CN108623538A - A kind of piperazine modified tetraphenylethylene derivative and its application - Google Patents
A kind of piperazine modified tetraphenylethylene derivative and its application Download PDFInfo
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- CN108623538A CN108623538A CN201810401046.2A CN201810401046A CN108623538A CN 108623538 A CN108623538 A CN 108623538A CN 201810401046 A CN201810401046 A CN 201810401046A CN 108623538 A CN108623538 A CN 108623538A
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- piperazine modified
- tetraphenylethylene derivative
- triphenylethylenes
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention discloses a kind of piperazine modified tetraphenylethylene derivative, structural formula is as shown in formula I, and the invention also discloses the preparation methods of above-mentioned piperazine modified tetraphenylethylene derivative：It is reacted 1 (4 ' bromophenyl) 1 by Suzuki, 2,2 triphenylethylenes and 4 (4 ' carbonate group, 1 piperazinyl) phenyl boric acid gneissic suite esters are coupled, concentrated again, extraction, drying, column chromatography etc. detach purification processes, finally obtain piperazine modified tetraphenylethylene derivative.The present invention also provides above-mentioned piperazine modified tetraphenylethylene derivatives in the mixed solvent dispersion of organic solvent/water, and as the method that fluoroscopic examination medium detects fragrant nitro explosive TNP, the minimum detection limit of TNP can reach 1 × 10‑6M is horizontal.
Description
Technical field
The invention belongs to organic photoelectric functional material technical fields, and in particular to a kind of piperazine modified tetraphenylethylene spreads out
Biology and its application, more particularly to the application in the detection of 2,4,6- trinitrophenol (TNP) of fragrant nitro explosive.
Background technology
Nitro-aromatic includes nitrobenzene (NB), 4- nitrotoleunes (4-NT), 2,4,6- trinitrophenols (TNP), 2,4,6-
Trinitrotoluene (TNT) etc. is the common composition of explosive, they have stronger explosions and lower safety coefficient.Mesh
Before, nitro compound receives huge concern in national security and environmental pollution etc., therefore, the detection of nitro compound
It is particularly important.
The detection technique for the fragrant nitro explosive developed at present includes mass spectrum, ion mobility spectrometry, electrochemical method and colorimetric
Method etc., but that there are sensitivity is low, selective effect is general or detection response time length etc. for these conventional determination methods
Disadvantage.
In addition, 2 in nitro-aromatic, 4,6- trinitrophenols (TNP) are a kind of chemical substances of great danger, when it
When being impacted with flame contact or by friction, heavy explosion will occur.Moreover, the intake of TNP can cause human poisoning, less serious case
The symptoms such as headache, Nausea and vomiting, abdominal pain are had, severe one can damage its red blood cell.But all nitro explosives are all
Show stronger electron affinity, it is difficult to detected TNP is specific from other nitro compounds, therefore, exploitation
The method of efficient specific detection TNP is then of great significance.
From 2001, since seminar of Tang is found that aggregation-induced emission (AIE) phenomenon, the phosphor with AIE performances
Expect that the application in chemistry and field of biological detection has become the hot spot of Recent study, explosive is carried out with AIE materials
Fluoroscopic examination is also paid much attention to.This is because on the one hand compared with traditional bomb determination method, fluoroscopic examination side
Method has high sensitivity, highly selective, response time short advantage；On the other hand, AIE materials can be in high concentration and state of aggregation
It is lower to keep efficient fluorescence, help to further increase detection sensitivity.
Invention content
The object of the present invention is to provide a kind of piperazine modified tetraphenylethylene derivatives, are detected as fluorescent probe molecule
Fragrant nitro explosive, the fluorescence detection high sensitivity, selectivity is strong, and the response time is short；And it being capable of specific detection TNP.
A kind of piperazine modified tetraphenylethylene derivative, structural formula is as shown in formula I：
Wherein, R is alkyl.
Preferably, the R is methyl, ethyl, propyl, isopropyl, butyl or tertiary butyl etc.；Further preferably, institute
The R stated is tertiary butyl.
The present invention also provides the preparation method of above-mentioned piperazine modified tetraphenylethylene derivative, operation is simple,
Reaction condition is mild, which is：Under inert gas protection, 1- (4 '-bromophenyl) -1,2,2- triphenylethylenes, 4-
(4 '-carbonate group -1- piperazinyls) phenyl boric acid gneissic suite ester and carbonate are dissolved in organic solvent A or organic solvent A and water
Catalyst is added in the mixed solvent, carries out Suzuki coupling reactions；It waits for that after reaction, product mixtures being cooled to room temperature,
Post-processing obtains piperazine modified tetraphenylethylene derivative shown in formula I.
In step (1), the reaction temperature of the Suzuki coupling reactions is 80~100 DEG C, and the reaction time is 5~30 small
When.
In step (1), the catalyst is tetra-triphenylphosphine palladium (Pd (Ph3P)4), dosage is 1- (4- bromophenyls)-
The 1~3% of the quality of 1,2,2- triphenylethylenes.
In step (1), the carbonate act as providing alkaline environment, and dosage is according to the use of in the mixed solvent water
Amount determines that percent concentration is 5~15%, can be in sodium carbonate, potassium carbonate, cesium carbonate, carbonic acid according to raw material and solvent case
It is selected in lithium a kind of.
In step (1), the organic solvent A is tetrahydrofuran, n,N-Dimethylformamide, N, N- dimethylacetamides
Amine, dimethyl sulfoxide (DMSO), dioxane or cyclohexanone.
In step (1), the in the mixed solvent water content of the organic solvent A and water is 5~30% by volume.
In step (1), the 1- (4 '-bromophenyl) -1,2,2- triphenylethylenes and 4- (4 '-carbonate group -1- piperazines
Base) phenyl boric acid gneissic suite ester molar ratio be 1:1.1~2.0, specific ratio is selected according to solvent for use and reaction temperature.
In step (1), the inert gas is high pure nitrogen, ordinary nitrogen or argon gas.
In step (2), the post-processing includes concentration, extraction, revolving and purification operations；The concentration operation is
Refer to and organic solvent A is removed by rotary evaporation, leaves a small amount of liquid, aqueous；The extracting operation refers to the raffinate after concentration
It is extracted with the mixture of dichloromethane and saturated salt solution, wherein the volume ratio of dichloromethane and saturated salt solution is 0.5~3:
1, merge organic phase, discards water phase；The revolving operation refers to the organic solvent removed by rotary evaporation in extract liquor；
The purification operations refer to by product mixtures by silica gel chromatograph post separation, and eluent is dichloromethane and petroleum ether (60
~90 DEG C) according to 1:The mixed solvent that 1 volume ratio is prepared.
The chemical equation provided by the invention for preparing above-mentioned piperazine modified tetraphenylethylene derivative is as follows：
Above-mentioned piperazine modified tetraphenylethylene derivative provided by the invention can be used as fluorescent probe molecule for examining
Survey fragrant nitro explosive.
The piperazine modified tetraphenylethylene derivative of the bright offer of this law is piperazinyl as the recognition unit of probe molecule
Group, sensing unit are tetraphenylethylene (TPE) group with AIE performances, and linking arm is phenyl ring, passes through covalent bond chain
It connects, the phenyl ring of linking arm phenyl ring and sensing unit TPE molecules forms big conjugatedπbond system, work as piperazine in the same plane
The fragrant nitro explosive of group identification and it is in connection after, the big conjugatedπbond system of probe molecule is destroyed, its fluorescence property is made to change
Become, show as fluorescent quenching, to have the function that the fragrant nitro explosive of identification.
The present invention provides be used for tetraphenylethylene derivative piperazine modified shown in formula I as fluorescent probe molecule
The method of the fragrant nitro explosive of detection, including：
(a) using tetraphenylethylene derivative piperazine modified shown in Formulas I as fluorescent probe molecule, it is with organic solvent B
Solvent, compound concentration are 1~10 × 10-6The solution of mol/L；
(b) water is added in the solution prepared to step (a), prepares the suspension of piperazine modified tetraphenylethylene derivative
Liquid；
(c) into suspension made from step (b), be added fragrant nitro explosive, detection suspension system fluorescence intensity with
The work that suspension system fluorescence intensity changes with fragrant nitro explosive concentration is drawn in the variation for fragrant nitro explosive content
Curve obtains the minimum detection limit of fragrant nitro explosive.
In step (a), the organic solvent B is tetrahydrofuran, acetonitrile, n,N-Dimethylformamide, dimethyl sulfoxide (DMSO)
Or dioxane.
In step (b), the volume ratio of the water addition and organic solvent B is 80~90%.
Piperazine modified tetraphenylethylene derivatives fluorescent probe molecule provided by the invention being capable of specificity with TNP molecules
Complexing, open probe molecule in piperazine ring, linking arm Benzene Molecule torsion, greatly destroy piperazine modified tetraphenylethylene
The big conjugated system of derivatives fluorescent probe molecule, in view of this, fluorescence detection method provided by the invention is particularly suitable for 2,
The detection of 4,6- trinitrophenols (TNP).
TNP detection methods provided by the invention are simple, are swift in response, and are not necessarily to additional catalyst；Detect TNP sensitivity
Height, detection limit is low, and the minimum detection limit of TNP can reach micromole (μM) magnitude.
It is commercially produced product, cost that the present invention, which prepares the raw material used in the piperazine modified tetraphenylethylene derivative,
It is low in cost and easily available, it is suitble to industrialized production, is expected to be used widely in terms of environmental pollution and public safety.
Compared with prior art, the invention has the advantages that：
1, the preparation method of fluoroscopic examination substance provided by the invention is simple, and reaction condition is mild, and raw material is easy to get, at low cost
It is honest and clean, it is suitble to industrialized production.
2, fluorescence detection method provided by the invention is simple, is swift in response, and detection can be completed without additional catalyst.
3, fluorescence detection high sensitivity provided by the invention selects high specificity, response time short；And it can be special
Property detection TNP, the minimum detection limit of TNP can reach micromole's magnitude.
Description of the drawings
Fig. 1 is 1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes that the embodiment of the present invention 1 is prepared
Hydrogen nuclear magnetic resonance spectrogram.
Fig. 2 is 1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes that the embodiment of the present invention 1 is prepared
Carbon-13 nmr spectra figure.
Fig. 3 is 1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes that the embodiment of the present invention 1 is prepared
Infrared spectrum.
Fig. 4 is the AIE of 1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes in inventive energy test case 1
Performance map；
Fig. 5 is that 1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes detect TNP's in application example 1 of the present invention
Fluorescence spectra.
Fig. 6 is that 1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes carry out TNP in application example 1 of the present invention
The relation curve that system fluorescence intensity changes with TNP concentration when fluoroscopic examination.
Fig. 7 is that 1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes carry out TNP in application example 1 of the present invention
Part of the TNP concentration from 1 μM to 6 μM on the relation curve that system fluorescence intensity changes with TNP concentration when fluoroscopic examination.The area
Between system fluorescence intensity change close to linear relationship with TNP concentration, be conducive to determine detection lower bound.
Specific implementation mode
For a further understanding of the present invention, with reference to embodiment to a kind of piperazine modified tetraphenyl provided by the invention
Ethene derivatives and its application are specifically described, and however, the present invention is not limited to these examples.The skilled practitioner
The non-intrinsically safe modifications and adaptations made under being instructed core concept of the present invention according to foregoing invention content still fall within the present invention's
Protection domain.
The synthesis of 1 1- of embodiment (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes
Under high pure nitrogen protection, by the 1- (4 '-bromophenyl) -1 of 411mg, 2,2- triphenylethylenes, 485mg 4- (4 ' -
Boc-1- piperazinyls) phenyl boric acid pinacol ester and 160mg sodium carbonate (1 ︰ of molar ratio, 1.2 ︰ 1.5) mixing after be dissolved in the four of 80mL
Water (the volume ratio 4 of hydrogen furans and 20mL:1) four triphenyls of 6.2mg are added in the in the mixed solvent prepared until completely dissolved
The dosage of phosphine palladium catalyst, tetra-triphenylphosphine palladium catalyst is 1- (4 '-bromophenyl) -1,1.5wt% of 2,2- triphenylethylenes,
It flows back under 90 DEG C of oil baths.Reaction removes oil bath after 12 hours, and system is made to naturally cool to room temperature.Part is removed with Rotary Evaporators
Organic solvent makes mixture be concentrated into the 1/3 of original volume.Then it is the dichloromethane and saturated salt solution of 1 ︰ 2 to use volume ratio
60mL extracts system, and coextraction three times, collects organic phase, anhydrous sodium sulfate is used in combination to carry out removing water process to it, dry
The volume that agent dosage regards extract liquor determines, 2g anhydrous sodium sulfates are added per 100mL extract liquors, stand 8~12 hours.Normal pressure mistake
Filter, removes the drier anhydrous sodium sulfate of water suction, removes organic solvent dichloromethane and tetrahydrofuran on a rotary evaporator；It will
Obtained residual solids object is eluant, eluent column with the petroleum ether (60~90 DEG C) and dichloromethane mixed solvent that volume ratio is 1 ︰ 1
Chromatography detaches, and finally obtains compound:1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes, yield 76.6%.
Its chemical constitution nucleus magnetic hydrogen spectrum, carbon-13 nmr spectra and infrared absorption spectrum identification；Nuclear magnetic resonance spectroscopy is as shown in Figure 1, core
Magnetic resonance carbon is composed as shown in Fig. 2, infrared absorption spectrum spectrogram is as shown in Figure 3.
The synthesis of 2 1- of embodiment (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes
Under ordinary nitrogen protection, by the 1- (4 '-bromophenyl) -1 of 411mg, 2,2- triphenylethylenes, 606mg 4- (4 ' -
Boc-1- piperazinyls) phenyl boric acid pinacol ester and 202mg potassium carbonate (1 ︰ of molar ratio, 1.5 ︰ 1.5) mixing after be dissolved in 100mL's
Water (the volume ratio 5 of acetonitrile and 20mL:1) four triphenylphosphines of 8.2mg are added in the in the mixed solvent prepared until completely dissolved
The dosage of palladium catalyst, tetra-triphenylphosphine palladium catalyst is 1- (4 '-bromophenyl) -1,2.0wt% of 2,2- triphenylethylenes,
It flows back under 100 DEG C of oil bath heatings.Reaction removes oil bath after 10 hours, and system is made to naturally cool to room temperature.It is removed with Rotary Evaporators
Part organic solvent is removed, mixture is made to be concentrated into the 1/3 of original volume.Then it is the dichloromethane and saturation of 1 ︰ 2 to use volume ratio
Saline solution 60mL extracts system, and coextraction three times, collects organic phase, and 5g anhydrous magnesium sulfates are added, and it is small to stand 8~12
When.Natural filtration removes the drier anhydrous magnesium sulfate of water suction, removes the acetonitrile solvent of dichloromethane on a rotary evaporator；
It is that eluant, eluent is used by petroleum ether (60~90 DEG C) and dichloromethane mixed solvent that obtained residual solids object volume ratio is 1 ︰ 1
Column chromatography detaches, and finally obtains compound:1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes, yield
58.1%.Its Identification of chemical structure is carried out according to synthesis example 1.
The synthesis of 3 1- of embodiment (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes
Under protection of argon gas, by the 1- of 410mg (4 '-bromophenyl) -1,2,2- triphenylethylenes, 485mg 4- (4 '-Boc-
1- piperazinyls) phenyl boric acid pinacol ester and 160mg sodium carbonate (1 ︰ of molar ratio, 1.2 ︰ 1.5) mixing after be dissolved in the tetrahydrochysene furan of 80mL
It mutters and the water of 20mL (volume ratio 4:1) tetra-triphenylphosphine palladium of 6.2mg is added in the in the mixed solvent prepared until completely dissolved
The dosage of catalyst, tetra-triphenylphosphine palladium catalyst is 1- (4 '-bromophenyl) -1,1.5wt% of 2,2- triphenylethylenes, at 90 DEG C
It flows back under oil bath.Reaction removes oil bath after 18 hours, and system is made to naturally cool to room temperature.It is organic that part is removed with Rotary Evaporators
Solvent makes mixture be concentrated into the 1/3 of original volume.Then it is the dichloromethane and saturated salt solution 60mL of 1 ︰ 2 to use volume ratio
System is extracted, coextraction three times, collects organic phase, is used in combination 4g anhydrous magnesium sulfates to carry out removing water process to it, system is quiet
It sets 8~12 hours.Natural filtration removes the drier of water suction, removes organic solvent on a rotary evaporator；The residual that will be obtained
The petroleum ether (60~90 DEG C) and dichloromethane mixed solvent that solids volume ratio is 1 ︰ 1 are eluant, eluent column chromatography point
From finally obtaining compound:1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes, yield 77.5%.Its chemistry knot
Structure identification is carried out according to synthesis example 1.
The synthesis of 4 1- of embodiment (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes
Under high pure nitrogen protection, by the 1- (4 '-bromophenyl) -1 of 1234mg, 2,2- triphenylethylenes, 1578mg 4-
It is dissolved in after the mixing of the sodium carbonate (1 ︰ of molar ratio, 1.3 ︰ 2.0) of (4 '-Boc-1- piperazinyls) phenyl boric acid pinacol ester and 636mg
The dioxane of 120mL and the water (volume ratio 4 of 30mL:1) in the mixed solvent prepared, is added 22.2mg until completely dissolved
Tetra-triphenylphosphine palladium catalyst, the dosage of tetra-triphenylphosphine palladium catalyst is 1- (4 '-bromophenyl) -1,2,2- triphenylethylenes
1.8wt% flows back under 90 DEG C of oil baths.Reaction removes oil bath after 12 hours, and system is made to naturally cool to room temperature.Use rotary evaporation
Instrument removes part organic solvent, and mixture is made to be concentrated into the 1/3 of original volume.Then use volume ratio be 1 ︰ 2 dichloromethane and
Saturated salt solution 60mL extracts system, coextraction four times, collects organic phase, 8g anhydrous magnesium sulfates is used in combination to remove it
Water process, system stand 12 hours.Natural filtration removes the drier of water suction, removes solvent on a rotary evaporator；It will obtain
Residual solids object with the petroleum ether (60~90 DEG C) and dichloromethane mixed solvent that volume ratio is 1 ︰ 1 be eluant, eluent column chromatography
Method detaches, and finally obtains compound:1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes, yield 81.1%.It is changed
Structural Identification is learned to carry out according to synthesis example 1.
The synthesis of 5 1- of embodiment (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes
Under high pure nitrogen protection, by the 1- (4 '-bromophenyl) -1 of 410mg, 2,2- triphenylethylenes, 485mg 4- (4 ' -
Boc-1- piperazinyls) phenyl boric acid pinacol ester and 112mg lithium carbonate (1 ︰ of molar ratio, 1.2 ︰ 1.5) mixing after be dissolved in the four of 80mL
Water (the volume ratio 4 of hydrogen furans and 20mL:1) four triphenyls of 6.2mg are added in the in the mixed solvent prepared until completely dissolved
The dosage of phosphine palladium catalyst, tetra-triphenylphosphine palladium catalyst is 1- (4 '-bromophenyl) -1,1.5wt% of 2,2- triphenylethylenes,
It flows back under 90 DEG C of oil baths.Reaction removes oil bath after 18 hours, and system is made to naturally cool to room temperature.Part is removed with Rotary Evaporators
Organic solvent makes mixture be concentrated into the 1/3 of original volume.Then it is the dichloromethane and saturated salt solution of 1 ︰ 2 to use volume ratio
60mL extracts system, and coextraction three times, collects organic phase, anhydrous sodium sulfate is used in combination to carry out removing water process to it, dry
The volume that agent dosage regards extract liquor determines, 2g anhydrous magnesium sulfates are added per 100mL extract liquors, stand 8 hours.Natural filtration removes
The drier for going water suction, removes solvent on a rotary evaporator；By the petroleum ether that obtained residual solids object volume ratio is 1 ︰ 1
(60~90 DEG C) are that eluant, eluent is detached with column chromatography with dichloromethane mixed solvent, finally obtain compound:1-(4′-Boc-
1- piperazinyls phenyl) -1,2,2- triphenylethylenes, yield 69.5%.Its Identification of chemical structure is carried out according to synthesis example 1.
The synthesis of 6 1- of embodiment (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes
Under high pure nitrogen protection, by the 1- (4 '-bromophenyl) -1 of 615mg, 2,2- triphenylethylenes, 728mg 4- (4 ' -
Boc-1- piperazinyls) phenyl boric acid pinacol ester and 202mg potassium carbonate (1 ︰ of molar ratio, 1.5 ︰ 1.5) mixing after be dissolved in 100mL's
Water (the volume ratio 5 of N,N-dimethylformamide and 20mL:1) in the mixed solvent prepared, is added 8.2mg until completely dissolved
Tetra-triphenylphosphine palladium catalyst, the dosage of tetra-triphenylphosphine palladium catalyst is 1- (4 '-bromophenyl) -1,2,2- triphenylethylenes
2wt% removes oil bath after being reacted 8 hours under 100 DEG C of oil bath heatings, system is made to naturally cool to room temperature.Use Rotary Evaporators
Part organic solvent is removed under reduced pressure, and mixture is made to be concentrated into the 1/3 of original volume.Then it is the dichloro of 1 ︰ 2 to use volume ratio
Methane and saturated salt solution 50mL extract three times concentrate, collect and merge organic phase, 4g anhydrous magnesium sulfates is used in combination to carry out it
Except water process, 8~12 hours are stood.Natural filtration removes the drier of water suction, removes solvent on a rotary evaporator；Will
The petroleum ether (60~90 DEG C) and dichloromethane mixed solvent that the residual solids object volume ratio arrived is 1 ︰ 1 are eluant, eluent column color
Spectrometry detaches, and finally obtains compound:1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes, yield 72.3%.Its
Identification of chemical structure is carried out according to synthesis example 1.
AIE performance tests example 1
Tetraphenylethylene derivative of the present invention has AIE performances, and detecting step is:
1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes that example example 1 is prepared are dissolved in tetrahydrochysene furan
In muttering, it is configured to a concentration of 1 × 10-4The mother liquor of M.It takes 1mL mother liquors to be transferred in 10mL volumetric flasks, the tetrahydrochysene furan of calculation amount is added
It mutters, deionized water constant volume is added dropwise under fast stirring, is finally configured to a concentration of 1 × 10-5M and water content are respectively 0~90%
Mixed solution, water content be percentage by volume.
Above-mentioned each solution is transferred to progress fluorescence spectrum test on the specimen holder of Fluorescence Spectrometer, excitation wavelength choosing rapidly
350nm is selected, selection gist is the wavelength of the absorption peak of the minimum energy of the ultraviolet-visible absorption spectroscopy of solution.Test equipment is
55 type Fluorescence Spectrometer of PerkinElmer LS, the fluorescence spectra measured are concluded in Fig. 4, by the spectrum in figure it is found that working as
When water content reaches 30% in the tetrahydrofuran solution of compound, the fluorescence of compound I starts to occur；With the increase of water content,
Fluorescence intensity gradually increases, and shows that the compound has AIE performances.
AIE performance tests example 2
Tetraphenylethylene derivative of the present invention has AIE performances, and testing procedure is:
It is molten that 1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes that example example 1 is prepared are dissolved in acetonitrile
In agent, it is configured to a concentration of 1 × 10-4The mother liquor of M.It takes 1mL mother liquors to be transferred in 10mL volumetric flasks, the acetonitrile of calculation amount is added,
Deionized water constant volume is added dropwise under fast stirring, is finally configured to a concentration of 1 × 10-5M and water content be respectively 0~90% it is mixed
Solution is closed, water content is percentage by volume.
Above-mentioned each solution is transferred to progress fluorescence spectrum test on the specimen holder of Fluorescence Spectrometer, excitation wavelength choosing rapidly
350nm is selected, selection gist is the wavelength of the absorption peak of the minimum energy of the ultraviolet-visible absorption spectroscopy of solution.Test equipment is
55 type Fluorescence Spectrometer of PerkinElmer LS.When water content reaches 50% in the acetonitrile solution of compound, compound I's
Fluorescence starts to occur；With continuing growing for water content, fluorescence intensity gradually increases, and shows that the compound has AIE performances.
AIE performance tests example 3
Tetraphenylethylene derivative of the present invention has AIE performances, and testing procedure is:
1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes that example example 1 is prepared are dissolved in dioxy six
In ring, it is configured to a concentration of 1 × 10-4The mother liquor of M.It takes 1mL mother liquors to be transferred in 10mL volumetric flasks, the dioxy six of calculation amount is added
Ring is added dropwise deionized water constant volume, is finally configured to a concentration of 1 × 10 under fast stirring-5M and water content are respectively 0~90%
Mixed solution, water content be percentage by volume.
Above-mentioned each solution is transferred to progress fluorescence spectrum test on the specimen holder of Fluorescence Spectrometer, excitation wavelength choosing rapidly
350nm is selected, selection gist is the wavelength of the absorption peak of the minimum energy of the ultraviolet-visible absorption spectroscopy of solution.Test equipment is
55 type Fluorescence Spectrometer of PerkinElmer LS.When water content reaches 50% in the tetrahydrofuran solution of compound, compound
The fluorescence of I starts to occur；With the increase of water content, fluorescence intensity gradually increases, and shows that the compound has AIE performances.
AIE performance tests example 4
Tetraphenylethylene derivative of the present invention has AIE performances, and testing procedure is:
1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes that example example 1 is prepared are dissolved in dimethyl
In sulfoxide, it is configured to a concentration of 1 × 10-4The mother liquor of M.It takes 1mL mother liquors to be transferred in 10mL volumetric flasks, the diformazan of calculation amount is added
Base sulfoxide is added dropwise deionized water constant volume, is finally configured to a concentration of 1 × 10 under fast stirring-5M and water content be respectively 0~
90% mixed solution, water content are percentage by volume.
Above-mentioned each solution is transferred to progress fluorescence spectrum test on the specimen holder of Fluorescence Spectrometer, excitation wavelength choosing rapidly
350nm is selected, selection gist is the wavelength of the absorption peak of the minimum energy of the ultraviolet-visible absorption spectroscopy of solution.Test equipment is
55 type Fluorescence Spectrometer of PerkinElmer LS.When water content reaches 60% in the dimethyl sulphoxide solution of compound, chemical combination
The fluorescence of object I starts to occur；With the increase of water content, fluorescence intensity gradually increases, and shows that the compound has AIE performances.
AIE performance tests example 5
Tetraphenylethylene derivative AIE performances of the present invention, detecting step are:
1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes that example example 1 is prepared are dissolved in N, N- bis-
In methylformamide, it is configured to a concentration of 1 × 10-4The mother liquor of M.It takes 1mL mother liquors to be transferred in 10mL volumetric flasks, calculation amount is added
N,N-Dimethylformamide, under fast stirring be added dropwise deionized water constant volume, be finally configured to a concentration of 1 × 10-5M and aqueous
Amount is respectively 0~90% mixed solution, and water content is percentage by volume.
Above-mentioned each solution is transferred to progress fluorescence spectrum test on the specimen holder of Fluorescence Spectrometer, excitation wavelength choosing rapidly
350nm is selected, selection gist is the wavelength of the absorption peak of the minimum energy of the ultraviolet-visible absorption spectroscopy of solution.Test equipment is
55 type Fluorescence Spectrometer of PerkinElmer LS.When water content reaches 60% in the N,N-dimethylformamide solution of compound
When, the fluorescence of compound I starts to occur；With the increase of water content, fluorescence intensity gradually increases, and shows that the compound has AIE
Performance.
TNP detects application example 1
AIE molecules of the present invention can be used for detecting TNP, and detecting step is:
By 1- (4 '-Boc-1- piperazinyls phenyl) -1,2,2- triphenylethylenes a concentration of 1 × 10-5M and water content is respectively
90% organic solvent/water mixed solution is tetrahydrofuran, acetonitrile, dioxy six as fluoroscopic examination medium, wherein organic solvent
One kind in ring, dimethyl sulfoxide (DMSO), n,N-Dimethylformamide, wherein water content are percent by volume.It is mixed with tetrahydrofuran/water
For bonding solvent, it is added TNP into fluoroscopic examination medium, the concentration of TNP is from 1 X 10-6M is gradually increased to 5 X 10-5M.With
The fluorescence intensity of the increase of TNP concentration, detection architecture gradually weakens.1 X 10 is added-6The TNP of M can cause the glimmering of detection architecture
Luminous intensity is decreased obviously, and data shown in fig. 5 illustrate that fluorescence intensity declines 10%.Fluorescence intensity I maps to TNP concentration,
It obtains Fig. 6 and relation curve that system fluorescence intensity shown in Fig. 7 changes with TNP concentration, passes through and determine TNP detections on curve
Lower bound is in 1 X 10-6M。
Detection method when using acetonitrile, dioxane, dimethyl sulfoxide (DMSO), N,N-dimethylformamide as organic solvent
It is identical as above-mentioned TNP detection application examples 1.
Claims (10)
1. a kind of piperazine modified tetraphenylethylene derivative, structural formula is as shown in formula I：
Wherein, R is alkyl.
2. piperazine modified tetraphenylethylene derivative according to claim 1, which is characterized in that the R be methyl,
Ethyl, propyl, isopropyl, butyl or tertiary butyl.
3. a kind of preparation method of piperazine modified tetraphenylethylene derivative according to claim 1 or 2, including：
Under inert gas protection, 1- (4 '-bromophenyl) -1,2,2- triphenylethylenes, 4- (4 '-carbonate group -1- piperazinyls)
Phenyl boric acid gneissic suite ester and carbonate are dissolved in organic solvent A or organic solvent A and the in the mixed solvent of water, and catalyst is added,
Carry out Suzuki coupling reactions；It waits for that after reaction, product mixtures being cooled to room temperature, post-processing obtains shown in formula I
Piperazine modified tetraphenylethylene derivative.
4. the preparation method of piperazine modified tetraphenylethylene derivative according to claim 3, which is characterized in that described
Suzuki coupling reaction conditions be：Catalyst is tetra-triphenylphosphine palladium, and reaction temperature is 80~100 DEG C, the reaction time is 5~
30 hours.
5. the preparation method of piperazine modified tetraphenylethylene derivative according to claim 3, which is characterized in that described
Organic solvent A be tetrahydrofuran, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), dioxane or
Cyclohexanone；The in the mixed solvent water content of the organic solvent A and water is 5~30% by volume.
6. the preparation method of piperazine modified tetraphenylethylene derivative according to claim 3, which is characterized in that described
1- (4 '-bromophenyl) -1,2,2- triphenylethylenes and 4- (4 '-carbonate group -1- piperazinyls) phenyl boric acid gneissic suite ester rub
You are than being 1:1.1~2.0；The dosage of the tetra-triphenylphosphine palladium is the 1 of 1- (4 '-bromophenyl) -1,2,2- triphenylethylenes
~3wt%.
7. piperazine modified tetraphenylethylene derivative according to claim 1 is as fluorescent probe molecule in the fragrant nitre of detection
Application in base explosive field.
8. application according to claim 7, which is characterized in that the fragrant nitro explosive is 2,4,6- trinitrobenzens
Phenol.
9. application according to claim 7 or 8, specifically includes：
(a) it using tetraphenylethylene derivative piperazine modified shown in Formulas I as fluorescent material, using organic solvent B as solvent, prepares
A concentration of 1~10 × 10-6The solution of mol/L；
(b) water is added in the solution prepared to step (a), prepares the suspension of piperazine modified tetraphenylethylene derivative；
(c) into suspension made from step (b), fragrant nitro explosive is added, detection suspension system fluorescence intensity is with virtue
It is bent to draw the work that suspension system fluorescence intensity changes with fragrant nitro explosive concentration for the variation of nitro explosive content
Line obtains the minimum detection limit of fragrant nitro explosive.
10. application according to claim 9, which is characterized in that in step (a), the organic solvent B is tetrahydrochysene furan
It mutters, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide (DMSO) or dioxane；In step (b), the water addition with it is organic
The volume ratio of solvent B is 80~90%.
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| CN109879809A (en) * | 2019-04-03 | 2019-06-14 | 南京信息工程大学 | A kind of united imidazole derivative of triphenylethylene modification and its preparation and application |
| CN110818614A (en) * | 2019-10-23 | 2020-02-21 | 黎明化工研究设计院有限责任公司 | Nitrogen-oxygen stable free radical with aggregation-induced emission function and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879809A (en) * | 2019-04-03 | 2019-06-14 | 南京信息工程大学 | A kind of united imidazole derivative of triphenylethylene modification and its preparation and application |
| CN109879809B (en) * | 2019-04-03 | 2022-03-11 | 南京信息工程大学 | Triphenylethylene modified bisimidazole derivative and preparation and application thereof |
| CN110818614A (en) * | 2019-10-23 | 2020-02-21 | 黎明化工研究设计院有限责任公司 | Nitrogen-oxygen stable free radical with aggregation-induced emission function and preparation method thereof |
| CN110818614B (en) * | 2019-10-23 | 2023-04-14 | 黎明化工研究设计院有限责任公司 | Nitrogen-oxygen stable free radical with aggregation-induced emission function and preparation method thereof |
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