CN108774246B - 并五噻吩同分异构体及其制备方法和应用 - Google Patents
并五噻吩同分异构体及其制备方法和应用 Download PDFInfo
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- CN108774246B CN108774246B CN201810662121.0A CN201810662121A CN108774246B CN 108774246 B CN108774246 B CN 108774246B CN 201810662121 A CN201810662121 A CN 201810662121A CN 108774246 B CN108774246 B CN 108774246B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229930192474 thiophene Natural products 0.000 claims abstract description 23
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 19
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- BDIWFCKBPZPBQT-UHFFFAOYSA-N tributyl(tributylstannylsulfanyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)S[Sn](CCCC)(CCCC)CCCC BDIWFCKBPZPBQT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 79
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 72
- 150000001875 compounds Chemical class 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 229910052786 argon Inorganic materials 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 238000010791 quenching Methods 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 23
- 230000000171 quenching effect Effects 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- HXOBTUJUBCBBAP-UHFFFAOYSA-N (4,5-dibromothiophen-2-yl)-trimethylsilane Chemical compound BrC=1C=C(SC=1Br)[Si](C)(C)C HXOBTUJUBCBBAP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 10
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 15
- 239000004065 semiconductor Substances 0.000 abstract description 15
- 230000005669 field effect Effects 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 3
- GKTQKQTXHNUFSP-UHFFFAOYSA-N thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)NC(=O)C2=C1 GKTQKQTXHNUFSP-UHFFFAOYSA-N 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 74
- 239000012074 organic phase Substances 0.000 description 57
- 239000012043 crude product Substances 0.000 description 49
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 33
- 238000001035 drying Methods 0.000 description 33
- 238000001914 filtration Methods 0.000 description 30
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 30
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 30
- 239000002904 solvent Substances 0.000 description 29
- 239000008346 aqueous phase Substances 0.000 description 28
- 239000007787 solid Substances 0.000 description 26
- 238000001819 mass spectrum Methods 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- 238000004440 column chromatography Methods 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 20
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 19
- 239000012071 phase Substances 0.000 description 19
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 15
- 229910002027 silica gel Inorganic materials 0.000 description 15
- 239000003480 eluent Substances 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 8
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 230000008034 disappearance Effects 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 4
- SVQNAHBAWUFDCX-UHFFFAOYSA-N 5,7,12,14-tetrathiatetracyclo[6.6.0.02,6.09,13]tetradeca-1(8),2(6),3,9(13),10-pentaene Chemical compound S1C2=C(C=C1)C=1SC=3SC=CC=3C=1S2 SVQNAHBAWUFDCX-UHFFFAOYSA-N 0.000 description 4
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 4
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 4
- 229940125773 compound 10 Drugs 0.000 description 4
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- 229940125833 compound 23 Drugs 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 4
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 3
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 3
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 3
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- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 3
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229940126657 Compound 17 Drugs 0.000 description 3
- YCJCKABRKZLYLG-UHFFFAOYSA-N S1C=CC2=C1C(SC1=C3C=CS1)=C3S2 Chemical compound S1C=CC2=C1C(SC1=C3C=CS1)=C3S2 YCJCKABRKZLYLG-UHFFFAOYSA-N 0.000 description 3
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- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
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- RZQBGNNDFBGXAZ-UHFFFAOYSA-N trimethyl-(6-trimethylsilyl-3,5,10,13,17-pentathiapentacyclo[9.6.0.02,9.04,8.012,16]heptadeca-1(11),2(9),4(8),6,12(16),14-hexaen-14-yl)silane Chemical compound C[Si](C1=CC2=C(C=3SC4=C(C=3S2)SC2=C4C=C(S2)[Si](C)(C)C)S1)(C)C RZQBGNNDFBGXAZ-UHFFFAOYSA-N 0.000 description 3
- ZJVFWBNFSVYISQ-UHFFFAOYSA-N 3,5,10,13,17-pentathiapentacyclo[9.6.0.02,9.04,8.012,16]heptadeca-1(11),2(9),4(8),6,12(16),14-hexaene Chemical compound S1C=CC2=C1C=1SC3=C(C=1S2)SC1=C3C=CS1 ZJVFWBNFSVYISQ-UHFFFAOYSA-N 0.000 description 2
- PPYOQBACCFTULQ-UHFFFAOYSA-N 4,8,10,12,16-pentathiapentacyclo[9.6.0.02,9.03,7.013,17]heptadeca-1(11),2(9),3(7),5,13(17),14-hexaene Chemical compound S1C=CC2=C1C1=C(SC3=C1C1=C(S3)C=CS1)S2 PPYOQBACCFTULQ-UHFFFAOYSA-N 0.000 description 2
- FEEPNBCHCRZKTA-UHFFFAOYSA-N 4,8,10,15,17-pentathiapentacyclo[9.6.0.02,9.03,7.012,16]heptadeca-1(11),2(9),3(7),5,12(16),13-hexaene Chemical compound S1C=CC2=C1SC=1C3=C(SC=12)SC1=C3SC=C1 FEEPNBCHCRZKTA-UHFFFAOYSA-N 0.000 description 2
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- 229960001701 chloroform Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- VGWBXRXNERKBSJ-UHFFFAOYSA-N dithieno[2,3-a:2',3'-d]thiophene Chemical compound C1=CSC2=C1SC1=C2SC=C1 VGWBXRXNERKBSJ-UHFFFAOYSA-N 0.000 description 2
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 2
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UTWCBAHFXFTRHG-UHFFFAOYSA-N 2,3,5-trimethylhexane-2,3-diol Chemical compound CC(C)CC(C)(O)C(C)(C)O UTWCBAHFXFTRHG-UHFFFAOYSA-N 0.000 description 1
- FRYRJNHMRVINIZ-UHFFFAOYSA-N B1CCOO1 Chemical compound B1CCOO1 FRYRJNHMRVINIZ-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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Abstract
本发明涉及并五噻吩同分异构体及其制备方法和应用,制备方法为:S1:将5‑三甲基硅基‑3‑溴‑2‑(5‑(三甲基硅基)噻吩‑3)‑二噻吩并[3,2‑b:2',3'‑d]噻吩或其同分异构体先加入烷基锂反应,再加入(PhSO2)2S关环;或将5‑三甲基硅基‑3‑溴‑2‑(5‑(三甲基硅基)噻吩‑3)‑二噻吩并[3,2‑b:2',3'‑d]噻吩或其同分异构体先加入LDA、C2Br2Cl4反应,再利用二(三丁基锡)硫醚、四三苯基磷钯或醋酸钯反应,制得2,7‑二(三甲基硅基)‑噻吩并[2',3':4,5]噻吩并[3,2‑b]噻吩并[3',2':4,5]噻吩并[2,3‑d]噻吩或其同分异构体;S2:将S1的产物脱TMS制得并五噻吩同分异构体。本发明制备的并五噻吩同分异构体可以作为有机半导体材料应用于有机场效应晶体管中。
Description
技术领域
本发明涉及并五噻吩同分异构体及其制备方法和应用,属于有机化合物的制备技术领域。
背景技术
噻吩稠环化合物作为新型的有机半导体材料受到人们的重视。并五噻吩作为并五苯的类似物,它由五个噻吩环稠合在一起,它有20种同分异构体,但是目前只有一种(化合物1)被合成。文献J.Am.Chem.Soc.,2005,127,13281(K.Xiao,Y.Liu,T.Qi,W.Zhang,F.Wang,J.Gao,W.Qiu,Y.Ma,G.Cui,S.Chen,X.Zhan,G.Yu,J.Qin,W.Hu,D.Zhu,)报道了化合物1的合成,方法如下:于噻吩并[3,2-b]噻吩在三氯甲烷中加入液溴得到2,3,5-三溴噻吩并[3,2-b]噻吩,于2,3,5-三溴噻吩并[3,2-b]噻吩中加入Zn粉、在醋酸溶液中加热回流得到3-溴噻吩并[3,2-b]噻吩,将3-溴噻吩并[3,2-b]噻吩在-78℃下逐滴加入n-BuLi反应40min,加入(PhSO2)2S在-78℃下搅拌1h,慢慢升至室温反应12h得到硫醚化合物,硫醚化合物在-10℃逐滴加入n-BuLi反应2h,加入CuCl2在室温下反应20h,得到化合物1,产率为21%,反应式如下式所示。
发明内容
本发明要解决的技术问题是:为解决现有技术中只有一种并五噻吩同分异构体被合成的技术问题,提供并五噻吩同分异构体及其制备方法和应用,以提供更多高性能的有机半导体材料。
本发明解决其技术问题所采用的技术方案是:
一种并五噻吩同分异构体的制备方法,该方法包括如下步骤:
S1:将或其同分异构体在惰性气体保护及有机溶剂存在的条件下,先在-90~-60℃的温度下加入烷基锂反应,再加入关环试剂(PhSO2)2S升至室温反应,最后加入淬灭剂淬灭反应,反应液经后处理得或其同分异构体;
或将或其同分异构体在惰性气体保护及有机溶剂存在的条件下,先在-90~-60℃的温度下加入LDA反应,再加入溴代试剂C2Br2Cl4升至室温反应,最后加入淬灭剂淬灭反应,反应液经后处理得或其同分异构体,再将或其同分异构体在惰性气体保护、有机溶剂及二(三丁基锡)硫醚存在的条件下,加入四三苯基磷钯或醋酸钯,在85-105℃下反应,反应液经后处理得或其同分异构体;
优选地,所述S1步骤中烷基锂为正丁基锂或特丁基锂,惰性气体为氩气或氮气;所述或其同分异构体与烷基锂、(PhSO2)2S的摩尔比为1:1.1-4.1:0.8-1.0;或其同分异构体与LDA、C2Br2Cl4的摩尔比为1:2.0-3.2:1-3;或其同分异构体与二(三丁基锡)硫醚、四三苯基磷钯或醋酸钯的摩尔比为1:0.8-1.2:0.06-0.08;
优选地,所述或其同分异构体的制备方法为:于或其同分异构体中加入5-三甲基硅基-3-(4,4,5,5,-四甲基-1,3,2-二氧杂环戊硼烷基)噻吩、碳酸盐、四三苯基磷钯或醋酸钯,在惰性气体保护下加入有机溶剂及无氧水,在85-105℃温度下反应,反应液经后处理制得;所述的同分异构体为 中的一种。
优选地,所述碳酸盐为K2CO3、Na2CO3或CsCO3,所述或其同分异构体与5-三甲基硅基-3-(4,4,5,5,-四甲基-1,3,2-二氧杂环戊硼烷基)噻吩、碳酸盐、四三苯基磷钯或醋酸钯的摩尔比为1:0.9-1.3:2.2-2.8:0.02-0.08。
优选地,所述或其同分异构体的制备方法为:将或其同分异构体在惰性气体保护及有机溶剂存在的条件下,-90~-60℃的温度下加入LDA反应,再加入碘升至室温反应,淬灭反应,反应液经后处理制得;所述为 中的一种,所述或其同分异构体与LDA、碘反应的摩尔比为1:1.2-1.8:1.0-1.5。
优选地,所述的制备方法为:于中加入2,3-二溴-5-三甲基硅基-噻吩、碳酸盐、四三苯基磷钯或醋酸钯,在惰性气体保护下加入有机溶剂及无氧水,在85-105℃温度下反应,反应液经后处理制得;所述碳酸盐为K2CO3、Na2CO3或CsCO3。
优选地,所述有机溶剂为乙醚、甲苯、三氯甲烷、二氯甲烷、四氢呋喃中的至少一种,所述淬灭剂为甲醇、水、饱和亚硫酸钠溶液、饱和硫代硫酸钠溶液中的至少一种。
本发明的有益效果是:
本发明采用全新的方法来合成并五噻吩同分异构体,原料易得,适用于大规模生产,制备得到的全新的并五噻吩同分异构体可以作为有机半导体材料应用于有机场效应晶体管中,具有优良的性能,在基底温度为室温时获得的性能为:迁移率0.006~0.06cm2/V/s,阈值电压-50~-10V,开关比104~105。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1是本发明化合物2的核磁共振氢谱图;图2为本发明化合物2的核磁共振碳谱图;图3为本发明化合物2的高分辨质谱图;图4为本发明化合物3的核磁共振氢谱图;图5为本发明化合物3的核磁共振碳谱图;图6为本发明化合物3的高分辨质谱图;图7为本发明化合物4的核磁共振氢谱图;图8为本发明化合物4的核磁共振碳谱图;图9为本发明化合物4的高分辨质谱图;图10为本发明化合物5的核磁共振氢谱图;图11为本发明化合物5的核磁共振碳谱图;图12为本发明化合物5的高分辨质谱图;图13为本发明化合物PTA-1的高分辨质谱图;图14为本发明化合物PTA-1的红外光谱图;图15为本发明所涉及化合物7的核磁共振氢谱图;图16为本发明所涉及化合物7的核磁共振碳谱图;图17为本发明所涉及化合物7的高分辨质谱图;图18为本发明所涉及化合物8的核磁共振氢谱图;图19为本发明所涉及化合物8的核磁共振碳谱图;图20为本发明所涉及化合物8的高分辨质谱图;图21为本发明所涉及化合物9的核磁共振氢谱图;图22为本发明所涉及化合物9的核磁共振碳谱图;图23为本发明所涉及化合物9的高分辨质谱图;图24为本发明所涉及化合物10的核磁共振氢谱图;图25为本发明所涉及化合物10的核磁共振碳谱图;图26为本发明所涉及化合物10的高分辨质谱图;图27为本发明所涉及化合物PTA-2的高分辨质谱图;图28为本发明所涉及化合物PTA-2的红外光谱图;图29为本发明所涉及化合物12的核磁共振氢谱图;图30为本发明所涉及化合物12的核磁共振碳谱图;图31为本发明所涉及化合物12的高分辨质谱图;图32为本发明所涉及化合物13的核磁共振氢谱图;图33为本发明所涉及化合物13的核磁共振碳谱图;图34为本发明所涉及化合物13的高分辨质谱图;图35为本发明所涉及化合物14的核磁共振氢谱图;图36为本发明所涉及化合物14的核磁共振碳谱图;图37为本发明所涉及化合物14的高分辨质谱图;图38为本发明所涉及化合物15的核磁共振氢谱图;图39为本发明所涉及化合物15的核磁共振碳谱图;图40为本发明所涉及化合物15的高分辨质谱图;图41为本发明所涉及化合物PTA-3的高分辨质谱图;图42为本发明所涉及化合物PTA-3的红外光谱图;图43为本发明所涉及化合物17的核磁共振氢谱图;图44为本发明所涉及化合物17的核磁共振碳谱图;图45为本发明所涉及化合物17的高分辨质谱图;图46为本发明所涉及化合物18的核磁共振氢谱图;图47为本发明所涉及化合物18的核磁共振碳谱图;图48为本发明所涉及化合物18的高分辨质谱图;图49为本发明所涉及化合物19的核磁共振氢谱图;图50为本发明所涉及化合物19的核磁共振碳谱图;图51为本发明所涉及化合物19的高分辨质谱图;图52为本发明所涉及化合物20的核磁共振氢谱图;图53为本发明所涉及化合物20的核磁共振碳谱图;图54为本发明所涉及化合物20的高分辨质谱图;图55为本发明所涉及化合物PTA-4的高分辨质谱图;图56为本发明所涉及化合物PTA-4的红外光谱图;图57为本发明所涉及化合物23的核磁共振氢谱图;图58为本发明所涉及化合物23的核磁共振碳谱图;图59为本发明所涉及化合物23的高分辨质谱图;图60为本发明所涉及化合物24的核磁共振氢谱图;图61为本发明所涉及化合物24的核磁共振碳谱图;图62为本发明所涉及化合物24的高分辨质谱图;图63为本发明所涉及化合物25的核磁共振氢谱图;图64为本发明所涉及化合物25的核磁共振碳谱图;图65为本发明所涉及化合物25的高分辨质谱图;图66为本发明所涉及化合物PTA-5的高分辨质谱图;图67为本发明所涉及化合物PTA-5的红外光谱图。
具体实施方式
现在结合附图对本发明作进一步详细的说明。这些附图均为简化的示意图,仅以示意方式说明本发明的基本结构,因此其仅显示与本发明有关的构成。
实施例1
本实施例提供一种噻吩并[2',3':4,5]噻吩并[3,2-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(PTA-1)的制备方法及产物性能测试,反应式如下:
步骤如下:
a、2-碘-3-溴-5-三甲基硅基-二噻吩并[3,2-b:2',3'-d]噻吩(2)的制备
于250mL Schlenk瓶中加入2-溴-5-三甲基硅基-二噻吩[3,2-b:2',3'-d]并噻吩(1)(0.6503g,1.87mmol),真空干燥0.5h,在氩气保护下加入100mL无水四氢呋喃,降低至-78℃,加入新制的LDA(2.24mmol,1.2eq),反应18h;在氩气保护下加入碘(0.5701g,2.24mmol,1.2eq),缓慢升至室温搅拌24h;低温下加饱和亚硫酸钠溶液淬灭。将反应液转移至500mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相,有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品1.028g;粗品用2×15mL乙醚洗涤,得到纯品0.7619g(黄色固体),产率:80%,Mp:151-153℃,1H NMR(400MHz,CDCl3)δ(ppm)7.37(s,1H),0.38(s,9H);13C NMR(100MHz,CDCl3):δ144.17,143.09,141.91,136.25,134.34,126.82,113.52,75.93,0.00;IR(KBr):3431,2952,2892(C-H)cm-1.HRMS(MALDI_DHB):m/zcalcd for[C11H10BrIS3Si]471.4972,found 471.7936。
b、5-三甲基硅基-3-溴-2-(5-(三甲基硅基)噻吩-3)-二噻吩并[3,2-b:2',3'-d]噻吩(3)的制备
于25mL Schlenk瓶中加入步骤a制备的化合物2(0.1334g,0.28mmol)及5-三甲基硅基-3-(4,4,5,5,-四甲基-1,3,2-二氧杂环戊硼烷基)噻吩(0.0862g,0.31mmol,1.1eq),K2CO3(0.0967g,0.70mmoL,2.5eq),Pd(PPh3)4(0.0065g,0.0056mmol,0.02eq),真空干燥0.5h,在氩气保护下加入5mL无水四氢呋喃,0.7mL无氧水;将Schlenk瓶转移到95℃油浴中,加热回流20h。将反应液转移至125mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×10mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1456g;粗品经柱层析(硅胶:300-400目,淋洗液:石油醚)纯化得化合物3(白色固体)0.0867g,产率:62%,Mp:113-114℃。1H NMR(400MHz,CDCl3)δ(ppm)8.04(s,1H),7.54((s,1H),7.36(s,1H),0.38(s,9H),0.37(s,9H).13C NMR(100MHz,CDCl3):δ144.60,143.42,142.43,141.61,136.28,134.80,134.07,133.38,128.70,127.34,126.93,100.61,0.00,-0.04.IR(KBr):2953,2895(C-H)cm-1.HRMS(MALDI_DHB):m/z calcd for[C18H21BrS4Si2]499.9248,found500.4673。
c、5-三甲基硅基-3-溴-2-(2-溴-5-(三甲基硅基)噻吩-3)-二噻吩并[3,2-b:2',3'-d]噻吩(4)的制备
于250mL Schlenk瓶中加入步骤b制备的化合物3(0.1613g,0.32mmol),真空干燥0.5h,在氩气保护下加入35mL无水乙醚;降低至-78℃,加入新制的LDA(0.0647g,0.64mmoL,2.0eq),反应过夜;在氩气保护下加入干燥C2Br2Cl4(0.1047g,0.32mmol,1eq)缓慢升至室温搅拌过夜;低温下加甲醇淬灭。将反应液转移至125mL的分液漏斗,分出水相,用3×10mLCH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.253g;粗品经柱层析(硅胶:300-400目,淋洗液:石油醚)纯化得化合物4(白色固体)0.181g,产率:97%,Mp:144-145℃。1H NMR(400MHz,CDCl3)δ(ppm)7.40(s,1H),7.26(s,1H),0.39(s,9H),0.35(s,9H);13C NMR(100MHz,CDCl3):δ143.81,143.64,142.68,142.24,131.77,137.66,136.25,134.50,131.06,129.53,126.93,118.04,-0.00,-0.14;IR(KBr):2954,2924,2856(C-H)cm-1;HRMS(MALDI_DHB):m/z calcd for[C18H20Br2S4Si2]577.8353,found 577.8347。
2,7-二(三甲基硅基)-噻吩并[2',3':4,5]噻吩并[3,2-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(5)的制备
方法一(步骤f):于250mL Schlenk瓶中加入步骤b制备的化合物3(0.1088g,0.22mmol),真空干燥0.5h,在氩气保护下加入40mL无水乙醚;降低至-78℃,加入n-BuLi(0.0155g,0.242mmol,1.1eq),反应2h;在氩气保护下加入干燥(PhSO2)2S(0.0692g,0.22mmol,1.0eq),缓慢升至室温搅拌20h;低温下加甲醇淬灭。将反应体系转移至125mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1055g。粗品2×15mL乙醚洗涤,得到纯品0.0304g(淡黄色固体),产率:31%。
方法二(步骤d):于25mL Schlenk瓶中加入步骤c制备的化合物4(0.098g,0.17mmol)、二(三丁基锡)硫醚(0.1042g,0.17mmol,1.0eq),在氩气保护下加入5mL无水甲苯,在氩气保护下加入四三苯基磷钯(0.0158g,0.0137mmol,0.08eq);将Schlenk瓶转移到95℃油浴中,加热回流24h;反应液经柱层析除去钯黑(湿法上样,CH2Cl2为淋洗剂,200-300目硅胶),用3×10mL CH2Cl2萃取水相,合并有机相。有机相用2×10mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.0523g;粗品2×15mL石油醚洗涤,得到纯品0.0371g(黄色固体),产率:48%,Mp:239-242℃,1H NMR(400MHz,CDCl3)δ(ppm)7.41(s,1H),7.39(s,1H),0.40(s,9H),0.39(s,9H);13C NMR(100MHz,CDCl3):δ146.12,142.97,142.53,141.99,140.78,136.80,134.12,130.80,126.82,124.37,0.00,-0.03;IR(KBr):2955(C-H)cm-1;HRMS(MALDI_DHB):m/z calcd for[C18H20S5Si2]451.9707,found 451.2068。
e、噻吩并[2',3':4,5]噻吩并[3,2-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(PTA-1)的制备
将步骤(4)制备的化合物5(0.2596g,0.57mmol)溶于30mL CHCl3中,加入三氟乙酸(TFA)(0.6498g,5.7mmol,10eq),室温下反应1h,薄层板跟踪原料消失,向体系中加几滴水淬灭反应,将该反应液移至125mL分液漏斗中,加入15mL水洗涤,振荡静置,分液,水相分别用3×10mL二氯甲烷萃取,合并有机相。有机相分别用20mL水、20mL饱和碳酸氢钠溶液、20mL水洗涤,无水MgSO4干燥,过滤,除去溶剂粗品经柱层析纯化得化合物PTA-1(淡黄色固体)0.1521g,产率:86%,Mp:239-242℃。HRMS(MALDI_DHB)m/z calcd for[C12H4S5]307.8911,found 307.8917[C12H4S5]。
PTA-1在基底温度为室温时获得的性能为:迁移率为0.02cm2/V/s,阈值电压为-10V,开关比为105,可以作为有机半导体材料应用于有机场效应晶体管中。
实施例2
本实施例提供一种噻吩并[3',2':4,5]噻吩并[2,3-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(PTA-2)的制备方法及产物性能测试,反应式如下:
步骤如下:
a、2-碘-3-溴-5-三甲基硅基-二噻吩[2,3-b:3',2'-d]并噻吩(7)的制备
于250mL Schlenk瓶中加入2-溴-5-三甲基硅基-二噻吩[2,3-b:3',2'-d]并噻吩(6)(1.0905g,3.14mmol),真空干燥0.5h,在氮气保护下加入100mL无水四氢呋喃;降低至-90℃,加入新制的LDA(0.5044g,4.71mmol,1.5eq),反应20h;在氮气保护下加入碘(0.9561g,3.14mmol,1.0eq),缓慢升至室温搅拌20h;低温下加饱和硫酸钠溶液淬灭。将反应体系转移至500mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品1.779g;粗品用2×15mL乙醚洗涤,得到纯品1.337g(黄色固体),产率:90%,Mp:146-147℃;1H NMR(400MHz,CDCl3)δ(ppm)7.73(s,1H),0.39(s,9H);13C NMR(100MHz,CDCl3):δ145.02,144.40,141.93,139.58,136.46,124.25,113.14,0.119,-0.13;IR(KBr):2950,2929,2858(C-H)cm-1;HRMS(MALDI_DHB)m/z calcd for[C11H10BrIS3Si]471.7936,found 471.7052[C11H10BrIS3Si]。
b、5-三甲基硅基-3-溴-2-(5-(三甲基硅基)噻吩-3)-二噻吩[2,3-b:3',2'-d]并噻吩(8)的制备
于25mL Schlenk瓶中加入步骤a制备的化合物7(0.4340g,0.92mmol),5-三甲基硅基-3-(4,4,5,5,-四甲基-1,3,2-二氧杂环戊硼烷基)噻吩(0.3177g,0.83mmol,0.9eq),Na2CO3(0.2141g,2.02mmoL,2.2eq),醋酸钯(0.0062g,0.0276mmol,0.03eq),真空干燥0.5h,在氩气保护下加入5mL无水四氢呋喃,0.7mL无氧水;将Schlenk瓶转移到85℃油浴中,加热回流24h。将反应体系转移至100mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相。有机相用2×10mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1456g。粗品经柱层析(硅胶:300-400目,淋洗液:石油醚)纯化得化合物8(白色固体)0.0867g,产率:62%,Mp:113-114℃;1H NMR(400MHz,CDCl3)δ(ppm)8.02(s,1H),7.83(s,1H),7.54(s,1H),0.40(s,9H),0.37(s,9H);13C NMR(100MHz,CDCl3):δ144.70,144.13,141.44,140.60,137.58,136.58,134.86,134.64,134.29,128.81,124.83,100.21,0.048,0.000;IR(KBr):3104,2953,2857(C-H)cm-1;HRMS(MALDI_DHB)m/z calcd for[C18H21BrS4Si2]499.9248,found 499.9248[C18H21BrS4Si2]。
c、5-三甲基硅基-3-溴-2-(2-溴-5-(三甲基硅基)噻吩-3)-二噻吩[2,3-b:3',2'-d]并噻吩(9)的制备
于250mL Schlenk瓶中加入步骤b制备的化合物8(0.5129g,1.02mmol),真空干燥0.5h,在氩气保护下加入40mL无水乙醚;降低至-78℃,加入新制LDA(0.3491g,3.26mmoL,3.2eq),反应2h;在氩气保护下加入干燥C2Br2Cl4(0.3329g,1.02mmol,1eq),缓慢升至室温搅拌24h;低温下加水淬灭。将反应体系转移至500mL的分液漏斗,分出水相,用3×10mLCH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.860g;粗品经柱层析(硅胶:300-400目,淋洗液:石油醚)纯化得到化合物9(白色固体)0.582g,产率:98%,Mp:173-174℃;1H NMR(400MHz,CDCl3)δ(ppm)7.82(s,1H),7.23(s,1H),0.40(s,9H),0.35(s,9H);13C NMR(100MHz,CDCl3):δ144.76,144.08,142.10,140.41,138.73,136.67,136.19,134.40,132.43,124.69,118.38,103.41,-0.00,-0.24;IR(KBr):2954,2857(C-H)cm-1.HRMS(MALDI_DHB)m/z calcd for[C18H20Br2S4Si2]577.8353,found 577.8356[C18H20Br2S4Si2]。
2,7-噻吩并[3',2':4,5]噻吩并[2,3-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(10)的制备
方法一(步骤f):于250mL Schlenk瓶中加入步骤b制备的化合物8(0.1088g,0.22mmol),真空干燥0.5h,在氩气保护下加入40mL无水乙醚;降低至-90℃,加入特丁基锂(0.0577g,0.902mmol,4.1eq),反应2.5h;在氩气保护下加入干燥(PhSO2)2S(0.0692g,0.22mmol,1.0eq),缓慢升至室温搅拌19h;低温下加水淬灭。将反应体系转移至125mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1055g。粗品2×15mL乙醚洗涤,得到纯品0.0304g(淡黄色固体),产率:31%。
方法二(步骤d):于25mL Schlenk瓶中加入步骤c制备的化合物9(0.1104g,0.19mmol),二(三丁基锡)硫醚(0.1165g,0.19mmol,1.0eq),在氩气保护下加入5mL无水甲苯,加入四三苯基磷钯(0.0176g,0.0152mmol,0.08eq)。Schlenk瓶转移到95℃油浴中,加热回流24h。将反应液经柱层析除去钯黑(湿法上样,CH2Cl2为淋洗剂,200-300目硅胶),用3×10mL CH2Cl2萃取水相,合并有机相。有机相用2×10mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1021g。粗品2×15mL石油醚洗涤,得到纯品10(淡黄色固体)0.0602g,产率:70%,Mp:212-214℃。1H NMR(400MHz,CDCl3)δ(ppm)7.43(s,1H),7.40(s,1H),0.40(s,9H),0.40(s,9H);13C NMR(100MHz,CDCl3):δ145.98,143.26,142.73,140.77,139.90,134.25,132.02,131.39,130.03,126.38,124.32,0.063,0.00;IR(KBr):3057,2954,2895(C-H)cm-1.HRMS(MALDI_DHB)m/z calcd for[C18H20S5Si2]451.9707,found 451.9714。
e、噻吩并[3',2':4,5]噻吩并[2,3-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(PTA-2)的制备
将化合物10(0.2457g,0.54mmol)溶于30mL CHCl3中,加入TFA(0.6156g,5.4mmol,10eq),室温下反应80min,薄层板跟踪原料消失,向体系中加几滴水淬灭反应。将该反应液移至250mL分液漏斗中,加入15mL水洗涤,振荡,静置,分液,水相分别用3×10mL二氯甲烷萃取,合并有机相;有机相分别用20mL水、5mL饱和碳酸氢钠溶液、5mL水洗涤,无水MgSO4干燥,过滤,除去溶剂粗品经柱层析纯化得化合物PTA-2(黄色固体)0.1420g,产率:85%,Mp:190-201℃;IR(KBr):3098,2956,2923,2860(C-H)cm-1.HRMS(MALDI_DHB)m/z calcd for[C12H4S5]307.8917,found 307.8913。
PTA-2在基底温度为室温时获得的性能为:迁移率为0.05cm2/V/s,阈值电压为-50V,开关比为105,可作为有机半导体材料应用于有机场效应晶体管中。
实施例3
本实施例提供一种噻吩并[3',2':4,5]噻吩并[3,2-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(PTA-3)的制备方法及产物性能测试,反应式如下:
步骤如下:
a、4-碘-5-溴-2-三甲基硅基-二噻吩并[2,3-b:2',3'-d]噻吩(12)的制备
于250mL Schlenk瓶中加入5-溴-2-三甲基硅基-二噻吩并[2,3-b:2',3'-d]噻吩(11)(0.2528g,0.73mmol),真空干燥0.5h,在氩气保护下加入100mL无水四氢呋喃;降低至-60℃,加入新制的LDA(0.1407g,1.314mmol,1.8eq),反应24h;在氩气保护下加入碘(0.2216g,1.10mmol,1.5eq),缓慢升至室温搅拌18h;低温下加饱和亚硫酸钠溶液淬灭。将反应体系转移至500mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.412g。粗品2×15mL乙醚洗涤,得到纯品0.283g(黄色固体),产率:84%,Mp:130-131℃。1H NMR(300MHz,CDCl3)δ(ppm)0.35(s,1H),0.38(s,9H).13C NMR(75MHz,CDCl3):δ146.15,143.98,140.25,139.98,133.44,124.38,112.29,75.01,-0.192.IR(KBr):3057,2950,2923,2857(C-H)cm-1.HRMS(MALDI_DHB)m/z calcd for[C11H10BrIS3Si]471.7936,found 471.7944。
b、2-三甲基硅基-5-溴-4-(5-(三甲基硅基)噻吩-3)-二噻吩[2,3-b:2',3'-d]并噻吩(13)的制备
于25mL Schlenk瓶中加入4-碘-5-溴-2-三甲基硅基-二噻吩并[2,3-b:2',3'-d]噻吩(12)(1.0486g,2.22mmol),5-三甲基硅基3-(4,4,5,5,-四甲基-1,3,2-二氧杂环戊硼烷基)噻吩(0.8130g,2.88mmol,1.3eq),CsCO3(1.345g,6.20mmoL,2.8eq),Pd(PPh3)4(0.128g,0.11mmol,0.05eq),真空干燥0.5h,在氮气保护下加入30mL无水四氢呋喃,0.15mL无氧水;Schlenk瓶转移到105℃油浴中,加热回流18h。将反应体系转移至125mL的分液漏斗,分出水相,用3×10mL CH2Cl2取水相,合并有机相;有机相用2×10mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品1.2014g。粗品经柱层析(硅胶:300-400目,淋洗液:石油醚)纯化得化合物13(白色晶体)0.5557g,产率:50%,Mp:108-110℃。1H NMR(400MHz,CDCl3)δ(ppm)8.02(d,J=1.0Hz,1H),7.55(t,J=9.1Hz,1H),7.37(s,1H),0.39(s,8H),0.37(s,7H);13C NMR(100MHz,CDCl3):δ145.94,144.49,143.32,141.49,140.28,134.80,134.07,132.75,128.52,126.85,124.67,100.08,0.00;IR(KBr):3114,3057,2954,2894(C-H)cm-1.HRMS(MALDI_DHB)m/z calcd for[C18H21BrS4Si2]499.4248,found 499.9242。
c、2-三甲基硅基-5-溴-4-(2-溴-5-(三甲基硅基)噻吩-3)-二噻吩[2,3-b:2',3'-d]并噻吩(14)的制备
将2-三甲基硅基-5-溴-4-(5-(三甲基硅基)噻吩-3)-二噻吩[2,3-b:2',3'-d]并噻吩(13)(0.1411g,0.28mmol)真空干燥0.5h,在氩气保护下加入50mL无水乙醚;降低至-60℃,加入新制LDA(0.0900g,0.84mmol,3.0eq),反应1.5h;在氩气保护下加入干燥C2Br2Cl4(0.0916g,0.28mmol,1eq),缓慢升至室温搅拌20h;低温下加甲醇淬灭。将反应体系转移至500mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1726g;粗品经柱层析(硅胶:300-400目,淋洗液:石油醚)纯化得化合物14(白色固体)0.1467g,产率:85%,Mp:138-140℃。1HNMR(400MHz,CDCl3)δ(ppm)δ7.39(1H),7.26(1H),0.38(s,9H),0.35(s,9H);13C NMR(100MHz,CDCl3):δ146.07,144.75,143.60,142.12,140.32,136.24,134.50,130.43,129.10,124.75,117.93,103.31,δ0.00,-0.18;IR(KBr):3064,2952,2896,2855(C-H)cm-1;HRMS(MALDI_DHB)m/z calcd for[C18H20Br2S4Si2]577.8353,found 577.8347。
2,6-噻吩并[3',2':4,5]噻吩并[3,2-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(15)的制备
方法一(步骤f):于250mL Schlenk瓶中加入步骤b制备的化合物13(0.1088g,0.22mmol),真空干燥0.5h,在氩气保护下加入40mL无水乙醚;降低至-60℃,加入n-BuLi(0.0352g,0.55mmol,2.5eq),反应1.5h;在氩气保护下加入干燥(PhSO2)2S(0.0629g,0.20mmol,0.9eq),缓慢升至室温搅拌18h;低温下加甲醇淬灭。将反应体系转移至125mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1055g。粗品2×15mL乙醚洗涤,得到纯品0.0304g(淡黄色固体),产率:31%。
方法二(步骤d):于25mL Schlenk瓶中加入2-三甲基硅基-5-溴-4-(2-溴-5-(三甲基硅基)吩-3-二噻吩[2,3-b:2',3'-d]并噻吩(14)(0.0668g,0.12mmol),二(三丁基锡)硫醚(0.0589g,0.096mmol,0.8eq),在氩气保护下加入5mL无水甲苯,加入醋酸钯(0.0016g,0.0072mmol,0.08eq);Schlenk瓶转移到105℃油浴中,加热回流18h。将反应液经柱层析除去钯黑(湿法上样,CH2Cl2为淋洗剂,200-300目硅胶),用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×10mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.0609g;粗品2×15mL石油醚洗涤,得到纯品15(淡黄色固体)0.0266g,产率:51%,Mp:219-220℃。1H NMR(400MHz,CDCl3)δ(ppm)7.42(s,1H),0.39(s,9H);13C NMR(100MHz,CDCl3):δ145.98,142.54,140.75,133.89,130.33,124.38,-0.00;IR(KBr):2955,2922,2855(C-H)cm-1;HRMS(MALDI_DHB)m/z calcd for[C18H20S4Si2]451.9707,found 451.9701。
e、噻吩并[3',2':4,5]噻吩并[3,2-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(PTA-3)的制备
将2,6-噻吩并[3',2':4,5]噻吩并[3,2-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(14)(0.0845g,0.22mmol)溶于30mL CHCl2中,加入TFA(0.2006g,1.76mmol,8eq),室温下反应20min,薄层板跟踪原料消失,向体系中加几滴水淬灭反应,将该反应液移至125mL分液漏斗中,加入15mL水洗涤,振荡,静置,分液,水相分别用3×10mL二氯甲烷萃取,合并有机相。有机相分别用20mL水、5mL饱和碳酸氢钠溶液、5mL水洗涤,无水MgSO4干燥,过滤,除去溶剂粗品经柱层析纯化得化合物PTA-3(黄色固体)0.0501g,产率:87%,Mp:246-249℃。IR(KBr):3098,2956,2923,2860(C-H)cm-1.HRMS(MALDI_DHB)m/z calcd for[C12H4S5]307.8917,found 307.8913.
PTA-3在基底温度为室温时获得的性能为:迁移率为0.06cm2/V/s,阈值电压为-18V,开关比为104,可以作为有机半导体材料应用于有机场效应晶体管中。
实施例4
本实施例提供一种噻吩并[2',3':4,5]噻吩并[2,3-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(PTA-4)的制备方法及产物性能测试,反应式如下:
步骤如下:
a、5-三甲基硅基-2-碘-3-溴-二噻吩并[2,3-b:2',3'-d]噻吩(17)的制备
于250mL Schlenk瓶中加入5-三甲基硅基-2-溴-二噻吩并[2,3-b:2',3'-d]噻吩(16)(0.5858g,1.69mmol),真空干燥0.5h,在氩气保护下加入100mL无水四氢呋喃;降低至-78℃,加入新制的LDA(0.2303g,2.02mmol,1.2eq),反应过夜;在氩气保护下加入碘(0.5136g,2.02mmol,1.2eq),缓慢升至室温搅拌过夜;低温下加饱和亚硫酸钠溶液淬灭。将反应体系转移至500mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.9310g;粗品2×15mL乙醚洗涤,得到纯品0.727g(白色固体),产率:91%,Mp:163-165℃。1H NMR(400MHz,CDCl3)δ(ppm)7.36(s,1H),0.38(s,9H);13C NMR(100MHz,CDCl3):δ146.34,144.41,141.83,140.28,133.88,124.63,112.84,75.41,-0.00;IR(KBr):2950,2929,2858(C-H)cm-1;HRMS(EI_DHB)m/z calcd for[C11H10BrIS3Si]471.7942,found 471.7944。
b、5-三甲基硅基-3-溴-2-(5-(三甲基硅基)噻吩-3)-二噻吩[2,3-b:2',3'-d]并噻吩(18)的制备
于25mL Schlenk瓶中加入5-三甲基硅基-2-碘-3-溴-二噻吩并[2,3-b:2',3'-d]噻吩(17)(0.1806g,0.38mmol),5-三甲基硅基3-(4,4,5,5,-四甲基-1,3,2-二氧杂环戊硼烷基)噻吩(0.1616g,0.57mmol,1.5eq),K2CO3(0.1313g,0.95mmoL,2.5eq),Pd(PPh3)4(0.0352g,0.08eq),真空干燥0.5h,在氩气保护下加入30mL无水四氢呋喃,0.95mL无氧水;Schlenk瓶转移到95℃油浴中,加热回流过夜。将反应体系转移至125mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相。有机相用2×10mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.2081g;粗品经柱层析(硅胶:300-400目,淋洗液:石油醚)纯化得化合物18(白色晶体)1493g,产率:78%,Mp:129-132℃。1H NMR(400MHz,CDCl3)δ(ppm)8.03(s,1H),7.55(s,1H),7.38(s,1H),0.40(s,9H),0.38(s,9H);13C NMR(100MHz,CDCl3):δ142.91,142.56,141.48,138.29,135.94,135.83,135.16,134.61,134.03,99.66,0.001,-0.014;IR(KBr):2953,2899,2858(C-H)cm-1;HRMS(EI_DHB)m/z calcd for[C18H21BrS4Si2]499.9248,found 499.9256。
c、5-三甲基硅基-3-溴-2-(2-溴-5-(三甲基硅基)噻吩-3)-二噻吩[2,3-b:2',3'-d]并噻吩(19)的制备
将5-三甲基硅基-3-溴-2-(5-(三甲基硅基)噻吩-3)-二噻吩[2,3-b:2',3'-d]并噻吩(18)(0.1529g,0.30mmol)真空干燥0.5h,在氮气保护下加入50mL无水乙醚;降低至-90℃,加入新制LDA(0.1529g,0.84mmol,2.8eq),反应2.5h;在氮气保护下加入干C2Br2Cl4(0.2931g,0.9mmol,3eq),缓慢升至室温搅拌18h;低温下加甲醇淬灭。将反应体系转移至500mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1798g;粗品经柱层析(硅胶:300-400目,淋洗液:石油醚)纯化得化合物19(白色固体)0.1505g,产率:85%,Mp:147-150℃。1HNMR(400MHz,CDCl3)δ(ppm)7.38(s,1H),7.23(s,1H),0.39(s,9H),0.34(s,9H);13C NMR(100MHz,CDCl3):δ142.89,142.67,142.24,138.16,137.41,136.12,135.76,134.39,132.81,125.75,118.25,102.80,-0.000,-0.182;IR(KBr):2953(C-H)cm-1;HRMS(EI_DHB)m/z calcd for[C18H20Br2S4Si2]577.8353,found 577.8349。
2,7-噻吩并[2',3':4,5]噻吩并[2,3-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(20)
方法一(步骤f):于250mL Schlenk瓶中加入步骤b制备的化合物18(0.1088g,0.22mmol),真空干燥0.5h,在氩气保护下加入40mL无水乙醚;降低至-78℃,加入n-BuLi(0.0296g,0.462mmol,2.1eq),反应2h;在氩气保护下加入干燥(PhSO2)2S(0.0534g,0.17mmol,0.8eq),缓慢升至室温搅拌24h;低温下加甲醇淬灭。将反应体系转移至125mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1055g。粗品2×15mL乙醚洗涤,得到纯品0.0304g(淡黄色固体),产率:31%。
方法二(步骤d):于25mL Schlenk瓶中加入5-三甲基硅基-3-溴-2-(2-溴-5-(三甲基硅基)噻吩-3-二噻吩[2,3-b:2',3'-d]并噻吩(19)(0.1185g,0.20mmol),二(三丁基锡)硫醚(0.1472g,0.24mmol,1.2eq),在氮气保护下加入5mL无水甲苯,加入四三苯基磷钯(0.0142g,0.012mmol,0.06eq);Schlenk瓶转移到85℃油浴中,加热回流24h。将反应液经柱层析除去钯黑(湿法上样,CH2Cl2为淋洗剂,200-300目硅胶),用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×10mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1021g。粗品2×15mL石油醚洗涤,得到纯品20(淡黄色固体)0.0313g,产率:34%,Mp:231-232℃。1H NMR(400MHz,CDCl3)δ(ppm)7.43(s,1H),7.40(s,1H),0.40(s,9H),0.40(s,9H);13C NMR(100MHz,CDCl3):δ145.98,143.26,142.73,140.77,139.90,134.25,132.02,131.39,130.03,126.38,124.32,0.00;IR(KBr):2953(C-H)cm-1;HRMS(EI_DHB)m/z calcdfor[C18H20S5Si2]451.9707,found 451.9714.
e、噻吩并[2',3':4,5]噻吩并[2,3-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(PTA-4)
将2,7-噻吩并[2',3':4,5]噻吩并[2,3-b]噻吩并[3',2':4,5]噻吩并[2,3-d]噻吩(20)(0.2457g,0.54mmol)溶于30mL THF中,加入四丁基氟化铵(1.694g,6.48mmol,12eq),室温下反应40min,薄层板跟踪原料消失,向体系中加几滴甲醇淬灭反应,将该反应液移至250mL分液漏斗中,加入15mL水洗涤,振荡,静置,分液,水相分别用3×10mL二氯甲烷萃取,合并有机相。有机相分别用20mL水、5mL饱和碳酸氢钠溶液、5mL水洗涤,无水MgSO4干燥,过滤,除去溶剂粗品经柱层析纯化得化合物PTA-4(黄色固体)0.1439g,产率:87%,Mp:226-227℃。IR(KBr):3095,2952,2920,2856(C-H)cm-1.HRMS(EI_DHB)m/z calcd for[C12H4S5]307.8017,found 307.8911。
PTA-4在基底温度为室温时获得的性能为:迁移率为0.05cm2/V/s,阈值电压为-50V,开关比为105,可以作为有机半导体材料应用于有机场效应晶体管中。
实施例5
本实施例提供一种噻吩并[2',3':4,5]噻吩并[2,3-b]噻吩并[2',3':4,5]噻吩并[3,2-d]噻吩(PTA-5)的制备方法及产物性能测试,反应式如下:
步骤如下:
a、2-三甲基硅基-4-(4,4,5,5,-四甲基-1,3,2-二氧杂环戊硼烷基)二噻吩并[3,2-b;2',3'-d]噻吩(22)的制备
于250mL Schlenk瓶中加入3-溴-5-三甲基硅基-二噻吩并[3,2-b:2',3'-d]噻吩(21)(0.5862g,1.69mmol),真空干燥0.5h,在氩气保护下加入100mL无水乙醚;降低至-78℃,加入叔丁基锂(0.1030g,1.61mmol,0.95eq),反应2h;在氩气保护下加入异丙基频那醇酯(2.03mmol,1.2eq),缓慢升至室温搅拌过夜;低温下加饱和亚硫酸钠溶液淬灭。将反应体系转移至500mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品;粗品用2×15mL乙醚洗涤,得到纯品0.5716g(白色固体),产率:90%。
b、5-三甲基硅基-3-(3-溴-5-(三甲基硅基)噻吩-2)-二噻吩并[3,2-b:2',3'-d]噻吩(23)的制备
于25mL Schlenk瓶中加入2-三甲基硅基-4-(4,4,5,5,-四甲基-1,3,2-二氧杂环戊硼烷基)二噻吩并[3,2-b;2',3'-d]噻吩(22)(0.6351g,1.61mmol),2,3-二溴-5-三甲基硅基-噻吩(0.3533g,1.34mmol,0.83eq),K2CO3(0.4672g,3.38mmoL,2.1eq),Pd(PPh3)4(0.0744g,0.0644mmol,0.04eq),真空干燥0.5h,在氩气保护下加入4mL无水四氢呋喃和4mL无水甲苯,3.37mL无氧水;将Schlenk瓶转移到95℃油浴中,加热回流过夜。将反应体系转移至100mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×10mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂,得到粗品0.6814g。粗品经柱层析(硅胶:300-400目,淋洗液:石油醚)纯化得化合物23(黄色固体)0.4808g,产率:71%。Mp:153-154℃;1HNMR(400MHz,CDCl3):δ(ppm)8.02(s,1H),7.56(s,1H),7.38(s,1H),0.39(s,9H),0.37(s,9H);13C NMR(100MHz,CDCl3)δ143.82,143.07,141.90,140.15,138.14,135.98,135.88,130.36,127.11,126.83,123.90,0.00,-0.19;IR(KBr):3105,2953,2894(C-H)cm-1;HRMS(EI_DHB)m/z calcd for[C18H21Si2S4Br]499.9248,found 499.9243。
c、2-溴-5-三甲基硅基-3-(5-(三甲基硅基)噻吩-3-溴-2)-二噻吩[3,2-b:2',3'-d]并噻吩(24)的制备
将5-三甲基硅基-3-(3-溴-5-(三甲基硅基)噻吩-2)-二噻吩并[3,2-b:2',3'-d]噻吩(23)(0.1512g,0.30mmol)加入到100mL Schlenk瓶中,向整个体系置换氩气三次,加入40mL无水乙醚,使原料溶解,转入低温仪中(-78℃),在氩气保护下逐滴加入LDA(0.1026g,0.90mmol,3eq),反应2h;在体系充满氩气的状态下,快速加入C2Br2Cl4(0.1075g,0.33mmol,1.1eq)(已经在室温抽2h),关闭低温仪,使其自然升至室温,反应过夜;反应结束后,加水在-78℃下将反应淬灭。将反应液旋出乙醚,用CH2Cl2将固体溶解,用500mL的分液漏斗进行萃取、洗涤:CH2Cl2(3×30mL)萃取,有机相用水(3×40mL)洗涤,采用无水MgSO4除水,漏斗过滤,旋出CH2Cl2,得到粗品:0.1801g。粗品经柱层析分离(上样方法:干法,淋洗剂:Hex,硅胶:300-400目),将收集得到的溶液通过旋蒸除去Hex,得到纯品24(黄色固体)产率88%。Mp:145-147℃。1H NMR(400MHz,CDCl3):δ(ppm)7.34(s,1H),7.22(s,1H),0.37(s,18H);13C NMR(100MHz,CDCl3)δ143.64,143.47,142.81,141.90,137.33,135.83,134.02,129.10,127.59,126.74,113.04,0.00,-0.15;IR(KBr):3073,2954,2923,2854(C-H)cm-1;HRMS(EI_DHB)m/z calcd for[C18H20Br2S4Si2]577.8353,found577.834。
2,7-二(三甲基硅基)-噻吩并[2',3':4,5]噻吩并[2,3-b]噻吩并[2',3':4,5]噻吩并[2,3-d]噻吩(25)的制备
方法一(步骤f):于100mL Schlenk瓶中加入5-三甲基硅基-3-(3-溴-5-(三甲基硅基)噻吩-2)-二噻吩并[3,2-b:2',3'-d]噻吩(23)(0.1118g,0.22mmol),真空干燥0.5h,在氩气保护下加入40mL无水乙醚;降低至-78℃,加入n-BuLi(0.0296g,0.462mmol,2.1eq),反应2h;在氩气保护下加入干燥(PhSO2)2S(0.0692g,0.22mmol,1.01eq),缓慢升至室温搅拌过夜;低温下加甲醇淬灭。将反应体系转移至250mL的分液漏斗,分出水相,用3×10mL CH2Cl2萃取水相,合并有机相。有机相用2×30mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.1131g。粗品2×15mL乙醚洗涤,得到纯品25(淡黄色固体)0.0303g,产率:30%。
方法二(步骤d):于25mL Schlenk瓶中加入2-溴-5-三甲基硅基-3-(3-溴-5-(三甲基硅基)噻吩-2)-二噻吩并[3,2-b:2',3'-d]噻吩(24)(0.0591g,0.10mmol),二(三丁基锡)硫醚(0.0613g,0.10mmol,1.0eq),在氩气保护下加入5mL无水甲苯,加入四三苯基磷钯(0.0094g,0.008mL,0.08eq);Schlenk瓶转移到95℃油浴中,加热回流24h。柱层析除去钯黑(湿法上样,CH2Cl2为淋洗剂,200-300目硅胶),用3×10mL CH2Cl2萃取水相,合并有机相;有机相用2×10mL水洗涤,用无水MgSO4干燥,过滤,除去溶剂得到粗品0.0523g;粗品2×15mL石油醚洗涤,得到纯品25(淡黄色固体)0.0194g,产率:42%。1H NMR(400MHz,CDCl3)δ(ppm)7.42(s,1H),7.40(s,1H),0.40(s,9H),0.39(s,9H);13C NMR(100MHz,CDCl3)δ143.31,142.81,142.64,142.31,140.38,136.72,134.33,132.19,131.86,130.21,126.85,126.37,0.03,0.00.IR(KBr):3063,2954,2896,2857(C-H)cm-1;HRMS(EI_DHB)m/z calcd for[C18H20 Si2 S5]451.9707,found 451.9701。
e、噻吩并[2',3':4,5]噻吩并[2,3-b]噻吩并[2',3':4,5]噻吩并[3,2-d]噻吩(PTA-5)的制备
将2,7-二(三甲基硅基)-噻吩并[2',3':4,5]噻吩并[2,3-b]噻吩并[2',3':4,5]噻[2,3-d]噻吩(25)(0.105g,0.23mmol)溶于30mL CHCl3中,加入三氟乙酸(TFA)(0.2622g,2.3mmol,10eq),室温下反应1h,薄层板跟踪原料消失,向体系中加几滴水淬灭反应,将该反应液移至250mL分液漏斗中,加入15mL水洗涤,振荡,静置,分液,水相分别用3×10mL二氯甲烷萃取,合并有机相。有机相分别用20mL水、5mL饱和碳酸氢钠溶液、5mL水洗涤,无水MgSO4干燥,过滤,除去溶剂粗品经柱层析纯化得化合物PTA-5(黄色固体)0.0608g,产率:85%。IR(KBr):3075,2921,2852(C-H)cm-1;HRMS(EI_DHB)m/z calcd for[C18 H4 Si5]307.8917,found 307.8911。
PTA-5在基底温度为室温时获得的性能为:迁移率为0.006cm2/V/s,阈值电压为-40V,开关比为105,可以作为有机半导体材料应用于有机场效应晶体管中。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (12)
1.一种并五噻吩同分异构体的制备方法,其特征在于,该方法包括如下步骤:
S1:将或其同分异构体在惰性气体保护及有机溶剂存在的条件下,先在-90~-60℃的温度下加入烷基锂反应,再加入关环试剂(PhSO2)2S升至室温反应,最后加入淬灭剂淬灭反应,反应液经后处理得或其同分异构体;
或将或其同分异构体在惰性气体保护及有机溶剂存在的条件下,先在-90~-60℃的温度下加入LDA反应,再加入溴代试剂C2Br2Cl4升至室温反应,最后加入淬灭剂淬灭反应,反应液经后处理得或其同分异构体,再将或其同分异构体在惰性气体保护、有机溶剂及二(三丁基锡)硫醚存在的条件下,加入四三苯基磷钯或醋酸钯,在85-105℃下反应,反应液经后处理得或其同分异构体;
所述的同分异构体为 所述 的制备方法为:于或其同分异构体中加入5-三甲基硅基-3-(4,4,5,5,-四甲基-1,3,2-二氧杂环戊硼烷基)噻吩、碳酸盐、四三苯基磷钯或醋酸钯,在惰性气体保护下加入有机溶剂及无氧水,在85-105℃温度下反应,反应液经后处理制得;所述的同分异构体为中的一种;
2.根据权利要求1所述的并五噻吩同分异构体的制备方法,其特征在于,所述S1步骤中烷基锂为正丁基锂或特丁基锂,惰性气体为氩气或氮气。
7.根据权利要求1所述的并五噻吩同分异构体的制备方法,其特征在于,所述碳酸盐为K2CO3、Na2CO3或Cs2CO3。
11.根据权利要求1所述的并五噻吩同分异构体的制备方法,其特征在于,所述有机溶剂为乙醚、甲苯、三氯甲烷、二氯甲烷、四氢呋喃中的至少一种。
12.根据权利要求1所述的并五噻吩同分异构体的制备方法,其特征在于,所述淬灭剂为甲醇、水、饱和亚硫酸钠溶液、饱和硫代硫酸钠溶液中的至少一种。
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