CN107082753A - A kind of compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property, preparation and application - Google Patents
A kind of compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property, preparation and application Download PDFInfo
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- CN107082753A CN107082753A CN201710349483.XA CN201710349483A CN107082753A CN 107082753 A CN107082753 A CN 107082753A CN 201710349483 A CN201710349483 A CN 201710349483A CN 107082753 A CN107082753 A CN 107082753A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 239000003471 mutagenic agent Substances 0.000 title claims abstract description 31
- 231100000707 mutagenic chemical Toxicity 0.000 title claims abstract description 31
- 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 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 14
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000012805 post-processing Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 9
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- UPMXNNIRAGDFEH-UHFFFAOYSA-N 3,5-dibromo-4-hydroxybenzonitrile Chemical compound OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005489 Bromoxynil Substances 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 238000003379 elimination reaction Methods 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000005885 boration reaction Methods 0.000 claims description 4
- -1 bromophenyl nitrile Chemical class 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 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 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims 2
- 150000002825 nitriles Chemical class 0.000 claims 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims 1
- 239000012965 benzophenone Substances 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 125000004799 bromophenyl group Chemical group 0.000 claims 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 238000000227 grinding Methods 0.000 abstract description 11
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 230000004936 stimulating effect Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
- C07C25/28—Halogenated styrenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property, preparation and application.A kind of compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property, it has the structure described in formula 1,2 or 3.The solid sample of this kind of compound is after mechanical force grinding, and the green fluorescence that fluorescence can be changed into after green, and grinding from blueness can revert to blue-fluorescence with spontaneous, show self-healing power mutagens color property.Therefore, this kind of compound is expected to apply in the field such as sensor and dynamic RAM.
Description
Technical field
The present invention relates to the new stimuli responsive luminescent material of a class and its application, a more particularly to class is new to be had from extensive
Compound, preparation and the application of the group containing tetraphenyl ethylene of multiple power mutagens color property.
Background technology
The intelligent color-changing material that stimulating to external world has response has in the real life of people before application widely
Scape, for example, they all have in fields such as optical recording, trademark anti-counterfeit, sensor, memory chip and data security protectings it is latent
Application value.Intelligent color-changing material can simply be divided into electrochromic material, photochromic material, thermochromism material
Material, gas-discoloration material and the emerging power grown up cause five major classes such as off-color material.Material with power mutagens color property is worked as
Stimulated by mechanical external force, when such as grinding, stretching and pressing, corresponding change, many feelings can occur for the optical property of material
These color changes are all macroscopic under condition.So far, realize that power causes the approach of metachromatism by document report
There are two kinds：It is a kind of be external force effect cause the chemical constitution of molecule changes, it is another be in the presence of external force change
The physics coherent condition of material.Former is the effect of external force so that material molecule is chemically reacted, that is, key of haveing been friends in the past it is disconnected
The formation with new keys is split, so as to cause glow color to change, latter is then point of material molecule in the presence of external force
Accumulation mode between sub- Interaction Force, molecule etc. is changed, and finally make it that glow color is changed.Power is caused
Off-color material has become one ten of intellectual material field as a kind of new stimuli responsive material, relative research
Divide important study hotspot.Mechanical force snesor based on power mutagens color developing material is expected to be used among people's daily life
Pressure sensing.Mechanical force significant color change and high sensitivity tool for the practical application that power causes off-color material before and after stimulating
There is very important meaning.Tetraphenyl ethylene group is a kind of good aggregation-induced emission group, based on tetraphenyl ethylene group structure
Build the acquisition that the tetraphenyl ethylene derivative with power mutagens color property is conducive to efficient to cause off-color material.Without using any thorn
The self- recoverage power that initial glow color spontaneous can be returned under conditions of swashing causes off-color material to have very big application prospect,
Such as self- recoverage power causes off-color material can be by using going to realize dynamic random storage device.Up to the present, with from extensive
The compound amounts of multiple power mutagens color property are very limited amount of.Therefore, the power mutagens color with self- recoverage property is developed glimmering
Luminescent material is extremely necessary.
The content of the invention
The technical problems to be solved by the invention be to provide a class it is new have self- recoverage power mutagens color property contain four
Compound, preparation and the application of styrene group.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property is provided, it has formula 1,2 or 3
Described structure：
A kind of preparation method of the compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property is provided, including
Following steps:
1) diphenyl methane is made into solvent in THF, n-BuLi makees highly basic, with 4- bromine hexichol first under conditions of nitrogen protection
Ketone occurs to add p-methyl benzenesulfonic acid work acid after substitution reaction, and toluene makees solvent, occurs elimination reaction under conditions of nitrogen protection, obtain
The tetraphenyl ethylene derivative 1-1 replaced to single bromine；
2) by step 1) the tetraphenyl ethylene derivative 1-1 that replaces of obtained single bromine makees solvent in THF, and n-BuLi is made strong
Alkali, the tetraphenyl ethylene for occurring to be acidified obtained boration through hydrochloric acid after substitution reaction with trimethylborate under conditions of nitrogen protection spreads out
Biological 1-2；
3) by step 2) the tetraphenyl ethylene derivative 1-2 of obtained boracic acidifying makees mixed solvent in toluene, second alcohol and water,
Potassium carbonate makees alkali, and four (triphenyl phosphorus) palladiums make catalyst, under conditions of nitrogen protection respectively with bromophenyl nitrile, m-bromoxynil and right
Brominal occurs coupling reaction and obtains corresponding target compound 1,2 and 3.
In such scheme, the preparation method of the compound 1,2 and 3 specifically includes following steps：
1) under the conditions of nitrogen atmosphere, diphenyl methane is added in the THF solvents for having been drained off air, stirred, plus
Enter n-BuLi and 4- bromine benzophenone, carry out substitution reaction, after reaction terminates, by white crude product, p-methyl benzenesulfonic acid and
N is filled through discharging the toluene of air and adding to vacuumize2In reaction vessel afterwards, elimination reaction is carried out, after reaction terminates, post processing,
Obtain white solid product 1-1；
2) under the conditions of nitrogen atmosphere, by step 1) obtained white solid product 1-1, n-BuLi and have been drained off sky
The THF of gas, which adds to vacuumize, fills N2In reaction vessel afterwards, trimethylborate and hydrochloric acid are added, the substitution for carrying out boration is anti-
Should, after reaction terminates, post processing obtains white solid product 1-2；
3) under the conditions of nitrogen atmosphere, by step 2) obtained white solid product 1-2, potassium carbonate, four (triphenyl phosphorus)
The mixed solvent of palladium and the toluene, ethanol, water for having been drained off air, which adds to vacuumize, fills N2In reaction vessel afterwards, adjacent bromine is added
Cyanophenyl, m-bromoxynil and to Brominal, occur coupling reaction, after reaction terminates, post processing obtains target product white solid
Compound 1,2 and 3.
In such scheme, step 1) in the mol ratio of diphenyl methane and 4- bromine benzophenone be 1.2:1 to 1.3:1 it
Between.
In such scheme, step 1) in the mol ratio of diphenyl methane and n-BuLi be 1.2:1 to 1.1:Between 1.
In such scheme, step 1) in the mol ratio of diphenyl methane and p-methyl benzenesulfonic acid be 6.5:1 to 6.7:Between 1.
In such scheme, step 1) in diphenyl methane be added under the conditions of 0 DEG C -2 DEG C have been drained off air THF it is molten
In agent, add and reacted after n-BuLi in nitrogen atmosphere under the conditions of 0 DEG C -2 DEG C 1-2 hours, then add 4- bromine benzophenone
React at room temperature 6-7 hour afterwards, be eventually adding p-methyl benzenesulfonic acid and have been drained off after the toluene of air under the conditions of 110 DEG C -120 DEG C
Elimination reaction 6-8 hours.
In such scheme, step 2) in step 1) mol ratio of obtained compound 1-1 and trimethylborate is 1:2.1~
1:2.2。
In such scheme, step 2) in：N-BuLi is added under the conditions of -78 DEG C to -80 DEG C containing white solid production
In product 1-1 and the THF for having been drained off air reaction vessel, stirred 3-4 hours under the conditions of maintaining the temperature at -78 DEG C to -80 DEG C,
Then trimethylborate is added, reaction 12-13 hours is stirred at room temperature, hydrochloric acid terminating reaction is added.
In such scheme, step 3) in step 2) obtained compound 1-2 is with bromophenyl nitrile, m-bromoxynil or to Brominal
Molar ratio be 1.1:1 to 1.2:Between 1.
In such scheme, step 3) in：Coupling reaction is reacted 16-18 hours for return stirring under the conditions of 80 DEG C to 85 DEG C.
In such scheme, step 3) in：Toluene, the volume ratio of second alcohol and water are 9:9:1 to 11:11:Between 1.
In such scheme, step 1) in post processing be：With 10% NaHCO3Solution three after aqueous solution washing reaction
It is secondary, the organic phase anhydrous Na of merging2SO4Dry, screw out solvent, pillar layer separation；Step 2) and step 3) in post processing
For：Extracted three times with dichloromethane, organic layer is washed three times with saturated common salt after extraction, the organic phase anhydrous Na of merging2SO4
Dry, screw out solvent, pillar layer separation.
The compound of the above-mentioned group containing tetraphenyl ethylene with self- recoverage power mutagens color property is preparing self- recoverage power mutagens
Application in color fluorescent material.
Beneficial effects of the present invention：
The compound that the present invention is provided is the new highly luminescent phosphor with self- recoverage power mutagens color property of a class
Material.The solid powder of this kind of compound by mechanical force after grinding, and fluorescence can be changed into green from blueness rapidly, show height
Sensitive mechanical force response property is spent, the green fluorescence after this kind of compound grinding can return to blue-fluorescence with self-healing, and
And the self- recoverage process of compound 1 and 2 can be completed in 10 minutes.It is expected to turn into novel mechanical power sensing material, and
Applied in the field such as pressure sensor and dynamic RAM.
Brief description of the drawings
Fig. 1, Fig. 2 and Fig. 3 are respectively compound 1,2 and 3 solid powder, mechanical force grinding under 365nm ultraviolet excitations
Solid line is product in the fluorescent emission spectrogram after solid powder self- recoverage after rear solid powder and mechanical force grinding, figure
Fluorescent emission spectrogram of the solid powder under 365nm ultraviolet excitations, pecked line is product solid powder after mechanical lapping
Fluorescent emission spectrogram, septal line be product mechanical force grind after solid powder self- recoverage after fluorescent emission spectrogram.
Embodiment
Embodiment 1：The synthesis of compound 1,2 and 3
Synthetic route is as follows：
N-BuLi is n-BuLi in reaction equation, and THF is tetrahydrofuran, and p-toluenesulfonic acid are to toluene
Sulfonic acid, toluene is toluene, B (OMe)3For trimethyl borate, HCl is hydrochloric acid, Pd (PPh3)4For four (triphenyl phosphorus) palladiums,
K2CO3For potassium carbonate, ethanol is ethanol, and water is water.
The synthetic method of compound 1,2 and 3 is identical.By taking the synthesis of compound 1 as an example, specific synthesis step is as follows：
1st, under conditions of 0 DEG C of temperature, 100ml three-necked flasks is vacuumized and fill N2After three times, 12mmol hexichol is added
Methylmethane and 50ml pass through water removal drying process and discharge the tetrahydrofuran of air, slowly squeeze into 10mmol n-BuLi,
Nitrogen atmosphere is always maintained at, 0 DEG C occurs n-BuLi and pulls out hydrogen reaction 1 hour, adds 9.5mmol 4- bromine benzophenone, reaction
Room temperature is returned to, is stirred 6 hours, saturated aqueous ammonium chloride is added and stops reaction, organic phase CH2Cl2Extraction, is eaten with saturation
Salt is washed three times, then uses anhydrous Na2SO4Dry, organic solvent is screwed out, by residue, 1.8mmol p-methyl benzenesulfonic acid and 60ml first
Benzene is added to bis- mouthfuls of flasks of 100ml, back flow reaction 6-8 hours, is cooled to room temperature, organic layer with 10% NaHCO3The aqueous solution is washed
Three times, the organic phase anhydrous Na of merging2SO4Dry, vacuum distillation steams solvent toluene, and pillar layer separation obtains white solid
Product 1-1.Yield：73.03%.1-1:1H NMR(400MHz,CDCl3):δ (ppm)=7.21 (d, J=8Hz, 2H), 7.13-
(d, J=8Hz, the 2H) of 7.08 (m, 9H), 7.03-7.00 (m, 6H), 6.89
2nd, 250ml three-necked flasks are vacuumized and fills N2After three times, 10mmol compound 1-1 are added, 120ml are added by removing
Water drying process and the tetrahydrofuran for discharging air, under the conditions of -78 DEG C, slowly squeeze into 12mmol n-BuLis, stirring 3 is small
When, 21mmol trimethylborates are slowly squeezed into, room temperature is returned to, stirred 12 hours, 10ml hydrochloric acid terminating reactions, organic phase is added
Use CH2Cl2Extraction, organic layer is washed three times with saturated common salt after extraction, the organic phase anhydrous Na of merging2SO4Dry, screw out
Organic solvent, pillar layer separation obtains white solid product 1-2.Yield：81.6%.1-2:1H NMR(400MHz,CDCl3):δ
=7.88 (d, J=8Hz, 2H), (ppm) 7.13-7.03 (m, 19H)
3rd, 100ml three-necked flasks are vacuumized and fills N2After three times, 0.95mmol compounds 1-2,0.86mmol neighbour are added
Brominal, 0.5g potassium carbonate, 50ml toluene, 50ml ethanol, 5ml water is always maintained at nitrogen atmosphere, stirring at normal temperature 40 minutes, plus
Enter 0.1g catalyst four (triphenyl phosphorus) palladium, 80 DEG C of backflows are stirred 16 hours, recover room temperature, organic layer is washed with saturated common salt
Three times, organic phase anhydrous Na2SO4Dry, vacuum distillation steams solvent toluene, and pillar layer separation obtains white solid product 1.
Yield：73.7%.1:1H NMR(400MHz,CDCl3):δ (ppm)=7.73 (d, J=8Hz, 1H), 7.60 (t, J=8Hz,
1H), 7.47 (d, J=8Hz, 1H), 7.40 (t, J=6Hz, 1H), 7.32-7.30 (m, 2H), 7.15-7.04 (m, 17H)
The product 1 of the embodiment under 365nm ultraviolet excitations solid powder, mechanical force grinding after solid powder and
Fluorescent emission spectrogram after solid powder after mechanical force grinding is placed 10 minutes at room temperature is as shown in Figure 1.Solid line is in figure
Fluorescent emission spectrogram of the product solid powder under 365nm ultraviolet excitations, pecked line is that product solid powder passes through mechanical grinding
Fluorescent emission spectrogram after mill, septal line be product mechanical force grind after solid powder place at room temperature 10 minutes after it is glimmering
Light emission spectrum figure.By Fig. 1, it will be seen that the solid powder of compound fluorescence emission spectrum after mechanical lapping
Emission peak occur red shift, its fluorescence color from blueness be changed into green, and pass through at room temperature place 10 minutes after, its fluorescence face
Color returns to initial conditions again, so as to show the power mutagens color property of obvious self recovery.It is similar to product 1, such as Fig. 2 institutes
Show, the solid powder of product 2 after mechanical force grinding places fluorescence color after 10 minutes at room temperature can be with self- recoverage to initially
Blueness, therefore it equally has the power mutagens color property of obvious self recovery.As shown in figure 3, for compared to product 1 and 2,
The self- recoverage effect of product 3 is poor, its can not self- recoverage completely to initial fluorescence emission peak, but observe by the naked eye, product 3
Fluorescence color substantially can be with self- recoverage to initial blueness.Product 1,2 and 3 is that very rare have self- recoverage power mutagens color
The luminophor of property, they are expected to apply in the field such as sensor and dynamic RAM.
Claims (10)
1. a kind of compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property, it has described in formula 1,2 or 3
Structure：
2. the preparation side of the compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property described in claim 1
Method, it is characterised in that:
Wherein：1st, the preparation method of the compound represented by 2 and 3, comprises the following steps：
1) diphenyl methane is made into solvent in THF, n-BuLi is made highly basic, sent out under conditions of nitrogen protection with 4- bromines benzophenone
P-methyl benzenesulfonic acid is added after raw substitution reaction and makees acid, toluene makees solvent, occurs elimination reaction under conditions of nitrogen protection, obtain list
The tetraphenyl ethylene derivative 1-1 of bromine substitution；
2) by step 1) the tetraphenyl ethylene derivative 1-1 that replaces of obtained single bromine makees solvent in THF, and n-BuLi makees highly basic, nitrogen
Occurs the tetraphenyl ethylene derivative for being acidified obtained boration after substitution reaction through hydrochloric acid under conditions of gas shielded with trimethylborate
1-2；
3) by step 2) the tetraphenyl ethylene derivative 1-2 of obtained boracic acidifying makees mixed solvent in toluene, second alcohol and water, carbonic acid
Potassium makees alkali, and four (triphenyl phosphorus) palladiums make catalyst, respectively with bromophenyl nitrile, m-bromoxynil and to bromobenzene under conditions of nitrogen protection
Nitrile occurs coupling reaction and obtains corresponding target compound 1,2 and 3.
3. the preparation of the compound of the group according to claim 2 containing tetraphenyl ethylene with self- recoverage power mutagens color property
Method, it is characterised in that：
1) under the conditions of nitrogen atmosphere, diphenyl methane is added in the THF solvents for having been drained off air, stirred, added just
Butyl lithium and 4- bromine benzophenone, carry out substitution reaction, after reaction terminates, by white crude product, p-methyl benzenesulfonic acid and have arranged
The toluene for going out air adds and vacuumizes and fill N2In reaction vessel afterwards, elimination reaction is carried out, after reaction terminates, post processing is obtained
White solid product 1-1；
2) under the conditions of nitrogen atmosphere, by step 1) obtained white solid product 1-1, n-BuLi and have been drained off air
THF, which adds to vacuumize, fills N2In reaction vessel afterwards, trimethylborate and hydrochloric acid are added, the substitution reaction of boration is carried out, instead
After should terminating, post processing obtains white solid product 1-2；
3) under the conditions of nitrogen atmosphere, by step 2) obtained white solid product 1-2, potassium carbonate, four (triphenyl phosphorus) palladiums and
The mixed solvent for having been drained off the toluene, ethanol, water of air adds and vacuumizes and fill N2In reaction vessel afterwards, bromophenyl is added
Nitrile, m-bromoxynil or to Brominal, occur coupling reaction, after reaction terminates, post processing obtains target product white solid chemical combination
Thing 1,2 and 3.
4. the preparation of the compound of the group according to claim 2 containing tetraphenyl ethylene with self- recoverage power mutagens color property
Method, it is characterised in that：Step 1) in diphenyl methane and 4- bromine benzophenone mol ratio be 1.2:1 to 1.3:Between 1；Step
It is rapid 1) in diphenyl methane and p-methyl benzenesulfonic acid mol ratio be 6.5:1 to 6.7:Between 1.
5. the preparation of the compound of the group according to claim 2 containing tetraphenyl ethylene with self- recoverage power mutagens color property
Method, it is characterised in that：Step 1) in diphenyl methane and n-BuLi mol ratio be 1.2:1 to 1.1:Between 1.
6. the preparation of the compound of the group according to claim 2 containing tetraphenyl ethylene with self- recoverage power mutagens color property
Method, it is characterised in that：Step 2) in step 1) mol ratio of obtained compound 1-1 and trimethylborate is 1:2.1~1:
2.2。
7. the compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property according to Claims 2 or 3
Preparation method, it is characterised in that：Step 1) in diphenyl methane the THF for having been drained off air is added under the conditions of 0 DEG C -2 DEG C
In solvent, add and reacted after n-BuLi in nitrogen atmosphere under the conditions of 0 DEG C -2 DEG C 1-2 hours, then add 4- bromine hexichol first
Reacted at room temperature 6-7 hour after ketone, be eventually adding p-methyl benzenesulfonic acid and have been drained off after the toluene of air in 110 DEG C of -120 DEG C of conditions
Lower elimination reaction 6-8 hours；
Step 2) in：N-BuLi is added to containing white solid product 1-1 and had been drained off under the conditions of -78 DEG C to -80 DEG C
In the THF of air reaction vessel, stirred under the conditions of maintaining the temperature at -78 DEG C to -80 DEG C 3-4 hours, then add boric acid three
Methyl esters, is stirred at room temperature reaction 12-13 hours, adds hydrochloric acid terminating reaction；
Step 3) in：Coupling reaction is reacted 16-18 hours for return stirring under the conditions of 80 DEG C to 85 DEG C.
8. the preparation of the compound of the group according to claim 2 containing tetraphenyl ethylene with self- recoverage power mutagens color property
Method, it is characterised in that：Step 3) in step 2) obtained compound 1-2 is with bromophenyl nitrile, m-bromoxynil or to Brominal
Molar ratio is 1.1:1 to 1.2:Between 1；
Step 3) in：Toluene, the volume ratio of second alcohol and water are 9:9:1 to 11:11:Between 1.
9. the preparation of the compound of the group according to claim 2 containing tetraphenyl ethylene with self- recoverage power mutagens color property
Method, it is characterised in that：Step 1) in post processing be：With 10% NaHCO3Solution after aqueous solution washing reaction three times,
The organic phase anhydrous Na of merging2SO4Dry, screw out solvent, pillar layer separation；Step 2) and step 3) in post processing be：With
Dichloromethane is extracted three times, and organic layer is washed three times with saturated common salt after extraction, the organic phase anhydrous Na of merging2SO4Dry,
Screw out solvent, pillar layer separation.
10. the compound of the group containing tetraphenyl ethylene with self- recoverage power mutagens color property described in claim 1 is being prepared certainly
Application in restoring force mutagens color fluorescent material.
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