CN107286179A - A kind of novel method for synthesizing of IDTT derivatives - Google Patents
A kind of novel method for synthesizing of IDTT derivatives Download PDFInfo
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- CN107286179A CN107286179A CN201710547656.9A CN201710547656A CN107286179A CN 107286179 A CN107286179 A CN 107286179A CN 201710547656 A CN201710547656 A CN 201710547656A CN 107286179 A CN107286179 A CN 107286179A
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- DZVHNCJSUAAOBG-UHFFFAOYSA-N CCCCCCc1ccc(C(c2cc(-c3c(C4(c5ccc(C=C)cc5)c5ccc(C=N)cc5)c([s]cc5)c5[s]3)c4cc2-2)(c3c-2[s]c2c3[s]cc2)c2ccc(C=C)cc2)cc1 Chemical compound CCCCCCc1ccc(C(c2cc(-c3c(C4(c5ccc(C=C)cc5)c5ccc(C=N)cc5)c([s]cc5)c5[s]3)c4cc2-2)(c3c-2[s]c2c3[s]cc2)c2ccc(C=C)cc2)cc1 DZVHNCJSUAAOBG-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
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Abstract
The present invention relates to organic solar batteries field, and in particular to a kind of novel method for synthesizing of IDTT derivatives.In a nitrogen environment, alkyl bromobenzene will be changed to be dissolved in the tetrahydrofuran of water removal, 78 ~ 80oThe hexane solution of n-BuLi is added under C, then by 2,5 dibromoterephthalic acid esters are added in reaction, 16 20h are reacted at room temperature, and reaction is quenched with water, ethyl acetate extraction, anhydrous sodium sulfate drying is spin-dried for, and in a nitrogen environment dissolves crude product dichloromethane, adds boron trifluoride ether solution, methanol is added after reacting at room temperature, after reaction terminates, it is quenched with water, dichloromethane extraction, separated with column chromatography, obtain IDTT and its derivative.This method is compared with the method for document report before, and post processing is easy, and obtained final product IDTT yield is higher, and environmental protection pressure is small, and energy consumption is low, safe.
Description
Technical field
The present invention relates to organic solar batteries field, and in particular to a kind of novel method for synthesizing of IDTT derivatives.
Background technology
Organic solar batteries are because with light weight, cost is low, preparation technology is simple, pliability good and can large area system
Standby the advantages of, as study hotspot in recent years.So that the species of organic photoelectrical material emerges in an endless stream, wherein being given by electronics
The heterojunction type photoelectric material development for the compound system that body material and electron acceptor material are constituted is more rapid.
IDTT is as a kind of new electron acceptor material, with fairly good stability, the symmetry of its structure and just
The thick aroma system of property can improve the delocalization of electronics, and intermolecular active force can improve charge mobility, with excellent light
Electrical property.
2012, the design such as Jen synthesized IDTT, and using it as matrix, it is modified, so as to its optical band gap
It is finely adjusted, design has synthesized donor material PIDTT-DFBT, and is prepared for organic solar with acceptor material PC71BM blendings
Battery device, its corresponding photovoltaic device energy transformation ratio is up to 5.72%；2015, Zhan et al. was same using IDTT as base
Body, is modified it, has designed and synthesized ITIC, as the acceptor material that a class is excellent, is blended with donor material PTB7-TH
Solar cell device is prepared for, PCE has been brought up to 7.52%, while also opening a new research field, donor material
Can be with acceptor material change by modifying fine setting；2017, be equally that Zhan et al. continues to expand such system, by simultaneously three thiophenes
Fen substitutes bithiophene, has synthesized the new IDTT derivatives of a class, and is fluorinated, and the acceptor material of gained is prepared into device
PCE has brought up to 11%.
By study find, based on IDTT modify small molecule receptor, have in visible region stronger absorption and
Broader absorption region, and its heat endurance of the device prepared and chemical stability are all fine.With prominent photoelectricity
Performance.In the photoelectric material of this system, with good application prospect.
Had been reported that in document before using being directly added into sulfuric acid and acetic acid and the 3 hours sides to prepare IDTT that flow back
Method, although this synthetic method can obtain the of a relatively high product of purity, but the method will use the concentrated sulfuric acid, while needing
Flowed back in acetic acid, therefore experimental implementation danger coefficient is higher, energy consumption is higher, and post processing is complicated, and solvent-oil ratio is larger, yield
It is not high.
This method can just be reacted at room temperature using boron trifluoride ether solution, and reaction is finally directly quenched with methanol
Go out, vacuum was spin-dried for post, compared with the method for document report before, post processing is easy, obtained final product IDTT production
Rate is higher, and environmental protection pressure is small, and energy consumption is low, safe.
The content of the invention
The present invention is intended to provide a kind of novel method for synthesizing of IDTT derivatives, the synthetic method is simple, easy to operate, it is organic
Solvent-oil ratio is small, and post processing is simple, and product yield is high, and purity is high.
The technical solution adopted in the present invention is：
A kind of novel method for synthesizing of IDTT derivatives, comprises the following steps：
Step (1), in a nitrogen environment, alkyl bromobenzene is dissolved in the tetrahydrofuran of water removal, alkyl bromobenzene is obtained molten
Liquid；
Step (2), at -78~-80 DEG C, the hexane of n-BuLi is added into alkyl bromide benzole soln obtained by step (1)
Solution, and react 0.9-1.2h；
Step (3), 2,5- dibromoterephthalic acids ester is added in reaction solution obtained by step (2), 16- is reacted at room temperature
20h, is allowed to reaction complete；
Step (4), reaction is quenched with water, and ethyl acetate extraction, anhydrous sodium sulfate drying is spin-dried for, and obtains crude product；
Step (5), in a nitrogen environment dissolves crude product dichloromethane, BFEE is added at 0~5 DEG C molten
Liquid, reacts 1-1.5h at room temperature；
Step (6), methanol is added into mixed solution obtained by step (5), reacts 16-20h, makes its reaction complete；
Step (7), after reaction terminates, is quenched with water, dichloromethane extraction, is separated with column chromatography, obtains IDTT derivatives
Thing.
Preferably, with molar ratio computing, alkyl bromobenzene:N-BuLi:2,5- dibromoterephthalic acid esters:BFEE
Solution=6:6:1:2.
Preferably, the concentration of alkyl bromide benzole soln described in step (1) is 0.020g/ml-0.030g/ml.
Preferably, alkyl bromobenzene and n-BuLi reaction temperature are -78 DEG C in step (2), and the reaction time is 1h；Step
(3) reaction temperature in is 25 DEG C, and the reaction time is 16h；Boron trifluoride ether solution is added in step (5) at 0 DEG C, is reacted
Temperature is 25 DEG C, and the reaction time is 17h.
Preferably, the volume ratio of eluant, eluent used in column chromatography is petroleum ether：Dichloromethane=15:1.
The advantage of the invention is that：
1st, this method simplicity is easily operated, and reaction condition is gentle, and overall production rate and the more original method of product purity have been carried
It is high.On the one hand method in document uses the concentrated sulfuric acid and acetic acid in the reaction, and operation is more dangerous；On the other hand, react
Process is required for heating, and energy consumption is more.
2nd, this method processing safety is high, and without heating, energy consumption is low.Heated with the use concentrated sulfuric acid of document report with acetic acid
The method of backflow is compared, and this method can just be reacted at room temperature using boron trifluoride ether solution, and reaction is quenched with methanol
Go out, environmental protection pressure is small compared with the method for document report, energy consumption is low, it is safe.
Brief description of the drawings
Fig. 1 is products therefrom IDTT hydrogen nuclear magnetic resonance spectrograms (the NMR VARIANMercury of the embodiment of the present invention 1
Plus400 type test conditions：500MHz)；
Fig. 2 is products therefrom IDTT-DM hydrogen nuclear magnetic resonance spectrograms (the NMR VARIANMercury of the embodiment of the present invention 2
Plus400 type test conditions：500MHz)；
Fig. 3 is products therefrom IDTT-M hydrogen nuclear magnetic resonance spectrograms (the NMR VARIANMercury of the embodiment of the present invention 3
Plus400 type test conditions：500MHz).
Embodiment
Below in conjunction with specific embodiment, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.
Embodiment 1:
In a nitrogen environment, 1- (4- bromophenyls) hexanes (578mg, 2.4mmol) are dissolved in the tetrahydrochysene furan of 10mL water removals
In muttering, added at -78 DEG C after the hexane solution (1mL, 2.4mmol) of 2.4M n-BuLis, reaction 1h, by 2,5- dibromos to benzene
Dicarboxylic acid esters (200mg, 0.4mmol) are added in reaction, and reaction is quenched with water after reacting 16h at room temperature, ethyl acetate extraction,
Anhydrous sodium sulfate drying is spin-dried for, and in a nitrogen environment dissolves crude product dichloromethane, BFEE is added at 0 DEG C molten
Liquid (1mL, 0.8mmol), reacts methanol 5mL is added after 1h at room temperature, 16h is reacted afterwards.After reaction terminates, it is quenched with water, two
Chloromethanes is extracted, and is separated with column chromatography, is obtained product IDTT (223.8mg).
Reaction equation figure involved by the synthetic method of the present invention is as follows：
As shown in figure 1, the structure has the different hydrogen of nine class chemical environments, and respectively positioned at 7.50 (2H), 7.28 (2H), 7.25
(2H), 7.18 (8H), 7.07 (8H), 2.55 (8H), 1.60-1.53 (8H), 1.35-1.29 (24H), 0.86 (12H) ppm, with
The spectrogram of document report is consistent, it is seen that the compound is correct, and obtained compound structure is：
Embodiment 2：
In a nitrogen environment, the bromo- ortho-xylenes of 4- (444mg, 2.4mmol) are dissolved in the tetrahydrofuran of 10mL water removals
In, added at -78 DEG C after the hexane solution (1mL, 2.4mmol) of 2.4M n-BuLis, reaction 1h, by 2,5- dibromos to benzene two
Formic acid esters (200mg, 0.4mmol) is added in reaction, and reaction is quenched with water after reacting 16h at room temperature, ethyl acetate extraction, nothing
Aqueous sodium persulfate is dried and is spin-dried for, and in a nitrogen environment dissolves crude product dichloromethane, boron trifluoride ether solution is added at 0 DEG C
(1mL, 0.8mmol), reacts methanol 5mL is added after 1h at room temperature, 16h is reacted afterwards.After reaction terminates, it is quenched with water, dichloro
Methane is extracted, and is separated with column chromatography, is obtained product IDTT-DM (238.5mg).
As shown in Fig. 2 the structure has the different hydrogen of eight class chemical environments, because part hydrogen has overlap problem, so hydrogen
Spectrum illustrate only the other hydrogen of five species above, respectively positioned at 7.49 (2H), 7.25 (4H), 6.97-7.05 (12H), 2.21
(12H), 2.17 (12H) ppm are consistent with the spectrogram of document report, it is seen that the compound is compound structure that is correct, obtaining
For：
Embodiment 3：
In a nitrogen environment, 4- toluene bromides (410mg, 2.4mmol) are dissolved in the tetrahydrofuran of 10mL water removals ,-
Added at 80 DEG C after the hexane solution (1mL, 2.4mmol) of 2.4M n-BuLis, reaction 1h, by 2,5- dibromoterephthalic acid esters
(200mg, 0.4mmol) is added in reaction, and reaction is quenched with water after reacting 16h at room temperature, ethyl acetate extraction, anhydrous slufuric acid
Sodium dry be spin-dried for, crude product dichloromethane is dissolved in a nitrogen environment, at 0 DEG C add boron trifluoride ether solution (1mL,
0.8mmol), methanol 5mL is added after reaction 1h at room temperature, 16h is reacted afterwards.After reaction terminates, it is quenched with water, dichloromethane extraction
Take, separated with column chromatography, obtain product IDTT-D (221.7mg).
As shown in figure 3, the structure has the different hydrogen of six class chemical environments, because part hydrogen has overlap problem, so hydrogen
Spectrum illustrate only the other hydrogen of five species above, respectively positioned at 7.53 (2H), 7.29 (4H), 7.22 (8H), 7.12 (8H), 2.20
(12H) ppm, it is consistent with the spectrogram of document report, it is seen that the compound is correct, and obtained compound structure is：
Embodiment 4:
In a nitrogen environment, 1- (4- bromophenyls) hexanes (578mg, 2.4mmol) are dissolved in the tetrahydrochysene furan of 10mL water removals
In muttering, added at -80 DEG C after the hexane solution (1mL, 2.4mmol) of 2.4M n-BuLis, reaction 1h, by 2,5- dibromos to benzene
Dicarboxylic acid esters (200mg, 0.4mmol) are added in reaction, and reaction is quenched with water after reacting 16h at room temperature, ethyl acetate extraction,
Anhydrous sodium sulfate drying is spin-dried for, and in a nitrogen environment dissolves crude product dichloromethane, BFEE is added at 0 DEG C molten
Liquid (1mL, 0.8mmol), reacts methanol 5mL is added after 1h at room temperature, afterwards reaction overnight 16-20h.After reaction terminates, water is used
It is quenched, dichloromethane extraction is separated with column chromatography, obtains product IDTT (200.6mg).
Embodiment 5:
In a nitrogen environment, 1- (4- bromophenyls) hexanes (578mg, 2.4mmol) are dissolved in the tetrahydrochysene furan of 10mL water removals
In muttering, added at -78 DEG C after the hexane solution (1mL, 2.4mmol) of 2.4M n-BuLis, reaction 1.5h, by 2,5- dibromos pair
Phthalic acid ester (200mg, 0.4mmol) is added in reaction, and reaction is quenched with water after reacting 16h at room temperature, ethyl acetate extraction
Take, anhydrous sodium sulfate drying is spin-dried for, in a nitrogen environment dissolve crude product dichloromethane, boron trifluoride second is added at 0 DEG C
Ethereal solution (1mL, 0.8mmol), reacts methanol 5mL is added after 1h at room temperature, afterwards reaction overnight 16-20h.After reaction terminates,
It is quenched with water, dichloromethane extraction is separated with column chromatography, obtains product IDTT (190.6mg).
Embodiment 6:
In a nitrogen environment, 1- (4- bromophenyls) hexanes (578mg, 2.4mmol) are dissolved in the tetrahydrochysene furan of 10mL water removals
In muttering, added at -78 DEG C after the hexane solution (1mL, 2.4mmol) of 2.4M n-BuLis, reaction 1h, by 2,5- dibromos to benzene
Dicarboxylic acid esters (200mg, 0.4mmol) are added in reaction, and reaction is quenched with water after reacting 16h at room temperature, ethyl acetate extraction,
Anhydrous sodium sulfate drying is spin-dried for, and in a nitrogen environment dissolves crude product dichloromethane, BFEE is added at 5 DEG C molten
Liquid (1mL, 0.8mmol), reacts methanol 5mL is added after 1h at room temperature, afterwards reaction overnight 16-20h.After reaction terminates, water is used
It is quenched, dichloromethane extraction is separated with column chromatography, obtains product IDTT (201.3mg).
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Understand, technical scheme can be modified or equivalent substitution, without departing from the essence of technical solution of the present invention
And scope.
Claims (5)
1. a kind of novel method for synthesizing of IDTT derivatives, it is characterised in that comprise the following steps：
Step (1), in a nitrogen environment, alkyl bromobenzene is dissolved in the tetrahydrofuran of water removal, alkyl bromide benzole soln is obtained；
Step (2), at -78~-80 DEG C, the hexane solution of n-BuLi is added into alkyl bromide benzole soln obtained by step (1),
And react 0.9-1.2h；
Step (3), 2,5- dibromoterephthalic acids ester is added in reaction solution obtained by step (2), 16-20h is reacted at room temperature, is made
Reaction completely；
Step (4), reaction is quenched with water, and ethyl acetate extraction, anhydrous sodium sulfate drying is spin-dried for, and obtains crude product；
Step (5), in a nitrogen environment dissolves crude product dichloromethane, and boron trifluoride ether solution is added at 0~5 DEG C,
1-1.5h is reacted at room temperature；
Step (6), methanol is added into mixed solution obtained by step (5), reacts 16-20h, makes its reaction complete；
Step (7), after reaction terminates, is quenched with water, dichloromethane extraction, is separated with column chromatography, obtains IDTT or it spreads out
It is biological.
2. the novel method for synthesizing of a kind of IDTT derivatives according to claim 1, it is characterised in that with molar ratio computing,
Alkyl bromobenzene:N-BuLi:2,5- dibromoterephthalic acid esters:Boron trifluoride ether solution=6:6:1:2.
3. a kind of novel method for synthesizing of IDTT derivatives according to claim 1, it is characterised in that institute in step (1)
The concentration for stating alkyl bromide benzole soln is 0.020g/ml-0.030g/ml.
4. a kind of novel method for synthesizing of IDTT derivatives according to claim 1, it is characterised in that alkane in step (2)
Bromide benzene is -78 DEG C with n-BuLi reaction temperature, and the reaction time is 1h；Reaction temperature in step (3) is 25 DEG C, during reaction
Between be 16h；Boron trifluoride ether solution is added in step (5) at 0 DEG C, reaction temperature is 25 DEG C, and the reaction time is 17h.
5. the novel method for synthesizing of a kind of IDTT derivatives according to claim 1, it is characterised in that used in column chromatography
The volume ratio of eluant, eluent is petroleum ether：Dichloromethane=15:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864142A (en) * | 2018-07-27 | 2018-11-23 | 武汉理工大学 | A kind of novel method for synthesizing of ITIC derivative |
| CN109256468A (en) * | 2018-07-31 | 2019-01-22 | 中国科学院合肥物质科学研究院 | A kind of hydridization solar cell and preparation method thereof integrated based on a variety of hetero-junctions performances |
| CN109378388A (en) * | 2018-08-20 | 2019-02-22 | 电子科技大学 | Efficient ternary organic solar batteries and preparation method thereof |
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| CN103649096A (en) * | 2011-07-19 | 2014-03-19 | 默克专利股份有限公司 | Organic semiconductors |
| CN104024263A (en) * | 2011-10-20 | 2014-09-03 | 默克专利有限公司 | Organic semiconductors |
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2017
- 2017-07-06 CN CN201710547656.9A patent/CN107286179A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103649096A (en) * | 2011-07-19 | 2014-03-19 | 默克专利股份有限公司 | Organic semiconductors |
| CN104024263A (en) * | 2011-10-20 | 2014-09-03 | 默克专利有限公司 | Organic semiconductors |
Non-Patent Citations (1)
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| YUN-XIANG XU，等: "Improved Charge Transport and Absorption Coeffi cient in Indacenodithieno[3,2-b]thiophene-based Ladder-Type Polymer Leading to Highly Effi cient Polymer Solar Cells", 《ADV. MATER.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864142A (en) * | 2018-07-27 | 2018-11-23 | 武汉理工大学 | A kind of novel method for synthesizing of ITIC derivative |
| CN109256468A (en) * | 2018-07-31 | 2019-01-22 | 中国科学院合肥物质科学研究院 | A kind of hydridization solar cell and preparation method thereof integrated based on a variety of hetero-junctions performances |
| CN109378388A (en) * | 2018-08-20 | 2019-02-22 | 电子科技大学 | Efficient ternary organic solar batteries and preparation method thereof |
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