CN106565940A - 一种高规整度头尾相接聚噻吩衍生物的制备方法 - Google Patents
一种高规整度头尾相接聚噻吩衍生物的制备方法 Download PDFInfo
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- CN106565940A CN106565940A CN201610882708.3A CN201610882708A CN106565940A CN 106565940 A CN106565940 A CN 106565940A CN 201610882708 A CN201610882708 A CN 201610882708A CN 106565940 A CN106565940 A CN 106565940A
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- 229920000123 polythiophene Polymers 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title description 26
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 229930192474 thiophene Natural products 0.000 claims abstract description 9
- 230000008878 coupling Effects 0.000 claims abstract description 6
- 238000010168 coupling process Methods 0.000 claims abstract description 6
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- 239000002994 raw material Substances 0.000 claims abstract description 6
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- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- -1 heteroalicyclic Chemical group 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 11
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- 101150003085 Pdcl gene Proteins 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- ZHGNHOOVYPHPNJ-UHFFFAOYSA-N Amigdalin Chemical compound FC(F)(F)C(=O)OCC1OC(OCC2OC(OC(C#N)C3=CC=CC=C3)C(OC(=O)C(F)(F)F)C(OC(=O)C(F)(F)F)C2OC(=O)C(F)(F)F)C(OC(=O)C(F)(F)F)C(OC(=O)C(F)(F)F)C1OC(=O)C(F)(F)F ZHGNHOOVYPHPNJ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
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- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 4
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 4
- 125000005152 trihalomethanesulfonyl group Chemical group 0.000 claims description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- QSVXMOKGHFNTEI-UHFFFAOYSA-N 2-bis[2-(dimethylamino)phenyl]phosphanyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1P(C=1C(=CC=CC=1)N(C)C)C1=CC=CC=C1N(C)C QSVXMOKGHFNTEI-UHFFFAOYSA-N 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910004373 HOAc Inorganic materials 0.000 claims description 2
- 125000005631 S-sulfonamido group Chemical group 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- LGVUAXNPXVXCCW-UHFFFAOYSA-M cesium;2,2-dimethylpropanoate Chemical compound [Cs+].CC(C)(C)C([O-])=O LGVUAXNPXVXCCW-UHFFFAOYSA-M 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Chemical group 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052711 selenium Chemical group 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 2
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P ORPNDFMZTDVBGA-UHFFFAOYSA-N 0.000 claims 1
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- 230000015572 biosynthetic process Effects 0.000 abstract description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 4
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- WQYWXQCOYRZFAV-UHFFFAOYSA-N 3-octylthiophene Chemical compound CCCCCCCCC=1C=CSC=1 WQYWXQCOYRZFAV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- WAOUDPOLPWAIGN-UHFFFAOYSA-N 3,4-dioctylthiophene Chemical compound CCCCCCCCC1=CSC=C1CCCCCCCC WAOUDPOLPWAIGN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- HMMGENQCQLCKQC-UHFFFAOYSA-N 3,4-bis(octylsulfonyl)thiophene Chemical compound CCCCCCCCS(=O)(=O)C1=CSC=C1S(=O)(=O)CCCCCCCC HMMGENQCQLCKQC-UHFFFAOYSA-N 0.000 description 1
- ZUDCKLVMBAXBIF-UHFFFAOYSA-N 3,4-dimethoxythiophene Chemical compound COC1=CSC=C1OC ZUDCKLVMBAXBIF-UHFFFAOYSA-N 0.000 description 1
- KBWHYRUAHXHHFO-UHFFFAOYSA-N 3-(bromomethyl)thiophene Chemical compound BrCC=1C=CSC=1 KBWHYRUAHXHHFO-UHFFFAOYSA-N 0.000 description 1
- RFSKGCVUDQRZSD-UHFFFAOYSA-N 3-methoxythiophene Chemical compound COC=1C=CSC=1 RFSKGCVUDQRZSD-UHFFFAOYSA-N 0.000 description 1
- SCDKSQGLSIZUKA-UHFFFAOYSA-N 3-octylsulfonylthiophene Chemical compound CCCCCCCCS(=O)(=O)C=1C=CSC=1 SCDKSQGLSIZUKA-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 1
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
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Abstract
一种高规整度头尾相接聚噻吩衍生物的制备方法，以取代噻吩为原料，在钯催化下直接C‑H/C‑H偶合缩聚制备多种聚噻吩衍生物，其合成通式如下所示：本发明的优点是：合成步骤简单、不需要对原料进行预处理，反应条件温和，反应效率高，制备的聚噻吩衍生物头尾相连的规整度高。
Description
技术领域
本发明涉及高分子聚合物材料的化学制备技术，特别是一种高规整度头尾相接聚噻吩衍生物的制备方法。
背景技术
聚(3-取代噻吩)(P3ST)具有优异的光电性质，良好的稳定性、溶解性和导电性以及可溶液加工等特点，已被广泛应用于有机光伏电池(OPV)、有机发光二极管(OLED)、有机场效应晶体管(OFET)和化学/生物传感器等各种光敏器件领域。大量的研究已经表明：影响P3ST光电性质的一个核心因素就是其聚合物的立体构型，立构规整性的P3ST具有更加优异的光电性能，而制备具有良好立体规整性的P3ST至今仍然是一个难题。这是由于3-位取代噻吩单体自身的不对称特点，并且噻吩的聚合反应一般都发生在噻吩环上更为活泼的2，5-位，因此必然导致噻吩单体偶合生成的聚合物中出现以下四种不同的连接方式，如下所示：
如果把噻吩环的2-位看作是“头”(Head)，5-位看作是“尾”(Tail)的话，那么这四种不同的连接方式可以分别简称为：头尾-头尾连接(HT-HT)、头尾-头头连接(HT-HH)、尾尾-头尾连接(TT-HT)和尾尾-头头连接(TT-HH)。在无规P3ST中，由于头头、尾尾键接方式使噻吩环之间空间扭转受阻，影响了聚合物的共平面性，进而阻碍了材料的紧密堆积，从而使材料的禁带宽度变宽，电导率降低。而等规P3ST中的头尾联接方式使其重复单元之间的空间位阻比较小，易于平面构型存在，这使其有效共轭长度增加，迁移率提高，带隙能降低，光谱红移。
为了制备区域规整性的P3ST，人们已经做了大量的研究工作，目前报道的主要合成方法如下所述：1)Fe(III)氧化合成法：这是最常采用的制备方法，该方法虽然合成路线简单、条件温和、对仪器设备要求低、产率和分子量较高等优势，但该方法重现性差，每一批次的样品有很大差异，而且合成的P3ST的规整性不高，还存在铁离子残留的问题。特别需要指出的是：这种聚合方法对3-位连有拉电子基团的噻吩单体不适用。2)Suzuki法、Stille法、McCullough法、Rieke法、GRIM法以及直接芳基化法等偶联聚合法。这些方法需要预先制备相应的金属有机化合物或卤代烃，单体合成方法严苛(如低温、无氧等)、步骤多、耗时、成本高，而且有些有机金属单体极不稳定不易合成，后续还存在聚合物需要封端和重金属污染等问题。另外，这些方法制备的P3ST衍生物其取代基主要为丁基、己基、辛基、十二烷基、环己基、苯基、烷氧基、烷硫基等供电子基团，而3-位以拉电子基团为取代基的研究相对较少，目前报道的含有酯基、亚胺等的P3ST衍生物主要采用Suzuki和Stille偶联聚合法。因此，打破单体选择的局限性，发展绿色、高效、低成本的聚合方法，制备3-位连有拉电子基团的高规整度的P3ST衍生物仍然是迫切的。
发明内容
本发明的目的是针对上述存在问题，提供一种高规整度头尾相接聚噻吩衍生物的制备方法，该方法基于钯催化氧化C-H/C-H偶合缩聚法制备，具有简洁、高效、环境友好等特点，有利于降低生产成本和工艺难度。
本发明的技术方案：
一种高规整度头尾相接聚噻吩衍生物的制备方法，以硫基取代的噻吩为原料，在钯催化下直接C-H/C-H偶合缩聚制备多种聚噻吩衍生物，其合成通式如下所示：
其中：R1和R2为H、C1-C30烷基、C1-C30烷基取代基、C3-C30环烷基、C3-C30环烷基取代基、C1-C30烷氧基、C1-C30烷硫基、C1-C30烷胺基、卤代C1-C30烷基、卤代C3-C30环烷基、卤代C1-C30烷氧基或卤代C1-C30烷硫基，且R1与R2可以相同也可以不同；烷基基团为取代或未取代，当烷基基团被取代时，取代基团为环烷基、芳基、杂芳基、杂脂环基、羟基、烷氧基、烷胺基、芳氧基、巯基、烷硫基、芳硫基、氰基、卤代、羰基、硫代羰基、O-氨基甲酰基、N-氨基甲酰基、O-硫代氨基甲酰基、N-硫代氨基甲酰基、C-酰氨基、N-酰氨基、S-亚磺酰氨基、N-亚磺酰氨基、C-羧基、O-羧基、异氰酸根合、氰硫基、异硫氰酸根合、硝基、甲硅烷基或三卤代甲烷磺酰基；环烷基基团为取代或未取代，当环烷基基团被取代时，取代基团为环烷基、芳基、杂芳基、杂脂环基、羟基、烷氧基、芳氧基、巯基、烷硫基、芳硫基、氰基、卤代、羰基、硫代羰基、O-氨基甲酰基、N-氨基甲酰基、O-硫代氨基甲酰基、N-硫代氨基甲酰基、C-酰氨基、N-酰氨基、S-亚磺酰氨基、N-亚磺酰氨基、C-羧基、O-羧基、异氰酸根合、氰硫基、异硫氰酸根合、硝基、甲硅烷基或三卤代甲烷磺酰基；X为硫、氮、氧或硒原子；n为0–2；m为0–2；具体制备步骤如下：
1)将取代噻吩、钯催化剂、氧化剂、碱、添加剂和溶剂加入反应容器中，氮气保护下、在30-150℃温度下反应1-72小时，得到反应液；
2)将上述反应液冷却至室温后倒入甲醇中，抽滤后将滤饼利用索氏提取器依次用甲醇、正己烷和氯仿提取，收集氯仿提取液；
3)将上述氯仿提取液浓缩至原体积的五十分之一，将浓缩液冷却至室温后直接滴入甲醇中，浓缩液与甲醇的体积比为1：30，静置沉淀，溶液变澄清后抽滤，滤饼在60℃真空干燥箱中干燥12h，制得固体粉末即为高规整度头尾相接聚噻吩衍生物。
所述钯催化剂为Pd(dppf)Cl2、Pd(OAc)2、PdCl2、PdCl2(MeCN)2、PdCl2(PhCN)2、Pd(OPiv)2、Pd2(dba)3、Pd(TFA)2、PdCl2(PPh3)2、Pd(OH)2、Pd(PPh3)4、Pd/C和反式—二(μ-乙酸)双[2-(二邻甲苯基膦)苄基]二钯(II)中的一种或两种以上任意比例的混合物；所述氧化剂为Ag2CO3、AgF、AgOAc、AgOTf、Ag2O、AgBF4、Cu(OAc)2、Cu(OTf)2、CuCl2、BQ(对苯醌)、K2S2O8和TBHP(过氧化叔丁醇)中的一种或两种以上任意比例的混合物；所述碱为Li2CO3、Na2CO3、K2CO3、Cs2CO3、NaHCO3、NaOAc、KOAc、CsOAc、K2HPO4、K3PO4、CsOPiv、KF和NEt3中的一种或两种以上任意比例的混合物；所述添加剂为PPh3、PCy3、P(t-Bu)3、三(邻甲氧基苯基)膦、三(邻(N,N-二甲胺基)苯基)膦、三(对甲基苯基)膦、三叔丁基膦氟硼酸盐、三环己基膦氟硼酸盐、PivOH(新戊酸)、TFA、HOAc、PTSA(对甲苯磺酸)、金刚烷酸、四丁基溴化铵和十六烷基三甲基溴化铵中的一种或两种以上任意比例的混合物；所述溶剂为甲苯、1，4-二氧六环、邻二甲苯、二甲苯、四氢呋喃、N、N-二甲基乙酰胺、N、N-二甲基甲酰胺和N-甲基-2-吡咯烷酮中的一种或两种以上任意比例的混合物。
所述反应液中3-位取代噻吩、钯催化剂、氧化剂、碱、添加剂的摩尔比为1：(0.0001-20)：(0.01-10)：(0-10)：(0-10)，反应液中3-位取代噻吩的浓度为0.01-1mol/L。
本发明的优点是：与现有技术路线相比，本发明具有简洁、高效、环境友好等特点，有利于降低生产成本和工艺难度。具体表现在：
1)所需原料简单易得，本专利不需要对原料进行预处理，可以直接进行聚合，而传统路线中合成该类化合物一般都要制备金属锡化物、硼化物或者卤代物；
2)避免了使用对空气敏感的试剂(如正丁基锂等)、有毒金属试剂以及产生有毒副产物等；尤其是可以兼容传统方法中拉电子基团，这些基团对调整和提高分子的材料性能具有潜在的重要价值；
3)该方法反应结束后不需要封端处理，这比其它聚合方法后处理简单，有助于大大提高材料的性能；
4)本专利制备的聚噻吩的规整度较高，可达99％，这对材料光电性能的提高具有重要的价值。
附图说明
图1为实施例1制备的聚合物的1H NMR图。
具体实施方式
下面结合具体实施方式对本发明作进一步描述，将有助于对本发明的理解。但并不能以此来限制本发明的权利范围，而本发明的权利范围应以权利要求书阐述的为准。
实施例1：
一种高规整度头尾相接聚噻吩衍生物的制备方法，所述聚噻吩衍生物的化学结构式如下：
结构式中：R1为H，R2为C8H17，X为S，n＝0，m＝2；
其制备步骤如下：
1)将3-甲氧基噻吩4.60g(40mmol)、正辛基硫醇14g(96mmol)和对甲苯磺酸0.60g溶于150mL干燥的甲苯中，80℃、氮气保护下磁力搅拌20h后，将反应液冷却到室温，旋蒸除去甲苯，剩余液用200mL水洗，分别用50mL乙醚萃取三次，有机相依次用饱和NaHCO3洗、盐水洗，MgSO4干燥，有机相旋转除去低沸点溶剂后，用减压蒸馏除去反应中过量的正辛基硫醇，残留液通过硅胶柱，石油醚做提取液，最后得无色液体3-辛硫基噻吩8.40g，产率：92％。1HNMR(400MHz,CDCl3)δ7.29(dd,J＝5.0,3.0Hz,1H),7.10(dd,J＝3.0Hz,1H),7.01(d,J＝5.0Hz,1H),2.83(td,J＝7.5Hz,2H),1.61(dd,J＝7.5Hz,2H),1.44–1.36(m,2H),1.26(s,8H),0.91–0.85(m,3H).13C NMR(100MHz,CDCl3)δ132.40(s),129.65(s),126.00(s),122.81(s),35.34(s),31.84(s),29.43(s),29.20(d),28.76(s),22.70(s),14.15(s).
2)将3-辛硫基噻吩1.0g(4.4mmol)溶于20mL CHCl3中，在0℃下分批加入纯度为75％的间氯过氧苯甲酸2.5g(10.8mmol)，室温下搅拌8-10小时；然后将反应液用饱和碳酸钠洗，用乙酸乙酯萃取，无水Na2SO4干燥，浓缩后得到无色液体1.1g，产率：96％。1H NMR(400MHz,CDCl3)δ8.07(s,1H),7.50–7.45(m,1H),7.39(d,1H),3.16–3.06(m,2H),1.73(dd,2H),1.36(d,2H),1.24(s,8H),0.87(t,3H).13C NMR(100MHz,CDCl3)δ139.77(s),132.54(s),128.37(s),126.01(s),56.59(s),31.65(s),28.92(d),28.20(s),22.62(d),14.07(s).
3)将3-辛基磺酰噻吩0.3g(1.15mmol)、醋酸铜0.46g(2.3mmol)、碳酸钾0.33g(2.4mmol)溶于4mL THF中，在90℃加热溶解，然后将溶于1mL THF的8.5mg醋酸钯的溶液加入反应瓶中，继续90℃搅拌，反应72小时；反应液冷却后倒入60mL甲醇中，抽滤，滤饼用索氏提取器提取，用甲醇、正己烷除去催化剂和低分子量的物质，最后用氯仿提取，收集氯仿提取液。旋蒸到剩2mL时，冷却后直接滴入60mL甲醇中，静置沉淀，溶液变澄清后抽滤，滤饼在60℃真空干燥箱中干燥12h，得黑红色固体目标产物0.298g，产率：99％(Mn＝9.7kDa，PDI＝1.71.)。1H NMR(400MHz,CDCl3)δ7.77(d,1H),3.21–2.91(m,2H),1.71(s,2H),1.26(d,10H),0.80(s,3H).
图1为制备的聚合物的1HNMR，图中表明：1H NMR(400MHz,CDCl3)δ7.77(d,1H),3.21–2.91(m,2H),1.71(s,2H),1.26(d,10H),0.80(s,3H).根据文献报道的方法，可知其立构规整度高达99％。
实施例2：
一种高规整度头尾相接聚噻吩衍生物的制备方法，所述聚噻吩衍生物的化学结构式如下：
结构式中：R1为H，R2为C8H17，X为S，n＝0，m＝1
其制备步骤如下：
1)将3-辛硫基噻吩1.0g(4.4mmol)溶于20mL CHCl3中，在0℃下分批加入纯度为75％的间氯过氧苯甲酸1.0g(4.4mmol)，加完后升至室温搅拌2小时。反应液用饱和碳酸钠洗，用乙酸乙酯萃取，无水Na2SO4干燥，浓缩，柱层析，石油醚作淋洗液，得到无色液体0.85g，产率：79％。1H NMR(400MHz,CDCl3)δ7.77(dd,J＝2.7,1.5Hz,1H),7.52(dd,J＝4.5,1.8Hz,1H),7.31–7.22(m,1H),3.08–2.74(m,2H),1.81–1.58(m,2H),1.35(dd,J＝63.6,3.8Hz,10H),0.88(dd,J＝4.7,2.2Hz,3H).13C NMR(100MHz,CDCl3)δ143.28(s),128.38(s),125.99(s),122.98(s),56.54(s),31.71(s),29.07(d,J＝14.0Hz),28.65(s),22.60(s),22.26(s),14.09(s).
2)将3-辛基亚砜基噻吩0.1g(0.41mmol)、醋酸钯4.6mg(20.5umol)、碳酸银0.22g(0.82mmol)、醋酸钾0.08g(0.82mmol)溶于2mLTHF中，在90℃加热溶解搅拌，反应48小时；反应液冷却后倒入60mL甲醇中，抽滤，滤饼用索氏提取器提取，依次用甲醇、正己烷和氯仿提取，收集氯仿提取液；再次用2mL氯仿溶解，滴入60mL甲醇中，静置沉淀，溶液变澄清后抽滤，滤饼在60℃真空干燥箱中干燥12h，得黑红色固体目标产物0.052g，产率：52％，(Mn＝6.9kDa，PDI＝1.76.)。1H NMR(400MHz,CDCl3)δ7.83–7.43(m,1H),3.25–2.82(m,2H),1.75(dd,J＝16.0,7.9Hz,2H),1.55–1.14(m,10H),0.86(s,3H).
实施例3：
一种高规整度头尾相接聚噻吩衍生物的制备方法，所述聚噻吩衍生物的化学结构式如下：
结构式中：R1为H、R2为C8H17、X为S，n＝1，m＝0
其制备步骤如下：
1)在100mL三口烧瓶中加入5mL甲醇，将钠0.13g切丝加入，等钠丝反应消失后，反应瓶转入冰水浴中，缓慢滴加正辛基硫醇0.83g(5.6mmol)，滴加完后继续磁力搅拌1小时，缓慢滴加3-溴甲基噻吩1.0g(5.6mmol)，滴加完成后提至室温，搅拌8-10小时，旋蒸除去甲醇，剩余液用200mL水洗，分别用50mL二氯甲烷萃取三次，水洗，有机相用Na2SO4干燥，过滤，浓缩，柱层析，石油醚作淋洗液，最后得无色液体3-辛硫基甲基噻吩1.15g，产率：85％。1HNMR(400MHz,CDCl3)δ7.31–7.22(m,1H),7.12–7.01(m,2H),3.72(s,2H),2.47–2.37(m,2H),1.60–1.47(m,2H),1.35–1.30(m,2H),1.27(d,J＝16.3Hz,8H),0.88(t,J＝6.9Hz,3H).13CNMR(100MHz,CDCl3)δ139.06(s),128.21(s),125.95(s),122.08(s),31.84(s),31.52(s),30.78(s),29.23(d,J＝2.5Hz),28.92(s),22.69(s),14.15(s).
2)3-辛硫基甲基噻吩0.1g(0.41mmol)、醋酸钯4.6mg(20.5umol)、碳酸银0.22g(0.82mmol)、醋酸钾0.08g(0.82mmol)溶于2mLTHF中，在90℃加热溶解搅拌，反应48小时。反应液冷却后倒入60mL甲醇中，抽滤，滤饼，滤液旋蒸，抽真空，得红色液体状目标产物0.025g，产率：25％，(Mn of3～4kDa，PDI＝1.00.)。
实施例4：
一种高规整度头尾相接聚噻吩衍生物的制备方法，所述聚噻吩衍生物的化学结构式如下：
结构式中：R1为H，R2为C8H17，X为S，n＝1，m＝1
其制备步骤如下：
1)将3-辛硫基甲基噻吩1.0g(4.1mmol)溶于20mL CHCl3中，在0℃下分批加入纯度为75％的间氯过氧苯甲酸0.94g(4.1mmol)，加完后反应提至室温搅拌8-10小时反应液用饱和碳酸钠洗，用乙酸乙酯萃取，无水Na2SO4干燥，浓缩后得到无色液体0.76g，产率：72％。1HNMR(400MHz,CDCl3)δ7.36(dd,J＝4.9,3.0Hz,1H),7.27(d,J＝1.6Hz,1H),7.06(dd,J＝4.9,1.2Hz,1H),4.04(s,2H),2.57(dt,J＝8.9,6.3Hz,2H),1.73(dt,J＝16.2,7.5Hz,2H),1.49–1.34(m,2H),1.27(dd,J＝8.1,5.5Hz,8H),0.88(t,J＝6.9Hz,3H).13C NMR(100MHz,CDCl3)δ129.69(s),128.52(s),126.71(s),125.08(s),52.35(s),50.96(s),31.73(s),30.06–28.38(m),22.54(d,J＝15.9Hz),14.10(s).
2)将3-辛亚砜基甲基噻吩0.1g(0.38mmol)、醋酸钯4.2mg(19.0umol)、碳酸银0.21g(0.76mmol)、醋酸钾0.074g(0.76mmol)溶于2mLTHF中，在90℃加热溶解搅拌，反应48小时；反应液冷却后倒入60mL甲醇中，抽滤，滤饼，滤液旋蒸，抽真空，得红色液体状目标产物0.02g，产率：20％，(Mn of2～4kDa，PDI＝1.00.)。
实施例5：
一种高规整度头尾相接聚噻吩衍生物的制备方法，所述聚噻吩衍生物的化学结构式如下：
结构式中：R1为SO2C8H17，R2为C8H17，X为S，n＝0，m＝2
其制备步骤如下：
1)将3，4-二甲氧基噻吩2.0g(13.8mmol)、正辛基硫醇10.1g(69mmol)与对甲苯磺酸0.50g溶于25mL干燥的甲苯中，80℃，氮气保护下磁力搅拌20h后，反应液冷却到室温下，旋蒸除去甲苯，剩余液用200mL水洗，分别用50mL乙醚萃取三次，有机相用饱和NaHCO3洗，盐水洗，MgSO4干燥，有机相旋转除去低沸点溶剂后，用减压蒸馏除去反应中过量的正辛基硫醇，残留液通过硅胶柱，石油醚做提取液，最后得无色液体3，4-二辛硫基噻吩5.57g，产率：75％。1H NMR(400MHz,CDCl3)δ7.08(s,2H),2.86(t,J＝7.4Hz,4H),1.67–1.60(m,4H),1.45–1.39(m,4H),1.27(s,16H),0.88(t,J＝6.8Hz,6H).13C NMR(100MHz,CDCl3)δ133.98(s),122.89(s),77.37(s),77.05(s),76.74(s),34.42(s),31.83(s),29.29–28.74(m),22.67(s),14.11(s).
2)将3，4-二辛硫基噻吩2.0g(13.8mmol)和三水合三氯化钌2.0g(13.8mmol)溶于10mL体积比1:1的丙酮-水的混合液中，室温下搅拌直至其全部溶解，将反应液冷却到0℃左右，分批加入高碘酸钠2.0g(13.8mmol)，加完后反应在室温下搅拌5h。反应液用饱和NaHSO3洗，乙醚萃取，无水Na2SO4干燥，粗产品柱层析，石油醚/乙酸乙酯＝3：1，得白色固体1.0g，产率：94％。1H NMR(400MHz,CDCl3)δ8.30(s,2H),3.58–3.51(m,4H),1.71(dd,4H),1.37(dd,4H),1.31–1.21(m,16H),0.86(t,6H).13C NMR(100MHz,CDCl3)δ139.01(s),137.68(s),77.35(s),77.03(s),76.72(s),55.86(s),31.67(s),28.94(d),28.13(s),22.54(d),14.08(s).
3)将3，4-二辛基磺酰噻吩300mg(0.68mmol)、碳酸银379mg(1.36mmol)、醋酸钾135mg(1.36mmol)溶于5mLDMAc中，在110℃加热溶解，然后将溶于1mLDMAc的28mg Pd(dppf)Cl2的溶液加入反应瓶中，继续110℃搅拌，反应48小时，反应液冷却后倒入60mL甲醇中，抽滤，滤饼，滤液旋蒸，抽真空，制得红色液体状目标产物0.01g，产率：10％，(Mn of 1～3kDa，PDI＝1.00.)。
从前述中可以理解，尽管为了示例性说明的目的描述了本发明的具体实施方案，但是在不偏离本发明的精神和范围的条件下，本领域所述技术人员可以作出各种变形或改进。这些变形或修改都应落入本申请所附权利要求的范围。
Claims (3)
1.一种高规整度头尾相接聚噻吩衍生物的制备方法，其特征在于以硫基取代的噻吩为原料，在钯催化下直接C-H/C-H偶合缩聚制备多种聚噻吩衍生物，其合成通式如下所示：
其中：R1和R2为H、C1-C30烷基、C1-C30烷基取代基、C3-C30环烷基、C3-C30环烷基取代基、C1-C30烷氧基、C1-C30烷硫基、C1-C30烷胺基、卤代C1-C30烷基、卤代C3-C30环烷基、卤代C1-C30烷氧基或卤代C1-C30烷硫基，且R1与R2可以相同也可以不同；烷基基团为取代或未取代，当烷基基团被取代时，取代基团为环烷基、芳基、杂芳基、杂脂环基、羟基、烷氧基、烷胺基、芳氧基、巯基、烷硫基、芳硫基、氰基、卤代、羰基、硫代羰基、O-氨基甲酰基、N-氨基甲酰基、O-硫代氨基甲酰基、N-硫代氨基甲酰基、C-酰氨基、N-酰氨基、S-亚磺酰氨基、N-亚磺酰氨基、C-羧基、O-羧基、异氰酸根合、氰硫基、异硫氰酸根合、硝基、甲硅烷基或三卤代甲烷磺酰基；环烷基基团为取代或未取代，当环烷基基团被取代时，取代基团为环烷基、芳基、杂芳基、杂脂环基、羟基、烷氧基、芳氧基、巯基、烷硫基、芳硫基、氰基、卤代、羰基、硫代羰基、O-氨基甲酰基、N-氨基甲酰基、O-硫代氨基甲酰基、N-硫代氨基甲酰基、C-酰氨基、N-酰氨基、S-亚磺酰氨基、N-亚磺酰氨基、C-羧基、O-羧基、异氰酸根合、氰硫基、异硫氰酸根合、硝基、甲硅烷基或三卤代甲烷磺酰基；X为硫、氮、氧或硒原子；n为0–2；m为0–2；具体制备步骤如下：
1)将取代噻吩、钯催化剂、氧化剂、碱、添加剂和溶剂加入反应容器中，氮气保护下、在30-150℃温度下反应1-72小时，得到反应液；
2)将上述反应液冷却至室温后倒入甲醇中，抽滤后将滤饼利用索氏提取器依次用甲醇、正己烷和氯仿提取，收集氯仿提取液；
3)将上述氯仿提取液浓缩至原体积的五十分之一，将浓缩液冷却至室温后直接滴入甲醇中，浓缩液与甲醇的体积比为1：30，静置沉淀，溶液变澄清后抽滤，滤饼在60℃真空干燥箱中干燥12h，制得固体粉末即为高规整度头尾相接聚噻吩衍生物。
2.根据权利要求1所述高规整度头尾相接聚噻吩衍生物的制备方法，其特征在于：所述钯催化剂为Pd(dppf)Cl2、Pd(OAc)2、PdCl2、PdCl2(MeCN)2、PdCl2(PhCN)2、Pd(OPiv)2、Pd2(dba)3、Pd(TFA)2、PdCl2(PPh3)2、Pd(OH)2、Pd(PPh3)4、Pd/C和反式—二(μ-乙酸)双[2-(二邻甲苯基膦)苄基]二钯(II)中的一种或两种以上任意比例的混合物；所述氧化剂为Ag2CO3、AgF、AgOAc、AgOTf、Ag2O、AgBF4、Cu(OAc)2、Cu(OTf)2、CuCl2、BQ(对苯醌)、K2S2O8和TBHP(过氧化叔丁醇)中的一种或两种以上任意比例的混合物；所述碱为Li2CO3、Na2CO3、K2CO3、Cs2CO3、NaHCO3、NaOAc、KOAc、CsOAc、K2HPO4、K3PO4、CsOPiv、KF和NEt3中的一种或两种以上任意比例的混合物；所述添加剂为PPh3、PCy3、P(t-Bu)3、三(邻甲氧基苯基)膦、三(邻(N,N-二甲胺基)苯基)膦、三(对甲基苯基)膦、三叔丁基膦氟硼酸盐、三环己基膦氟硼酸盐、PivOH(新戊酸)、TFA、HOAc、PTSA(对甲苯磺酸)、金刚烷酸、四丁基溴化铵和十六烷基三甲基溴化铵中的一种或两种以上任意比例的混合物；所述溶剂为甲苯、1，4-二氧六环、邻二甲苯、二甲苯、四氢呋喃、N、N-二甲基乙酰胺、N、N-二甲基甲酰胺和N-甲基-2-吡咯烷酮中的一种或两种以上任意比例的混合物。
3.根据权利要求1所述高规整度头尾相接聚噻吩衍生物的制备方法，其特征在于：所述反应液中3-位取代噻吩、钯催化剂、氧化剂、碱、添加剂的摩尔比为1：(0.0001-20)：(0.01-10)：(0-10)：(0-10)，反应液中3-位取代噻吩的浓度为0.01-1mol/L。
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| CN118772380A (zh) * | 2023-04-03 | 2024-10-15 | 天津理工大学 | 酯基取代聚噻吩的制备方法 |
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