CN102329299A - Star-shaped oligothiophene derivative, preparation method and application thereof - Google Patents
Star-shaped oligothiophene derivative, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a star-shaped oligothiophene derivative, a preparation method and application thereof. The derivative is 1, 3-di(2'-(5'-aldehyde)-thienyl)-5-(2'-thienyl)-benzene and is obtained by reacting N, N-dimethylformamide with phosphorus oxychloride, and then, reacting with 1, 3, 5-tri(2'-thienyl)-benzene, hydrolyzing a reaction product, sucking a filtrate and separating the filtrate. The derivative further can be 1, 3, 5-tri(2'-(5'-cyano)-thienyl)-benzene and is obtained by reacting a dichloromethane solution of the 1, 3, 5-tri(2'-thienyl)-benzene with chlorosulfonyl isocyanate, and then, reacting with the N, N-dimethylformamide, hydrolyzing, extracting and purifying a reaction product. The product prepared by the method has good chemical stability and environmental stability, and can be used as an organic electrochromic material to be used for assembling an organic electrochromic device. By using the product, the defects that an inorganic electrochromic material is difficult to form a film, is not suitable to be processed flexibly and cannot be degraded in toxicity are overcome.
Description
Technical field
The present invention relates to organic polymer photovaltaic material technical field, be specifically related to star-like Uniformpoly thiophene derivative and preparation method thereof and application.
Background technology
Electrochromism is meant that material produces stable reversible change phenomenon at the optical properties (transsmissivity, reflectivity or specific absorption) of ultraviolet-visible light or near infrared region under the extra electric field effect, show as the reversible change of color and transparency in appearance.Material with electrochromic property is called electrochromic material.Electrochromic material has been showed good application prospects in the fields such as dimming glass of demonstration, building energy conservation glass, automotive anti-glare rear vision mirror, automobile or aircraft.And the polymerization degree and polymerization position can be controlled, high purity Uniformpoly thiophene with definite molecular weight; Because of its five-membered ring structure, meet Huckel's rule, have moderate energy gap; The spectral response of broad; Good environmental stability and thermostability in recent years, are used as functional organic material and research and develop.Up to the present, according to the research and development target of Uniformpoly thiophene, design, synthesized various Uniformpoly thiophene derivatives as light, electric functional organic material.These Uniformpoly thiophene derivatives mainly are used to the research of the following aspects: the relation of the electric conductivity of resulting ion radical salt with conjugate length studied through electrochemical doping in (1); (2) the research and development Uniformpoly thiophene derivative is as the photoelectric characteristic of photoelectric conversion material; (3) the research Uniformpoly thiophene derivative is sent out the characteristics of luminescence of material as organic electroluminescent.
In view of Uniformpoly thiophene derivative is π-Department of Electronics's conjugate beam, the electric material of one type of excellent performance, therefore, the kind and the Application Areas thereof that enlarge Uniformpoly thiophene derivative seem particularly important.
At present, electrochromic material almost is inorganic transition metal oxide entirely, and the manufacturing cost of inorganic electrochromic material is higher, is difficult for film forming, unsuitable flexible processing, and also some inorganic transition metal oxide also has nondegradable toxicity.
Summary of the invention
In order to solve the defective and the deficiency of existing correlation technique; Enlarge the kind and the Application Areas thereof of Uniformpoly thiophene derivative simultaneously; The present invention provides star-like Uniformpoly thiophene derivative and preparation method thereof and application; Prepared star-like Uniformpoly thiophene derivative is easy to film forming, is easy to flexible processing, can be used as the organic electrochromic material and is used to assemble the organic electrochromic device.
Star-like Uniformpoly thiophene derivative provided by the present invention is 1, and 3-two (2
'-(5
'-aldehyde radical)-thienyl)-5-(2
'-thienyl)-and benzene (abbreviating 3TB-2CHO as), have molecular structure as follows:
（1）
Its structural characterization data are following:
Mass spectrum: m/z 380.9 (M+);
Proton nmr spectra: δ (ppm): 9.96 (s, 2H), 8.15 ~ 8.05 (m, 4H), 8.03 (s, 3H), 7.85 (d, 1H), 7.71 (d, 1H), 7.25 (t, 1H);
Ir spectra: (KBr method, cm
-1): 1650 (ν
C=O).
As another kind of structure, star-like Uniformpoly thiophene derivative of the present invention is 1,3, and 5-three (2
'-(5
'-cyanic acid)-thienyl)-benzene (abbreviating 3TB-3CN as), have molecular structure as follows:
（2）
Its structural characterization data are following:
Mass spectrum: m/z 400.6 (M+);
Proton nmr spectra: δ (ppm): 7.98 (s, 3H), 7.71 (d, 3H), 7.26 (d, 3H);
Ir spectra: (KBr method, cm
-1): 2265 (ν
C ≡ N).
The preparation process of said 3TB-2CHO is following:
(1) under the nitrogen protection, to
N,
NSlowly drip POCl3 in the-N, 30 ℃～65 ℃ of control reaction temperature, stirring reaction 20 minutes～30 minutes obtains reaction solution;
(2) in the reaction solution that step (1) obtains, add 1,3,5-three (2
'-thienyl)-and benzene, stirring reaction 35 minutes～45 minutes obtains reaction soln;
(3) in the reaction soln that step (2) obtains, add zero(ppm) water and be hydrolyzed, obtain flocks, be 3-two (2
'-(5
'-aldehyde radical)-thienyl)-5-(2
'-thienyl)-and the crude product of benzene, suction filtration goes out flocks, utilizes chromatographic column that crude product is separated, and promptly obtains pure 3-two (2
'-(5
'-aldehyde radical)-thienyl)-5-(2
'-thienyl)-benzene.
The washing fluid of said chromatographic column adopting is a toluene.
Said each preparation process is all carried out in microwave reactor.
Said 1,3,5-three (2
'-(5
'-cyanic acid)-thienyl)-preparation process of benzene is following:
(1) under the nitrogen protection, with 1,3,5-three (2
'-thienyl)-and benzene and methylene chloride mixing, get mixed solution; In mixed solution, slowly drip Sulfuryl chloride isocyanate, 30 ℃～65 ℃ of control reaction temperature stirring reaction 40-60 minute, obtain reaction solution;
(2) in the reaction solution that step (1) obtains, add
N,
N-N, stirring reaction 15 minutes～25 minutes obtains reaction soln;
(3) in the reaction soln that step (2) obtains, add the zero(ppm) water hydrolysis, get hydrolyzed solution; Use the dichloromethane extraction hydrolyzed solution, the organic layer after the extraction is used anhydrous sodium sulfate drying, remove by filter sodium sulfate after, get filtrating; Behind the methylene dichloride in the pressure reducing and steaming filtrating, obtain 1,3,5-three (2
'-(5
'-cyanic acid)-thienyl)-crude product of benzene, crude product separates with chromatographic column, promptly obtains purely 1,3, and 5-three (2
'-(5
'-cyanic acid)-thienyl)-benzene.
It is the mixed solvent of methylene dichloride and sherwood oil that said chromatographic column is separated the washing fluid that adopts.
Each step of said preparation is all carried out in microwave reactor.
The application of star-like Uniformpoly thiophene derivative of the present invention in preparation organic electrochromic device, step; As follows:
The first step, the method for employing vacuum plating, at the star-like homogeneous polythiophene derivative film of ITO conductive glass surface vapor deposition, film thickness is 100nm～130nm;
Second step was an ionogen with the perchloric acid 4-butyl amine, and acetonitrile is a solvent, is mixed with electrolyte solution;
The 3rd step; Using vapor deposition to have ITO conductive glass and the colourless transparent glass of star-like homogeneous polythiophene derivative film to be assembled into thickness is 1 millimeter～1.5 millimeters electrolyzer; In groove, add the electrolyte solution of being prepared; Insert diameter simultaneously and be 0.5 millimeter～0.8 millimeter platinum line, respectively with ITO conductive glass and platinum line as electrode, be packaged into the organic electrochromic device
When apply+when 2.5 V and-2.5 V voltages, in the device, the 3TB-2CHO film can take place faint yellow and russet reversible change; When apply+when 1.9 V and-1.9 V voltages, in the device, the 3TB-3CN film can take place faint yellow and orange-red reversible change.
Compared with prior art, the present invention has following advantage:
(1) the inorganic electrochromic device that overcome with inorganic electrochromic material assembling of the present invention has the manufacturing cost height, is difficult for film forming, unsuitablely flexiblely processes and has a toxic shortcoming of non-degradable;
(2) the prepared star-like Uniformpoly thiophene derivative of the present invention not only has better chemistry and environmental stability, and its oxidation state is with to go back ortho states also more stable, and its electrochromic property also is stable.
Embodiment
Below in conjunction with embodiment, the present invention is done detailed description further, but be not limited thereto.
Embodiment 1
1), the preparation of 3TB-2CHO:
The first step under protection of nitrogen gas, adds in there-necked flask
N,
N-N slowly drips POCl3,30 ℃ of control reaction temperature, and stirring reaction 65 minutes obtains reaction solution;
Second step added 1,3 in above-mentioned reaction solution, 5-three (2
'-thienyl)-and benzene, stirring reaction 35 minutes obtains reaction soln;
In the 3rd step, after reaction finishes, in the reaction soln of the second step gained, add the zero(ppm) water hydrolysis; The flocks that obtains is the crude product of 3TB-2CHO; Vacuum filtration goes out flocks, with chromatographic column flocks is separated then, obtains the pure products of 3TB-2CHO.
The structural characterization data of 3TB-2CHO are following:
Mass spectrum: m/z 380.9 (M+);
Proton nmr spectra: δ (ppm): 9.96 (s, 2H), 8.15 ~ 8.05 (m, 4H), 8.03 (s, 3H), 7.85 (d, 1H), 7.71 (d, 1H), 7.25 (t, 1H).
Ir spectra: (KBr method, cm
-1): 1650 (ν
C=O).
2), the preparation of 3TB-3CN:
The first step under protection of nitrogen gas, adds 1,3 in there-necked flask, 5-three (2
'-thienyl)-and benzene and methylene chloride, slowly drip Sulfuryl chloride isocyanate, 30 ℃ of control reaction temperature, stirring reaction 65 minutes obtains reaction solution;
In second step, in above-mentioned reaction solution, add
N,
N-N, stirring reaction 15 minutes obtains reaction soln;
The 3rd step after reaction finishes, added the zero(ppm) water hydrolysis in the reaction soln of the second step gained, the organic layer anhydrous sodium sulfate drying with using behind the dichloromethane extraction removes by filter sodium sulfate, gets filtrating; Methylene dichloride in the pressure reducing and steaming filtrating promptly obtains the crude product of 3TB-3CN, with chromatographic column crude product is separated purification then, obtains the pure products of 3TB-3CN.
Each step reaction of preparation 3TB-2CHO and 3TB-3CN is all carried out in microwave reactor.
For 3TB-2CHO, the washing fluid that chromatographic separation adopts is a toluene; For 3TB-3CN, the washing fluid that chromatographic separation adopts is the mixed solvent of methylene dichloride and sherwood oil.
The structural characterization data of 3TB-3CN are following:
Mass spectrum: m/z 400.6 (M+);
Proton nmr spectra: δ (ppm): 7.98 (s, 3H), 7.71 (d, 3H), 7.26 (d, 3H);
Ir spectra: (KBr method, cm
-1): 2265 (ν
C ≡ N).
3), organic electrochromic preparation of devices
The first step, the method for employing vacuum plating, at the star-like homogeneous polythiophene derivative film of ITO conductive glass surface vapor deposition, its thickness is 100nm.
Second step was an ionogen with the perchloric acid 4-butyl amine, and acetonitrile is a solvent, is mixed with electrolyte solution.
The 3rd step; Using vapor deposition to have ITO conductive glass and the colourless transparent glass of star-like homogeneous polythiophene derivative film to be assembled into thickness is 1 millimeter electrolyzer; In groove, add the electrolyte solution of being prepared; Insert diameter simultaneously and be 0.5 millimeter platinum line, respectively with electroconductive ITO glass and platinum line as electrode, be packaged into the organic electrochromic device.
The 4th step, when apply+when 2.5 V and-2.5 V voltages, in the device, the 3TB-2CHO film can take place faint yellow and russet reversible change; When apply+when 1.9 V and-1.9 V voltages, in the device, the 3TB-3CN film can take place faint yellow and orange-red reversible change;
Embodiment 2
1), the preparation of 3TB-2CHO:
The first step under protection of nitrogen gas, adds in there-necked flask
N,
N-N slowly drips POCl3,45 ℃ of control reaction temperature, and stirring reaction 40 minutes gets reaction solution;
Second step added 1,3 in above-mentioned reaction solution, 5-three (2
'-thienyl)-and benzene, stirring reaction 30 minutes obtains reaction soln;
The 3rd step after reaction finishes, added the zero(ppm) water hydrolysis in above-mentioned reaction soln, obtain flocks, and vacuum filtration goes out flocks, is the crude product of 3TB-2CHO, separates with chromatographic column then, obtains the pure products of 3TB-2CHO.
The structural characterization data of 3TB-2CHO are following:
Mass spectrum: m/z 380.9 (M+);
Proton nmr spectra: δ (ppm): 9.96 (s, 2H), 8.15 ~ 8.05 (m, 4H), 8.03 (s, 3H), 7.85 (d, 1H), 7.71 (d, 1H), 7.25 (t, 1H);
Ir spectra: (KBr method, cm
-1): 1650 (ν
C=O).
2), the preparation of 3TB-3CN:
The first step under protection of nitrogen gas, adds 1,3 in there-necked flask, 5-three (2
'-thienyl)-and benzene and methylene chloride, slowly drip Sulfuryl chloride isocyanate, 45 ℃ of control reaction temperature, stirring reaction 45 minutes gets reaction solution;
In second step, in above-mentioned reaction solution, add
N,
N-N, stirring reaction 20 minutes obtains reaction soln;
The 3rd step after reaction finishes, added the zero(ppm) water hydrolysis in above-mentioned reaction soln, use anhydrous sodium sulfate drying with the organic layer behind the dichloromethane extraction, remove by filter sodium sulfate after, get filtrating; Methylene dichloride in the pressure reducing and steaming filtrating promptly obtains the crude product of 3TB-3CN, with chromatographic column crude product is separated purification then, promptly obtains the pure products of 3TB-3CN.
Each step reaction of 3TB-2CHO and 3TB-3CN is all carried out in microwave reactor.
For 3TB-2CHO, the washing fluid that chromatographic separation adopts is a toluene; For 3TB-3CN, the washing fluid that chromatographic separation adopts is the mixed solvent of methylene dichloride and sherwood oil.
The structural characterization data of 3TB-3CN are following:
Mass spectrum: m/z 400.6 (M+);
Proton nmr spectra: δ (ppm): 7.98 (s, 3H), 7.71 (d, 3H), 7.26 (d, 3H);
Ir spectra: (KBr method, cm
-1): 2265 (ν
C ≡ N).
3), organic electrochromic preparation of devices
The first step, the method for employing vacuum plating, at the star-like homogeneous polythiophene derivative film of electroconductive ITO glass surface vapor deposition, its thickness is 115nm;
Second step was an ionogen with the perchloric acid 4-butyl amine, and acetonitrile is a solvent, is mixed with electrolyte solution;
The 3rd step; Having electroconductive ITO glass and the colourless transparent glass of star-like homogeneous polythiophene derivative film to be assembled into thickness with vapor deposition is 1.3 millimeters electrolytic cell; In groove, add the electrolyte solution of being prepared; Insert diameter simultaneously and be 0.7 millimeter platinum line; Respectively with electroconductive ITO glass and platinum line as electrode, be packaged into the organic electrochromic device;
The 4th step, when apply+when 2.5 V and-2.5 V voltages, in the device, the 3TB-2CHO film can take place faint yellow and russet reversible change; When apply+when 1.9 V and-1.9 V voltages, in the device, the 3TB-3CN film can take place faint yellow and orange-red reversible change.
Embodiment 3
1), the preparation of 3TB-2CHO:
The first step under protection of nitrogen gas, adds in there-necked flask
N,
N-N slowly drips POCl3,65 ℃ of control reaction temperature, and stirring reaction obtained reaction solution in 20 minutes;
Second step added 1,3 in above-mentioned reaction solution, 5-three (2
'-thienyl)-and benzene, stirring reaction obtained reaction soln in 35 minutes;
The 3rd step after reaction finishes, added the zero(ppm) water hydrolysis in the reaction soln of the second step gained, obtain flocks, and vacuum filtration goes out flocks, is the crude product of 3TB-2CHO, separates with chromatographic column then, obtains the pure products of pure 3TB-2CHO.
The structural characterization data of 3TB-2CHO are following:
Mass spectrum: m/z 380.9 (M+);
Proton nmr spectra: δ (ppm): 9.96 (s, 2H), 8.15 ~ 8.05 (m, 4H), 8.03 (s, 3H), 7.85 (d, 1H), 7.71 (d, 1H), 7.25 (t, 1H);
Ir spectra: (KBr method, cm
-1): 1650 (ν
C=O).
2), the preparation of 3TB-3CN:
The first step under protection of nitrogen gas, adds 1,3 in there-necked flask, 5-three (2
'-thienyl)-and benzene and methylene chloride, slowly drip Sulfuryl chloride isocyanate, 65 ℃ of control reaction temperature, stirring reaction 20 minutes obtains reaction solution;
In second step, in above-mentioned reaction solution, add
N,
N-N, stirring reaction 25 minutes obtains reaction soln;
In the 3rd step, after reaction finishes, in resulting reaction soln of second step, add the zero(ppm) water hydrolysis; Organic layer with behind the dichloromethane extraction is used anhydrous sodium sulfate drying; Get filtrating after removing by filter sodium sulfate, behind the methylene dichloride in the pressure reducing and steaming filtrating, promptly obtain the crude product of 3TB-3CN; Separate with chromatographic column then, promptly obtain the pure products of 3TB-3CN.
Each step reaction of 3TB-2CHO and 3TB-3CN is all carried out in microwave reactor.
For 3TB-2CHO, the washing fluid that chromatographic separation adopts is a toluene; For 3TB-3CN, the washing fluid that chromatographic separation adopts is the mixed solvent of methylene dichloride and sherwood oil.
The structural characterization data of 3TB-3CN are following:
Mass spectrum: m/z 400.6 (M+);
Proton nmr spectra: δ (ppm): 7.98 (s, 3H), 7.71 (d, 3H), 7.26 (d, 3H);
Ir spectra: (KBr method, cm
-1): 2265 (ν
C ≡ N).
3), organic electrochromic preparation of devices
The first step, the method for employing vacuum plating, at the star-like homogeneous polythiophene derivative film of electroconductive ITO glass surface vapor deposition, its thickness is 130nm.
Second step was an ionogen with the perchloric acid 4-butyl amine, and acetonitrile is a solvent, is mixed with electrolyte solution.
The 3rd step; Having electroconductive ITO glass and the colourless transparent glass of star-like homogeneous polythiophene derivative film to be assembled into thickness with vapor deposition is 1.5 millimeters electrolytic cell; In groove, add the electrolyte solution of being prepared; Insert diameter simultaneously and be 0.8 millimeter platinum line; Respectively with electroconductive ITO glass and platinum line as electrode, be packaged into the organic electrochromic device;
The 4th step, when apply+when 2.5 V and-2.5 V voltages, in the device, the 3TB-2CHO film can take place faint yellow and russet reversible change; When apply+when 1.9 V and-1.9 V voltages, in the device, the 3TB-3CN film can take place faint yellow and orange-red reversible change.
Claims (9)
1. star-like Uniformpoly thiophene derivative is characterized in that it being 1, and 3-two (2
'-(5
'-aldehyde radical)-thienyl)-5-(2
'-thienyl)-and benzene, have following molecular structure:
（1）
Or 1,3,5-three (2
'-(5
'-cyanic acid)-thienyl)-benzene, have following molecular structure:
（2）。
2. the said 3-two (2 of claim 1
'-(5
'-aldehyde radical)-thienyl)-5-(2
'-thienyl)-and the preparation method of benzene, it is characterized in that preparation process is following:
(1) under the nitrogen protection, to
N,
NSlowly drip POCl3 in the-N, 30 ℃～65 ℃ of control reaction temperature, stirring reaction 20 minutes～30 minutes obtains reaction solution;
(2) in the reaction solution that step (1) obtains, add 1,3,5-three (2
'-thienyl)-and benzene, stirring reaction 35 minutes～45 minutes obtains reaction soln;
(3) in the reaction soln that step (2) obtains, add zero(ppm) water and be hydrolyzed, the flocks that obtains is 3-two (2
'-(5
'-aldehyde radical)-thienyl)-5-(2
'-thienyl)-and the crude product of benzene, suction filtration goes out flocks, and with chromatographic column flocks is separated purification, promptly obtains pure 3-two (2
'-(5
'-aldehyde radical)-thienyl)-5-(2
'-thienyl)-benzene.
3. preparation method according to claim 2, the washing fluid that it is characterized in that said chromatographic column adopting is a toluene.
4. according to claim 2 or 3 described preparing methods, it is characterized in that said each preparation process all carries out in microwave reactor.
5. claim 1 is said 1,3, and 5-three (2
'-(5
'-cyanic acid)-thienyl)-preparation method of benzene, it is characterized in that preparation process is following:
(1) under the nitrogen protection, with 1,3,5-three (2
'-thienyl)-and benzene and methylene chloride mixing, get mixed solution; In mixed solution, slowly drip Sulfuryl chloride isocyanate, 30 ℃～65 ℃ of control reaction temperature stirring reaction 40-60 minute, obtain reaction solution;
(2) in the reaction solution that step (1) obtains, add
N,
N-N, stirring reaction 15 minutes～25 minutes obtains reaction soln;
(3) in the reaction soln that step (2) obtains, add the zero(ppm) water hydrolysis, obtain hydrolyzed solution; Use the dichloromethane extraction hydrolyzed solution, the organic layer after the extraction is used anhydrous sodium sulfate drying, remove by filter sodium sulfate after, get filtrating; Behind the methylene dichloride in the pressure reducing and steaming filtrating, obtain 1,3,5-three (2
'-(5
'-cyanic acid)-thienyl)-crude product of benzene, crude product separates with chromatographic column, promptly obtains purely 1,3, and 5-three (2
'-(5
'-cyanic acid)-thienyl)-benzene.
6. method according to claim 5 is characterized in that it is the mixed solvent of methylene dichloride and sherwood oil that said chromatographic column is separated the washing fluid that adopts.
7. according to claim 5 or 6 described preparing methods, it is characterized in that each step of said preparation all carries out in microwave reactor.
8. the application of the described star-like Uniformpoly thiophene derivative of claim 1 in preparation organic electrochromic device.
9. application according to claim 8 is characterized in that step is following:
The first step, the method for employing vacuum plating, at the star-like homogeneous polythiophene derivative film of ITO conductive glass surface vapor deposition, film thickness is 100nm～130nm;
Second step was an ionogen with the perchloric acid 4-butyl amine, and acetonitrile is a solvent, is mixed with electrolyte solution;
The 3rd step; Using vapor deposition to have ITO conductive glass and the colourless transparent glass of star-like homogeneous polythiophene derivative film to be assembled into thickness is 1 millimeter～1.5 millimeters electrolyzer; In electrolyzer, add the electrolyte solution of being prepared; Insert diameter simultaneously and be 0.5 millimeter～0.8 millimeter platinum line, respectively with ITO conductive glass and platinum line as electrode, be packaged into the organic electrochromic device.
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Cited By (2)
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| CN103374022A (en) * | 2013-07-02 | 2013-10-30 | 华南理工大学 | Oligothiophene derivative and preparation method thereof |
| CN109020948A (en) * | 2018-08-03 | 2018-12-18 | 浙江工业大学 | A kind of benzene-bigeminy thiophene derivant and the preparation method and application thereof |
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| US20050179032A1 (en) * | 2002-07-26 | 2005-08-18 | Marcus Halik | Octupolar molecules used as organic semiconductors |
| CN1730478A (en) * | 2005-08-30 | 2006-02-08 | 华南理工大学 | Uniformpoly thiophene derivative and its preparation method and uses |
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| US20050179032A1 (en) * | 2002-07-26 | 2005-08-18 | Marcus Halik | Octupolar molecules used as organic semiconductors |
| CN1730478A (en) * | 2005-08-30 | 2006-02-08 | 华南理工大学 | Uniformpoly thiophene derivative and its preparation method and uses |
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Cited By (3)
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| CN103374022A (en) * | 2013-07-02 | 2013-10-30 | 华南理工大学 | Oligothiophene derivative and preparation method thereof |
| CN103374022B (en) * | 2013-07-02 | 2016-01-06 | 华南理工大学 | Oligopoly thiophene derivative and preparation method thereof |
| CN109020948A (en) * | 2018-08-03 | 2018-12-18 | 浙江工业大学 | A kind of benzene-bigeminy thiophene derivant and the preparation method and application thereof |
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| CN102329299B (en) | 2013-10-30 |
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