CN106749315A - 8 hexyl thiophenes simultaneously [3 ', 2 ':3,4] benzo [1,2 c] carbazole compound and its synthetic method - Google Patents
8 hexyl thiophenes simultaneously [3 ', 2 ':3,4] benzo [1,2 c] carbazole compound and its synthetic method Download PDFInfo
- Publication number
- CN106749315A CN106749315A CN201611197432.1A CN201611197432A CN106749315A CN 106749315 A CN106749315 A CN 106749315A CN 201611197432 A CN201611197432 A CN 201611197432A CN 106749315 A CN106749315 A CN 106749315A
- Authority
- CN
- China
- Prior art keywords
- benzo
- hexyls
- carbazole
- thieno
- 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.)
- Granted
Links
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- -1 carbazole compound Chemical class 0.000 title claims abstract description 32
- 238000010189 synthetic method Methods 0.000 title abstract description 13
- QZVHYFUVMQIGGM-UHFFFAOYSA-N 2-Hexylthiophene Chemical class CCCCCCC1=CC=CS1 QZVHYFUVMQIGGM-UHFFFAOYSA-N 0.000 title abstract 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 title abstract 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229930192474 thiophene Natural products 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 claims abstract description 4
- 238000007146 photocatalysis Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 33
- 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 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 12
- 238000002360 preparation method Methods 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 125000000707 boryl group Chemical group B* 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
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- 238000003756 stirring Methods 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 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
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- MDOAAHGPXOGVQG-UHFFFAOYSA-N ethene;propane Chemical compound C=C.CCC MDOAAHGPXOGVQG-UHFFFAOYSA-N 0.000 claims 1
- 241001597008 Nomeidae Species 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 230000005669 field effect Effects 0.000 abstract description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- 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
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 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
- 0 Cc1cc(-c2c([C@@](**)C3)ccc(C)c2)c3cc1 Chemical compound Cc1cc(-c2c([C@@](**)C3)ccc(C)c2)c3cc1 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-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
- 150000001875 compounds Chemical class 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
- 238000004140 cleaning Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005516 engineering process Methods 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
- 229910052763 palladium Inorganic materials 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
- 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 class C=CC1=CC=CS1 ORNUPNRNNSVZTC-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
- QCNANSHOVAHMSD-UHFFFAOYSA-N C=CC1=CC=CC1 Chemical compound C=CC1=CC=CC1 QCNANSHOVAHMSD-UHFFFAOYSA-N 0.000 description 1
- BFIMMTCNYPIMRN-UHFFFAOYSA-N Cc1cc(C)c(C)c(C)c1 Chemical compound Cc1cc(C)c(C)c(C)c1 BFIMMTCNYPIMRN-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
- 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
- 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
- 150000001716 carbazoles Chemical class 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
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical class [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 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
- 230000000977 initiatory effect Effects 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
- 230000000873 masking effect Effects 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 class 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
- GKTQKQTXHNUFSP-UHFFFAOYSA-N thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)NC(=O)C2=C1 GKTQKQTXHNUFSP-UHFFFAOYSA-N 0.000 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
-
- 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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Abstract
The present invention relates to 8 hexyl thiophenes simultaneously [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 thiophenes of a class favorable solubility simultaneously [3 ', 2 ' with 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, it is easy to popularization and application.8 hexyl thiophenes simultaneously [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
(it is under the jurisdiction of present invention relates particularly to a class 8- hexyls-thieno [3 ', 2 ' 3,4] benzo [1,2-c] carbazole compound
Sulphur azepine [5] helicene compound) and its synthetic method, belong to technical field of organic synthesis.
Background technology
Helicene compound especially hetero atom helicene compound and its synthetic method be currently organic synthesis field research
Focus.It is as follows on hetero atom [5] helicene compound progress 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 is by the use of phenyl ring as single ring, benzo [h] isoquinolin as containing
Nitrogen systems have synthesized 1- azepines and/or 3- azepines [5] helicene, referring to Abbate, S.；Bazzini,C.；Caronna,T.,et
al.Tetrahedron,2006,62,139-148)；Adam six nitrogen with 2,9- dimethyl -1,10- phenanthrolines as 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 electric property to helicene material,
Optical property and photorefractive property are favourable, referring to Maiorana, S.；Papagni,A.；Licandro,E.,
Tetrahedron,2003,59,6481–6488.In a word, research of the prior art to azepine [5] helicene is more, 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 are studied ring-closure reaction always.Tanaka reconciles biaryl coupling reaction according to metal, makes
Use TiCl3, DME and Zn-Cu compounds 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, takes nearly 40 hours.Ogawa is according to oxy-
Cope rearrangement reactions, use KH, 18- crown ether -6, THF, NaBH4, EtOH etc. synthesized 2- acetates [5] helicene, referring to
Ogawa, Y., et al., Tetrahedron Lett.2002,43,7827-7829, but use the method from closed loop precursor
Also need to be reacted by 6 steps to final helicene, reactions steps are too many, cumbersome.Shawn is acted on according to olefin metathesis, is used
Microwave heating technique, seal pipe, dichloromethane 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 requirement it is higher, used catalyst compared with
It is expensive, cause synthesis relatively costly.Ichikawa according to a gram type cyclisation is paid, using magic acid, hexafluoroisopropanol, triphenyl tetrafluoro
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 the method is comparatively laborious from closed loop precursor to final spiral shell
Alkene also needs to the reaction of 3 steps, and reagent needed for reaction is somewhat expensive.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 costly.Ruch is using benzylamine, palladium, the double diphenylphosphine -9,9- dimethyl xanthenes of 4,5-
Synthesize a series of helicene with cesium carbonate, referring to Ruch, A.A., Org.Biomol.Chem.2016,14,8123-8140, but
The method is comparatively laborious, and accessory substance is more.In sum, much there are Material synthesis and answer in these routes and synthetic method
Miscellaneous, reactions steps are more, the reaction time is long, high cost, the shortcomings of operate and post-process loaded down with trivial details, its practical and economic worth is subject to very
Big limitation.
The content of the invention
In view of the shortcomings of the prior art, the present invention is intended to provide 8- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c]
Carbazole compound and its synthetic method.
Summary of the invention：
The present invention with carbazole derivates and thiophene derivant be initial action raw material, by photocatalysis ring-closure reaction, can be with
Preparing a class has sulphur azepine [5] helicene compound of good solubility and extensive use, there is not yet suchization in current material
Report in terms of compound and its synthetic method.
Detailed description of the invention：
The present invention is achieved through the following technical solutions：
1st, 8- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound
8- hexyls-thieno [3 ', 2 ' of the invention:3,4] benzo [1,2-c] carbazole compound, with shown in formula I
Structure：
Wherein, substituent R1-R8It is independently each H, C1-C6Alkyl, halogen, boryl, containing C, H, N, O, S atom
Aromatic rings or aromatic heterocycle；R9It is n-hexyl.
According to currently preferred, substituent R1-R8It is independently each H, C1-C6Alkyl, Cl, Br, boryl, benzene or
Thiophene；R9It is n-hexyl.
It is further preferred that R3It is C1-C6Alkyl, Cl, Br, boryl, benzene or thiophene,；R1、R2、R4-R8It is H；R9For just
Hexyl.
It is more highly preferred to, above-mentioned generalformulaⅰcompound is one of following：
8- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a)
The bromo- 8- hexyls-thienos [3 ', 2 ' of 11-:3,4] benzo [1,2-c] carbazole I (b)
(trimethylphenyl) boryl -8- of 11- bis- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (c)
11- thiophene -8- hexyls-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)
2nd, 8- hexyls-thieno [3 ', 2 ':3,4] synthetic method of benzo [1,2-c] carbazole compound
8- hexyls-thieno [3 ', 2 ' of the invention:3,4] synthetic method of benzo [1,2-c] carbazole compound, with
Trans- 9- n-hexyls -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；Expoxy propane；hv:Ultraviolet light；
R1-R9As described in above-mentioned general structure I.
8- hexyls-thieno [3 ', 2 ' of the invention:3,4] synthetic method of benzo [1,2-c] carbazole compound, bag
Include following steps：
(1) the organic solvent way of distillation is purified, preserves stand-by under an inert atmosphere；
(2) by trans- 9- n-hexyls -3- (2- thiophene-vinyl) carbazole derivates and iodine with mol ratio (1-2):1 is added to
In the organic solvent of step (1) purifying, stirred in dissolving, the concentration that solute in solution is made after being completely dissolved is 0.0005-0.2
Mol/L, leads to inert gas 20-120 minutes；
(3) under lasting stirring state, during expoxy propane added into the solution obtained by step (2), solution in ethylene third is made
The concentration of alkane is 0.05-3.0 mol/Ls；
(4) with the high-pressure sodium lamp of 100-800W through solution 10-120 minutes obtained by quartz glass irradiating step (3) extremely
Reaction terminates, and obtains crude product；
(5) vacuum rotates out solvent, and the crude product of gained is dissolved in dichloromethane, is successively 5- with mass fraction
60% Na2S2O3Solution and distillation water washing；
(6) separating-purifying is carried out to organic filtrate and obtains product.
According to currently preferred,
Organic solvent described in step (1) is selected from the one kind in benzene, toluene, n-hexane, tetrahydrofuran or dichloromethane.
Separating-purifying in step (6) refer to organic filtrate extracted, washed, being dried, being spin-dried for, silica gel column chromatography,
Recrystallization obtains product after separating.
According to the present invention it is further preferred that 8- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a)
Preparation method, comprises the following steps：
(1) organic solvent-benzene is purified with the method for air-distillation, preserves stand-by under an inert atmosphere；
(2) trans- 9- n-hexyls -3- (2- thiophene-vinyl) carbazole 0.45mmol and iodine 0.45mmol is added to step
(1) in the 500ml organic solvent-benzenes of purifying, stirred in dissolving, after being completely dissolved, lead to inert gas 20-60 minutes；
(3) under lasting stirring state, by the solution obtained by 18ml expoxy propane addition step (2), solution middle ring is made
The concentration of Ethylene Oxide is 0.4-0.6 mol/Ls；
(4) with the high-pressure sodium lamp of 500-800W through solution 10-60 minutes obtained by quartz glass irradiating step (3) to anti-
Crude product should be terminated to obtain；
(5) vacuum rotates out solvent, and the crude product of gained is dissolved in dichloromethane, is successively 15- with mass fraction
20% Na2S2O3Solution and distillation water washing；
(6) organic filtrate extracted, washed, being dried, being spin-dried for, silica gel column chromatography, recrystallization separating-purifying after, obtain
8- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a).
Excellent results of the invention are as follows：
It is of the invention with carbazole derivates and thiophene derivant as raw material compared with existing helicene derivative, extremely short
8- hexyls-the thieno [3 ', 2 ' of a class 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, it is easy to popularization and application.Experiment proves 8- hexyls-thieno [3 ', 2 ':
3,4] benzo [1,2-c] carbazole compound has good dissolubility in different organic solvents, is conducive to carrying for the compound
Pure, masking；Various sulphur azepine [5] helicene compounds can be obtained by accessing different substituents.8- hexyls-thiophene that the present invention is provided
Fen 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 field such as non-linear, chiral liquid crystal and biological medicine.
Brief description of the drawings
Fig. 1 is the hydrogen spectrogram of trans- 9- n-hexyls -3- (2- thiophene-vinyl) carbazole II (a)；Abscissa is chemical shift
δ, unit：ppm.
Fig. 2 is the carbon spectrogram of trans- 9- n-hexyls -3- (2- thiophene-vinyl) carbazole II (a)；Abscissa is chemical shift
δ, unit：ppm.
Fig. 3 is the mass spectrogram of trans- 9- n-hexyls -3- (2- thiophene-vinyl) carbazole II (a)；Abscissa is mass-to-charge ratio m/
z；Ordinate is relative intensity, unit：%.
Fig. 4 is 8- hexyls-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- hexyls-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- hexyls-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
With reference to embodiment, the present invention is described further, but not limited to this.Instrument is described as follows with reagent：
High-pressure sodium lamp (Beijing Zhong Jiaojin sources Science and Technology Ltd.), benzene is purified with the method for air-distillation, remaining examination
It is pure that agent is chemistry.
The trans- 9- n-hexyls -3- of raw material (2- thiophene-vinyl) carbazole (II) (a-e) used in embodiment is utilized
It is prepared by Heck reactions.
Below by taking the preparation method of the raw material II (a) of embodiment 1 as an example, reaction equation is as follows：
Preparation process is as follows：
3- bromine 9- n-hexyl carbazoles：At normal temperatures, to addition magneton, 3- bromine carbazoles in dried 250ml single-necked flasks
(4.92g, 0.02mol), TBAB (TBAB, (n-C4H9)4BrN, 3g, 9.2mmol), NaOH (1.2g,
0.03mol) with 80ml acetone, stir.It is stirred at reflux at a temperature of 60 DEG C, after reacting 2-4 hours, stops reaction, is treated
It is using constant pressure funnel that the mixing of (4.26ml, 0.03mol) 1- bromos 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 reacting 24 hours, stops reaction.Will
The acetone of residual rotates out, and residue is extracted using water and dichloromethane, after cleaning extract with distilled water, with nothing
Water magnesium sulfate is dried, and then rotates out by dichloromethane, obtains crude product.Using silica gel column chromatography separating-purifying product,
Eluent is pure petroleum ether, finally obtains white solid 5.3g, and yield is 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-hexyls -3- (2- thiophene-vinyl) carbazole：At normal temperatures, in dried 100ml there-necked flasks
Add magneton, the bromo- 9- n-hexyls carbazoles (2.15g, 6.5mmol) of 3-, 2- vinyl thiophenes (0.70g, 6.5mmol), potassium carbonate
The N of (0.90g, 6.5mmol), triphenylphosphine (1.70g, 6.5mmol), palladium (0.196g, 1mmol) and 30ml, N- diformazans
Base formamide (DMF), stirs, fully dissolving.Using wireway to argon gas is led to 20-40 minutes in reaction phase, then take out true
It is empty 3 times.Reaction system is stirred at reflux at a temperature of 100 DEG C, is reacted 40-50 hours, stop reaction.Water is mutually poured into reaction
In, then water is mutually extracted 3 times with dichloromethane.After cleaning extract with distilled water, dried with anhydrous magnesium sulfate, 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, yellow solid 0.59g is finally obtained, yield is 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- hexyls-thieno [3 ', 2 ':3,4] preparation of benzo [1,2-c] carbazole (I a)
8- hexyls-thieno [3 ', 2 ':3,4] preparation of benzo [1,2-c] carbazole (I a), step is as follows：
(1) organic solvent-benzene is purified with the method for air-distillation, preserves stand-by under an inert atmosphere；
(2) trans- 9- n-hexyls -3- (2- thiophene-vinyl) carbazole 0.45mmol and iodine 0.46mmol is added to step
(1) in the 500ml organic solvent-benzenes of purifying, quickly stirred in dissolving, after being completely dissolved, lead to inert gas 20-60 minutes；
(3) under lasting stirring state, by the solution obtained by 18ml expoxy propane addition step (2), solution middle ring is made
The concentration of Ethylene Oxide is 0.4-0.6 mol/Ls；
(4) with the high-pressure sodium lamp of 500-800W W through solution 10-60 minutes obtained by quartz glass irradiating step (3) extremely
Reaction terminates to obtain crude product；
(5) vacuum rotates out solvent, and the crude product of gained is dissolved in dichloromethane, is successively 15- with mass fraction
20% Na2S2O3Solution and distillation water washing；
(6) organic filtrate extracted, washed, being dried, being spin-dried for, silica gel column chromatography, recrystallization separating-purifying after, obtain
8- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a).Yield 0.039g, yield is 24%.
The compound the experiment proved that to be had well in n-hexane, toluene, dichloroethanes, ethyl acetate, acetonitrile, methyl alcohol
Dissolubility.
Now by 8- hexyls-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-hexyls -3- of raw material (2- thiophene-vinyl) carbazoles and product 8- hexyls-thieno [3 ', 2 ':3,4] benzene
And the nuclear magnetic resoance spectrum, mass spectrum of [1,2-c] carbazole are as shown in drawings.
Embodiment 2：11-8- hexyls-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- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I
The preparation of (c)
Chemical equation is as follows：
Embodiment 4：11- thiophene -8- hexyls-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 (9)
1.8- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound, it is characterised in that with the institute of formula I
The structure shown：
Wherein, substituent R1-R8It is independently each H, C1-C6Alkyl, halogen, boryl, containing C, H, N, O, S atom aromatic rings
Or aromatic heterocycle；R9It is n-hexyl.
2. 8- hexyls-thieno [3 ', 2 ' as claimed in claim 1:3,4] benzo [1,2-c] carbazole compound, its feature
It is, substituent R1-R8It is independently each H, C1-C6Alkyl, Cl, Br, boryl, benzene or thiophene；R9It is n-hexyl.
3. 8- hexyls-thieno [3 ', 2 ' as claimed in claim 1 or 2:3,4] benzo [1,2-c] carbazole compound, its
It is characterised by, R3It is C1-C6Alkyl, Cl, Br, boryl, benzene or thiophene,；R1、R2、R4-R8It is H；R9It is n-hexyl.
4. 8- hexyls-thieno [3 ', 2 ' as claimed in claim 1 or 2:3,4] benzo [1,2-c] carbazole compound, its
It is characterised by, generalformulaⅰcompound is one of following：
8- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (a)
The bromo- 8- hexyls-thienos [3 ', 2 ' of 11-:3,4] benzo [1,2-c] carbazole I (b)
(trimethylphenyl) boryl -8- of 11- bis- hexyls-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole I (c)
11- thiophene -8- hexyls-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)
5. 8- hexyls-thieno [3 ', 2 ' as claimed in claim 1 or 2:3,4] system of benzo [1,2-c] carbazole compound
Preparation Method, it is characterised in that with trans- 9- n-hexyls -3- (2- thiophene-vinyl) carbazole derivates as raw material, by photocatalysis
Ring-closure reaction is prepared.
Chemical equation is as follows：
Reagent and condition:Benzene；I2:Iodine；Expoxy propane；hv:Ultraviolet light；
R1-R9As described in above-mentioned general structure I.
6. 8- hexyls-thieno [3 ', 2 ' as claimed in claim 5:3,4] preparation of benzo [1,2-c] carbazole compound
Method, it is characterised in that comprise the following steps：
(1) the organic solvent way of distillation is purified, preserves stand-by under an inert atmosphere；
(2) by trans- 9- n-hexyls -3- (2- thiophene-vinyl) carbazole derivates and iodine with mol ratio (1-2):1 is added to step
(1) in the organic solvent of purifying, stirred in dissolving, the concentration of solute in solution is made after being completely dissolved for 0.0005-0.2 rubs
You/liter, lead to inert gas 20-120 minutes；
(3) under lasting stirring state, during expoxy propane added into the solution obtained by step (2), solution in ethylene propane is made
Concentration is 0.05-3.0 mol/Ls；
(4) with the high-pressure sodium lamp of 100-800W through solution 10-120 minutes obtained by quartz glass irradiating step (3) to reaction
Terminate, obtain crude product；
(5) vacuum rotates out solvent, and the crude product of gained is dissolved in dichloromethane, is successively 5-60%'s with mass fraction
Na2S2O3Solution and distillation water washing；
(6) separating-purifying is carried out to organic filtrate and obtains product.
7. 8- hexyls-thieno [3 ', 2 ' as claimed in claim 6:3,4] preparation of benzo [1,2-c] carbazole compound
Method, it is characterised in that the organic solvent described in step (1) is selected from benzene, toluene, n-hexane, tetrahydrofuran or dichloromethane
In one kind.
8. 8- hexyls-thieno [3 ', 2 ' as claimed in claim 6:3,4] preparation of benzo [1,2-c] carbazole compound
Method, it is characterised in that the separating-purifying in step (6) refer to organic filtrate extracted, washed, being dried, being spin-dried for, silica gel
Column chromatography, recrystallization obtain product after separating.
9. 8- hexyls-thieno [3 ', 2 ' as claimed in claim 4:3,4] preparation method of benzo [1,2-c] carbazole I (a),
Comprise the following steps：
(1) organic solvent-benzene is purified with the method for air-distillation, preserves stand-by under an inert atmosphere；
(2) that trans- 9- n-hexyls -3- (2- thiophene-vinyl) carbazole 0.45mmol and iodine 0.45mmol is added into step (1) is pure
In the 500ml organic solvent-benzenes of change, stirred in dissolving, after being completely dissolved, lead to inert gas 20-60 minutes；
(3) under lasting stirring state, by the solution obtained by 18ml expoxy propane addition step (2), solution in ethylene third is made
The concentration of alkane is 0.4-0.6 mol/Ls；
(4) tied through solution 10-60 minutes obtained by quartz glass irradiating step (3) to reaction with the high-pressure sodium lamp of 500-800W
Beam obtains crude product；
(5) vacuum rotates out solvent, and the crude product of gained is dissolved in dichloromethane, is successively 15-20% with mass fraction
Na2S2O3Solution and distillation water washing；
(6) organic filtrate extracted, washed, being dried, being 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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| WO2014098455A1 (en) * | 2012-12-17 | 2014-06-26 | 주식회사 두산 | Novel organic compound and organic electroluminescent element comprising same |
| CN105810837A (en) * | 2015-01-16 | 2016-07-27 | 三星显示有限公司 | Organic light-emitting device |
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| WO2014098455A1 (en) * | 2012-12-17 | 2014-06-26 | 주식회사 두산 | Novel organic compound and organic electroluminescent element comprising same |
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