CN106749315B - 8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound and its synthetic method - Google Patents
8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound and its synthetic method Download PDFInfo
- Publication number
- CN106749315B CN106749315B CN201611197432.1A CN201611197432A CN106749315B CN 106749315 B CN106749315 B CN 106749315B CN 201611197432 A CN201611197432 A CN 201611197432A CN 106749315 B CN106749315 B CN 106749315B
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- China
- Prior art keywords
- hexyl
- benzo
- thieno
- carbazole
- thiophene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- -1 8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound Chemical class 0.000 title claims abstract description 33
- 238000010189 synthetic method Methods 0.000 title abstract description 13
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229930192474 thiophene Natural products 0.000 claims abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 13
- UGFOTZLGPPWNPY-UHFFFAOYSA-N 7h-benzo[c]carbazole Chemical compound C1=CC=CC2=C3C4=CC=CC=C4NC3=CC=C21 UGFOTZLGPPWNPY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000010898 silica gel chromatography Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 230000002045 lasting effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000007363 ring formation reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims 1
- MDOAAHGPXOGVQG-UHFFFAOYSA-N ethene;propane Chemical compound C=C.CCC MDOAAHGPXOGVQG-UHFFFAOYSA-N 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
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- 241001597008 Nomeidae Species 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
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- 238000012805 post-processing Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- UOYPNWSDSPYOSN-UHFFFAOYSA-N hexahelicene Chemical group C1=CC=CC2=C(C=3C(=CC=C4C=CC=5C(C=34)=CC=CC=5)C=C3)C3=CC=C21 UOYPNWSDSPYOSN-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
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- JKPCLJPYZMKPHM-UHFFFAOYSA-N pentahelicene Chemical compound C1=CC=C2C3=C4C5=CC=CC=C5C=CC4=CC=C3C=CC2=C1 JKPCLJPYZMKPHM-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000707 boryl group Chemical group B* 0.000 description 4
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- ZADYHNRFHQXTOH-UHFFFAOYSA-N heptahelicene Chemical compound C1=CC=C2C3=C(C=4C(=CC=C5C=CC=6C(C=45)=CC=CC=6)C=C4)C4=CC=C3C=CC2=C1 ZADYHNRFHQXTOH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- ORNUPNRNNSVZTC-UHFFFAOYSA-N 2-vinylthiophene Chemical compound C=CC1=CC=CS1 ORNUPNRNNSVZTC-UHFFFAOYSA-N 0.000 description 1
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- AJELTBZXWAHPDD-UHFFFAOYSA-N B(O)(O)O.[C] Chemical compound B(O)(O)O.[C] AJELTBZXWAHPDD-UHFFFAOYSA-N 0.000 description 1
- BVGTZOPFMIYVLQ-UHFFFAOYSA-N BrC1=CC=CC=2C3=CC=CC=C3N(C12)CCCCCC Chemical compound BrC1=CC=CC=2C3=CC=CC=C3N(C12)CCCCCC BVGTZOPFMIYVLQ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000006550 Oxy-Cope rearrangement reaction Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229910007565 Zn—Cu Inorganic materials 0.000 description 1
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- FZICDBOJOMQACG-UHFFFAOYSA-N benzo[h]isoquinoline Chemical compound C1=NC=C2C3=CC=CC=C3C=CC2=C1 FZICDBOJOMQACG-UHFFFAOYSA-N 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QNDPUZFBWUBSNH-UHFFFAOYSA-I magic acid Chemical compound OS(F)(=O)=O.F[Sb](F)(F)(F)F QNDPUZFBWUBSNH-UHFFFAOYSA-I 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3613—Organic materials containing Sulfur
- G02F1/3614—Heterocycles having S as heteroatom
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3619—Organometallic compounds
-
- 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
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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Abstract
The present invention relates to 8- hexyl-thienos [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound (I) and its synthetic method.The present invention, using the method for photocatalysis closed loop, obtains 8- hexyl-thieno [3 ', 2 ' of a kind of favorable solubility using carbazole derivates and thiophene derivant as raw material:3,4] benzo [1,2-c] carbazole compound.Synthetic method operation of the present invention is simple, and post-processing is simple, application easy to spread.8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound is expected to be used widely in fields such as organic electroluminescent, organic field-effect tube, organic second-order non-linear, chiral liquid crystal and biological medicines.
Description
Technical field
Present invention relates particularly to a kind of 8- hexyl-thieno [3 ', 2 ' 3,4] benzo [1,2-c] carbazole compounds (to be under the jurisdiction of
Sulphur azepine [5] helicene compound) and its synthetic method, belong to technical field of organic synthesis.
Background technique
Helicene compound especially hetero atom helicene compound and its synthetic method are currently the research of organic synthesis field
Hot spot.It is as follows about the progress of hetero atom [5] helicene compound in recent years：Caronna is with symmetrical stilbenes
Double miscellaneous nitrogen [5] helicenes of Material synthesis, referring to Bazzini, C.；Brovelli,S.；Caronna,T.,et
al.Eur.J.Org.Chem.2005,1247-1257；Abbate, which is used as using phenyl ring as single ring, benzo [h] isoquinolin, to be contained
Nitrogen systems have synthesized 1- azepine and/or 3- azepine [5] helicene, referring to Abbate, S.；Bazzini,C.；Caronna,T.,et
al.Tetrahedron,2006,62,139-148)；Adam is using 2,9- dimethyl -1,10- phenanthroline as six nitrogen of Material synthesis
Miscellaneous [5] helicene, referring to Adam, R.；Ballesteros-Garrido,R.；Vallcorba,O.,et al.Tetrahedron
Lett.2013,54,4316–4319.In helicene structure introducing hetero-atoms be proved to the electric property to helicene material,
Optical property and photorefractive property are advantageous, referring to Maiorana, S.；Papagni,A.；Licandro,E.,
Tetrahedron,2003,59,6481–6488.In short, the prior art is more to the research of azepine [5] helicene, and for sulphur nitrogen
There is not been reported for the research of miscellaneous [5] helicene.
The synthesis of helicene is related to a series of chemical reaction, wherein a vital step is：Ring-closure reaction.Since helicene
Since being found for the first time, people always study ring-closure reaction.Tanaka reconciles biaryl coupling reaction according to metal, makes
Use TiCl3, DME and Zn-Cu compound synthesized [7] helicene, referring to Tanaka, K., et al., J.Org.Chem.1997,
62,4465-4470), but the method is more complicated, and the reaction time is long, nearly 40 hours time-consuming.Ogawa is according to oxy-
Cope rearrangement reaction uses KH, 18- crown ether -6, THF, NaBH4, EtOH etc. synthesized 2- acetate [5] helicene, referring to
Ogawa, Y., et al., Tetrahedron Lett.2002,43,7827-7829, but use this method from closed loop precursor
It also needs to react by 6 steps to final helicene, reaction step is too many, cumbersome.Shawn is acted on according to olefin metathesis, is used
Microwave heating technique, seal pipe, methylene chloride and ruthenium catalyst have synthesized a series of helicenes, referring to hawn, K.C., et al.,
Angew.Chem.Int.Ed.2006,45,2923-2926, but the method reaction condition require it is relatively high, used catalyst compared with
It is expensive, cause synthesis cost higher.Ichikawa utilizes magic acid, hexafluoroisopropanol, triphenyl tetrafluoro according to gram type cyclisation is paid
Boric acid carbon and 1,2- dichloroethanes have synthesized a series of helicenes, referring to Ichikawa, J., et al.,
Angew.Chem.Int.Ed.2008,47,4870-4873, but this method is comparatively laborious from closed loop precursor to final spiral shell
Alkene also needs 3 steps to react, and it is somewhat expensive to react required reagent.Oyama has synthesized two using platinum chloride and 1,2- dichloroethanes
Methyl silicon [7] helicene, referring to Oyama, H., et al., Org.Lett.2013,15 (9), 2104-2107, but the method makes
Platinum chloride catalyst is more expensive.Ruch utilizes benzylamine, palladium acetate, the bis- diphenylphosphine -9,9- xanthphos of 4,5-
A series of helicene has been synthesized with cesium carbonate, referring to Ruch, A.A., Org.Biomol.Chem.2016,14,8123-8140, but
The method is comparatively laborious, and by-product is more.It is answered in conclusion these routes and synthetic method much have Material synthesis
It is miscellaneous, reaction step is more, the reaction time is long, it is at high cost, operate and post-process the disadvantages of loaded down with trivial details, practical and economic value is by very
Big limitation.
Summary of the invention
In view of the deficiencies of the prior art, the present invention is intended to provide 8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c]
Carbazole compound and its synthetic method.
Summary of the invention：
The present invention is starting reaction raw materials with carbazole derivates and thiophene derivant, can be with by photocatalysis ring-closure reaction
A kind of sulphur azepine [5] helicene compound with good solubility and extensive use of preparation, there is not yet suchization in current material
Report in terms of conjunction object and its synthetic method.
Detailed description of the invention：
The invention is realized by the following technical scheme：
1,8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound
8- hexyl-thieno [3 ', 2 ' of the invention:3,4] benzo [1,2-c] carbazole compound has shown in general formula I
Structure：
Wherein, substituent R1-R8Independent is H, C1-C6Alkyl, halogen, boryl, containing C, H, N, O, S atom
Aromatic rings or aromatic heterocycle；R9For n-hexyl.
It is preferred according to the present invention, substituent R1-R8Independent is H, C1-C6Alkyl, Cl, Br, boryl, benzene or
Thiophene；R9For n-hexyl.
It is further preferred that R3For C1-C6Alkyl, Cl, Br, boryl, benzene or thiophene,；R1、R2、R4-R8For H；R9It is positive
Hexyl.
More preferably, above-mentioned generalformulaⅰcompound is one of following：
8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a)
The bromo- 8- hexyl-thieno [3 ', 2 ' of 11-:3,4] benzo [1,2-c] carbazole I (b)
(trimethylphenyl) boryl -8- of 11- bis- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (c)
11- thiophene -8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (d)
8- thiophene-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (e)
2,8- hexyl-thieno [3 ', 2 ':3,4] synthetic method of benzo [1,2-c] carbazole compound
8- hexyl-thieno [3 ', 2 ' of the invention:3,4] synthetic method of benzo [1,2-c] carbazole compound, with
Trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole derivates are raw material, are prepared by photocatalysis ring-closure reaction.
Chemical equation is as follows：
Reagent and condition:Benzene；I2:Iodine；Propylene oxide；hv:Ultraviolet light；
R1-R9As described in above-mentioned general structure I.
8- hexyl-thieno [3 ', 2 ' of the invention:3,4] synthetic method of benzo [1,2-c] carbazole compound, packet
Include following steps：
(1) organic solvent is purified with the way of distillation, is saved under an inert atmosphere stand-by；
(2) by trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole derivates and iodine with molar ratio (1-2):1 is added to
In the organic solvent of step (1) purifying, is stirred in dissolution, the concentration 0.0005-0.2 of solute in solution is made after being completely dissolved
Mol/L is led to inert gas 20-120 minutes；
(3) under lasting stirring state, propylene oxide is added in step (2) resulting solution, solution in ethylene third is made
The concentration of alkane is 0.05-3.0 mol/L；
(4) quartz glass irradiating step (3) are penetrated resulting solution 10-120 minutes extremely with the high-pressure sodium lamp of 100-800W
Reaction terminates, and obtains crude product；
(5) vacuum rotates out solvent, is successively 5- with mass fraction in methylene chloride by the dissolution of resulting crude product
60% Na2S2O3Solution and distillation water washing；
(6) separating-purifying is carried out to organic filtrate and obtains product.
It is preferred according to the present invention,
Organic solvent described in step (1) is selected from one of benzene, toluene, n-hexane, tetrahydrofuran or methylene chloride.
Separating-purifying in step (6) refer to organic filtrate is extracted, is washed, is dried, is spin-dried for, silica gel column chromatography,
Product is obtained after recrystallization separation.
According to the present invention it is further preferred that 8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a)
Preparation method includes the following steps：
(1) method by organic solvent-benzene air-distillation is purified, and is saved under an inert atmosphere stand-by；
(2) trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole 0.45mmol and iodine 0.45mmol is added to step
(1) it in the 500ml organic solvent-benzene purified, stirs in dissolution, after being completely dissolved, leads to inert gas 20-60 minutes；
(3) under lasting stirring state, 18ml propylene oxide is added in step (2) resulting solution, solution middle ring is made
The concentration of Ethylene Oxide is 0.4-0.6 mol/L；
(4) with the high-pressure sodium lamp of 500-800W through quartz glass irradiating step (3) resulting solution 10-60 minutes to anti-
It should terminate to obtain crude product；
(5) vacuum rotates out solvent, is successively 15- with mass fraction in methylene chloride by the dissolution of resulting crude product
20% Na2S2O3Solution and distillation water washing；
(6) organic filtrate extracted, washed, being dried, is spin-dried for, after silica gel column chromatography, recrystallization separating-purifying, being obtained
8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a).
Excellent results of the invention are as follows：
Compared with existing helicene derivative, the present invention is using carbazole derivates and thiophene derivant as raw material, extremely short
8- hexyl-thieno [3 ', 2 ' of a kind of favorable solubility is obtained in time:3,4] benzo [1,2-c] carbazole compound.This
Invention synthetic method operation is simple, and post-processing is simple, application easy to spread.Experiments have shown that 8- hexyl-thieno [3 ', 2 ':
3,4] benzo [1,2-c] carbazole compound has good dissolubility in different organic solvents, is conducive to mentioning for the compound
Pure, film；It can get a variety of sulphur azepine [5] helicene compounds by accessing different substituents.8- hexyl-thiophene provided by the invention
Pheno simultaneously [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound can be in organic electroluminescent, organic field-effect tube, organic second
It is used widely in the fields such as non-linear, chiral liquid crystal and biological medicine.
Detailed description of the invention
Fig. 1 is the hydrogen spectrogram of trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole II (a)；Abscissa is chemical shift
δ, unit：ppm.
Fig. 2 is the carbon spectrogram of trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole II (a)；Abscissa is chemical shift
δ, unit：ppm.
Fig. 3 is the mass spectrogram of trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole II (a)；Abscissa is mass-to-charge ratio m/
z；Ordinate is relative intensity, unit：%.
Fig. 4 is 8- hexyl-thieno [3 ', 2 ':3,4] the hydrogen spectrogram of benzo [1,2-c] carbazole I (a)；Abscissa is δ, single
Position：ppm.
Fig. 5 is 8- hexyl-thieno [3 ', 2 ':3,4] the carbon spectrogram of benzo [1,2-c] carbazole I (a)；Abscissa is δ, single
Position：ppm.
Fig. 6 is 8- hexyl-thieno [3 ', 2 ':3,4] mass spectrogram of benzo [1,2-c] carbazole I (a)；Abscissa is matter lotus
Compare m/z；Ordinate is relative intensity, unit：%.
Specific embodiment
The present invention will be further explained with reference to the examples below, but not limited to this.Instrument is described as follows with reagent：
High-pressure sodium lamp (Beijing source Zhong Jiaojin Science and Technology Ltd.), the method for benzene air-distillation is purified, remaining examination
Agent is that chemistry is pure.
The trans- 9- n-hexyl -3- of raw material used in embodiment (2- thiophene-vinyl) carbazole (II) (a-e) utilizes
Heck reaction preparation.
Below by taking the preparation method of the raw material II (a) of embodiment 1 as an example, reaction equation is as follows：
Preparation step is as follows：
3- bromine 9- n-hexyl carbazole：At normal temperature, magneton, 3- bromine carbazole are added into dried 250ml single-necked flask
(4.92g, 0.02mol), tetrabutylammonium bromide (TBAB, (n-C4H9)4BrN, 3g, 9.2mmol), sodium hydroxide (1.2g,
0.03mol) with 80ml acetone, stir evenly.60 DEG C at a temperature of be stirred at reflux, reaction 2-4 hour after, stop react, to
It is using constant pressure funnel that the mixing of (4.26ml, 0.03mol) 1- bromo n-hexane and acetone is molten when reaction system is air-cooled to room temperature
Liquid is slowly added dropwise into flask.Reaction system is stirred at reflux at a temperature of 50-70 DEG C, after reaction 24 hours, stops reaction.It will
Remaining acetone rotates out, is extracted using water and methylene chloride to residue, wash with distilled water after extract liquor, with nothing
Water magnesium sulfate is dry, then rotates out by methylene chloride, obtains crude product.Using silica gel column chromatography separating-purifying product,
Eluent is pure petroleum ether, finally obtains white solid 5.3g, yield 80%.1H NMR(400MHz,CDCl3,δ):8.19
(s, 1H), 8.03 (d, J=8Hz, 1H), 7.53-7.45 (m, 2H), 7.39 (d, J=8.4Hz, 1H), 7.25 (t, J=5.4Hz,
1H), 7.21 (t, J=3.8Hz, 1H), 4.25 (t, J=7.2Hz, 2H), 1.87-1.80 (m, 2H), 1.37-1.24 (m, 6H),
0.88 (t, J=8.0Hz, 3H)13C NMR(400MHz,CDCl3,δ):140.73,139.09,128.21,126.31,
124.58,123.07,121.84,120.53,119.17,111.51,110.10,108.92,43.22,31.54,28.87,
26.93,22.51,13.97.
Trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole：At normal temperature, into dried 100ml three-necked flask
Magneton, the bromo- 9- n-hexyl carbazole (2.15g, 6.5mmol) of 3-, 2- vinyl thiophene (0.70g, 6.5mmol), potassium carbonate is added
The N of (0.90g, 6.5mmol), triphenylphosphine (1.70g, 6.5mmol), palladium acetate (0.196g, 1mmol) and 30ml, N- diformazan
Base formamide (DMF), stirs evenly, and sufficiently dissolves.Led into reaction phase argon gas 20-40 minutes using gas-guide tube, is then taken out true
It is 3 times empty.Reaction system is stirred at reflux at a temperature of 100 DEG C, is reacted 40-50 hours, reaction is stopped.Water is mutually poured into reaction
In, then water phase is extracted 3 times with methylene chloride.It is dry with anhydrous magnesium sulfate wash with distilled water after extract liquor, then by two
Chloromethanes rotates out, obtains crude product.Using silica gel column chromatography separating-purifying product, eluent is petroleum ether：Dichloromethane
Alkane=25：1, finally obtain yellow solid 0.59g, yield 25%.1H NMR(400MHz,CD2Cl2,δ):8.22(s,1H),
8.14 (d, J=7.6Hz, 1H), 7.66 (dd, J=2.67Hz, 1H), 7.52-7.42 (m, 3H), 7.34 (d, J=16.4Hz,
1H), 7.27 (dd, J=4.9Hz, 1H), 7.22 (dd, J=6.3Hz, 2H), 7.14 (t, J=7.8Hz, 1H), 7.06 (dd, J=
2.8Hz, 1H), 4.32 (t, J=7.2Hz, 2H), 1.89 (t, J=7.4Hz, 2H), 1.35-1.30 (m, 6H), 0.90 (t, J=
7Hz,3H).13C NMR(400MHz,CD2Cl2,δ):143.59,140.90,140.25,129.31,128.00,127.56,
125.82,125.12,124.13,123.46,123.09,122.68,120.26,119.06,118.95,118.27,109.06,
108.97,43.17,31.56,28.90,26.89,22.53,13.75.HRMS(m/z):360.1789[M+H]+(Calcd for
C24H25NS:360.1741).
Embodiment 1：8- hexyl-thieno [3 ', 2 ':3,4] preparation of benzo [1,2-c] carbazole (I a)
8- hexyl-thieno [3 ', 2 ':3,4] preparation of benzo [1,2-c] carbazole (I a), steps are as follows：
(1) method by organic solvent-benzene air-distillation is purified, and is saved under an inert atmosphere stand-by；
(2) trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole 0.45mmol and iodine 0.46mmol is added to step
(1) it in the 500ml organic solvent-benzene purified, quickly stirs in dissolution, after being completely dissolved, leads to inert gas 20-60 minutes；
(3) under lasting stirring state, 18ml propylene oxide is added in step (2) resulting solution, solution middle ring is made
The concentration of Ethylene Oxide is 0.4-0.6 mol/L；
(4) quartz glass irradiating step (3) are penetrated resulting solution 10-60 minutes extremely with the high-pressure sodium lamp of 500-800W W
Reaction terminates to obtain crude product；
(5) vacuum rotates out solvent, is successively 15- with mass fraction in methylene chloride by the dissolution of resulting crude product
20% Na2S2O3Solution and distillation water washing；
(6) organic filtrate extracted, washed, being dried, is spin-dried for, after silica gel column chromatography, recrystallization separating-purifying, being obtained
8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a).Yield 0.039g, yield 24%.
The compound in n-hexane, toluene, dichloroethanes, ethyl acetate, acetonitrile, methanol the experiment proved that have good
Dissolubility.
Now by 8- hexyl-thieno [3 ', 2 ':3,4] Spectrum Analysis of benzo [1,2-c] carbazole is as follows：
1H NMR(300MHz,CDCl3,δ):8.33 (s, 2H), 7.78-7.74 (m, 2H), 7.40 (dd, J=4Hz, 4H),
7.31 (dd, J=5.3Hz, 1H), 7.17 (dd, J=2.8Hz, 1H), 4.29 (t, J=7.2Hz, 2H), 1.91 (t, J=
7.2Hz, 2H), 1.43-1.38 (m, 2H), 1.37-1.31 (m, 4H), 0.92 (t, J=7Hz, 3H)
13C NMR(300MHz,CDCl3,δ):139.78,139.71,139.59,133.85,127.67,126.66,
126.57,126.08,124.40,123.49,123.46,123.27,118.64,118.09,115.39,109.38,109.20,
43.24,31.61,29.27,27.00,22.58,14.03.
HRMS(m/z):358.1619[M+H]+(Calcd for C24H23NS:358.1585).
The trans- 9- n-hexyl -3- of raw material (2- thiophene-vinyl) carbazole and product 8- hexyl-thieno [3 ', 2 ':3,4] benzene
And the nuclear magnetic resoance spectrum, mass spectrum of [1,2-c] carbazole are as shown in the picture.
Embodiment 2：11-8- hexyl-thieno [3 ', 2 ':3,4] preparation of benzo [1,2-c] carbazole I (b)
Chemical equation is as follows：
Embodiment 3：(trimethylphenyl) boryl -8- of 11- bis- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I
(c) preparation
Chemical equation is as follows：
Embodiment 4：11- thiophene -8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (d)
Chemical equation is as follows：
Embodiment 5：8- thiophene-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (e)
Chemical equation is as follows：
Claims (7)
1. 8- hexyl-thieno [3 ', 2 ' with structure shown in general formula I:3,4] benzo [1,2-c] carbazole compound
Preparation method, which is characterized in that, as raw material, urged by light using trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole derivates
Change ring-closure reaction to be prepared；
Chemical equation is as follows：
Reagent and condition:Benzene；I2:Iodine；Propylene oxide；hv:Ultraviolet light；
Wherein, substituent R1-R8Independent is H, C1-C6Alkyl, halogen, containing C, H, N, O, S atom aromatic rings or virtue
Fragrant heterocycle；R9For n-hexyl.
2. 8- hexyl-thieno [3 ', 2 ' as described in claim 1:3,4] preparation of benzo [1,2-c] carbazole compound
Method, which is characterized in that substituent R in general formula I1-R8Independent is H, C1-C6Alkyl, Cl, Br, benzene or thiophene；R9For
N-hexyl.
3. 8- hexyl-thieno [3 ', 2 ' as claimed in claim 1 or 2:3,4] system of benzo [1,2-c] carbazole compound
Preparation Method, which is characterized in that R in general formula I3For C1-C6Alkyl, Cl, Br, benzene or thiophene,；R1、R2、R4-R8For H；R9It is positive oneself
Base.
4. 8- hexyl-thieno [3 ', 2 ' as claimed in claim 1 or 2:3,4] system of benzo [1,2-c] carbazole compound
Preparation Method, which is characterized in that generalformulaⅰcompound is one of following：
8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a)
The bromo- 8- hexyl-thieno [3 ', 2 ' of 11-:3,4] benzo [1,2-c] carbazole I (b)
11- thiophene -8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (d)
5. 8- hexyl-thieno [3 ', 2 ' as described in claim 1:3,4] preparation of benzo [1,2-c] carbazole compound
Method, which is characterized in that include the following steps：
(1) organic solvent is purified with the way of distillation, is saved under an inert atmosphere stand-by；
(2) by trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole derivates and iodine with molar ratio (1-2):1 is added to step
(1) it in the organic solvent purified, is stirred in dissolution, the concentration 0.0005-0.2 of solute in solution is made to rub after being completely dissolved
You/liter, lead to inert gas 20-120 minutes；
(3) under lasting stirring state, propylene oxide is added in step (2) resulting solution, solution in ethylene propane is made
Concentration is 0.05-3.0 mol/L；
(4) it is extremely reacted within resulting solution 10-120 minutes with the high-pressure sodium lamp of 100-800W through quartz glass irradiating step (3)
Terminate, obtains crude product；
(5) vacuum rotates out solvent, is successively 5-60%'s with mass fraction in methylene chloride by the dissolution of resulting crude product
Na2S2O3Solution and distillation water washing；
(6) separating-purifying is carried out to organic filtrate and obtains product.
6. 8- hexyl-thieno [3 ', 2 ' as claimed in claim 5:3,4] preparation of benzo [1,2-c] carbazole compound
Method, which is characterized in that the separating-purifying in step (6) refer to organic filtrate is extracted, is washed, is dried, is spin-dried for, silica gel
Product is obtained after column chromatography, recrystallization separation.
7. 8- hexyl-thieno [3 ', 2 ' as claimed in claim 4:3,4] preparation method of benzo [1,2-c] carbazole I (a),
Include the following steps：
(1) method by organic solvent-benzene air-distillation is purified, and is saved under an inert atmosphere stand-by；
(2) that trans- 9- n-hexyl -3- (2- thiophene-vinyl) carbazole 0.45mmol and iodine 0.45mmol is added to step (1) is pure
It in the 500ml organic solvent-benzene of change, stirs in dissolution, after being completely dissolved, leads to inert gas 20-60 minutes；
(3) under lasting stirring state, 18ml propylene oxide is added in step (2) resulting solution, solution in ethylene third is made
The concentration of alkane is 0.4-0.6 mol/L；
(4) it is tied with the high-pressure sodium lamp of 500-800W through quartz glass irradiating step (3) extremely reaction in resulting solution 10-60 minutes
Beam obtains crude product；
(5) vacuum rotates out solvent, is successively 15-20% with mass fraction in methylene chloride by the dissolution of resulting crude product
Na2S2O3Solution and distillation water washing；
(6) organic filtrate extracted, washed, being dried, is spin-dried for, silica gel column chromatography, recrystallization separating-purifying after, obtain 8- oneself
Base-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a).
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