CN101602703B - Pyrrole group-containing compound and preparation method and application thereof - Google Patents
Pyrrole group-containing compound and preparation method and application thereof Download PDFInfo
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- CN101602703B CN101602703B CN2009100630448A CN200910063044A CN101602703B CN 101602703 B CN101602703 B CN 101602703B CN 2009100630448 A CN2009100630448 A CN 2009100630448A CN 200910063044 A CN200910063044 A CN 200910063044A CN 101602703 B CN101602703 B CN 101602703B
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- 0 *C(C#N)=CC1=CC[C@@](C=Cc(cc2)ccc2N(c2ccccc2)c2ccccc2)N1C1=CC=C(*)CC1 Chemical compound *C(C#N)=CC1=CC[C@@](C=Cc(cc2)ccc2N(c2ccccc2)c2ccccc2)N1C1=CC=C(*)CC1 0.000 description 1
- AUGOAUKEERZFRM-JJKYIXSRSA-N O=Cc1ccc(/C=C/C2C=CC(N(c3ccccc3)c3ccccc3)=CC2)[n]1C(C=C1)=CCC1c(cc1)ccc1N(c1ccccc1)c1ccccc1 Chemical compound O=Cc1ccc(/C=C/C2C=CC(N(c3ccccc3)c3ccccc3)=CC2)[n]1C(C=C1)=CCC1c(cc1)ccc1N(c1ccccc1)c1ccccc1 AUGOAUKEERZFRM-JJKYIXSRSA-N 0.000 description 1
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Abstract
The invention discloses a pyrrole group-containing compound and a preparation method and the application thereof. The general structure of the compound is shown rightward, wherein R is shown rightward. Based on the expression shown above, the invention builds a conjugated system by Witting reaction, Vilsmeier reaction and Knoevena gel condensation reaction; and by Suzuki reaction, the invention induces different space groups of triphenylamine and pyrrole on N atom of pyrrole, and finally obtains the target compound. The compound of the invention has favorable photoelectric property and optical trapping capability, the value of molar absorption coefficient of the invention is higher, the compound can be used as dye sensitizer, the reaction condition of the preparation method is mild, and the yield is high.
Description
Technical field
The present invention relates to the compound and preparation method thereof of pyrrole group-containing and as the purposes of dye sensitizing agent.
Background technology
Since 20th century, along with the development of world economy and the sharp increase of population, the energy, population, environment etc. become the following 50 years human significant problems that need to be resolved hurrily day by day.At present, energy consumption mainly comes from fossil oil, because the fossil oil reserves are limited and the problem of environmental pollution that brought, people begin sight is invested renewable energy source.In such as environmental friendliness, the reproducible energy such as wind energy, bioenergy, tidal energy, hydroelectricity and underground heat, the application prospect of sun power is the most wide.The numerous and confused input that strengthens the renewable energy source research work in countries in the world is in the hope of solving the energy and environmental problem as early as possible.
1839, French scientist Becquerel found that the metal electrode that has been coated with silver halide particle has produced photoelectric current in electrolytic solution, and from then on people have carried out a large amount of work in photoelectricity conversion field.Up to the appearance of the semiconductor solar cell of first practicality in 1954, the idea of " conversion of solar energy is become electric energy " really becomes a reality finally.1991, the Switzerland scientist
Deng utilizing nanotechnology first the transformation efficiency of dye sensitization solar battery is brought up to 7.1%.From then on, dye sensitized nano crystal salar battery (DSSC) be born thereupon and fast development get up.
The dye sensitizing agent that research is at present used mainly is divided into following two classes: Organometallic dye sensitizing agent and nonmetal organic dye sensitized dose.With respect to Organometallic dye, nonmetal organic dye has following advantage as the photosensitizers of DSSC: specific absorbance is more much higher than metal complexes, and the ability that absorbs visible light is stronger; Diversity structure makes molecular designing become possibility, introduces different substituting groups and can adjust absorption spectrum at an easy rate; Do not use precious metal, can reduce cost; And can assess by computer simulation design novel metalloid organic dye and to its photoelectrochemistry character etc.
In recent years, the performance based on the DSSC of pure organic dye has had significant raising.Under the AM1 condition, have based on the DSSC of indoline dyestuff D149 and to surpass 9% effciency of energy transfer.In the triturating of this type of dye sensitizing agent, people are doing a large amount of work aspect design D-π-A type dye molecule.Common electron donor(ED) (D) has coumarins, fluorenes class, quinoline, triphenylamine and carbazoles, half flower cyanines and phthalocyanines, porphyrin class etc., they all have electron donation preferably, and electron acceptor(EA) (A) still cyanoacetic acid at present with the most use, it can not only be at TiO
2Adsorb effectively on the surface, and good stability.And give the pi-conjugated system of body and acceptor for connection mainly is polyenoid class and phenyl ring class.Heterocyclic compound is owing to have lower resonance energy and electron rich, can improve the charge transfer in the dye molecule effectively and obtained extensive concern.What study morely is thiophene-based, as connecting thiophene, thiophthene etc.In recent years, be that the dye molecule of conjugated bridge has also been obtained comparatively gratifying result with the furans.But the rare report of dye molecule based on the strong pyrroles of electron rich.
Summary of the invention
The objective of the invention is to remedy the deficiencies in the prior art, provide pyrrole group-containing compound and preparation method thereof and as the purposes of dye sensitizing agent, this compounds has excellent photoelectric performance and good light capturing ability, its molar absorptivity (ε) value is bigger, and preparation method's reaction conditions gentleness, productive rate is higher.
The technical scheme that realizes the object of the invention is: the compound of pyrrole group-containing, and its general structure is:
Wherein, R is
Or
The present invention also provides the preparation method of the compound of above-mentioned pyrrole group-containing, may further comprise the steps:
(1) under the condition of ice bath, with the trichlorine phosphine oxide (POCl that newly steams
3) and N, dinethylformamide (DMF) is 1: 1～2 mixed by the ratio of amount of substance, is stirred to solution and is glassy, dropwise adds 1 of compound 1 then, the 2-dichloroethane solution makes POCl
3With the ratio of the amount of substance of compound 1 be 1～1.5: 1, fully reaction under the room temperature, after reaction finishes, be cooled to room temperature, add saturated aqueous sodium carbonate again, fully stir the back chloroform extraction, collecting after organic phase and drying remove wherein moisture, is eluent with the chloroform, with silica gel chromatography column chromatography for separation purifying, vacuum-drying obtains compound 2; The structural formula of described compound 1 is
The structural formula of compound 2 is
(2) under the shielding gas atmosphere, compound 3 is placed reaction vessel and make it be dissolved in capacity anhydrous tetrahydro furan (THF), add tert.-butoxy potassium (t-BuOK) rapidly, making the compound 3 and the ratio of the amount of substance of t-BuOK is 1: 1.5～5, and at room temperature stirred 10～30 minutes, the THF solution that dropwise adds compound 2 then, making the compound 3 and the ratio of the amount of substance of compound 2 is 1.2～1.5: 1, stirs under the room temperature it is fully reacted; After reaction finishes, product is added water stir, use chloroform extraction, collect after organic phase and drying remove wherein moisture, again with sherwood oil and ethyl acetate by volume 10～20: 1 blended mixed solution be eluent, with product with silica gel chromatography column chromatography for separation purifying, vacuum-drying obtains compound 4; The structural formula of described compound 3 is
The structural formula of compound 4 is
(3) under the condition of ice bath, with the POCl that newly steams
3With DMF be 1: 1～2 mixed by the ratio of amount of substance, be stirred to solution and be glassy, dropwise add 1 of compound 4 then, the 2-dichloroethane solution makes POCl
3With the mol ratio of compound 4 be 1～1.5: 1, under the room temperature fully the reaction; After reaction finishes, be cooled to room temperature, add saturated aqueous sodium carbonate again, fully stir the back chloroform extraction, collecting after organic phase and drying remove wherein moisture, is eluent with the chloroform, with product with silica gel chromatography column chromatography for separation purifying, vacuum-drying obtains compound 5, and its structural formula is
(4) under the shielding gas atmosphere, in reaction vessel, add the tetra-triphenylphosphine palladium (Pd (PPh of compound 5, triphenylamine list boric acid, yellow soda ash and catalytic amount
3)
4), the mol ratio that makes compound 5, triphenylamine list boric acid and yellow soda ash is 1: 1.1～1.5: 10～15, adds capacity THF and capacity deoxidized water then, in 70～80 ℃ of reflux it is fully reacted; After reaction finishes, being cooled to room temperature, using chloroform extraction then, collect organic phase and drying and remove wherein moisture, is eluent again with the chloroform, through silica gel chromatography column chromatography for separation purifying, obtains compound 6, and its structural formula is
Perhaps under the shielding gas atmosphere, in reaction vessel, add compound 5, N-hexyl carbazole-3-boric acid, yellow soda ash and and the Pd (PPh of catalytic amount
3)
4, the mol ratio that makes compound 5, N-hexyl carbazole-3-boric acid and yellow soda ash is 1: 1.1～1.5: 10～15, adds capacity THF and capacity deoxidized water then, in 70～80 ℃ of reflux it is fully reacted; After reaction finishes, being cooled to room temperature, using chloroform extraction then, collect organic phase and drying and remove wherein moisture, is eluent again with the chloroform, through silica gel chromatography column chromatography for separation purifying, obtains compound 7, and its structural formula is
(5) be that 1: 1.1～1.5 compound 6 and cyanoacetic acid are dissolved in the capacity acetonitrile with the ratio of amount of substance, add the piperidines of catalytic amount, in 75～85 ℃ of reflux it is fully reacted then; After reaction finishes, be cooled to room temperature, be spin-dried for, obtain thick product; With the chloroform is eluent, and thick product through silica gel chromatography column chromatography for separation purifying, is obtained compound L I-1, and its structural formula is
Perhaps be that 1: 1.1～1.5 compound 7 and cyanoacetic acid are dissolved in the capacity acetonitrile, add the piperidines of catalytic amount, in 75～85 ℃ of reflux it is fully reacted then the ratio of amount of substance; After reaction finishes, be cooled to room temperature, be spin-dried for, obtain thick product; With the chloroform is eluent, and thick product through silica gel chromatography column chromatography for separation purifying, is obtained compound L I-2, and its structural formula is
Shielding gas is nitrogen or argon gas described in above-mentioned steps (2) and the step (4).
The compound of pyrrole group-containing of the present invention is as dye sensitizing agent.
The present invention be from
With
Set out, make up conjugated system, be reflected on pyrroles's the N atom by Suzuki again and draw different spacer groups triphenylamine and carbazole, finally obtain target compound by Wittig reaction, Vilsmeier reaction and Knoevenagel condensation reaction.The invention has the advantages that:
(1) the present invention is incorporated into the pyrroles in two key conjugated systems first, synthesized pyrrole group-containing compound, test result shows, they all have excellent photoelectric performance, wherein the overall cell efficiency based on compound L I-1 has reached 7.21%, be about under the equal conditions 91% of at present best dyestuff N719;
(2) the present invention fully uses pyrroles's constructional feature, inserts triphenylamine and carbazole on pyrroles's N, to reduce molecule at TiO
2The congregation on surface, make the compound that finally obtains can adsorbed close at TiO
2The surface.
(3) compound of a series of pyrrole group-containings of the present invention all has good light capture ability, and their molar absorptivity (ε) value is all bigger, compound L I-1 particularly, and when absorbing wavelength was 448nm, its ε value had reached 40500M
-1Cm
-1, be much higher than the ε value 14100M of N719
-1Cm
-1
(4) compound of the present invention can be used as dye sensitizing agent, and preparation method's reaction conditions gentleness, and productive rate is higher.
Embodiment
In order to understand content of the present invention better, below in conjunction with specific embodiment content of the present invention is described further, but protection content of the present invention is not limited to following examples.
Raw material used in the embodiment of the invention can be buied by market, or available methods known in the art are synthetic obtains.
Embodiment 1 compound L I-1's is synthetic
Synthetic route is as follows:
(1) under the condition of ice bath, with the POCl that newly steams
3(6.91g, 45.0mmol) join DMF (5.26g, 72.0mmol) in, be stirred to solution and be glassy.Dropwise add then compound 1 (6.66g, 30.0mmol) 1,2-dichloroethane solution (40mL, 1, the amount of 2-ethylene dichloride is enough to make compound 1 to dissolve fully to get final product), room temperature reaction reacted fully in 4 hours.After reaction finishes, product is cooled to room temperature, adds saturated aqueous sodium carbonate (500mL), continue to stir 2 hours.Use chloroform extraction then, collect organic phase and use anhydrous Na
2SO
4Dry.With the chloroform is eluent, with product silica gel chromatography column chromatography, and separation and purification, vacuum-drying gets white solid (4.85g, productive rate 64.7%), measures its fusing point and usefulness
1H NMR characterizes structure, confirms that this white solid is a compound 2.Mp＝93～94℃.
1H?NMR(CDCl
3)δ(ppm)：9.57(s，1H，-CHO)，7.58(d，J＝8.1Hz，2H，ArH)，7.23(d，J＝8.1Hz，2H，ArH)，7.15(s，1H，ArH)，7.05(s，1H，ArH)，6.42(s，1H，ArH).
(2) under nitrogen (or argon gas) atmosphere, with compound 3 (3.98g, 10.1mmol) place Shiran gram (Schlenk) pipe and be dissolved in the anhydrous THF of 20mL (amount of THF can make compound 3 dissolve fully and get final product), (1.88g 16.8mmol) also at room temperature stirred 10 minutes to add t-BuOK rapidly.Then, (2.05g, behind THF solution 8.37mmol) (20mL, the consumption of THF are enough to make compound 2 to dissolve fully get final product), stirred overnight at room temperature is fully reacted it dropwise to add compound 2.After reaction finishes, add an amount of water and stir, use chloroform extraction 3 times, collect organic phase and also use anhydrous Na
2SO
4Drying obtains thick product.(wherein the volume ratio of sherwood oil and ethyl acetate is 10～20: 1) be eluent, with this thick product silica gel chromatography column chromatography, separation and purification with the mixed solution of sherwood oil and ethyl acetate, vacuum-drying, get yellow oil (2.50g, productive rate 75.0%), it is carried out
1H NMR characterizes, and confirms that this yellow oil is a compound 4.
1H?NMR(CDCl
3)δ(ppm)：7.58(d，J＝8.7Hz，2H，ArH)，7.25-7.19(m，7H，ArH)，7.07(d，J＝8.1Hz，4H，ArH)，7.03-6.94(m，5H，ArH)，6.85-6.80(m，2H，ArH?and-CH＝CH-)，6.66-6.60(m，2H，ArH?and-CH＝CH-)，6.32(s，1H，ArH).
(3) under the condition of ice bath, with the POCl that newly steams
3(1.16g, 7.63mmol) join DMF (0.75g, 10.2mmol) in, be stirred to solution and be glassy.Dropwise add then compound 4 (2.50g, 5.10mmol) 1,2-dichloroethane solution (20mL, 1, the amount of 2-ethylene dichloride is enough to make compound 4 to dissolve fully to get final product), room temperature reaction spends the night and reacts fully.After reaction finishes, be cooled to room temperature, add the aqueous solution (500mL) of saturated sodium carbonate, continue to stir 2 hours.Use chloroform extraction, collect organic phase and use anhydrous Na
2SO
4Drying obtains thick product.With the chloroform is eluent, with this thick product silica gel chromatography column chromatography, and separation and purification, vacuum-drying gets yellow solid (2.00g, productive rate 75.7%), measures its fusing point and employing
1H NMR characterizes its structure, confirms that this yellow solid is a compound 5.Mp＝99～100℃.
1H?NMR(CDCl
3)δ(ppm)：9.99and?9.39(s，1H，-CHO)，7.64(d，J＝2.7Hz，1H，ArH)，7.61(d，J＝3.0Hz，1H，ArH)，7.29-7.18(m，6H，ArH?and-CH＝CH-)，7.14(d，J＝8.7Hz，2H，ArH)，7.11-6.98(m，7H，ArH)，6.96(d，J＝8.7Hz，2H，ArH)，6.84-6.81(m，1H，ArH)，6.74-6.68(m，1H，ArH)，6.36(d，J＝15.6Hz，1H，-CH＝CH-).
(4) under argon gas (or nitrogen) atmosphere, in the Schlenk pipe, add compound 5 (200mg, 0.385mmol), triphenylamine list boric acid (134mg, 0.462mmol), yellow soda ash (408mg, 3.85mmol) and the Pd (PPh of catalytic amount
3)
4, add 10mL THF and 5mL deoxidized water (consumption of THF and deoxidized water be enough to make compound 5, triphenylamine list boric acid and yellow soda ash to dissolve fully get final product) then, refluxing in 70～80 ℃ fully reacted it in 40 hours.After reaction finishes, product is cooled to room temperature, uses chloroform extraction, collect organic phase, use anhydrous Na
2SO
4Drying obtains thick product.With the chloroform is eluent, and with this thick product silica gel chromatography column chromatography, separation and purification gets red solid (150mg, 85.4%), measures its fusing point and employing
1H NMR characterizes structure, confirms that this red solid is a compound 6.Mp＝119～120℃.
1H?NMR(CDCl
3)δ(ppm)：9.79and?9.41(s，1H，-CHO)，7.71-7.64(m，2H，ArH)，7.55-7.48(m，3H，ArH)，7.44(d，J＝8.1Hz，1H，ArH)，7.36(d，J＝8.1Hz，2H，ArH)，7.31-7.21(m，4H，ArH)，7.15-7.11(m，8H，ArH)，7.08-6.85(m，13H，ArH?and-CH＝CH-)，6.79(d，J＝15.6Hz，1H，-CH＝CH-)，6.72-6.68(m，1H，ArH)，6.52-6.44(m，1H，ArH).
(5) with compound 6 (160mg, 0.230mmol) and cyanoacetic acid (21.9mg, 0.260mmol) be dissolved in the 60mL acetonitrile (amount of acetonitrile be enough to make compound 6 and cyanoacetic acid to dissolve fully get final product), add 10 μ L piperidines, reaction solution refluxes in 75～85 ℃ and it was fully reacted in 3 hours.After reaction finishes, be cooled to room temperature, be spin-dried for, obtain thick product.With the chloroform is eluent, with this thick product through the silica gel chromatography column chromatography, separation and purification, red solid (150mg, 85.4%), measure its fusing point and adopt IR,
1H NMR,
13C NMR and MS characterize its structure, confirm that this red solid is compound L I-1.Adopt the ultraviolet-visible absorption spectroscopy method, when wavelength is 448nm, record the molar absorptivity of compound L I-1
Mp＝239～240℃.IR(thin?film)，υ(cm
-1)：2223(-CN).
1H?NMR(CDCl
3)δ(ppm)：8.44(s，1H，-CH＝)，8.00(s，1H，ArH)，7.75(d，J＝8.1Hz，2H，ArH)，7.67(d，J＝9.0Hz，4H，ArH)，7.55(d，J＝8.1Hz，2H，ArH)，7.49(d，J＝8.1Hz，4H，ArH)，7.40(d，J＝8.1Hz，4H，ArH)，7.26-6.93(m，8H，ArH?and-CH＝CH-)，6.70(s，2H，ArH)，6.45(d，J＝16.8Hz，1H，-CH＝CH-).
13C?NMR(CDCl
3)δ(ppm)：169.5，148.9，148.1，147.7，147.3，141.1，137.6，137.4，133.3，133.0，129.9，129.6，128.2，128.0，127.8，126.2，125.2，124.9，123.8，123.5，122.8，118.3，113.4，110.2.MS(MALDI-TOF)，m/z[M+1]
+：751.5，calcd，750.3.Anal.Calcd?for：C
52H
38N
4O
2：C，83.18；H，5.10；N，7.46；Found：C，83.25；H，5.54；N.7.14.
Embodiment 2 compound L I-2's is synthetic
Synthetic route is as follows:
(1) under argon gas (or nitrogen) atmosphere, in the Schlenk pipe, add the compound 5 that obtains among the embodiment 1 (400mg, 0.770mmol), N-hexyl carbazole-3-boric acid (273mg, 0.92mmol), yellow soda ash (816mg, 7.70mmol) and the Pd (PPh of catalytic amount
3)
4, add 6mL THF and 3mL deoxidized water (consumption of THF and deoxidized water be enough to make compound 5, N-hexyl carbazole-3-boric acid and yellow soda ash to dissolve fully get final product) then, refluxing in 70～80 ℃ fully reacted it in 40 hours.After reaction finishes, be cooled to room temperature, use chloroform extraction then, collect organic phase and use anhydrous Na
2SO
4Dry.With the chloroform is eluent, and through the silica gel chromatography column chromatography, separation and purification gets orange thick solid (320mg, 60.2%), adopts with dried product
1H NMR characterizes its structure, confirms that this orange thick solid is a compound 7.
1H?NMR(CDCl
3)δ(ppm)：10.04and?9.80(s，1H，-CHO)，8.46(s，1H，ArH)，8.35-8.15(m，2H，ArH)，7.82-7.73(m，4H，ArH)，7.48-7.26(m，12H，ArH)，7.10-6.88(m，8H，ArH)，6.75(d，J＝18.9Hz，2H，-CH＝CH-)，4.34(s，br，2H，-N-CH
2-)，1.90(s，br，2H，-CH
2-)，1.32(s，br，6H，-CH
2-)，0.86(s，br，3H，-CH
3).
(2) with compound 7 (180mg, 0.260mmol) and cyanoacetic acid (26.6mg, 0.310mmol) be dissolved in the 60mL acetonitrile (consumption of acetonitrile be enough to make compound 7 and cyanoacetic acid to dissolve fully get final product), add 10 μ L piperidines, reaction solution refluxes in 75～85 ℃ and it was fully reacted in 6 hours.After reaction finishes, be cooled to room temperature, be spin-dried for, obtain thick product.With the chloroform is eluent, with this thick product through the silica gel chromatography column chromatography, separation and purification, red solid (145mg, 73.5%), measure its fusing point and adopt IR,
1H NMR,
13C NMR and MS characterize its structure, confirm that this red solid is compound L I-2.Adopt the ultraviolet-visible absorption spectroscopy method, when wavelength is 415nm, record molar absorptivity ε=27900M of compound L I-2
-1Cm
-1Mp＝136～137℃.IR(thin?film)，υ(cm
-1)：2223(-CN).
1H?NMR(CDCl
3)δ(ppm)：8.47(s，1H，-CH＝)，8.35(s，1H，ArH)，8.16(d，J＝7.5Hz，1H，ArH)，7.83(d，J＝8.1Hz，2H，ArH)，7.73(d，J＝7.8Hz，2H，ArH)，7.51-7.46(m，6H，ArH)，7.26-7.23(m，7H，ArH)，7.12-6.90(m，8H，ArH?and-CH＝CH-)，6.75(s，2H，ArH)，4.34(s，br，2H，-N-CH
2-)，1.90(s，br，2H，-CH
2-)，1.39-1.26(m，6H，-CH
2-)，0.88(s，br，3H，-CH
3).
13C?NMR(CDCl
3)δ(ppm)：167.5，148.8，147.4，142.6，141.2，140.5，137.1，130.7，130.1，129.6，128.4，128.2，126.2，125.2，124.9，123.8，123.7，123.0，122.8，120.7，119.3，118.3，113.6，110.1，109.4，109.2，43.5，31.8，29.2，27.2，22.8，14.3.MS(MALDI-TOF)，m/z[M
+]：756.6，calcd，756.3.Anal.Calcd?for：C
52H
44N
4O
2：C，82.51；H，5.86；N，7.40；Found：C，82.25；H，6.25；N，7.09.
After collecting organic phase in the embodiment of the invention, be to use anhydrous Na
2SO
4Drying also can adopt other siccative, as long as can remove the moisture in the organic phase and do not react with organic phase.
Compound L I-1 of the present invention and LI-2 are as dye sensitizing agent.The overall cell efficiency η that records as dye sensitizing agent with compound L I-1 of the present invention and compound L I-2 is respectively 7.21% and 4.62%.
Claims (4)
1. the compound of pyrrole group-containing is characterized in that this structural general formula is:
Wherein,
2. the preparation method of the compound of the described pyrrole group-containing of claim 1 is characterized in that may further comprise the steps:
(1) under the condition of ice bath, with the POCl that newly steams
3With DMF be 1: 1～2 mixed by the ratio of amount of substance, be stirred to solution and be glassy, dropwise add 1 of compound 1 then, the 2-dichloroethane solution makes POCl
3With the ratio of the amount of substance of compound 1 be 1～1.5: 1, fully reaction under the room temperature, after reaction finishes, be cooled to room temperature, add saturated aqueous sodium carbonate again, fully stir the back chloroform extraction, collecting after organic phase and drying remove wherein moisture, is eluent with the chloroform, with silica gel chromatography column chromatography for separation purifying, vacuum-drying obtains compound 2; The structural formula of described compound 1 is
The structural formula of compound 2 is
(2) under the shielding gas atmosphere, compound 3 is placed reaction vessel and make it be dissolved in the anhydrous THF of capacity, add t-BuOK rapidly, making the compound 3 and the ratio of the amount of substance of t-BuOK is 1: 1.5～5, and at room temperature stirred 10～30 minutes, the THF solution that dropwise adds compound 2 then, making the compound 3 and the ratio of the amount of substance of compound 2 is 1.2～1.5: 1, stirs under the room temperature it is fully reacted; After reaction finishes, product is added water stir, use chloroform extraction, collect after organic phase and drying remove wherein moisture, again with sherwood oil and ethyl acetate by volume 10～20: 1 blended mixed solution be eluent, with product with silica gel chromatography column chromatography for separation purifying, vacuum-drying obtains compound 4; The structural formula of described compound 3 is
The structural formula of compound 4 is
(3) under the condition of ice bath, with the POCl that newly steams
3With DMF be 1: 1～2 mixed by the ratio of amount of substance, be stirred to solution and be glassy, dropwise add 1 of compound 4 then, the 2-dichloroethane solution makes POCl
3With the mol ratio of compound 4 be 1～1.5: 1, under the room temperature fully the reaction; After reaction finishes, be cooled to room temperature, add saturated aqueous sodium carbonate again, fully stir the back chloroform extraction, collecting after organic phase and drying remove wherein moisture, is eluent with the chloroform, with product with silica gel chromatography column chromatography for separation purifying, vacuum-drying obtains compound 5, and its structural formula is
(4) under the shielding gas atmosphere, in reaction vessel, add the Pd (PPh of compound 5, triphenylamine list boric acid, yellow soda ash and catalytic amount
3)
4, the mol ratio that makes compound 5, triphenylamine list boric acid and yellow soda ash is 1: 1.1～1.5: 10～15, adds capacity THF and capacity deoxidized water then, in 70～80 ℃ of reflux it is fully reacted; After reaction finishes, being cooled to room temperature, using chloroform extraction then, collect organic phase and drying and remove wherein moisture, is eluent again with the chloroform, through silica gel chromatography column chromatography for separation purifying, obtains compound 6, and its structural formula is
Perhaps under the shielding gas atmosphere, in reaction vessel, add compound 5, N-hexyl carbazole-3-boric acid, yellow soda ash and and the Pd (PPh of catalytic amount
3)
4, the mol ratio that makes compound 5, N-hexyl carbazole-3-boric acid and yellow soda ash is 1: 1.1～1.5: 10～15, adds capacity THF and capacity deoxidized water then, in 70～80 ℃ of reflux it is fully reacted; After reaction finishes, being cooled to room temperature, using chloroform extraction then, collect organic phase and drying and remove wherein moisture, is eluent again with the chloroform, through silica gel chromatography column chromatography for separation purifying, obtains compound 7, and its structural formula is
(5) be that 1: 1.1～1.5 compound 6 and cyanoacetic acid are dissolved in the capacity acetonitrile with the ratio of amount of substance, add the piperidines of catalytic amount, in 75～85 ℃ of reflux it is fully reacted then; After reaction finishes, be cooled to room temperature, be spin-dried for, obtain thick product; With the chloroform is eluent, and thick product through silica gel chromatography column chromatography for separation purifying, is obtained compound L I-1, and its structural formula is
Perhaps be that 1: 1.1～1.5 compound 7 and cyanoacetic acid are dissolved in the capacity acetonitrile, add the piperidines of catalytic amount, in 75～85 ℃ of reflux it is fully reacted then the ratio of amount of substance; After reaction finishes, be cooled to room temperature, be spin-dried for, obtain thick product; With the chloroform is eluent, and thick product through silica gel chromatography column chromatography for separation purifying, is obtained compound L I-2, and its structural formula is
3. the preparation method of the compound of pyrrole group-containing according to claim 2, it is characterized in that: shielding gas is nitrogen or argon gas described in step (2) and the step (4).
4. the compound of pyrrole group-containing as claimed in claim 1 is as the purposes of dye sensitizing agent.
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