CN105152973B - stilbene derivative and preparation method and application thereof - Google Patents
stilbene derivative and preparation method and application thereof Download PDFInfo
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- CN105152973B CN105152973B CN201510514340.0A CN201510514340A CN105152973B CN 105152973 B CN105152973 B CN 105152973B CN 201510514340 A CN201510514340 A CN 201510514340A CN 105152973 B CN105152973 B CN 105152973B
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000004044 response Effects 0.000 claims abstract description 8
- GDWXALVJBAAUJN-UHFFFAOYSA-N diethyl 4-methoxyphenyl phosphate Chemical compound CCOP(=O)(OCC)OC1=CC=C(OC)C=C1 GDWXALVJBAAUJN-UHFFFAOYSA-N 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000002441 reversible effect Effects 0.000 claims description 11
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 238000010898 silica gel chromatography Methods 0.000 claims description 6
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 6
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 6
- 238000012805 post-processing Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 235000021286 stilbenes Nutrition 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006130 Horner-Wadsworth-Emmons olefination reaction Methods 0.000 abstract 1
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000005286 illumination Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- -1 Potassium alkoxide Chemical class 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000008876 conformational transition Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- DHTQKXHLXVUBCF-UHFFFAOYSA-N diethyl phenyl phosphate Chemical compound CCOP(=O)(OCC)OC1=CC=CC=C1 DHTQKXHLXVUBCF-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a stilbene derivative (I) with light stimulus response fluorescence conversion performance, which is prepared by the following steps: firstly, carrying out Suzuki reaction on p-bromobenzaldehyde (II) and 4-triphenylamine borate (III) to generate a triphenylamine Intermediate (IV); reacting the triphenylamine Intermediate (IV) with 4-methoxyphenyl diethyl phosphate (V) through Horner-Wadsworth-Emmons to generate a target product; the light stimulus response fluorescence conversion performance of the stilbene derivative (I) has the characteristics of high contrast, recoverability and flexible bending, and the synthesis method is simple and can be applied to the fields of fluorescence switches, sensors, storage, display and the like;
Description
(1) technical field
The present invention relates to a kind of diphenyl ethylene derivatives and preparation method thereof and as reversible photostimulation fluorescence transition material
Application, it is adaptable to sensor, it is false proof, storage and display.
(2) background technology
The phenomenon that fluorescence color changes when material is subjected to photostimulation is referred to as photochromism, with light-induced variable
The material of color phenomenon at least has two kinds of molecular configuration changes.After by photostimulation, intramolecule structure changes, and causes
There is cis-trans isomerism change in molecule so that material becomes another kind of transconfiguration from cis-structure, the photophysical property of material with
Change.Then after the process such as heating, solvent, the structure of molecule can revert to original, realize what fluorescence color changed
Reversibility.
Photochromic pigment is added in transparent resin, photochromic material is made, can be used for sunglass lens, the country exists
Light-sensitive sunglasses aspect has started to application.Photochromic pigment and high polymer are linked together, can be made with photochromic
The material of energy, it is very promising in photoelectric technology and light controlling device.It is thin transparent plastic can be made with photochromic material
Film, is attached to or is embedded on vehicle glass or glass pane, and sun exposure changes colour at once, makes daylight not dazzling, protects vision, it is ensured that peace
Entirely, and can play a part of to adjust indoor and vapour vehicle interior temperature；With molten people or can be mixed in plastic sheeting, as agricultural greenhouse
Agricultural film, increases the yield of agricultural product, veterinary antibiotics etc..Another important purposes is used as military hidden material, for example
The clothing of army personnel and the outer housing of fight weapon etc..
In recent years, photochromic material is used for into optical information storage, light regulation and control, photoswitch, optical device materials, optical information
The fields such as genetic material, modifying gene chip material are subject to the extensive concern in global range.China's researcher utilizes Novel hot
Wen Dings spirooxazine material to carry out erasable high-density optical information Store research aspect and makes further progress.They design synthesis
A kind of Xin Xing Luo oxazine molecule SOFC with good open loop body heat stability.This kind of novel photochromic material is deposited for information
Storage shows good stability, and can enter being repetitively written and wiping for row information, and can be applicable to based on two-photon skill
The multi-layer three-dimension high-density optical information Store of art, shows very strong application prospect.
(3) content of the invention
First purpose of the present invention is to provide a kind of stilbene that fluorescence transformation performance is responded with reversible photostimulation
Derivant, it has, and contrast is high, can recover, flexible bending the characteristics of.
Second object of the present invention is to provide a kind of method for simply preparing the diphenyl ethylene derivatives.
Third object of the present invention is that the diphenyl ethylene derivatives are used as into reversible photostimulation fluorescence transition material.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of diphenyl ethylene derivatives shown in formula (I)：
Described diphenyl ethylene derivatives are in the case of by photostimulation because molecule conformation transition causes fluorescent emission to become
Change and reversible photostimulation is presented and responds change in fluorescence phenomenon, i.e., be converted to from a kind of fluorescent emission under extraneous photostimulation various glimmering
Light emission state, the material Jing after photostimulation can return to not stimulated front fluorescent state by certain means.
Specifically, described diphenyl ethylene derivatives by natural lighting effect after, under uviol lamp by illumination before
Blue-fluorescence is transformed into yellow-green fluorescence, high with contrast, the characteristics of fluorescence color transformation is more.
The fluorescence transformation performance of described diphenyl ethylene derivatives (I) can voluntarily be recovered by mode of heating, such as outside
After boundary's natural lighting effect, described diphenyl ethylene derivatives (I) become light under uviol lamp by the blue-fluorescence before non-illumination
Yellow-green fluorescence according to after, then described material is carried out into heat treatment, described material can voluntarily return to original under uviol lamp
The blue-fluorescence come before non-illumination.
In addition, the characteristics of fluorescence transformation performance of described diphenyl ethylene derivatives (I) also has flexible bending：Passing through
External force is acted on, and with crystalline state flexible bending, is removed external force and is recovered automatically to original state.
Present invention also offers a kind of preparation method of diphenyl ethylene derivatives shown in formula (I), described preparation method is pressed
Following steps are carried out：
(1) p-bromobenzaldehyde and the reaction productions of 4- boric acid triphenylamine Jing Suzuki shown in formula (III) by shown in formula (II)
(IV) intermediate of triphenylamine class shown in；
(2) triphenylamine class intermediate shown in formula (IV) again with 4- methoxyphenyls diethyl phosphate Jing shown in formula (V)
Horner-Wadsworth-Emmons reactions generate diphenyl ethylene derivatives shown in formula (I).
Specifically, the preparation method of diphenyl ethylene derivatives shown in a kind of formula (I), described preparation method is as follows
Carry out：
(1) p-bromobenzaldehyde shown in formula (II), 4- boric acid triphenylamines, palladium shown in formula (III) are dissolved in into deionization
Water/isopropanol volume ratio 1：In 1.5～3 mixed solvent, tripotassium phosphate is added, 10～15min of room temperature reaction is used afterwards full
Reaction is quenched with saline solution, reactant liquor is post-treated to obtain triphenylamine class intermediate shown in formula (IV)；
P-bromobenzaldehyde shown in the formula (II) and 4- boric acid triphenylamines, palladium, the throwing of tripotassium phosphate shown in formula (III)
The ratio of the amount of material matter is 1：0.8～2：0.1～0.3：1.2～2；
(2) under the conditions of lucifuge, triphenylamine class intermediate shown in the formula (IV) that step (1) is obtained and 4- first shown in formula (V)
Phenyl diethyl phosphate is dissolved in tetrahydrofuran A, is cooled to -10～0 DEG C, add potassium tert-butoxide and insulation reaction 10～
20min, then clear-cutting forestland is to 8～16h of room temperature reaction, be quenched reaction with saturated aqueous common salt afterwards, and reactant liquor is post-treated
To diphenyl ethylene derivatives shown in formula (I)；
The thing that feeds intake of triphenylamine class intermediate and 4- methoxyphenyl diethyl phosphates shown in formula (V) shown in the formula (IV)
The ratio of the amount of matter is 1：0.5～2.0；The potassium tert-butoxide feeds intake mass ratio for 1 with triphenylamine class intermediate shown in formula (IV)：
5～20.
In the preparation method step (1), recommend the volumetric usage of the mixed solvent (in terms of wherein isopropanol) with formula
(II) quality of p-bromobenzaldehyde shown in is calculated as 20～35mL/g.
In step (1), the method for the reactant liquor post processing is：Saturated aqueous common salt is quenched after reaction, reactant liquor acetic acid
Ethyl ester is extracted, and collects organic faciess, uses saturated common salt water washing, anhydrous magnesium sulfate to be dried, and is filtered, and takes filtrate reduced in volume, remaining
Thing carries out silica gel column chromatography separation, with petrol ether/ethyl acetate volume ratio 30：1 mixed liquor eluting, collects and contains target compound
Eluent, be evaporated off after solvent be dried, obtain final product triphenylamine class intermediate shown in formula (IV).
In step (2), preferably the volumetric usage of the tetrahydrofuran A is with the quality of triphenylamine class intermediate shown in formula (IV)
It is calculated as 15～30mL/g.The feeding mode for recommending the potassium tert-butoxide is：Potassium tert-butoxide is dissolved in tetrahydrofuran B and obtains tertiary fourth
Potassium alkoxide solution, then add as a solution in reaction system；It is preferred that the volumetric usage of the tetrahydrofuran B is with potassium tert-butoxide
Quality is calculated as 35～50mL/g.
It should be noted that term " tetrahydrofuran A ", " tetrahydrofuran B ", without special implication, are referred both on ordinary meaning
Tetrahydrofuran, be labeled as " A ", " B " and be only intended to distinguish the tetrahydrofuran used in different operating step.
In step (2), the method for the reactant liquor post processing is：Saturated aqueous common salt is quenched after reaction, reactant liquor acetic acid
Ethyl ester is extracted, and collects organic faciess, uses saturated common salt water washing, anhydrous magnesium sulfate to be dried, and is filtered, and takes filtrate reduced in volume, remaining
Thing carries out silica gel column chromatography separation, with petrol ether/ethyl acetate volume ratio 15：1 mixed liquor eluting, collects and contains target compound
Eluent, be evaporated off after solvent be dried, obtain final product diphenyl ethylene derivatives shown in formula (I).
The present invention passes through nuclear magnetic resonance, NMR (NMR), gas chromatography mass spectrometry (GC-MS), elemental analysis diphenyl ethylene derivatives
(I) crystal structure of diphenyl ethylene derivatives (I), is characterized by single crystal X-ray diffraction, by differential scanning calorimetry
(DSC) its structure change temperature transition point and crystal property are tested, material surface pattern is observed by scanning electron microscope (SEM), led to
Cross the photophysical property of uv-visible absorption spectroscopy and fluorescence spectrum characterization material.
There is diphenyl ethylene derivatives (I) of the present invention reversible photostimulation fluorescence to change performance, therefore can be used as one kind
Reversible photostimulation fluorescence transition material, is particularly used in and prepares reversible photostimulation response fluorescence transformation device, for example：The hexichol
The crystalline solid or powder solid of ethene derivatives (I), can be by existing film technique with the side of the coated film in substrate
Formula is obtained with photostimulation response performance by way of being doped in the polymer such as polymethyl methacrylate
Fluorescence changes device.
Compared with prior art, the beneficial effects of the present invention is：The invention provides a kind of have photostimulation response glimmering
Light changes the organic molecule diphenyl ethylene derivatives (I) of performance, the photostimulation response fluorescence of the diphenyl ethylene derivatives (I)
Transformation performance has that contrast is high, can recover, flexible bending the characteristics of, and its synthetic method is simple, glimmering as reversible photostimulation
Light transition material prepares device conveniently, can be applicable to the fields such as fluorescent switch, sensor, storage and display.
(4) illustrate
Fig. 1 be in the embodiment of the present invention 5,6 diphenyl ethylene derivatives (I) before and after light stimulation-heat treatment in uviol lamp
Under photo；
Fig. 2 be (straight) before diphenyl ethylene derivatives (I) flexible bending in the embodiment of the present invention 7, in (bending), rear (extensive
Fluorescence photo again)；
Fig. 3 is the scanning electron microscope of (recovery) after diphenyl ethylene derivatives (I) flexible bending in the embodiment of the present invention 7
Photo.
(5) specific embodiment
Below technical scheme is described further with specific embodiment, but protection scope of the present invention is not limited
In this.
The illumination wavelength that diphenyl ethylene derivatives (I) and fluorescence converter are subject in the embodiment of the present invention about 190～
Between 400nm.
Embodiment 1
By p-bromobenzaldehyde (II) 0.92g (5mmol), 4- boric acid triphenylamine (III) 1.88g (6.5mmol), palladium
0.11g (0.5mmol) is dissolved in deionized water 10mL/ isopropanol 25mL mixed solvents, adds tripotassium phosphate 1.27g (6mmol).
10min is reacted in air ambient room temperature.After reaction saturated aqueous common salt is quenched, it is extracted with ethyl acetate (50mL × 3 time), closes
And organic faciess, use saturated common salt water washing, anhydrous magnesium sulfate to be dried.Filter, filtrate Jing concentrating under reduced pressure, residue silica gel column layer
Analysis is separated, with the volume ratio of petrol ether/ethyl acetate as 30：1 mixed solvent eluting, collects the eluting containing target compound
Liquid, is evaporated off being dried after solvent, obtains yellow powder product triphenylamine class intermediate (IV) 1.56g, and yield is 90%.The knot of material
Structure confirms to be characterized as below：1H NMR (500MHz, DMSO) δ 10.03 (s, 1H), 7.97 (d, J=8.4Hz, 2H), 7.88 (d, J=
8.3Hz,2H),7.75–7.69(m,2H),7.40–7.33(m,4H),7.15–7.07(m,6H),7.06–7.02(m,2H).MS
m/z:349.2。
Embodiment 2
By p-bromobenzaldehyde (II) 0.92g (5mmol), 4- boric acid triphenylamine (III) 1.56g (4mmol), palladium
0.11g (0.5mmol) is dissolved in deionized water 10mL/ isopropanol 25mL mixed solvents, adds tripotassium phosphate 1.27g (6mmol).
10min is reacted in air ambient room temperature.After reaction saturated aqueous common salt is quenched, it is extracted with ethyl acetate (50mL × 3 time), closes
And organic faciess, use saturated common salt water washing, anhydrous magnesium sulfate to be dried.Filter, filtrate Jing concentrating under reduced pressure, residue silica gel column layer
Analysis is separated, with the volume ratio of petrol ether/ethyl acetate as 30：1 mixed solvent eluting, collects the eluting containing target compound
Liquid, is evaporated off being dried to obtain yellow powder product triphenylamine class intermediate (IV) 1.27g after solvent, and yield is 68%.
Embodiment 3：
Weigh triphenylamine intermediate (IV) 1.74g (5mmol), 4- methoxyphenyl diethyl phosphates (V) of above-mentioned synthesis
2.58g (10mmol) is dissolved in 45mL tetrahydrofurans and obtains mixed solution.Potassium tert-butoxide 0.11g (1mmol) is dissolved in into 5mL tetrahydrochysenes
In furan, and the tetrahydrofuran solution of gained potassium tert-butoxide is slowly added in above-mentioned mixed solution at 0 DEG C, insulated and stirred
Reaction 15min after gradually recovery temperature to room temperature, and be stirred at room temperature reaction 8h, add saturated aqueous common salt terminating reaction.So
After be extracted with ethyl acetate (45mL × 3), merge organic faciess, use saturated common salt water washing, anhydrous magnesium sulfate is dried, and filters, filter
Liquid Jing concentrating under reduced pressure, residue is separated with silica gel column chromatography, with the volume ratio of petrol ether/ethyl acetate as 15：1 mixed solvent
Eluting, collects the eluent containing target compound, is evaporated off being dried after solvent, obtains pale yellow powder product diphenyl ethylene derivatives
(I) 1.35g, yield is 60%.Reaction and post processing whole process lucifuge.The structural confirmation of material is characterized as below：1H NMR
(500MHz, DMSO) δ 7.64 (d, J=4.6Hz, 4H), 7.56 (t, J=5.8Hz, 2H), 7.38-7.34 (m, 2H), 7.33
(dd, J=10.1,2.7Hz, 4H), 7.23 (t, J=13.3Hz, 2H), 7.10 (dd, J=6.3,0.9Hz, 2H), 7.08-7.06
(m, 6H), 6.96 (d, J=8.8Hz, 2H), 3.78 (d, J=7.5Hz, 3H) .MS m/z:453.2.
Embodiment 4
Weigh triphenylamine class intermediate (IV) 2.80g (8mmol), the 4- methoxyphenyl diethyl phosphates of above-mentioned synthesis
(V) 1.29g (5mmol) is dissolved in 50mL tetrahydrofurans and obtains mixed solution.Potassium tert-butoxide 0.14 (1.2mmol) is dissolved in into 5mL
In tetrahydrofuran, and the tetrahydrofuran solution of gained potassium tert-butoxide is slowly added in above-mentioned mixed solution at 0 DEG C, is incubated
Gradually recovery temperature, to room temperature, and is stirred at room temperature reaction 8h after stirring reaction 15min, adds saturated aqueous common salt to terminate anti-
Should.Then it is extracted with ethyl acetate (45mL × 3 time), merges organic faciess, uses saturated common salt water washing, anhydrous magnesium sulfate to be dried,
Filter, filtrate Jing concentrating under reduced pressure, residue is separated with silica gel column chromatography, with the volume ratio of petrol ether/ethyl acetate as 15：1
Mixed solvent eluting, collects the eluent containing target compound, is evaporated off being dried after solvent, obtains pale yellow powder product hexichol second
Ene derivative (I) 0.89g, yield is 40%.
Embodiment 5
The present invention diphenyl ethylene derivatives pressed powder (I) in uviol lamp exhibits blue fluorescence, when this blue colour fluorescent powder
End is exposed to recrystallization fluorescence color in illumination and is changed into yellow-green fluorescence by original blue-fluorescence.
Embodiment 6
The diphenyl ethylene derivatives pressed powder (I) of the present invention is in uviol lamp exhibits blue fluorescence, the fluorescence face after illumination
Color is changed into yellow green, is positioned over heat treatment in 80 DEG C of baking oven again afterwards, finds the sample obtained after heat treatment in uviol lamp
Lower fluorescence color reverts to original blue-fluorescence.
Embodiment 7
Diphenyl ethylene derivatives pressed powder (I) recrystallization of the present invention, fluorescence color is yellow green after illumination, afterwards
Its crystal is independently chosen into one, it is found that it can carry out flexible bending, to be removed and recover straight form after external force, show crystal
Can be flexible luminous.
Claims (10)
1. diphenyl ethylene derivatives shown in a kind of formula (I)：
2. the preparation method of diphenyl ethylene derivatives shown in a kind of formula as claimed in claim 1 (I), it is characterised in that described
Preparation method carry out as follows：
(1) p-bromobenzaldehyde and the reactions of 4- boric acid triphenylamine Jing Suzuki shown in formula (III) generate formula (IV) by shown in formula (II)
Shown triphenylamine class intermediate；
(2) triphenylamine class intermediate shown in formula (IV) again with 4- methoxyphenyls diethyl phosphate Jing Horner- shown in formula (V)
Wadsworth-Emmons reaction generates diphenyl ethylene derivatives shown in formula (I)；
3. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 2, it is characterised in that described system
Preparation Method is carried out as follows：
(1) p-bromobenzaldehyde shown in formula (II), 4- boric acid triphenylamines, palladium shown in formula (III) are dissolved in into deionized water/different
Propanol volume ratio 1：In 1.5～3 mixed solvent, tripotassium phosphate is added, 10～15min of room temperature reaction is eaten afterwards with saturation
Saline is quenched reaction, and reactant liquor is post-treated to obtain triphenylamine class intermediate shown in formula (IV)；
The thing that feeds intake of p-bromobenzaldehyde shown in the formula (II) and 4- boric acid triphenylamines, palladium, tripotassium phosphate shown in formula (III)
The ratio of the amount of matter is 1：0.8～2：0.1～0.3：1.2～2；
(2) under the conditions of lucifuge, triphenylamine class intermediate shown in the formula (IV) that step (1) is obtained and 4- methoxyl groups shown in formula (V)
Phosphenylic acid diethylester is dissolved in tetrahydrofuran A, is cooled to -10～0 DEG C, adds potassium tert-butoxide and 10～20min of insulation reaction,
Then clear-cutting forestland is quenched reaction with saturated aqueous common salt afterwards to 8～16h of room temperature reaction, and reactant liquor is post-treated to obtain formula (I)
Shown diphenyl ethylene derivatives；
Triphenylamine class intermediate shown in the formula (IV) and the material that feeds intake of 4- methoxyphenyl diethyl phosphates shown in formula (V)
The ratio of amount is 1：0.5～2.0；The potassium tert-butoxide feeds intake mass ratio for 1 with triphenylamine class intermediate shown in formula (IV)：5～
20。
4. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 3, it is characterised in that step (1)
In, the volumetric usage of isopropanol is calculated as 20～35mL/g with the quality of p-bromobenzaldehyde shown in formula (II) in the mixed solvent.
5. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 3, it is characterised in that step (1)
In, the method for the reactant liquor post processing is：Saturated aqueous common salt is quenched after reaction, and reactant liquor is extracted with ethyl acetate, and collection has
Machine phase, uses saturated common salt water washing, anhydrous magnesium sulfate to be dried, and filters, and takes filtrate reduced in volume, and residue carries out silica gel column chromatography
Separate, with petrol ether/ethyl acetate volume ratio 30：1 mixed liquor eluting, collects the eluent containing target compound, is evaporated off molten
It is dried after agent, obtains final product triphenylamine class intermediate shown in formula (IV).
6. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 3, it is characterised in that step (2)
In, the volumetric usage of the tetrahydrofuran A is calculated as 15～30mL/g with the quality of triphenylamine class intermediate shown in formula (IV).
7. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 3, it is characterised in that the tertiary fourth
The feeding mode of potassium alcoholate is：Potassium tert-butoxide is dissolved in tetrahydrofuran B and obtains potassium tert-butoxide solution, then added as a solution
In reaction system；The volumetric usage of the tetrahydrofuran B is calculated as 35～50mL/g with the quality of potassium tert-butoxide.
8. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 3, it is characterised in that step (2)
In, the method for the reactant liquor post processing is：Saturated aqueous common salt is quenched after reaction, and reactant liquor is extracted with ethyl acetate, and collection has
Machine phase, uses saturated common salt water washing, anhydrous magnesium sulfate to be dried, and filters, and takes filtrate reduced in volume, and residue carries out silica gel column chromatography
Separate, with petrol ether/ethyl acetate volume ratio 15：1 mixed liquor eluting, collects the eluent containing target compound, is evaporated off molten
It is dried after agent, obtains final product diphenyl ethylene derivatives shown in formula (I).
9. application of the diphenyl ethylene derivatives (I) as claimed in claim 1 as reversible photostimulation fluorescence transition material.
10. diphenyl ethylene derivatives (I) as claimed in claim 1 as reversible photostimulation fluorescence transition material prepare it is reversible
Photostimulation response fluorescence changes the application in device, and the method for the application is：Stilbene described in claim 1 is derived
The crystalline solid or powder solid of thing (I), by way of existing film technique is with the coated film in substrate or passes through
The mode being doped in polymethyl methacrylate is obtained the transformation device of the fluorescence with photostimulation response performance.
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