CN103952001B - A kind of near-infrared fluorine boron two pyrroles's fluorescent dye and preparation method thereof - Google Patents
A kind of near-infrared fluorine boron two pyrroles's fluorescent dye and preparation method thereof Download PDFInfo
- Publication number
- CN103952001B CN103952001B CN201410193015.4A CN201410193015A CN103952001B CN 103952001 B CN103952001 B CN 103952001B CN 201410193015 A CN201410193015 A CN 201410193015A CN 103952001 B CN103952001 B CN 103952001B
- Authority
- CN
- China
- Prior art keywords
- pyrroles
- fluorescent dye
- acid
- fluorine boron
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 CO*1C(*)=CCC1 Chemical compound CO*1C(*)=CCC1 0.000 description 2
Abstract
The present invention relates to a kind of near-infrared fluorine boron two pyrroles's fluorescent dye and preparation method thereof, halo iso-indoles imines is used to couple with boric acid class reagent Suzuki, then synthesize with acid catalyzed condensation, launching wavelength and be all higher than 669nm in various solvents, the emission spectrum of such dyestuff and derivant thereof is up to 748nm；This fluorochrome has the optical physics chemical property that higher fluorescence quantum yield (0.67 1) and preferable light stability etc. are excellent, has a good application prospect in the field such as laser dye, bioanalysis.
Description
Technical field
The present invention relates to functional fluorescent dyes, organic chemical industry and technical field of fine, be specifically related to one the reddest
Outer fluorine boron two pyrroles's fluorescent dye and preparation method thereof.
Background technology
Fluorine boron two pyrroles's molecule is the fluorescence dye that the class optical physics chemical property just grown up for nearly twenties years is excellent
Material molecule, at the bioanalysis such as probe and biomarker detection, medical treatment, laser dye, electroluminescent material, dye sensitization electricity
There is extraordinary application prospect in the fields such as pond, light trapping antenna system, and application is extremely extensive, especially long wave near-infrared fluorine boron two
Pyrroles's molecule.Therefore, near-infrared fluorine boron two pyrroles's fluorescent dye synthesis by bigger concern.Synthesize longwave absorption at present
The approach of the near-infrared Novel BODIPY flourescent dye launched generally has following several: 1) introduce aryl, vinyl, styryl, virtue
[Rurack, the K. such as acetenyl；Kollmannsberger,M.；Daub.J.et al.Angew.Chem.Int.Ed.2001,40,
385.；Buyukcakir,O.；Bozdemir,O.A.；Kolemen.S.et al.Org.Lett.2009,11,4644.] increase
Add conjugation and introduce push-and-pull electronics [Baruah, M.；Qin,W.；Vallqe,R.A.L.et al.Org.Lett.2005,7,
4377.] system；2) rigid planar structure [Wang, the Y.W. of molecule are increased；Descalzo,A.B.；Shen,Z.et
al.Chem.Eur.J.2010,16,2887.；Jiao,C.；Zhu,L.；Wu,J.et al.Chem.Eur.J.2011,17,
6610.]；3) fixing rotatable group [Kowada, T.；Yamaguchi,S.；Ohe,K.Org.Lett.2010,12,296.]；
4) synthesis Aza-BODIPY [Zhao, W.；Carreira,E.M.Angew.Chem.Int.Ed.2005,44,1677.；Zhao,
W.；Carreira,E.M.Chem.Eur.J.2006,12,7254.].
Chem.Eur.J.2012,18,3893-3905
Figure1.Synthetic strategies toward symmetric Isoindole-BODIPYs is existing at present
The route such as Figure1 of symmetrical isoindoles fluorine boron two pyrroles of some synthesis.Noboru Ono seminar history Taoist scripture allusion quotation is inverse
Diels-Alder synthetic route A (Figure1) [Shen Z.；Rurack K.；Uno H.et al.Chem.Eur.J.2004,
10,4853.；Wada M.；Ito S.；Uno H.et al.Tetrah.Lett., 2001,42,6711.], by benzaldehyde with
Corresponding azole derivatives is condensed, aoxidizes, is coordinated synthetic intermediate, and then the high-temperature heating by 220 DEG C can be by intermediate
It is converted into more stable symmetrical isoindoles fluorine boron two pyrroles.But its subject matter existed is to prepare to relate to inverse D-A reaction, needs
Wanting the high temperature of 220 DEG C, common functional groups can not be compatible；Raw material in synthetic route B is unstable due to the high activity of alfa position.Close
Raw material azole derivatives in route C is become to relate to the complexity of specific pyrroles's molecule complete synthesis, and limitednumber synthetic route (Uppal,
T.；Hu,X.；Fronczek,F.R.Chem.Eur.J.2012,18,3893-3905)；Haugland and Kang uses synthesis road
Line D neighbour's benzene dicarbonyl compound and azanol reaction, obtain iso-indoles two methylene, and coordination obtains symmetrical iso-indoles BODIPY fluorescence dye
Material [Haugland, R.P.；Kang, H.C.US5433896A, US08/246,790,1995], but adjacent benzene dicarbonyl compound closes
Becoming and relate to the lead tetra-acetate that environmental pollution is serious, sewage discharge has problems..
Synthetic method is complicated (raw material is expensive, severe reaction conditions, and productivity is low) at present, and limitednumber；It is difficult to commercialization.Cause
The method of this relatively simple maturation of necessary exploitation synthesizes near-infrared fluorine boron two pyrroles's fluorescence dye that fluorescence quantum yield is high
Material molecule.
Summary of the invention
It is an object of the invention to provide a kind of near-infrared fluorine boron two pyrroles's fluorescent dye and preparation method thereof, expand
The conjugated structure of BODIPY precursor structure increases its conjugation scope, and then synthesizes the novel near-infrared of a class function admirable
Novel BODIPY flourescent dye and derivant thereof.
Concrete technical scheme is as follows:
A kind of near-infrared fluorine boron two pyrroles's fluorescent dye, its general structure is:
Further, X is NH, O, S or CH=CH.
Further, R1、R2、R3、R4、R5For H, C1-12Alkyl, CH=CH-CH=CH, cycloalkyl, phenyl, naphthyl, F,
Cl、Br、I、OR6、NR6R7, CN, (CH=CH2)(C6H4)R6、(CH2)mO(CH2)nH、(CH2)nCOOM、(CH2)mCOM or (CH2)mSO3M。
Further, wherein R6、R7For identical or different H, C1-12Straight chain or branched alkyl, C1-12Cycloalkyl,
(CH2)mO(CH2)nH、(CH2)mCOOM、(CH2) mCOM or (CH2)mSO3M；N, m=0 15；M=H, Li, Na, K, NH4。
A kind of isoindoles near-infrared fluorine boron two pyrroles's fluorescent dye, its general structure is:
Further, R3、R4、R5For H, C1-12Alkyl, CH=CH-CH=CH, cycloalkyl, phenyl, naphthyl, F, Cl,
Br、I、OR6、NR6R7, CN, (CH=CH2)(C6H4)R6、(CH2)mO(CH2)nH、(CH2)nCOOM、(CH2)mCOM or (CH2)mSO3M。
Further, wherein R6、R7For identical or different H, C1-12Straight chain or branched alkyl, C1-12Cycloalkyl,
(CH2)mO(CH2)nH、(CH2)mCOOM、(CH2) mCOM or (CH2)mSO3M；N, m=0 15；M=H, Li, Na, K, NH4。
The preparation method of above-mentioned near-infrared fluorine boron two pyrroles's fluorescent dye, comprises the steps:
(1) halo iso-indoles imines couples with boric acid class reagent Suzuki；
(2) synthesize with acid catalyzed condensation.
Further, in step (1), halo iso-indoles imines and boric acid class reagent Suzuki couple and have prepared a series of aldehyde；
And/or, step (2) uses acid catalyzed condensation 4h.
Further, also comprise the steps:
(3) adding boron trifluoride diethyl etherate after triethylamine processes, room temperature is coordinated；
(4) extraction, washing, it is dried, concentrating under reduced pressure；
(5) this isoindoles near-infrared fluorine boron two pyrroles's fluorescent dye prepared is separated through silica gel column chromatography.
Compared with currently available technology, the present invention uses the Suzuki coupling reaction of classics, utilizes organic boronic as instead
Nucleophilic moiety in Ying, greatly promotes the carbon carbon coupling with Metal Palladium as catalyst.Boronic acid derivatives has many other to have
The advantage that machine metal is incomparable.First, boric acid can coexist with some other active group, such as halogen, shuttle base etc..The
Two, reagent and the hypotoxicity of by-product after reaction.Under suitable alkali effect, organoboron reagent can react efficiently with halogen,
Generate new carbon-carbon bond.In conjunction with Kevin Burgess seminar with pyrroles's aldehyde for raw material self-condensation synthesis BODIPY dyestuff
New method, uses the single raw material of pyrroles's aldehyde, and synthetic route is simple, and the productivity that is swift in response is high, convenient post-treatment, product spectrum performance
The advantages such as excellence.In conjunction with above advantage, it is glimmering to synthesize symmetrical asymmetric near-infrared that we are intended to develop a kind of novel method
Photoinitiator dye is i.e. coupled by simple ripe Suzuki and is prepared for a series of iso-indoles aldehyde, and then acid catalysis realizes.
Use halo iso-indoles imines to couple with boric acid class reagent Suzuki, then synthesize with acid catalyzed condensation, transmitted wave
Length is all higher than 669nm in various solvents, and the emission spectrum of such dyestuff and derivant thereof is up to 748nm；This fluorochrome
There is the optical physics chemical property that higher fluorescence quantum yield (0.67-1) and preferable light stability etc. are excellent, contaminate at laser
The fields such as material, bioanalysis have a good application prospect.
Specifically:
The first, the present invention developed in the first the new method efficiently preparing β position phenyl ring modification Novel BODIPY flourescent dye, improves existing
Some BODIPY fluorochromes deficiency in structure and synthetic method.While precursor structure β position is modified, on 3
Introduce kinds of aromatic ring conjugation structure and increase its conjugation scope, optimize the spectrochemical property of this compounds so that it is absorb and launch
Spectrum generation red shift, thus obtain fluorine boron two azole derivatives of a class hyperfluorescence.Its emission maximum spectrum reach 669nm with
On.
Second, initial feed of the present invention has been commercialized, cheap and easy to get；Synthesis is coupled different by Suzuki
Indolal, method is ripe, and technique is simple, and reaction is efficiently.
3rd, the present invention is simultaneously suitable for synthesizing symmetrical and asymmetric isoindoles near infrared fluorescent dye molecule.
Accompanying drawing explanation
Fig. 1 is the X-ray single crystal diffraction structure chart of dyestuff 1；
Fig. 2 is the X-ray single crystal diffraction structure chart of dyestuff 2；
Fig. 3 is the X-ray single crystal diffraction structure chart of dyestuff 4；
Fig. 4 is this relative methylene blue (standard substance) of fluorochrome 1 in DMF solvent under 500 watts of xenon lamps irradiate
Uv absorption change i.e. light stability；
Fig. 5 is this relative methylene blue (standard substance) of fluorochrome 2 in DMF solvent under 500 watts of xenon lamps irradiate
Uv absorption change i.e. light stability；
Fig. 6 is the uv absorption figure of BODIPY1 in different solvents；
Fig. 7 is the fluorescence emission spectrum of BODIPY1 in different solvents；
Fig. 8 is near-infrared fluorine boron two pyrroles's fluorescent dye general structure.
Detailed description of the invention
Describing the present invention below according to accompanying drawing, it is that the one in numerous embodiments of the present invention is the most real
Execute example.
The general structure of this near-infrared fluorine boron two pyrroles's fluorescent dye and derivant thereof is I:
In formula: X is NH, O, S, CH=CH；R1、R2、R3、R4、R5For H, C1-12Alkyl, CH=CH-CH=CH, cycloalkanes
Base, phenyl, naphthyl, F, Cl, Br, I, OR6、NR6R7, CN, (CH=CH2)(C6H4)R6、(CH2)mO(CH2)nH、(CH2)nCOOM、
(CH2)mCOM or (CH2)mSO3M；R6、R7For identical or different H, C1-12Straight chain or branched alkyl, C1-12Cycloalkyl, (CH2)mO(CH2)nH、(CH2)mCOOM、(CH2) mCOM or (CH2)mSO3M；N, m=0 15；M=H, Li, Na, K, NH4。
Isoindoles near infrared fluorescent dye preferred structure is formula II:
In formula II: R3、R4、R5For H, C1-12Alkyl, CH=CH-CH=CH, cycloalkyl, phenyl, naphthyl, F, Cl,
Br、I、OR6、NR6R7, CN, (CH=CH2)(C6H4)R6、(CH2)mO(CH2)nH、(CH2)nCOOM、(CH2)mCOM or (CH2)mSO3M；R6、R7For identical or different H, C1-12Straight chain or branched alkyl, C1-12Cycloalkyl, (CH2)mO(CH2)nH、(CH2)
mCOOM、(CH2) mCOM or (CH2)mSO3M；N, m=0 15；M=H, Li, Na, K, NH4。
The preparation of such near-infrared fluorine boron two pyrroles's fluorescent dye " one kettle way " can be carried out by following experimental procedure: the different Yin of halo
Diindyl imines and boric acid class reagent Suzuki couple and have prepared a series of aldehyde, then use acid catalyzed condensation 4h, and triethylamine adds after processing
Entering boron trifluoride diethyl etherate, room temperature is coordinated 2h, through extracting, and washing, it is dried, concentrating under reduced pressure, then separates prepared being somebody's turn to do through silica gel column chromatography
Isoindoles near-infrared fluorine boron two pyrroles's fluorescent dye.Above-mentioned organic solvent is selected from toluene, chlorobenzene, o-Dimethylbenzene, xylol.
Lewis acid described above is selected from POCl3、POBr3、HCl、HBr、CH3SO3H、CF3SO3H。
Embodiment 1:
The synthesis of dyestuff 2-2a:
Weigh imines 400mg, 3-methoxyphenylboronic acid 532mg (2.2e.q.) and be placed in 100mL Slack reactor, add
15mL toluene, 10mL1M Na2CO3Solution, 2mL ethanol, in liquid nitrogen environment after solidification, evacuation, logical argon, in triplicate,
Catalyst Pd (PhP is added in ar gas environment3)460mg, again evacuation, logical argon, in triplicate.Question response device recovery room
Temperature is placed in 80 DEG C of oil baths heating 12h.Point plate, imine reaction is complete, and reaction terminates.It is extracted with ethyl acetate, concentrates, mistake
Post, obtains 1-1 yellow powder 335mg, productivity 83.8%.1H NMR(300MHz,CDCl3) δ 9.91 (s, 1H), 8.02 (t, J=
4.8Hz, 2H), 7.50-7.37 (m, 4H), 7.26 (t, J=7.5Hz, 1H), 7.02 (d, J=7.2Hz, 1H), 3.92 (s, 3H)
；13CNMR(75MHz,CDCl3)δ173.9,161.0,130.5,127.5,124.4,124.0,122.1,122.0,121.9,
120.0,117.6,115.2,115.1,112.9,112.8,55.5.HRMS(ESI)calcd.for C16H13NO2[M+H]+:
252.1019,found252.1019.
In 50mL round-bottomed flask, under argon shield, add 20mL CH2Cl2, add aldehyde (90mg, 0.5mmol), and add
Enter to have been dissolved in the POCl in 1mL dichloromethane3(0.47ml,5mmol).After reaction 4h, under room temperature, add 1.0mL diisopropyl
Amine, after 10min is stirred at room temperature, adds 1.2mL boron trifluoride diethyl etherate, seals round-bottomed flask.After 2h is stirred at room temperature, extraction, it is dried,
Concentrating under reduced pressure, then (fixing is silica gel mutually, and eluent is petroleum ether and the mixture that methylene chloride volume ratio is 9/1 through column chromatography
System) obtain bright green crystal 1, productivity is 76%.1H NMR(300MHz,CDCl3)δ7.91(s,3H),7.69(s,2H),7.44-
7.29(m,10H),7.02(s,2H),3.85(s,6H)；13C NMR(75MHz,CDCl3)δ159.2,151.6,134.3,
132.2,130.5,129.2,129.1,127.7,125.3,123.7,122.7,118.9,115.8,115.4,110.0,
55.3.HRMS(EI)calcd.for C31H24O2N2BF2[M+H]+:505.1893,found505.1893.
Embodiment 2:
Weigh imines 400mg, 4-methoxyphenylboronic acid 532mg (2.2e.q.), repeat aforesaid operations, obtain 2-1b yellow
Powder 350mg, productivity 87.5%.1H NMR(300MHz,CDCl3) δ 9.87 (s, 1H), 7.98 (d, J=6.9Hz, 2H), 7.77
(d, J=8.1Hz, 2H), 7.41 (s, 1H), 7.26 (s, 1H), 7.10-7.07 (m, 2H), 3.90 (s, 3H)；13CNMR(75MHz,
CDCl3)δ173.0,160.4,135.8,135.7,133.2,133.1,129.5,127.4,123.9,123.5,123.0,
122.1,121.8,117.4,114.6,55.4.HRMS(ESI)calcd.for C16H13NO2[M+H]+:252.1019,
found252.1019.
In 50mL round-bottomed flask, under argon shield, add 20ml CH2Cl2, add aldehyde (90mg, 0.5mmol), and add
Enter to have been dissolved in the POCl in 1mL dichloromethane3(0.47ml, 5mmol), solution is become from the faint yellow yellow green that becomes immediately again
For green and along with the growth color in response time is gradually deepened.After reaction 4h, under room temperature, add 1.0mL diisopropylamine, room temperature
After stirring 10min, add 1.2mL boron trifluoride diethyl etherate, seal round-bottomed flask.After 2h is stirred at room temperature, extraction, it is dried, reduces pressure dense
Contracting, then must through column chromatography (fixing be silica gel mutually, and eluent is that petroleum ether and methylene chloride volume are than the mixed system being 10/1)
To bright green crystal, productivity is 64%.1H NMR(300MHz,CDCl3)δ7.84-7.65(m,8H),7.45(s,2H),7.26
(s,3H),7.03(s,4H),3.85(s,6H)；13C NMR(75MHz,CDCl3)δ160.5,151.3,134.2,131.8,
130.4,128.8,127.5,125.1,123.7,123.6,118.9,113.9,113.5,55.3.HRMS(EI)calcd.for
C31H24O2N2BF2[M+H]+:505.1893,found505.1898.
Embodiment 3:
Weigh imines 400mg, 4-tert-butylbenzeneboronic acid 624mg (2.2e.q.), repeat aforesaid operations, obtain 3-1 yellow powder
348mg, productivity 79%.1H NMR(300MHz,CDCl3) δ 9.90 (s, 1H), 8.01 (t, 2H), 7.78 (d, J=8.1Hz, 2H),
7.57 (d, J=8.1Hz, 2H), 7.41 (s, 1H), 7.24 (s, 1H), 1.39 (s, 9H)；13C NMR(75MHz,CDCl3)δ
173.1,152.5,134.3,132.4,127.7,127.4,127.3,126.4,123.9,123.7,122.1,121.8,
117.5,34.9,31.2.HRMS(ESI)calcd.for C19H19NO[M+H]+:278.1539,found278.1539.
In 50ml round-bottomed flask, under argon shield, add 20ml CH2Cl2, add aldehyde (90mg, 0.5mmol), and add
Enter to have been dissolved in the POCl in 1mL dichloromethane3(0.47ml,5mmol).After reaction 4h, under room temperature, add 1.0ml diisopropyl
Amine, after 10min is stirred at room temperature, adds 1.2mL boron trifluoride diethyl etherate, seals round-bottomed flask.After 2h is stirred at room temperature, extraction, it is dried,
Concentrating under reduced pressure, then (fixing is silica gel mutually, and eluent is petroleum ether and the mixture that methylene chloride volume ratio is 10/1 through column chromatography
System) obtain bright green crystal 3, productivity is 73%.1H NMR(300MHz,CDCl3)δ7.90-7.44(m,14H),7.26(s,
3H),1.38(s,18H)；13C NMR(75MHz,CDCl3)δ152.5,151.8,134.2,130.7,130.0,128.9,
128.2,127.6,125.3,125.1,123.9,118.9,114.3,34.9,31.3.HRMS(EI)calcd.for
C37H36N2BF2[M+H]+:557.2934,found557.2944。
Embodiment 4:
The synthesis of dyestuff 2-2d:
Weigh imines 400mg, 4-fluorobenzoic boric acid 491mg (2.2e.q.), repeat aforesaid operations, obtain 2-1d yellow powder
300mg, productivity 53%.1H NMR(300MHz,CDCl3) δ 9.92 (s, 1H), 8.01 (d, J=9Hz, 1H), 7.95 (d, J=
8.4Hz,1H),7.80(s,2H),7.43(s,1H),7.30-7.26(m,3H)；13C NMR(75MHz,CDCl3)δ174.0,
165.0,129.8,129.7,127.9,127.7,126.9,126.6,124.3,121.8,118.5,118.2,117.8,
117.0,116.7.HRMS(ESI)calcd.for C15H10FNO[M+H]+:240.0819,found240.0819.
In 50ml round-bottomed flask, under argon shield, add 20mLCH2Cl2, add aldehyde (90mg, 0.5mmol), and add
Enter to have been dissolved in the POCl in 1mL dichloromethane3(0.47ml,5mmol).After reaction 4h, under room temperature, add 1.0mL diisopropyl
Amine, after 10min is stirred at room temperature, adds 1.2mL boron trifluoride diethyl etherate, seals round-bottomed flask.After 2h is stirred at room temperature, extraction, it is dried,
Be concentrated under reduced pressure to give thick product, then through column chromatography (fixing is silica gel mutually, eluent be petroleum ether be 9/ with methylene chloride volume ratio
The mixed system of 1) obtain bright green crystal, productivity is 41%.1H NMR(300MHz,CDCl3)δ7.94-7.82(m,6H),
7.61(s,2H),7.59(s,2H),7.26-7.20(m,7H).HRMS(EI)calcd.forC29H15N2BF4[M+H]+:
481.1494,found481.1494.
Embodiment 5:
The synthesis of dyestuff 2-2e:
Weigh imines 400mg, 2-methyl-5-thienyl boric acid 498mg (2.2e.q.), repeat aforesaid operations, obtain 2-1e yellow
Powder 322mg, productivity 84%.1H NMR(300MHz,CDCl3) δ 9.86 (s, 1H), 8.07 (d, J=8.4Hz, 1H), 7.97 (d,
J=8.4Hz, 1H), 7.54 (d, J=3.3Hz1H), 7.41 (s, 1H), 7.26 (s, 1H), 6.877 (d, J=2.7Hz, 1H),
2.59(s,3H)；13C NMR(75MHz,CDCl3)δ171.9,128.9,127.9,126.6,125.6,125.5,123.5,
122.9,122.6,121.0,120.5,118.4,116.5,14.4.HRMS(ESI)calcd.for C14H12NOS[M+H]+:
242.0634,found242.0634.
In 50ml round-bottomed flask, under argon shield, add 20ml CH2Cl2, add aldehyde (90mg, 0.5mmol), and
Adding the POCl3 (0.47ml, 5mmol) having been dissolved in 1mL dichloromethane, solution is become yellow green again from faint yellow immediately
Become green and along with the growth color in response time is gradually deepened.After reaction 4h, under room temperature, add 1.0mL diisopropylamine, room
After temperature stirring 10min, add 1.2mL boron trifluoride diethyl etherate, seal round-bottomed flask.After being stirred at room temperature 2, extraction, it is dried, reduces pressure dense
Contracting, then must through column chromatography (fixing be silica gel mutually, and eluent is that petroleum ether and methylene chloride volume are than the mixed system being 10/1)
To bright green crystal, productivity is 46%.1H NMR(300MHz,CDCl3) δ 8.06 (d, J=5.4Hz, 2H), 7.75 (d, J=
8.1Hz, 4H), 7.69 (s, 1H), 7.45 (s, 3H), 7.32-7.26 (m, 2H), 6.94 (d, J=5.4Hz, 2H), 2.62 (s,
1H)；HRMS(EI)calcd.for C27H20N2S2BF2[M+H]+:485.1124,found485.1198.
Embodiment 6:
Weighing aldehyde 6-1100mg, 2,4-dimethyl pyrrole 83.7mg (2e.q.), proper amount of methanol is made solvent and is placed in 100mL circle
End flask, fully dissolves, and takes 0.6mL concentrated hydrochloric acid and is slowly added drop-wise in round-bottomed flask, reacts 12h point plate, and completely, bottle wall has in reaction
Solid adhere to, filter filtering residue for coordination precursor, use CH2Cl2Dissolve, add diisopropylamine 100mL, after stirring 10min, add three
Boron fluoride ether 100mL, solution is become shiny red from kermesinus immediately, and reaction 2h obtains green crystal 112mg, gross production rate 72%.1H NMR(300MHz,CDCl3) δ 8.06 (d, J=8.7Hz, 2H), 7.84 (d, J=7.5Hz, 1H), 7.67 (s, 1H), 7.50
(s,1H),7.40-7.26(m,3H),6.03(s,1H),4.54(s,2H),2.53(s,3H),2.30(s,3H)；13C NMR
(75MHz,CDCl3)δ153.7,149.3,138.2,135.4,132.7,132.4,131.1,130.2,129.7,129.3,
128.2,126.0,124.2,118.8,116.3,14.6,11.3.
Figure one, figure two, figure three are that structure to dyestuff 1,2 and 4 has been made and accurately being pointed out respectively by single crystal diffraction, and lead to
Cross different angles and observe the single crystal diffraction figure of dyestuff 1,2 and 4.
Dyestuff 1,2,3,4,5 is at polar solvent the most of the same race (acetonitrile, methanol, dichloromethane, toluene, oxolane, hexamethylene
Alkane) spectroscopic data
The fluorescence quantum yields of2-2a,b,c,d and2-4b were calculated
Using ZnPc in DMF solution (Φ=0.28) as the standard；The fluorescence quantum
Yields of2-2e were calculated using danza3a in DCM (Φ=0.36) as the standard；
The fluorescence quantum yields of2-3,2-4a were calculated using Cresyl
Diolet perchlorate in anhydrous methanol solution (Φ=0.54) as the standard.
Table one
Above in conjunction with accompanying drawing, the present invention is exemplarily described, it is clear that the present invention implements not by aforesaid way
Restriction, as long as have employed method design and the various improvement that carry out of technical scheme of the present invention, or the most improved direct application
In other occasion, all within protection scope of the present invention.
Claims (2)
1. the preparation method of near-infrared fluorine boron two pyrroles's fluorescent dye, it is characterised in that comprise the steps:
(1) halo iso-indoles imines couples with boric acid class reagent Suzuki；
(2) synthesize with acid catalyzed condensation；
(3) adding boron trifluoride diethyl etherate after diisopropylamine processes, room temperature is coordinated；
(4) extraction, washing, it is dried, concentrating under reduced pressure；
(5) this isoindoles near-infrared fluorine boron two pyrroles's fluorescent dye prepared is separated through silica gel column chromatography；
Described halo iso-indoles imines in step (1) is speciallyDescribed boric acid class reagent is 3-methoxybenzene boron
Acid；4-methoxyphenylboronic acid；4-tert-butylbenzeneboronic acid, 4-fluorobenzoic boric acid or 2-methyl-5-thienyl boric acid；
Acid-specific in step (2) is POCl3；
Prepared near-infrared fluorine boron two pyrroles's fluorescent dye, its structure is
2. the preparation method of near-infrared fluorine boron two pyrroles's fluorescent dye as claimed in claim 1, it is characterised in that in step (1)
Halo iso-indoles imines and boric acid class reagent Suzuki couple and are prepared for a series of aldehyde；And/or, step contracts by acid catalysis in (2)
Close 4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410193015.4A CN103952001B (en) | 2014-05-08 | 2014-05-08 | A kind of near-infrared fluorine boron two pyrroles's fluorescent dye and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410193015.4A CN103952001B (en) | 2014-05-08 | 2014-05-08 | A kind of near-infrared fluorine boron two pyrroles's fluorescent dye and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103952001A CN103952001A (en) | 2014-07-30 |
| CN103952001B true CN103952001B (en) | 2016-09-14 |
Family
ID=51329366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410193015.4A Expired - Fee Related CN103952001B (en) | 2014-05-08 | 2014-05-08 | A kind of near-infrared fluorine boron two pyrroles's fluorescent dye and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103952001B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6465350B2 (en) * | 2015-03-09 | 2019-02-06 | 公立大学法人首都大学東京 | Novel organic compounds and their use |
| CN105602276B (en) * | 2016-01-30 | 2017-07-28 | 苏州大学 | Polymerizable near infrared fluorescent dye monomer and preparation method thereof, purposes |
| CN109234759B (en) * | 2018-11-02 | 2019-10-25 | 陕西师范大学 | A kind of synthetic method of BODIPY |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5433896A (en) * | 1994-05-20 | 1995-07-18 | Molecular Probes, Inc. | Dibenzopyrrometheneboron difluoride dyes |
| JP2008109097A (en) * | 2006-09-28 | 2008-05-08 | Toray Ind Inc | Material for photovolatic element and the photovolatic element |
| CN101302353A (en) * | 2008-07-02 | 2008-11-12 | 大连理工大学 | Long wavelength boron dipyrromethene dye and preparation thereof |
| CN102702774A (en) * | 2012-04-11 | 2012-10-03 | 安徽师范大学 | Near infrared fluoro-boron dipyrrole fluorescent dyes and synthesis method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3868099B2 (en) * | 1998-03-06 | 2007-01-17 | 三井化学株式会社 | Dibenzopyromethene boron chelate compound and optical recording medium comprising the same |
| JP2005060459A (en) * | 2003-08-08 | 2005-03-10 | Toyo Ink Mfg Co Ltd | Organic electroluminescent element material and organic electroluminescent element |
-
2014
- 2014-05-08 CN CN201410193015.4A patent/CN103952001B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5433896A (en) * | 1994-05-20 | 1995-07-18 | Molecular Probes, Inc. | Dibenzopyrrometheneboron difluoride dyes |
| JP2008109097A (en) * | 2006-09-28 | 2008-05-08 | Toray Ind Inc | Material for photovolatic element and the photovolatic element |
| CN101302353A (en) * | 2008-07-02 | 2008-11-12 | 大连理工大学 | Long wavelength boron dipyrromethene dye and preparation thereof |
| CN102702774A (en) * | 2012-04-11 | 2012-10-03 | 安徽师范大学 | Near infrared fluoro-boron dipyrrole fluorescent dyes and synthesis method thereof |
Non-Patent Citations (4)
| Title |
|---|
| "An Accurate and Efficient Method to Predict the Electronic Excitation Energies of BODIPY Fluorescent Dyes";Jia-Nan Wang et al.;《Journal of Computational Chemistry》;20121101;第34卷;566-575 * |
| "Chemistry at Boron:Synthesis and Properties of Red to Near-IR Fluorescent Dyes Based on Boron-Substituted Diisoindolomethene Frameworks";Gilles Ulrich et al.;《J.Org.Chem.》;20110418;第76卷;4489-4505 * |
| "Red/Near-Infrared Light-Emitting Organic-Inorganic Hybrids Doped with Covalently Bound Boron Dipyrromethene (BOBIPY) Dyes via Microwave-Assisted One-Pot Process";Yuichi Kajiwara et al.;《Bull.Chem.Soc.Jpn.》;20110430;第84卷(第5期);471-481 * |
| "Synthesis of multi-branched dipyrromethene dyes with soluble diethynylphenyl links";Alexandre Haefele et al.;《Tetrahedron Letters》;20080410;第49卷;3716-3721 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103952001A (en) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Verbelen et al. | Direct palladium-catalysed C–H arylation of BODIPY dyes at the 3-and 3, 5-positions | |
| Clarke et al. | Recent developments in the synthesis of the BODIPY dyes | |
| CN105732680B (en) | A kind of BODIPY derivatives of middle position alkoxyl phenyl substitution and the substitution of 2,6 strong donor residues and preparation method thereof | |
| Wang et al. | Regioselective 2, 6-dihalogenation of BODIPYs in 1, 1, 1, 3, 3, 3-hexafluoro-2-propanol and preparation of novel meso-alkyl polymeric BODIPY dyes | |
| CN103172650A (en) | Strong fluorescence fluoro-boron dipyrrole compound containing triphenylamine structure as well as preparation method and application thereof | |
| CN103952001B (en) | A kind of near-infrared fluorine boron two pyrroles's fluorescent dye and preparation method thereof | |
| CN102532933A (en) | Synthetic and purifying method of near-infrared indole hepatmethine cyanine dye | |
| CN102702768A (en) | Novel red BODIPY fluorescent dye and preparation method and application thereof | |
| CN108774121A (en) | A kind of method that visible light catalytic prepares alpha-aromatic-β-trifluoromethyl ketone compound | |
| CN109734736A (en) | Seven yuan of fluorine boron fluorescent dyes of one kind and its synthetic method | |
| CN105541876A (en) | Anthraquinone-bridged N-heterocyclic carbene metal complex and preparation method and application thereof | |
| CN109320489A (en) | A kind of color alkyl compound and preparation method thereof | |
| CN106565408B (en) | 1,5, 9-trisubstituted coronene compound and synthesis method thereof | |
| CN101665492A (en) | 1, 6, 7, 12-tetraphenyl perylene bisimide derivant and preparation method thereof | |
| CN106188152B (en) | A kind of near-infrared metal complex and its preparation and application | |
| Wang et al. | Catalytic asymmetric aryl transfer: Highly enantioselective preparation of (R)-and (S)-diarylmethanols catalyzed by the same chiral ferrocenyl aziridino alcohol | |
| CN104628753B (en) | Meso-triphenylamine-substituted 3,5-aryl-modified boron dipyrromethene fluorophore derivatives and preparation method thereof | |
| Yin et al. | Positive charge-dependent cell targeted staining and DNA detection | |
| CN109575242B (en) | Cross-conjugated polymer, and preparation method and application thereof | |
| CN112662196B (en) | Imidazopyridine dye and synthesis method and application thereof | |
| CN103694173A (en) | Acridone derivatives and synthesis method thereof | |
| JP6108341B2 (en) | Kay ion sensor dye | |
| CN109233325B (en) | Asymmetric benzo-fluoro-boron dipyrrole fluorescent dye and preparation method thereof | |
| CN106366041A (en) | Fluorescent probe for continuously recognizing palladium ions and CO and application | |
| Ji et al. | Copper-catalyzed cyclization reaction: synthesis of trifluoromethylated indolinyl ketones |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160914 Termination date: 20190508 |