CN109234759B - A kind of synthetic method of BODIPY - Google Patents
A kind of synthetic method of BODIPY Download PDFInfo
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Abstract
The invention discloses a kind of synthetic methods for being commercialized BODIPY, it is basic raw material with two kinds of chloro BODIPY that electrochemistry halogenation generates, the synthesis of a variety of commercialization BODIPY is completed by Suzuki coupling reaction, ester hydrolysis reaction, acyl esterification, entire synthetic route is environmentally protective, economical and efficient, two kinds of chloro BODIPY properties of electrochemistry preparation are stable and easy to store, it is easily operated, it may be implemented to restrain standby, the synthesis cost of these commercializations BODIPY is greatly saved, realizes their production domesticization.
Description
Technical field
The invention belongs to the synthesis technical fields of fluorescent dye, and in particular to a kind of synthetic method for being commercialized BODIPY.
Background technique
From nineteen sixty-eight, since Treibs and Kreuzer synthesize Novel BODIPY flourescent dye compound for the first time, by half a century
Development Novel BODIPY flourescent dye as a kind of newer dye composition, receive extensive attention, at the same also become one kind
Most common fluorescent dye compound.BODIPY dye has the advantage that (1) main body knot compared with other dye compositions
Structure is generally not directly connected amino, hydroxyl etc., therefore insensitive to pH value；(2) fluorescence quantum yield is higher, and some is in water very
To the level for being close to 0.1；(3) BODIPY dyestuff has preferable photostability compared with fluorescein, flower mountain valley with clumps of trees and bamboo dyestuff etc.；(4)
Since its fluorescence spectrum half-peak is narrow, the high sensitivity in fluorescence identifying label；(5) molar absorption coefficient is high, extinction efficiency
It is higher.
With biochemistry, the rapid development of organic chemistry, BODIPY dye composition with its unique property and advantage,
In fields such as optical dynamic therapy, pH probe, ion identification, photocatalysis, protein labeling, cell imaging, proteome analysis
It is widely used.Compound of the Novel BODIPY flourescent dye as a kind of great scientific research value and practical value, to it
The year of structure and application more than nearly 60 is in research and probe, has been developed that thousands of BODIPY dye compositions, however mesh
Preceding commercially valuable BODIPY compound, only more than 40 kinds, the structure of common commercialization BODIPY is as follows:
Above-mentioned commercialization BODIPY compound is external import at present, and the country is without production.Existing literature it is disclosed about
The factors such as the synthesis step of BODIPY compound is longer, larger to the consumption of raw material, and synthetic yield is low, and environmental pollution is serious, make
It is very expensive in price.Therefore, developing and optimizing commercialization BODIPY compound synthesis route is one very significant
Work.
Summary of the invention
The purpose of the present invention is to provide the method for economic, efficient synthesis commercialization BODIPY a kind of, this method is used
Environmentally protective electrochemical method has synthesized the BODIPY compound of chloro by electrochemistry halogenating reaction, closes as raw material
At a variety of commercialized BODIPY.
For above-mentioned purpose, the technical solution adopted in the present invention includes the following steps:
1, using acetonitrile as solvent, compound 1 or compound 1 ' and lithium chloride is passed through electric current at room temperature, electrochemistry occurs
Halogenating reaction obtains compound 2 or compound 2 '；
2, using toluene as solvent, under nitrogen protection, by compound 2 and compound 3, compound 4, sodium carbonate, four (triphens
Base phosphine) palladium is heated to reflux, or compound 2 ' and compound 3, sodium carbonate, tetrakis triphenylphosphine palladium are heated to reflux, occur
Suzuki coupling reaction generates compound 5 or compound 5 '；
3, using the mixed liquor of tetrahydrofuran and water as solvent, compound 5 or compound 5 ' and hydrochloric acid are subjected to ester hydrolysis, it is raw
At compound 6 or compound 6 '；
4, using methylene chloride as solvent, by compound 6 or compound 6 ', N, bis- succinimidyl carbonate of N'- is three
Ethamine effect is lower to occur acyl esterification, generates compound 7 or compound 7 '；
In formula,
In above-mentioned steps 1, the molar ratio of the preferably described compound 1 or compound 1 ' and lithium chloride is 1:2~5, electrochemistry
Halogenating reaction uses constant current mode；Wherein synthesized reference SCI document " A.Thompson, the et of compound 1
Al.Chem.Commun., 2013,49,816 ", synthesized reference document " C.A.Alabi, the et of compound 1 '
The synthetic method of al.Bioconjugate Chem.2017,28,907-912 " report is completed.
In above-mentioned steps 2, the preferably compound 2 and compound 3, compound 4, tetrakis triphenylphosphine palladium, sodium carbonate
Molar ratio 1:1.5~3:1.5~3:0.02~1:2~4, the compound 2 ' and compound 3, tetrakis triphenylphosphine palladium, carbonic acid
Molar ratio 1:1.5~3:0.02~1:2~4 of sodium.
In above-mentioned steps 3, molar ratio 1:4~8 of the preferably described compound 5 or compound 5 ' and hydrochloric acid.
In above-mentioned steps 4, the preferably described compound 6 or compound 6 ' and triethylamine, N, bis- succinimido carbonic acid of N'-
Molar ratio 1:1~3:1~3 of ester.
Beneficial effects of the present invention are as follows:
The present invention passes through electrochemistry preparation process prepare compound 2, environmentally protective, and realizes the gram-grade system of compound 2
It is standby, the material storage of sufficient amount is provided for synthesis commercialization BODIPY derivative.And subsequent Suzuki is coupled, hydrolysis is anti-
It answers, acyl esterification, all realizes 70% or more yield, significantly reduce the synthesis cost of commercialization BODIPY, undoubtedly
It is a kind of more economical, more efficient synthetic method.
Specific embodiment
Below with reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited in these
Embodiment.
Embodiment 1
1,1.03g (5.3mmol) compound 1 is dissolved in 60mL acetonitrile, 0.91g (21.2mmol) lithium chloride is added, adopts
Electricity consumption synthesizer, constant current mode, 3mA electric current stir 8h at room temperature.To which after reaction, reaction solution is transferred in round-bottomed flask
After reduced pressure, purified with column chromatography, obtain 0.92g yellow solid compound 2, yield 66%, structural characterization data are
:1H NMR(600MHz,CHCl3- d) δ: 7.13 (s, 1H), 7.07 (d, J=4.2Hz, 2H), 6.42 (d, J=4.4Hz, 2H)；13C NMR(151MHz,CDCl3)δ:145.7,134.1,131.4,127.9,119.1.
2,200mg (0.76mmol) compound 2 is dissolved in 5mL toluene, 1mL 2.5mol/L (2.5mmol) carbonic acid is added
Sodium water solution, 43mg (0.04mmol) tetrakis triphenylphosphine palladium, 145mg (1.14mmol) thiophene -2- boric acid 3-1 are protected in nitrogen
Reaction solution is heated to reflux 5h under shield, to after reaction, be extracted with separatory funnel, organic phase is dried over anhydrous sodium sulfate, subtracts
After pressure concentration, column chromatographic purifying obtains 180mg brown solid compound 5-1, yield 80%, structural characterization data are as follows:1H
NMR(600MHz,CHCl3- d) δ: 8.28 (dd, J=3.9,1.0Hz, 1H), 7.57 (dd, J=5.0,1.0Hz, 1H), 7.21
(dd, J=5.0,3.9Hz, 1H), 7.13-7.06 (m, 2H), 6.99-6.94 (m, 1H), 6.90-6.83 (m, 1H), 6.39 (d, J
=4.1Hz, 1H)；13C NMR(151MHz,CDCl3)δ153.6,141.5,137.8,133.3,132.8,132.7,132.3,
130.9,129.5,128.1,126.0,121.8,117.7.
150mg (0.48mmol) compound 5-1 is dissolved in 5mL toluene, is added 0.5mL 2.5mol/L (1.25mmol)
Aqueous sodium carbonate, 27.7mg (0.02mmol) tetrakis triphenylphosphine palladium, 201.2mg (0.96mmol) 4- (2- methoxyl group -2- oxygen
For ethyoxyl) phenyl boric acid 4-1, reaction solution is heated to reflux 5h under nitrogen protection, to after reaction, be extracted with separatory funnel
It taking, after organic phase is dried over anhydrous sodium sulfate, is concentrated under reduced pressure, column chromatographic purifying obtains 190mg brown solid compound 5-2,
Yield is 75%, structural characterization data are as follows:1H NMR(600MHz,CHCl3- d) δ: 8.11 (d, J=3.9Hz, 1H), 7.96 (d, J
=8.6Hz, 2H), 7.46 (d, J=5.0Hz, 1H), 7.17-7.11 (m, 2H), 7.07 (d, J=4.2Hz, 1H), 7.04 (d, J
=4.4Hz, 1H), 7.00 (d, J=8.5Hz, 2H), 6.80 (d, J=4.3Hz, 1H), 6.65 (d, J=4.2Hz, 1H), 4.71
(s,2H),3.84(s,3H)；13C NMR(151MHz,CDCl3)δ169.1,159.0,158.4,150.7,136.7,134.0,
131.4,131.3,129.9,129.2,129.1,126.1,126.0,120.8,120.7,114.5,65.3,52.3.
3,120mg (0.27mmol) compound 5-2 is dissolved in 5mL tetrahydrofuran and water volume ratio for the mixed solvent of 4:1
In, 1mL4mol/L hydrochloric acid is added, 10h is stirred at room temperature, to after reaction, be extracted with separatory funnel, organic phase is through anhydrous
After sodium sulphate drying, reduced pressure, column chromatographic purifying obtains 93mg brown solid compound 6-1, yield 80%.
4,80mg (0.18mmol) compound 6-1 is dissolved in 5mL methylene chloride, 0.03mL (0.22mmol) three second is added
Amine, bis- succinimidyl carbonate of 64mg (0.23mmol) N, N'-, stir 3h at room temperature, to be concentrated under reduced pressure after the reaction was completed,
Column chromatographic purifying obtains 85.6mg red brown solid compound 7-1, yield 75%.
Embodiment 2
1, compound 2 is synthesized according to the method for 1 step 1 of embodiment.
2, compound 5-1 is synthesized according to the method for 1 step 2 of embodiment.
130mg (0.42mmol) compound 5-1 is dissolved in 5mL toluene, is added 0.3mL 2.5mol/L (0.75mmol)
Aqueous sodium carbonate, 24.3mg (0.03mmol) tetrakis triphenylphosphine palladium, 148.7mg (0.63mmol) (E)-(4- (2- methoxy
Base -2- oxygen ethyoxyl) styryl) boric acid 4-2, reaction solution is heated to reflux 5h under nitrogen protection, to after reaction, use
Separatory funnel extraction, after organic phase is dried over anhydrous sodium sulfate, is concentrated under reduced pressure, column chromatographic purifying obtains 143mg red brown solid
Compound 5-3, yield 73%, structural characterization data are as follows:1H NMR(600MHz,CHCl3- d) δ: 8.20 (dd, J=3.8,
1.1Hz, 1H), 7.64-7.56 (m, 3H), 7.47 (dd, J=5.1,1.1Hz, 1H), 7.32 (d, J=16.3Hz, 1H), 7.21
(dd, J=5.1,3.8Hz, 1H), 7.05 (s, 1H), 7.03 (d, J=4.5Hz, 1H), 6.98 (d, J=4.3Hz, 1H), 6.94
(dd, J=6.6,2.1Hz, 3H), 6.79 (d, J=4.3Hz, 1H), 4.69 (s, 2H), 3.83 (s, 3H)；13C NMR(151MHz,
CDCl3)δ:169.0,158.9,156.6,149.2,137.4,136.8,136.6,134.4,130.6,130.2,129.8,
129.4,129.0,128.8,128.7,123.9,119.7,117.7,117.3,115.0,65.3,52.3.
2,120mg (0.27mmol) compound 5-3 is dissolved in 5mL tetrahydrofuran and water volume ratio for the mixed solvent of 4:1
In, 2mL 4mol/L hydrochloric acid is added, 10h is stirred at room temperature, to after reaction, be extracted with separatory funnel, organic phase is through nothing
After aqueous sodium persulfate drying, reduced pressure, column chromatographic purifying obtains 93mg brown solid compound 6-2, yield 80%.
4,80mg (0.18mmol) compound 6-2 is dissolved in 5mL methylene chloride, 0.03mL (0.22mmol) three second is added
Amine, bis- succinimidyl carbonate of 64mg (0.23mmol) N, N'-, stir 3h at room temperature, to be concentrated under reduced pressure after the reaction was completed,
Column chromatographic purifying obtains 85.6mg bronzing compound 7-2, yield 75%.
Embodiment 3
1,1.2g (4.3mmol) compound 1 ' is dissolved in 60mL acetonitrile, 273mg (6.4mmol) lithium chloride is added, used
Electro synthesis device, constant current mode, 2mA electric current stir 10h at room temperature.To which after reaction, reaction solution is transferred in round-bottomed flask
After reduced pressure, purified with column chromatography, obtains 1.17g tan solid Compound 2 ', yield 86%, structural characterization data
Are as follows:1H NMR(600MHz,CHCl3- d) δ: 7.11 (s, 1H), 7.06 (d, J=4.3Hz, 1H), 6.97 (d, J=4.2Hz, 1H),
6.43 (d, J=4.3Hz, 1H), 6.35 (d, J=4.2Hz, 1H), 3.69 (s, 3H), 3.34 (t, J=7.5Hz, 2H), 2.79
(t, J=7.5Hz, 2H)；13C NMR(151MHz,CDCl3):δ172.5,164.0,142.1,135.7,133.2,132.4,
129.3,127.8,120.3,117.5,51.8,32.8,24.3.
2,300mg (0.96mmol) compound 2 ' is dissolved in 5mL toluene, 2mL 2.5mol/L (5mmol) carbonic acid is added
Sodium water solution, 55.5mg (0.05mmol) tetrakis triphenylphosphine palladium, 183.6mg (1.44mmol) thiophene -2- boric acid 3-1, in nitrogen
Reaction solution is heated to reflux 5h under gas shielded, to after reaction, be extracted with separatory funnel, organic phase is dry through anhydrous sodium sulfate
After dry, reduced pressure, column chromatographic purifying obtains 289.1mg tan solid Compound 5 ' -1, yield 85%, structural characterization
Data are as follows:1H NMR(400MHz,CHCl3-d)δ:7.97-7.87(m,2H),7.56-7.40(m,3H),7.21(s,1H),7.09
(d, J=4.2Hz, 1H), 7.03 (d, J=4.2Hz, 1H), 6.64 (dd, J=4.2,1.2Hz, 1H), 6.38 (d, J=4.2Hz,
1H), 3.67 (s, 3H), 3.31 (t, J=7.5Hz, 2H), 2.75 (t, J=7.5Hz, 2H)；13C NMR(100MHz,CDCl3)δ:
172.7,161.4,158.8,136.3,134.9,132.4,130.6,130.3,129.7,129.4,129.3,129.3,
128.3,128.1,120.3,119.2,51.75,33.0,24.2.
3,200mg (0.55mmol) compound 5 ' -1 is dissolved in 5mL tetrahydrofuran and water volume ratio for the mixed solvent of 4:1
In, 1mL 4mol/L hydrochloric acid is added, 10h is stirred at room temperature, to after reaction, be extracted with separatory funnel, organic phase is through nothing
After aqueous sodium persulfate drying, reduced pressure, column chromatographic purifying obtains 144mg brown solid compound 6 ' -1, yield 75%.
4,120mg (0.35mmol) compound 6 ' -1 is dissolved in 5mL methylene chloride, 0.05mL (0.39mmol) three is added
Bis- succinimidyl carbonate of ethamine and 107.6mg (0.42mmol) N, N'-, stirs 3h, to subtract after the reaction was completed at room temperature
Pressure concentration, column chromatographic purifying, obtain 110mg red brown solid compound 7 ' -1, yield 70%, structural characterization data are as follows:1H NMR(600MHz,CHCl3- d) δ: 8.20-8.16 (m, 1H), 7.55-7.47 (m, 1H), 7.20 (dd, J=5.1,3.9Hz,
1H), 7.13 (s, 1H), 7.05 (d, J=4.4Hz, 1H), 6.99 (d, J=4.1Hz, 1H), 6.81 (d, J=4.3Hz, 1H),
6.44 (d, J=4.1Hz, 1H), 3.46 (t, J=7.4Hz, 2H), 3.11 (t, J=7.3Hz, 2H), 2.84 (d, J=6.8Hz,
4H)；13C NMR(150MHz,CDCl3)δ169.0,167.7,157.9,151.6,137.1,134.7,133.7,131.6,
131.1,129.8,129.5,129.2,126.9,120.6,118.7,30.2,25.6,23.6.
Embodiment 4
1, compound 2 ' is synthesized according to the method for 3 step 1 of embodiment.
2,400mg (1.27mmol) compound 2 ' is dissolved in 5mL toluene, 2.5mL2.5mol/L (5mmol) carbonic acid is added
Sodium water solution, 73.4mg (0.06mmol) tetrakis triphenylphosphine palladium, 232.3mg (1.44mmol) phenyl boric acid 3-2, in nitrogen protection
Lower that reaction solution is heated to reflux 5h, to after reaction, be extracted with separatory funnel, organic phase is dried over anhydrous sodium sulfate, depressurizes
After concentration, column chromatographic purifying obtains 385.3mg tan solid Compound 5 ' -2, yield 85%, structural characterization data are as follows:1H NMR(400MHz,CHCl3- d) δ: 7.97-7.87 (m, 2H), 7.56-7.40 (m, 3H), 7.21 (s, 1H), 7.09 (d, J=
4.2Hz, 1H), 7.03 (d, J=4.2Hz, 1H), 6.64 (dd, J=4.2,1.2Hz, 1H), 6.38 (d, J=4.2Hz, 1H),
3.67 (s, 3H), 3.31 (t, J=7.5Hz, 2H), 2.75 (t, J=7.5Hz, 2H)；13C NMR(100MHz,CDCl3)δ:
172.7,161.4,158.8,136.3,134.9,132.4,130.6,130.3,129.7,129.4,129.3,129.3,
128.3,128.1,120.3,119.2,51.75,33.0,24.2.
3,300mg (0.84mmol) compound 5 ' -2 is dissolved in 5mL tetrahydrofuran and water volume ratio for the mixed solvent of 4:1
In, 1mL4mol/L hydrochloric acid is added, 10h is stirred at room temperature, to after reaction, be extracted with separatory funnel, organic phase is through anhydrous
After sodium sulphate drying, reduced pressure, column chromatographic purifying obtains 230.6mg brown solid compound 6 ' -2, yield 80%.
4,200mg (0.58mmol) compound 6 ' -2 is dissolved in 5mL methylene chloride, 0.1mL (0.70mmol) three is added
Bis- succinimidyl carbonate of ethamine and 193.3mg (0.70mmol) N, N'-, stirs 3h, to subtract after the reaction was completed at room temperature
Pressure concentration, column chromatographic purifying, obtain 193mg red brown solid compound 7 ' -2, yield 75%, structural characterization data are as follows:1H NMR(600MHz,CHCl3- d) δ: 7.92 (dt, J=5.9,1.6Hz, 2H), 7.48 (dt, J=10.4,6.6Hz, 3H),
7.24 (s, 1H), 7.12 (d, J=4.2Hz, 1H), 7.04 (d, J=4.3Hz, 1H), 6.66 (d, J=4.2Hz, 1H), 6.45
(d, J=4.2Hz, 1H), 3.40 (t, J=7.3Hz, 2H), 3.06 (t, J=7.2Hz, 2H), 2.86-2.79 (m, 4H)；13C
NMR(150MHz,CDCl3)δ:168.9,167.7,159.5,159.0,136.7,134.9,132.2,130.9,130.5,
129.9,129.4,129.4,129.3,120.7,119.2,30.1,25.6,23.6.
Embodiment 5
1, compound 2 ' is synthesized according to the method for 3 step 1 of embodiment.
2,500mg (1.60mmol) compound 2 ' is dissolved in 5mL toluene, 1mL 2.5mol/L (6.4mmol) carbon is added
Acid sodium aqueous solution, 92.3mg (0.08mmol) tetrakis triphenylphosphine palladium, 445.4mg (2.56mmol) ((1E, 3E) -4- phenyl fourth
Base -1,3- dialkylene -1- base) boric acid 3-3, reaction solution is heated to reflux 5h under nitrogen protection, to after reaction, use liquid separation
Funnel extraction, after organic phase is dried over anhydrous sodium sulfate, is concentrated under reduced pressure, column chromatographic purifying obtains 540mg Tan solid chemical combination
Object 5 ' -3, yield 83%, structural characterization data are as follows:1H NMR(600MHz,CHCl3-d)δ:7.49-7.44(m,2H),7.36
(dd, J=8.4,6.9Hz, 2H), 7.3-7.27 (m, 1H), 7.24-7.15 (m, 2H), 7.13-7.08 (m, 1H), 7.04 (s,
1H), 7.00 (d, J=4.5Hz, 1H), 6.92 (d, J=4.1Hz, 1H), 6.87-6.80 (m, 2H), 6.33 (d, J=4.1Hz,
1H), 3.71 (s, 3H), 3.35 (t, J=7.6Hz, 2H), 2.81 (t, J=7.6Hz, 2H)；13C NMR(150MHz,CDCl3)δ
172.8,158.9,156.2,138.6,137.5,136.6,134.9,130.4,129.0,128.9,128.8,128.6,
127.0,125.2,122.7,117.9,117.2,51.8,33.1,24.2.
3,400mg (0.98mmol) compound 5 ' -3 is dissolved in 5mL tetrahydrofuran and water volume ratio for the mixed solvent of 4:1
In, 2mL4mol/L hydrochloric acid is added, 10h is stirred at room temperature, to after reaction, be extracted with separatory funnel, organic phase is through anhydrous
After sodium sulphate drying, reduced pressure, column chromatographic purifying obtains 301.0mg brown solid compound 6 ' -3, yield 78%.
4,300mg (0.76mmol) compound 6 ' -3 is dissolved in 5mL methylene chloride, 0.14mL (0.99mmol) three is added
Bis- succinimidyl carbonate of ethamine and 233.7mg (0.91mmol) N, N'-, stirs 3h, to subtract after the reaction was completed at room temperature
Pressure concentration, column chromatographic purifying, obtain 273mg red brown solid compound 7 ' -3, yield 73%, structural characterization data are as follows:1H NMR(600MHz,CHCl3- d) δ: 7.48 (d, J=7.6Hz, 2H), 7.36 (t, J=7.5Hz, 2H), 7.29 (t, J=
7.4Hz, 1H), 7.21 (d, J=8.1Hz, 2H), 7.19-7.11 (m, 1H), 7.06 (s, 1H), 7.03 (d, J=4.5Hz, 1H),
6.94 (d, J=4.1Hz, 1H), 6.90-6.82 (m, 2H), 6.40 (d, J=4.1Hz, 1H), 3.44 (t, J=7.4Hz, 2H),
3.12 (t, J=7.4Hz, 2H), 2.85 (s, 4H)；13C NMR(151MHz,CDCl3)δ169.0,167.7,156.8,156.5,
139.1,137.9,136.9,136.6,134.9,130.8,128.9,128.8,128.8,128.7,127.1,125.4,
122.6,117.9,117.5,30.3,25.6,23.6.
Claims (7)
1. a kind of synthetic method of BODIPY, it is characterised in that this method includes the following steps:
(1) using acetonitrile as solvent, compound 1 or compound 1 ' and lithium chloride is passed through electric current at room temperature, electrochemistry halogen occurs
Generation reaction, obtains compound 2 or compound 2 '；
(2) using toluene as solvent, under nitrogen protection, by compound 2 and compound 3, compound 4, sodium carbonate, four (triphenyls
Phosphine) palladium is heated to reflux, or compound 2 ' and compound 3, sodium carbonate, tetrakis triphenylphosphine palladium are heated to reflux, Suzuki occurs
Coupling reaction generates compound 5 or compound 5 '；
(3) using the mixed liquor of tetrahydrofuran and water as solvent, compound 5 or compound 5 ' and hydrochloric acid is subjected to ester hydrolysis, generated
Compound 6 or compound 6 '；
In formula,
2. the synthetic method of BODIPY according to claim 1, it is characterised in that this method contains and includes the following steps:
Using methylene chloride as solvent, by compound 6 or compound 6 ', N, bis- succinimidyl carbonate of N'- is made in triethylamine
With lower generation acyl esterification, compound 7 or compound 7 ' are generated；
In formula,
3. the synthetic method of BODIPY according to claim 1 or 2, it is characterised in that: in step (1), the compound 1
Or the molar ratio of compound 1 ' and lithium chloride is 1:2~5, electrochemistry halogenating reaction uses constant current mode.
4. the synthetic method of BODIPY according to claim 1 or 2, it is characterised in that: in step (2), the compound 2
With molar ratio 1:1.5~3:1.5~3:0.02~1:2~4 of compound 3, compound 4, tetrakis triphenylphosphine palladium, sodium carbonate.
5. the synthetic method of BODIPY according to claim 1 or 2, it is characterised in that: in step (2), the compound
2 ' with compound 3, tetrakis triphenylphosphine palladium, sodium carbonate molar ratio 1:1.5~3:0.02~1:2~4.
6. the synthetic method of BODIPY according to claim 1 or 2, it is characterised in that: in step (3), the compound 5
Or molar ratio 1:4~8 of compound 5 ' and hydrochloric acid.
7. the synthetic method of BODIPY according to claim 2, it is characterised in that: the compound 6 or compound 6 ' with
Triethylamine, N, molar ratio 1:1~3:1~3 of bis- succinimidyl carbonate of N'-.
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| FR2940653B1 (en) * | 2008-12-29 | 2011-02-04 | Centre Nat Rech Scient | NOVEL FLUORESCENT DIPYRROMETHEN-BOROSUBSTITUTE COMPOUNDS AND THEIR USE FOR DIAGNOSIS |
| CN102492306A (en) * | 2011-12-19 | 2012-06-13 | 大连理工大学 | Boron-dipyrromethene dye containing sulfur and halogen, and preparation method thereof |
| SG11201403368WA (en) * | 2011-12-22 | 2014-07-30 | Univ Singapore | Bodipy structure fluorescence probes for diverse biological applications |
| CN103952001B (en) * | 2014-05-08 | 2016-09-14 | 安徽师范大学 | A kind of near-infrared fluorine boron two pyrroles's fluorescent dye and preparation method thereof |
| CN106008582A (en) * | 2016-07-27 | 2016-10-12 | 东莞理工学院 | Fluorene and carbazole bridging-based A-D-A type double-center BODIPY (boron-dipyrrolemethene) derivative and preparation method for same |
| CN106565762B (en) * | 2016-11-17 | 2018-10-23 | 陕西师范大学 | A kind of in situ BODIPY classes dyestuff for generating near-infrared fluorescent and its preparation and application |
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