CN107759612A - The method that single conveyor screw was fixed and split into tetraphenyl ethylene propeller-type structure - Google Patents
The method that single conveyor screw was fixed and split into tetraphenyl ethylene propeller-type structure Download PDFInfo
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- CN107759612A CN107759612A CN201610688164.7A CN201610688164A CN107759612A CN 107759612 A CN107759612 A CN 107759612A CN 201610688164 A CN201610688164 A CN 201610688164A CN 107759612 A CN107759612 A CN 107759612A
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- 0 *C1C=CC(C(c2ccc(*)cc2)=C(c2ccc(*)cc2)c2ccc(*)cc2)=CC1 Chemical compound *C1C=CC(C(c2ccc(*)cc2)=C(c2ccc(*)cc2)c2ccc(*)cc2)=CC1 0.000 description 12
- JSNZQPQAJMWARG-UHFFFAOYSA-N C1N(C2)N3CN2CN1C3 Chemical compound C1N(C2)N3CN2CN1C3 JSNZQPQAJMWARG-UHFFFAOYSA-N 0.000 description 1
- QLZPYMLFOLBKNV-UHFFFAOYSA-N CC(C(C=C1)C(c(cc2)ccc2O)=C(C(CC2)=CC=C2O)C(CC2)=CC=C2O)C=C1O Chemical compound CC(C(C=C1)C(c(cc2)ccc2O)=C(C(CC2)=CC=C2O)C(CC2)=CC=C2O)C=C1O QLZPYMLFOLBKNV-UHFFFAOYSA-N 0.000 description 1
- LGWPEHHGBOPMHP-GNUNVXCFSA-N CC(CC=C(C=C1)/C(/c(cc2CO)ccc2OC2)=C(\c(cc3)cc(CO)c3OC3)/c(cc4CO)ccc4OCc4ccc2cc4)=C1NCc1ccc3cc1 Chemical compound CC(CC=C(C=C1)/C(/c(cc2CO)ccc2OC2)=C(\c(cc3)cc(CO)c3OC3)/c(cc4CO)ccc4OCc4ccc2cc4)=C1NCc1ccc3cc1 LGWPEHHGBOPMHP-GNUNVXCFSA-N 0.000 description 1
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Abstract
The invention provides tetraphenyl ethylene (TPE) propeller-type conformation separation that one kind will have aggregation-induced emission (AIE), and the method for splitting into single left-hand screw body and right-hand screw body.Four phenyl of tetraphenyl ethylene are connected into four rings between each other by using short chain, tetraphenyl ethylene propeller-type conformation is fixed.Chromatogram is prepared by chirality, tetraphenyl ethylene propeller-type structure is split into left-hand screw body and right-hand screw body.After tetraphenyl ethylene propeller-type conformation is fixed, fluorescence quantum yield increases substantially, in the solid state with all there is hyperfluorescence in solution, and show aggregation-induced emission effect.Single conveyor screw has up to 502oSpecific rotatory power, strong circular dichroism effect, and circular polarization fluorescence (CPL) can be launched.
Description
Technical field
The invention belongs to chemical field, it is related to tetraphenyl ethylene propeller-type structure and fixes, splits and their chiral light
Learn performance.
Background technology
Helical molecule not only has novel structure and beautiful profile, and its spiral chirality is in physiological function regulation, hand
Property sensing, asymmetry catalysis, photoelectric material etc. also has huge application prospect, be always the focus and Disciplinary Frontiers of research
(Adv.Mater.2015,1-16；Chem.Soc.Rev.2013,42,1051-1095).The tool that this loyalty of Tang in 2001 et al. is found
Have the organic compound of aggregation-induced emission (Aggregation-Induced Emission, AIE) phenomenon photoelectric material with
And chemistry and biology sensor etc. have great application value, cause extremely extensive attention and research
(Chem.Rev.2015,115,11718–11940；Chem.Sci.2015,6,5347–5365).The spiral of most AIE compounds
Paddle structure is that it has the determinant of aggregation-induced emission characteristic, but because propeller arrangement is not fixed easily, it is resulting
AIE molecular spirals chirality is not researched and developed and applied so far.Tetraphenyl ethylene (TPE) and its derivative are most typicallies and studied most
More AIE compounds, TPE four phenyl are connected into cyclization in intramolecular with rigid short chain, the rotation of phenyl ring is limited, makes four benzene
The propeller arrangement of ethene is fixed up, with regard to that can obtain with the TPE spiral isomers for stablizing propeller arrangement, for chiral light
Learn the research of performance, such as circular dichroism spectra, circular polarization fluorescence.Due to AIE effects, after propeller arrangement is fixed, fluorescence is significantly
Degree enhancing, this kind of TPE conveyor screws chiral Recognition, asymmetry catalysis, bio-imaging, fluorescent whitening agent, Organic Light Emitting Diode,
All many-sides such as 3D display are by with important application prospect.
The content of the invention
It is an object of the invention to provide a kind of AIE compounds for having and stablizing propeller-type structure, can split into single
Conveyor screw, transmitting hyperfluorescence, there is strong circular dichroism spectra signal and chiral fluorescent emission.
It is a further object to provide the preparation method of the AIE compounds of this stable propeller-type structure.
Realize the technical scheme is that：
It is provided by the invention with stablizing the AIE compounds of propeller-type structure with structure shown in following formula (I)：
In formula (I)：
Each X stands alone as O, NH or CH at the same time or separately2；
Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、CH2OH、COONa、NH2、SO3Na or CONHR, wherein CONHR
And CO2R in R is alkyl or APEO chain；
Each R2H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R
It is alkyl or APEO chain with the R in CONHR；
The preparation method of formula (I) compound provided by the invention, comprises the following steps：
Step 1：Formula II compound, hexamethylenetetramine and trifluoroacetic acid are added in round-bottomed flask, described Formula II
Compound is 4,4 ', 4 ", 4 " '-tetrahydroxy or 4,4 ', 4 ", 4 " '-tetramino tetraphenyl ethylene or 4,4 ', 4 ", 4 " '-tetramethyl four
Styrene, the Formula II compound be by document Chem.Asian J.2011,6,2376-2381 disclose methods synthesis be made；Formula
II compounds, hexamethylenetetramine, the charge ratio of trifluoroacetic acid are followed successively by：0.5-2g：1-2g：10-50mL；Reactant mixture
Heating reflux reaction about 3h, frozen water is added, 2-4h is stirred at room temperature, is extracted with ethyl acetate；After extract merges, with anhydrous sulphur
Sour sodium is dried, and is filtered, and is evaporated under reduced pressure, obtained crude product purified by silica gel column chromatography separating purification (eluant, eluent：Ethyl acetate/oil
Ether 1:4 volume ratios), the formula III compound of yellow is obtained, reaction equation is as follows：
In Formula II：Each X stands alone as O, NH or CH at the same time or separately2；
In formula III：Each X stands alone as O, NH or CH at the same time or separately2；
Step 2：Formula III compound, 1,4- xylylene bromides, Anhydrous potassium carbonate and drying are added in reaction vessel
Acetonitrile, their charge ratio are followed successively by 200-800mg：300-900mg：300-700mg：50-300mL, reactant mixture add
Heat backflow 3-6h, reaction finish, and add appropriate dichloromethane and water, separate organic layer, and water layer extracts 2-3 with dichloromethane
It is secondary, anhydrous sodium sulfate drying, filtering, evaporated under reduced pressure solvent, residue silica gel column chromatogram separating purification (eluant, eluent：Acetic acid second
Ester：Dichloromethane 1:50 volume ratios) obtain yellow formula IV compound, reaction equation are as follows：
In formula III：Each X stands alone as O, NH or CH at the same time or separately2；
In formula IV：Each X stands alone as O, NH or CH at the same time or separately2；Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、
CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R in R and CONHR is alkyl or APEO chain；
Step 3：Formula IV compound, sodium borohydride, THF and ethanol are added in reaction vessel, their weight ratio is successively
For 100-500mg：200-600mg：10-50mL：20-60mL, after stirring 1-3h at room temperature, a small amount of water is slowly added into, uses dichloro
Methane extracts, anhydrous sodium sulfate drying, and filtering, filtrate is evaporated to dryness, residue silica gel column chromatogram separating purification (eluant, eluent：
Methanol：Dichloromethane 1:30 volume ratios) obtain white Formula V compound, reaction equation are as follows：
In formula IV：Each X stands alone as O, NH or CH at the same time or separately2；Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、
CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R in R and CONHR is alkyl or APEO chain；
In Formula V：Each X stands alone as O, NH or CH at the same time or separately2；Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、
CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R in R and CONHR is alkyl or APEO chain；
Step 4：Formula V compound and dichloromethane are added in reaction vessel, adds pyridine under ice cooling, 4, then
The dichloromethane solution of thionyl chloride is added dropwise, 0.5h drips, and Formula V compound, dichloromethane, pyridine and thionyl chloride feed intake
Proportioning is followed successively by 100-300mg：10-50mL：0.1-1mL：0.2-1.2mL, 3-5h is stirred at room temperature, add a small amount of water, with two
Chloromethanes extracts, anhydrous sodium sulfate drying, and filtering, filtrate is evaporated to dryness, residue silica gel column chromatogram separating purification (elution
Agent：Ethyl acetate：Petroleum ether 1:8 volume ratios) obtain white Formula IV compound, reaction equation are as follows：
In formula (V)：
Each X stands alone as O, NH or CH at the same time or separately2；
Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R
It is alkyl or APEO chain with the R in CONHR；
In Formula IV：
Each X stands alone as O, NH or CH at the same time or separately2；
Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R
It is alkyl or APEO chain with the R in CONHR；
Step 5：Added in reaction vessel Formula IV compound, KI, Anhydrous potassium carbonate, the acetonitrile of drying, to benzene two
Amphyl/p-phenylene diamine derivative or para-xylene derivative, their charge ratio are followed successively by 200-400mg：100-
300mg：50-150mg：50-300mL：30-100mg；After reactant mixture is heated to reflux 12-24h, solvent is evaporated, added suitable
The dichloromethane and water of amount, organic layer is separated, water layer is extracted 2-3 times with dichloromethane, organic phase anhydrous sodium sulfate drying, mistake
Filter, filtrate decompression are evaporated, residue silica gel column chromatogram separating purification (eluant, eluent：Ethyl acetate：Petroleum ether 1:4 volume ratios)
It is as follows to white compound of formula I, reaction equation：
In formula I：
Each X stands alone as O, NH or CH at the same time or separately2；
Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CONHR
And CO2R in R is alkyl or APEO chain；
Each R2H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R
It is alkyl or APEO chain with the R in CONHR；
It is provided by the invention tetraphenyl ethylene propeller-type structure is split into left-hand screw body and right-hand screw body method be：With
Chirality prepares high pressure liquid chromatography post, and mobile phase is volume ratio 80：20 methylene chloride-methanol mixed solvent, right can be wanted
Described formula (I) compound is asked to be split as two peaks of left-hand screw body and right-hand screw body, the retention time at peak 1 is 2.455min, its
Corresponding molecular structure is the left-hand screw body in formula (I) compound；The retention time at peak 2 is 3.430min, its corresponding molecule
Structure is the right-hand screw body in formula (I) compound.
The specific synthesis road with AIE compounds i.e. formula (I) compound for stablizing propeller-type structure provided by the invention
Line is as follows:
0.5-2g formulas (II) compound, 1-2g hexamethylenetetramines and 10-50mL trifluoroacetic acids are added to round-bottomed flask
In, reactant mixture heating reflux reaction about 3h, with TLC detections reaction until raw material disappears.Frozen water is added, stirs 2- at room temperature
4h, it is extracted with ethyl acetate.After extract merges, with anhydrous sodium sulfate drying, filter, be evaporated under reduced pressure, obtained crude product is used
Silica gel column chromatogram separating purification (eluant, eluent：Ethyl acetate/petroleum ether 1:4 volume ratios), formula (III) compound of yellow is obtained,
Yield 70%.
In reaction vessel/round-bottomed flask in add 200-800mg formulas (III) compound, 300-900mg1,4- dibromo first
The acetonitrile that base benzene, 300-700mg Anhydrous potassium carbonates and 50-300mL are dried, reactant mixture are heated to reflux 3-6h.React
To finish, add appropriate dichloromethane and water, separate organic layer, water layer is extracted 2-3 times with dichloromethane, anhydrous sodium sulfate drying,
Filtering, evaporated under reduced pressure solvent, residue silica gel column chromatogram separating purification (eluant, eluent：Ethyl acetate：Dichloromethane 1:50 volumes
Than) obtain yellow formula (IV) compound, yield 43%.
100-500mg formulas (IV) compound, 200-600mg sodium borohydrides, 10-50mL tetrahydrochysene furans are added in reaction vessel
Mutter and 20-60mL ethanol, after stirring 1-3h at room temperature, be slowly added into a small amount of water.Extracted with dichloromethane, anhydrous sodium sulfate is done
Dry, filtering, filtrate is evaporated to dryness.Residue silica gel column chromatogram separating purification (eluant, eluent：Methanol：Dichloromethane 1:30 volumes
Than) obtain obtaining white formula (V) compound, yield 85%.
100-300mg formulas (V) compound and 10-50mL dichloromethane are added in reaction vessel, is added under ice cooling, 4
Enter 0.1-1mL pyridines, 0.2-1.2mL thionyl chlorides are then added dropwise, after 0.5h is dripped, stir 3-5h at room temperature.Add a small amount of
Water, extracted, anhydrous sodium sulfate drying, filtered with dichloromethane, filtrate is evaporated to dryness.Residue silica gel column chromatogram separating purification
(eluant, eluent：Ethyl acetate：Petroleum ether 1:8 volume ratios) obtain obtaining white formula (VI) compound, yield 75%.
Formula 200-400mg (VI) compound, 100-300mg KIs, the anhydrous carbon of 50-150mg are added in reaction vessel
Acetonitrile, the 30-100mg hydroquinones that sour potassium, 50-300mL are dried, reactant mixture are heated to reflux 12-24h.Reaction finishes,
Solvent is evaporated.Appropriate dichloromethane and water are added, separates organic layer, water layer is extracted 2-3 times with dichloromethane, organic phase nothing
Aqueous sodium persulfate is dried.Filtering, filtrate decompression are evaporated, residue silica gel column chromatogram separating purification (eluant, eluent：Ethyl acetate：Stone
Oily ether 1:4 volume ratios) obtain white formula (I) compound, yield 54%.
In formula (I), X, R1And R2It can be a kind of above-mentioned atom and substituent simultaneously, also can be above-mentioned different original simultaneously
Son and substituent.
Structure determination：
Structure is determined by means of testing such as NMR, HRMS, Advances in crystal X-ray diffraction, IR, Mp, UV-Vis, fluorescence spectrums.
Tetraphenyl ethylene (TPE) the propeller-type conformation with aggregation-induced emission (AIE) is consolidated the invention provides one kind
It is fixed, and the method for splitting into single left-hand screw body and right-hand screw body.It is by using short chain that four phenyl of tetraphenyl ethylene are mutual
Four rings are connected into, tetraphenyl ethylene propeller-type conformation can be fixed, and prepare chromatogram by chirality, by tetraphenyl ethylene spiral
Paddle type structure splits into left-hand screw body and right-hand screw body.After tetraphenyl ethylene propeller-type conformation is fixed, fluorescence quantum yield is big
Amplitude improves, and not only in the solid state, also has hyperfluorescence in the solution, and show aggregation-induced emission effect.Single spiral
Body has up to 502 ° of specific rotatory power, strong circular dichroism effect, and can launch circular polarization fluorescence (CPL).Single spiral
Body is in tetrahydrofuran solution, greatest circle polarized fluorescence dissymmetry factor (glum) it is 3.3 × 10-3, in water and tetrahydrofuran volume
Than for 90:In 10 suspension, maximum nearly 1 times of dissymmetry factor increase, is 6.2 × 10-3。
" formula (I) compound " in present patent application with " tetraphenyl ethylene propeller-type molecule I " refers to same compound, energy
It is used alternatingly.
The invention will be further described by the following examples, and the scope of the protection of present patent application includes following implementation
Example, but it is not limited to the following example.
Brief description of the drawings
1H-NMR spectrums of Fig. 1 tetraphenyl ethylene propeller-type molecules I in DMSO；
13C H NMR spectroscopies of Fig. 2 tetraphenyl ethylene propeller-type molecules I (formula (I) compound) in DMSO；
Fig. 3 tetraphenyl ethylene propeller-type molecules I high resolution mass spectrum；
Fig. 4 tetraphenyl ethylene propeller-type molecules I (formula (I) compound) crystal structure, the left-hand screw body M- comprising equivalent
I and right-hand screw body P-I.Solvent molecule has been omitted；
The crystal knot for the single conveyor screw M-I that Fig. 5 tetraphenyl ethylene propeller-type molecules I (formula (I) compound) is split into
Structure.Solvent molecule has been omitted；
Two single conveyor screw M-I and P-I that Fig. 6 tetraphenyl ethylene propeller-type molecules I (formula (I) compound) is split out
Circular dichroism spectra in tetrahydrofuran solution.Concentration 5mg/mL (5.8 × 10-3M)；
The single conveyor screw M-I and P-I that Fig. 7 formulas (I) compound (tetraphenyl ethylene propeller-type molecule I) is split out is four
Chiral fluorescence emission spectrum in hydrogen tetrahydrofuran solution；
Two single conveyor screws that Fig. 8 formulas (I) compound is split out are 90 in volume ratio:10 water/tetrahydrofuran suspension
In circular polarization fluorescence spectrum.
Embodiment
Embodiment 1
Tetraphenyl ethylene propeller-type molecule I (in general expression I, X=O；R1=H；R2=H) synthesis：
0.5-2g formulas (II) compound, 1-2g hexamethylenetetramines and 10-50mL trifluoroacetic acids are added to round-bottomed flask
In, reactant mixture heating reflux reaction about 3h, with TLC detections reaction until raw material disappears.Frozen water is added, stirs 2- at room temperature
4h, it is extracted with ethyl acetate.After extract merges, with anhydrous sodium sulfate drying, filter, be evaporated under reduced pressure, obtained crude product is used
Silica gel column chromatogram separating purification (eluant, eluent：Ethyl acetate/petroleum ether 1:4 volume ratios), formula (III) compound of yellow is obtained,
Yield 70%.
In reaction vessel/round-bottomed flask in add 200-800mg formulas (III) compound, 300-900mg1,4- dibromo first
The acetonitrile that base benzene, 300-700mg Anhydrous potassium carbonates and 50-300mL are dried, reactant mixture are heated to reflux 3-6h.React
To finish, add appropriate dichloromethane and water, separate organic layer, water layer is extracted 2-3 times with dichloromethane, anhydrous sodium sulfate drying,
Filtering, evaporated under reduced pressure solvent, residue silica gel column chromatogram separating purification (eluant, eluent：Ethyl acetate：Dichloromethane 1:50 volumes
Than) obtain yellow formula (IV) compound, yield 43%.
100-500mg formulas (IV) compound, 200-600mg sodium borohydrides, 10-50mL tetrahydrochysene furans are added in reaction vessel
Mutter and 20-60mL ethanol, after stirring 1-3h at room temperature, be slowly added into a small amount of water.Extracted with dichloromethane, anhydrous sodium sulfate is done
Dry, filtering, filtrate is evaporated to dryness.Residue silica gel column chromatogram separating purification (eluant, eluent：Methanol：Dichloromethane 1:30 volumes
Than) obtain obtaining white formula (V) compound, yield 85%.
100-300mg formulas (V) compound and 10-50mL dichloromethane are added in reaction vessel, is added under ice cooling, 4
Enter 0.1-1mL pyridines, 0.2-1.2mL thionyl chlorides are then added dropwise, after 0.5h is dripped, stir 3-5h at room temperature.Add a small amount of
Water, extracted, anhydrous sodium sulfate drying, filtered with dichloromethane, filtrate is evaporated to dryness.Residue silica gel column chromatogram separating purification
(eluant, eluent：Ethyl acetate：Petroleum ether 1:8 volume ratios) obtain obtaining white formula (VI) compound, yield 75%.
Formula 200-400mg (VI) compound, 100-300mg KIs, the anhydrous carbon of 50-150mg are added in reaction vessel
Acetonitrile, the 30-100mg hydroquinones that sour potassium, 50-300mL are dried, reactant mixture are heated to reflux 12-24h.Reaction finishes,
Solvent is evaporated.Appropriate dichloromethane and water are added, separates organic layer, water layer is extracted 2-3 times with dichloromethane, organic phase nothing
Aqueous sodium persulfate is dried.Filtering, filtrate decompression are evaporated, residue silica gel column chromatogram separating purification (eluant, eluent：Ethyl acetate：Stone
Oily ether 1:4 volume ratios) obtain white formula (I) compound, yield 54%.
Formula (I) compound1H-NMR spectrums are shown in Fig. 1,13C-NMR spectrums are shown in Fig. 2, and HRMS spectrums are shown in Fig. 3.
Embodiment 2
High pressure liquid chromatography post is prepared with chirality, mobile phase is volume ratio 80：20 methylene chloride-methanol mixed solvent,
Formula (I) compound can be split as to two peaks of left-hand screw body and right-hand screw body, the retention time at peak 1 is 2.455min, the guarantor at peak 2
It is 3.430min to stay the time.The percent enantiomeric excess of the 2 two single conveyor screws in peak 1 and peak is more than 99%.Through single-crystal x-penetrate
Line diffraction, the left-hand screw body and right-hand screw body of equivalent are included in formula (I) compound, is a racemic modification；Corresponding to peak 1
Molecular structure be formula (I) compound in left-hand screw body, referred to as M-I；Peak 2 is then right-hand screw body, referred to as P-I.Formula (I) compound
And M-I mono-crystalline structures, see Fig. 4 and Fig. 5.
Embodiment 3
In the tetrahydrofuran that concentration is 5mg/mL, M-I specific rotatory powers [α]20 D=+479 °；P-I specific rotatory powers [α]20 D
=-502 °.Absolute fluorescence quantum yield in tetrahydrofuran：Formula (I) compound 79%；M-I is that 94%, P-I is also 94%；
It is 95 in volume ratio:Absolute fluorescence quantum yield in 5 water/tetrahydrofuran suspension：Formula (I) compound 88%；M-I is
85%, P-I are also 85%.
Embodiment 4
Two single conveyor screws that formula (I) compound is split out are dissolved in tetrahydrofuran solution respectively, are made into concentration
For 5mg/mL solution, circular dichroism spectra is determined, the M-I chromatographic signal of greatest circle two is+188, the P-I chromatographic signal of greatest circle two
For -186, mirror each other, it is left-hand screw body to illustrate certain one, and one is right-hand screw body.See Fig. 6.
Embodiment 5
Two single conveyor screw M-I and P-I that formula (I) compound is split out are dissolved in tetrahydrofuran solution respectively,
Concentration is made into as 1.0 × 10-3M solution, determine circular polarization fluorescence spectrum, the tetrahydrofuran solution tool of the two single conveyor screws
There are circular polarization fluorescence signal, and mirror each other, M-I and P-I are calculated circular polarization fluorescence dissymmetry factor and are respectively
(glum) it is 3.1 × 10-3With 3.3 × 10-3.M-I and P-I are dissolved in a small amount of tetrahydrofuran solution respectively, then added big
Water is measured, it is 90 to make the volume ratio of water and tetrahydrofuran:10, concentration is made into as 1.0 × 10-3M suspension, determine circular polarization fluorescence
Spectrum, the suspension of two single conveyor screws have the circular polarization fluorescence signal more stronger than its solution, and mirror each other, M-
The circular polarization fluorescence dissymmetry factor difference (g that I and P-I are calculatedlum) it is 6.2 × 10-3With 5.0 × 10-3。
Two single conveyor screw M-I and P-I are shown in Fig. 7 and figure respectively in solution and the circular polarization fluorescence spectrum in suspension
8.Fig. 7 is circular polarization fluorescence of the two single conveyor screw M-I and P-I splitting out of formula (I) compound in tetrahydrofuran solution
Spectrum.Concentration 1.0 × 10-3M.Circular polarization fluorescence dissymmetry factor：M-I, 3.1 × 10-3；P-I, 3.3 × 10-3.Fig. 8 is formula (I)
Two single conveyor screws that compound is split out are 90 in volume ratio:Circular polarization fluorescence light in 10 water/tetrahydrofuran suspension
Spectrum.Concentration 1.0 × 10-3M.Circular polarization fluorescence dissymmetry factor：M-I, 6.2 × 10-3；P-I, 5.0 × 10-3。
Claims (6)
1. with the compound of structure shown in following formula (I)：
In formula (I)：
Each X stands alone as O, NH or CH at the same time or separately2；
Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、CH2OH、COONa、NH2、SO3Na or CONHR, wherein CONHR and
CO2R in R is alkyl or APEO chain；
Each R2H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R and
R in CONHR is alkyl or APEO chain.
2. the preparation method of compound described in claim 1, comprises the following steps：
Step 1：Formula II compound, hexamethylenetetramine and trifluoroacetic acid are added in round-bottomed flask, described Formula II chemical combination
Thing is 4,4 ', 4 ", 4 " '-tetrahydroxy or 4,4 ', 4 ", 4 " '-tetramino tetraphenyl ethylene or 4,4 ', the benzene second of 4 ", 4 " '-tetramethyl four
Alkene, the Formula II compound be by document Chem.Asian J.2011,6,2376-2381 disclose methods synthesis be made；Formula II
Compound, hexamethylenetetramine, the charge ratio of trifluoroacetic acid are followed successively by：0.5-2g：1-2g：10-50mL；Reactant mixture heats
Back flow reaction about 3h, frozen water is added, 2-4h is stirred at room temperature, is extracted with ethyl acetate；After extract merges, anhydrous sodium sulfate is used
Dry, filter, be evaporated under reduced pressure, obtained crude product purified by silica gel column chromatography separating purification (eluant, eluent：Ethyl acetate/petroleum ether 1:4
Volume ratio), the formula III compound of yellow is obtained, reaction equation is as follows：
In Formula II：Each X stands alone as O, NH or CH at the same time or separately2；
In formula III：Each X stands alone as O, NH or CH at the same time or separately2；
Step 2：Formula III compound, 1,4- xylylene bromides, Anhydrous potassium carbonate and the second dried are added in reaction vessel
Nitrile, their charge ratio are followed successively by 200-800mg：300-900mg：300-700mg：50-300mL, reactant mixture heating
Flowed back 3-6h, and reaction finishes, and adds appropriate dichloromethane and water, separates organic layer, and water layer is extracted 2-3 times with dichloromethane,
Anhydrous sodium sulfate drying, filtering, evaporated under reduced pressure solvent, residue silica gel column chromatogram separating purification (eluant, eluent：Ethyl acetate：
Dichloromethane 1:50 volume ratios) obtain yellow formula IV compound, reaction equation are as follows：
In formula III：Each X stands alone as O, NH or CH at the same time or separately2；
In formula IV：Each X stands alone as O, NH or CH at the same time or separately2；Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、
CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R in R and CONHR is alkyl or APEO chain；
Step 3：Formula IV compound, sodium borohydride, THF and ethanol, their weight ratio is added in reaction vessel to be followed successively by
100-500mg：200-600mg：10-50mL：20-60mL, after stirring 1-3h at room temperature, a small amount of water is slowly added into, uses dichloromethane
Alkane extracts, anhydrous sodium sulfate drying, and filtering, filtrate is evaporated to dryness, residue silica gel column chromatogram separating purification (eluant, eluent：First
Alcohol：Dichloromethane 1:30 volume ratios) obtain white Formula V compound, reaction equation are as follows：
In formula IV：Each X stands alone as O, NH or CH at the same time or separately2；Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、
CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R in R and CONHR is alkyl or APEO chain；
In Formula V：Each X stands alone as O, NH or CH at the same time or separately2；Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、
CH2OH、COONa、NH2Or SO3Na, wherein CO2R in R and CONHR is alkyl or APEO chain；
Step 4：Formula V compound and dichloromethane are added in reaction vessel, pyridine is added under ice cooling, 4, is then added dropwise
The dichloromethane solution of thionyl chloride, 0.5h are dripped, Formula V compound, dichloromethane, the charge ratio of pyridine and thionyl chloride
It is followed successively by 100-300mg：10-50mL：0.1-1mL：0.2-1.2mL, 3-5h is stirred at room temperature, add a small amount of water, use dichloromethane
Alkane extracts, anhydrous sodium sulfate drying, and filtering, filtrate is evaporated to dryness, residue silica gel column chromatogram separating purification (eluant, eluent：Second
Acetoacetic ester：Petroleum ether 1:8 volume ratios) obtain white Formula IV compound, reaction equation are as follows：
In formula (V)：
Each X stands alone as O, NH or CH at the same time or separately2；
Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R and
R in CONHR is alkyl or APEO chain；
In Formula IV：
Each X stands alone as O, NH or CH at the same time or separately2；
Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R and
R in CONHR is alkyl or APEO chain；
Step 5：Formula IV compound, KI, Anhydrous potassium carbonate, the acetonitrile of drying, hydroquinones is added in reaction vessel to spread out
Biology/p-phenylene diamine derivative or para-xylene derivative, their charge ratio are followed successively by 200-400mg：100-
300mg：50-150mg：50-300mL：30-100mg；After reactant mixture is heated to reflux 12-24h, solvent is evaporated, added suitable
The dichloromethane and water of amount, organic layer is separated, water layer is extracted 2-3 times with dichloromethane, organic phase anhydrous sodium sulfate drying, mistake
Filter, filtrate decompression are evaporated, residue silica gel column chromatogram separating purification (eluant, eluent：Ethyl acetate：Petroleum ether 1:4 volume ratios)
It is as follows to white compound of formula I, reaction equation：
In formula I：
Each X stands alone as O, NH or CH at the same time or separately2；
Each R1H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CONHR and
CO2R in R is alkyl or APEO chain；
Each R2H, Cl, OH, CO are stood alone as at the same time or separately2R、CONHR、CH2OH、COONa、NH2Or SO3Na, wherein CO2R and
R in CONHR is alkyl or APEO chain.
A kind of 3. method that tetraphenyl ethylene propeller-type structure is split into left-hand screw body and right-hand screw body, it is characterised in that use
Chirality prepares high pressure liquid chromatography post, and mobile phase is volume ratio 80：20 methylene chloride-methanol mixed solvent, right can be wanted
Described formula (I) compound is asked to be split as two peaks of left-hand screw body and right-hand screw body, the retention time at peak 1 is 2.455min, its
Corresponding molecular structure is the left-hand screw body in formula (I) compound；The retention time at peak 2 is 3.430min, its corresponding molecule
Structure is the right-hand screw body in formula (I) compound.
4. the compound described in claim 1 is split into the application of single left-hand screw body and/or right-hand screw body.
5. single the left-hand screw body and/or right-hand screw body that split to obtain as the compound described in claim 1.
6. the application for single the left-hand screw body and/or right-hand screw body for splitting to obtain as the compound described in claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111039920A (en) * | 2018-10-12 | 2020-04-21 | 山东大学 | Chiral tetraphenylethylene and synthesis method thereof |
| CN111205450A (en) * | 2018-11-22 | 2020-05-29 | 香港科技大学深圳研究院 | Application and preparation method of tetraphenylethylene isomer |
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Non-Patent Citations (3)
| Title |
|---|
| HAI-TAO FENG等: "Fluorescence Turn-on Enantioselective Recognition of both Chiral Acidic Compounds and α-Amino Acids by a Chiral Tetraphenylethylene Macrocycle Amine", 《JOC》 * |
| JIN-HUA WANG等: "Tetraphenylethylene imidazolium macrocycle: synthesis and selective fluorescence turn-on sensing of pyrophosphate anions", 《RSV ADV.》 * |
| 冯海涛等: "具有聚集诱导发光效应的四苯乙烯大环的合成及性能的研究", 《全国第十七届大环化合暨第九届超分子化学学术研讨会论文摘要集》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039920A (en) * | 2018-10-12 | 2020-04-21 | 山东大学 | Chiral tetraphenylethylene and synthesis method thereof |
| CN111039920B (en) * | 2018-10-12 | 2021-01-12 | 山东大学 | Chiral tetraphenylethylene and synthesis method thereof |
| CN111205450A (en) * | 2018-11-22 | 2020-05-29 | 香港科技大学深圳研究院 | Application and preparation method of tetraphenylethylene isomer |
| CN111205450B (en) * | 2018-11-22 | 2022-12-16 | 香港科技大学深圳研究院 | Application and preparation method of tetraphenylethylene isomer |
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