CN105367592B - 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 PDFInfo
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- AKBDWIXCYPMDIV-UHFFFAOYSA-O C=[NH+]c1ccc(NO)[nH]1 Chemical compound C=[NH+]c1ccc(NO)[nH]1 AKBDWIXCYPMDIV-UHFFFAOYSA-O 0.000 description 1
- PCGYWFIVZRFHEB-UHFFFAOYSA-N CCCCCCCC(C)[n]1c(ccc(Br)c2)c2c2ccccc12 Chemical compound CCCCCCCC(C)[n]1c(ccc(Br)c2)c2c2ccccc12 PCGYWFIVZRFHEB-UHFFFAOYSA-N 0.000 description 1
- JBCANTOSOMYYHX-SFHVURJKSA-N CCCCCCCC[n]1c(C=CC2=C[C@@H]22)c2c2c1cccc2 Chemical compound CCCCCCCC[n]1c(C=CC2=C[C@@H]22)c2c2c1cccc2 JBCANTOSOMYYHX-SFHVURJKSA-N 0.000 description 1
- 0 Cc1ccc(C(C(*2*3(N)N)=CC=C2c2ccc[n]2)=C(C=C2)*3=C2c2ccc[n]2)[n]1 Chemical compound Cc1ccc(C(C(*2*3(N)N)=CC=C2c2ccc[n]2)=C(C=C2)*3=C2c2ccc[n]2)[n]1 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N Cc1ccc[s]1 Chemical compound Cc1ccc[s]1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
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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
Technical field：
The present invention relates to boron fluoride is complexed two pyrrole methenyl fluorescent dye fields, a kind of middle position alkyl thiophene is specifically related to
Boron fluoride two pyrroles's methine derivative organic dyestuff of complexing that fen replaces and 3,5 strong donor residues replace.
Background technology：
Boron fluoride two pyrroles's methines of complexing (4,4 '-Difluoro-4-bora-3a, 4a-diaza-sindacene, referred to as
BODIPY) fluorochrome has stronger spectral absorption, higher photostability, just wide since the nineteen sixty-eight reported first
General concern, has been applied to the fields such as life science, solar cell, environmental energy science.
Research shows that the spectral absorption scope of dye molecule is wider, and performance is more excellent.In order that the absorption of BODIPY dyestuffs
Near infrared region is reached with launch wavelength, Many researchers select the middle position in fluorine boron parent nucleus to introduce donor groups to extend dyestuff
The conjugated system of molecule is allowed to form larger planar structure.2012, M.Ravikanth seminars reported two kinds of meso-
Novel B ODIPY dye molecule that position furans replaces, show middle position furans replace after dye molecule and fluorine boron parent nucleus plane be total to
Yoke degree is greatly improved, and spectral absorption red shift is obvious.
It is similar with furan structure in view of thiophene, and electron is higher, therefore present invention design has synthesized middle position alkyl
The BODIPY dyestuffs that thiophene replaces, and an alkyl is connected in thiphene ring increasing the dissolubility of dye molecule, while
3,5 introduce the electron donating groups such as thiophene, duplex thiophene, carbazole, fluorenes and triphenylamine to increase the conjugation chain length of dye molecule, make
Planar conjugate it is higher, effectively widen the absorption spectrum of BODIPY dyestuffs.
The content of the invention：
It is an object of the invention to provide the boron fluoride network that a kind of middle position alkylthrophene replaces and 3,5 strong donor residues replace
Two pyrroles's methine derivatives are closed, it has good stability, has in fields such as life science, solar cell, environmental energy
Potential using value.
It is a further object to provide the fluorination that the middle position alkylthrophene replaces and 3,5 strong donor residues replace
Boron is complexed the preparation method of two pyrroles's methine derivatives.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of middle position alkylthrophene replaces and boron fluoride two pyrroles's methines of complexing of 3,5 strong donor residues replacements derive
Thing, the chemical constitution with formula (I)：
In formula (I),
Boron fluoride two pyrroles's methine derivatives of complexing that a kind of middle position alkylthrophene replaces and 3,5 strong donor residues replace
Preparation method, comprise the following steps：
(1) 2- bromothiophenes and 1- brominated alkanes are reacted in the presence of butyl lithium and obtains intermediate 1, its structure is：
(2) intermediate 1 and 1- formylpiperidines are reacted, obtains intermediate 2, its structure is：
(3) intermediate 2 and pyrroles are reacted under the catalysis of catalyst, obtains intermediate 3, its structure is：
(4) intermediate 3 and N- bromo-succinimides are reacted, obtains intermediate 4, its structure is：
(5) by intermediate 4 Jing after tetrachloroquinone oxidation, then react with BFEE, obtain intermediate 5, its structure
For：
(6) 4,4 '-two (1,1- dimethylhexanyl) triphenylamines are reacted at room temperature with N- bromo-succinimides, is obtained
Intermediate 6, its structure is：
(7) intermediate 6 and duplex pinacol boron ester are reacted under the catalytic action of catalyst, obtains intermediate 7, its knot
Structure is：
(8) carbazole and 1- bromines normal octane are reacted, obtains intermediate 8, its structure is：
(9) intermediate 8 and N- bromo-succinimides are reacted, obtains intermediate 9, its structure is：
(10) intermediate 9 and duplex pinacol boron ester are reacted under the catalysis of catalyst, obtains intermediate 10, its structure
For：
(11) iodo- 9, the 9- dimethyl fluorenes of 2- and duplex pinacol boron ester are reacted under the catalysis of catalyst, obtains centre
Body 11, its structure is：
(12) intermediate 5 and 2- (tributyl tin) thiophene are reacted in the presence of catalyst by Stille, obtains mesh
Dyestuff BDP1 is marked, its structure is：
(13) by intermediate 5 and the double thiophene reactions of 5- (tributyl tin) -2,2'-, target dyestuff BDP2, its structure are obtained
For：
(14) intermediate 5 is reacted with intermediate 10, obtains target dyestuff BDP3, its structure is：
(15) intermediate 5 is reacted with intermediate 11, obtains target dyestuff BDP4, its structure is：
(16) intermediate 5 is reacted with intermediate 7, obtains target dyestuff BDP5, its structure is：
Used as the preferred of above-mentioned technical proposal, the reaction medium reacted described in step (1)-(16) is tetrahydrofuran, just
One or more mixing of hexane, dichloromethane, petroleum ether, ethyl acetate, dimethyl sulfoxide (DMSO), toluene, chloroform, ethanol.
Used as the preferred of above-mentioned technical proposal, step (3), (7), (10), (11), catalyst described in (12) are Pd
(dppf)Cl2, InCl3, Pd (PPh3)4In one kind.
Used as the preferred of above-mentioned technical proposal, in step (12)-(16), the reaction time of the reaction is 20-36h, instead
Temperature is answered to be 90-120 DEG C.
Preparing for partial target dyestuff BDP1, BDP2, BDP3, BDP4 and BDP5 involved in the present invention can be with following
Chemical equation is representing：
Compared with prior art, the invention has the advantages that：
(1) present invention synthesizes the pyrrolidines of 3,5- dibromos two, then Jing with 2- bromothiophenes as initiation material by series reaction
TCQ oxidations, BFEE complexing obtain 3, the 5- dibromo fluorine boron intermediates of middle position alkylthrophene replacement, and finally recycling should
Intermediate carries out Suzuki/Stille coupling reactions with various modification groups, obtains the replacement of middle position alkylthrophene and 3,5 thiophenes
The target dye molecule that the strong electron unit such as fen, duplex thiophene, carbazole, fluorenes and triphenylamine replaces.
(2) analyzed by the spectrum to several target products and electrochemical data, it can be seen that such middle position alkylthrophene
The boron fluoride of replacement and 3,5 strong donor residues replacements is complexed the absorption spectrum of two pyrroles's methine derivative organic dyestuff to be occurred
Substantially red shift, absorbs the whole visible ray of interval covering, and maximum absorption wavelength extends near infrared region, and absorbs interval whole
Inside there is stronger extinction coefficient.
Description of the drawings：
Fig. 1:BDP11HNMR nuclear magnetic spectrums.
Fig. 2:BDP21HNMR nuclear magnetic spectrums.
Fig. 3:BDP31HNMR nuclear magnetic spectrums.
Fig. 4:BDP41HNMR nuclear magnetic spectrums.
Fig. 5:BDP51HNMR nuclear magnetic spectrums.
Fig. 6:BDP113CNMR nuclear magnetic spectrums.
Fig. 7:BDP213CNMR nuclear magnetic spectrums.
Fig. 8:BDP313CNMR nuclear magnetic spectrums.
Fig. 9:BDP413CNMR nuclear magnetic spectrums.
Figure 10:BDP513CNMR nuclear magnetic spectrums.
Figure 11:BDP1 mass-spectrograms.
Figure 12:BDP2 mass-spectrograms.
Figure 13:BDP3 mass-spectrograms.
Figure 14:BDP4 mass-spectrograms.
Figure 15:BDP5 mass-spectrograms.
Specific embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
(1) synthesis of intermediate 1 (2- octyl thiophenes)
In 250ml there-necked flasks, it is separately added into 2- bromothiophene 4g (24.5mmol) and 60mL newly steams tetrahydrofuran, loads onto perseverance
Pressure dropping funel, vacuumizes, and is passed through argon gas protection, reaction unit is placed in cryogenic thermostat reactor and is cooled to -78 DEG C, stirring
The hexane solution (2.7M) of 9.1ml (24.5mmol) n-BuLi is added dropwise over by constant pressure funnel down, at -78 DEG C
Continue to react 2h, then be slowly added dropwise 4.7mL (27mmol) 1- bromine normal octanes, after reaction 0.5h, reaction bulb is moved to and is stirred under room temperature
Mix overnight.Stop reaction, 150mL deionized waters are added in reaction bulb, with dichloromethane three times (50ml × 3) are extracted, it is organic
Layer Jing saturated common salts water washing three times (50mL × 3) again, merges organic phase, and anhydrous magnesium sulfate is dried overnight.Filtrate is collected by filtration,
Remove solvent under reduced pressure, residue carries out silica gel (200-300 mesh) column chromatography for separation, obtains colourless liquid with petroleum ether as eluant, eluent
Body 4.3g, yield 89%.1H NMR(400MHz,CDCl3) δ 7.10 (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 bulbs, 2- octyl thiophene 3g (15.3mmol) and 35mL anhydrous tetrahydro furans are separately added into, are extracted
Air in system, is passed through argon gas protection, reaction bulb is placed in cryogenic thermostat reactor and is cooled to -78 DEG C, and stirring is lower using note
Emitter is added dropwise over the hexane solution (2.7M) of 5.7mL (15.3mmol) n-BuLi, continues to react 1.5h at -78 DEG C,
1.3mL (16.8mmol) 1- formylpiperidines are slowly added dropwise again, after reaction 0.5h, reaction bulb is moved to and is stirred overnight under room temperature.Stop
Only react, weak yellow liquid 2.3g, yield 68% are obtained after purification process.1H NMR(600MHz,CDCl3)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).13C NMR(151MHz,CDCl3)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 (the pyrrolylmethyl thiophene of 5- octyl groups -2- two)
5- octyl thiophenes -2- formaldehyde 1.5g (6.7mmol) and the new pyrroles for steaming are sequentially added in 100mL single port bottles
34.6mL (502.5mmol), extracts air in system, is passed through argon gas protection, stirring reaction under room temperature, after 10min, to reactant
InCl is rapidly added in system340mg (0.20mmol), continues magnetic agitation 4h under lucifuge, solution is changed into deep from fluorescence is faint yellow
Color, adds NaOH 1g (25mmol) solid particle terminating reaction, is further continued for stirring 30min.NaOH solids are filtered to remove, will be filtered
Liquid vacuum distillation removes superfluous pyrroles, the crude product petroleum ether in reaction bulb：Ethyl acetate=10:1 (v/v) is used as wash-out
Agent silica gel column chromatography is separated, and obtains orange solid product 1.2g, yield 52.7%.1H NMR(600MHz,CDCl3)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).13C NMR(151MHz,
CDCl3)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- (pyrrolylmethyl of 3,5- dibromos two) thiophene)
Pyrrolylmethyls thiophene 2g (5.9mmol) of 5- octyl groups -2- two are sequentially added in 100mL there-necked flasks and 40mL newly steams four
Hydrogen furans, loads onto constant pressure funnel, vacuumizes, and is passed through argon gas protection, reaction bulb is placed in cryogenic thermostat reactor and is cooled down
To -78 DEG C, weigh N- bromo-succinimide 2.2g (12.4mmol) and be dissolved in addition in appropriate anhydrous tetrahydro furan in three batches
To constant pressure funnel, and it is slowly dropped in reaction bulb, in order to reduce the generation of accessory substance, need to strictly controls rate of addition,
It is unsuitable too fast.TLC detects course of reaction, treats to add 50mL water terminating reactions in the complete backward reaction bulb of raw material fundamental reaction.
Dichloromethane extracted several times, organic layer are used to use saturated common salt water washing 3 times (150mL × 3) again, merge organic phase, anhydrous slufuric acid
Magnesium is dried overnight.Filtrate is collected by filtration, solvent, residue petroleum ether is removed under reduced pressure：Ethyl acetate=30:1 (v/v) conducts are washed
De- agent carries out silica gel (200-300 mesh) column chromatography for separation, obtains dark solid 1g, yield 35%.1H NMR(600MHz,CDCl3)
δ 7.96 (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).13C NMR(151MHz,CDCl3)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- (pyrrolylmethyl of 3,5- dibromos two) thiophene 1g is sequentially added in 100mL there-necked flasks
(2mmol), the dichloromethane that tetrachloroquinone 0.59g (2.4mmol) and 50mL is dried, magnetic agitation under room temperature, fully oxidized 8h.
Argon gas protection is passed through, Jing syringes are slowly added dropwise triethylamine 11.2mL (80mmol), BFEE is subsequently added dropwise over again
12.6mL (100mmol), the process reaction heat release acutely, need to strictly control the rate of addition of BFEE, after dripping
Continue magnetic agitation reaction 4h.Stop reaction, reaction mixture is poured in the 200mL 0.1M NaOH aqueous solution, use dichloromethane
Alkane extracted several times, are washed with water three times, merge organic phase, and anhydrous sodium sulfate drying is overnight.Filtrate is collected by filtration, is removed under reduced pressure molten
Agent, residue petroleum ether：Ethyl acetate=5：1 (v/v) is eluant, eluent silica gel column chromatography separating purification, obtains mauve solid
Body 0.82g, yield 75%.1H NMR(600MHz,CDCl3) δ 7.34 (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).13C NMR(151MHz,CDCl3)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 (the bromo- N of 4-, N-bis- (4- (2- methylheptyls) phenyl) aniline)
In 250mL there-necked flasks, 4,4 '-two (1,1- dimethylhexanyl) triphenylamine 5g (10.7mmol) and nothing are sequentially added
Water DMF 100mL, load onto constant pressure funnel, weigh N- bromo-succinimide 1.9g (10.7mmol) and are dissolved in 30mL dryings
DMF is simultaneously added to constant pressure funnel, in being added dropwise to reaction bulb, magnetic agitation reaction 12h under room temperature.Stop reaction, will
Reaction mixture is poured in 300mL water, dichloromethane extracted several times, the substantial amounts of washing of organic layer, merges organic phase, anhydrous sulphur
Sour magnesium is dried overnight.Filtrate is collected by filtration, solvent is removed under reduced pressure, residue carries out silica gel (200- with petroleum ether as eluant, eluent
300 mesh) column chromatography for separation, obtain white solid 5.3g, yield 92.8%.1H NMR(600MHz,CDCl3) δ 7.31 (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) (N, N-bis- (4- (2- methylheptyls) phenyl) -4- (4,4,5,5- tetramethyl -1,3,2- dioxas of intermediate 7
Pentaborane) aniline) synthesis
Add in 200mL single port bottles bromo- 4,4- bis- (two -2- methylheptyls) the triphenylamine 2g (3.7mmol) of compound 4-,
Duplex pinacol boron ester 2.1g (8.2mmol), potassium acetate 2.1g (22.2mmol), Pd (dppf) Cl2 150mg(0.21mmol)
And 80mL DMF, vacuumizing, under argon gas protection, at 95 DEG C, magnetic agitation reacts 24h to control oil bath temperature.Stop reaction, instead
Answer mixture to be cooled to after room temperature to pour in 200mL water, with dichloromethane three times (50mL × 3) are extracted, then use saturated aqueous common salt
Washing for several times, merges organic phase, and anhydrous magnesium sulfate is dried.Remove solvent, residue petroleum ether under reduced pressure：Ethyl acetate=20:1
Silica gel (200-300 mesh) column chromatography for separation is carried out for eluant, eluent, white solid 1.85g is obtained, yield is 84%.1H NMR
(600MHz,CDCl3) δ 7.64 (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- octylcarbazols)
In 250mL there-necked flasks, 5g (15.4mmol) carbazole, 100mL DMSO, 0.25g (1.1mmol) are sequentially added
TEBA and 25mL sodium hydroxide solutions (50wt%), dropwise addition 3.3g (16.9mmol) 1- bromines are just pungent in 0.5h under magnetic agitation
Alkane, room temperature reaction 8h stops reaction, adds hydrochloric acid to adjust PH=7 in reactant liquor, is extracted with ethyl acetate (3 × 50mL), merges
Organic layer and with saturated common salt water washing 3 times, anhydrous magnesium sulfate is dried overnight, distilling off solvent after filtration, residue oil
Ether is eluant, eluent column chromatography for separation, obtains white crystal 5.4g, yield 80%.1H NMR(400MHz,CDCl3), 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- octylcarbazols of 3-)
In 250mL single port bottles, 9- octylcarbazol 4g (24.0mmol), NBS 8.5g (48.0mmol) are sequentially added,
80mL anhydrous tetrahydro furans, under argon gas protection, after being heated to 80 DEG C of magnetic agitation reaction 24h, stop reaction, and reactant mixture is cold
But pour in 300mL distilled water to room temperature, be extracted with ethyl acetate 3 times, organic layer is washed 3 times again with saturated common salt, is merged
Organic phase, anhydrous sodium sulfate drying is overnight.Remove solvent, residue by silicagel column chromatography, with petroleum ether under reduced pressure：Ethyl acetate=
30:1 (v/v) be eluant, eluent, isolated white solid 6.1g, yield 78%.1H NMR(400MHz,CDCl3),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) conjunction of intermediate 10 (3- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes) -9- octylcarbazols)
Into
The bromo- 9- octylcarbazols 2g (5.6mmol) of 3-, duplex pinacol boron ester 1.7g are sequentially added in 100mL there-necked flasks
(6.7mmol), potassium acetate 2.7g (28mmol), Pd (dppf) Cl2150mg (0.21mmol) and 80mL DMF, with similar synthesis
The method of intermediate 7 obtains white solid 1.7g, yield 76%.1H NMR(400MHz,CDCl3),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:calcd for C26H36BNO2:405.300；
found 405.333[M]+。
(11) intermediate 11 (2- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes) -9,9- dimethyl fluorenes)
Synthesis
Iodo- 9, the 9- dimethyl fluorenes 2g (6.3mmol) of 2-, duplex pinacol boron ester 1.9g are added in there-necked flask
(7.5mmol), potassium acetate 2.9g (30mmol), Pd (dppf) Cl2150mg (0.21mmol) and 80mL DMF, with similar synthesis
The method of intermediate 7 obtains white solid 1.6g, yield 80%.1H NMR(600MHz,CDCl3)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 bottles, intermediate 5 (200mg, 0.37mmol) is dissolved in into 20ml toluene, adds 2- (tributyls
Tin) thiophene (330mg, 0.88mmol), tetrakis triphenylphosphine palladium (11mg, 0.01mmol) vacuumizes, and is passed through argon gas protection, plus
To flowing back, magnetic agitation reacts 48h to heat.Stop reaction, reaction mixture is cooled to room temperature, in pouring 150ml distilled water into, uses three
Chloromethanes extracts three times (50ml × 3), and organic layer uses saturated common salt water washing for several times again, merges organic phase, and anhydrous sodium sulfate is done
It is dry overnight to filter, filtrate is collected, remove solvent, residue petroleum ether under reduced pressure：Dichloromethane：Ethyl acetate=10:2:1(v/
V/v) silica gel (300-400 mesh) column chromatography for separation is carried out for eluant, eluent, obtains aubergine solid 81mg, yield 40%.1H NMR
(600MHz,CDCl3) δ 8.19 (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=6.0Hz 2H),
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).13C
NMR(151MHz,CDCl3)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:calcd for C29H29BF2N2S3:550.155,found:550.360[M]+.
Embodiment 2
The synthesis of BDP2
Intermediate 5 (200mg, 0.37mmol) and the double thiophene 402mg of 5- (tributyl tin) -2,2'- are added in there-necked flask
(0.88mmol), aubergine solid 103mg, yield 39% are obtained with the method for similar synthesis BDP1.1H NMR(600MHz,
CDCl3) δ 8.13 (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).13C NMR(151MHz,CDCl3)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:calcd for C37H33BF2N2S5:714.131,found:686.332[M-28]+.
Embodiment 3
The synthesis of BDP3
In 100ml single port bottles, sequentially add intermediate 5 (200mg, 0.37mmol), 3- (4,4,5,5- tetramethyl -1,
3,2- dioxaborolanes) -9- octylcarbazol 357mg (0.82mmol), tetrakis triphenylphosphine palladium 11mg (0.01mmol),
50mL toluene and 30mL (2mol/L) sodium carbonate liquor, exclude air, argon gas protection, controlling reaction temperature at 90 DEG C, magnetic force
Stirring reaction 36h.Stop reaction, reaction mixture is cooled to into room temperature, in pouring 200mL distilled water into, use chloroform extraction
For several times, organic layer uses again saturated common salt water washing three times (150mL × 3), merges organic phase, and anhydrous magnesium sulfate is dried overnight.Subtract
Pressure is evaporated off solvent, residue petroleum ether：Dichloromethane：Ethyl acetate=10:2:1 (v/v/v) carries out silica gel for eluant, eluent
(300-400 mesh) column chromatography for separation is purified, and obtains aubergine solid 150mg, yield 41%.1H NMR(600MHz,CDCl3)δ
8.70 (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).13C NMR(151MHz,CDCl3)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:calcd for C61H71BF2N4S:940.546,found:940.631
[M]+.
Embodiment 4
The synthesis of BDP4
Intermediate 5 (200mg, 0.37mmol) and 2- (4,4,5,5- tetramethyl -1,3,2- dioxas are added in there-necked flask
Ring pentaborane) -9,9- dimethyl fluorene 282mg (0.82mmol), obtain aubergine solid with the method for similar synthetic dyestuffs BDP3
137mg, yield 48%.1H NMR(600MHz,CDCl3) δ 8.02 (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).13C NMR(151MHz,CDCl3)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:calcd for
C51H49BF2N2S:770.368,found:770.479[M]+.
Embodiment 5
The synthesis of BDP5
Sequentially add intermediate 5 (200mg, 0.37mmol), N in there-necked flask, N-bis- (4- (2- methylheptyls) phenyl)-
4- (4,4,5,5- tetramethyl -1,3,2- dioxaborolans) aniline 526mg (0.82mmol), with the method for similar synthesis BDP3
Obtain aubergine solid 137mg, yield 35%.1H NMR(600MHz,CDCl3) δ 7.78 (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).13C NMR(151MHz,CDCl3)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:calcd for
C89H115BF2N4S:1320.890,found:1321.053[M]+.
Target dyestuff BDP1-BDP5 is in CH in above-described embodiment2Cl2Ultravioletvisible absorption light in solution and on solid film
Modal data is shown in Table 1, and the related data of target dyestuff BDP1-BDP5 electrochemical properties is shown in Table 2 in embodiment.
The spectroscopic data of the dyestuff BDP1-BDP5 of table 1
a In CH2Cl2.
b Deposited onto quartz substrate by the spin-coating technique from
CH2Cl2 solution。
The cyclic voltammetric data of the dyestuff BDP1-BDP5 of table 2
a Eg was estimated from the absorption thresholds from absorption
spectra of dyes absorbed in film,Eg=1240/ λonset.
b Eox onset,onset oxidation potential
c.Eox p,oxidation peak potential
d E red the reduction potential,was calculated from Eox onset–Eg.
e EHOMO=[- (Eox onset-0.54)-4.8]eV,ELUMO=EHOMO+Eg eV.
As it can be seen from table 1 five kinds of target dyestuffs have three absorption bands in ultraviolet visible light region.3,5 introducing thiophene
BDP1 and 3,5 unsubstituted BODIPY compare, and by 520nm red shifts to 628nm, this is due to thiphene ring to maximum absorption wavelength
Electron donation is strong, is introduced into that effectively conjugation can be formed with fluorine boron parent nucleus during BODIPY parent nucleus 3,5.3,5- positions introduce
The BDP2 absorption spectrums of duplex thiophene are further widened, and maximum absorption wavelength reaches 696nm, compare BDP1 red shifts 68nm, this
It is because duplex thiophene is higher with the conjugation of parent nucleus.The maximum absorption wavelength red shift of dyestuff BDP3 to 623nm, this is because
Carbazole unit itself has strong electron effect and cavity transmission ability, after 3,5- positions introduce carbazole, between fluorine boron parent nucleus
Intramolecular electron transfer effect strengthen.The 3 of dyestuff BDP4,5 introduce the fluorenes unit for having similar quality with carbazole, maximum
Absorbing wavelength red shift is to 601nm.The 3 of dyestuff BDP5,5 are replaced by the triaryl amine with alkyl, and maximum absorption wavelength red shift is extremely
670nm, the introducing of 3,5 triaryl amines effectively strengthens conjugation and electron transfer capacity between same BODIPY parent nucleus, makes
There is obvious red shift in the maximum absorption wavelength for obtaining dye molecule.Can also be seen that five kinds of dyestuffs on solid film most from table 1
Big absorbing wavelength is respectively 654nm, 752nm, 653nm, 625nm, 681nm, compares its maximum absorption wave in dichloromethane
Red shift respectively 26nm, 56nm, 30nm, 24nm, 11nm are grown, and absorption region is widened.Illustrate dye molecule on solid film
Gather, intermolecular pi-pi accumulation effect strengthens, so that maximum absorption spectrum red shift and widening.
As can be seen from Table 2 first oxidizing potential of target dyestuff BDP1-BDP5 be respectively 1.10eV, 1.14eV,
0.89eV, 1.15eV and 0.91eV.In target dyestuff 3,5 introducing donor monomer thiophene, duplex thiophene and fluorenes, dye molecule
The first oxidizing potential be 1.14 or so, stability is preferable；When 3,5 donor monomers are carbazole and triphenylamine, the first of dyestuff
Oxidizing potential is 0.9 or so, and less stable illustrates the size of donor monomer space structure itself to whole dye molecule
Oxidizing potential and stability of molecule produce certain impact.The HOMO energy levels of BDP3 and BDP5 are respectively -5.15eV and -5.17eV,
It is more slightly larger than the HOMO energy levels of other three kinds of dye molecules, illustrate when substituent is carbazole and triphenylamine, two kinds of dyestuffs
The injection in hole is more beneficial for, the hole mobility for making whole molecule is improved.
The present invention illustrates detailed synthetic method by above-described embodiment, but the invention is not limited in said method, i.e.,
Do not mean that the present invention has to rely on above-mentioned reaction condition and could implement.Person of ordinary skill in the field is it will be clearly understood that right
Any improvement of the present invention, the change of equivalence replacement and reaction actual conditions to reaction dissolvent catalyst of the present invention etc., fall
Within the scope of protection scope of the present invention and disclosure.
Claims (4)
1. a kind of middle position alkylthrophene replacement and 3, boron fluoride two pyrroles's methine derivatives of complexing that 5 strong donor residues replace,
Characterized in that, having the chemical constitution of formula (I)：
In formula (I),
N is 8.
2. the boron fluoride complexing that a kind of middle position alkylthrophene as claimed in claim 1 replaces and 3,5 strong donor residues replace
The preparation method of two pyrroles's methine derivatives, it is characterised in that comprise the following steps：
(1) 2- bromothiophenes and 1- brominated alkanes are reacted in the presence of butyl lithium and obtains intermediate 1, its structure is：
(2) intermediate 1 and 1- formylpiperidines are reacted, obtains intermediate 2, its structure is：
(3) intermediate 2 and pyrroles are reacted under the catalysis of catalyst, obtains intermediate 3, its structure is：
(4) intermediate 3 and N- bromo-succinimides are reacted, obtains intermediate 4, its structure is：
(5) by intermediate 4 Jing after tetrachloroquinone oxidation, then react with BFEE, obtain intermediate 5, its structure is：
(6) 4,4 '-two (1,1- dimethylhexanyl) triphenylamines are reacted at room temperature with N- bromo-succinimides, obtains centre
Body 6, its structure is：
(7) intermediate 6 and duplex pinacol boron ester are reacted under the catalytic action of catalyst, obtains intermediate 7, its structure
For：
(8) carbazole and 1- bromines normal octane are reacted, obtains intermediate 8, its structure is：
(9) intermediate 8 and N- bromo-succinimides are reacted, obtains intermediate 9, its structure is：
(10) intermediate 9 and duplex pinacol boron ester are reacted under the catalysis of catalyst, obtains intermediate 10, its structure is：
(11) iodo- 9, the 9- dimethyl fluorenes of 2- and duplex pinacol boron ester are reacted under the catalysis of catalyst, obtain intermediate 11,
Its structure is：
(12) intermediate 5 and 2- (tributyl tin) thiophene are reacted in the presence of catalyst by Stille, obtains target dye
Expect BDP1, its structure is：
(13) by intermediate 5 and the double thiophene reactions of 5- (tributyl tin) -2,2'-, target dyestuff BDP2 is obtained, its structure is：
(14) intermediate 5 is reacted with intermediate 10, obtains target dyestuff BDP3, its structure is：
(15) intermediate 5 is reacted with intermediate 11, obtains target dyestuff BDP4, its structure is：
(16) intermediate 5 is reacted with intermediate 7, obtains target dyestuff BDP5, its structure is：
Wherein, catalyst described in step (3) is InCl3, step (7), (10), (11), catalyst described in (12) are Pd
(dppf)Cl2、Pd(PPh3)4In one kind.
3. the boron fluoride complexing that a kind of middle position alkylthrophene as claimed in claim 2 replaces and 3,5 strong donor residues replace
The preparation method of two pyrroles's methine derivatives, it is characterised in that described in step (1)-(16) react reaction medium be DMF,
Tetrahydrofuran, n-hexane, dichloromethane, petroleum ether, ethyl acetate, dimethyl sulfoxide (DMSO), toluene, chloroform, one kind of ethanol or several
Plant mixing.
4. the boron fluoride complexing that a kind of middle position alkylthrophene as claimed in claim 2 replaces and 3,5 strong donor residues replace
The preparation method of two pyrroles's methine derivatives, it is characterised in that in step (12)-(16), the reaction time of the reaction is 20-
36h, reaction temperature is 90-120 DEG C.
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