CN105111102A - Stilbene nitrile derivative and preparation method and application thereof - Google Patents
Stilbene nitrile derivative and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 22
- USLPZCOPYRKTGY-UHFFFAOYSA-N 2-(2-phenylethenyl)benzonitrile Chemical class N#CC1=CC=CC=C1C=CC1=CC=CC=C1 USLPZCOPYRKTGY-UHFFFAOYSA-N 0.000 title abstract 5
- 239000000463 material Substances 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 15
- 230000002441 reversible effect Effects 0.000 claims abstract description 15
- 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 14
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims abstract description 3
- -1 Toluylene nitrile Chemical class 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 150000001412 amines Chemical class 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000010898 silica gel chromatography Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 2
- XDJAAZYHCCRJOK-UHFFFAOYSA-N 4-methoxybenzonitrile Chemical compound COC1=CC=C(C#N)C=C1 XDJAAZYHCCRJOK-UHFFFAOYSA-N 0.000 abstract 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 230000008859 change Effects 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NZHFAJNUQOLBCV-BGABXYSRSA-N COc1ccc(/C=C(/c(cc2)ccc2-c(cc2)ccc2N(c2ccccc2)c2ccccc2)\C#N)cc1 Chemical compound COc1ccc(/C=C(/c(cc2)ccc2-c(cc2)ccc2N(c2ccccc2)c2ccccc2)\C#N)cc1 NZHFAJNUQOLBCV-BGABXYSRSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008876 conformational transition Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a stilbene nitrile derivative shown in formula , which is prepared by the following steps: carrying out Suzuki reaction on p-bromobenzaldehyde shown in a formula (II) and 4-triphenylamine borate shown in a formula (III) to generate a triphenylamine intermediate shown in a formula (IV); carrying out Knoevenagel condensation reaction on the triphenylamine intermediate shown in the formula (IV) and 4-methoxy benzonitrile shown in the formula (V) to generate the stilbene nitrile derivative; the stilbene nitrile derivative has the characteristics of high contrast, self-recovery and good cyclicity, and the synthesis method is simple, and the stilbene nitrile derivative can be used as a reversible force-stimulated fluorescent switch material in the fields of fluorescent switches, sensors, storage, display and the like.
Description
(1) technical field
The present invention relates to a kind of Toluylene nitrile derivative and preparation method thereof and stimulate the application of fluorescent switch material as reversible force, be applicable to sensor, false proof, store and indicating meter.
(2) background technology
The phenomenon that fluorescence color changes when 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 subject to stimulates, intramolecular action power changes, and causes packing of molecules mode to change, and make material become in order another kind of or partial order, disordered structure from a kind of ordered structure, the photophysical property of material changes thereupon.Then after the process such as heating, solvent, the accumulation mode of molecule can revert to original, realizes the reversibility of fluorescence color change.At present this few class of small molecules, oligopolymer, liquid crystal and doped polymer is mainly concentrated on to the research with piezallochromy phenomenon, the state such as the U.S., Japan scientist after deliberation relatively go deep into.
(the J.Am.Chem.Soc. such as YasuhikoSagara, 2007,129:1520 – 1521) synthesize and found to have the pyrene derivatives that four N-hexyl paraphenylene terephthalamide bases are formed, when being subject to power and stimulating, material becomes green fluorescence by blue-fluorescence originally, again can become blue-fluorescence after heating.This is due to phenyl ring between molecule and the change of the change of torsion(al)angle and the ratio of clustered pattern and hydrogen bond between pyrene ring, finally makes the fluorescence color of material change.
(the AsianJ.Chem. such as Chi Zhenguo, 2011,6 (3): 808-811) tetraphenyl ethylene derivative has been synthesized, when material is subject to power stimulation, the fluorescence color of solid becomes yellow by original green, reverts to original strong green fluorescence after heat treated.This be due to aromatic ring between space steric effect make all or part of space structure distortion of molecule.Space structure due to distortion makes pi-pi bond reaction force attenuation, and after forces are applied, molecular conformation complanation or molecular slippage, conjugated degree is increased, and fluorescence color changes.
But at present the material fluorescence color of the reversible piezochromic phenomenon of report mainly under External Force Acting changes, and the fluorescence color of rare pressure controllable and the change of intensity; In addition, realize reversible temperature and be generally greater than 100 DEG C (J.Am.Chem.Soc.2010,132,13675 – 13683), thus significantly limit the application of this type of material.Under controlled external force stimulates, realize the controlled transformation of fluorescence color and recover voluntarily after removal external force stimulates, in actual life, there is using value widely.
(3) summary of the invention
First object of the present invention is to provide a kind of Toluylene nitrile derivative with reversible force stimuli responsive fluorescent switch performance, its have contrast gradient high, can recover voluntarily, feature that cyclicity is good.
Second object of the present invention is to provide the method for the described Toluylene nitrile derivative of a kind of simple preparation.
3rd object of the present invention is that described Toluylene nitrile derivative stimulates the application of fluorescent switch material in preparation reversible force stimuli responsive fluorescent switch device as reversible force.
For achieving the above object, the present invention adopts following technical scheme:
Toluylene nitrile derivative shown in a kind of formula (I):
Described Toluylene nitrile derivative is when stressed, reversible force stimuli responsive Enhancement of Fluorescence is presented because molecule conformation transition causes fluorescence intensity change, that is: external force stimulate under be converted to multiple fluorescent emission state from a kind of fluorescent emission, through the post-stimulatory material of external force can return to not stressed before fluorescent state.
Concrete, described Toluylene nitrile derivative is after being subject to the effect of 1atm ~ 12.09GPa pressure, and the fluorescent orange become pressurized by the green fluorescence before not pressing under ultraviolet lamp after is until red fluorescence, and have contrast gradient high, fluorescence color changes many features.
The fluorescent switch performance of described Toluylene nitrile derivative (I) is recovered voluntarily by release mode, such as after the effect of 1atm ~ 12.09GPa pressure, fluorescent orange after described Toluylene nitrile derivative (I) becomes pressurized by the green fluorescence before not pressing under ultraviolet lamp is until red fluorescence, again described Toluylene nitrile derivative is carried out 12.09GPa ~ 1atm release effect, it can return to the green fluorescence before originally not exerting pressure voluntarily under ultraviolet lamp.
In addition, the fluorescent switch performance of described Toluylene nitrile derivative (I) also has the feature of pressure controllable: after the power stimulation-self-recoverage circulation of quantitative pressure, have good color transition.
Present invention also offers the preparation method of the Toluylene nitrile derivative shown in a kind of formula (I), described preparation method for: the 4-boric acid triphenylamine shown in the p-bromobenzaldehyde shown in formula (II) and formula (III) reacts the triphen amine intermediate shown in production (IV) through Suzuki; Triphen amine intermediate shown in formula (IV) again with the 4-methoxy cyanophenyl shown in formula (V) through the Toluylene nitrile derivative shown in Knoevenagel condensation reaction production (I).
Concrete, the preparation method of the Toluylene nitrile derivative shown in a kind of formula (I), described preparation method carries out as follows:
(1), under nitrogen protection, shown in formula (II), 4-boric acid triphenylamine shown in p-bromobenzaldehyde and formula (III) is in organic solvent, at catalyst P d [P (C
6h
5)
3]
4under the effect of (tetrakis triphenylphosphine palladium) and alkaline matter, back flow reaction 16 ~ 48h, reaction solution is through aftertreatment afterwards, obtains triphen amine intermediate shown in formula (IV);
Described organic solvent is the mixed solution of toluene/tetrahydrofuran (THF) volume ratio 1:0.5 ~ 1; Described alkaline matter is sodium carbonate or salt of wormwood; 4-boric acid triphenylamine, catalyst P d [P (C shown in p-bromobenzaldehyde and formula (III) shown in described formula (II)
6h
5)
3]
4, alkaline matter the ratio of the amount of substance that feeds intake be 1:0.8 ~ 1.2:0.01 ~ 0.03:1.2 ~ 2;
(2) in solvent chromatographic ethanol, shown in the formula (IV) that step (1) obtains, 4-methoxy cyanophenyl shown in triphen amine intermediate and formula (V) is under the katalysis of sodium methylate, in room temperature reaction 3 ~ 5h, in reaction system, solid is separated out, filter, after filter cake washing, drying, obtain Toluylene nitrile derivative shown in formula (I);
Shown in described formula (IV), shown in triphen amine intermediate and formula (V), the ratio of the amount of substance that feeds intake of 4-methoxy cyanophenyl is 0.8 ~ 1.2:1; Shown in described sodium methylate and formula (IV), the ratio of the amount of substance that feeds intake of triphen amine intermediate is 1:5 ~ 20.
In preparation method's step (1) of the present invention, the volumetric usage of described organic solvent (toluene in wherein) is recommended to count 20 ~ 35mL/g with the quality of p-bromobenzaldehyde formula (II) Suo Shi.
In step (1), the method of described reaction solution aftertreatment is: after reaction terminates, reaction solution is cooled to room temperature, with chloroform extraction after concentrating under reduced pressure, extraction gained organic phase is respectively through saturated aqueous sodium carbonate washing, saturated common salt water washing, anhydrous magnesium sulfate drying, filtration, get filtrate and carry out concentrating under reduced pressure, gained enriched material carries out silica gel column chromatography separation, with the mixed solution of sherwood oil/chloroform volume ratio 150:1 for eluent, collect the elutriant containing target compound, steaming desolventizes rear drying, obtains triphen amine intermediate shown in formula (IV).
In step (2), the volumetric usage of described solvent chromatographic ethanol is recommended to count 30 ~ 50mL/g with the quality of 4-methoxy cyanophenyl.
Concrete optimum, recommend the preparation method of the Toluylene nitrile derivative shown in described formula (I) to be:
(1) under nitrogen protection, by 4-boric acid triphenylamine, catalyst P d [P (C shown in p-bromobenzaldehyde formula (II) Suo Shi, formula (III)
6h
5)
3]
4be dissolved in the mixed solution of toluene/tetrahydrofuran (THF) volume ratio 1:0.5 ~ 1, then 2.0mol/L aqueous sodium carbonate or 2.0mol/L wet chemical is added, back flow reaction 16 ~ 48h, reaction solution is cooled to room temperature afterwards, with chloroform extraction after concentrating under reduced pressure, extraction gained organic phase is washed through saturated aqueous sodium carbonate respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, get filtrate and carry out concentrating under reduced pressure, gained enriched material carries out silica gel column chromatography separation, with the mixed solution of sherwood oil/chloroform volume ratio 150:1 for eluent, collect the elutriant containing target compound, steaming desolventizes rear drying, obtain triphen amine intermediate shown in formula (IV), 4-boric acid triphenylamine, catalyst P d [P (C shown in p-bromobenzaldehyde and formula (III) shown in described formula (II)
6h
5)
3]
4, sodium carbonate or salt of wormwood the ratio of the amount of substance that feeds intake be 1:0.8 ~ 1.2:0.01 ~ 0.03:1.2 ~ 2,
(2) shown in the formula (IV) step (1) obtained, shown in triphen amine intermediate and formula (V), 4-methoxy cyanophenyl is dissolved in chromatographic ethanol, then sodium methylate is added, react to there being precipitation to generate under room temperature, staticly settle under being placed in-20 ~ 25 DEG C of conditions again, separate out solid particulate, generate until no longer include new solid particulate, reaction system is filtered, dry after filter cake absolute ethanol washing, obtain Toluylene nitrile derivative shown in target product formula (I).
The present invention is by nucleus magnetic resonance (NMR), gas chromatography mass spectrometry (GC-MS), elemental analysis Toluylene nitrile derivative (I), the crystalline structure of Toluylene nitrile derivative (I) is characterized by X-ray diffraction (XRD), its structural changes temperature transition point and crystal property is tested by differential scanning calorimetry (DSC), observe its surface topography by scanning electron microscope (SEM), characterize its photophysical property by uv-visible absorption spectroscopy and fluorescence spectrum.
Toluylene nitrile derivative of the present invention (I) has reversible force stimulates fluorescent switch performance, therefore can be used as a kind of reversible force stimulation fluorescent switch material, can specifically for preparation reversible force stimuli responsive fluorescent switch device, such as, the crystalline solid of described Toluylene nitrile derivative (I) or powder solid, the mode applying Toluylene nitrile derivative film by existing film technique in substrate obtains the fluorescent switch device with power stimuli responsive performance.
Describedly in substrate, apply the concrete grammar of Toluylene nitrile derivative film such as by existing film technique: Toluylene nitrile derivative be dissolved in methylene dichloride, being prepared into Toluylene nitrile derivative concentration is 10
-2the dichloromethane solution of mol/L, be positioned over diameter be 0.2mm and be connected with air compressor spray gun in, by spray gun, described solution is sprayed clean quartz plate, treats solvent evaporates, namely obtain Toluylene nitrile derivative film.
Compared with prior art, beneficial effect of the present invention is: the organic molecule Toluylene nitrile derivative (I) that the invention provides a kind of power of having stimuli responsive fluorescent switch performance, the power stimuli responsive fluorescent switch performance of described Toluylene nitrile derivative (I) have contrast gradient high, can recover voluntarily, feature that cyclicity is good, and synthetic method is simple, it stimulates fluorescent switch material to can be applicable to the fields such as fluorescent switch, sensor, storage and display as reversible force.
(4) accompanying drawing explanation
Fig. 1 is Toluylene nitrile derivative pressed powder (I) photo under ultraviolet lamp and fluorescence spectrum thereof after normal pressure grinding in the embodiment of the present invention 5;
Fig. 2 be in the embodiment of the present invention 6 Toluylene nitrile derivative pressed powder (I) after controllable ration force, and the photo after controllable ration release under ultraviolet lamp;
Fig. 3 be in the embodiment of the present invention 6 Toluylene nitrile derivative pressed powder (I) after controllable ration force, and the fluorescence spectrum after controllable ration release;
Fig. 4 is the power stimulation-self-recoverage circulation Raman spectrum performance of Toluylene nitrile derivative (I) in the embodiment of the present invention 7.
(5) embodiment
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto.
The reactive force that in the embodiment of the present invention, Toluylene nitrile derivative (I) and fluorescent switch device are subject to is between 1atm ~ 12.09GPa.
Embodiment 1
P-bromobenzaldehyde (II) 0.92g (5mmol), 4-boric acid triphenylamine (III) 1.73g (6mmol), tetrakis triphenylphosphine palladium 0.11g (0.1mmol) are dissolved in toluene 50mL/ tetrahydrofuran (THF) 30mL mixing solutions, add aqueous sodium carbonate (2.0M, 3mL).Under nitrogen atmosphere, 90 DEG C of reaction 36h are warming up to.Reaction solution cools, after removing solvent under reduced pressure, secondary with chloroform extraction (50mL × 3), merges organic phase, respectively through saturated aqueous sodium carbonate and saturated common salt water washing, finally uses anhydrous magnesium sulfate drying.Filter, filtrate is through concentrating under reduced pressure, residuum silica gel column chromatography is separated, eluent is the volume ratio of sherwood oil/chloroform is the mixed solvent of 150/1, collect the elutriant containing target compound, dry after removing solvent under reduced pressure, obtain yellow powder product triphen amine intermediate (IV) 1.16g, yield is 75%.The structural confirmation of material characterizes as follows:
1hNMR (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) .MSm/z:349.2
Embodiment 2
P-bromobenzaldehyde (II) 0.92g (5mmol), 4-boric acid triphenylamine (III) 1.56g (4mmol), tetrakis triphenylphosphine palladium 0.16g (0.15mmol) are dissolved in toluene 40mL/ tetrahydrofuran (THF) 25mL mixing solutions, add aqueous sodium carbonate (2.0M, 3mL).Under nitrogen atmosphere, 90 DEG C of reaction 24h are warming up to.Reaction solution cools, and after removing solvent under reduced pressure, with chloroformic solution extraction (30mL × 3), merges organic phase, respectively through saturated aqueous sodium carbonate and saturated common salt water washing, finally uses anhydrous magnesium sulfate drying.Filter, filtrate is through concentrating under reduced pressure, residuum silica gel column chromatography is separated, eluent is the volume ratio of chloroform/sherwood oil is the mixed solvent of 150/1, collect the elutriant containing target compound, dry after removing solvent under reduced pressure, obtain yellow powder product triphen amine intermediate (IV) 1.31g, yield is 70%.
Embodiment 3:
Take triphen amine intermediate (IV) 4.19g (12mmol) of above-mentioned synthesis, 4-methoxy cyanophenyl (V) 1.33g (10mmol) and sodium methylate 0.06g (1mmol) to be dissolved in 30ml chromatographic ethanol.At room temperature stirring reaction 4h, termination reaction in time having a large amount of solid particulate to separate out.Then reaction system is put into-20 DEG C of refrigerator overnight, filter afterwards, filter cake, with ethanol rinse (50mL × 3), obtains orange powder after seasoning, i.e. target product toluylene nitrile derivative (I) 3.82g, and yield is 80%.The structural confirmation of material characterizes as follows:
1hNMR (500MHz, CDCl3): δ 7.93 (d, J=8.3Hz, 2H); 7.68 (t, J=16.2Hz, 2H); 7.64-7.61 (m, 2H); (7.52 d, J=8.3Hz, 2H); 7.44 (s, 1H); (7.29 t, J=7.6Hz, 4H); 7.10 (dd, J=47.4,5.5Hz, 8H); 6.99-6.95 (m, 2H); (3.86 s, 3H) .MSm/z:478.4
Embodiment 4
Take triphen amine intermediate (IV) 2.80g (8mmol) of above-mentioned synthesis, 4-methoxy cyanophenyl (V) 1.33g (10mmol) and sodium methylate 0.03g (0.5mmol) to be dissolved in 30ml chromatographically pure ethanol.At room temperature stirring reaction 3h, termination reaction in time having a large amount of solid particulate to separate out.Then reaction system is put into-20 DEG C of refrigerator overnight, filter afterwards, filter cake, with ethanol rinse (50mL × 3), obtains orange powder after seasoning, i.e. target product toluylene nitrile derivative (I) 3.06g, and yield is 80%.
Embodiment 5
Toluylene nitrile derivative pressed powder (I) 0.1g of the present invention spreads on quartz plate or is placed in mortar, strong green fluorescence is shown under ultraviolet lamp, obvious fluorescence variable color is there is not when being subject to key and scraping shearing force or pestle effect, removing external force, part of the force still keeps strong green fluorescence.
Embodiment 6
Toluylene nitrile derivative pressed powder (I) 0.1g of the present invention spreads over the ruby bottom surface of DAC instrument, be carry out in 1atm ~ 12.09GPa in static liquid pressure range, pressure effect controlled in real time, observe fluorescence color under ultraviolet lamp from the strong green red red shift to high wavelength, until become redness.Release gradually in 12.09GPa ~ 1atm pressure range, to find under ultraviolet lamp sample from redness gradually blue shift revert to original strong green fluorescence.
Embodiment 7
Stressed Toluylene nitrile derivative (I) will do not executed, the sample being depressed into 1atm is unloaded after pressurization causes 12.09GPa, Raman test is done under identical Variable Conditions, the Raman spectrum of both discoveries is almost overlapping consistent, and interpret sample has good reversible cycle performance and recycling performance.
Claims (9)
1. the Toluylene nitrile derivative shown in a formula (I):
2. the preparation method of Toluylene nitrile derivative shown in a formula as claimed in claim 1 (I), it is characterized in that, described preparation method for: the 4-boric acid triphenylamine shown in the p-bromobenzaldehyde shown in formula (II) and formula (III) reacts the triphen amine intermediate shown in production (IV) through Suzuki; Triphen amine intermediate shown in formula (IV) again with the 4-methoxy cyanophenyl shown in formula (V) through the Toluylene nitrile derivative shown in Knoevenagel condensation reaction production (I);
3. preparation method as claimed in claim 2, it is characterized in that, described preparation method carries out as follows:
(1), under nitrogen protection, shown in formula (II), 4-boric acid triphenylamine shown in p-bromobenzaldehyde and formula (III) is in organic solvent, at catalyst P d [P (C
6h
5)
3]
4with under the effect of alkaline matter, back flow reaction 16 ~ 48h, reaction solution is through aftertreatment afterwards, obtains triphen amine intermediate shown in formula (IV);
Described organic solvent is the mixed solution of toluene/tetrahydrofuran (THF) volume ratio 1:0.5 ~ 1; Described alkaline matter is sodium carbonate or salt of wormwood; 4-boric acid triphenylamine, catalyst P d [P (C shown in p-bromobenzaldehyde and formula (III) shown in described formula (II)
6h
5)
3]
4, alkaline matter the ratio of the amount of substance that feeds intake be 1:0.8 ~ 1.2:0.01 ~ 0.03:1.2 ~ 2;
(2) in solvent chromatographic ethanol, shown in the formula (IV) that step (1) obtains, 4-methoxy cyanophenyl shown in triphen amine intermediate and formula (V) is under the katalysis of sodium methylate, in room temperature reaction 3 ~ 5h, in reaction system, solid is separated out, filter, after filter cake washing, drying, obtain Toluylene nitrile derivative shown in formula (I);
Shown in described formula (IV), shown in triphen amine intermediate and formula (V), the ratio of the amount of substance that feeds intake of 4-methoxy cyanophenyl is 0.8 ~ 1.2:1; Shown in described sodium methylate and formula (IV), the ratio of the amount of substance that feeds intake of triphen amine intermediate is 1:5 ~ 20.
4. preparation method as claimed in claim 3, it is characterized in that, in step (1), the volumetric usage of the toluene in described organic solvent counts 20 ~ 35mL/g with the quality of p-bromobenzaldehyde formula (II) Suo Shi.
5. preparation method as claimed in claim 3, it is characterized in that, in step (1), the method of described reaction solution aftertreatment is: after reaction terminates, reaction solution is cooled to room temperature, with chloroform extraction after concentrating under reduced pressure, extraction gained organic phase is washed through saturated aqueous sodium carbonate respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, get filtrate and carry out concentrating under reduced pressure, gained enriched material carries out silica gel column chromatography separation, with the mixed solution of sherwood oil/chloroform volume ratio 150:1 for eluent, collect the elutriant containing target compound, steaming desolventizes rear drying, obtain triphen amine intermediate shown in formula (IV).
6. preparation method as claimed in claim 3, it is characterized in that, in step (2), the volumetric usage of described solvent chromatographic ethanol counts 30 ~ 50mL/g with the quality of 4-methoxy cyanophenyl.
7. preparation method as claimed in claim 3, it is characterized in that, described preparation method is:
(1) under nitrogen protection, by 4-boric acid triphenylamine, catalyst P d [P (C shown in p-bromobenzaldehyde formula (II) Suo Shi, formula (III)
6h
5)
3]
4be dissolved in the mixed solution of toluene/tetrahydrofuran (THF) volume ratio 1:0.5 ~ 1, then 2.0mol/L aqueous sodium carbonate or 2.0mol/L wet chemical is added, back flow reaction 16 ~ 48h, reaction solution is cooled to room temperature afterwards, with chloroform extraction after concentrating under reduced pressure, extraction gained organic phase is washed through saturated aqueous sodium carbonate respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, get filtrate and carry out concentrating under reduced pressure, gained enriched material carries out silica gel column chromatography separation, with the mixed solution of sherwood oil/chloroform volume ratio 150:1 for eluent, collect the elutriant containing target compound, steaming desolventizes rear drying, obtain triphen amine intermediate shown in formula (IV), 4-boric acid triphenylamine, catalyst P d [P (C shown in p-bromobenzaldehyde and formula (III) shown in described formula (II)
6h
5)
3]
4, sodium carbonate or salt of wormwood the ratio of the amount of substance that feeds intake be 1:0.8 ~ 1.2:0.01 ~ 0.03:1.2 ~ 2,
(2) shown in the formula (IV) step (1) obtained, shown in triphen amine intermediate and formula (V), 4-methoxy cyanophenyl is dissolved in chromatographic ethanol, then sodium methylate is added, react to there being precipitation to generate under room temperature, staticly settle under being placed in-20 ~ 25 DEG C of conditions again, separate out solid particulate, generate until no longer include new solid particulate, reaction system is filtered, dry after filter cake absolute ethanol washing, obtain Toluylene nitrile derivative shown in target product formula (I).
8. Toluylene nitrile derivative shown in formula (I) as claimed in claim 1 stimulates the application of fluorescent switch material in preparation reversible force stimuli responsive fluorescent switch device as a kind of reversible force, the method of described application is: crystalline solid or the powder solid of getting described Toluylene nitrile derivative, and the mode being applied Toluylene nitrile derivative film by existing film technique in substrate obtains the fluorescent switch device with power stimuli responsive performance.
9. apply as claimed in claim 8, it is characterized in that, the described method applying Toluylene nitrile derivative film by existing film technique in substrate is: Toluylene nitrile derivative be dissolved in methylene dichloride, being prepared into Toluylene nitrile derivative concentration is 10
-2the dichloromethane solution of mol/L, be positioned over diameter be 0.2mm and be connected with air compressor spray gun in, by spray gun, described solution is sprayed clean quartz plate, treats solvent evaporates, namely obtain Toluylene nitrile derivative film.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152973A (en) * | 2015-08-20 | 2015-12-16 | 浙江工业大学 | stilbene derivative and preparation method and application thereof |
| CN105294464A (en) * | 2015-08-20 | 2016-02-03 | 浙江工业大学 | Triphenylamine derivative and preparation method and application thereof |
| CN106278939A (en) * | 2016-08-11 | 2017-01-04 | 重庆大学 | The metachroic organic aggregate material of Fluorescence Increasing of one class Glassless |
| CN108530641A (en) * | 2018-02-01 | 2018-09-14 | 苏州大学 | A kind of supermolecule polymer and preparation method thereof based on alpha-cyano diphenylethyllene small molecule |
| CN109134396A (en) * | 2018-08-20 | 2019-01-04 | 浙江工业大学 | cyano diphenylethylene compound with stable Z/E configuration in excited state, and preparation method and application thereof |
| CN112482263A (en) * | 2020-11-12 | 2021-03-12 | 招商局重庆交通科研设计院有限公司 | Overload detection road surface and vehicle overload detection method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090161516A1 (en) * | 2005-05-05 | 2009-06-25 | Mempile Inc. | Methacrylate-bound photoismerizable chromophore, methods for its synthesis and of its intermediates |
| CN102911082A (en) * | 2012-06-08 | 2013-02-06 | 浙江工业大学 | Triphenylamine derivatives, and preparation method and application thereof |
| CN103086918A (en) * | 2012-12-29 | 2013-05-08 | 浙江工业大学 | Toluylene nitrile derivative with D-A structure and synthesis method and application thereof |
| CN103102286A (en) * | 2012-12-08 | 2013-05-15 | 浙江工业大学 | Triphenylamine derivatives as well as preparation method and application thereof |
| CN103641743A (en) * | 2013-12-09 | 2014-03-19 | 浙江工业大学 | Tristyrene nitrile derivative as well as preparation method and application thereof |
| CN103910652A (en) * | 2014-04-22 | 2014-07-09 | 安徽大学 | Method for aqueous phase synthesis of cyano-substituted styrene compound |
| EP2806018A1 (en) * | 2013-05-20 | 2014-11-26 | The Procter & Gamble Company | Encapsulates |
-
2015
- 2015-07-20 CN CN201510428702.4A patent/CN105111102B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090161516A1 (en) * | 2005-05-05 | 2009-06-25 | Mempile Inc. | Methacrylate-bound photoismerizable chromophore, methods for its synthesis and of its intermediates |
| CN102911082A (en) * | 2012-06-08 | 2013-02-06 | 浙江工业大学 | Triphenylamine derivatives, and preparation method and application thereof |
| CN103102286A (en) * | 2012-12-08 | 2013-05-15 | 浙江工业大学 | Triphenylamine derivatives as well as preparation method and application thereof |
| CN103086918A (en) * | 2012-12-29 | 2013-05-08 | 浙江工业大学 | Toluylene nitrile derivative with D-A structure and synthesis method and application thereof |
| EP2806018A1 (en) * | 2013-05-20 | 2014-11-26 | The Procter & Gamble Company | Encapsulates |
| CN103641743A (en) * | 2013-12-09 | 2014-03-19 | 浙江工业大学 | Tristyrene nitrile derivative as well as preparation method and application thereof |
| CN103910652A (en) * | 2014-04-22 | 2014-07-09 | 安徽大学 | Method for aqueous phase synthesis of cyano-substituted styrene compound |
Non-Patent Citations (1)
| Title |
|---|
| 肖锦平等: "3-苯基-7-氨基香豆素和香豆素类型荧光增白剂", 《染料与染色》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152973A (en) * | 2015-08-20 | 2015-12-16 | 浙江工业大学 | stilbene derivative and preparation method and application thereof |
| 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 |
| CN106278939A (en) * | 2016-08-11 | 2017-01-04 | 重庆大学 | The metachroic organic aggregate material of Fluorescence Increasing of one class Glassless |
| CN108530641A (en) * | 2018-02-01 | 2018-09-14 | 苏州大学 | A kind of supermolecule polymer and preparation method thereof based on alpha-cyano diphenylethyllene small molecule |
| CN108530641B (en) * | 2018-02-01 | 2021-06-18 | 苏州大学 | Supermolecule polymer based on alpha-cyano diphenyl ethylene micromolecules and preparation method thereof |
| CN109134396A (en) * | 2018-08-20 | 2019-01-04 | 浙江工业大学 | cyano diphenylethylene compound with stable Z/E configuration in excited state, and preparation method and application thereof |
| CN112482263A (en) * | 2020-11-12 | 2021-03-12 | 招商局重庆交通科研设计院有限公司 | Overload detection road surface and vehicle overload detection method |
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