CN103086918B - Toluylene nitrile derivative with D-A structure and synthesis method and application thereof - Google Patents
Toluylene nitrile derivative with D-A structure and synthesis method and application thereof Download PDFInfo
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- -1 Toluylene nitrile Chemical class 0.000 title claims abstract description 19
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 239000000463 material Substances 0.000 claims abstract description 18
- 230000002441 reversible effect Effects 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 claims description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- 238000010189 synthetic method Methods 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical class N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 7
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 7
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 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 claims description 7
- 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 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical group OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims 1
- 230000000638 stimulation Effects 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000002904 solvent Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 18
- 229960004756 ethanol Drugs 0.000 description 10
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- 239000012043 crude product Substances 0.000 description 8
- 238000007669 thermal treatment Methods 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical class CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 235000014493 Crataegus Nutrition 0.000 description 1
- 241001092040 Crataegus Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical group CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical class 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
- 230000009466 transformation Effects 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a toluylene nitrile derivative with a D-A structure and a synthesis method and application thereof. A structural formula of the toluylene nitrile derivative with the D-A structure is represented by the formula (I) or (II). The toluylene nitrile derivative with the D-A structure can be taken as reversible force to stimulate a fluorescence switch material, and the force stimulation has the characteristics of high contract, automatic recovery and good circulation in response to fluorescence switch performance. The synthesis method is simple; and the toluylene nitrile derivative can be taken as the reversible force to conveniently stimulate devices made of the fluorescence switch material, 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 structure suc as formula the toluylene carbonitrile derivatives with D-A structure and synthetic method and the application shown in (I) or formula (II), especially as the application of pressure sensitive.
(2) background technology
When being applied in mechanical force, the phenomenon that the fluorescence color of material changes is called piezallochromy, and the phenomenon of this uniqueness makes it in fields such as sensing, false proof, storage and demonstrations, present huge commercial promise.
After the power that is subject to stimulates, the interaction force of molecule-molecule changes, and causes the accumulation mode of molecule to change, and makes molecule become in order another kind of or partial order, disordered structure from a kind of ordered structure, thereby causes that the spectrum of material changes.When being heated or be placed in organic solvent atmosphere, return to again original accumulation mode, realize the reversibility that fluorescence color changes.The at present research for this phenomenon mainly concentrates on these several classes of organic molecule, liquid crystal and doped polymer, and the U.S., Japan and other countries are to the existing larger input of the research of this respect.
(the J. Am. Chem. Soc. such as Koji Araki, 2007,129:1520-1521) synthetic end position replaces the pyrene analog derivative of N-hexyl, when the power that is subject to stimulates, the fluorescence color of pressed powder changes (by blueness, being converted to green), and after being heated, returns to original color.This is due to the variation of phenyl ring and pyrene unit torsion(al)angle, to cause the transformation of glow color.(the Asian J. Chem. such as Xu, 2011,6 (3): 808-811) synthetic tetraphenyl ethene derivatives, while pressing to material equally, the fluorescence color of pressed powder has become yellow by green, and after thermal treatment, reverts to original strong green fluorescence.This compound has the space structure of distortion, intermolecular pi-pi bond reactive force a little less than, after the power that is subject to stimulates, molecular conformation is tending towards complanation, and molecular chain conjugated degree is increased, fluorescence color changes.
Yet, the fluorescent material with reversible piezochromic phenomenon of reporting from molecular structure is at present very limited, design the toluylene carbonitrile derivatives that a class has D-A structure herein, such material shows the variation (polarity is to nonpolar) of ruddiness-gold-tinted in the solvent of opposed polarity, and the material of separating out from corresponding solvent shows same colour-change; This material is realized opening and recovering voluntarily of fluorescence under certain condition under external force stimulates simultaneously, has using value widely in actual life.
(3) summary of the invention
The object of the invention is to provide a class and has the new compound that reversible power stimulates fluorescent switch performance---there is toluylene carbonitrile derivatives and synthetic method and its application as reversible power stimulation fluorescent switch material of D-A structure.
Below technical scheme of the present invention is described further.
The invention provides two kinds of toluylene carbonitrile derivatives with D-A structure, its structure is suc as formula shown in (I) or formula (II):
The present invention also provides the synthetic method of the toluylene carbonitrile derivatives with D-A structure shown in formula (I), comprises the steps:
1) shown in the 4-cyanobenzaldehyde shown in formula (III) and formula (IV), bromine nitrile benzyl is generated to the bromo toluylene nitrile intermediate shown in formula V through Knoevenagel condensation reaction under sodium methylate catalysis; Reaction formula is as follows:
2) 4 shown in the bromo toluylene nitrile intermediate shown in formula V and formula (VI), 4 '-dimethyl pentanoic under palladium and three tertiary butyl phosphine catalysts, under cesium carbonate exists through toluylene carbonitrile derivatives shown in C-N linked reaction production (I); Reaction formula is as follows:
Knoevenagel condensation reaction described in step 1) is that the compound that contains active methylene group and aldehyde are under base catalysis, there is dehydration condensation and generate α, the process of beta-unsaturated carbonyl compound and analogue thereof, this reaction is at room temperature carried out conventionally, reaction solvent is selected the conventional organic solvent that does not participate in reaction, as ethanol, preferred color of choice spectrum level ethanol.As for each raw material consumption in step 1), those of ordinary skills can select according to routine, and sodium methylate is catalytic amount conventionally, is enough or excessive, so that aubepine fully reacts and is advisable to bromine nitrile benzyl.4-cyanobenzaldehyde in step 1) of the present invention, to the molar ratio of bromine nitrile benzyl, sodium methylate, be 1:0.4 ~ 2.5:0.02 ~ 0.25, be preferably 1:1 ~ 2:0.05 ~ 0.20; The volumetric usage of described reaction solvent is counted 5 ~ 20 mL/g with the quality of 4-cyanobenzaldehyde.
The present invention is concrete recommends described step 1) to operate as follows: by bromine nitrile benzyl is dissolved with chromatographic ethanol shown in the 4-cyanobenzaldehyde shown in formula (III) and formula (IV), add catalyzer sodium methylate, under room temperature, carry out Knoevenagel condensation reaction to there being precipitation to generate, then direct filtration, filter cake obtains the bromo toluylene nitrile intermediate shown in formula V with dehydrated alcohol recrystallization.
Step 2) described C-N linked reaction is Buchwald – Hartwig linked reaction (reaction of Buchwald-Hartwig), claim again Buchwald – Hartwig reaction, amine and fragrant halogen generation cross-coupling reaction under palladium catalysis and alkali existence, produce C-N key, generate the process of the N-arylation product of amine, reaction solvent can be selected the conventional methyl-2-pyrrolidone for this reaction, N,N-DIMETHYLACETAMIDE, m-xylene, toluene etc., and reaction is under reflux conditions carried out conventionally.Each raw material consumption those of ordinary skills can select according to routine, and common two (tri-butyl phosphine) palladium is catalytic amount, and pentanoic is enough or excessive, so that bromo toluylene nitrile intermediate fully reacts and is advisable.As preferably, described bromo toluylene nitrile intermediate, 4, the molar ratio of 4 '-dimethyl pentanoic, cesium carbonate, palladium is 1:0.8 ~ 1.2:1 ~ 3:0.02 ~ 0.05, and three tertiary butyl phosphine consumptions are counted 4 ~ 10 mL/mmol with the mole number of palladium; This reaction is recommended in toluene to be carried out under reflux temperature, and described toluene consumption is recommended as 10 ~ 20 mL/g in bromo toluylene nitrile intermediate.
The present invention is concrete recommends described step 2) according to carrying out as follows: get the bromo toluylene nitrile intermediate, 4 shown in the formula V that step 1) obtains, 4 '-dimethyl pentanoic and cesium carbonate are dissolved in toluene, add palladium and three tertiary butyl phosphines, under reflux temperature, react 16 ~ 48 hours, by thin layer plate chromatogram tracking, after reacting completely, reaction solution obtains the toluylene carbonitrile derivatives shown in formula (I) through aftertreatment.Described aftertreatment can be adopted with the following method: reaction solution dichloromethane extraction, organic phase saturated common salt water washing, and with anhydrous magnesium sulfate drying, filter, filtrate obtains crude product through concentrating under reduced pressure, and crude product dissolves with methylene dichloride, with chromatography column separated [methylene dichloride: sherwood oil=1:1 ~ 200(volume ratio)], methylene dichloride-sherwood oil elutriant that collection contains product, distillation, except desolventizing, obtains the toluylene carbonitrile derivatives shown in formula (I).
The present invention also provides the synthetic method of the toluylene carbonitrile derivatives with D-A structure shown in formula (II), comprises the steps:
A) by shown in the 4-boric acid triphenylamine shown in formula (VI) and formula (IV) to bromine nitrile benzyl under tetrakis triphenylphosphine palladium catalysis under the existence of basic cpd through the benzyl cyanide class intermediate shown in Suzuki linked reaction production (VII); Reaction formula is as follows:
B) the 4-cyanobenzaldehyde shown in the benzyl cyanide class intermediate shown in formula (VII) and formula (III) under sodium methylate catalysis through toluylene carbonitrile derivatives shown in Knoevenagel condensation reaction production (II); Reaction formula is as follows:
Suzuki linked reaction described in step a) of the present invention, under nitrogen protection, carry out, preferred reaction solvent is the mixed solvent of toluene and tetrahydrofuran (THF), wherein the volume ratio of toluene and tetrahydrofuran (THF) is 5 ~ 4:3 ~ 2, and the volumetric usage of described reaction solvent is to count 70-90 mL/g to the quality of bromine nitrile benzyl; Described basic cpd is preferably sodium carbonate or salt of wormwood; Under the described preferred reflux temperature of Suzuki linked reaction, carry out.As preferably, to bromine nitrile benzyl, 4-boric acid triphenylamine, tetrakis triphenylphosphine palladium, be 1:0.8 ~ 1.2:0.01 ~ 0.03:1.2 ~ 2 with the ratio of the amount of substance of basic cpd.
The present invention is concrete recommends described step a) according to carrying out as follows: by 4-boric acid triphenylamine, bromine nitrile benzyl and basic cpd are dissolved in the mixed solvent of toluene and tetrahydrofuran (THF); add tetrakis triphenylphosphine palladium; back flow reaction 16 ~ 48 h under nitrogen protection; by thin layer plate chromatogram tracking; after reacting completely, reaction solution obtains the benzyl cyanide class intermediate shown in formula (VII) through aftertreatment.Described aftertreatment can be adopted with the following method: reaction solution dichloromethane extraction, organic phase saturated common salt water washing, and with anhydrous magnesium sulfate drying, filter, filtrate obtains crude product through concentrating under reduced pressure, crude product dissolves with methylene dichloride, and the separation of use chromatography column [methylene dichloride: sherwood oil=1:1 ~ 200(volume ratio)], obtain the benzyl cyanide class intermediate shown in formula (VII).
Knoevenagel condensation reaction described in step b) of the present invention, preferably described in the molar ratio of 4-cyanobenzaldehyde, bromo toluylene nitrile intermediate, sodium methylate be 1:0.4 ~ 2.5:0.05 ~ 0.4, be preferably 1:1 ~ 2:0.2 ~ 0.4; Described Knoevenagel condensation reaction is preferably carried out in chromatographic grade ethanol under room temperature, and the volumetric usage of described chromatographic ethanol is counted 50 ~ 80 mL/g with the quality of 4-cyanobenzaldehyde.
The present invention is concrete recommends described step b) according to carrying out as follows: get benzyl cyanide class intermediate, the 4-cyanobenzaldehyde shown in the formula (VII) that step (1) obtains and dissolve with chromatographic ethanol, add catalyzer sodium methylate, under room temperature, carry out Knoevenagel condensation reaction to there being precipitation to generate, then direct filtration, filter cake obtains the toluylene carbonitrile derivatives shown in formula (II) with dehydrated alcohol recrystallization.
Toluylene carbonitrile derivatives of the present invention (I), (II) have reversible power stimulates fluorescent switch performance, therefore can be used as a kind of reversible power, stimulate fluorescent switch material, can be specifically for preparing reversible power stimuli responsive fluorescent switch device, for example, crystalline solid or the powder solid of described derivative (I), (II), can or make the fluorescent switch device with power stimuli responsive performance by the mode being doped in the polymkeric substance such as polymethylmethacrylate by the mode of film technique coated film in substrate.
Compared with prior art, beneficial effect of the present invention is: the organic molecule that the invention provides a kind of power of having stimuli responsive fluorescent switch performance---toluylene carbonitrile derivatives (I), (II), the power stimuli responsive fluorescent switch performance of described organic molecule have contrast gradient high, can recover voluntarily, feature that cyclicity is good, and synthetic method is simple, it stimulates fluorescent switch material fabricate devices convenient as reversible power, can be applicable to the fields such as fluorescent switch, sensor, storage and demonstration.
(4) accompanying drawing explanation
Fig. 1 is the photo before and after the pressed powder (I) in the embodiment of the present invention 3 is exerted pressure, after thermal treatment and solvent treatment under ultraviolet lamp; A) be the fluorescence B without material after excess pressure stimulation and solvent treatment) be the fluorescence C through pressure treatment rear film) be the fluorescence of powder after Overheating Treatment.
Fig. 2 is pressed powder in the embodiment of the present invention 7 fluorescence spectrum before and after exerting pressure, after thermal treatment and solvent treatment; In figure, a is stressed front, and b is stressed fluorescence spectrum afterwards or after grinding.
Fig. 3 is the photo before and after the pressed powder (II) in the embodiment of the present invention 7 is exerted pressure, after thermal treatment and solvent treatment under ultraviolet lamp; A) be the fluorescence B without material after excess pressure stimulation and solvent treatment) be the fluorescence C through pressure treatment rear film) be the fluorescence of powder after Overheating Treatment.
Fig. 4 is pressed powder (II) in the embodiment of the present invention 7 fluorescence spectrum before and after exerting pressure, after thermal treatment and solvent treatment; In figure, a is stressed front, and b is that stressed c afterwards or after grinding is heat treated, and d is the fluorescence spectrum of solvent treatment.
Fig. 5 is the photo before and after the pressed powder (II) in the embodiment of the present invention 7 is exerted pressure, after thermal treatment and solvent treatment under ultraviolet lamp; A) be the fluorescence B without material after excess pressure stimulation and solvent treatment) be the fluorescence C through pressure treatment rear film) be the fluorescence of powder after Overheating Treatment.
Fig. 6 is pressed powder (II) in the embodiment of the present invention 7 fluorescence spectrum before and after exerting pressure, after thermal treatment and solvent treatment; In figure, a is stressed front, and b is that stressed c afterwards or after grinding is heat treated, and d is the fluorescence spectrum of solvent treatment.
Fig. 7 is that the power of the pressed powder (II) in the embodiment of the present invention 12 stimulate-is recovered cycle performance certainly
(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:
Will be to bromine nitrile benzyl 4 g(20 mmol), 4-cyanobenzaldehyde 1.57 g(12 mmol) and sodium methylate 0.12 g(2 mmol) be dissolved in 30 mL chromatographic grade ethanol.Stirring reaction termination reaction when having a large amount of solid particulate at room temperature.Reaction solution direct filtration, filter cake obtains bromo toluylene nitrile intermediate 3.34 g shown in formula V with dehydrated alcohol recrystallization, and yield is 90%.The result of structure of matter test:
1h NMR (500 MHz, CDCl
3) δ 7.98 (d, J=8.5 Hz, 2H), 7.77 (d, J=8.5 Hz, 2H), 7.62 (d, J=9.0 Hz, 2H), 7.58 (d, J=9.0 Hz, 2H), 7.54 (s, 1H);
13c NMR (125 MHz, CDCl
3) δ 139.7,137.5,132.7,132.5,132.4,129.6,127.7,124.5,118.1,116.8,114.3,113.8; MS (EI): m/z 308.0[M
+].
Embodiment 2:
Will be to bromine nitrile benzyl 1.96 g(10 mmol), 4-cyanobenzaldehyde 1.05 g(8 mmol) and sodium methylate 0.03 g(0.5 mmol) be dissolved in 30 mL chromatographic grade ethanol.At room temperature stirring reaction has been treated a large amount of solid particulate termination reactions.Reaction solution direct filtration, filter cake obtains bromo toluylene nitrile intermediate 2.22 g shown in formula V with dehydrated alcohol recrystallization, and yield is 90%.
Embodiment 3:
Weigh toluylene nitrile intermediate (V) the 1.55 g(5 mmol of bromo synthetic in embodiment 1), 4,4 '-dimethyl pentanoic, 1.18 g(6 mmol), cesium carbonate 2 g(10 mmol) be dissolved in 25 mL toluene.Under atmosphere of inert gases, add palladium 0.033 g(0.2 mmol) and 1 mL tri-tertiary butyl phosphines, heat 110 ℃ of reaction 24 h.After reacting completely, reaction solution dichloromethane extraction, saturated common salt water washing 3 times for organic phase, and with anhydrous magnesium sulfate drying, filter, filtrate obtains crude product through concentrating under reduced pressure, and residuum dissolves with methylene dichloride, the separation of use chromatography column [methylene dichloride: sherwood oil=1:1 ~ 200(volume ratio)], methylene dichloride-sherwood oil elutriant that collection contains product (I), distillation, except desolventizing, obtains yellow solid product (I) 1.49 g, and yield is 70%.Its structural formula is determined as follows: the structural confirmation of material characterizes as follows:
1h NMR (500 MHz, CDCl
3) δ 7.79 (s, 1H), 7.61 (dd, J=19.0,7.5 Hz, 4H); 7.41 (d, J=7.5 Hz, 2H), 7.12 (d, J=7.5 Hz, 6H); 7.03 (d, J=7.5 Hz, 4H), 2.34 (s, 6H);
13c NMR (125 MHz, CDCl
3); δ 141.3,141.2, and 140.8,138.7,135.7,133.4,130.2,129.8,128.1,126.2,125.3,125.2,120.6,119.1,110.9,106.6,21.1; MS (EI): m/z 425.2; Anal. Calcd for C
30h
23n
3: C, 84.68; H, 5.45; N, 9.87. Found:C, 84.55; H, 5.39; N, 10.06.
Embodiment 4:
Weigh toluylene nitrile intermediate (IV) the 1.57g(5 mmol of the above-mentioned synthetic bromo of embodiment 1), 4,4 '-dimethyl pentanoic, 0.79 g(4 mmol), cesium carbonate 2 g(10 mmol) be dissolved in 25 mL toluene.Under atmosphere of inert gases, add palladium 0.033 g(0.2 mmol) and 1 mL tri-tertiary butyl phosphines, heat 110 ℃ of reaction 24 h.After reacting completely, reaction solution dichloromethane extraction, saturated common salt water washing 3 times for organic phase, and with anhydrous magnesium sulfate drying, filter, filtrate obtains crude product through concentrating under reduced pressure, and residuum dissolves with methylene dichloride, the separation of use chromatography column [methylene dichloride: sherwood oil=1:1 ~ 200(volume ratio)], methylene dichloride-sherwood oil elutriant that collection contains product (I), distillation, except desolventizing, obtains yellow solid product (I) 0.94 g, and yield is 55%.
Embodiment 5:
To bromine nitrile benzyl (IV) 0.98 g(5 mmol), 4-boric acid triphenylamine 1.73 g(6 mmol), tetrakis triphenylphosphine palladium 0.11 g(0.1 mmol) be dissolved in toluene 50 mL/ tetrahydrofuran (THF) 30 mL solution, add aqueous sodium carbonate (2.0 M, 3 mL).Under nitrogen atmosphere, be warming up to 90 ℃ of reaction 36 h.After reacting completely, reaction solution dichloromethane extraction, saturated common salt water washing 3 times for organic phase, and with anhydrous magnesium sulfate drying, filter, filtrate obtains crude product through concentrating under reduced pressure, residuum dissolves with methylene dichloride, with chromatography column separated [methylene dichloride: sherwood oil=1:1 ~ 200(volume ratio)], obtain yellow powder product (VII) 1.26 g, yield is 70%.
1H?NMR?(500?MHz,?CDCl
3)?δ?7.60?(d,?J?=?8.0?Hz,?2H),?7.47?(d,?J?=?8.5?Hz,?2H),?7.39?(d,?J?=?8.0?Hz,?2H),?7.30?(d,?J?=?8.5?Hz,?4H),?7.16?(d,?J?=?8.5?Hz,?6H),?7.06?(t,?J?=?7.5?Hz,?2H),?3.80?(s,?2H);?
13C?NMR?(125?MHz,?CDCl
3);?δ?145.4,?143.3,?143.0,?133.1,?129.8,?129.6,?129.5,?129.4,?126.3,?126.2,?125.1,?124.9,?119.5,?23.8;?MS(EI):?m/z?360.0.
Embodiment 6:
To bromine nitrile benzyl (IV) 0.98 g(5 mmol), 4-boric acid triphenylamine 1.16 g(4 mmol), tetrakis triphenylphosphine palladium 0.11 g(0.1 mmol) be dissolved in toluene 50 mL/ tetrahydrofuran (THF) 30 mL solution, add aqueous sodium carbonate (2.0 M, 3 mL).Under nitrogen atmosphere, be warming up to 90 ℃ of reaction 24 h.After reacting completely, reaction solution dichloromethane extraction, saturated common salt water washing 3 times for organic phase, and with anhydrous magnesium sulfate drying, filter, filtrate obtains crude product through concentrating under reduced pressure, residuum dissolves with methylene dichloride, with chromatography column separated [methylene dichloride: sherwood oil=1:1 ~ 200(volume ratio)], obtain yellow powder product (VII) 0.73 g, yield is 51%.
Embodiment 7:
Weigh synthetic benzyl cyanide class intermediate (VII) 1.8 g(5 mmol in embodiment 5), 4-cyanobenzaldehyde 0.4 g(3 mmol) and sodium methylate 0.12 g(2 mmol) be dissolved in 30 mL chromatographic grade ethanol.Stirring reaction termination reaction when having a large amount of solid particulate at room temperature.Reaction solution direct filtration, filter cake obtains yellow powder (II) 1.3 g with dehydrated alcohol recrystallization, and yield is 92%.
1H?NMR?(500?MHz,?CDCl
3)?δ?8.00?(d,?J?=?8.3?Hz,?2H),?7.84-7.74?(m,?4H),?7.69?(d,?J?=?8.5?Hz,?2H),?7.58?(s,?1H),?7.53?(d,?J?=?11.0?Hz,?2H),?7.33-7.28?(m,?4H),?7.16?(d,?J?=?7.5?Hz,?6H),?7.08?(t,?J?=?8.0?Hz,?2H);?
13C?NMR?(125?MHz,?CDCl
3);?δ?148.1,?147.5,?142.5,?138.5,?138.0,?133.0,?132.7,?131,8,?130.1,?129.6,?129.4,?127.7,?126.7,?124.8,?123.4,?123.3,?118.3,?117.2,?115.1;?MS(EI):?m/z?473.2;?Anal.?Calcd?for?C
34H
23N
3:?C,?86.23;?H,?4.90;?N,?8.87.?Found:?C,?86.35;?H,?4.85;?N,?4.83.
Embodiment 8:
Weigh synthetic benzyl cyanide class intermediate (VII) 1.8 g(5 mmol in embodiment 5), 4-cyanobenzaldehyde 0.52 g(4 mmol) and sodium methylate 0.12 g(2 mmol) be dissolved in 30 mL chromatographic grade ethanol.Stirring reaction termination reaction when having a large amount of solid particulate at room temperature.Reaction solution direct filtration, filter filter cake obtains yellow powder (II) 1.76 g with dehydrated alcohol recrystallization, and yield is 92%.
Embodiment 9:
Get toluylene carbonitrile derivatives shown in the embodiment of the present invention 3 formulas (I), be that yellow solid product 0.1 g spreads on sheet glass or is placed in mortar and under ultraviolet lamp, is shown as yellow fluorescence (Figure 1A), when being subject to the shear action that key scrapes or use pestle to grind to occur red (Figure 1B), remove after External Force Acting, part of the force still keeps red fluorescence.
By above-mentioned, through the post-stimulatory sample of exertin, be placed in 120 ℃ of baking oven 5 min, the red fluorescence part of part of the force, becomes yellow fluorescence (Fig. 1 C).To, through the post-stimulatory sample of exertin, after normal hexane solvent treatment, return to again original color (Figure 1A) in addition.Fig. 2 is stressed front curve a, and the fluorescence spectrum of stressed rear curve b, can obviously find out, glow color red shift after grinding.
Embodiment 10:
Getting toluylene carbonitrile derivatives 0.1 g shown in the embodiment of the present invention 7 formulas (II) spreads on sheet glass or is placed in mortar and under ultraviolet lamp, be shown as yellow-green fluorescence (Fig. 3 A), when being subject to the shear action that key scrapes or use pestle to grind lightly, there is fluorescent orange (Fig. 3 B), after external force is removed, part of the force still keeps fluorescent orange.
By above-mentioned, through the post-stimulatory sample of exertin, be placed in 120 ℃ of baking oven 5 min, the fluorescent orange of part of the force becomes yellow fluorescence (Fig. 3 C); To, through the post-stimulatory sample of exertin, after normal hexane solvent treatment, return to again original color (Fig. 3 A) in addition.Fig. 4 is stressed front curve a, after stressed rear curve c and thermal stimulus curve b and solvent stimulate after curve d fluorescence spectrum, can obviously find out, glow color red shift after grinding returns to again original color after solvent stimulates.
Embodiment 11:
Getting toluylene carbonitrile derivatives 0.1 g shown in the embodiment of the present invention 7 formulas (II) spreads on sheet glass or is placed in mortar and under ultraviolet lamp, be shown as yellow-green fluorescence (Fig. 5 A), when being subject to the shear action that key scrapes or use pestle to grind at full tilt, there is red fluorescence (Fig. 5 B), after external force is removed, part of the force still keeps red fluorescence.
By above-mentioned, through the post-stimulatory sample of exertin, be placed in 120 ℃ of baking oven 5 min, the fluorescent orange of part of the force becomes yellow fluorescence (Fig. 5 C); To, through the post-stimulatory sample of exertin, after normal hexane solvent treatment, return to again original color (Fig. 5 A) in addition.Fig. 4 is stressed front curve a, after stressed rear curve c and thermal stimulus curve b and solvent stimulate after curve d fluorescence spectrum, can obviously find out, glow color red shift after grinding returns to again original color after solvent stimulates.
Embodiment 12:
Toluylene carbonitrile derivatives shown in the formula that embodiment 7 makes (II), its fluorescence quantum efficiency is 19.9%, fully presses rear fluorescence color and occurs, its fluorescence quantum efficiency will be 8%.Then after normal hexane is processed, obtain powder, its fluorescence intensity obviously improves.So repeatedly exert pressure and solvent treatment 5-30 time after, find that it still has good fluorescent switch performance.
Claims (9)
1. the toluylene carbonitrile derivatives with D-A structure, its structure is suc as formula shown in (I) or formula (II):
2. a synthetic method with the toluylene carbonitrile derivatives of D-A structure as claimed in claim 1, is characterized in that: the structure of the described toluylene carbonitrile derivatives with D-A structure is suc as formula shown in (I), and its synthetic method comprises the steps:
1) shown in the 4-cyanobenzaldehyde shown in formula (III) and formula (IV), bromine nitrile benzyl is generated to the bromo toluylene nitrile intermediate shown in formula V through Knoevenagel condensation reaction under sodium methylate catalysis;
2) the bromo toluylene nitrile intermediate and 4 shown in formula (V), 4 '-dimethyl pentanoic under palladium and three tertiary butyl phosphine catalysts, under cesium carbonate exists through toluylene carbonitrile derivatives shown in C-N linked reaction production (I);
3. the synthetic method with the toluylene carbonitrile derivatives of D-A structure as claimed in claim 2, it is characterized in that: described step 1) to 4-cyanobenzaldehyde, to the ratio of the amount of substance of bromine nitrile benzyl, sodium methylate, be 1:0.4～2.5:0.02～0.25, Knoevenagel condensation reaction is carried out in chromatographic grade ethanol under room temperature.
4. the synthetic method with the toluylene carbonitrile derivatives of D-A structure as claimed in claim 2, it is characterized in that: the nitrile of bromo toluylene described step 2) intermediate, 4, the molar ratio of 4 '-dimethyl pentanoic, cesium carbonate, palladium is 1:0.8～1.2:1～3:0.02～0.05, and three tertiary butyl phosphine consumptions are 4～10mL/mmol palladium; C-N linked reaction is carried out in toluene under reflux temperature.
5. a synthetic method with the toluylene carbonitrile derivatives of D-A structure as claimed in claim 1, is characterized in that: the structure of the described toluylene carbonitrile derivatives with D-A structure is suc as formula shown in (II), and its synthetic method comprises the steps:
A) by shown in the 4-boric acid triphenylamine shown in formula (VI) and formula (IV) to bromine nitrile benzyl under tetrakis triphenylphosphine palladium catalysis under the existence of basic cpd through the benzyl cyanide class intermediate shown in Suzuki linked reaction production (VII);
B) the 4-cyanobenzaldehyde shown in the benzyl cyanide class intermediate shown in formula (VII) and formula (III) under sodium methylate catalysis through toluylene carbonitrile derivatives shown in Knoevenagel condensation reaction production (II);
6. the synthetic method with the toluylene carbonitrile derivatives of D-A structure as claimed in claim 5, is characterized in that during described step a) being 1:0.8～1.2:0.01～0.03:1.2～2 to the molar ratio of bromine nitrile benzyl, 4-boric acid triphenylamine, tetrakis triphenylphosphine palladium and basic cpd; Described basic cpd is sodium carbonate or salt of wormwood; Described Suzuki linked reaction is carried out under nitrogen protection in the mixed solvent of toluene and tetrahydrofuran (THF) under reflux temperature.
7. the synthetic method with the toluylene carbonitrile derivatives of D-A structure as claimed in claim 5, is characterized in that described step b) described in the molar ratio of 4-cyanobenzaldehyde, benzyl cyanide class intermediate, sodium methylate be 1:0.4～2.5:0.05～0.4; Described Knoevenagel condensation reaction is carried out in chromatographic grade ethanol under room temperature.
8. the toluylene carbonitrile derivatives with D-A structure as claimed in claim 1 stimulates the application of fluorescent switch material as reversible power.
9. application as claimed in claim 8, is characterized in that: described reversible power stimulates fluorescent switch material specifically for preparing reversible power stimuli responsive fluorescent switch device.
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