CN105061463B - A kind of nine yuan of fused-ring derivatives and its synthetic method and application - Google Patents
A kind of nine yuan of fused-ring derivatives and its synthetic method and application Download PDFInfo
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- CN105061463B CN105061463B CN201510504626.0A CN201510504626A CN105061463B CN 105061463 B CN105061463 B CN 105061463B CN 201510504626 A CN201510504626 A CN 201510504626A CN 105061463 B CN105061463 B CN 105061463B
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- yuan
- fused
- reaction
- field effect
- ring derivatives
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 230000005669 field effect Effects 0.000 claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 72
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- -1 pinacol borates Chemical class 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 238000004440 column chromatography Methods 0.000 claims description 14
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- 238000000034 method Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [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 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 235000011056 potassium acetate Nutrition 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical class OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
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- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 2
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
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- 239000000243 solution Substances 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- 206010011224 Cough Diseases 0.000 description 17
- 239000000843 powder Substances 0.000 description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- GXNSCMIFUUDYMT-UHFFFAOYSA-N 1-octylindeno[2,1-a]fluorene Chemical compound C(CCCCCCC)C1=C2C=C3C(=CC=C4C=5C=CC=CC=5C=C34)C2=CC=C1 GXNSCMIFUUDYMT-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 8
- QJTQKPNNQVLHHO-UHFFFAOYSA-N 9h-carbazole;1h-indole Chemical compound C1=CC=C2NC=CC2=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 QJTQKPNNQVLHHO-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 125000000913 palmityl 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])C([H])([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 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 208000032825 Ring chromosome 2 syndrome Diseases 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000017858 demethylation Effects 0.000 description 3
- 238000010520 demethylation reaction Methods 0.000 description 3
- PJULCNAVAGQLAT-UHFFFAOYSA-N indeno[2,1-a]fluorene Chemical compound C1=CC=C2C=C3C4=CC5=CC=CC=C5C4=CC=C3C2=C1 PJULCNAVAGQLAT-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000011574 phosphorus Substances 0.000 description 3
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- 150000003222 pyridines Chemical class 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
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- WMNSZBZIINUTNR-UHFFFAOYSA-N 1-benzothiophene;1h-indole Chemical compound C1=CC=C2NC=CC2=C1.C1=CC=C2SC=CC2=C1 WMNSZBZIINUTNR-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
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- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
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- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical class CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- UCGLOIUEXYZMIU-UHFFFAOYSA-N 1h-indole;thiophene Chemical class C=1C=CSC=1.C1=CC=C2NC=CC2=C1 UCGLOIUEXYZMIU-UHFFFAOYSA-N 0.000 description 1
- 229910017107 AlOx Inorganic materials 0.000 description 1
- LWBFNUKTNRHYKJ-UHFFFAOYSA-N Br.CCCCCCCCCCCCCCCC Chemical compound Br.CCCCCCCCCCCCCCCC LWBFNUKTNRHYKJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*)(c1c2)c(cc(cc3)-c4ccccc4S(C)=O)c3-c1cc1c2-c(ccc(-c(cccc2)c2S(C)=O)c2)c2[N+]1 Chemical compound CC(*)(c1c2)c(cc(cc3)-c4ccccc4S(C)=O)c3-c1cc1c2-c(ccc(-c(cccc2)c2S(C)=O)c2)c2[N+]1 0.000 description 1
- AMBPAMKAOCOWKD-UHFFFAOYSA-N CS(C(CCC=C1)=C1Br)=O Chemical compound CS(C(CCC=C1)=C1Br)=O AMBPAMKAOCOWKD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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Abstract
The present invention relates to a kind of nine yuan of fused-ring derivatives and its synthetic method and applications.The present invention carries out simultaneously ring reaction by the way that five-membered ring unit is coupled sulfoxide group benzene unit, obtains a kind of aromatic compound with nine yuan of macrocyclic structures.Such nine yuan of fused ring compounds have high thermal stability and high hole mobility, can be applied in organic field effect tube device as active layer, obtain the organic field effect tube of high-performance and high stability.
Description
Technical field
The invention belongs to organic photoelectric technical fields, and in particular to a kind of nine yuan of fused-ring derivatives and its synthetic method with answer
With.
Background technology
The report of organic field effect tube can trace back to the eighties in last century earliest, Ando in 1986 et al. electrifications
Method has synthesized the p-type semiconductor material based on polythiophene unit, but at that time, and the hole mobility of material only has 10- 5cm2V-1s-1, current on/off ratio also only have 100 (Appl.Phys.Lett., 1986,49 (18), 1210-1212).Finally simultaneously
The appearance of pentaphene small molecule makes the development of OFET materials has significantly to leap, and Jackson et al. was prepared in 1997
Go out the regular pentacene small molecule OFET devices of packing structure, obtains up to 1.5cm2V-1s-1Hole mobility and 108's
Switching current ratio (IEEE Electr.Device L., 1997,18 (12), 606-608).But hereafter more high mobility
The report of OFET materials is more rare, and report of the OFET materials in terms of threshold voltage and stability is more rarely seen, therefore is carrying
High mobility reduces threshold voltage, also has prodigious excavation space in terms of increasing the stability of device.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to synthesize the small of the big conjugate planes of nine-atomic ring structure
Molecular organic semiconductor material, such material has higher mobility, suitable for organic field effect tube.
The purpose of the present invention is to provide a kind of nine yuan of condensed ring analog derivative structure small molecules of high mobility.
Nine yuan of fused-ring derivatives of the present invention are obtained by ring-closure reaction and oxidation reaction.
Nine yuan of fused-ring derivatives of one kind of the present invention, chemical structural formula are as follows：
Wherein nine yuan of condensed ring form big conjugate planes structure
R1For C1~C30Straight chain or branched alkyl；
R2For H, C1~C30Straight chain or branched alkyl, OC1~OC30Straight chain or branched alkyl；
R3、R4、R5、R6It is identical or different, it is H, C1~C30Straight chain or branched alkyl, OC1~OC30Straight chain or
Person's branched alkyl, F, CF3Or(wherein R7For H, C1~C30Straight chain or branched alkyl, OC1~OC30's
Straight chain or branched alkyl, F or CF3)；
X, Y includes following combination：X=S, Y=O；Or X=S, Y are free of any element；
Z=O, S, Se, N, P, C, Si, Ge or Sn.
Described nine yuan of fused-ring derivatives of one kind, synthetic route are as follows：
Wherein compound 4 and compound 5 are nine yuan of fused-ring derivatives；
The synthesis step of nine yuan of fused-ring derivatives of one kind is as follows：
(1) 1 molar equivalent five yuan of fused ring compounds of alkylated 3,9- dibromos are dissolved in dioxane, inert gas ring
The potassium acetate of 2~5 molar equivalents double pinacol borates and 5~10 molar equivalents is added in border, stirs, raising temperature to 50~
The bis- Diphenyl phosphino ferrocene palladium chlorides reactions of 1,1'- of 0.01-0.055 molar equivalents 5~24 hours are added at 120 DEG C, instead
It is cooled to room temperature after answering and filters, filtrate obtains product 2 after column chromatography purifies；
(2) 1 molar equivalent product 2 is dissolved in toluene, 2- bromines (methanesulfinyl) benzene of 2~4 molar equivalents is added,
The tetrabutylammonium bromide of 0.05~0.2 molar equivalent and the tetrakis triphenylphosphine palladium of 0.02-0.1 molar equivalents, are heated to reflux
Reaction 2~24 hours, after reaction, is cooled to room temperature, extracts, dry, and column chromatography purifies to obtain product 3；
(3) 1 molar equivalent product 3 is added in trifluoromethanesulfonic acid or trifluoroacetic acid, while is added 1.5-4.0 moles
The phosphorus pentoxide of equivalent reacts at room temperature 5~24 hours, reaction solution is added drop-wise in water and is taken out after reaction under confined conditions
Filter, filter residue are heated to reflux after drying in pyridine 2~12 hours, and extraction, column chromatography purification, recrystallization, obtain after reaction
Product 4；
(4) 1 molar equivalent product 4 is dissolved in dichloromethane, the 3- chloroperoxybenzoic acids of 4~30 molar equivalents is added,
It is reacted under ice bath 5~10 hours, soda lye wash, extraction, dry, column chromatography purification, recrystallization is used to obtain nine yuan after reaction
Fused-ring derivatives small molecule product 5.
Such nine yuan of fused-ring derivatives have hole mobility that is high and stablizing, and mobility is between 0.1~5.0 square
Centimetre per volts per second.Application that can be as active layer in organic field effect tube device；Organic effect is brilliant
The thickness of the active layer of body tube device is 20-1000 nanometers；The active layer of the organic field effect tube device is to pass through
Solution processing method is realized, including spin coating, brushing, spraying, dip-coating, roller coating, silk-screen printing, printing or inkjet printing methods；Wherein
Solvent for use is organic solvent；The preparation of the active layer of the organic field effect tube device is to carry out in air.
Compared with prior art, the present invention has the advantage that as follows with technique effect：
Provide a kind of synthetic method of big condensed ring class aromatic compound；Due to and ring introducing, increase the rigid of molecule
Property and flatness, so that the conjugacy of molecule is increased, the thermal stability to can not only improve material can also improve material biography
Lead hole ability.Currently, most of organic field effect tube material is made in the glove box of inert gas shielding
It is standby and obtain, however the big condensed ring class aromatic compound synthesized by the present invention can carry out preparing organic effect crystal in air
The active layer of tube device, and show good hole migration performance and stability.Implementation through the invention, will set for future
Meter and the organic effect tube material for synthesizing high mobility, low cost and high stability provide certain guidance basis.
Description of the drawings
Fig. 1 is 4 differential scanning calorimetric curve figure of compound.
Fig. 2 is 4 thermal gravimetric analysis curve figure of compound.
Fig. 3 is 4 solution absorption spectra figure of compound.
Fig. 4 is the abosrption spectrogram of 4 film of compound.
Fig. 5 is 4 solution launching light spectrogram of compound.
Fig. 6 is 4 film launching light spectrogram of compound.
Fig. 7 is 4 Cyclic voltamogram curve graph of compound.
Fig. 8 is 4 transfer characteristic curve figure of compound.
Specific implementation mode
Each component monomer proposed by the invention is illustrated with reference to embodiment, example that the present invention is not limited thereto.
The synthesis of 1 3,9- of embodiment, bis- bromo- 5,11- double hexadecyls indole carbazoles (1)
3,9- dibromos indole carbazole (1.0g, 2.4mmol) is dissolved in the tri- mouthfuls of burnings of 250mL for filling 40mL dimethyl sulfoxide (DMSO)s
Bottle in, while be added mass fraction be 50% potassium hydroxide solution (1.4mL) and tetrabutylammonium bromide (77mg,
0.24mmol), 30min being stirred in nitrogen atmosphere, hexadecane bromide (2.2g, 7.2mmol) is added later.Reaction is warming up to 65 DEG C
And react 4h.The reaction was cooled to room temperature later is poured into 300mL methanol and stirs.Filter and use N,N-dimethylformamide,
Methanol and acetone wash 1-3 times, finally obtain pale yellow powder shape solid 1.5g, yield 72%.
Bis- (penta ring -2- bases of 4,4,5,5- tetramethyl -1,3,2- dioxies the boron) -5,11- double hexadecyls of 2 3,9- of embodiment
The synthesis of indole carbazole (2)
By 3,9-, bis- bromo- 5,11- double hexadecyls indole carbazoles (1.0g, 1.1mmol), potassium acetate (1.08g, 11mmol)
Be dissolved in the 100mL three neck round bottom flask equipped with 50mL dioxane with double pinacol borates (0.9g, 3.5mmol) and
It is stirred in nitrogen atmosphere.Temperature rapidly joined when rising to 80 DEG C the bis- Diphenyl phosphino ferrocene palladium chlorides of 1,1'- (40mg,
0.055mmol).Reaction is cooled to room temperature and filters after carrying out for 24 hours.Filtrate head product is obtained with silica gel/dichloromethane column chromatography
To yellow needle-like crystals 0.7g, yield 63%.
The synthesis of embodiment 3 3,9- bis- (2- first sulfenyls phenyl) -5,11- double hexadecyls indole carbazole (3)
By the K of 10mL 2M2CO3Solution, 3,9- bis- (4,4,5,5- tetramethyls -1,3, penta ring -2- bases of 2- dioxies boron) -5,
11- double hexadecyls indole carbazole (2.0g, 2.1mmol) and 2- bromines (methanesulfinyl) benzene (1.42g, 6.5mmol) are dissolved in
In 100mL toluene solutions, while tetrakis triphenylphosphine palladium (100mg) and tetrabutylammonium bromide (60mg) is added, reaction is heated back
Stream is for 24 hours.The reaction was cooled to room temperature later and is extracted with dichloromethane.Organic phase is dried, and is evaporated under reduced pressure and with silica gel, acetic acid second
Ester/petroleum ether (volume ratio 1:2) it is that mobile phase carries out column chromatography, obtains clear yellow viscous oily liquid (1.25g, 61%).
4 5,11- double hexadecyls two of embodiment [2-b, 3；8-b, 9] benzo [d] thiophene indole [3,2-b] carbazole (4)
Synthesis
3,9- bis- (2- first sulfenyls phenyl) -5,11- double hexadecyls indole carbazole (2.1g, 2.2mmol) is added to
15mL trifluoromethanesulfonic acids, and 1.0g phosphorus pentoxides are added.Reaction is stirred for 24 hours at room temperature, is later slowly dropped to reaction solution
In ice water, filters and dry filter residue obtains pale yellow powder solid.Pale yellow powder is dissolved into 100mL pyridines, nitrogen gas
12h demethylations are heated to reflux in atmosphere.The reaction was cooled to room temperature later, is neutralized with hydrochloric acid and is extracted with dichloromethane, crude product
With silica gel, petroleum ether/dichloromethane (volume ratio 2:1) it is that mobile phase carries out chromatographic column, then is obtained with re-crystallizing in ethyl acetate
Yellow powdery solid (0.8g, 40%).Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8 are respectively the differential of compound 4
Scanning calorimetric curve figure, thermal gravimetric analysis curve figure, solution absorption spectra figure, the abosrption spectrogram of film, solution launching light spectrogram,
Film launching light spectrogram, Cyclic voltamogram curve graph and transfer characteristic curve figure.By test it is known that compound 4 has
There is relatively high thermal stability, heat decomposition temperature is close to 400 degrees Celsius；Optical property shows that compound 4 is than wider band
Gap macromolecular, and if be polar compound, there is weaker solvent polarity effect in polar solvent；Electrochemical Characterization table
The minimum non-occupied orbital energy level of face compound 4 is close to -5.0 electron-volts；It is characterized by organic field effect tube, chemical combination
The hole mobility of object is more than that 0.1 centimeters per volt is per second.
5 5,11- double hexadecyls two of embodiment [2-b, 3；8-b, 9] benzo [d]-S, S- dioxy thiophene indoles [3,2-b]
The synthesis of carbazole (5)
By 5,11- double hexadecyls two [2-b, 3；8-b, 9] benzo [d] thiophene indole [3,2-b] carbazole (156mg,
0.17mmol) it is dissolved in 10mL dichloromethane and is stirred under condition of ice bath with 3- chloroperoxybenzoic acids (570mg, 3.3mmol)
Mix 10h.Reaction solution is poured into later in the sodium hydrate aqueous solution of 10% cold mass concentration and stirs 30min, extraction, drying.
Organic layer is washed with water (150mL × 3), concentrates and simultaneously crosses chromatographic column, and eluant, eluent polarity is that (volume ratio is dichloromethane/tetrahydrofuran
10:1), pale yellow powder (117mg, 70%) is obtained with ethyl alcohol recrystallization later.
The synthesis of 6 6,6 ', 12,12 '-four octyl indenofluorene (6) of embodiment
Indenofluorene (254mg, 1.0mmol) is added in tri- mouthfuls of flasks of 150mL, and 60mL anhydrous tetrahydro furans are added
The temperature of reaction solution is dropped to -78 DEG C by dissolving at this time, and 2.4M n-BuLi (4.2mL, 10mmol) are slowly added dropwise after stablizing in temperature,
2h is kept the temperature later, is added at one time 1- bromooctanes (2.9g, 15mmol) and is reacted overnight.Stop reaction, reaction solution is concentrated, it
It is extracted and is washed with water 2-3 times with dichloromethane afterwards, cross chromatographic column, eluant, eluent polarity is petroleum ether/dichloromethane (volume ratio 5:
1) white solid (390mg, 0.56mmol), yield 56%, are obtained with ethyl alcohol recrystallization later.
The synthesis of 7 2,8- of embodiment, bis- bromo- 6,6 ', 12,12 '-four octyl indenofluorenes (7)
Copper bromide (10g, 44.8mmol) is diluted in 100mL water, and emerging alumina powder (20g) in addition, stirring
Moisture is evaporated under reduced pressure after uniformly, it is spare brown ceramic powder may finally to be obtained.By 6,6 ', 12,12 '-four octyl indenofluorenes
(0.7g, 1mmol) is dissolved in 30mL carbon tetrachloride solutions, and the brown ceramic powder 3g prepared is added, and is heated to reflux 10h i.e.
It can.Stop reacting later and be cooled to room temperature, reaction solution is filtered to and used carbon tetrachloride extraction filtrate, crosses chromatographic column, eluant, eluent
Polarity petroleum ether/dichloromethane (volume ratio 6:1) white powder (516mg, 60%), is finally obtained.
8 2,8- of embodiment, bis- (penta ring -2- bases of 4,4,5,5- tetramethyl -1,3,2- dioxies boron) -6,6 ', 12,12 '-four is pungent
The synthesis of base indenofluorene (8)
By 2,8- bis- bromo- 6,6 ', 12,12 '-four octyl indenofluorenes (0.86g, 1.0mmol), potassium acetate (0.93g,
10mmol) it is dissolved in tri- mouthfuls of round bottoms of the 100mL equipped with 50mL dioxane with double pinacol borates (0.9g, 3.5mmol) and burns
It is stirred in bottle and in nitrogen atmosphere.Temperature rapidly joins 1,1'- bis- Diphenyl phosphino ferrocene palladium chlorides when rising to 80 DEG C
(40mg,0.055mmol).Reaction is cooled to room temperature and filters after carrying out for 24 hours.Filtrate head product silica gel/dichloromethane column
Chromatography, obtains white solid (477mg, 50%) with recrystallizing methanol later.
The synthesis of embodiment 9 2,8- bis- (2- first sulfenyls phenyl) -6,6 ', 12,12 '-four octyl indenofluorenes (9)
By the K of 10mL 2M2CO3Solution, 2,8- bis- (4,4,5,5- tetramethyls -1,3, penta ring -2- bases of 2- dioxies boron) -6,
6 ', 12,12 '-four octyl indenofluorenes (0.96g, 1.0mmol) and 2- bromines (methanesulfinyl) benzene (660mg, 3.0mmol) dissolving
In 100mL toluene solutions, while tetrakis triphenylphosphine palladium (70mg) and tetrabutylammonium bromide (40mg) is added, reaction is heated back
Stream is for 24 hours.The reaction was cooled to room temperature later and is extracted with dichloromethane.Organic phase is dried, and is evaporated under reduced pressure and with silica gel, acetic acid second
Ester/petroleum ether (volume ratio 1:2) it is that mobile phase progress column chromatography obtains yellow solid (0.6g, 61%).
10 6,6 ', 12,12 '-four octyl of embodiment, two [2,3-b；8,9-b] benzo [d] thiophene indenofluorene (10) synthesis
2,8- bis- (2- first sulfenyls phenyl) -6,6 ', 12,12 '-four octyl indenofluorenes (0.98g, 1.0mmol) are added to
5mL trifluoromethanesulfonic acids, and 0.5g phosphorus pentoxides are added.Reaction is stirred for 24 hours at room temperature, and reaction solution is slowly dropped to ice later
In water, filters and dry filter residue obtains pale yellow powder solid.Pale yellow powder is dissolved into 50mL pyridines, in nitrogen atmosphere
It is heated to reflux 12h demethylations.The reaction was cooled to room temperature later, is neutralized with hydrochloric acid and is extracted with dichloromethane, organic phase is slightly produced
Object crosses chromatographic column, eluant, eluent polarity petroleum ether/dichloromethane (volume ratio 3:1), then with ethyl alcohol recrystallization white powder is obtained
Shape solid (0.36g, 40%).
11 6,6 ', 12,12 '-four octyl of embodiment, two [2,3-b；8,9-b] benzo [d]-S, S- dioxy thiophene indenofluorene
(11) synthesis
By 6,6 ', 12,12 '-four octyl, two [2,3-b；8,9-b] benzo [d] thiophene indenofluorene (0.92g, 1.0mmol) and
3- chloroperoxybenzoic acids (3.46g, 20mmol) are dissolved in 100mL dichloromethane and stir 10h under condition of ice bath.Later will
Reaction solution pours into the sodium hydrate aqueous solution of 10% cold mass concentration and stirs 30min.(150mL × 3) are washed with water in organic layer,
Chromatographic column is concentrated and crosses, eluant, eluent polarity is dichloromethane/tetrahydrofuran (volume ratio 10:1) it, is obtained later with ethyl alcohol recrystallization
To pale yellow powder (0.69g, 70%).
Embodiment 12 5,5 ', 7,7 '-tetramethyl benzo [b] [1] benzo thiophene coughs up the conjunction that [3,2-f] [1] benzo thiophene coughs up (12)
At
By 2,2 ", 4 ', 6 '-four bromo- 1,1 ':3 ', 1 "-ortho-terphenyl (546mg, 1.0mmol) is added to 250mL flasks
In, with (300 milliliters) dissolvings of anhydrous ether, 0 DEG C is cooled to, 2.4M n-BuLi (4.2mL, 10mmol) are slowly added dropwise, is kept the temperature
Dimethyldichlorosilane (1.94g, 15mmol) is diluted with 10mL n-hexanes and is added in reaction solution, reacted at room temperature by 2h
12h.Stop reaction, reaction solution dichloromethane is extracted and washed, with petroleum ether/dichloromethane (volume ratio 1:1) it is flowing
Chromatographic column is mutually crossed, white solid (137mg, 40%) is obtained.
13 3,9- of embodiment, bis- bromo- 5,5 ', 7,7 '-tetramethyl benzo [b] [1] benzo thiophenes cough up [3,2-f] [1] benzo thiophene
Cough up the synthesis of (13)
5,5 ', 7,7 '-tetramethyl benzo [b] [1] benzo thiophenes are coughed up [3,2-f] [1] benzo thiophene to cough up (0.34g, 1.0mmol)
It is dissolved in 50mL tetrahydrofurans, bromine (0.3mL, 5.0mmol) is slowly added dropwise under condition of ice bath, stop reaction after reacting 8h.
Reaction solution is concentrated, extracted with dichloromethane and is washed, obtains crude product (0.25g, 50%) with ethyl alcohol recrystallization later.
Embodiment 14 3,9- bis- (penta ring -2- bases of 4,4,5,5- tetramethyl -1,3,2- dioxies boron) -5,5 ', 7,7 '-tetramethyls
Base benzo [b] [1] benzo thiophene coughs up the synthesis that [3,2-f] [1] benzo thiophene coughs up (14)
By bis- bromo- 5,5 ', 7,7 '-tetramethyl benzo [b] [1] benzo thiophenes of 3,9- cough up [3,2-f] [1] benzo thiophene cough up (0.5g,
1.0mmol), potassium acetate (0.93g, 10mmol) and double pinacol borates (1.02g, 4mmol) are dissolved in equipped with 50mL dioxies
It is stirred in the 100mL three neck round bottom flask of six rings and in nitrogen atmosphere.Temperature rapidly joins 1,1'- bis- hexichol when rising to 80 DEG C
Base phosphine ferrocene palladium chloride (40mg, 0.055mmol).Reaction is cooled to room temperature and filters after carrying out for 24 hours.Filtrate head product
With silica gel/dichloromethane column chromatography, faint yellow solid (226mg, 38%) is obtained with recrystallizing methanol later.
Embodiment 15 3,9- bis- (2- first sulfenyls phenyl) -5,5 ', 7,7 '-tetramethyl benzo [b] [1] benzo thiophene cough up [3,
2-f] [1] benzo thiophene coughs up the synthesis of (15)
By the K of 10mL 2M2CO3Solution, 3,9- bis- (4,4,5,5- tetramethyls -1,3, penta ring -2- bases of 2- dioxies boron) -5,
5 ', 7,7 '-tetramethyl benzo [b] [1] benzo thiophenes cough up [3,2-f] [1] benzo thiophene and cough up (1.20g, 2.0mmol) and 2- bromines (first Asia
Sulfonyl) benzene (1.31g, 6.0mmol) is dissolved in 100mL toluene solutions, while be added tetrakis triphenylphosphine palladium (100mg) and
Tetrabutylammonium bromide (50mg), reaction are heated to reflux for 24 hours.The reaction was cooled to room temperature later and is extracted with dichloromethane.It is organic
It is mutually dry, it is evaporated under reduced pressure and with silica gel, ethyl acetate/petroleum ether (volume ratio 1:1) it is that mobile phase carries out column chromatography, obtains light
Yellow solid (0.7g, 56%).
16 5,5 ', 7,7 '-tetramethyl two of embodiment [2-b, 3；9,10-b] benzo [d] thiophene benzo [b] [1] benzo thiophene
Cough up the synthesis that [3,2-f] [1] benzo thiophene coughs up (16)
- 5,5 ', 7,7 '-tetramethyl benzo [b] [1] benzo thiophenes of 3,9- bis- (2- first sulfenyls phenyl) cough up [3,2-f] [1] benzene
And thiophene coughs up (1.24g, 2.0mmol) and is added to 8mL trifluoromethanesulfonic acids, and 0.5g phosphorus pentoxides are added.Reaction is stirred at room temperature
For 24 hours, reaction solution is slowly dropped in ice water later, filters and dry filter residue obtains pale yellow powder solid.By yellowish toner
End is dissolved into 100mL pyridines, and 8h demethylations are heated to reflux in nitrogen atmosphere.The reaction was cooled to room temperature later, in hydrochloric acid
It is extracted with and with dichloromethane, organic phase crude product crosses chromatographic column, eluant, eluent polarity petroleum ether/dichloromethane (volume ratio 1:
1) white powdery solids (0.67g, 60%), then with ethyl alcohol recrystallization are obtained.
It is prepared by 17 FET device of embodiment
Prepare field-effect transistor and the field effect behavior of compound be measured, device be contact type, use it is golden as
Source electrode and drain electrode, specific device architecture are Al/AlOx:Nd/PMMA/ICzBT/Au.Using glass as substrate, splashed in glass surface
One layer of aluminium is penetrated as grid, while (preparation of above substrate has manufacturer as gate insulation layer in one layer of aluminium oxide of the performance of aluminium plating
It completes, can be directly commercially available).Since the surface of aluminium oxide is more coarse, it is unfavorable for the film forming of compound, therefore in gate insulation
(PMMA, is made into the n-butyl acetate solution that mass fraction is 3% to one strata methyl methacrylate of layer surface spin coating, and rejection film turns
Fast 2000rpm, film thickness 130nm, 220 DEG C of annealing 30min in nitrogen glove box) improve interfacial contact, compound is prepared
At the toluene solution of mass fraction 0.7%, 2000rpm rotating speeds rejection film (30~40nm of film thickness) on PMMA is moved back for 100 DEG C in air
Fire processing 10min, later 3 × 10-4One layer of molybdenum oxide (MoO is deposited in the vacuum degree of Pa3, 0.01~0.05nm/ of evaporation rate
S, film thickness about 45nm), then source electrode and drain electrode of the gold evaporation as device under similarity condition.Device is in no encapsulating
It is tested in the atmospheric environment that humidity is about 70%.The transistor device length and width raceway groove ratio (W/L) of preparation is 500/70 μm.
The photoelectric properties of transistor are tested on Semiconductor Parameter Analyzer (Aglient 4155C) and step instrument, test environment
For atmosphere at room temperature atmosphere.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all the present invention
All any modification, equivalent and improvement etc., should be included in the protection of the claims in the present invention made by within spirit and principle
Within the scope of.
Claims (7)
1. the synthetic method of a kind of nine yuan of fused-ring derivatives, the chemical structural formula of nine yuan of fused-ring derivatives are as follows：
Its structure is limited by following (1)；
(1) wherein nine yuan of condensed ring form big conjugate planes structure,
R1For C1~C30Straight chained alkyl or C1~C30Branched alkyl；
R2For H, C1~C30Straight chained alkyl, C1~C30Branched alkyl, OC1~OC30Straight chained alkyl or OC1~OC30Branch
Alkyl；
R3、R4、R5、R6It is identical or different, it is H, C1~C30Straight chained alkyl, C1~C30Branched alkyl, OC1~OC30Straight chain
Alkyl, OC1~OC30Branched alkyl, F, CF3OrWherein R7For H, C1~C30Straight chained alkyl, C1~C30Branched alkane
Base, OC1~OC30Straight chained alkyl, OC1~OC30Branched alkyl, F or CF3；
X, Y includes following combination：X=S, Y=O are not present；
Z=N or P；It is characterized in that, synthetic route is as follows：
Wherein compound 4 and compound 5 are nine yuan of fused-ring derivatives.
2. synthetic method according to claim 1, which is characterized in that synthesis step is as follows：
(1) 1 molar equivalent five yuan of fused ring compounds of alkylated 3,9- dibromos are dissolved in dioxane, in inert gas environment
The potassium acetate of 2~5 molar equivalents double pinacol borates and 5~10 molar equivalents is added, stirring increases temperature to 50~120
DEG C when the bis- Diphenyl phosphino ferrocene palladium chlorides of 1,1'- of 0.01-0.055 molar equivalents be added react 5~24 hours, reaction is tied
Beam postcooling is to room temperature and filters, and filtrate obtains product 2 after column chromatography purifies；
(2) 1 molar equivalent product 2 is dissolved in toluene, 2- bromines (methanesulfinyl) benzene of 2~4 molar equivalents of addition, 0.05~
The tetrabutylammonium bromide of 0.2 molar equivalent and the tetrakis triphenylphosphine palladium of 0.02-0.1 molar equivalents, heating reflux reaction 2~
24 hours, after reaction, it is cooled to room temperature, extracted, dry, column chromatography purifies to obtain product 3；
(3) 1 molar equivalent product 3 is added in trifluoromethanesulfonic acid or trifluoroacetic acid, while 1.5-4.0 molar equivalents is added
Phosphorus pentoxide, under confined conditions react at room temperature 5~24 hours, reaction solution is added drop-wise in water and is filtered after reaction,
Filter residue is heated to reflux after drying in pyridine 2~12 hours, and extraction, column chromatography purification, recrystallization, obtain product after reaction
4；
(4) 1 molar equivalent product 4 is dissolved in dichloromethane, the 3- chloroperoxybenzoic acids of 4~30 molar equivalents, ice bath is added
Lower reaction 5~10 hours uses soda lye wash, extraction, dry, column chromatography purification, recrystallization to obtain nine yuan of condensed ring after reaction
Derivative small molecule product 5.
3. a kind of nine yuan of fused-ring derivatives according to claim 1, which is characterized in that such nine yuan of fused-ring derivatives have
Hole mobility that is high and stablizing, mobility are per second between 0.1~5.0 centimeters per volt.
4. the answering in organic field effect tube device as active layer of a kind of nine yuan of fused-ring derivatives described in claim 1
With.
5. a kind of nine yuan of fused-ring derivatives according to claim 4 are as active layer in organic field effect tube device
Application, it is characterised in that：The thickness of the active layer of organic field effect tube device is 20-1000 nanometers.
6. a kind of nine yuan of fused-ring derivatives according to claim 4 are as active layer in organic field effect tube device
Application, it is characterised in that：The active layer of the organic field effect tube device be realized by solution processing method, including
Spin coating, brushing, spraying, dip-coating, roller coating, printing or inkjet printing methods；Wherein solution processing solvent for use is organic solvent.
7. a kind of nine yuan of fused-ring derivatives according to claim 4 are as active layer in organic field effect tube device
Application, it is characterised in that：The preparation of the active layer of the organic field effect tube device is to carry out in air.
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| PCT/CN2015/100035 WO2017028460A1 (en) | 2015-08-15 | 2015-12-31 | Nine-membered fused ring derivative, synthesis method therefor, and application thereof |
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| EP3306690B1 (en) * | 2016-10-05 | 2022-09-07 | Raynergy Tek Inc. | Organic semiconducting compounds |
| JP7101669B2 (en) * | 2016-11-25 | 2022-07-15 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Bisbenzofuran Condensation 2,8-diaminoindeno [1,2-B] Fluorene Derivatives and Related Compounds as Materials for Organic Electroluminescence Devices (OLEDs) |
| CN110582502A (en) * | 2016-12-06 | 2019-12-17 | 巴斯夫欧洲公司 | Thieno-indeno-monomers and polymers |
| CN106866940A (en) * | 2017-01-17 | 2017-06-20 | 华南理工大学 | A kind of conjugated polymer for being based on 3,7 naphtho- sulphur dibenzofuran units and preparation method and application |
| CN106916163A (en) * | 2017-02-28 | 2017-07-04 | 华南理工大学 | Based on heteroaromatic and 3 S, the bipolarity small molecule emitter material of S dioxydibenze bithiophene units and its preparation method and application |
| CN107987255B (en) * | 2017-11-22 | 2019-12-03 | 华南协同创新研究院 | Containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring unit polymer and its preparation method and application |
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| JP5390959B2 (en) * | 2009-06-30 | 2014-01-15 | ウシオケミックス株式会社 | Organic semiconductor compound having sulfone structure |
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| "Conjugated Ladder-Type Heteroacenes Bearing Pyrrole and Thiophene Ring Units: Facile Synthesis and Characterization";Peng Gao et al.;《J. Org. Chem.》;20081111;第73卷(第23期);第9207-9213页 * |
| "Heteroheptacenes with Fused Thiophene and Pyrrole Rings";Peng Gao et al.;《Chem. Eur. J.》;20100326;第16卷;第5119-5128页 * |
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