CN107235990A - 多取代吲哚并噻吩及衍生物及其合成方法 - Google Patents
多取代吲哚并噻吩及衍生物及其合成方法 Download PDFInfo
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- CN107235990A CN107235990A CN201710435422.5A CN201710435422A CN107235990A CN 107235990 A CN107235990 A CN 107235990A CN 201710435422 A CN201710435422 A CN 201710435422A CN 107235990 A CN107235990 A CN 107235990A
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- China
- Prior art keywords
- substituted
- acid
- alkyl
- methyl
- indoles
- Prior art date
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- Granted
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 24
- 150000002475 indoles Chemical class 0.000 title claims abstract description 18
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 title claims abstract description 10
- -1 ketone compounds Chemical class 0.000 claims abstract description 70
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000005864 Sulphur Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000007848 Bronsted acid Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 125000000623 heterocyclic group Chemical group 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 150000002576 ketones Chemical class 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 14
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 14
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 12
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- XQFARSXVMYNQRL-UHFFFAOYSA-N acetylene chlorobenzene Chemical group C#C.ClC1=CC=CC=C1 XQFARSXVMYNQRL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- JBVRAGDTHUAQGB-UHFFFAOYSA-N 1,6-dimethylindole Chemical compound CC1=CC=C2C=CN(C)C2=C1 JBVRAGDTHUAQGB-UHFFFAOYSA-N 0.000 claims description 2
- DQQBLGJGQJEAAQ-UHFFFAOYSA-N 1,7-dimethylindole Chemical compound CC1=CC=CC2=C1N(C)C=C2 DQQBLGJGQJEAAQ-UHFFFAOYSA-N 0.000 claims description 2
- DACIGVIOAFXPHW-UHFFFAOYSA-N 1-(1-adamantyl)ethanone Chemical class C1C(C2)CC3CC2CC1(C(=O)C)C3 DACIGVIOAFXPHW-UHFFFAOYSA-N 0.000 claims description 2
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical class BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 claims description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical class ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims description 2
- QRRKZFCXXBFHSV-UHFFFAOYSA-N 1-ethylindole Chemical class C1=CC=C2N(CC)C=CC2=C1 QRRKZFCXXBFHSV-UHFFFAOYSA-N 0.000 claims description 2
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical class COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 claims description 2
- JDFIJVJKRTZYCK-UHFFFAOYSA-N 1-propan-2-ylindole Chemical class C1=CC=C2N(C(C)C)C=CC2=C1 JDFIJVJKRTZYCK-UHFFFAOYSA-N 0.000 claims description 2
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical class ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 claims description 2
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 claims description 2
- YOMBUJAFGMOIGS-UHFFFAOYSA-N 2-fluoro-1-phenylethanone Chemical class FCC(=O)C1=CC=CC=C1 YOMBUJAFGMOIGS-UHFFFAOYSA-N 0.000 claims description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 claims description 2
- UAUJZFNYIBXEDG-UHFFFAOYSA-N 5-chloro-1-methylindole Chemical class ClC1=CC=C2N(C)C=CC2=C1 UAUJZFNYIBXEDG-UHFFFAOYSA-N 0.000 claims description 2
- RDZSNJCMRDNQNB-UHFFFAOYSA-N 5-fluoro-1-methylindole Chemical class FC1=CC=C2N(C)C=CC2=C1 RDZSNJCMRDNQNB-UHFFFAOYSA-N 0.000 claims description 2
- HQNPKVBTBJUMTR-UHFFFAOYSA-N 5-methoxy-1-methylindole Chemical class COC1=CC=C2N(C)C=CC2=C1 HQNPKVBTBJUMTR-UHFFFAOYSA-N 0.000 claims description 2
- YDLOPHRVGMIZDX-UHFFFAOYSA-N 6-chloro-1-methylindole Chemical class C1=C(Cl)C=C2N(C)C=CC2=C1 YDLOPHRVGMIZDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- CRFJRGSTIQFTQW-UHFFFAOYSA-N acetylene fluorobenzene Chemical group C#C.FC1=CC=CC=C1 CRFJRGSTIQFTQW-UHFFFAOYSA-N 0.000 claims description 2
- UGLXZBZLTWYGTA-UHFFFAOYSA-N acetylene propylbenzene Chemical group C#C.C(CC)C1=CC=CC=C1 UGLXZBZLTWYGTA-UHFFFAOYSA-N 0.000 claims description 2
- QDJZBFLFHUMZBE-UHFFFAOYSA-N acetylene;bromobenzene Chemical group C#C.BrC1=CC=CC=C1 QDJZBFLFHUMZBE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- URCAYJXJXYLGTI-UHFFFAOYSA-N ethene fluorobenzene Chemical class C=C.FC1=CC=CC=C1 URCAYJXJXYLGTI-UHFFFAOYSA-N 0.000 claims description 2
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 239000011664 nicotinic acid Substances 0.000 claims description 2
- 229960003512 nicotinic acid Drugs 0.000 claims description 2
- 235000001968 nicotinic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical class ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical class CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- HQYHVZWPPFAVCP-UHFFFAOYSA-N tert-butylbenzene pentan-3-one Chemical class C(C)C(=O)CC.C(C)(C)(C)C1=CC=CC=C1 HQYHVZWPPFAVCP-UHFFFAOYSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 5
- 238000006467 substitution reaction Methods 0.000 claims 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 claims 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- PZNYKBLADPHGMI-UHFFFAOYSA-N 1,5-dimethylindole Chemical compound CC1=CC=C2N(C)C=CC2=C1 PZNYKBLADPHGMI-UHFFFAOYSA-N 0.000 claims 1
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 claims 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical class COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 claims 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims 1
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 claims 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- AXNBHOOQHIIQFA-UHFFFAOYSA-N [S].C(F)(F)F Chemical compound [S].C(F)(F)F AXNBHOOQHIIQFA-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 17
- 150000001336 alkenes Chemical class 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 14
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 abstract description 8
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229930192474 thiophene Natural products 0.000 abstract description 3
- 150000003577 thiophenes Chemical class 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 162
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 42
- 238000005160 1H NMR spectroscopy Methods 0.000 description 41
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- FFRYBJUZUCTFGC-UHFFFAOYSA-N 4h-thieno[2,3-b]indole Chemical class C1=CC=C2C(C=CS3)=C3NC2=C1 FFRYBJUZUCTFGC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- MLNKXLRYCLKJSS-RMKNXTFCSA-N (2e)-2-hydroxyimino-1-phenylethanone Chemical compound O\N=C\C(=O)C1=CC=CC=C1 MLNKXLRYCLKJSS-RMKNXTFCSA-N 0.000 description 1
- ZPRQXVPYQGBZON-UHFFFAOYSA-N 2-bromo-1h-indole Chemical compound C1=CC=C2NC(Br)=CC2=C1 ZPRQXVPYQGBZON-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- RSTZCEHWJCIAAT-UHFFFAOYSA-N C(C)C(=O)CC.FC=1C=CC=CC1 Chemical compound C(C)C(=O)CC.FC=1C=CC=CC1 RSTZCEHWJCIAAT-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种多取代吲哚并噻吩及衍生物及其合成方法。本发明首次采用在布朗斯特酸的催化下,在空气氛围中,将吲哚类化合物,烯、炔、酮类化合物和硫粉转化为一种2‑取代噻吩并[2,3‑b]吲哚及衍生物的技术方案,制得分子结构稳定,化学性质优良的产品及其附加产品;在布朗斯特酸的催化下,空气氛围中,将吲哚类化合物,烯、炔、酮类化合物和硫粉转化为一种2‑取代噻吩并[2,3‑b]吲哚及衍生物的技术方案,反应原料廉价易得,且不需要经过预处理,反应的原子经济性高;反应只需要使用廉价的布朗斯特酸,减少环境污染,节约原材料,减少反应成本;整个反应体系简单,反应条件温和,反应设备较少,实验操作简便,用料来源广泛。
Description
技术领域
本发明涉及一种多取代吲哚并噻吩及衍生物及其合成方法,属于有机化合物合成技术领域。
背景技术
噻吩并[2,3-b]吲哚及其衍生物是一类重要的芳杂环化合物,分子内含有较大的共轭体系和强的分子内电子转移,这种特殊的刚性稠环结构使噻吩并[2,3-b]吲哚类化合物表现出许多独特的性能及生物活性,在光电材料、染料、医药、超分子识别等多领域具有潜在的应用。现有合成此类化合物的方法存在合成步骤复杂,需要采取多步合成工艺才能完成,并且需要添加过渡金属催化剂、化学当量的金属氧化剂等缺点。
发明内容
本发明为了填补现有技术的空白,提供一种分子结构稳定、化学性质优良的多取代吲哚并噻吩及衍生物。
本发明还提供一种多取代吲哚并噻吩及衍生物的合成方法。
本发明解决其技术问题所采用的技术方案是:本发明提供一种多取代吲哚并噻吩及衍生物,其通式为式Ⅰ:
其中
R1选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基,酰基;取代或非取代的C6-C20芳基,苄基,苯磺酰基,苯甲酰基;取代或非取代的含有氮,氧,硫原子的杂环基团;取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基;
R2选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基;取代或非取代的C6-C20芳基;取代或非取代的含有氮,氧,硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基;
R3选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基;取代或非取代的C6-C20芳基;取代或非取代的含有氮,氧,硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基,金刚烷基;
本发明还提供一种合成多取代吲哚并噻吩及衍生物的方法,以布朗斯特酸类化合物作催化剂,包括以下步骤:
加入吲哚类化合物,烯类化合物、炔类化合物或酮类化合物,硫粉,催化剂和有机溶剂;
将反应物充分混合,空气氛围下,加热反应;
纯化得到产物。
优选地,本发明的合成方法,所述吲哚类化合物,是选自C8-C20芳香类吲哚,其通式为式Ⅱ:
其中
R1选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基,酰基;取代或非取代的C6-C20芳基,苄基,苯磺酰基,苯甲酰基;取代或非取代的含有氮,氧,硫原子的杂环基团;取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基;
R2选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基;取代或非取代的C6-C20芳基;取代或非取代的含有氮,氧,硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基。
优选地,本发明的合成方法,所述吲哚类化合物选自:1-甲基吲哚,1,5-二甲基吲哚,1-甲基-5-甲氧基吲哚,1-甲基-5-氟吲哚,1-甲基-5-氯吲哚,1-甲基-5溴吲哚,1-甲基-5-碘吲哚,1,6-二甲基吲哚,1-甲基-6-氯吲哚,1,7-二甲基吲哚,1-H-吲哚,1-乙基吲哚,1-异丙基吲哚。
优选地,本发明的合成方法,所述烯类化合物、炔类化合物或酮类化合物,其通式分别为式Ⅲ、Ⅳ、Ⅴ:
其中
R3选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基;取代或非取代的C6-C20芳基;取代或未取代的含有氮,氧,硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基,金刚烷基;
R4选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基;取代或非取代的C6-C20芳基;取代或未取代的含有氮,氧,硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基,金刚烷基。
优选地,本发明的合成方法,所述烯类化合物选自:苯乙烯,4-甲基苯乙烯,4-甲氧基苯乙烯,4-氟苯乙烯,4-氯苯乙烯,4-溴苯乙烯,2-氯苯乙烯。
优选地,本发明的合成方法,其特征在于所述炔类化合物选自:苯乙炔,4-甲基苯乙炔,4-乙基基苯乙炔,4-正丙基苯乙炔,4-正戊基苯乙炔,4-甲氧基苯乙炔,4-乙氧基苯乙炔,4-氟苯乙炔,4-氯苯乙炔,4-溴苯乙炔,2-氯苯乙炔,1-辛炔,1,2-二苯乙炔,3,3-二甲基丁炔。
优选地,本发明的合成方法,所述酮类化合物选自:苯乙酮,4-甲基苯乙酮,4-异丁基苯乙酮,4-叔丁基苯乙酮,4-甲氧基苯乙酮,4-氟苯乙酮,4-氯苯乙酮,4-溴苯乙酮,4-碘苯乙酮,2-甲基苯乙酮,2-氟苯乙酮,2-氯苯乙酮,3-甲基苯乙酮,3-甲氧基苯乙酮,3-氟苯乙酮,3-氯苯乙酮,3-溴苯乙酮,3-三氟甲基苯乙酮,2,4-二甲基苯乙酮,3,4-二甲氧基苯乙酮,3,4-二氯苯乙酮,1-乙酰基萘,2-乙酰基萘,1-乙酰基金刚烷,3-甲基-2-丁酮。
优选地,本发明的合成方法,所述布朗斯特酸类化合物选自:甲酸、乙酸、异丁酸、环丙基甲酸、环己烷羧酸、三氟乙酸、对甲苯磺酸、甲磺酸、三氟甲磺酸、特戊酸、苯甲酸、对羟基苯甲酸、对硝基苯甲酸、乙酸酐、三氟乙酸酐、烟酸、盐酸、硫酸、硝酸、磷酸、氢碘酸、氢溴酸中的一种或多种。
优选地,本发明的合成方法,所述反应氛围为:空气氛围;吲哚类化合物与烯类化合物、炔类化合物或酮类化合物与硫粉与催化剂的摩尔比为1.0:1.1-5.0:3.0-8.0:3.0-10.0;同时,反应温度为110℃-160℃;反应时长为8h-24h;所述有机溶剂为:N,N-二甲基甲酰胺和/或N,N-二甲基乙酰胺。
本发明相比现有技术所产生的有益效果:
(Ⅰ)本发明首次采用在布朗斯特酸的催化下,在空气氛围中,将吲哚类化合物,烯(炔、酮)化合物和硫粉转化为一种2-取代噻吩并[2,3-b]吲哚及衍生物的技术方案,制得分子结构稳定,化学性质优良的产品及其附加产品;(Ⅱ)在布朗斯特酸的催化下,空气氛围中,将吲哚类化合物,烯(炔、酮)化合物和硫粉转化为一种2-取代噻吩并[2,3-b]吲哚及衍生物的技术方案,反应原料廉价易得,且不需要经过预处理,反应的原子经济性高;(Ⅲ)在布朗斯特酸的催化下,空气氛围中,将吲哚类化合物,烯(炔、酮)化合物和硫粉转化为一种2-取代噻吩并[2,3-b]吲哚及衍生物的技术方案,反应不需要使用金属催化剂或当量的金属氧化剂,只需要使用廉价的布朗斯特酸,减少环境污染,节约原材料,减少反应成本;(Ⅳ)在布朗斯特酸的催化下,空气氛围中,将吲哚类化合物,烯(炔、酮)化合物和硫粉转化为一种2-取代噻吩并[2,3-b]吲哚及衍生物的技术方案,采用一锅直接选择性的合成目标产物且收率高,克服了现有多步合成方法带来的人、财、物巨大浪费的困境,节约了大量的研制时间与生产周期;(Ⅴ)在布朗斯特酸的催化下,空气氛围中,将吲哚类化合物,烯(炔、酮)化合物和硫粉转化为一种2-取代噻吩并[2,3-b]吲哚及衍生物的技术方案,克服了现有多步合成方法带来的产品实施成本较高的困境,从而使产品的实际应用大大地提前进入,为提早工业化生产创造了基础条件;(Ⅵ)在布朗斯特酸的催化下,空气氛围中,将吲哚类化合物,烯(炔、酮)化合物和硫粉转化为一种2-取代噻吩并[2,3-b]吲哚及衍生物的技术方案,它工艺科学、合理,操作容易,反应步骤少,所需设备少;(Ⅶ)在布朗斯特酸的催化下,空气氛围中,将吲哚类化合物,烯(炔、酮)化合物和硫粉转化为一种2-取代噻吩并[2,3-b]吲哚及衍生物的技术方案,它具有原料广泛,低投入、高产出,易于进一步大批量生产和普及推广;(Ⅷ)在布朗斯特酸的催化下,空气氛围中,将吲哚类化合物,烯(炔、酮)化合物和硫粉转化为一种2-取代噻吩并[2,3-b]吲哚及衍生物的技术方案,它具有反应体系简单,反应条件温和,反应设备较少,实验操作简便,用料来源广泛,用户和应用易于扩展,产品利用价值较高,市场商业化前景可以预期等特点。
本发明2-取代噻吩并[2,3-b]吲哚、衍生物及其合成方法,可广泛应用于光电,印染,医药,超分子识别等多个领域;特别适合无金属催化,多组分一锅法高效选择性合成2-取代噻吩并[2,3-b]吲哚类化合物的研究与开发。
附图说明
为了证明本发明的产物,本发明提供部分实施例的核磁氢谱图和核磁碳谱图。
图1a和1b实施例1产物的核磁谱图;
图2a和2b实施例2产物的核磁谱图;
图3a和3b实施例3产物的核磁谱图;
图4a和4b实施例4产物的核磁谱图;
图5a和5b实施例5产物的核磁谱图;
图6a和6b实施例6产物的核磁谱图;
图7a和7b实施例7产物的核磁谱图;
图8a和8b实施例8产物的核磁谱图;
图9a和9b实施例9产物的核磁谱图;
图10a和10b实施例10产物的核磁谱图;
图11a和11b实施例11产物的核磁谱图;
图12a和12b实施例12产物的核磁谱图;
图13a和13b实施例13产物的核磁谱图;
图14a和14b实施例14产物的核磁谱图;
图15a和15b实施例15产物的核磁谱图;
图16a和16b实施例16产物的核磁谱图;
图17a和17b实施例17产物的核磁谱图;
图18a和18b实施例18产物的核磁谱图;
图19a和19b实施例19产物的核磁谱图;
图20a和20b实施例20产物的核磁谱图;
图21a和21b实施例21产物的核磁谱图;
图22a和22b实施例22产物的核磁谱图;
图23a和23b实施例23产物的核磁谱图;
图24a和24b实施例24产物的核磁谱图;
图25a和25b实施例25产物的核磁谱图;
图26a和26b实施例26产物的核磁谱图;
图27a和27b实施例27产物的核磁谱图;
图28a和28b实施例28产物的核磁谱图;
图29a和29b实施例29产物的核磁谱图;
图30a和30b实施例30产物的核磁谱图;
图31a和31b实施例31产物的核磁谱图;
图32a和32b实施例32产物的核磁谱图;
图33a和33b实施例33产物的核磁谱图;
图34a和34b实施例34产物的核磁谱图;
图35a和35b实施例35产物的核磁谱图;
图36a和36b实施例36产物的核磁谱图;
图37a和37b实施例37产物的核磁谱图;
图38a和38b实施例38产物的核磁谱图;
图39a和39b实施例39产物的核磁谱图;
图40a和40b实施例40产物的核磁谱图;
图41a和41b实施例41产物的核磁谱图;
图42a和42b实施例42产物的核磁谱图;
其中a为氢谱图,b为碳谱图。
具体实施方式
现在结合附图对本发明作进一步详细的说明。这些附图均为简化的示意图,仅以示意方式说明本发明的基本结构,因此其仅显示与本发明有关的构成。
反应方程式为:
实施例1-46
步骤1:将吲哚类化合物(具体物质见表1)、烯(炔、酮)类化合物(具体物质见表1)和硫粉加入反应容器中,将布朗斯特酸(具体物质见表1)溶液加入反应容器中也可以分别向容器中布朗斯特酸(具体物质见表1)和有机溶剂(具体物质见表1);
步骤2:将反应容器均匀加热(如油浴加热)至表1中所述的温度,吲哚类化合物、烯(炔、酮)类化合物和硫粉在溶剂中进行反应,并持续表1中所述的时间;
步骤3:提纯步骤
表1:实施例1-46中吲哚类化合物、烯(炔、酮)类化合物、布朗斯特酸、吲哚类化合物、烯(炔、酮)类化合物、硫粉和布朗斯特酸的摩尔比、反应温度和反应时间
*为吲哚类化合物、烯(炔、酮)类化合物、硫粉和布朗斯特酸的摩尔比
上述实施例的反应中,布朗斯特酸使烯(炔、酮)类化合物进攻吲哚类化合物3号位,将无机硫转化成有机C-S键最终生成欲得到的化合物。
将步骤3后反应容器内的物质进行转化率检测并进行核磁共振,部分实施例的结果如下:
实施例1产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ7.80(d,J=7.8Hz,1H),7.64–7.62(m,3H),7.37(dd,J=15.7,7.7Hz,3H),7.31–7.27(m,1H),7.25–7.23(m,1H),7.21–7.17(m,1H),3.85(s,3H);13C NMR(100MHz,ppm):δ144.1,142.0,135.78,135.73,129.0,126.6,125.1,123.5,122.2,122.0,119.6,119.4,114.3,109.1,32.4.
实施例2产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.78(d,J=7.8,1H),7.55(s,1H),7.51(d,J=8.2,2H),7.33–7.31(m,1H),7.29–7.25(m,1H),7.20–7.16(m,3H),3.81(s,3H),2.36(s,3H);13C NMR(100MHz,CDCl3,ppm):δ143.8,142.0,136.5,136.0,133.0,129.6,125.1,123.5,122.2,121.9,119.5,119.3,113.7,109.1,32.3,21.2.
实施例3产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.80(d,J=7.8,1H),7.58(s,1H),7.55–7.53(m,2H),7.36–7.34(m,1H),7.28(t,J=7.6,1H),7.20–7.17(m,3H),3.85(s,3H),2.60(t,J=7.8,2H),1.70–1.64(m,2H),0.97(t,J=7.3,3H);13C NMR(100MHz,CDCl3,ppm):δ143.7,141.9,141.3,136.0,133.2,129.0,125.1,123.4,122.2,121.9,119.5,119.3,113.7,109.1,37.7,32.3,24.5,13.8.
实施例4产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.79(d,J=7.7,1H),7.57(s,1H),7.53(d,J=8.2,2H),7.35–7.33(m,1H),7.30–7.26(m,1H),7.20–7.14(m,3H),3.84(s,3H),2.48(d,J=7.2,2H),1.88(dt,J=13.5,6.8,1H),0.93(d,J=6.6,6H);13C NMR(100MHz,CDCl3,ppm):δ143.7,141.9,140.3,136.0,133.2,129.7,124.9,123.4,122.2,121.9,119.5,119.3,113.7,109.1,45.1,32.3,30.3,22.4.
实施例5产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.79(d,J=7.7,1H),7.57–7.55(m,3H),7.41–7.39(m,2H),7.34–7.32(m,1H),7.29–7.25(m,1H),7.20–7.16(m,1H),3.83(s,3H),1.35(s,9H);13C NMR(100MHz,CDCl3,ppm):δ149.8,143.8,142.0,135.9,133.0,125.9,124.9,123.5,122.2,121.9,119.5,119.3,113.8,109.1,34.6,32.3,31.4.
实施例6产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.79(d,J=7.8,1H),7.56–7.54(m,2H),7.49(s,1H),7.36–7.34(m,1H),7.30–7.26(m,1H),7.18(t,J=7.4,1H),6.93(d,J=8.7,2H),3.85(s,3H),3.84(s,3H);13C NMR(100MHz,CDCl3,ppm):δ158.7,143.5,141.9,135.8,128.6,126.6,123.4,122.2,121.8,119.4,119.3,114.4,113.2,109.1,55.4,32.3.
实施例7产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm)δ=7.79(d,J=7.8,1H),7.53(d,J=8.2,2H),7.48(s,1H),7.35–7.33(m,1H),7.29–7.25(m,1H),7.20–7.16(m,1H),6.93–6.90(m,2H),4.06(q,J=7.0,2H),3.85(s,3H),1.43(t,J=7.0,3H);13C NMR(100MHz,CDCl3,ppm)δ158.1,143.4,141.9,128.4,126.5,123.4,122.2,121.8,119.4,119.3,115.0,113.1,109.1,63.6,32.3,14.9.
实施例7产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.78(d,J=7.8,1H),7.56–7.52(m,2H),7.50(s,1H),7.34–7.246(m,2H),7.19(t,J=7.3,1H),7.06(t,J=8.6,2H),3.81(s,3H);13C NMR(100MHz,CDCl3,ppm):δ=161.8(d,J=246.0),143.9,142.0,134.6,132.0,132.0,126.8(d,J=7.8),123.5,122.2,122.1,119.5(d,J=27.5),115.9(d,J=21.8),114.3,109.1,32.4.
实施例9产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ7.78(d,J=7.8Hz,1H),7.56(s,1H),7.51(d,J=8.5Hz,2H),7.34–7.30(m,4H),7.19(t,J=7.3Hz,1H),3.81(s,3H);13C NMR(100MHz,CDCl3,ppm):δ144.1,142.0,134.2,134.2,132.0,129.0,126.1,123.5,122.1,122.0,119.6,119.3,114.7,109.1,32.25.
实施例10产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.81(d,J=7.7,1H),7.49–7.47(m,1H),7.38–7.36(m,1H),7.33(s,1H),7.31–7.27(m,2H),7.25–7.23(m,2H),7.21–7.17(m,1H),3.87(s,3H),2.53(s,3H);13C NMR(100MHz,CDCl3,ppm):δ144.5,141.9,136.4,135.1,134.3,130.8,130.7 127.5,126.0,123.0,122.2,121.9,119.4,119.3,117.6,109.0,32.4,21.4.
实施例11产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.82(d,J=7.7,1H),7.70(s,1H),7.60(dd,J=7.7,1.7,1H),7.48(dd,J=7.9,1.3,1H),7.37–7.36(m,1H),7.32–7.28(m,2H),7.24–7.18(m,2H),3.87(s,3H);13C NMR(100MHz,CDCl3,ppm):δ145.3,142.1,134.1,132.2,131.4,131.1,130.6,128.0,127.0,122.9,122.2,122.1,119.6,119.4,119.2,109.1,32.4.
实施例12产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.79(d,J=7.8,1H),7.60(s,1H),7.44–7.42(m,2H),7.34–7.32(m,1H),7.30–7.28(m,1H),7.24–7.22(m,1H),7.21–7.17(m,1H),7.05(d,J=7.3,1H),3.82(s,3H),2.39(s,3H);13C NMR(100MHz,CDCl3,ppm):δ144.0,142.0,138.6,135.9,135.7,128.9,127.5,125.9,123.5,122.3,122.2,122.0,119.5,119.3,114.2,109.1,32.3,21.6.
实施例13产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.78(d,J=7.7,1H),7.60(s,1H),7.33–7.15(m,6H),6.79–6.77(m,1H),3.85(s,3H),3.81(s,3H);13C NMR(100MHz,CDCl3,ppm):δ160.1,144.1,142.0,137.1,135.5,130.0,123.5,122.2,122.1,119.6,119.4,117.8,114.6,112.1,110.8,109.2,55.4,32.3.
实施例14产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.81(d,J=7.8,1H),7.65(s,1H),7.61(t,J=1.9,1H),7.50–7.48(m,1H),7.37(d,J=8.2,1H),7.33–7.27(m,2H),7.21–7.18(m,2H),3.87(s,3H);13C NMR(100MHz,CDCl3,ppm):δ144.4,142.1,137.6,134.9,133.9 130.129,126.4,125.0,123.6,123.1,122.3,122.2,119.8,119.4,115.2,109.2,32.4.
实施例15产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.84(s,1H),7.80(d,J=7.8,1H),7.76–7.30(m,1H),7.67(s,1H),7.46–7.45(m,2H),7.35–7.28(m,2H),7.24–7.19(m,1H),3.83(s,3H);13CNMR(100MHz,CDCl3,ppm):δ=143.3(d,J=234.6),136.6,133.7,131.6,131.2,129.4,128.0,123.7,122.9(q,J=4.1),122.4,122.1,121.6(q,J=3.6),119.6(d,J=38.5).115.5,109.2,32.4.
实施例16产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.80(d,J=7.8,1H),7.38–7.35(m,2H),7.30–7.27(m,2H),7.19(t,J=7.4,1H),7.11(s,1H),7.05(d,J=7.8,1H),3.86(s,3H),2.48(s,3H),2.36(s,3H);13C 13C NMR(100MHz,CDCl3,ppm):δ144.3,141.8,137.3,136.2,134.4,132.2,131.6,130.6,126.7,122.9,122.2,121.8,119.4,119.2,117.4,109.0,32.4,21.2,21.1.
实施例17产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.80(d,J=7.7,1H),7.50(s,1H),7.36–7.34(m,1H),7.30–7.27(m,1H),7.21–7.14(m,3H),6.89(d,J=8.2,1H),3.97(s,3H),3.91(s,3H),3.85(s,3H);13C NMR(100MHz,CDCl3,ppm):δ149.3,148.3,143.5,141.9,135.8,129.0,123.4,122.2,121.9,119.5,119.3,117.9,113.5,111.7,109.1,108.9,56.1,56.0,32.4.
实施例18产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.79(d,J=7.8,1H),7.68(t,J=1.2,1H),7.61(s,1H),7.41(d,J=1.2,2H),7.37–7.35(m,1H),7.33–7.29(m,1H),7.23–7.19(m,1H),3.85(s,3H);13C NMR(100MHz,CDCl3,ppm):δ144.4,142.1,135.9,133.0,132.6,130.7,129.9,126.5,124.1,123.6,122.4,122.1,119.8,119.4,115.6,109.2,32.4.
实施例19产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=8.43–8.41(m,1H),7.92–7.90(m,1H),7.86–7.84(m,2H),7.65(dd,J=7.1,1.2,1H),7.54–7.49(m,4H),7.41–7.38(m,1H),7.34–7.30(m,1H),7.24–7.20(m,1H),3.90(s,3H);13C NMR(100MHz,CDCl3,ppm):δ144.7,141.9,134.0,133.4,132.7,132.3,128.5,128.4,128.1,126.5,126.1,126.0,125.3,123.2,122.2,122.0,119.5,119.4,118.7,109.1,32.44.
实施例20产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=8.01(d,J=1.0,1H),7.85–7.79(m,4H),7.75(s,1H),7.50–7.40(m,3H),7.37–7.35(m,1H),7.32–7.28(m,1H),7.23–7.19(m,1H),3.87(s,1H);13C NMR(100MHz,CDCl3,ppm):δ144.2,142.1,135.8,133.9,133.2,132.4,128.5,127.79,127.75,126.58,125.56,123.9,123.7,122.8,122.3,122.1,119.6,119.4,114.8,109.2,32.4.
实施例21产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.73(d,J=7.7,1H),7.32–7.30(m,1H),7.24–7.21(m,1H),7.16–7.12(m,1H),7.07(s,1H),2.11(s,3H),2.05–2.04(m,6H),1.79(s,6H);13C NMR(100MHz,CDCl3,ppm):δ150.6,142.3,141.7,122.2,121.6,121.3,119.0,118.9,111.1,108.8,45.2,36.9,36.8,32.2,29.0.
实施例22产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.73(d,J=7.8,1H),7.33–7.31(m,1H),7.26–7.22(m,1H),7.17–7.13(m,1H),7.04(s,1H),3.82(s,3H),2.88(t,J=7.5,2H),1.76–1.69(m,2H),1.34–1.29(m,5H),0.91–0.88(m,4H);13C NMR(100MHz,CDCl3,ppm):δ142.7,141.6,137.7,122.0,121.9,121.3,119.03,118.98,114.8,108.9,32.2,31.9,31.7,31.2,28.7,22.6,14.1
实施例23产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.54–7.49(m,3H),7.43–7.34(m,4H),7.31–7.27(m,2H),7.25–7.18(m,4H),7.06–7.01(m,1H),3.88(s,3H);13C NMR(100MHz,CDCl3,ppm):δ142.7,142.1,136.3,135.3,131.4,130.0,129.2,128.5,128.4,127.4,126.6,123.6,122.5,122.0,119.2,119.1,108.9,100.0,32.2.
实施例24产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.73(d,J=7.8,1H),7.32(d,J=8.2,1H),7.24–7.22(m,1H),7.15(t,J=7.4,1H),7.09(s,1H),3.82(s,3H),1.46(s,9H);13C NMR(100MHz,CDCl3,ppm):δ149.7,142.6,141.6,122.2,121.5,121.3,119.1,118.9,111.9,108.9,35.2,32.6,32.2.
实施例25产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.73(d,J=7.8,1H),7.32(d,J=8.2,1H),7.26–7.22(m,1H),7.16–7.13(m,1H),7.07(d,J=1.0,1H),3.81(s,3H),1.40(d,J=6.8,6H);13CNMR(100MHz,CDCl3,ppm):δ145.4,142.4,141.7,122.1,121.7,121.3,119.1,119.0,112.6,108.9,32.2,31.0,24.9.
实施例26产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.635–7.627(m,1H),7.61–7.59(m,3H),7.40–7.36(m,2H),7.25–7.21(m,2H),7.11(dd,J=8.3,1.3,1H),3.84(s,3H),2.50(s,3H);13CNMR(100MHz,CDCl3,ppm):δ144.2,140.4,135.9,135.4,128.9,128.9,126.5,125.1,123.4,123.2,122.4,119.3,114.3,108.8,32.4,21.5.
实施例27产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.64–7.63(m,1H),7.62–7.61(m,1H),7.59(s,1H),7.38(t,J=7.8,2H),7.30(d,J=2.4,1H),7.25–7.23(m,2H),6.93(dd,J=8.9,2.5,1H),3.91(s,3H),3.84(s,3H);13C NMR(100MHz,CDCl3,ppm):δ154.1,144.5,137.2,135.8,135.3,128.9,126.5,125.1,123.2,1222.5,114.12,111.2,109.7,102.4,56.0,32.5.
实施例28产物的核磁数据如下:
11H NMR(100MHz,CDCl3,ppm):δ=7.74(t,J=1.2,1H),7.62–7.59(m,2H),7.53(s,1H),7.38(t,J=7.7,2H),7.27–7.22(m,4H),3.81(s,3H);13C NMR(100MHz,CDCl3,ppm):δ145.0,140.3,136.4,135.5,129.0,127.9,126.9,125.2,123.0,122.8,122.0,118.9,113.9,101.0,32.4.
实施例29产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.90(d,J=1.9,1H),7.62–7.60(m,2H),7.53(s,1H),7.41–7.34(m,3H),7.27–7.23(m,1H),7.19(d,J=8.7,1H),3.82(s,3H);13C NMR(100MHz,CDCl3,ppm):δ144.8,140.5,136.4,135.4,129.0,126.8,125.2,124.6,123.5,122.6,121.9,113.9,112.7,110.4,32.4.
实施例30产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=8.10(d,J=1.6,1H),7.62–7.59(m,2H),7.54–7.51(m,2H),7.41–7.37(m,2H),7.27–7.23(m,2H),7.10(d,J=8.6,1H),3.81(s,3H);13CNMR(100MHz,CDCl3,ppm):δ144.6,141.1,136.6,135.4,130.2,129.0,128.1,126.9,125.2,124.4,122.5,113.9,111.0,82.7,32.4.
实施例31产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.68(d,J=8.0,1H),7.63–7.61(m,2H),7.59(s,1H),7.39–7.35(m,2H),7.24–7.20(m,1H),7.14(s,1H),7.02(d,J=8.0,1H),3.82(s,3H),2.53(s,3H);13C NMR(100MHz,CDCl3,ppm):δ143.6,142.4,135.9,135.4,132.0,129.0,126.5,125.1,123.5,121.1,120.1,119.0,114.3,109.4,32.3,22.0.
实施例32产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.69(d,J=8.4,1H),7.63–7.61(m,2H),7.57(s,1H),7.41–7.34(m,4H),7.16(dd,J=8.4,1.8,1H),3.84(s,3H);13C NMR(100MHz,CDCl3,ppm):δ144.5,142.3,136.6,135.5,129.0,128.0,126.9,125.3,123.3,120.7,120.04,120.00,114.0,109.4,32.5.
实施例33产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.64–7.60(m,3H),7.57(s,1H),7.39–7.35(m,2H),7.24–7.20(m,1H),7.05(t,J=7.5,1H),6.97(d,J=7.1,1H),4.08(s,3H),2.78(s,3H);13C NMR(100MHz,CDCl3,ppm):δ145.4,140.7,135.8,135.6,128.9,126.6,125.1,125.1,123.4,123.2,121.2,119.9,117.5,114.3,36.4,19.6.
实施例34产物的核磁数据如下:
1H NMR(100MHz,Acetone,ppm):δ=10.76(s,1H),7.84–7.82(m,2H),7.69(dd,J=8.4,1.1,2H),7.52(d,J=8.1,1H),7.41(t,J=7.8,2H),7.27–7.20(m,2H),7.16–7.12(m,1H);13C NMR(100MHz,Acetone,ppm):δ142.0,140.9,135.8,135.6,129.0,126.6,125.3,124.8,122.3,122.2,119.5,118.9,113.9,111.6.
实施例35产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.81(d,J=7.8,1H),7.65–7.63(m,3H),7.40–7.36(m,3H),7.29(dd,J=7.2,0.9,1H),7.24–7.17(m,2H),4.29(q,J=7.3,2H),1.53(t,J=7.3,3H);13C NMR(100MHz,CDCl3,ppm):δ142.7,139.4,135.8,135.4,128.9,128.8,126.5,125.1,123.6,123.3,122.5,119.4,114.1,108.8,40.9,21.4,13.8.
实施例36产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.81(d,J=7.6,1H),7.65–7.63(m,3H),7.42–7.35(m,3H),7.29–7.25(m,2H),7.20–7.16(m,1H),4.86(dt,J=13.5,6.8,1H),1.64(d,J=6.8,6H);13C NMR(100MHz,CDCl3,ppm):δ141.0,139.7,136.2,135.6,128.9,126.6,125.2,124.8,122.2,121.9,119.4,119.3,113.6,109.4,47.8,20.9.
实施例37产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.64–7.61(m,3H),7.60(s,1H),7.37(t,J=7.8,2H),7.25–7.21(m,2H),7.10(dd,J=8.3,1.2,1H),4.26(q,J=7.2,2H),2.50(s,3H),1.51(t,J=7.3,3H);13C NMR(100MHz,CDCl3,ppm):δ142.7,139.4,135.8,135.4,128.9,128.8,126.5,125.1,123.6,123.3,122.5,119.4,114.2,108.8,40.9,21.4,13.8.
实施例38产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.63–7.59(m,3H),7.37(t,J=7.7,2H),7.30(d,J=2.4,1H),7.26–7.21(m,2H),6.92(dd,J=8.9,2.5,1H),4.24(q,J=7.3,2H),3.90(s,3H),1.50(t,J=7.3,3H);13C NMR(100MHz,CDCl3,ppm):δ154.1,143.1,136.3,135.8,135.3,128.9,126.5,125.1,123.6,122.7,114.0,111.1,109.8,102.5,56.1,41.1,13.9.
实施例39产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.58(s,1H),7.57–7.53(m,2H),7.49(s,1H),7.23-7.21(m,1H),7.11–7.04(m,3H),3.80(s,3H),2.50(s,3H);13C NMR(100MHz,CDCl3,ppm):δ=161.8(d,J=246.1),144.0,140.4,134.2,132.1(d,J=3.3),128.9,126.7(d,J=7.9),123.4,122.7(d,J=83.6),119.3,115.9(d,J=21.8),114.3,108.8,32.4,21.5.
实施例40产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.45–7.43(m,2H),7.25–7.23(m,1H),7.17–7.13(m,2H),7.02(td,J=9.1,2.5,1H),6.89(d,J=8.2,1H),3.98(s,3H),3.92(s,3H),3.84(s,3H);13C NMR(100MHz,CDCl3,ppm):δ157.8(d,J=234.8),149.3,148.4,144.8,138.4,136.0,128.7,123.0(d,J=4.1),122.3(d,J=10.2),117.9,113.2,111.6,109.8,109.6(d,J=5.4),109.5,108.9,104.8(d,J=24.2),56.1,56.0,32.6.
实施例42产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=7.74(t,J=1.7,1H),7.61(d,J=7.7,1H),7.55(s,1H),7.48(d,J=7.8,1H),7.33–7.31(m,1H),7.24–7.18(m,1H),7.06(t,J=7.5,1H),6.97(d,J=7.2,1H),4.04(s,3H),2.76(s,3H);13C NMR(100MHz,CDCl3,ppm):δ145.7,140.7,137.8,133.5,130.4,129.2,127.7,125.3,123.5,123.1,121.2,120.0,117.6,115.3,36.5,19.6.
实施例43产物的核磁数据如下:
1H NMR(100MHz,CDCl3,ppm):δ=8.17(s,1H),7.83(s,1H),7.78–7.73(m,1H),7.63(s,1H),7.60(s,1H),7.47(d,J=5.0,2H),7.25(d,J=8.3,1H),7.09(d,J=8.2,1H),2.50(s,3H);13C NMR(100MHz,CDCl3,ppm):δ141.0,140.0,136.4,134.3,131.5,131.2,129.8,129.4,128.2,125.8,125.5,124.2,123.1(q,J=3.8),122.5,121.8-121.5(m),119.4,114.9,111.1,21.5.
表 实施例1-46反应的转化率及产物图
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (10)
1.一种多取代吲哚并噻吩及衍生物,其特征在于,其通式为式Ⅰ:
其中
R1选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基,酰基;取代或非取代的C6-C20芳基,苄基,苯磺酰基,苯甲酰基;取代或非取代的含有氮,氧,硫原子的杂环基团;取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基;
R2选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基;取代或非取代的C6-C20芳基;取代或非取代的含有氮,氧,硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基;
R3选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基;取代或非取代的C6-C20芳基;取代或非取代的含有氮,氧,硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基,金刚烷基。
2.一种合成权利要求1所述的多取代吲哚并噻吩及衍生物的方法,其特征在于,以布朗斯特酸类化合物作催化剂,包括以下步骤:
(Ⅰ)加入吲哚类化合物,烯类化合物、炔类化合物或酮类化合物,硫粉,催化剂和有机溶剂;
(Ⅱ)将反应物充分混合,空气氛围下,加热反应;
(Ⅲ)纯化得到产物。
3.根据权利要求2所述的合成方法,其特征在于,所述吲哚类化合物,是选自C8-C20芳香类吲哚,其通式为式Ⅱ:
其中
R1选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基,酰基;取代或非取代的C6-C20芳基,苄基,苯磺酰基,苯甲酰基;取代或非取代的含有氮,氧,硫原子的杂环基团;取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基;
R2选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基;取代或非取代的C6-C20芳基;取代或非取代的含有氮,氧,硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基。
4.根据权利要求3所述的合成方法,其特征在于,所述吲哚类化合物选自:1-甲基吲哚,1,5-二甲基吲哚,1-甲基-5-甲氧基吲哚,1-甲基-5-氟吲哚,1-甲基-5-氯吲哚,1-甲基-5溴吲哚,1-甲基-5-碘吲哚,1,6-二甲基吲哚,1-甲基-6-氯吲哚,1,7-二甲基吲哚,1-H-吲哚,1-乙基吲哚,1-异丙基吲哚。
5.根据权利要求2或3所述的合成方法,其特征在于,所述烯类化合物、炔类化合物或酮类化合物,其通式分别为式Ⅲ、Ⅳ、Ⅴ:
其中
R3选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基;取代或非取代的C6-C20芳基;取代或未取代的含有氮,氧,硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基,金刚烷基;
R4选自:
氢原子;C1-C10的直链烷基、支链烷基、环状烷基;取代或非取代的C6-C20芳基;取代或未取代的含有氮,氧,硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C10的直链烷基、支链烷基、环状烷基,卤素,硝基,氨基,甲氧基,苯基,砜基,羧基,脂基,醛基,三氟甲基,三氟甲氧基,金刚烷基。
6.根据权利要求5所述的合成方法,其特征在于,所述烯类化合物选自:苯乙烯,4-甲基苯乙烯,4- 甲氧基苯乙烯,4-氟苯乙烯,4-氯苯乙烯,4-溴苯乙烯,2-氯苯乙烯。
7.根据权利要求5所述的合成方法,其特征在于所述炔类化合物选自:苯乙炔,4-甲基苯乙炔,4-乙基基苯乙炔,4-正丙基苯乙炔,4-正戊基苯乙炔,4-甲氧基苯乙炔,4-乙氧基苯乙炔,4-氟苯乙炔,4-氯苯乙炔,4-溴苯乙炔,2-氯苯乙炔,1-辛炔,1,2-二苯乙炔,3,3-二甲基丁炔。
8.根据权利要求5所述的合成方法,其特征在于,所述酮类化合物选自:苯乙酮,4-甲基苯乙酮,4-异丁基苯乙酮,4-叔丁基苯乙酮,4-甲氧基苯乙酮,4-氟苯乙酮,4-氯苯乙酮,4-溴苯乙酮,4-碘苯乙酮,2-甲基苯乙酮,2-氟苯乙酮,2-氯苯乙酮,3-甲基苯乙酮,3-甲氧基苯乙酮,3-氟苯乙酮,3-氯苯乙酮,3-溴苯乙酮,3-三氟甲基苯乙酮,2,4-二甲基苯乙酮,3,4-二甲氧基苯乙酮,3,4-二氯苯乙酮,1-乙酰基萘,2-乙酰基萘,1-乙酰基金刚烷,3-甲基-2-丁酮。
9.根据权利要求2-8任一项所述的合成方法,其特征在于,所述布朗斯特酸类化合物选自:甲酸、乙酸、异丁酸、环丙基甲酸、环己烷羧酸、三氟乙酸、对甲苯磺酸、甲磺酸、三氟甲磺酸、特戊酸、苯甲酸、对羟基苯甲酸、对硝基苯甲酸、乙酸酐、三氟乙酸酐、烟酸、盐酸、硫酸、硝酸、磷酸、氢碘酸、氢溴酸中的一种或多种。
10.根据权利要求2-9任一项所述的合成方法,其特征在于,所述反应氛围为:空气氛围;吲哚类化合物与烯类化合物、炔类化合物或酮类化合物与硫粉与催化剂的摩尔比为1.0:1.1-5.0:3.0-8.0:3.0-10.0;同时,反应温度为110℃-160℃;反应时长为8h-24h;所述有机溶剂为:N,N-二甲基甲酰胺和/或N,N-二甲基乙酰胺。
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