CN105367592A - Boron fluoride complexing bi-pyrrole methylidyne derivative substituted by meso-position alkyl thiophene and 3,5-position electron-donating group and preparation method of derivative - Google Patents

Boron fluoride complexing bi-pyrrole methylidyne derivative substituted by meso-position alkyl thiophene and 3,5-position electron-donating group and preparation method of derivative Download PDF

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CN105367592A
CN105367592A CN201510642416.8A CN201510642416A CN105367592A CN 105367592 A CN105367592 A CN 105367592A CN 201510642416 A CN201510642416 A CN 201510642416A CN 105367592 A CN105367592 A CN 105367592A
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boron fluoride
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CN105367592B (en
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赵鸿斌
廖俊旭
王育才
张文涛
彭敏
李柏鸿
刘晓杰
朱威
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Yuncheng Chengyuan Pharmaceutical Technology Co ltd
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Dongguan University of Technology
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Abstract

The invention discloses a boron fluoride complexing bi-pyrrole methylidyne derivative substituted by meso-position alkyl thiophene and a 3,5-position electron-donating group and a preparation method of the derivative. According to the method, 2-bromothiophene serves as a starting raw material, dipyrrylmethanes substituted by meso-position alkyl thiophene is synthesized through a series of reactions, NBS bromination is conducted, and 3,5-dibromo bi-pyrrolidine is obtained; then, TCQ oxidation and boron trifluoride ether complexing are conducted, a 3,5-boron dibromo fluorine intermediate with the meso-position containing alkyl thiophene is obtained, then the intermediate is utilized to conduct an Suzuki/Stille coupled reaction with a variety of modification groups, the boron fluoride complexing bi-pyrrole methylidyne derivative substituted by a 3,5-position donor unit is obtained, and the structural formula can be found in formula I. The boron fluoride complexing bi-pyrrole methylidyne derivative substituted by meso-position alkyl thiophene and the 3,5-position electron-donating group has good stability and has potential application value in the fields of life science, solar cells, environment, energy and the like.

Description

A kind of meta alkylthrophene replaces and 3,5 donor residuess replace boron fluoride complexing two pyrroles methine derivative and preparation method thereof
Technical field:
The present invention relates to boron fluoride complexing two pyrrole methenyl fluorescent dye field, be specifically related to the boron fluoride complexing two pyrroles methine derivative organic dye that a kind of meta alkylthrophene replaces and 3,5 strong donor residuess replace.
Background technology:
Boron fluoride complexing two pyrroles methine (4,4 '-Difluoro-4-bora-3a, 4a-diaza-sindacene, being called for short BODIPY) fluorochrome has stronger spectral absorption, higher light stability, just by extensive concern since nineteen sixty-eight reported first, the fields such as life science, solar cell, environmental energy science are applied to.
Research shows that the spectral absorption scope of dye molecule is wider, and performance is more excellent.In order to the absorption and emission wavelength that make BODIPY dyestuff reach near infrared region, Many researchers selects the conjugate system expanding dye molecule at the meta introducing donor groups of fluorine boron parent nucleus to make it to form larger two dimensional structure.2012, M.Ravikanth seminar reported the novel B ODIPY dye molecule that two kinds of meso-position furans replace, and show that the conjugated degree of the dye molecule after the replacement of meta furans and fluorine boron parent nucleus plane improves greatly, spectral absorption red shift is obvious.
Consider thiophene and furan structure similar, and give electro stronger, therefore the BODIPY dyestuff that replaces of design and synthesis of the present invention meta alkylthrophene, and in thiphene ring, be connected to an alkyl to increase the solvability of dye molecule, simultaneously 3, introduce the conjugation chain length that the electron-donating groups such as thiophene, duplex thiophene, carbazole, fluorenes and triphenylamine increase dye molecule for 5, make it planar conjugate stronger, effectively widen the absorption spectrum of BODIPY dyestuff.
Summary of the invention:
The object of this invention is to provide the replacement of a kind of meta alkylthrophene and 3, the boron fluoride complexing two pyrroles methine derivative that 5 strong donor residuess replace, it has satisfactory stability, has potential using value in fields such as life science, solar cell, environmental energy.
Another object of the present invention is to provide the preparation method of the boron fluoride complexing two pyrroles methine derivative of the replacement of this meta alkylthrophene and 3,5 strong donor residues replacements.
For achieving the above object, the present invention is by the following technical solutions:
The boron fluoride complexing two pyrroles methine derivative that a kind of meta alkylthrophene replaces and 3,5 strong donor residuess replace, has the chemical structure of logical formula I:
In formula I,
The preparation method of the boron fluoride complexing two pyrroles methine derivative of a kind of meta alkylthrophene replacement and 3,5 strong donor residues replacements, comprises the following steps:
(1) 2-bromothiophene and 1-brominated alkanes are obtained by reacting intermediate 1 under the effect of butyllithium, its structure is:
(2) intermediate 1 and 1-formylpiperidine are reacted, obtain intermediate 2, its structure is:
(3) reacted under the catalysis of catalyzer with pyrroles by intermediate 2, obtain intermediate 3, its structure is:
(4) intermediate 3 and N-bromo-succinimide are reacted, obtain intermediate 4, its structure is:
(5) by intermediate 4 after tetrachlorobenzoquinone oxidation, then react with boron trifluoride diethyl etherate, obtain intermediate 5, its structure is:
(6) 4,4 '-two (2-methylheptyl) triphenylamines and N-bromo-succinimide are at room temperature reacted, obtain intermediate 6, its structure is:
(7) intermediate 6 and duplex tetramethyl ethylene ketone boron ester are reacted under the katalysis of catalyzer, obtain intermediate 7, its structure is:
(8) carbazole and 1-bromine octane are reacted, obtain intermediate 8, its structure is:
(9) intermediate 8 and N-bromo-succinimide are reacted, obtain intermediate 9, its structure is:
(10) intermediate 9 and duplex tetramethyl ethylene ketone boron ester are reacted under the catalysis of catalyzer, obtain intermediate 10, its structure is:
(11) iodo-for 2-9,9-dimethyl fluorenes and duplex tetramethyl ethylene ketone boron ester are reacted under the catalysis of catalyzer, obtain intermediate 11, its structure is:
(12) intermediate 5 and 2-(tributyl tin) thiophene are reacted by Stille under the effect of catalyzer, obtain target dyestuff BDP1, its structure is:
(13) intermediate 5 and the two thiophene of 5-(tributyl tin)-2,2'-are reacted, obtain target dyestuff BDP2, its structure is:
(14) intermediate 5 and intermediate 10 are reacted, obtain target dyestuff BDP3, its structure is:
(15) intermediate 5 and intermediate 11 are reacted, obtain target dyestuff BDP4, its structure is:
(16) intermediate 5 and intermediate 7 are reacted, obtain target dyestuff BDP5, its structure is:
Preferred as technique scheme, the reaction medium of reaction described in step (1)-(16) is one or more mixing of tetrahydrofuran (THF), normal hexane, methylene dichloride, sherwood oil, ethyl acetate, dimethyl sulfoxide (DMSO), toluene, chloroform, ethanol.
Preferred as technique scheme, catalyzer described in step (3), (7), (10), (11), (12) is Pd (dppf) Cl 2, InCl 3, Pd (PPh 3) 4in one.
Preferred as technique scheme, in step (12)-(16), the reaction times of described reaction is 20-36h, and temperature of reaction is 90-120 DEG C.
The preparation of partial target dyestuff BDP1, BDP2, BDP3, BDP4 and BDP5 involved in the present invention can represent with chemical equation below:
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention with 2-bromothiophene for starting raw material, by series reaction synthesis 3,5-dibromo two tetramethyleneimine, 3 of meta alkylthrophene replacement is obtained again through TCQ oxidation, boron trifluoride diethyl etherate complexing, 5-dibromo fluorine boron intermediate, finally recycle this intermediate and multiple modification group carries out Suzuki/Stille linked reaction, obtain meta alkylthrophene replace and 3,5 thiophene, duplex thiophene, carbazole, fluorenes and triphenylamines etc. by force to the target dye molecule that electronic unit replaces.
(2) spectrum to several target product and electrochemical data analysis is passed through, the replacement of such meta alkylthrophene and 3 can be found out, all there is obvious red shift in the absorption spectrum of the boron fluoride complexing two pyrroles methine derivative organic dye of 5 strong donor residues replacements, whole visible ray is covered between uptake zone, maximum absorption wavelength extends near infrared region, and has stronger optical extinction coefficient in whole uptake zone.
Accompanying drawing illustrates:
Fig. 1: BDP1 1hNMR nuclear magnetic spectrum.
Fig. 2: BDP2 1hNMR nuclear magnetic spectrum.
Fig. 3: BDP3 1hNMR nuclear magnetic spectrum.
Fig. 4: BDP4 1hNMR nuclear magnetic spectrum.
Fig. 5: BDP5 1hNMR nuclear magnetic spectrum.
Fig. 6: BDP1 13cNMR nuclear magnetic spectrum.
Fig. 7: BDP2 13cNMR nuclear magnetic spectrum.
Fig. 8: BDP3 13cNMR nuclear magnetic spectrum.
Fig. 9: BDP4 13cNMR nuclear magnetic spectrum.
Figure 10: BDP5 13cNMR nuclear magnetic spectrum.
Figure 11: BDP1 mass-spectrogram.
Figure 12: BDP2 mass-spectrogram.
Figure 13: BDP3 mass-spectrogram.
Figure 14: BDP4 mass-spectrogram.
Figure 15: BDP5 mass-spectrogram.
Embodiment:
For a better understanding of the present invention, below by embodiment, the present invention is further described, and embodiment, only for explaining the present invention, can not form any restriction to the present invention.
(1) synthesis of intermediate 1 (2-octyl thiophene)
In 250ml there-necked flask; add 2-bromothiophene 4g (24.5mmol) and 60mL respectively and newly steam tetrahydrofuran (THF); load onto constant pressure funnel; vacuumize; pass into argon shield; reaction unit is placed in cryogenic thermostat reactor and is cooled to-78 DEG C; dropwise added the hexane solution (2.7M) of 9.1ml (24.5mmol) n-Butyl Lithium by constant pressure funnel under stirring; reaction 2h is continued at-78 DEG C; slowly drip 4.7mL (27mmol) 1-bromine octane again; after reaction 0.5h, reaction flask is moved to room temperature for overnight.Stopped reaction, adds 150mL deionized water in reaction flask, and with dichloromethane extraction three times (50ml × 3), organic layer is again through saturated common salt water washing three times (50mL × 3), and merge organic phase, anhydrous magnesium sulfate drying spends the night.Collecting by filtration filtrate, removes solvent under reduced pressure, and resistates sherwood oil carries out silica gel (200-300 order) column chromatography for separation as eluent, obtains colourless liquid 4.3g, productive rate 89%. 1HNMR(400MHz,CDCl 3)δ7.10(d,J＝5.13Hz,1H),6.91(d,J＝5.12Hz,1H),6.78(d,J＝3.21Hz,1H),2.82(t,J＝7.5Hz,2H,),1.68(m,2H),1.28(m,10H),0.88(t,J＝6.9Hz,3H)
(2) synthesis of intermediate 2 (5-octyl thiophene-2-formaldehyde)
In 100mL reaction flask; add 2-octyl thiophene 3g (15.3mmol) and 35mL anhydrous tetrahydro furan respectively; extract air in system; pass into argon shield; reaction flask is placed in cryogenic thermostat reactor and is cooled to-78 DEG C; stir the hexane solution (2.7M) that lower use syringe dropwise adds 5.7mL (15.3mmol) n-Butyl Lithium; reaction 1.5h is continued at-78 DEG C; slowly drip 1.3mL (16.8mmol) 1-formylpiperidine again; after reaction 0.5h, reaction flask is moved to room temperature for overnight.Stopped reaction, obtains weak yellow liquid 2.3g after purification process, productive rate 68%. 1HNMR(600MHz,CDCl 3)δ9.82(s,1H),7.61(d,J＝3.7Hz,1H),6.90(d,J＝3.7Hz,1H),2.87(t,J＝7.6Hz,2H),1.71(dt,J＝15.2,7.6Hz,2H),1.38-1.25(m,10H),0.88(t,J＝7.0Hz,3H). 13CNMR(151MHz,CDCl 3)δ182.71,157.86,141.59,137.07,125.84,31.82,31.29,30.86,29.24,29.16,29.03,22.65,14.09.
(3) synthesis of intermediate 3 (5-octyl group-2-two pyrrolylmethyl thiophene)
5-octyl thiophene-2-formaldehyde 1.5g (6.7mmol) and the new pyrroles 34.6mL (502.5mmol) steamed is added successively in 100mL single port bottle; extract air in system, pass into argon shield, stirred at ambient temperature reacts; after 10min, in reaction system, add InCl rapidly 340mg (0.20mmol), continues magnetic agitation 4h under lucifuge, and solution becomes dark color from fluorescence is faint yellow, adds NaOH1g (25mmol) solid particulate termination reaction, then continues to stir 30min.Cross and filter NaOH solid, superfluous pyrroles is removed in filtrate decompression distillation, crude product sherwood oil in reaction flask: ethyl acetate=10:1 (v/v) is separated as eluent silica gel column chromatography, obtains orange solid product 1.2g, productive rate 52.7%. 1HNMR(600MHz,CDCl 3)δ7.74(s,2H),6.54(s,1H),6.53(d,J＝2.8Hz,1H),6.51(s,2H),6.07(s,2H),5.95(s,2H),5.48(s,1H),1.64-1.56(m,2H),1.34-1.16(m,10H),0.85(t,J＝6.8Hz,3H). 13CNMR(151MHz,CDCl 3)δ145.29,142.93,132.38,125.14,123.47,117.52,108.38,107.12,39.34,32.01,31.76,30.36,29.47,29.38,29.35,22.83,14.30.
(4) synthesis of intermediate 4 (5-octyl group-2-(3,5-dibromo two pyrrolylmethyl) thiophene)
In 100mL there-necked flask, add 5-octyl group-2-two pyrrolylmethyl thiophene 2g (5.9mmol) and 40mL successively newly steam tetrahydrofuran (THF); load onto constant pressure funnel; vacuumize; pass into argon shield; reaction flask is placed in cryogenic thermostat reactor and is cooled to-78 DEG C; take N-bromo-succinimide 2.2g (12.4mmol) to be dissolved in three batches in appropriate anhydrous tetrahydro furan and to join constant pressure funnel; and be slowly added drop-wise in reaction flask; in order to reduce the generation of by product; strictly need control rate of addition, unsuitable too fast.TLC detection reaction process, treats to add 50mL water termination reaction in the backward reaction flask that raw material primitive reaction is complete.With dichloromethane extraction several, organic layer uses saturated common salt water washing 3 times (150mL × 3) again, and merge organic phase, anhydrous magnesium sulfate drying spends the night.Collecting by filtration filtrate, removes solvent under reduced pressure, resistates sherwood oil: ethyl acetate=30:1 (v/v) carries out silica gel (200-300 order) column chromatography for separation as eluent, obtains dark solid 1g, productive rate 35%. 1HNMR(600MHz,CDCl 3)δ7.96(s,2H),6.66(d,J＝3.4Hz,1H),6.61(d,J＝3.3Hz,1H),6.08(d,J＝3.1Hz,2H),5.95(d,J＝3.0Hz,2H),5.51(s,1H),2.74(t,J＝7.6Hz,2H),1.67-1.59(m,2H),1.36-1.23(m,10H),0.88(t,J＝6.9Hz,3H). 13CNMR(151MHz,CDCl 3)δ146.00,140.97,132.84,125.47,123.58,110.60,109.02,97.49,39.46,31.87,31.56,30.23,29.32,29.23,29.20,22.68,14.14.
(5) synthesis of intermediate 5
Compound 5-octyl group-2-(3 is added successively in 100mL there-necked flask, 5-dibromo two pyrrolylmethyl) methylene dichloride of thiophene 1g (2mmol), tetrachlorobenzoquinone 0.59g (2.4mmol) and 50mL drying, room temperature lower magnetic force stirs, fully oxidized 8h.Pass into argon shield; triethylamine 11.2mL (80mmol) is slowly dripped through syringe; dropwise add boron trifluoride diethyl etherate 12.6mL (100mmol) more subsequently; this process reaction heat release is violent; need the strict rate of addition controlling boron trifluoride diethyl etherate, drip rear continuation magnetic agitation reaction 4h.Stopped reaction, pours in the 200mL0.1MNaOH aqueous solution by reaction mixture, with dichloromethane extraction several, then wash three times with water, merge organic phase, anhydrous sodium sulfate drying spends the night.Collecting by filtration filtrate, removes solvent under reduced pressure, resistates sherwood oil: ethyl acetate=5:1 (v/v) is eluent silica gel column chromatography separating purification, obtains mauve solid 0.82g, productive rate 75%. 1HNMR(600MHz,CDCl 3)δ7.34(d,J＝3.5Hz,1H),7.18(d,J＝4.1Hz,2H),6.94(d,J＝3.4Hz,1H),6.56(d,J＝4.2Hz,2H),2.90(t,J＝7.6Hz,2H),1.76-1.71(m,2H),1.44-1.24(m,10H),0.89(t,J＝6.8Hz,3H). 13CNMR(151MHz,CDCl 3)δ154.09,136.14,134.71,133.57,131.53,130.49,125.91,122.43,31.84,31.49,30.42,29.26,29.18,29.17,22.66,14.12.
(6) synthesis of intermediate 6 (two (4-(2-methylheptyl) phenyl) aniline of bromo-N, the N – of 4-)
In 250mL there-necked flask, add 4 successively, 4 '-two (2-methylheptyl) triphenylamine 5g (10.7mmol) and dry DMF 100mL, load onto constant pressure funnel, take N-bromo-succinimide 1.9g (10.7mmol) be dissolved in the DMF of 30mL drying and join constant pressure funnel, dropwise join in reaction flask, room temperature lower magnetic force stirring reaction 12h.Stopped reaction, pours in 300mL water by reaction mixture, for several times, a large amount of washing of organic layer, merge organic phase, anhydrous magnesium sulfate drying spends the night dichloromethane extraction.Collecting by filtration filtrate, removes solvent under reduced pressure, and resistates sherwood oil carries out silica gel (200-300 order) column chromatography for separation as eluent, obtains white solid 5.3g, productive rate 92.8%. 1HNMR(600MHz,CDCl 3)δ7.31(d,J＝8.7Hz,2H),7.27(d,J＝8.5Hz,4H),6.99(d,J＝8.6Hz,4H),6.92(d,J＝8.9Hz,2H),1.74(s,4H),1.43-1.36(m,12H),0.81-0.76(m,18H).
(7) synthesis of intermediate 7 (two (4-(2-methylheptyl) phenyl)-4-(4,4,5,5-tetramethyl--1,3, the 2-dioxaborolan) aniline of N, N –)
Compound 4-bromo-4,4-bis-(two-2-methylheptyls) triphenylamine 2g (3.7mmol), duplex tetramethyl ethylene ketone boron ester 2.1g (8.2mmol), potassium acetate 2.1g (22.2mmol), Pd (dppf) Cl is added in 200mL single port bottle 2150mg (0.21mmol) and 80mLDMF, vacuumizes, and under argon shield, controls oil bath temperature at 95 DEG C, magnetic agitation reaction 24h.Stopped reaction, reaction mixture is poured into after being cooled to room temperature in 200mL water, with dichloromethane extraction three times (50mL × 3), then uses saturated common salt water washing for several times, merges organic phase, anhydrous magnesium sulfate drying.Remove solvent under reduced pressure, resistates sherwood oil: ethyl acetate=20:1 is that eluent carries out silica gel (200-300 order) column chromatography for separation, and obtain white solid 1.85g, productive rate is 84%. 1HNMR(600MHz,CDCl 3)δ7.64(d,J＝8.5Hz,2H),7.25(d,J＝8.6Hz,4H),7.01(d,J＝8.6Hz,4H),6.98(d,J＝8.5Hz,2H),1.71(s,4H),1.42-1.35(m,12H),1.33(s,12H),0.78-0.71(m,18H).
(8) synthesis of intermediate 8 (9-octylcarbazol)
In 250mL there-necked flask, add 5g (15.4mmol) carbazole successively, 100mLDMSO, 0.25g (1.1mmol) TEBA and 25mL sodium hydroxide solution (50wt%), in 0.5h, 3.3g (16.9mmol) 1-bromine octane is dripped under magnetic agitation, room temperature reaction 8h, stopped reaction, add hydrochloric acid in reaction solution and regulate PH=7, be extracted with ethyl acetate (3 × 50mL), merge organic layer and use saturated common salt water washing 3 times, anhydrous magnesium sulfate drying spends the night, distilling off solvent after filtering, residuum sherwood oil is eluent column chromatography for separation, obtain white crystal 5.4g, yield 80%. 1HNMR(400MHz,CDCl 3)，δ:8.15(d,J＝1.5Hz,J＝8Hz,2H),7.50(d,2H),7.45(d,J＝8Hz,2H),7.26(d,2H),4.35(t,J＝8Hz,2H),1.95-1.85(m,2H),1.50-1.20(m,10H),0.92(t,J＝6.5Hz,3H)。
(9) synthesis of intermediate 9 (the bromo-9-octylcarbazol of 3-)
In 250mL single port bottle; add 9-octylcarbazol 4g (24.0mmol) successively, NBS8.5g (48.0mmol), 80mL anhydrous tetrahydro furan; under argon shield; after being heated to 80 DEG C of magnetic agitation reaction 24h, stopped reaction, reaction mixture is poured into after being cooled to room temperature in 300mL distilled water; be extracted with ethyl acetate 3 times; organic layer washes 3 times with saturated common salt again, and merge organic phase, anhydrous sodium sulfate drying spends the night.Remove solvent under reduced pressure, residue by silicagel column chromatography, with sherwood oil: ethyl acetate=30:1 (v/v) is eluent, be separated and obtain white solid 6.1g, productive rate 78%. 1HNMR(400MHz,CDCl 3),δ:8.21(s,1H),8.05(d,1H),7.53(d,1H),7.48(d,J＝7.2Hz,1H),7.40(d,1H),7.27(t,J＝12.0Hz,2H),4.26(t,2H),1.84(m,2H),1.25(m,10H),0.85(t,3H)。
(10) synthesis of intermediate 10 (3-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes)-9-octylcarbazol)
3-bromo-9-octylcarbazol 2g (5.6mmol) is added successively, duplex tetramethyl ethylene ketone boron ester 1.7g (6.7mmol), potassium acetate 2.7g (28mmol), Pd (dppf) Cl in 100mL there-necked flask 2150mg (0.21mmol) and 80mLDMF, obtains white solid 1.7g by the method for similar synthetic intermediate 7, productive rate 76%. 1HNMR(400MHz,CDCl 3),δ:8.60(s,1H),8.13(d,J＝7.6Hz,1H),7.92(d,J＝8.1Hz,1H),7.45(d,J＝7.3Hz,1H),7.40(t,J＝9.5Hz,2H),7.23(d,J＝7.0Hz,1H),4.30(t,J＝6.9Hz,2H),1.90-1.86(m,2H),1.44(s,12H),1.36-1.28(m,10H),0.85(t,J＝13.6Hz,3H)。MALDI-TOF-MS,m/z:calcdforC 26H 36BNO 2:405.300；found405.333[M] +。
(11) synthesis of intermediate 11 (2-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes)-9,9-dimethyl fluorenes)
Iodo-9, the 9-dimethyl fluorene 2g (6.3mmol) of 2-are added, duplex tetramethyl ethylene ketone boron ester 1.9g (7.5mmol), potassium acetate 2.9g (30mmol), Pd (dppf) Cl in there-necked flask 2150mg (0.21mmol) and 80mLDMF, obtains white solid 1.6g by the method for similar synthetic intermediate 7, productive rate 80%. 1HNMR(600MHz,CDCl 3)δ7.91(s,1H),7.85(d,J＝7.5Hz,1H),7.76(t,J＝6.8Hz,2H),7.48-7.45(m,1H),7.37-7.34(m,2H),1.53(s,6H),1.40(s,12H).
Embodiment 1
The synthesis of BDP1
In 100ml single port bottle; by intermediate 5 (200mg; 0.37mmol) be dissolved in 20ml toluene, then add 2-(tributyl tin) thiophene (330mg, 0.88mmol); tetrakis triphenylphosphine palladium (11mg; 0.01mmol), vacuumize, pass into argon shield; be heated to backflow, magnetic agitation reaction 48h.Stopped reaction, reaction mixture is cooled to room temperature, pour in 150ml distilled water, with chloroform extraction three times (50ml × 3), organic layer uses saturated common salt water washing for several times again, merge organic phase, anhydrous sodium sulfate drying spends the night, filter, collect filtrate, remove solvent under reduced pressure, resistates sherwood oil: methylene dichloride: ethyl acetate=10:2:1 (v/v/v) carries out silica gel (300-400 order) column chromatography for separation for eluent, obtain red-purple solid 81mg, productive rate 40%. 1HNMR(600MHz,CDCl 3)δ8.19(d,J＝3.6Hz,2H),7.48(d,J＝5.0Hz,2H),7.29(d,J＝3.5Hz,1H),7.22-7.16(m,4H),6.92(d,J＝3.5Hz,1H),6.84(d,J＝4.3Hz,2H),2.91(t,J＝6.0Hz2H),1.78-1.73(m,2H),1.46-1.25(m,10H),0.99(t,J＝7.4Hz,1H)0.92(t,J＝7.0Hz,3H). 13CNMR(151MHz,CDCl 3)δ151.68,149.81,136.22,134.40,132.36,132.09,131.20,131.14,131.09,130.16,129.03,125.12,120.47,33.66,31.54,30.33,30.01,29.72,28.88,22.58,14.09.MALDI-TOF-MS,m/z:calcdforC 29H 29BF 2N 2S 3:550.155,found:550.360[M] +.
Embodiment 2
The synthesis of BDP2
In there-necked flask, add intermediate 5 (200mg, 0.37mmol) and the two thiophene 402mg (0.88mmol) of 5-(tributyl tin)-2,2'-, obtain red-purple solid 103mg, productive rate 39% by the method for similar synthesis BDP1. 1HNMR(600MHz,CDCl 3)δ8.13(d,J＝4.0Hz,2H),7.31-7.26(m,7H),7.17(d,J＝4.3Hz,2H),7.06-7.04(m,2H),6.90(d,J＝3.2Hz,1H),6.83(d,J＝4.3Hz,2H),2.90(t＝6.5,2H),1.78-1.72(m,2H),1.45-1.24(m,10H),0.98(t,J＝7.4Hz,3H). 13CNMR(151MHz,CDCl 3)δ151.52,148.89,140.99,136.89,136.72,136.66,133.02,132.44,132.18,131.97,129.91,128.12,125.82,125.53,125.10,124.70,120.41,33.67,31.55,30.34,30.02,28.90,28.29,22.59,14.10.MALDI-TOF-MS,m/z:calcdforC 37H 33BF 2N 2S 5:714.131,found:686.332[M-28] +.
Embodiment 3
The synthesis of BDP3
In 100ml single port bottle; add intermediate 5 (200mg, 0.37mmol), 3-(4,4 successively; 5; 5-tetramethyl--1,3,2-dioxaborolanes)-9-octylcarbazol 357mg (0.82mmol), tetrakis triphenylphosphine palladium 11mg (0.01mmol), 50mL toluene and 30mL (2mol/L) sodium carbonate solution; excluding air; argon shield, controls temperature of reaction at 90 DEG C, magnetic agitation reaction 36h.Stopped reaction, is cooled to room temperature by reaction mixture, pours in 200mL distilled water, and with chloroform extraction several, organic layer uses saturated common salt water washing three times (150mL × 3) again, and merge organic phase, anhydrous magnesium sulfate drying spends the night.Remove solvent under reduced pressure, resistates sherwood oil: methylene dichloride: ethyl acetate=10:2:1 (v/v/v) purifies for eluent carries out silica gel (300-400 order) column chromatography for separation, obtains red-purple solid 150mg, productive rate 41%. 1HNMR(600MHz,CDCl 3)δ8.70(s,2H),8.14(d,J＝7.5Hz,2H),8.07(d,J＝8.6Hz,2H),7.92(d,J＝8.3Hz,1H),7.46-7.42(m,2H),7.40-7.35(m,4H),7.30(d,J＝4.2Hz,2H),7.21(d,J＝7.7Hz,2H),6.94(d,J＝3.2Hz,1H),6.79(d,J＝4.2Hz,2H),4.24(t,J＝7.3Hz,4H),2.94(t,J＝7.6Hz,2H),1.88-1.82(m,4H),1.80-1.76(m,2H),1.36-1.19(m,30H),1.01(t,J＝7.4Hz,3H),0.88-0.83(m,6H). 13CNMR(151MHz,CDCl 3)δ159.10,142.61,141.09,140.91,132.09,130.07,127.69,125.78,125.60,123.67,123.24,122.84,122.06,120.69,120.59,119.22,119.18,108.80,108.74,108.43,108.10,83.59,43.24,43.12,31.80,29.39,29.36,29.18,29.02,28.95,27.33,22.61,14.09.MALDI-TOF-MS,m/z:calcdforC 61H 71BF 2N 4S:940.546,found:940.631[M] +.
Embodiment 4
The synthesis of BDP4
Intermediate 5 (200mg is added in there-necked flask, 0.37mmol) with 2-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes)-9,9-dimethyl fluorene 282mg (0.82mmol), obtains red-purple solid 137mg by the method for similar synthetic dyestuff BDP3, productive rate 48%. 1HNMR(600MHz,CDCl 3)δ8.02(s,2H),7.89(d,J＝9.2Hz,2H),7.76-7.70(m,4H),7.41(d,J＝8.1Hz,2H),7.39(d,J＝3.5Hz,1H),7.34-7.29(m,2H),6.96(d,J＝3.4Hz,1H),6.75(d,J＝4.2Hz,2H),2.98-2.91(m,2H),1.81-1.75(m,2H),1.48(s,12H),1.39-1.23(m,10H),1.01(t,J＝7.3Hz,3H). 13CNMR(151MHz,CDCl 3)δ158.62,154.41,153.32,151.87,140.51,138.70,136.05,133.89,132.45,131.65,130.57,128.72,127.67,127.00,125.20,124.02,122.60,120.79,120.42,119.65,83.75,46.95,33.73,30.06,29.77,29.69,29.35,27.08,24.93,22.32,13.85.MALDI-TOF-MS,m/z:calcdforC 51H 49BF 2N 2S:770.368,found:770.479[M] +.
Embodiment 5
The synthesis of BDP5
Intermediate 5 (200mg is added successively in there-necked flask, 0.37mmol), N, two (4-(2-methylheptyl) the phenyl)-4-(4 of N –, 4,5,5-tetramethyl--1,3,2-dioxaborolan) aniline 526mg (0.82mmol), obtain red-purple solid 137mg, productive rate 35% by the method for similar synthesis BDP3. 1HNMR(600MHz,CDCl 3)δ7.78(d,J＝8.8Hz,4H),7.62(d,J＝8.4Hz,4H),7.44(d,J＝8.7Hz,1H),7.24(d,J＝8.6Hz,8H),7.18(d,J＝4.3Hz,2H),7.07(d,J＝8.6Hz,8H),6.89(d,J＝3.5Hz,1H),6.65(d,J＝4.3Hz,2H),2.92-2.89(m,2H),1.83(d,J＝8.6Hz,2H),1.71(d,J＝11.8Hz,8H),1.37-1.25(m,24H),0.98(t,J＝7.4Hz,3H),0.78-0.73(m,36H). 13CNMR(151MHz,CDCl 3)δ151.04,149.14,145.67,145.10,144.48,144.07,135.70,130.53,127.13,127.08,127.02,126.18,125.15,124.96,124.56,124.46,124.36,123.54,120.90,119.97,57.21,57.18,38.28,38.21,32.45,31.79,31.72,31.44,29.96,29.69,29.37,29.25,27.19,24.87,22.34,14.14.MALDI-TOF-MS,m/z:calcdforC 89H 115BF 2N 4S:1320.890,found:1321.053[M] +.
In above-described embodiment, target dyestuff BDP1-BDP5 is at CH 2cl 2ultraviolet-visible absorption spectroscopy data in solution and on solid film are in table 1, and in embodiment, the related data of target dyestuff BDP1-BDP5 electrochemical properties is in table 2.
The spectroscopic data of table 1 dyestuff BDP1-BDP5
aInCH 2Cl 2.
bDepositedontoquartzsubstratebythespin-coatingtechniquefromCH 2Cl 2solution。
The cyclic voltammetric data of table 2 dyestuff BDP1-BDP5
aE gwasestimatedfromtheabsorptionthresholdsfromabsorptionspectraofdyesabsorbedinfilm,E g＝1240/λ onset.
bE ox onset,onsetoxidationpotential
c.E ox p,oxidationpeakpotential
dE redthereductionpotential,wascalculatedfromE ox onset–E g.
eE HOMO＝[-(E ox onset-0.54)-4.8]eV,E LUMO＝E HOMO+E geV.
As can be seen from Table 1, five kinds of target dyestuffs all have three absorption bands in ultraviolet-visible district.The BDP1 and 3 of 3,5 introducing thiophene, compares without the BODIPY replaced for 5, and maximum absorption wavelength is by 520nm red shift to 628nm, and this is because thiphene ring electron donation is strong, is introduced into and can forms effective conjugation with fluorine boron parent nucleus to during BODIPY parent nucleus 3,5.The BDP2 absorption spectrum that duplex thiophene is introduced in 3,5-position is widened further, and maximum absorption wavelength reaches 696nm, compares BDP1 red shift 68nm, and this is because the conjugative effect of duplex thiophene and parent nucleus is stronger.The maximum absorption wavelength red shift of dyestuff BDP3 is to 623nm, this is because carbazole unit itself has strong to electronic effect and cavity transmission ability, after carbazole is introduced in 3,5-position, and in molecule between fluorine boron parent nucleus, electronic migration effect strengthens.3,5 of dyestuff BDP4 introduce the fluorenes unit with carbazole with similar quality, and maximum absorption wavelength red shift is to 601nm.3 of dyestuff BDP5,5 are replaced by the triaryl amine with alkyl, maximum absorption wavelength red shift to 670nm, 3, the introducing of 5 triaryl amine effectively strengthens conjugative effect between same BODIPY parent nucleus and electron transfer capacity, makes the maximum absorption wavelength of dye molecule that obvious red shift occur.From table 1, it can also be seen that the maximum absorption wavelength of five kinds of dyestuffs on solid film is respectively 654nm, 752nm, 653nm, 625nm, 681nm, compare its maximum absorption wavelength in methylene dichloride respectively red shift 26nm, 56nm, 30nm, 24nm, 11nm, and absorption region is widened.Describe dye molecule to gather on solid film, intermolecular pi-pi accumulation effect strengthens, thus makes maximum absorption spectrum red shift and widen.
First oxidizing potential of target dyestuff BDP1-BDP5 is respectively 1.10eV, 1.14eV, 0.89eV, 1.15eV and 0.91eV as can be seen from Table 2.When target dyestuff 3,5 introduces donor monomer thiophene, duplex thiophene and fluorenes, the first oxidizing potential of dye molecule is about 1.14, and stability is better; 3,5 donor monomer be carbazole and triphenylamine time, the first oxidizing potential of dyestuff is about 0.9, less stable, illustrates that the size of the space structure of donor monomer own produces certain influence to the oxidizing potential of whole dye molecule and stability of molecule.The HOMO energy level of BDP3 and BDP5 is respectively-5.15eV and-5.17eV, more slightly larger than the HOMO energy level of other three kinds of dye molecules, illustrate when substituting group be carbazole and triphenylamine time, these two kinds of dyestuffs are more conducive to the injection in hole, and the hole mobility of whole molecule is improved.
The present invention illustrates detailed synthetic method by above-described embodiment, but the present invention is not limited to aforesaid method, does not namely mean that the present invention must rely on above-mentioned reaction conditions and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, replaces and react the change etc. of actual conditions to the equivalence of reaction solvent catalyzer of the present invention, all drops within protection scope of the present invention and open scope.

Claims (5)

1. the boron fluoride complexing two pyrroles methine derivative of a meta alkylthrophene replacement and 3,5 strong donor residues replacements, is characterized in that having the chemical structure of logical formula I:
In formula I,
2. the preparation method of the boron fluoride complexing two pyrroles methine derivative of a kind of meta alkylthrophene replacement as claimed in claim 1 and 3,5 strong donor residues replacements, is characterized in that, comprise the following steps:
(1) 2-bromothiophene and 1-brominated alkanes are obtained by reacting intermediate 1 under the effect of butyllithium, its structure is:
(2) intermediate 1 and 1-formylpiperidine are reacted, obtain intermediate 2, its structure is:
(3) reacted under the catalysis of catalyzer with pyrroles by intermediate 2, obtain intermediate 3, its structure is:
(4) intermediate 3 and N-bromo-succinimide are reacted, obtain intermediate 4, its structure is:
(5) by intermediate 4 after tetrachlorobenzoquinone oxidation, then react with boron trifluoride diethyl etherate, obtain intermediate 5, its structure is:
(6) 4,4 '-two (2-methylheptyl) triphenylamines and N-bromo-succinimide are at room temperature reacted, obtain intermediate 6, its structure is:
(7) intermediate 6 and duplex tetramethyl ethylene ketone boron ester are reacted under the katalysis of catalyzer, obtain intermediate 7, its structure is:
(8) carbazole and 1-bromine octane are reacted, obtain intermediate 8, its structure is:
(9) intermediate 8 and N-bromo-succinimide are reacted, obtain intermediate 9, its structure is:
(10) intermediate 9 and duplex tetramethyl ethylene ketone boron ester are reacted under the catalysis of catalyzer, obtain intermediate 10, its structure is:
(11) iodo-for 2-9,9-dimethyl fluorenes and duplex tetramethyl ethylene ketone boron ester are reacted under the catalysis of catalyzer, obtain intermediate 11, its structure is:
(12) intermediate 5 and 2-(tributyl tin) thiophene are reacted by Stille under the effect of catalyzer, obtain target dyestuff BDP1, its structure is:
(13) intermediate 5 and the two thiophene of 5-(tributyl tin)-2,2'-are reacted, obtain target dyestuff BDP2, its structure is:
(14) intermediate 5 and intermediate 10 are reacted, obtain target dyestuff BDP3, its structure is:
(15) intermediate 5 and intermediate 11 are reacted, obtain target dyestuff BDP4, its structure is:
(16) intermediate 5 and intermediate 7 are reacted, obtain target dyestuff BDP5, its structure is:
3. a kind of meta alkylthrophene replacement as claimed in claim 2 and 3, the preparation method of the boron fluoride complexing two pyrroles methine derivative of 5 strong donor residues replacements, it is characterized in that, the reaction medium of reaction described in step (1)-(16) is one or more mixing of DMF, tetrahydrofuran (THF), normal hexane, methylene dichloride, sherwood oil, ethyl acetate, dimethyl sulfoxide (DMSO), toluene, chloroform, ethanol.
4. a kind of meta alkylthrophene replacement as claimed in claim 2 and 3, the preparation method of the boron fluoride complexing two pyrroles methine derivative of 5 strong donor residues replacements, it is characterized in that, catalyzer described in step (3), (7), (10), (11), (12) is Pd (dppf) Cl 2, InCl 3, Pd (PPh 3) 4in one.
5. a kind of meta alkylthrophene replacement as claimed in claim 2 and 3, the preparation method of the boron fluoride complexing two pyrroles methine derivative of 5 strong donor residues replacements, it is characterized in that, in step (12)-(16), the reaction times of described reaction is 20-36h, and temperature of reaction is 90-120 DEG C.
CN201510642416.8A 2015-09-29 2015-09-29 Boron fluoride complexing bi-pyrrole methylidyne derivative substituted by meso-position alkyl thiophene and 3,5-position electron-donating group and preparation method of derivative Expired - Fee Related CN105367592B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106188112A (en) * 2016-07-09 2016-12-07 东莞理工学院 A kind of 2 substituted asymmetric fluorine boron complexation two pyrroles's methine derivants of thienyl and preparation method thereof
CN111808126A (en) * 2020-08-06 2020-10-23 大连理工大学 A-pi-D-pi-A type BODIPY micromolecule photovoltaic material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103232484A (en) * 2013-05-20 2013-08-07 南京工业大学 Method for synthesizing diquinoline aza-fluorine boron complex
CN104073018A (en) * 2014-05-09 2014-10-01 天津大学 A series of 2,3,5,6-quaterthiophene substituted BODIPY (boron dipyrromethene) dyes with long wave absorption characteristics and preparation method of 2,3,5,6-quaterthiophene substituted BODIPY dyes
CN104530105A (en) * 2014-12-29 2015-04-22 东莞理工学院 Benzothiadiazole or benzodithiophene-bridged bis-boron-dipyrrolemethene (BODIPY) derivative organic dye and preparation method thereof
CN104559286A (en) * 2014-12-23 2015-04-29 东莞理工学院 Triphenylamine-BODIPY derivative organic dye and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103232484A (en) * 2013-05-20 2013-08-07 南京工业大学 Method for synthesizing diquinoline aza-fluorine boron complex
CN104073018A (en) * 2014-05-09 2014-10-01 天津大学 A series of 2,3,5,6-quaterthiophene substituted BODIPY (boron dipyrromethene) dyes with long wave absorption characteristics and preparation method of 2,3,5,6-quaterthiophene substituted BODIPY dyes
CN104559286A (en) * 2014-12-23 2015-04-29 东莞理工学院 Triphenylamine-BODIPY derivative organic dye and preparation method thereof
CN104530105A (en) * 2014-12-29 2015-04-22 东莞理工学院 Benzothiadiazole or benzodithiophene-bridged bis-boron-dipyrrolemethene (BODIPY) derivative organic dye and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106188112A (en) * 2016-07-09 2016-12-07 东莞理工学院 A kind of 2 substituted asymmetric fluorine boron complexation two pyrroles's methine derivants of thienyl and preparation method thereof
CN106188112B (en) * 2016-07-09 2019-02-26 东莞理工学院 A kind of asymmetric fluorine boron complexing bodipy derivative and preparation method thereof that 2- thienyl replaces
CN111808126A (en) * 2020-08-06 2020-10-23 大连理工大学 A-pi-D-pi-A type BODIPY micromolecule photovoltaic material and preparation method and application thereof

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