CN103012751B - Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer - Google Patents
Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer Download PDFInfo
- Publication number
- CN103012751B CN103012751B CN201210502479.XA CN201210502479A CN103012751B CN 103012751 B CN103012751 B CN 103012751B CN 201210502479 A CN201210502479 A CN 201210502479A CN 103012751 B CN103012751 B CN 103012751B
- Authority
- CN
- China
- Prior art keywords
- preparation
- group
- pyrrolo
- thienyl
- carbonyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to preparation method of a bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer, which belongs to the technical field of chemical preparation of high-molecular polymer materials. According to the preparation method, under an appropriate condition, bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone as a raw material A and a dibromo-(hybrid) aromatic compound as a raw material B are directly react to obtain a target copolymer. Compared with the traditional method, the preparation method provided by the invention has obvious advantages, prevents the preparation link of an organic metal reagent, decreases the preparation steps, increases the overall yield, reduces the cost, prevents a great amount of toxic and harmful organic metal reagent wastes from being generated and is more conductive to the industrialized production.
Description
Technical field
The present invention relates to two thienyl pyrrolo-[3, the 4-c] pyrroles-Isosorbide-5-Nitrae-diketone of a class and the preparation method of (mixing) arene copolymer, belong to the chemical preparation techniques of macromolecule polymer material.
Background technology
Pyrrolo-[3,4-c] pyrroles-1,4-diones polymkeric substance has special planar molecular structure, good intermolecular accumulation can be formed, there is unique photoelectric property, as low in energy gap, electron/hole mobility is high, molar absorptivity is large, particularly the absorption near infrared spectrum region is strong, fluorescent emission is strong, quantum yield is high, has good light, thermostability simultaneously, is thus paid close attention to widely in fields such as biological chemistry, medicine and pharmacology, analytical chemistry and Materials science and applies.In recent years, utilize this base polymer to develop various photovoltaic functional materials and become domestic and international very active field.Such as in polymer solar battery, utilize this base polymer, not only can make the solar cell to visible light wave range " transparent ", series-connected cell can also be made, efficiency is up to 9.5%, reach current polymer solar battery electricity conversion maximum [see (a) Huo, L.; Hou, J.; Yang, Y.et al.Macromolecules 2009,42,6564; (b) Bijleveld, J.C.; Gevaerts, V.S.; Janssen, R.A.J.et al.Adv.Mater.2010,22, E242; (c) Woo, C.H.; Beaujuge, P.M.; Fr é chet, J.M.J.et al.J.Am.Chem.Soc.2010,132,15547; (d) Dou, L.; You, J.; Yang, Y.et al.Nat.Photonics 2012,6,180; (e) Chen, C.-C.; Dou, L.; Yang, Y.et al.ACS Nano 2012,6,7185; (f) Qu, S.; Tian, H.Chem.Commun.2012,48,3039; (g) Dou, L.; Chang, W.-H.; Yang, Y.et al.Adv.Mater.2012, DOI:10.1002/adma.201203827.]; , in addition at organic field effect tube [see (a) Sonar, P.; Singh, S.P.; Li, Y.; Dodabalapur, A.et al.Adv.Mater.2010,22,5409; (b) Li, Y.; Singh, S.P.; Sonar, P.Adv.Mater.2010,22,4862; (c) Cho, S.; Lee, J.; Yang, C.Adv.Funct.Mater.2011,21,1910; (d) Adil, D.; Kanimozhi, C.; Patil, S.; Guha, S.et al.ACS Appl.Mater.Interfaces 2011,3,1463; (e) Ha, J.S.; Kim, K.H.; Choi, D.H.J.Am.Chem.Soc.2011,133,10364; (f) Li, Y.; Sonar, P.et al.J.Am.Chem.Soc.2011,133,2198; (g) Nielsen, C.B.; Turbiez, M.; McCulloch, I.Adv.Mater.2012, DOI:10.1002/adma.201201795], sensor is [see (a) Qu, Y.; Hua, J.; Tian, H.Org.Lett.2010,12,3320; (b) He, F.; Liu, L.; Li, L.Adv.Funct.Mater.2011,21,3143; (c) Deng, L.; Wu, W.; Zhang, C.et al.J.Org.Chem.2011,76,9294; (d) Qu, Y.; Qu, S.; Qu, D.et al.Sensor.Actuat.B-Chem.2012,173,225; (e) Jin, R.Theor.Chem.Acc.2012,131,1; (f) Holcombe, T.W.; Yum, J.-H.; Graetzel, M.Chem.Commun.2012,48,10724.], fluorescent probe is [see Jeong, Y.-H.; Lee, C.-H.; Jang, W.-D.Chem.Asian J.2012,7,1566.], one dimension microcosmic wire is [see Palai, A.K.; Lee, J.; , Pyo, S.et al.Org.Electron.2012,13,2553.] dye sensitization solar battery is [see (a) Qu, S.; Wu, W.; Tian, H.et al.J.Phys.Chem.C 2010,114,1343; (b) Kanimozhi, C.; Balraju, P.; Sharma, G.D.; Patil, S.J.Phys.Chem.C 2010,114,3287; (c) Guo, F.-L.; Qu, S.-Y.; Hua, J.-L.et al.Synthetic Met.2010,160,1767; (d) Warnan, J.; Favereau, L.; Odobel, F.et al.J.Photoch.Photobio.A 2011,226,9; (f) Warnan, J.; Pellegrin, Y.; Blart, E.; Odobel, F.Chem.Commun.2012,48,675; (g) Qu, S.; Qin, C.; Tian, H.; Han, L.Chem.Commun.2012,48,6972; (h) Tang, J.; Qu, S.; Hua, J.et al.Sol.Energy 2012,86,2306; (i) Qu, S.; Qin, C.; Tian, H.; Han, L.et al.Chem.Asian J.2012, DOI:10.1002/asia.201200648.], dyestuff is [see (a) Mizuguchi, J.J.Imaging Sci.Techn.2005,49,35; (b) Hayashi, K.; Morii, H.; Ichimura, K.et al.J.Mater.Chem.2007,17,527; ], fluorescent material is [see (a) Fischer, G.; Isomaeki-Krondahl, M.; Zumbusch, A.Chem.Eur.J.2009,15,4857; (b) Fischer, G.M.; Daltrozzo, E.; Zumbusch, A.Angew.Chem.Int.Ed.2011,50,1406; (b) Jin, Y.; Xu, Y.; Cao, D.Dyes Pigments 2011,90,311; (c) Buerckstuemmer, H.; Weissenstein, A.; Bialas, D.; , Wuerthner, F.J.Org.Chem.2011,76,2426.] electroluminescent material is [see (a) Cao, D.; Liu, Q.; Zeng, W.et al.Macromolecules 2006,39,8347; (b) Qiao, Z.; Peng, J.; Cao, D.et al.Polymer 2010,51,1016; (c) Xu, Y.; Jin, Y.; Cao, D.et al.Synthetic Met.2010,160,2135; (d) Jin, Y.; Xu, Y.; Cao, D.et al.Polymer 2010,51,5726; (e) Xu, Y.; Jin, Y.; Cao, D.et al.J.Macromol.Sci.A 2010,47,1059; (f) Qiao, Z.; Xu, Y.; The aspect such as Cao, D.et al.Synthetic Met.2010,160,1544.], this base polymer also has good performance and huge application to dive scape.
Pyrrolo-[3,4-c] pyrroles-1,3 of 4-diketone skeleton, 6 can connect two phenyl, furyl, thienyl or selenium phenolic group simultaneously, because thiophene electron rich, high reaction activity, many reaction site are easy to the features such as chemically modified, two thienyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diones polymkeric substance becomes one of focus molecule be concerned about most in many fields such as current photovoltaic material.But up to now, preparing this base polymer is all by traditional transition metal-catalyzed C – X/C – M (X=halogen or pseudohalogen, M=SnR
3, B (OR)
2deng) linked reaction obtains, as Suzuki coupling, Stille linked reaction etc.But this quasi-tradition linked reaction shortcoming is obvious: (1) is from starting raw material virtue (mixing) ring to coupled product, experience at least three organic synthesis steps, relate to the synthesis of intermediate product C – X compound, the synthesis of C – M compound and linked reaction, step is many, route is long, organic synthesis complicated operation, condition is harsh, and overall yield is low; (2) one of reaction intermediate is organometallic reagent, preparation difficulty is high, except raw material (acid reagent, organotin reagent etc.) is expensive, complex steps, condition harshness (as anhydrous and oxygen-free environment etc.), operation easier increase, and also reduce total recovery, raise the cost; Simultaneously, raw material organometallic reagent poor stability, what have can not stand ensuing linked reaction, and what have can not be produced and stable existence even at all, which greatly limits the popularity of raw material and product, limit the possibility of material being carried out to molecular modification and character adjustment; (3) traditional linked reaction can produce the organometallic reagent waste of equivalent, as tin reagent waste, poisons human and livestock health, causes environmental pollution.
It solves an above-mentioned difficult problem, provide the preparation method of two thienyl pyrrolo-[3, the 4-c] pyrroles-Isosorbide-5-Nitrae-diketone of a kind of efficient, succinct, eco-friendly preparation and (mixing) arene copolymer.
Summary of the invention
The object of the invention is to the deficiency existed for prior art, a kind of more succinct compared with traditional method, efficient, eco-friendly pair of thienyl pyrrolo-[3 is provided, 4-c] pyrroles-1, the preparation method of 4-diketone and (mixing) aromatic hydrocarbons multipolymer, avoid the preparation link of organometallic reagent, adopt the method for the direct coupling polymerization of C – H/C – Br, shorten synthetic route, improve overall yield, reduce cost, also avoid producing a large amount of poisonous and hazardous organometallic reagent waste.
The technical scheme that the present invention solves this problem adopts following syntheti c route, as accompanying drawing 1:
(1) in the reactor of drying, two thienyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-derovatives, two bromos (mixing) arene compounds, catalyzer, part, additive, alkali and solvent is added.All raw materials are mixed, reacts 0.1 ~ 96 hour at 25 ~ 150 DEG C under anhydrous and oxygen-free condition;
(2) after completion of the reaction reaction flask is cooled to room temperature, adds a small amount of stirring solvent even, pour the mixed system of methyl alcohol and water into, stir, filter, apparatus,Soxhlet's put into by the solid collected, use methyl alcohol, acetone, normal hexane extraction successively, remaining solid uses chloroform extraction again, collects chloroformic solution, concentrated, concentrated solution is slowly instilled in a large amount of methyl alcohol, separate out a large amount of solid, suction filtration obtains filter cake, obtains subject copolymers after vacuum-drying.
Wherein in step (1), catalyzer is one or more in Palladous chloride, palladium, trifluoracetic acid palladium, two (acetonitrile) Palladous chloride, two (cyanophenyl) Palladous chloride, two (triphenylphosphine) Palladous chloride, tetrakis triphenylphosphine palladium, trans-two (μ-acetic acid) two [o-(two (o-tolyl phosphino-) phenmethyl] two palladiums (II), preferred Palladous chloride, palladium and trans-two (μ-acetic acid) two [o-(two (o-tolyl phosphino-) phenmethyl] two palladiums (II).
Wherein in step (1), part is for containing Phosphorus or nitrogenous class part, triphenylphosphine, three (o-methoxyphenyl) phosphine, three (p-methylphenyl) phosphine, di-t-butyl monomethyl phosphine a tetrafluoro borate, 2-dicyclohexylphosphino-2'-(N, N dimethylamine)-biphenyl, 2-dicyclohexylphosphontetrafluoroborate-2', 6'-dimethoxy-biphenyl, three (adjacent (N, N-dimethylamino) phenyl) phosphine, tricyclohexyl phosphine a tetrafluoro borate, tri-butyl phosphine a tetrafluoro borate, pyridine, one or more in dipyridyl, be preferably triphenylphosphine, tricyclohexyl phosphine a tetrafluoro borate, three (o-methoxyphenyl) phosphine and pyridines.
Wherein in step (1), additive is trimethylacetic acid, adamantane acid, 2, one or more in 2-acid dimethyl, acetic acid, trifluoracetic acid, tosic acid, Tetrabutyl amonium bromide, cetyl trimethylammonium bromide, preferred trimethylacetic acid, adamantane acid and Tetrabutyl amonium bromide.
Wherein in step (1), alkali is one or more in Quilonum Retard, salt of wormwood, sodium carbonate, cesium carbonate, Trilithium phosphate, sodium phosphate, potassiumphosphate, phosphoric acid caesium, Potassium ethanoate, sodium-acetate, Lithium Acetate, cesium acetate, preferred salt of wormwood, cesium carbonate, potassiumphosphate and Potassium ethanoate.
Wherein in step (1), solvent is polar solvent, and described polar solvent is tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, acetonitrile; Or be non-polar solvent, described non-polar solvent is one or more mixed solvents in toluene, dimethylbenzene, trimethylbenzene, normal hexane, preferred tetrahydrofuran (THF), dimethylbenzene, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE: tetrahydrofuran (THF)=1:1 (v/v) and N,N-dimethylacetamide: dimethylbenzene=1:1 (v/v).
Wherein in step (1), two thienyl pyrrolo-[3,4-c] pyrroles-1,4-derovatives: two bromos (mixing) arene compounds: catalyzer: part: additive: the mol ratio of alkali is 1:(0.1 ~ 10): (0.005 ~ 2): (0 ~ 4): (0 ~ 10): (0.1 ~ 10), preferred proportion is 1:(0.5 ~ 1.5): (0.01 ~ 0.2): (0 ~ 0.8): (0 ~ 4.0): (2.0 ~ 3.5).
Wherein in step (1), temperature of reaction is 25 ~ 150 DEG C, and preferable reaction temperature is 90 ~ 135 DEG C.
Wherein in step (1), the reaction times is 0.1 ~ 96 hour, preferably 3 ~ 48 hours.
Wherein in step (1), the concentration of two thienyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-derovatives is 0.01 ~ 1mol/L, preferably 0.1 ~ 0.5mol/L.
Described two thienyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-derovatives general structures are:
Wherein R
1for hydrogen, alkyl, ester group, carbonyl, substituted aryl, substituted heteroaryl or ether chain; R
2and R
3be respectively in hydrogen, fluorine, alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl, substituted aryl, substituted heteroaryl or ether chain one or both.Substituted radical wherein in substituted aryl and substituted heteroaryl is one or more in fluorine, alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl, cyano group, nitro, aryl, heteroaryl or ether chain.Carbochain wherein in alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl or ether chain to be carbon number be 0 ~ 40 straight or branched.
Described two bromos (mixing) arene compounds general structure is following one:
Wherein R
4, R
5, R
6, R
7, R
8and R
9be respectively in hydrogen, fluorine, alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl, substituted aryl, substituted heteroaryl or ether chain one or both.Substituted radical wherein in substituted aryl and substituted heteroaryl is one or more in fluorine, alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl, cyano group, nitro, aryl, heteroaryl or ether chain.Carbochain wherein in alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl or ether chain to be carbon number be 0 ~ 40 straight or branched.X and Y is carbon, oxygen, nitrogen, sulphur, phosphorus, selenium, silicon, the 4th or five main group element atoms.Wherein m is the integer of 1 ~ 10.
Compared with prior art, the present invention is more succinct, efficient, the environmental friendliness of traditional method comparatively, is specially:
1. the present invention adopts the direct coupling of C – H/C – Br, shortens at least one step organic synthesis step, improve building-up reactions overall yield, reduce cost than technologies of preparing such as traditional C – X/C – M;
2. raw material stable chemical nature, is easy to synthesis, is conducive to reducing technology difficulty;
3. this technology is avoided preparing organometallic reagent, adds the diversity of product Suo Dai functional group, is conducive to carrying out molecular modification and character adjustment to material;
4. avoid producing organo-metallic waste, improve Atom economy and environment friendly.
In sum, technology of the present invention is advantageously in suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the syntheti c route of two thienyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone and (mixing) arene copolymer.
Fig. 2 is the UV-visible-near infrared absorption of embodiment 1 gained subject copolymers in chloroformic solution.
Fig. 3 is the UV-visible-near infrared absorption of embodiment 1 gained subject copolymers filminess.
Embodiment
Below in conjunction with embodiment, the invention will be further described, will contribute to the understanding of the present invention.But interest field of the present invention can not be limited with this, and interest field of the present invention should being as the criterion with claims elaboration.
Embodiment 1:
Step (1): 2, two (the 2-octyldodecyl)-3 of 5-, two (2-thienyl) pyrrolo-[3 of 6-, 4-c] pyrroles-1, 4-diketone (1.72g, 2.0mmol), 4, 7-bis-bromo-2, 1, 3-diazosulfide (588mg, 2.0mmol), catalyzer is palladium (22mg, 0.1mmol), part is triphenylphosphine (105mg, 0.4mmol), additive is trimethylacetic acid (204mg, 2.0mmol), alkali is salt of wormwood (829mg, 6.0mmol), solvent is N, N-N,N-DIMETHYLACETAMIDE (10mL), mentioned reagent is added reactor, stir post-heating to 120 DEG C under anhydrous and oxygen-free condition, react 24 hours,
Step (2): after completion of the reaction reaction flask is cooled to room temperature, adds a small amount of chloroform and stirs, pour the mixed system of methyl alcohol and water into, stirs, and filters.Apparatus,Soxhlet's put into by the solid collected, use methyl alcohol, acetone, normal hexane extraction successively, remaining solid part uses chloroform extraction again, collects chloroformic solution, concentrated, concentrated solution is slowly instilled sedimentation in a large amount of methyl alcohol, and separate out a large amount of solid, suction filtration obtains filter cake, after vacuum-drying, obtain subject copolymers 1.79g, productive rate is 90%, M
n=23500Da, M
w/ M
n=4.13.Proton nmr spectra (deuterochloroform is solvent, Bruker AMX-400 type nuclear magnetic resonance analyser)
1h NMR (400MHz, CDCl
3):
1h NMR (400MHz, CDCl
3): δ=0.83 (br, 12H), 1.21-1.57 (m, 64H), 2.00 (br, 2H), 3.98 (br, 4H), 7.82-7.98 (m, 4H), 9.10 (br, 2H) ppm.
Embodiment 2:
Step (1): 2, two (the 2-octyldodecyl)-3 of 5-, two (2-(the 4-fluorine thiophene) base) pyrrolo-[3 of 6-, 4-c] pyrroles-1, 4-diketone (1.79g, 2.0mmol), 4, 7-bis-bromo-5, 6-dimethyl-2, 1, 3-diazosulfide (515mg, 1.6mmol), catalyzer is trans-two (μ-acetic acid) two [o-(two (o-tolyl phosphino-) phenmethyl] two palladiums (II) (18.8mg, 0.02mmol), part is three (o-methoxyphenyl) phosphine (28.2mg, 0.08mmol), additive is adamantane acid (541mg, 3.0mmol), alkali is cesium carbonate (2.28g, 7.0mmol), solvent is tetrahydrofuran (THF) (4mL), mentioned reagent is added in reactor, stir post-heating to 90 DEG C under anhydrous and oxygen-free condition, react 48 hours,
Step (2): the operation steps (2) with reference to example 1 obtains subject copolymers 1.39g, and productive rate is 82%, M
n=14600Da, M
w/ M
n=4.67.Proton nmr spectra (deuterochloroform is solvent, Bruker AMX-400 type nuclear magnetic resonance analyser)
1h NMR (400MHz, CDCl
3):
1h NMR (400MHz, CDCl
3): δ=0.85 (br, 12H), 1.20-1.60 (m, 64H), 2.05-2.21 (m, 8H), 4.00 (br, 4H), 9.15 (br, 2H) ppm.
Embodiment 3:
Step (1): 2, two (2-(2-oxyethyl group) oxyethyl group) methyl of 5-)-3, two (the 2-(3 of 6-, 4-thioxene base)) pyrrolo-[3, 4-c] pyrroles-1, 4-diketone (1.12g, 2.0mmol), 2, the bromo-N-of 7-bis-(2-octyldodecyl) carbazole (1.51g, 2.5mmol), catalyzer is Palladous chloride (7.1mg, 0.04mmol), part is tricyclohexyl phosphine a tetrafluoro borate (14.7mg, 0.04mmol), not doping, alkali is potassiumphosphate (849mg, 4.0mmol), solvent is N, N-N,N-DIMETHYLACETAMIDE/dimethylbenzene=1:1 (v/v, 20mL), mentioned reagent is added in reactor, stir post-heating to 135 DEG C under anhydrous and oxygen-free condition, react 3 hours,
Step (2): the operation steps (2) with reference to example 1 obtains subject copolymers 1.73g, and productive rate is 86%, M
n=32000Da, M
w/ M
n=3.85.Proton nmr spectra (deuterochloroform is solvent, Bruker AMX-400 type nuclear magnetic resonance analyser)
1h NMR (400MHz, CDCl
3): δ=0.79 (br, 6H), 1.16-1.61 (m, 38H), 1.96-2.35 (m, 13H), 3.20-4.41 (m, 18H), 7.57-8.07 (m, 6H) ppm.
Embodiment 4:
Step (1): 2, two (the 2-octyldodecyl)-3 of 5-, two (the 2-(3 of 6-, 4-thioxene base)) pyrrolo-[3, 4-c] pyrroles-1, 4-diketone (1.84g, 2.0mmol), 4, 7-bis-bromo-5, 6-dimethyl-2, 1, 3-diazosulfide (1.29g, 4.0mmol), catalyzer is palladium (2.2mg, 0.01mmol), do not add part, not doping, alkali is sodium carbonate (339mg, 3.2mmol), solvent is N, N-N,N-DIMETHYLACETAMIDE/tetrahydrofuran (THF)=1:1 (v/v, 2.5mL), mentioned reagent is added in reactor, stir under anhydrous and oxygen-free condition, be heated to 60 DEG C, react 80 hours,
Step (2): the operation steps (2) with reference to example 1 obtains subject copolymers 0.496g, productive rate 23%, M
n=9500Da, M
w/ M
n=2.05.Proton nmr spectra (deuterochloroform is solvent, Bruker AMX-400 type nuclear magnetic resonance analyser)
1h NMR (400MHz, CDCl
3): δ=0.85 (br, 12H), 1.22-1.59 (m, 64H), 2.01-2.35 (m, 20H), 4.02 (br, 4H) ppm.
Embodiment 5:
Step (1): 2, two (eicosyl)-3 of 5-, two (the 2-(3 of 6-, 4-dimethoxy-thiophene base)) pyrrolo-[3, 4-c] pyrroles-1, 4-diketone (1.96g, 2.0mmol), 2, 3-dimethyl-6, 7-bis-fluoro-5, 8-bis-bromo quinoxaline (352mg, 1.0mmol), catalyzer is trifluoracetic acid palladium (266mg, 0.8mmol), do not add part, additive is Tetrabutyl amonium bromide (1.29g, 4.0mmol), alkali is Potassium ethanoate (785mg, 8.0mmol), solvent is N-Methyl pyrrolidone (40mL), mentioned reagent is added in reactor, stir under anhydrous and oxygen-free condition, be heated to 150 DEG C, react 2 hours,
Step (2): the operation steps (2) with reference to example 1 obtains subject copolymers 0.211g, productive rate 18%, M
n=8700Da, M
w/ M
n=1.72.Proton nmr spectra (deuterochloroform is solvent, Bruker AMX-400 type nuclear magnetic resonance analyser)
1h NMR (400MHz, CDCl
3): δ=0.82 (br, 6H), 1.20-1.61 (m, 68H), 1.98-2.12 (m, 4H), 2.99 (br, 6H), 3.85-4.35 (m, 16H) ppm.
Embodiment 6:
Step (1): 2, two (4-(the n-dodecane oxygen base) phenyl)-3 of 5-, two (2-(the thienyl)) pyrrolo-[3 of 6-, 4-c] pyrroles-1, 4-diketone (1.64g, 2.0mmol), 3, 3 '-two (n-dodecane oxygen base)-4, 4 '-two bromo-1, 2-toluylene (1.41g, 2.0mmol), catalyzer is tetra-triphenylphosphine palladium (116mg, 0.1mmol), part is pyridine (396mg, 5.0mmol), additive is acetic acid (300mg, 5.0mmol), alkali is Quilonum Retard (739mg, 10mmol), solvent is 1, 4-dioxane (8mL), mentioned reagent is added in reactor, stir under anhydrous and oxygen-free condition, be heated to 100 DEG C, react 55 hours,
Step (2): the operation steps (2) with reference to example 1 obtains subject copolymers 0.738g, productive rate 27%, M
n=6400Da, M
w/ M
n=1.85.Proton nmr spectra (deuterochloroform is solvent, Bruker AMX-400 type nuclear magnetic resonance analyser)
1h NMR (400MHz, CDCl
3): δ=0.85 (br, 12H), 1.18-1.75 (m, 72H), 1.95 (br, 8H), 4.11 (br, 8H), 7.19 (br, 2H), 7.44-7.65 (m, 14H), 7.79 (br, 2H), 8.95 (br, 2H) ppm.
Embodiment 7:
The subject copolymers obtained in embodiment 1 is dissolved in trichloromethane, is mixed with 1.0 × 10
-5the solution of mol/L concentration, gets 2.5mL and puts into quartz colorimetric utensil, measures the UV-visible-near infrared absorption of solution, records λ
max=857nm, ε=6.20 × 10
4lmol
-1cm
-1.UV-visible-near infrared absorption as shown in Figure 2.
Embodiment 8:
The subject copolymers that embodiment 1 obtains is dissolved in trichloromethane, is mixed with the strong solution of 3 ~ 5mg/mL concentration, get 2 ~ 3 and drop in clean Quartz glass surfaces, obtain the uniform film of thickness by spin-coating instrument.Measure the UV-visible-near infrared absorption of film, measure λ
max=807nm, λ
onset=1015nm.UV-visible-near infrared absorption as shown in Figure 3.
Claims (11)
1. two thienyl pyrrolo-[3, the 4-c] pyrroles-Isosorbide-5-Nitrae-derovatives of a class and the preparation method of (mixing) arene copolymer, is characterized in that preparation process is as follows:
(1) in the reactor of drying, two thienyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-derovatives, two bromos (mixing) arene compounds, catalyzer, part, additive, alkali and solvent is added; All raw materials are mixed, reacts 0.1 ~ 96 hour at 25 ~ 150 DEG C under anhydrous and oxygen-free condition;
(2) after completion of the reaction reaction flask is cooled to room temperature, adds a small amount of stirring solvent even, pour the mixed system of methyl alcohol and water into, stir, filter, apparatus,Soxhlet's put into by the solid collected, use methyl alcohol, acetone, normal hexane extraction successively, remaining solid uses chloroform extraction again, collects chloroformic solution, concentrated, concentrated solution is slowly instilled in a large amount of methyl alcohol, separate out a large amount of solid, suction filtration obtains filter cake, obtains subject copolymers after vacuum-drying.
2. preparation method according to claim 1, is characterized in that in step (1), two thienyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-derovatives general structure is:
Wherein R
1for hydrogen, alkyl, ester group, carbonyl, substituted aryl, substituted heteroaryl or ether chain; R
2and R
3be respectively in hydrogen, fluorine, alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl, substituted aryl, substituted heteroaryl or ether chain one or both; Substituted radical wherein in substituted aryl and substituted heteroaryl is one or more in fluorine, alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl, cyano group, nitro, aryl, heteroaryl or ether chain; Carbochain wherein in alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl or ether chain to be carbon number be 0 ~ 40 straight or branched.
3. preparation method according to claim 1, is characterized in that in step (1), two bromos (mixing) arene compounds general structure is following one:
Wherein R
4, R
5, R
6, R
7, R
8and R
9be respectively in hydrogen, fluorine, alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl, substituted aryl, substituted heteroaryl or ether chain one or both; Substituted radical wherein in substituted aryl and substituted heteroaryl is one or more in fluorine, alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl, cyano group, nitro, aryl, heteroaryl or ether chain; Carbochain wherein in alkyl, alkoxyl group, alkylamino, alkylthio, ester group, amide group, carbonyl or ether chain to be carbon number be 0 ~ 40 straight or branched; X and Y is carbon, oxygen, nitrogen, sulphur, phosphorus, selenium, silicon, the 4th or five main group element atoms; Wherein m is the integer of 1 ~ 10.
4. preparation method according to claim 1, is characterized in that catalyzer in step (1) is one or more in Palladous chloride, palladium, trifluoracetic acid palladium, two (acetonitrile) Palladous chloride, two (cyanophenyl) Palladous chloride, two (triphenylphosphine) Palladous chloride, tetrakis triphenylphosphine palladium, trans-two (μ-acetic acid) two [o-(two (o-tolyl phosphino-) phenmethyl] two palladiums (II).
5. preparation method according to claim 1, it is characterized in that in step (1), part is for containing Phosphorus or nitrogenous class part, triphenylphosphine, three (o-methoxyphenyl) phosphine, three (p-methylphenyl) phosphine, di-t-butyl monomethyl phosphine a tetrafluoro borate, 2-dicyclohexylphosphino-2'-(N, N dimethylamine)-biphenyl, 2-dicyclohexylphosphontetrafluoroborate-2', 6'-dimethoxy-biphenyl, three (adjacent (N, N-dimethylamino) phenyl) phosphine, tricyclohexyl phosphine a tetrafluoro borate, tri-butyl phosphine a tetrafluoro borate, pyridine, one or more in dipyridyl.
6. preparation method according to claim 1, it is characterized in that additive in step (1) is one or more in trimethylacetic acid, adamantane acid, 2,2-acid dimethyls, acetic acid, trifluoracetic acid, tosic acid, Tetrabutyl amonium bromide, cetyl trimethylammonium bromide.
7. preparation method according to claim 1, is characterized in that alkali in step (1) is one or more in Quilonum Retard, salt of wormwood, sodium carbonate, cesium carbonate, Trilithium phosphate, sodium phosphate, potassiumphosphate, phosphoric acid caesium, Potassium ethanoate, sodium-acetate, Lithium Acetate, cesium acetate.
8. preparation method according to claim 1, it is characterized in that in step (1), solvent is polar solvent, described polar solvent is tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, acetonitrile.
9. preparation method according to claim 1, it is characterized in that in step (1), solvent is non-polar solvent, described non-polar solvent is one or more mixed solvents in toluene, dimethylbenzene, trimethylbenzene, normal hexane.
10. preparation method according to claim 1, it is characterized in that two thienyl pyrrolo-[3 in step (1), 4-c] pyrroles-Isosorbide-5-Nitrae-derovatives: two bromos (mixing) arene compounds: catalyzer: part: additive: the mol ratio of alkali is 1:(0.1 ~ 10): (0.005 ~ 2): (0 ~ 4): (0 ~ 10): (0.1 ~ 10).
11. preparation methods according to claim 1, is characterized in that the reaction density of two thienyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-derovatives in step (1) is 0.01 ~ 1mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210502479.XA CN103012751B (en) | 2012-11-30 | 2012-11-30 | Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210502479.XA CN103012751B (en) | 2012-11-30 | 2012-11-30 | Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103012751A CN103012751A (en) | 2013-04-03 |
| CN103012751B true CN103012751B (en) | 2015-05-20 |
Family
ID=47961891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210502479.XA Expired - Fee Related CN103012751B (en) | 2012-11-30 | 2012-11-30 | Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103012751B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774318B (en) * | 2015-04-08 | 2017-02-01 | 中国科学院化学研究所 | 2,2'-di(benzothiophene) ethylene polymer as well as preparation method and application thereof |
| CN105837799B (en) * | 2016-04-19 | 2018-04-03 | 中国科学院化学研究所 | A kind of dicarbapentaborane bridging pyrrolo-pyrrole-dione polymer and preparation method and application |
| WO2019041047A1 (en) * | 2017-08-31 | 2019-03-07 | UNIVERSITé LAVAL | Fluorinated dithienyl-diketopyrrolopyrrole monomers and polymers and uses thereof |
| CN110283304B (en) * | 2019-06-12 | 2021-12-28 | 南京邮电大学 | Dithienobenzene diimide-based conjugated polymer and preparation method and application thereof |
| KR20220160424A (en) | 2021-05-27 | 2022-12-06 | 삼성전자주식회사 | Polymer semiconductor, stretchable polymer thin film, and electronic device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2033983A2 (en) * | 2007-09-06 | 2009-03-11 | Xerox Corporation | Diketopyrrolopyrrole-Based Polymers |
| EP2034537A2 (en) * | 2007-09-06 | 2009-03-11 | Xerox Corporation | Diketopyrrolopyrrole-based derivatives for thin film transistors |
| CN102203160A (en) * | 2008-10-31 | 2011-09-28 | 巴斯夫欧洲公司 | Diketopyrrolopyrrole polymers for use in organic semiconductor devices |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2571919B1 (en) * | 2010-05-19 | 2018-07-11 | Basf Se | Diketopyrrolopyrrole polymers for use in organic semiconductor devices |
-
2012
- 2012-11-30 CN CN201210502479.XA patent/CN103012751B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2033983A2 (en) * | 2007-09-06 | 2009-03-11 | Xerox Corporation | Diketopyrrolopyrrole-Based Polymers |
| EP2034537A2 (en) * | 2007-09-06 | 2009-03-11 | Xerox Corporation | Diketopyrrolopyrrole-based derivatives for thin film transistors |
| CN102203160A (en) * | 2008-10-31 | 2011-09-28 | 巴斯夫欧洲公司 | Diketopyrrolopyrrole polymers for use in organic semiconductor devices |
Non-Patent Citations (2)
| Title |
|---|
| 孙丽,等.一种新型吡咯并吡咯二酮衍生物的设计与合成.《精细化工》.2012,第29卷(第7期),625-631. * |
| 赵金龙.钯催化的碳氢活化反应研究.《中国博士学位论文全文数据库(工程科技Ⅰ辑)》.2012,(第1期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103012751A (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103012751B (en) | Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer | |
| CN103788111B (en) | Two-dimensional conjugated organic molecule photovoltaic material of a kind of solution processable and preparation method thereof and application | |
| CN109666033B (en) | Conjugated small molecule based on nona-fused heterocycle and preparation method and application thereof | |
| CN102391269B (en) | Zinc protoporphyrin containing heterocyclic ring as well as synthesis and applications of zinc protoporphyrin containing heterocyclic ring and metal complex of zinc protoporphyrin containing heterocyclic ring | |
| CN103435782B (en) | Organic semiconducting materials containing 9,9 '-difluorenylene and derivant thereof and preparation method thereof and application | |
| CN104086752A (en) | Benzodithiophene polymer, its preparation method, semiconductor composition containing it, and solar cell using it | |
| CN112094400B (en) | Orange red-green display electrochromic material based on quinacridone-bithiophene and preparation method thereof | |
| CN108948327A (en) | A kind of quinoxaline conjugated polymer and preparation method thereof and its application in polymer solar cells | |
| CN109796581B (en) | Narrow-band conjugated polymer containing low polyethylene glycol side chain structure and preparation method and application thereof | |
| CN103193912B (en) | Copolymer containing zinc-phthalocyanine group on side chain and preparation method thereof | |
| CN106188506A (en) | One class closes polymer-metal complex dye sensitizing agent of Cu (II) and preparation method thereof containing 8 8-hydroxyquinoline derivatives | |
| CN109748925A (en) | The aromatic condensed ring structure unit and its synthetic method and application that a kind of alkoxy replaces | |
| CN105153189A (en) | Narrow-band-gap oligomer containing quinone type Methyl-Dioxocyano-Pyridine unit, and preparation method and application thereof | |
| CN110408009A (en) | It is a kind of for improving the hole transmission layer and preparation method thereof of perovskite solar cell stability | |
| CN106977528A (en) | Organic dyestuff containing three Thienopyrroles thiophene and its application in DSSC | |
| CN103360397B (en) | Dithienyl pyrrolo-pyrrole-dione-naphthyl conjugate derivative and its preparation method and application | |
| CN103242526A (en) | Method for preparing light-responsive hyperbranched zinc phthalocyanine polymers | |
| CN108192083B (en) | Conjugated polymer containing trifluoromethyl as well as preparation method and application thereof | |
| CN102070771A (en) | Perylene diimide photoelectric functional materials and preparation method thereof | |
| CN107057399B (en) | Organic dyestuff and its preparation method and application based on asymmetric three Thienopyrroles | |
| CN104592499B (en) | Three bithiophene class conjugated polymer materials and preparation method and application | |
| CN103965449B (en) | A kind of containing iridium light functional polymer and preparation method thereof | |
| CN102295641A (en) | Star-type three-dimensional conjugate molecule based on triphenylamine-benzothiadiazole, and preparation method and application thereof | |
| CN101962380A (en) | Novel organic conjugated molecule and application thereof to organic solar cell | |
| CN108659019A (en) | Perovskite hole mobile material and preparation method thereof based on triptycene parent nucleus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150520 Termination date: 20151130 |
|
| EXPY | Termination of patent right or utility model |