown in formula I and organic solvent b is 5～10mg/ml; Described organic solvent b is the one in sherwood oil, toluene, ethyl acetate and dimethyl sulfoxide (DMSO);
2. piezallochromy organogel as claimed in claim 1, is characterized in that: shown in described formula I, triphenylamine derivative is prepared as follows:
(1) by shown in formula (II), bromine nitrile benzyl and 4-boric acid triphenylamine being reacted to the intermediate of triphenylamine derivative shown in production (III) through Suzuki;
(2) intermediate of the triphenylamine derivative shown in formula (III) again with to n-Hexadecane oxygen benzaldehyde through the triphenylamine derivative shown in Knoevenagel condensation reaction production (I);
3. piezallochromy organogel as claimed in claim 2, it is characterized in that described step (1) carries out as follows: taking shown in 4-boric acid triphenylamine and formula II to bromine nitrile benzyl as raw material, taking tetrakis triphenylphosphine palladium as catalyzer, in organic solvent a and alkaline aqueous solution, under protection of inert gas, back flow reaction 16～48h, after reaction finishes, reaction solution a aftertreatment, obtains intermediate shown in formula III; Described alkaline aqueous solution is aqueous sodium carbonate or wet chemical; The mixed solution that described organic solvent a is toluene and tetrahydrofuran (THF) or the mixed solution of toluene and dehydrated alcohol.
4. piezallochromy organogel as claimed in claim 3, the method that it is characterized in that reaction solution a aftertreatment in described step (1) is: after reaction finishes, after being cooled to room temperature, reaction solution a uses chloroform extraction, after taking off the water washing of layer extraction liquid saturated common salt, use anhydrous magnesium sulfate drying, filter, filtrate is dry through being evaporated to, get enriched material and carry out silica gel column chromatography taking the chloroform of volume ratio 1:150 and sherwood oil mixed solution as eluent, TLC follows the tracks of detection, the elutriant that collection contains target components, eluent is removed in distillation, obtain intermediate shown in formula III.
5. piezallochromy organogel as claimed in claim 3, is characterized in that in described step (1) that to the feed intake ratio of amount of substance of bromine nitrile benzyl and 4-boric acid triphenylamine, tetrakis triphenylphosphine palladium be 1:1～1.2:0.01～0.1; The concentration of described alkaline aqueous solution is 2mol/L, and the volumetric usage of described alkaline aqueous solution is to count 0.3～0.5ml/mmol to bromine nitrile benzyl amount of substance; The described organic solvent a mixed solution with volume ratio 5:3 that is toluene and tetrahydrofuran (THF) with the mixed solution of volume ratio 5:3 or toluene and dehydrated alcohol, the volumetric usage of described organic solvent a is to count 5～8ml/mmol to bromine nitrile benzyl amount of substance.
6. piezallochromy organogel as claimed in claim 2, step (2) described in it is characterized in that is carried out as follows: by intermediate shown in formula (III), to n-Hexadecane oxygen benzaldehyde and sodium methylate mixing, with anhydrous alcohol solution, at room temperature stirring reaction 3～9h, after reacting completely, reaction solution b is spent the night-20 DEG C of placements, filter, filter cake is dried for three times afterwards with dehydrated alcohol drip washing, obtains triphenylamine derivative shown in formula I.
7. piezallochromy organogel as claimed in claim 6, it is characterized in that intermediate shown in step (2) Chinese style (III) and the ratio of amount of substance that n-Hexadecane oxygen benzaldehyde, sodium methylate are fed intake are 1:1～1.2:0.1～1, the volumetric usage of described dehydrated alcohol is counted 5～20ml/mmol with the amount of intermediate materials shown in formula (III).
8. piezallochromy organogel as claimed in claim 1, it is characterized in that piezallochromy organogel prepared as follows: at 35～120 DEG C, triphenylamine derivative shown in formula (I) is dissolved with organic solvent b, be mixed with the mixed solution that final concentration is 5～10mg/ml, obtain described piezallochromy organogel after then mixed solution being cooled to room temperature.
9. described in claim 8, piezallochromy organogel, as an application for reversible power stimulation fluorescence transition material, is characterized in that described application is the mechanical force senser element of preparing fluorescence display with piezallochromy organogel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210533688.0A CN103102286B (en) | 2012-12-08 | 2012-12-08 | Triphenylamine derivatives as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210533688.0A CN103102286B (en) | 2012-12-08 | 2012-12-08 | Triphenylamine derivatives as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103102286A CN103102286A (en) | 2013-05-15 |
| CN103102286B true CN103102286B (en) | 2014-12-03 |
Family
ID=48310520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210533688.0A Active CN103102286B (en) | 2012-12-08 | 2012-12-08 | Triphenylamine derivatives as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103102286B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294464A (en) * | 2015-08-20 | 2016-02-03 | 浙江工业大学 | Triphenylamine derivative and preparation method and application thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111102B (en) * | 2015-07-20 | 2017-07-28 | 浙江工业大学 | stilbene nitrile derivative and preparation method and application thereof |
| CN105152973B (en) * | 2015-08-20 | 2017-04-12 | 浙江工业大学 | stilbene derivative and preparation method and application thereof |
| CN106883168A (en) * | 2017-02-14 | 2017-06-23 | 湖州师范学院 | The method for manufacturing thin film and application of a kind of triphenylamine derivative and its doping |
| CN109081784B (en) * | 2018-10-09 | 2021-05-14 | 浙江工业大学 | Triphenylamine derivative and preparation method and application thereof |
| CN109612610B (en) * | 2018-11-06 | 2020-11-03 | 重庆大学 | Hydrogel-based color-changeable electronic skin and preparation method thereof |
| CN110028427B (en) * | 2019-05-06 | 2021-08-20 | 吉林大学 | Pressure-induced fluorescence color-changing material containing 9, 10-bis (diphenylmethylene) anthracene structure and application thereof in pressure detection |
| CN114634546B (en) * | 2022-03-22 | 2023-07-28 | 湖州学院 | High-luminous-power electrochromic material from red to near infrared and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110286777A1 (en) * | 2010-05-19 | 2011-11-24 | Akihiro Sugino | Lubricant and image forming apparatus and process cartridge using same |
| JP2012103333A (en) * | 2010-11-08 | 2012-05-31 | Mitsubishi Chemicals Corp | Electrophotographic photoreceptor, electrophotographic photoreceptor cartridge, and image forming apparatus |
| CN102603567A (en) * | 2012-01-18 | 2012-07-25 | 浙江工业大学 | Stilbene nitrile derivatives, and preparation method and application thereof |
-
2012
- 2012-12-08 CN CN201210533688.0A patent/CN103102286B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110286777A1 (en) * | 2010-05-19 | 2011-11-24 | Akihiro Sugino | Lubricant and image forming apparatus and process cartridge using same |
| JP2012103333A (en) * | 2010-11-08 | 2012-05-31 | Mitsubishi Chemicals Corp | Electrophotographic photoreceptor, electrophotographic photoreceptor cartridge, and image forming apparatus |
| CN102603567A (en) * | 2012-01-18 | 2012-07-25 | 浙江工业大学 | Stilbene nitrile derivatives, and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Cyanostilbene-based derivatives: mechanical stimuli-responsive luminophors with aggregation-induced emission enhancement;Zhang,Yujian 等;《Photochemical & Photobiological Sciences》;20120622;第11卷(第9期);第1419页右栏第2-3段 * |
| D-A结构的9,9-二芳基芴类发光材料的合成、表征及性能;欧阳密 等;《物理化学学报》;20110630;第27卷(第6期);第1516-1524页 * |
| Synthesis and Characterization of Conjugated Pyridine-(N-diphenylamino) Acrylonitrile Derivatives: Photophysical Properties;M.Judith Percino 等;《Journal of Materials Science Research》;20120401;第1卷(第2期);第181-192页 * |
| Zhang,Yujian 等.Cyanostilbene-based derivatives: mechanical stimuli-responsive luminophors with aggregation-induced emission enhancement.《Photochemical & Photobiological Sciences》.2012,第11卷(第9期),第1419页右栏第2-3段. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294464A (en) * | 2015-08-20 | 2016-02-03 | 浙江工业大学 | Triphenylamine derivative and preparation method and application thereof |
| CN105294464B (en) * | 2015-08-20 | 2017-04-12 | 浙江工业大学 | Triphenylamine derivative and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103102286A (en) | 2013-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103102286B (en) | Triphenylamine derivatives as well as preparation method and application thereof | |
| CN102603567B (en) | Stilbene nitrile derivatives, and preparation method and application thereof | |
| CN102911082B (en) | Triphenylamine derivatives, and preparation method and application thereof | |
| CN104530105B (en) | Two boron fluoride complexings two pyrroles's methine derivative organic dyestuff of a kind of diazosulfide or benzene 1,4-Dithiapentalene bridging and preparation method thereof | |
| CN102936494B (en) | Design of multifunctional self-powered electrochromic material and integrated electrochromic device | |
| CN108586290B (en) | Amino-substituted tetraphenylethylene derivative, preparation method thereof and application thereof in gas detection | |
| CN103524404B (en) | Pyridine-triphenylamine-anthracene conjugated molecule with aggregation-induced emission property and preparation method thereof | |
| CN107325130A (en) | The synthesis of Xin Xing perylene diimide class annular metal iridium complexes and its application for regulating and controlling phosphorescence dual emission using solution concentration | |
| CN105111102B (en) | stilbene nitrile derivative and preparation method and application thereof | |
| CN103086918A (en) | Toluylene nitrile derivative with D-A structure and synthesis method and application thereof | |
| CN104312576A (en) | Piezochromic material, preparation method and applications thereof | |
| CN104927842A (en) | CuIN2P-type red light emitting material with cuprous complexes | |
| CN108947766B (en) | Fluorine-containing tetraphenylethylene compound and preparation method and application thereof | |
| CN108033940A (en) | A kind of fluorescent material with piezallochromy and solvatochromism | |
| CN103992271A (en) | Organic fluorescent gel compound based on naphthalimide and preparation method and application thereof | |
| CN114634546A (en) | High-luminous-power photochromic material from red to near infrared and preparation method thereof | |
| CN107459488B (en) | Isolonglifolane base and pyrimidine -2- amine Schiff bases fluorescent chemicals and preparation method thereof | |
| CN104961770A (en) | Pyronyl phosphine ligand based cuprous-complex green phosphorescent material | |
| CN109081784B (en) | Triphenylamine derivative and preparation method and application thereof | |
| CN111574578B (en) | Circular polarization luminescent material with intelligent response multicolor conversion and preparation method and application thereof | |
| CN101870675B (en) | Novel organogel compound and preparation method thereof | |
| CN103641743A (en) | Tristyrene nitrile derivative as well as preparation method and application thereof | |
| CN110117235A (en) | The compound and its preparation method and application of color shifting properties is caused with aggregation-induced emission and power | |
| CN113603610B (en) | Naphthalene hydrazide organic gel factor and preparation method and application thereof | |
| CN104004508B (en) | A kind of preparation method of the mixed metallized polymer film material of electric conductivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |