CN103952001A - Near-infrared fluorine-boron dipyrrole fluorochrome and preparation method thereof - Google Patents
Near-infrared fluorine-boron dipyrrole fluorochrome and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a near-infrared fluorine-boron dipyrrole fluorochrome and a preparation method thereof. According to the method, halogenated isoindole imine and a boric acid reagent Suzuki are coupled, and then the near-infrared fluorine-boron dipyrrole fluorochrome is synthesized through acid catalysis condensation, wherein the emission wavelengths of the fluorochrome in various solvents are greater than 669nm, and the emission spectrum of the fluorochrome and derivatives thereof can reach 748nm. The fluorochrome has relatively high fluorescence quantum yield (0.67-1) and excellent optical physicochemical properties, such as light stability, and has a good application prospect in fields like laser dye and bioanalysis.
Description
Technical field
The present invention relates to functional fluorescent dyes, organic chemical industry and fine chemical technology field, be specifically related to a kind of near infrared fluorine boron two pyrroles's fluorescence dyes and preparation method thereof.
Background technology
Fluorine boron two pyrroles's molecules are luminescent dye molecules of the class optical physics chemical property excellence that just grows up for nearly twenties years, there is extraordinary application prospect in fields such as the bioanalysis such as probe and biomarker detection, medical treatment, laser dyes, electroluminescent material, dye-sensitized cell, light trapping antenna systems, apply extremely extensive, especially long wave near infrared fluorine boron two pyrroles's molecules.Therefore, near infrared fluorine boron two pyrroles's fluorescence dyes syntheticly receive larger concern.The approach that at present synthetic long wave absorbs the near infrared BODIPY fluorescence dye of transmitting has following several conventionally: 1) introduce [Rurack, the K. such as aryl, vinyl, styryl, fragrant ethynyl; 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 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 increase molecule; 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) synthetic 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
Current existing synthetic symmetrical isoindoles fluorine boron two pyrroles' of Figure1.Synthetic strategies toward symmetric Isoindole-BODIPYs route is as Figure1.Noboru Ono seminar history Taoist scripture allusion quotation is against 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 phenyl aldehyde and corresponding pyrrole derivative condensation, oxidation, coordination synthetic intermediate, then intermediate can be converted to more stable symmetrical isoindoles fluorine boron two pyrroles by the heat of 220 DEG C.Relate to contrary D-A reaction but the subject matter of its existence is preparation, need the high temperature of 220 DEG C, common functional group can not be compatible; Raw material in synthetic route B is because the high reactivity of alfa position is unstable.It is complete synthesis that synthetic route C Raw pyrrole derivative relates to the complexity of specific pyrroles's molecule, and the limited synthetic route of kind (Uppal, T.; Hu, X.; Fronczek, F.R.Chem.Eur.J.2012,18,3893-3905); Haugland and Kang adopt the adjacent benzene dicarbonyl compound of synthetic route D and azanol reaction, obtain isoindole two methylenes, and coordination obtains symmetrical isoindole BODIPY fluorescence dye [Haugland, R.P.; Kang, H.C.US5433896A, US08/246,790,1995], but the synthetic serious lead tetra-acetate of environmental pollution that relates to of adjacent benzene dicarbonyl compound, sewage discharge existing problems.。
Current synthetic method complexity (raw material is expensive, severe reaction conditions, productive rate is low), and kind is limited; Be difficult to commercialization.Therefore the comparatively simple ripe method of necessary exploitation is synthesized near infrared fluorine boron two pyrroles's luminescent dye molecules that fluorescence quantum yield is high.
Summary of the invention
The object of the present invention is to provide a kind of near infrared fluorine boron two pyrroles's fluorescence dyes and preparation method thereof, the conjugated structure of expanding BODIPY precursor structure increases its conjugation scope, and then synthesizes novel near infrared BODIPY fluorescence dye and the derivative thereof of a class excellent property.
Concrete technical scheme is as follows:
A kind of near infrared fluorine boron two pyrroles's fluorescence dyes, its general structure is:
Further, X is NH, O, S or CH=CH.
Further, R
1, R
2, R
3, R
4, R
5for H, C
1-12alkyl, CH=CH-CH=CH, cycloalkyl, phenyl, naphthyl, F, Cl, Br, I, OR
6, NR
6r
7, CN, (CH=CH
2) (C
6h
4) R
6, (CH
2)
mo (CH
2)
nh, (CH
2)
ncOOM, (CH
2)
mcOM or (CH
2)
msO
3m.
Further, R wherein
6, R
7for identical or different H, C
1-12straight chain or branched-chain alkyl, C
1-12cycloalkyl, (CH
2)
mo (CH
2)
nh, (CH
2) mCOOM, (CH
2) mCOM or (CH
2) mSO
3m; N, m=0 – 15; M=H, Li, Na, K, NH
4.
A kind of isoindoles near infrared fluorine boron two pyrroles's fluorescence dyes, its general structure is:
Further, R
3, R
4, R
5for H, C
1-12alkyl, CH=CH-CH=CH, cycloalkyl, phenyl, naphthyl, F, Cl, Br, I, OR
6, NR
6r
7, CN, (CH=CH
2) (C
6h
4) R
6, (CH
2)
mo (CH
2)
nh, (CH
2)
ncOOM, (CH
2)
mcOM or (CH
2)
msO
3m.
Further, R wherein
6, R
7for identical or different H, C
1-12straight chain or branched-chain alkyl, C
1-12cycloalkyl, (CH
2)
mo (CH
2)
nh, (CH
2) mCOOM, (CH
2) mCOM or (CH
2) mSO
3m; N, m=0 – 15; M=H, Li, Na, K, NH
4.
The preparation method of above-mentioned near infrared fluorine boron two pyrroles's fluorescence dyes, comprises the steps:
(1) halo isoindole imines and boric acid class reagent Suzuki are coupled;
(2) synthetic with acid catalysis condensation.
Further, in step (1), halo isoindole imines and boric acid class reagent Suzuki are coupled and have prepared a series of aldehyde; And/or, in step (2), use acid catalysis condensation 4h.
Further, also comprise the steps:
(3) triethylamine adds boron trifluoride diethyl etherate, room temperature coordination after processing;
(4) extraction, washing, dry, concentrating under reduced pressure;
(5) separate and make this isoindoles near infrared fluorine boron two pyrroles's fluorescence dyes through silica gel column chromatography.
Compared with currently available technology, the present invention adopts classical Suzuki linked reaction, utilizes organic boronic as the nucleophilic part in reaction, has promoted greatly the carbon carbon coupling taking palladium metal as catalyzer.Boric acid derivatives has the incomparable advantage of many other organo-metallic.The first, boric acid can coexist with some other active group, as halogen, and shuttle base etc.The second, the hypotoxicity of reagent and by product after reaction.Under suitable alkali effect, organoboron reagent can react efficiently with halogen, generates new carbon-carbon bond.In conjunction with the novel method of Kevin Burgess seminar synthetic BODIPY dyestuff of self condensation taking pyrroles's aldehyde as raw material, adopt the single raw material of pyrroles's aldehyde, synthetic route is simple, and the productive rate that is swift in response is high, convenient post-treatment, the advantages such as product spectrum property excellence.In conjunction with above advantage, we are intended to develop a kind of novel method and synthesize symmetrical asymmetric near infrared fluorescent dye and be coupled and prepared a series of isoindole aldehyde by the Suzuki of simple maturation, and then acid catalysis realizes.
Adopt halo isoindole imines and boric acid class reagent Suzuki to be coupled, then synthetic with acid catalysis condensation, emission wavelength is all greater than 669nm in all kinds of SOLVENTS, and the emmission spectrum of such dyestuff and derivative thereof can reach 748nm; This fluorochrome has the optical physics chemical property that higher fluorescence quantum yield (0.67-1) and good light stability etc. are excellent, has a good application prospect in the field such as laser dyes, bioanalysis.
Specifically:
The first, first the present invention has developed the novel method that efficient preparation β position phenyl ring is modified BODIPY fluorescence dye, improves the deficiency of existing BODIPY fluorochrome in structure and synthetic method.When precursor structure β position is modified, on 3, introduce kinds of aromatic ring conjugation structure and increase its conjugation scope, optimized the spectrochemical property of this compounds, make its Absorption and emission spectra generation red shift, thereby obtain fluorine boron two pyrrole derivative of a class hyperfluorescenceZeng Yongminggaoyingguang.More than its emission maximum spectrum reaches 669nm.
The second, initial feed of the present invention is become commercialized, cheap and easy to get; Be coupled synthetic isoindole aldehyde by Suzuki, method maturation, technique is simple, and reaction is efficient.
The 3rd, the present invention is applicable to synthetic symmetry and asymmetric isoindoles near infrared fluorescent dye molecule simultaneously.
Brief description of the drawings
Fig. 1 is the X-ray single crystal diffraction structure iron of dyestuff 1;
Fig. 2 is the X-ray single crystal diffraction structure iron of dyestuff 2;
Fig. 3 is the X-ray single crystal diffraction structure iron of dyestuff 4;
Fig. 4 is light stability for the uv-absorbing of this fluorochrome 1 relative methylene blue (reference material) in DMF solvent under 500 watts of xenon lamps irradiate changes;
Fig. 5 is light stability for the uv-absorbing of these fluorochrome 2 relative methylene blues (reference material) in DMF solvent under 500 watts of xenon lamps irradiate changes;
Fig. 6 is the uv-absorbing 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 fluorescence dye general structures.
Embodiment
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
The general structure of these near infrared fluorine boron two pyrroles's fluorescence dyes and derivative thereof is I:
In general formula: X is NH, O, S, CH=CH; R
1, R
2, R
3, R
4, R
5for H, C
1-12alkyl, CH=CH-CH=CH, cycloalkyl, phenyl, naphthyl, F, Cl, Br, I, OR
6, NR
6r
7, CN, (CH=CH
2) (C
6h
4) R
6, (CH
2)
mo (CH
2)
nh, (CH
2)
ncOOM, (CH
2)
mcOM or (CH
2)
msO
3m; R
6, R
7for identical or different H, C
1-12straight chain or branched-chain alkyl, C
1-12cycloalkyl, (CH
2)
mo (CH
2)
nh, (CH
2) mCOOM, (CH
2) mCOM or (CH
2) mSO
3m; N, m=0 – 15; M=H, Li, Na, K, NH
4.
Isoindoles near infrared fluorescent dye preferred structure is formula II:
In general formula I I: R
3, R
4, R
5for H, C
1-12alkyl, CH=CH-CH=CH, cycloalkyl, phenyl, naphthyl, F, Cl, Br, I, OR
6, NR
6r
7, CN, (CH=CH
2) (C
6h
4) R
6, (CH
2)
mo (CH
2)
nh, (CH
2)
ncOOM, (CH
2)
mcOM or (CH
2)
msO
3m; R
6, R
7for identical or different H, C
1-12straight chain or branched-chain alkyl, C
1-12cycloalkyl, (CH
2)
mo (CH
2)
nh, (CH
2) mCOOM, (CH
2) mCOM or (CH
2) mSO
3m; N, m=0 – 15; M=H, Li, Na, K, NH
4.
Such near infrared fluorine boron two pyrroles's fluorescence dye " one kettle way " preparations can be undertaken by following experimental procedure: halo isoindole imines and boric acid class reagent Suzuki are coupled and have prepared a series of aldehyde, then use acid catalysis condensation 4h, triethylamine adds boron trifluoride diethyl etherate after processing, room temperature coordination 2h, through extraction, washing, dry, concentrating under reduced pressure, then separate and make this isoindoles near infrared fluorine boron two pyrroles's fluorescence dyes through silica gel column chromatography.Above-mentioned organic solvent is selected from toluene, chlorobenzene, o-Xylol, p-Xylol.Lewis acid described above is selected from POCl
3, POBr
3, HCl, HBr, CH
3sO
3h, CF
3sO
3h.
Embodiment 1:
Dyestuff 2-2a's is synthetic:
Take imines 400mg, 3-methoxyphenylboronic acid 532mg (2.2e.q.) is placed in 100mL Slack reactor, adds 15mL toluene, 10mL1M Na
2cO
3solution, 2mL ethanol, after solidifying, vacuumizes in liquid nitrogen environment, and logical argon gas in triplicate, adds catalyst P d (PhP in ar gas environment
3)
460mg, vacuumizes again, logical argon gas, in triplicate.Question response device recovery room temperature is placed in 80 DEG C of oil baths and heats 12h.Point plate, imine reaction is complete, and reaction finishes.Be extracted with ethyl acetate, concentrated, cross post, obtain 1-1 yellow powder 335mg, productive rate 83.8%.
1H?NMR(300MHz,CDCl
3)δ9.91(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,CDCl
3)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?C
16H
13NO
2[M+H]
+:252.1019,found252.1019.
In 50mL round-bottomed flask, under argon shield, add 20mL CH
2cl
2, add aldehyde (90m
g, 0.5mmol), and add the POCl being dissolved in 1mL methylene dichloride
3(0.47ml, 5mmol).After reaction 4h, under room temperature, add 1.0mL Diisopropylamine, after stirring at room temperature 10min, add 1.2mL boron trifluoride diethyl etherate, sealing round-bottomed flask.After stirring at room temperature 2h, extraction, dry, concentrating under reduced pressure, then through column chromatography (stationary phase is silica gel, elutriant be sherwood oil with methylene chloride volume than the mixed system that is 9/1) obtain bright green crystal 1, productive rate is 76%.
1H?NMR(300MHz,CDCl
3)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,CDCl
3)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?C
31H
24O
2N
2BF
2[M+H]
+:505.1893,found505.1893.
Embodiment 2:
Take imines 400mg, 4-methoxyphenylboronic acid 532mg (2.2e.q.), repeats aforesaid operations, obtains 2-1b yellow powder 350mg, productive rate 87.5%.
1H?NMR(300MHz,CDCl
3)δ9.87(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,CDCl
3)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?C
16H
13NO
2[M+H]
+:252.1019,found252.1019.
In 50mL round-bottomed flask, under argon shield, add 20ml CH
2cl
2, add aldehyde (90mg, 0.5mmol), and add the POCl being dissolved in 1mL methylene dichloride
3(0.47ml, 5mmol), solution becomes that yellow-green colour becomes green again and along with the growth color in reaction times is deepened gradually from faint yellow immediately.After reaction 4h, under room temperature, add 1.0mL Diisopropylamine, after stirring at room temperature 10min, add 1.2mL boron trifluoride diethyl etherate, sealing round-bottomed flask.After stirring at room temperature 2h, extraction, dry, concentrating under reduced pressure, then through column chromatography (stationary phase is silica gel, elutriant be sherwood oil with methylene chloride volume than the mixed system that is 10/1) obtain bright green crystal, productive rate is 64%.
1H?NMR(300MHz,CDCl
3)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,CDCl
3)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?C
31H
24O
2N
2BF
2[M+H]
+:505.1893,found505.1898.
Embodiment 3:
Take imines 400mg, 4-tert.-butylbenzene boric acid 624mg (2.2e.q.), repeats aforesaid operations, obtains 3-1 yellow powder 348mg, productive rate 79%.
1H?NMR(300MHz,CDCl
3)δ9.90(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,CDCl
3)δ173.1,152.5,134.3,132.4,127.7,127.4,127.3,126.4,123.9,123.7,122.1,121.8,117.5,34.9,31.2.HRMS(ESI)calcd.for?C
19H
19NO[M+H]
+:278.1539,found278.1539.
In 50ml round-bottomed flask, under argon shield, add 20ml CH
2cl
2, add aldehyde (90mg, 0.5mmol), and add the POCl being dissolved in 1mL methylene dichloride
3(0.47ml, 5mmol).After reaction 4h, under room temperature, add 1.0ml Diisopropylamine, after stirring at room temperature 10min, add 1.2mL boron trifluoride diethyl etherate, sealing round-bottomed flask.After stirring at room temperature 2h, extraction, dry, concentrating under reduced pressure, then through column chromatography (stationary phase is silica gel, elutriant be sherwood oil with methylene chloride volume than the mixed system that is 10/1) obtain bright green crystal 3, productive rate is 73%.
1H?NMR(300MHz,CDCl
3)δ7.90-7.44(m,14H),7.26(s,3H),1.38(s,18H)；
13C?NMR(75MHz,CDCl
3)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?C
37H
36N
2BF
2[M+H]
+:557.2934,found557.2944。
Embodiment 4:
Dyestuff 2-2d's is synthetic:
Take imines 400mg, 4-fluorobenzoic boric acid 491mg (2.2e.q.), repeats aforesaid operations, obtains 2-1d yellow powder 300mg, productive rate 53%.
1H?NMR(300MHz,CDCl
3)δ9.92(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,CDCl
3)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?C
15H
10FNO[M+H]
+:240.0819,found240.0819.
In 50ml round-bottomed flask, under argon shield, add 20mLCH
2cl
2, add aldehyde (90mg, 0.5mmol), and add the POCl being dissolved in 1mL methylene dichloride
3(0.47ml, 5mmol).After reaction 4h, under room temperature, add 1.0mL Diisopropylamine, after stirring at room temperature 10min, add 1.2mL boron trifluoride diethyl etherate, sealing round-bottomed flask.After stirring at room temperature 2h, extraction, dry, concentrating under reduced pressure obtains thick product, then through column chromatography (stationary phase is silica gel, elutriant be sherwood oil with methylene chloride volume than the mixed system that is 9/1) obtain bright green crystal, productive rate is 41%.
1H?NMR(300MHz,CDCl
3)δ7.94-7.82(m,6H),7.61(s,2H),7.59(s,2H),7.26-7.20(m,7H).HRMS(EI)calcd.forC
29H
15N
2BF
4[M+H]
+:481.1494,found481.1494.
Embodiment 5:
Dyestuff 2-2e's is synthetic:
Take imines 400mg, 2-methyl-5-thienyl boric acid 498mg (2.2e.q.), repeats aforesaid operations, obtains 2-1e yellow powder 322mg, productive rate 84%.
1H?NMR(300MHz,CDCl
3)δ9.86(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,CDCl
3)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?C
14H
12NOS[M+H]
+:242.0634,found242.0634.
In 50ml round-bottomed flask; under argon shield, add 20ml CH2Cl2; add aldehyde (90mg; 0.5mmol); and add the POCl3 (0.47ml being dissolved in 1mL methylene dichloride; 5mmol), solution becomes that yellow-green colour becomes green again and along with the growth color in reaction times is deepened gradually from faint yellow immediately.After reaction 4h, under room temperature, add 1.0mL Diisopropylamine, after stirring at room temperature 10min, add 1.2mL boron trifluoride diethyl etherate, sealing round-bottomed flask.After stirring at room temperature 2, extraction, dry, concentrating under reduced pressure, then through column chromatography (stationary phase is silica gel, elutriant be sherwood oil with methylene chloride volume than the mixed system that is 10/1) obtain bright green crystal, productive rate is 46%.
1H?NMR(300MHz,CDCl
3)δ8.06(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?C
27H
20N
2S
2BF
2[M+H]
+:485.1124,found485.1198.
Embodiment 6:
Take aldehyde 6-1100mg, 2,4-dimethyl pyrrole 83.7mg (2e.q.), appropriate methyl alcohol makees solvent and is placed in 100mL round-bottomed flask, fully dissolves, getting 0.6mL concentrated hydrochloric acid is slowly added drop-wise in round-bottomed flask, reaction 12h point plate, reacts completely, and bottle wall has solid to adhere to, filter to such an extent that filter residue is coordination precursor, use CH
2cl
2dissolve, add Diisopropylamine 100mL, after stirring 10min, add boron trifluoride diethyl etherate 100mL, solution becomes shiny red from garnet immediately, and reaction 2h obtains green crystal 112mg, overall yield 72%.
1H?NMR(300MHz,CDCl
3)δ8.06(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,CDCl
3)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 mono-, figure bis-, figure tri-accurately point out for respectively the structure of dyestuff 1,2 and 4 having been made by single crystal diffraction, and observe the single crystal diffraction figure of dyestuff 1,2 and 4 by different angles.
Dyestuff 1,2,3,4,5 is at the spectroscopic data of polar solvent not of the same race (acetonitrile, methyl alcohol, methylene dichloride, toluene, tetrahydrofuran (THF), hexanaphthene)
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
By reference to the accompanying drawings the present invention is exemplarily described above; obviously specific implementation of the present invention is not subject to the restrictions described above; as long as the various improvement that adopted method design of the present invention and technical scheme to carry out; or directly apply to other occasion without improvement, all within protection scope of the present invention.
Claims (10)
1. near infrared fluorine boron two pyrroles's fluorescence dyes, is characterized in that, its general structure is:
2. near infrared fluorine boron two pyrroles's fluorescence dyes as claimed in claim 1, is characterized in that X=NH, O, S or CH=CH.
3. near infrared fluorine boron two pyrroles's fluorescence dyes as claimed in claim 1 or 2, is characterized in that R
1, R
2, R
3, R
4, R
5for H, C
1-12alkyl, CH=CH-CH=CH, cycloalkyl, phenyl, naphthyl, F, Cl, Br, I, OR
6, NR
6r
7, CN, (CH=CH
2) (C
6h
4) R
6, (CH
2)
mo (CH
2)
nh, (CH
2)
ncOOM, (CH
2)
mcOM or (CH
2)
msO
3m.
4. near infrared fluorine boron two pyrroles's fluorescence dyes as claimed in claim 3, is characterized in that, wherein R
6, R
7for identical or different H, C
1-12straight chain or branched-chain alkyl, C
1-12cycloalkyl, (CH
2)
mo (CH
2)
nh, (CH
2) mCOOM, (CH
2) mCOM or (CH
2) mSO
3m; N, m=0 – 15; M=H, Li, Na, K, NH
4.
5. near infrared fluorine boron two pyrroles's fluorescence dyes, is characterized in that, its general structure is:
6. near infrared fluorine boron two pyrroles's fluorescence dyes as claimed in claim 5, is characterized in that R
3, R
4, R
5for H, C
1-12alkyl, CH=CH-CH=CH, cycloalkyl, phenyl, naphthyl, F, Cl, Br, I, OR
6, NR
6r
7, CN, (CH=CH
2) (C
6h
4) R
6, (CH
2)
mo (CH
2)
nh, (CH
2)
ncOOM, (CH
2)
mcOM or (CH
2)
msO
3m.
7. near infrared fluorine boron two pyrroles's fluorescence dyes as claimed in claim 6, is characterized in that, wherein R
6, R
7for identical or different H, C
1-12straight chain or branched-chain alkyl, C
1-12cycloalkyl, (CH
2)
mo (CH
2)
nh, (CH
2) mCOOM, (CH
2) mCOM or (CH
2) mSO
3m; N, m=0 – 15; M=H, Li, Na, K, NH
4.
8. the preparation method of near infrared fluorine boron two pyrroles's fluorescence dyes as described in claim 1-7, is characterized in that, comprises the steps:
(1) halo isoindole imines and boric acid class reagent Suzuki are coupled;
(2) synthetic with acid catalysis condensation.
9. the preparation method of near infrared fluorine boron two pyrroles's fluorescence dyes as claimed in claim 8, is characterized in that, in step (1), halo isoindole imines and boric acid class reagent Suzuki are coupled and have prepared a series of aldehyde; And/or, in step (2), use acid catalysis condensation 4h.
10. the preparation method of near infrared fluorine boron two pyrroles's fluorescence dyes as described in claim 8 or 9, is characterized in that, also comprises the steps:
(3) triethylamine adds boron trifluoride diethyl etherate, room temperature coordination after processing;
(4) extraction, washing, dry, concentrating under reduced pressure;
(5) separate and make this isoindoles near infrared fluorine boron two pyrroles's fluorescence dyes through silica gel column chromatography.
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