CN108640942B - Alkyl side chain phenyl boron fluorine complex and preparation method and application thereof - Google Patents
Alkyl side chain phenyl boron fluorine complex and preparation method and application thereof Download PDFInfo
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- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 25
- XBCKYZQFDJWWRV-UHFFFAOYSA-N C1(=CC=CC=C1)[B].[F] Chemical compound C1(=CC=CC=C1)[B].[F] XBCKYZQFDJWWRV-UHFFFAOYSA-N 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000010668 complexation reaction Methods 0.000 title description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 15
- OBQRODBYVNIZJU-UHFFFAOYSA-N (4-acetylphenyl)boronic acid Chemical compound CC(=O)C1=CC=C(B(O)O)C=C1 OBQRODBYVNIZJU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 96
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 14
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 239000012312 sodium hydride Substances 0.000 claims description 12
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 229960001701 chloroform Drugs 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 claims description 4
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical group CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 4
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 229940017219 methyl propionate Drugs 0.000 claims description 4
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 4
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003512 Claisen condensation reaction Methods 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000004220 aggregation Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical class [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 abstract description 4
- 208000003174 Brain Neoplasms Diseases 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 238000003384 imaging method Methods 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 abstract description 2
- -1 triphenyl vinyl compound Chemical class 0.000 abstract description 2
- 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 abstract 1
- 239000007787 solid Substances 0.000 description 60
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 32
- 238000004440 column chromatography Methods 0.000 description 24
- 238000010992 reflux Methods 0.000 description 23
- 239000012043 crude product Substances 0.000 description 16
- 239000003208 petroleum Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- VUQVJIUBUPPCDB-UHFFFAOYSA-N (1-bromo-2,2-diphenylethenyl)benzene Chemical group C=1C=CC=CC=1C(Br)=C(C=1C=CC=CC=1)C1=CC=CC=C1 VUQVJIUBUPPCDB-UHFFFAOYSA-N 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- 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 7
- 230000008859 change Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 230000009920 chelation Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- YFSQMOVEGCCDJL-UHFFFAOYSA-N boron monofluoride Chemical class F[B] YFSQMOVEGCCDJL-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
-
- 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
-
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a preparation method of a series of piezochromic boron fluorine complexes with different alkyl chain lengths, which comprises the following steps: (1) reacting halogen-containing triphenyl vinyl compound with 4-acetylphenylboronic acid to synthesize tetraphenyl ethylene monoketone; (2) reacting tetraphenyl vinyl monoketone with esters to obtain tetraphenyl vinyl beta-diketone compounds with different alkyl chain lengths; (3) the synthesized tetraphenyl vinyl beta-diketone compounds with different alkyl chain lengths are respectively complexed with boron trifluoride ethyl ether to obtain a series of boron fluorine complexes with different alkyl chain lengths. The boron-fluorine complex disclosed by the invention has excellent molecular aggregation induced fluorescence effect, and also has excellent characteristics of piezochromicity, wide wavelength range movement and the like, the synthesis of the materials provides a new thought for the research of the color changing mechanism of the piezochromicity materials, and the materials are expected to be widely applied in the fields of brain tumor imaging technology, near-infrared probe technology, photoelectric devices and the like.
Description
Technical Field
The invention relates to an alkyl side chain phenyl boron fluorine complex and a preparation method and application thereof, belonging to the field of organic synthesis.
Background
The mechanical friction color-changing (MFC) material has huge application prospect in the aspects of information safety, memory devices, sensors, fluorescent switches and the like due to the unique molecular Aggregation Induced Emission (AIE), high luminous efficiency, force-induced color-changing property, solvent color-changing and other excellent characteristics. As a novel intelligent material, the chromophore of the material responds with the increase of mechanical force such as grinding, pressing and the like, and then the color of the material is changed.
Since the discovery of the tribo-chromic properties of materials, scientists have synthesized many molecules with MFC properties and studied their photochemical properties. In 2001, molecular aggregation-induced fluorescence effects were first reported by Tangben faith et al, and the results of the studies showed that when a molecule exists in isolation, there is no fluorescence emission, and only when it is in an aggregated state, strong fluorescence is emitted. In the reports at present, many materials have AIE effect and force discoloration, and the two properties often exist simultaneously. It is found that the solid state fluorescence emission spectrum of the substance with AIE effect changes under the action of mechanical force in the synthesized liquid crystal molecules, crystalline solid state molecules and dye-doped polymers. It is reported that the mechanism of origin of this phenomenon is attributed to the structural change thereof by mechanical force during the solid-state molecular aggregation, resulting in the change of the light emitting property thereof. In addition, Sagara et al report that a liquid crystal pyrene derivative emits yellow light when in a cubic phase, but forms a column-like phase after being subjected to a mechanical force to exhibit blue light because the compound can undergo a crystal-form emission transition between an ordered and a disordered state, thereby causing a change in optical properties.
The fluorine boron compound is a typical dye with excellent luminescence characteristics, and has a large extinction coefficient, a two-photon absorption cross section, high fluorescence quantum efficiency and a unique room temperature phosphorescence phenomenon in a solid state. Mirochnik et al have studied the solid state luminescence properties of the fluoroboron compounds, and have found that these dyes exhibit fluorescence and thermal properties depending on the size of the molecule. Nguyen and the like synthesize a series of diphenyl fluorine boron compounds, and the difference of alkyl chains is found to have certain influence on solid-state luminous performance and mechanical force discoloration performance.
Therefore, the length of the alkyl chain is changed to synthesize a series of phenyl boron fluorine compounds with different alkyl chain lengths, and the application of the fluorescent material in the fields of photoelectric devices and the like can be greatly expanded. At present, few piezochromic materials are reported (Chinese patent applications 201711034227.8, 201710349483.X), the synthesis process is complex, the time consumption is long, and the synthesis conditions are harsh, so that more piezochromic materials with simple processes need to be developed.
Disclosure of Invention
In view of the technical current situation, the invention provides a series of phenyl boron fluorine complexes with different alkyl chain lengths, and provides a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an alkyl side chain phenyl boron fluorine complex has a structure shown in formula (I):
wherein n is 2,3,4,5
The synthesis method of the alkyl side chain phenyl boron fluorine complex comprises the following steps:
(1) reacting halogen-containing triphenylethylene (II) with 4-acetylphenylboronic acid to prepare tetraphenylvinyl monoketone (III);
in the formula (II), X is halogen element;
(2) claisen condensation: preparing tetraphenyl vinyl beta-diketone (IV) by condensing tetraphenyl vinyl monoketone (III) and carboxylic ester;
(3) preparation of phenyl boron fluorine complex: reacting tetraphenyl vinyl beta-diketone (IV) with boron trifluoride ethyl ether to obtain a final product (I).
The method comprises the following steps:
preferably, in the step (1), the reaction solvent is toluene or xylene, the halogen is Br, Cl or F, the molar ratio of the halogen-containing triphenylethylene (II) to 4-acetylphenylboronic acid is 1: 1.02-1.10, the reaction temperature is 90-110 ℃, the reaction time is 20-30h, and the reaction catalyst is palladium tetratriphenylphosphine, potassium carbonate and tetrabutylammonium bromide; wherein, palladium tetratriphenylphosphine: potassium carbonate: the mass ratio of the tetrabutylammonium bromide is 0.04-0.06: 5-6: 3-4, and the amount of the tetrabutylammonium bromide is 0.4-0.6 times of the mass of the halogen-containing triphenylethylene (II).
Further preferably, in the step (2), the carboxylic ester is methyl propionate, methyl butyrate, methyl valerate or methyl caproate, and the reaction solvent is tetrahydrofuran, dichloromethane or chloroform.
Further preferably, step (2), the molar ratio of tetraphenylvinyl monoketone (iii): the carboxylic ester is 1:1-1:3, the reaction catalyst is sodium hydride, the addition amount of the sodium hydride is 4-5 times of the molar amount of the tetraphenyl vinyl monoketone (III), the reaction temperature is 40-70 ℃, and the reaction time is 3-7 hours.
Further preferably, the reaction solvent in step (3) is dichloromethane, chloroform, dimethyl sulfoxide or tetrahydrofuran.
Further preferably, in the step (3), the molar volume ratio of the tetraphenyl vinyl beta-diketone to the boron trifluoride diethyl etherate is 1:2-1:6, wherein the molar weight is mmol, and the volume is ml, and the reaction is carried out for 3-6 hours at 30 ℃ under the protection of nitrogen.
Further preferably, the solvent used in step (3) is dichloromethane, trichloromethane, dimethyl sulfoxide or tetrahydrofuran.
The invention also provides application of the piezochromicity of the phenyl boron fluorine complex with different alkyl chain lengths in fluorescent materials.
According to the invention, through combining the structure of the tetraphenyl vinyl group and the beta-diketone with different chain lengths, a series of tetraphenyl vinyl beta-diketone compounds with chelation are prepared firstly, and then the compounds are coordinated with the borofluoride substance to obtain a series of phenyl borofluoride complexes with different alkyl chain lengths, so that the series of compounds have excellent piezochromicity and molecular aggregation induced fluorescence.
Firstly, synthesizing tetraphenyl vinyl monoketone by using low-price halogen-containing triphenylethylene and 4-acetylphenylboronic acid; then carrying out Claisen condensation reaction on the tetraphenyl vinyl monoketone and different esters for 3-7h to prepare tetraphenyl vinyl beta-diketone with different alkyl chain lengths; by utilizing the excellent chelation of a beta-diketone compound, the prepared tetraphenyl vinyl beta-diketone with different alkyl chain lengths is coordinated with boron trifluoride ethyl ether, and finally a series of phenyl boron fluorine complexes with excellent piezochromic property are prepared.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: the phenyl boron fluorine complexes provided by the invention have strong molecular aggregation induced luminescence effect, excellent piezochromic effect and wide color change range, and can widen the application market of the dyes in the aspects of luminescent devices and the like. And the preparation method of the series of phenyl boron fluorine complexes has simple steps and easy implementation, greatly shortens the reaction time and improves the reaction efficiency. The series of phenyl boron fluorine complexes have simple synthesis process, low raw material price, short reaction period and wide color change range, so the research and application process of the series of phenyl boron fluorine complexes in the fields of organic photoelectricity, sensors, information safety and the like can be promoted and promoted.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) 7.5g (22.35 mmol) of 2-bromo-1, 1, 2-triphenylethylene (II) and 3.75g (22.85 mmol) of 4-acetylphenylboronic acid and 0.05g (0.0435 mmol) of tetrakistriphenylphosphine palladium, 5.5g (39.8 mmol) of potassium carbonate, 3.61g (11.2 mmol) of tetrabutylammonium bromide were charged into a dry reaction vessel which was purged with nitrogen, 80ml of toluene was added as a solvent, heated under reflux at 100 ℃ for 24 hours, cooled to room temperature, and the crude product of tetraphenylvinyl monoketone (III) was extracted with dichloromethane, petroleum ether: column chromatography with dichloromethane ═ 1:1 gave 6.68g of white solid in 80% yield.
(2) 1.56g (4 mmol) of the white solid and 0.37g (4 mmol) of methyl propionate are introduced into a dry reaction vessel which is purged with nitrogen, 30ml of tetrahydrofuran is added as a solvent, 0.3975g (16.5 mmol) of sodium hydride is added after the white solid is completely dissolved, the mixture is heated under reflux at 50 ℃ for 4 hours, cooled to room temperature, and the product is rotary evaporated to slightly dry, petroleum ether: and (3) carrying out column chromatography purification on dichloromethane-3: 2 to obtain a brown solid which is directly used for the next synthesis reaction.
(3) The above 0.43(1 mmol) brown solid was dissolved in 120ml of dichloromethane, 2ml of boron trifluoride diethyl etherate was added dropwise to the reaction vessel after introducing nitrogen gas, after heating at 30 ℃ under reflux for 4 hours, dichloromethane was removed by rotary evaporation, and the resulting crude product was subjected to column chromatography to obtain an orange crystalline solid.
Example 2
(1) 7.5g (22.39 mmol) of 2-bromo-1, 1, 2-triphenylethylene (II) and 4.03g (24.58 mmol) of 4-acetylphenylboronic acid and 0.06g of palladium tetratriphenylphosphine, 5.96g of potassium carbonate, 3.97g of tetrabutylammonium bromide were charged into a dry reaction vessel which was purged with nitrogen, 80ml of xylene was added, reflux was heated at 100 ℃ for 24 hours, and cooled to room temperature, and the crude product of tetraphenylvinyl monoketone (III) was extracted with dichloromethane, petroleum ether: column chromatography with dichloromethane ═ 1:1 gave 6.71g of a white solid in 80% yield.
(2) 1.56g (4 mmol) of the white solid and 1.11g (12 mmol) of methyl propionate are introduced into a dry reaction vessel which is purged with nitrogen, 30ml of dichloromethane is added as a solvent, 0.3975g (16.5 mmol) of sodium hydride are added after the white solid is completely dissolved, the mixture is heated under reflux at 55 ℃ for 3 hours, cooled to room temperature, and the product is rotary evaporated to slightly dry, petroleum ether: and (3) carrying out column chromatography purification on dichloromethane-3: 2 to obtain a brown solid which is directly used for the next synthesis reaction.
(3) The above 0.43(1 mmol) brown solid was dissolved in 120ml of dichloromethane, 6ml of boron trifluoride diethyl etherate was added dropwise to the reaction vessel after introducing nitrogen gas, after heating to 30 ℃ under reflux for 4 hours, dichloromethane was removed by rotary evaporation, and the resulting crude product was subjected to column chromatography to obtain an orange crystalline solid.
Example 3
(1) 7.5g (22.39 mmol) of 2-bromo-1, 1, 2-triphenylethylene (II) and 3.75g (22.87 mmol) of 4-acetylphenylboronic acid and 0.05g (0.0435 mmol) of tetrakistriphenylphosphine palladium, 5.5g (39.8 mmol) of potassium carbonate, 3.61g (11.2 mmol) of tetrabutylammonium bromide were charged into a dry reaction vessel charged with nitrogen, 80ml of toluene were added, 100 ℃ was heated under reflux for 24 hours, cooled to room temperature, and the crude product of tetraphenylvinyl monoketone (III) was extracted with dichloromethane, petroleum ether: column chromatography with dichloromethane ═ 1:1 gave 6.68g of white solid in 80% yield.
(2) 1.56g (4 mmol) of the white solid and 0.413g (4 mmol) of methyl butyrate are added into a dry reaction vessel which is filled with nitrogen, 30ml of tetrahydrofuran solvent is added, 0.3975g (16.5 mmol) of sodium hydride is added after the white solid is completely dissolved, heating reflux is carried out at 60 ℃, the reaction is carried out for 5 hours, the reaction product is cooled to room temperature, and the product is evaporated to be slightly dry, petroleum ether: and (4) carrying out column chromatography purification on dichloromethane (8: 5), and directly using the obtained dark brown solid for the next synthetic reaction.
(3) The above-mentioned 0.44(1 mmol) brown solid was dissolved in 120ml of dichloromethane, 2ml of boron trifluoride diethyl etherate was added dropwise to the reaction vessel after introducing nitrogen gas, the mixture was heated at 30 ℃ under reflux for 3 hours, dichloromethane was removed by rotary evaporation, and the obtained crude product was subjected to column chromatography to obtain a red crystalline solid.
Example 4
(1) 7.5g (22.39 mmol) of 2-bromo-1, 1, 2-triphenylethylene (II) and 3.75g (22.87 mmol) of 4-acetylphenylboronic acid and 0.05g (0.0435 mmol) of tetrakistriphenylphosphine palladium, 5.5g (39.8 mmol) of potassium carbonate, 3.61g (11.2 mmol) of tetrabutylammonium bromide were charged into a dry reaction vessel charged with nitrogen, 80ml of toluene were added, 100 ℃ was heated under reflux for 24 hours, cooled to room temperature, and the crude product of tetraphenylvinyl monoketone (III) was extracted with dichloromethane, petroleum ether: column chromatography with dichloromethane ═ 1:1 gave 6.68g of white solid in 80% yield.
(2) 1.56g (4 mmol) of the white solid and 1.239g (12 mmol) of methyl butyrate are added into a dry reaction vessel which is filled with nitrogen, 30ml of tetrahydrofuran solvent is added, 0.3975g (16.5 mmol) of sodium hydride is added after the white solid is completely dissolved, the mixture is heated and refluxed at 60 ℃, reacted for 5 hours, cooled to room temperature, and the product is evaporated to a slight dryness, petroleum ether: and (4) carrying out column chromatography purification on dichloromethane (8: 5), and directly using the obtained dark brown solid for the next synthetic reaction.
(3) The above-mentioned 0.44(1 mmol) brown solid was dissolved in 120ml of dichloromethane, 2ml of boron trifluoride diethyl etherate was added dropwise to the reaction vessel after introducing nitrogen gas, the mixture was heated at 30 ℃ under reflux for 3 hours, dichloromethane was removed by rotary evaporation, and the obtained crude product was subjected to column chromatography to obtain a red crystalline solid.
Example 5
(1) 7.5g (22.39 mmol) of 2-bromo-1, 1, 2-triphenylethylene (II) and 3.75g (22.87 mmol) of 4-acetylphenylboronic acid and 0.05g (0.0435 mmol) of tetrakistriphenylphosphine palladium, 5.5g (39.8 mmol) of potassium carbonate, 3.61g (11.2 mmol) of tetrabutylammonium bromide were charged into a dry reaction vessel charged with nitrogen, 80ml of toluene were added, 100 ℃ was heated under reflux for 24 hours, cooled to room temperature, and the crude product of tetraphenylvinyl monoketone (III) was extracted with dichloromethane, petroleum ether: column chromatography with dichloromethane ═ 1:1 gave 6.68g of white solid in 80% yield.
(2) 1.56g (4 mmol) of the white solid and 0.464g (4 mmol) of methyl valerate are introduced into a dry reaction vessel which is purged with nitrogen, 30ml of tetrahydrofuran solvent is added, 0.3975g (16.5 mmol) of sodium hydride are added after the white solid is completely dissolved, the mixture is heated under reflux at 65 ℃ for 5 hours, cooled to room temperature, and the product is rotary evaporated to slightly dry, petroleum ether: and (4) carrying out column chromatography purification on dichloromethane-3: 4 to obtain a dark brown solid which is directly used for the next synthetic reaction.
(3) The above-mentioned 0.46(1 mmol) brown solid was dissolved in 50ml of tetrahydrofuran, 2ml of boron trifluoride diethyl etherate was added dropwise to the reaction vessel after introducing nitrogen gas, the reaction vessel was heated at 30 ℃ under reflux for 6 hours, then tetrahydrofuran was removed by rotary evaporation, and the obtained crude product was subjected to column chromatography to obtain a red crystalline solid.
Example 6
(1) 7.5g (22.39 mmol) of 2-bromo-1, 1, 2-triphenylethylene (II) and 3.75g (22.87 mmol) of 4-acetylphenylboronic acid and 0.05g (0.0435 mmol) of tetrakistriphenylphosphine palladium, 5.5g (39.8 mmol) of potassium carbonate, 3.61g (11.2 mmol) of tetrabutylammonium bromide were charged into a dry reaction vessel charged with nitrogen, 80ml of toluene were added, 100 ℃ was heated under reflux for 24 hours, cooled to room temperature, and the crude product of tetraphenylvinyl monoketone (III) was extracted with dichloromethane, petroleum ether: column chromatography with dichloromethane ═ 1:1 gave 6.68g of white solid in 80% yield.
(2) 1.56g (4 mmol) of the white solid and 1.38g (12 mmol) of methyl valerate are introduced into a dry reaction vessel which is purged with nitrogen, 30ml of tetrahydrofuran is added as a solvent, 0.3975g (16.5 mmol) of sodium hydride are added after the white solid is completely dissolved, the mixture is heated under reflux at 65 ℃ for 4 hours, cooled to room temperature, and the product is rotary evaporated to slightly dry, petroleum ether: and (4) carrying out column chromatography purification on dichloromethane-3: 4 to obtain a dark brown solid which is directly used for the next synthetic reaction.
(3) The above-mentioned 0.46(1 mmol) brown solid was dissolved in 50ml of tetrahydrofuran, 2ml of boron trifluoride diethyl etherate was added dropwise to the reaction vessel after introducing nitrogen gas, the reaction vessel was heated at 30 ℃ under reflux for 6 hours, then tetrahydrofuran was removed by rotary evaporation, and the obtained crude product was subjected to column chromatography to obtain a red crystalline solid.
Example 7
(1) 7.5g (22.39 mmol) of 2-bromo-1, 1, 2-triphenylethylene (II) and 3.75g (22.87 mmol) of 4-acetylphenylboronic acid and 0.05g (0.0435 mmol) of tetrakistriphenylphosphine palladium, 5.5g (39.8 mmol) of potassium carbonate, 3.61g (11.2 mmol) of tetrabutylammonium bromide were charged into a dry reaction vessel charged with nitrogen, 80ml of toluene were added, 100 ℃ was heated under reflux for 24 hours, cooled to room temperature, and the crude product of tetraphenylvinyl monoketone (III) was extracted with dichloromethane, petroleum ether: column chromatography with dichloromethane ═ 1:1 gave 6.68g of white solid in 80% yield.
(2) 1.56g (4 mmol) of the white solid and 0.520g (4 mmol) of methyl hexanoate are introduced into a dry reaction vessel which is purged with nitrogen, 30ml of tetrahydrofuran is added as a solvent, 0.3975g (16.5 mmol) of sodium hydride is added after the white solid is completely dissolved, the mixture is heated under reflux at 65 ℃ for 6 hours, cooled to room temperature, and the product is rotary evaporated to slightly dry, petroleum ether: and (4) carrying out column chromatography purification on dichloromethane-8: 5, and directly using the obtained brown solid for the next synthetic reaction.
(3) The above-mentioned brown solid 0.47(1 mmol) was dissolved in 50ml of tetrahydrofuran, 2ml of boron trifluoride diethyl etherate was added dropwise to the reaction vessel after introducing nitrogen gas, after heating to 30 ℃ under reflux for 4 hours, tetrahydrofuran was removed by rotary evaporation, and the obtained crude product was subjected to column chromatography to obtain an orange crystalline solid.
Example 8
(1) 7.5g (22.39 mmol) of 2-bromo-1, 1, 2-triphenylethylene (II) and 3.75g (22.87 mmol) of 4-acetylphenylboronic acid and 0.05g (0.0435 mmol) of tetrakistriphenylphosphine palladium, 5.5g (39.8 mmol) of potassium carbonate, 3.61g (11.2 mmol) of tetrabutylammonium bromide were charged into a dry reaction vessel purged with nitrogen, 80ml of toluene was added, 100 ℃ was heated under reflux for 24 hours, cooled to room temperature, and the crude product of tetraphenylvinyl monoketone (III) was extracted with dichloromethane, petroleum ether: column chromatography with dichloromethane ═ 1:1 gave 6.68g of white solid in 80% yield.
(2) 1.56g (4 mmol) of the white solid and 1.56g (12 mmol) of methyl hexanoate were charged into a dry reaction vessel purged with nitrogen, 30ml of tetrahydrofuran solvent was added, 0.3975g (16.5 mmol) of sodium hydride was added after the white solid was completely dissolved, the mixture was heated under reflux at 65 ℃ for 5 hours, cooled to room temperature, and the product was rotary evaporated to slightly dry, petroleum ether: and (4) carrying out column chromatography purification on dichloromethane-8: 5, and directly using the obtained brown solid for the next synthetic reaction.
(3) The above-mentioned brown solid 0.47(1 mmol) was dissolved in 50ml of tetrahydrofuran, 2ml of boron trifluoride diethyl etherate was added dropwise to the reaction vessel after introducing nitrogen gas, after heating to 30 ℃ under reflux for 4 hours, tetrahydrofuran was removed by rotary evaporation, and the obtained crude product was subjected to column chromatography to obtain an orange crystalline solid.
Effect example 1
The results of examining the phenylboron-fluoro complex (I) prepared in examples 1 to 8 are shown in Table 1 below.
TABLE 1 yields and product properties of examples 1-7
| Examples | Yield/%) | Melting Point/. degree.C | Product performance | Molecular aggregation induced fluorescence effect |
| 1 | 51.2 | 186 | Orange crystalline solid | Is provided with |
| 2 | 55.0 | 187 | Orange crystalline solid | Is provided with |
| 3 | 57.2 | 203 | Red crystalline solid | Is provided with |
| 4 | 59.3 | 201 | Red crystalline solid | Is provided with |
| 5 | 49.5 | 207 | Red crystalline solid | Is provided with |
| 6 | 48.7 | 207 | Red crystalline solid | Is provided with |
| 7 | 50.2 | 209 | Orange crystalline solid | Is provided with |
| 8 | 49.4 | 208 | Orange crystalline solid | Is provided with |
Effect example 2
The fluorescence emission wavelength positions of the synthesized products of examples 1-8 and the products of examples 1-8 after pressing are shown in Table 2 below, and it can be seen from Table 2 that the grinding causes the blue shift of the maximum emission wavelength of the products. The table explains the piezochromic property of the material in detail, and the product is expected to be applied in the fields of brain tumor imaging technology, near infrared probe technology, photoelectric devices and the like.
The results of examining the phenyl boron fluoro complex (I) prepared in examples 1 to 8 are shown in Table 2 below.
Table 2 wavelength change before and after grinding of the products of examples 1-8
The synthesis effect of other conditions in the synthesis method of the present invention is equivalent to the above embodiment, and will not be described herein again.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. An alkyl side chain phenyl boron fluorine complex of formula (I):
wherein n is 2,3,4, 5.
2. The method for synthesizing an alkyl side chain phenylboron fluorine complex as claimed in claim 1, wherein:
(1) reacting halogen-containing triphenylethylene (II) with 4-acetylphenylboronic acid to prepare tetraphenylvinyl monoketone (III);
wherein X is a halogen element;
(2) claisen condensation: preparing tetraphenyl vinyl beta-diketone (IV) by condensing tetraphenyl vinyl monoketone and carboxylic ester;
(3) reacting tetraphenyl vinyl beta-diketone (IV) with boron trifluoride ethyl ether to obtain a final product (I).
3. The method for synthesizing an alkyl side chain phenylboron fluoro complex as claimed in claim 2, wherein: in the step (1), a reaction solvent is toluene or xylene, the halogen is Br, Cl or F, the molar ratio of the halogen-containing triphenylethylene (II) to 4-acetylphenylboronic acid is 1: 1.02-1.10, the reaction temperature is 90-110 ℃, the reaction time is 20-30h, and the reaction catalysts are palladium tetratriphenylphosphine, potassium carbonate and tetrabutylammonium bromide; wherein, palladium tetratriphenylphosphine: potassium carbonate: the mass ratio of the tetrabutylammonium bromide is 0.04-0.06: 5-6: 3-4, and the amount of the tetrabutylammonium bromide is 0.4-0.6 times of the mass of the halogen-containing triphenylethylene (II).
4. The method of synthesizing an alkyl side chain phenylboron-fluoro complex as claimed in claim 2, wherein: in the step (2), the carboxylic ester is methyl propionate, methyl butyrate, methyl valerate or methyl caproate, and the reaction solvent is tetrahydrofuran, dichloromethane or trichloromethane.
5. The method of synthesizing an alkyl side chain phenylboron-fluoro complex as claimed in claim 2, wherein: in the step (2), the mole ratio of tetraphenylvinyl monoketone (III): the carboxylic ester is 1:1-1:3, the reaction catalyst is sodium hydride, the addition amount of the sodium hydride is 4-5 times of the molar amount of the tetraphenyl vinyl monoketone (III), the reaction temperature is 40-70 ℃, and the reaction time is 3-7 hours.
6. The method of synthesizing an alkyl side chain phenylboron-fluoro complex as claimed in claim 4, wherein: in the step (3), the mole ratio of the tetraphenyl vinyl beta-diketone to the boron trifluoride diethyl etherate is 1:2-1:6, wherein the mole unit is mmol, the volume unit is ml, and the mixture is heated to 30-35 ℃ under the protection of nitrogen to react for 3-6 hours.
7. The method of synthesizing an alkyl side chain phenylboron-fluoro complex as claimed in claim 4, wherein: the solvent used in the step (3) is dichloromethane, trichloromethane, dimethyl sulfoxide or tetrahydrofuran.
8. Use of the alkyl side chain phenyl boron fluorine complex of claim 1 in a piezochromic fluorescent material at room temperature.
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| "新型β-二酮类有机硼配合物的设计、合成及力致变色性能研究";齐云鹏;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20180115(第01期);摘要、正文第17页图2-1、第17页第2段、第18页第4-5行、第21页第6-9行、第22页第5-7行 * |
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