CN106117113B - 多取代咔唑、衍生物及其合成方法 - Google Patents
多取代咔唑、衍生物及其合成方法 Download PDFInfo
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- CN106117113B CN106117113B CN201610512443.8A CN201610512443A CN106117113B CN 106117113 B CN106117113 B CN 106117113B CN 201610512443 A CN201610512443 A CN 201610512443A CN 106117113 B CN106117113 B CN 106117113B
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 21
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title claims abstract 4
- -1 polysubstituted carbazole compound Chemical class 0.000 claims abstract description 87
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000002576 ketones Chemical class 0.000 claims abstract description 27
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 23
- 150000002475 indoles Chemical class 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940107816 ammonium iodide Drugs 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 10
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 8
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical compound C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 claims description 6
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 claims description 4
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- ZAJNGDIORYACQU-UHFFFAOYSA-N decan-2-one Chemical compound CCCCCCCCC(C)=O ZAJNGDIORYACQU-UHFFFAOYSA-N 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- JZJWCDQGIPQBAO-UHFFFAOYSA-N 1-(4-iodophenyl)ethanone Chemical compound CC(=O)C1=CC=C(I)C=C1 JZJWCDQGIPQBAO-UHFFFAOYSA-N 0.000 claims description 3
- QLATXALTCNYKEO-UHFFFAOYSA-N 2-chloro-1-methylindole Chemical compound C1=CC=C2N(C)C(Cl)=CC2=C1 QLATXALTCNYKEO-UHFFFAOYSA-N 0.000 claims description 3
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 claims description 3
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- PZNYKBLADPHGMI-UHFFFAOYSA-N 1,5-dimethylindole Chemical compound CC1=CC=C2N(C)C=CC2=C1 PZNYKBLADPHGMI-UHFFFAOYSA-N 0.000 claims description 2
- JYAQYXOVOHJRCS-UHFFFAOYSA-N 1-(3-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(Br)=C1 JYAQYXOVOHJRCS-UHFFFAOYSA-N 0.000 claims description 2
- BAYUSCHCCGXLAY-UHFFFAOYSA-N 1-(3-methoxyphenyl)ethanone Chemical compound COC1=CC=CC(C(C)=O)=C1 BAYUSCHCCGXLAY-UHFFFAOYSA-N 0.000 claims description 2
- ARKIFHPFTHVKDT-UHFFFAOYSA-N 1-(3-nitrophenyl)ethanone Chemical compound CC(=O)C1=CC=CC([N+]([O-])=O)=C1 ARKIFHPFTHVKDT-UHFFFAOYSA-N 0.000 claims description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 claims description 2
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 claims description 2
- ZDPAWHACYDRYIW-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1 ZDPAWHACYDRYIW-UHFFFAOYSA-N 0.000 claims description 2
- QCZZSANNLWPGEA-UHFFFAOYSA-N 1-(4-phenylphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1C1=CC=CC=C1 QCZZSANNLWPGEA-UHFFFAOYSA-N 0.000 claims description 2
- NJZQOCCEDXRQJM-UHFFFAOYSA-N 1-benzylindole Chemical compound C1=CC2=CC=CC=C2N1CC1=CC=CC=C1 NJZQOCCEDXRQJM-UHFFFAOYSA-N 0.000 claims description 2
- YYYVODQGPSIUNS-AATRIKPKSA-N 1-methyl-3-[(e)-2-nitroethenyl]benzene Chemical compound CC1=CC=CC(\C=C\[N+]([O-])=O)=C1 YYYVODQGPSIUNS-AATRIKPKSA-N 0.000 claims description 2
- WGSVFWFSJDAYBM-UHFFFAOYSA-N 2-nitroprop-1-enylbenzene Chemical group [O-][N+](=O)C(C)=CC1=CC=CC=C1 WGSVFWFSJDAYBM-UHFFFAOYSA-N 0.000 claims description 2
- HQNPKVBTBJUMTR-UHFFFAOYSA-N 5-methoxy-1-methylindole Chemical compound COC1=CC=C2N(C)C=CC2=C1 HQNPKVBTBJUMTR-UHFFFAOYSA-N 0.000 claims description 2
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 claims description 2
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 claims description 2
- DPFWUAYMRGTMAM-UHFFFAOYSA-N 2-fluoro-1-methylindole Chemical compound C1=CC=C2N(C)C(F)=CC2=C1 DPFWUAYMRGTMAM-UHFFFAOYSA-N 0.000 claims 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims 2
- BQOIOXRQQPRNCO-UHFFFAOYSA-N (2-chloro-2-nitroethenyl)benzene Chemical compound [O-][N+](=O)C(Cl)=CC1=CC=CC=C1 BQOIOXRQQPRNCO-UHFFFAOYSA-N 0.000 claims 1
- UYFJYGWNYQCHOB-UHFFFAOYSA-N 1-(4-tert-butylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)(C)C)C=C1 UYFJYGWNYQCHOB-UHFFFAOYSA-N 0.000 claims 1
- LWZBTVYFUVWJLB-UHFFFAOYSA-N 2-bromo-1-methylindole Chemical compound C1=CC=C2N(C)C(Br)=CC2=C1 LWZBTVYFUVWJLB-UHFFFAOYSA-N 0.000 claims 1
- NLPHXWGWBKZSJC-UHFFFAOYSA-N 4-acetylbenzonitrile Chemical compound CC(=O)C1=CC=C(C#N)C=C1 NLPHXWGWBKZSJC-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 claims 1
- NMILWYUYIFMKTE-UHFFFAOYSA-N methyl 1-methylindole-6-carboxylate Chemical compound COC(=O)C1=CC=C2C=CN(C)C2=C1 NMILWYUYIFMKTE-UHFFFAOYSA-N 0.000 claims 1
- JCDWETOKTFWTHA-UHFFFAOYSA-N methylsulfonylbenzene Chemical compound CS(=O)(=O)C1=CC=CC=C1 JCDWETOKTFWTHA-UHFFFAOYSA-N 0.000 claims 1
- 229930192474 thiophene Natural products 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 70
- 238000003786 synthesis reaction Methods 0.000 abstract description 70
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 23
- 239000011261 inert gas Substances 0.000 abstract description 16
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 abstract description 15
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 abstract description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 abstract description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003814 drug Substances 0.000 abstract description 6
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 abstract description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 abstract description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 abstract description 5
- 230000005622 photoelectricity Effects 0.000 abstract description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 238000012827 research and development Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 216
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 110
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 54
- 238000005160 1H NMR spectroscopy Methods 0.000 description 54
- 239000001257 hydrogen Substances 0.000 description 53
- 229910052739 hydrogen Inorganic materials 0.000 description 53
- 150000001716 carbazoles Chemical class 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 125000000623 heterocyclic group Chemical group 0.000 description 22
- 239000007789 gas Substances 0.000 description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 12
- 150000002367 halogens Chemical class 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 12
- 230000005311 nuclear magnetism Effects 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 4
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 4
- UGFOTZLGPPWNPY-UHFFFAOYSA-N 3.4-Benzo-carbazol Natural products C1=CC=CC2=C3C4=CC=CC=C4NC3=CC=C21 UGFOTZLGPPWNPY-UHFFFAOYSA-N 0.000 description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 3
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- VUIMBZIZZFSQEE-UHFFFAOYSA-N 1-(1h-indol-3-yl)ethanone Chemical compound C1=CC=C2C(C(=O)C)=CNC2=C1 VUIMBZIZZFSQEE-UHFFFAOYSA-N 0.000 description 2
- IGJQUJNPMOYEJY-UHFFFAOYSA-N 2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1 IGJQUJNPMOYEJY-UHFFFAOYSA-N 0.000 description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- WEGYGNROSJDEIW-UHFFFAOYSA-N 3-Acetylpyridine Chemical compound CC(=O)C1=CC=CN=C1 WEGYGNROSJDEIW-UHFFFAOYSA-N 0.000 description 2
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N 4-methyl-1h-indole Chemical compound CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical group CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 2
- UAUJZFNYIBXEDG-UHFFFAOYSA-N 5-chloro-1-methylindole Chemical class ClC1=CC=C2N(C)C=CC2=C1 UAUJZFNYIBXEDG-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000008424 iodobenzenes Chemical class 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000000144 pharmacologic effect Effects 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 2
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- HGBLUTOUXDOKTN-UHFFFAOYSA-N C1(CCCCCCC1)=O.CC(CCC)=O Chemical compound C1(CCCCCCC1)=O.CC(CCC)=O HGBLUTOUXDOKTN-UHFFFAOYSA-N 0.000 description 1
- ZYOUNOPGEAAOFI-UHFFFAOYSA-N CC(C)C(C)CCCC1CCCCC1=O Chemical compound CC(C)C(C)CCCC1CCCCC1=O ZYOUNOPGEAAOFI-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- UUCUQJHYUPXDHN-UHFFFAOYSA-N N-Acetylindole Chemical compound C1=CC=C2N(C(=O)C)C=CC2=C1 UUCUQJHYUPXDHN-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- GJSJZQZEDAUFBH-UHFFFAOYSA-N benzene;pentan-3-one Chemical compound CCC(=O)CC.C1=CC=CC=C1 GJSJZQZEDAUFBH-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
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Abstract
一种多取代咔唑、衍生物及其合成方法,首次以碘化铵作催化剂,在惰性气体保护下,用乙腈,二氯乙烷,四氢呋喃,N,N‑二甲基乙酰,苯,氯苯,邻二氯苯,环己烷,1,4‑二氧六环,苯甲醚,苯甲腈,二甲苯,三氟甲苯,甲苯,三甲苯等作有机溶剂,首次用吲哚,烯,酮(醛)三种简单组分选择性合成多取代咔唑及衍生物的技术方案;克服了现有合成方法存在合成步骤复杂,需要采取多步合成方法才能完成,需要过渡金属催化剂、化学当量的金属氧化剂等缺点;可广泛用于光电,印染,医药,超分子识别等多个领域;本发明可广泛应用于光电,印染,医药,超分子识别等多个领域;特别适合无金属催化,多组分一锅法选择性合成多取代咔唑类化合物的研究与开发。
Description
技术领域
本发明涉及一种多取代咔唑、衍生物及其合成方法。
背景技术
咔唑及其衍生物是一类重要的含氮芳杂环化合物,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咔唑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广泛应用。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,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
针对上述情况,本发明的目的是提供一种多取代咔唑及衍生物,它分子结构稳定、化学性质优良,它既是重要的分子切块,又是含生理活性和药理活性的化合物片段。
本发明的又一目的是提供一种制备多取代咔唑及衍生物的方法,它工艺科学、合理,操作容易,反应步骤少,所需设备简单,所用原料廉价易得且不需要进行预处理,反应能极大限度地保持原子经济性,投入低、产出高,易于工业化生产和普及推广。
为了实现上述目的,一种多取代咔唑及衍生物,它的通式为式Ⅰ:
其中,
R1选自:氢原子;C1-C10的直链,支链,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,支链,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,支链,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,支链,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,支链,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,支链,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;R4选自:氢原子;C1-C10的直链,支链,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,支链,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;R5选自:氢原子;C1-C10的直链,支链,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,支链,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;R6选自:氢原子;C1-C10的直链,支链,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,支链,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。
为了实现上述另一目的,一种合成多取代咔唑及衍生物的方法,以碘类化合物作催化剂、惰性气体的保护下,将吲哚类、酮(醛)类和烯烃类化合物与有机溶剂进行混合,经加热反应、纯化得到产物的过程构成了咔唑类化合物的反应体系及通式,包括以下步骤:
(Ⅰ)加入吲哚类化合物、酮(醛)类化合物、烯烃类化合物、催化剂和有机溶剂;
(Ⅱ)将反应物充分混合,充入1atm惰性气体,加热反应;
(Ⅲ)纯化得到产物。
为了提高本发明的综合性能,实现结构、效果优化,其进一步的措施是:
所述的吲哚类化合物,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,支链,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,支链,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,支链,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,支链,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。
所述的合成方法,式Ⅱ中的C8-C20芳香类吲哚选自:吲哚,1-甲基吲哚,1-乙基吲哚,1-丙基吲哚,1-丁基吲哚,1-癸基吲哚,1-乙酰基吲哚,1-苯基吲哚,1-苄基吲哚,1-苯乙酰基吲哚,1-嘧啶基吲哚,1-吡啶基吲哚,4-甲基吲哚,4-氟吲哚,4-氯吲哚,4-溴吲哚,4-碘吲哚,4-硝基吲哚,4-羧酸甲酯吲哚,4-甲氧基吲哚,5-甲基吲哚,5-氟吲哚,5-氯吲哚,5-溴吲哚,5-碘吲哚,5-硝基吲哚,5-羧酸甲酯吲哚,5-甲氧基吲哚,6--甲基吲哚,6-甲氧基吲哚,6-氟吲哚,6-氯吲哚,6-溴吲哚,6-碘吲哚,6-羧酸甲酯吲哚,6-硝基吲哚,7-甲基吲哚,7-甲氧基吲哚,7-氟吲哚,7-氯吲哚,7-溴吲哚,7-碘吲哚,7-羧酸甲酯吲哚,7-硝基吲哚,1,4-二甲基吲哚,1,5-二甲基吲哚,1,6-二甲基吲哚,1,7-二甲基吲哚,1-甲基-4-氟吲哚,1-甲基-5-氟吲哚,1-甲基-5-氯吲哚,1-甲基-6-氟吲哚,1-甲基-7-氟吲哚,1-甲基-4-氯吲哚,1-甲基-5-氯吲哚,1-甲基-6-氯吲哚,1-甲基-7-氯吲哚,1-甲基-4-溴吲哚,1-甲基-5-溴吲哚,1-甲基-6-溴吲哚,1-甲基-7-溴吲哚,1-甲基-4-碘吲哚,1-甲基-5-碘吲哚,1-甲基-6-碘吲哚,1-甲基-7-碘吲哚,1-甲基-4-甲氧基吲哚,1-甲基-5-甲氧基吲哚,1-甲基-6-甲氧基吲哚,1-甲基-7-甲氧基吲哚,1-甲基-4-羧酸甲酯吲哚,1-甲基-5-羧酸甲酯吲哚,1-甲基-6-羧酸甲酯吲哚,1-甲基-7-羧酸甲酯吲哚,1-甲基-4-羧酸甲酯吲哚,1-甲基-5-羧酸甲酯吲哚,1-甲基-6-羧酸甲酯吲哚,1-甲基-7-羧酸甲酯吲哚。
所述的合成方法,所述的酮(醛)类化合物,其通式为式Ⅲ:
其中,
R3选自:氢原子;C1-C10的直链,支链,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,支链,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;R4选自:氢原子;C1-C10的直链,支链,环状烷基;取代或非取代的C6-C7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,支链,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。
所述的合成方法,所述的酮(醛)类化合物选自:环己酮,4-甲基环己酮,4-乙基环己酮,4-异丙基环己酮,4-正戊基环己酮,4-叔戊基环己酮,4-环丙基环己酮,4-苯基环己酮,4-(3-噻吩基)环己酮,4-(3-(5-氯噻吩基))环己酮,4-(4-硝基苯基)环己酮,环庚酮,环戊酮环辛酮,环十二酮,2-戊酮,2-己酮,4-甲基-2-戊酮,2-庚酮,2-辛酮,2-壬酮,2-癸酮,2-二十酮,3-戊酮,4-庚酮,5-壬酮,8-十五酮,苯丙酮,对甲基苯丙酮,对氯苯丙酮,对硝基苯丙酮,苯乙酮,4-甲基苯乙酮,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,4-硝基苯乙酮,4-氨基苯乙酮,4-羧酸甲酯苯乙酮,4-苯基苯乙酮,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,4-碘苯乙酮, 3-硝基苯乙酮,3-氨基苯乙酮,3羧酸甲酯苯乙酮,3-苯基苯乙酮,2-甲基苯乙酮,2-甲氧基苯乙酮,2-氟苯乙酮,2-氯苯乙酮,2-溴苯乙酮,2-碘苯乙酮,2-硝基苯乙酮,2-氨基苯乙酮,2-羧酸甲酯苯乙酮,2-苯基苯乙酮,2-乙酰噻吩,2-乙酰呋喃,2-乙酰吡咯,2-乙酰吡啶,2-乙酰萘,1-乙酰萘,3-乙酰吡啶,4-乙酰吡啶,2-乙酰吲哚,3-乙酰吲哚,2-乙酰苯并噻吩,3-乙酰苯并噻吩,2-乙酰苯并呋喃,3-乙酰苯并呋喃,乙醛,丙醛,丁醛,戊醛,己醛,庚醛,辛醛,壬醛,癸醛,苯乙醛,苯丙醛。
所述的合成方法,所述的烯烃类化合物,其通式为式Ⅳ:
其中,
R5选自:氢原子;C1-C10的直链,支链,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,支链,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;R6选自:氢原子;C1-C10的直链,支链,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,支链,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。
所述的合成方法,所述的烯烃类化合物选自:反式硝基苯乙烯,反-4-甲基-β-硝基苯乙烯,反-4-甲氧基-β-硝基苯乙烯,反-4-氟-β-硝基苯乙烯,反-4-氯-β-硝基苯乙烯,反-4-溴-β-硝基苯乙烯,反-4-碘-β-硝基苯乙烯,反-4-硝基-β-硝基苯乙烯,反-4-氰基-β-硝基苯乙烯,反-4-羟基-β-硝基苯乙烯,反-3-甲基-β-硝基苯乙烯,反-3-甲氧基-β-硝基苯乙烯,反-3-氟-β-硝基苯乙烯,反-3-氯-β-硝基苯乙烯,反-3-溴-β-硝基苯乙烯,反-3-碘-β-硝基苯乙烯,反-3-硝基-β-硝基苯乙烯,反-3-氰基-β-硝基苯乙烯,反-3-羟基-β-硝基苯乙烯,反-2-甲基-β-硝基苯乙烯,反-2-甲氧基-β-硝基苯乙烯,反-2-氟-β-硝基苯乙烯,反-2-氯-β-硝基苯乙烯,反-2-溴-β-硝基苯乙烯,反-2-碘-β-硝基苯乙烯,反-2-硝基-β-硝基苯乙烯,反-2-氰基-β-硝基苯乙烯,反-2-羟基-β-硝基苯乙烯,1-苯基-2-硝基丙烯,反-4-(硝基乙烯基)苯硼酸。
所述的合成方法,所述的碘类化合物选自:碘化铵、碘化钾、碘化钠、碘化亚铜、碘化钯、碘酸钾、碘酸钠、高碘酸钠、单质碘、碘苯、碘苯二乙酯、双(三氟乙酰氧基)碘苯中的一种或数种;所述的反应氛围为:惰性气体;所述的有机溶剂为:乙腈,二氯乙烷,四氢 呋喃,N,N-二甲基乙酰,苯,氯苯,环己烷,1,4-二氧六环,苯甲醚,苯甲腈,二甲苯,三氟甲苯,甲苯,三甲苯。
所述的合成方法,吲哚类化合物与酮(醛)类化合物与烯烃类化合物与催化剂的摩尔比为1:0.5-10.0:0.5-6.0:0.01-1.0;同时,反应温度为20℃-200℃。
本发明涉及一种多取代咔唑、衍生物及其合成方法,首次以碘化铵作催化剂,在惰性气体保护下,用乙腈,二氯乙烷,四氢呋喃,N,N-二甲基乙酰,苯,氯苯,邻二氯苯,环己烷,1,4-二氧六环,苯甲醚,苯甲腈,二甲苯,三氟甲苯,甲苯,三甲苯等作有机溶剂,首次用吲哚,烯,酮(醛)三种简单组分选择性合成多取代咔唑类化合物的技术方案;克服了现有合成方法存在合成步骤复杂,需要采取多步合成才能完成,还需要过渡金属催化剂、化学当量的金属氧化剂等困难;可广泛用于光电,印染,医药,超分子识别等多个领域;无金属催化,多组分一锅法选择性合成多取代咔唑及衍生物的方法,拥有巨大的商业市场、潜在的研究价值和应用开发前景。
本发明相比现有技术所产生的有益效果:
(Ⅰ)本发明首次采用在碘化铵的催化下,用惰性气体作为保护气,将吲哚类、酮(醛)类和烯烃类化合物转化为一种多取代咔唑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)在碘类化合物的催化下,用惰性气体作为保护气,将吲哚类、酮(醛)类和烯烃类化合物转化为一种多取代咔唑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)在碘类化合物的催化下,用惰性气体作为保护气,将吲哚类、酮(醛)类和烯烃类化合物转化为一种多取代咔唑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,只需要使用碘化铵和惰性气体,减少了环境污染,节约了原材料,减少了反应成本;(Ⅳ)在碘类化合物的催化下,用惰性气体作为保护气,将吲哚类、酮(醛)类和烯烃类化合物转化为一种多取代咔唑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)在碘类化合物的催化下,用惰性气体作为保护气,将吲哚类、酮(醛)类和烯烃类化合物转化为一种多取代咔唑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)在碘类化合物的催化下,用惰性气体作为保护气,将吲哚类、酮(醛)类和烯烃类化合物转化为一种多取代咔唑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)在碘类化合物催化下,用惰性气体作为保护气,将吲哚类、酮(醛)类和烯烃类化合物转化为一种多取代咔唑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)在碘类化合物催化下,用惰性气体作为保护气,将吲哚类、酮(醛)类和烯烃类化合物转化为一种多取代咔唑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。
本发明多取代咔唑、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,多组分一锅法选择性合成多取代咔唑类化合物的研究与开发。
下面结合附图和实施例对本发明作进一步详细说明。
附图说明
图1为本发明化合物的合成路线图。图2为本发明各实施例对应的化合物。
图3-1实施例1产物的核磁氢谱图。图3-2实施例1产物的核磁碳谱图。
图4-1实施例2产物的核磁氢谱图。图4-2实施例2产物的核磁碳谱图。
图5-1实施例3产物的核磁氢谱图。图5-2实施例3产物的核磁碳谱图。
图6-1实施例4产物的核磁氢谱图。图6-2实施例4产物的核磁碳谱图。
图7-1实施例5产物的核磁氢谱图。图7-2实施例5产物的核磁碳谱图。
具体实施方式
结合本发明化合物的合成路线图,多取代咔唑、衍生物及其原理如图1所示:它包括首次采用碘化铵作催化剂,用惰性气体作为保护气,乙腈,二氯乙烷,四氢呋喃,N,N-二甲基乙酰,苯,氯苯,环己烷,1,4-二氧六环,苯甲醚,苯甲腈,二甲苯,三氟甲苯,甲苯,三甲苯等作有机溶剂,首次用吲哚,烯,酮(醛)三种简单组分选择性合成多取代咔唑类化合物的技术方案,克服了现有合成方法存在合成步骤复杂,需要采取多步合成工艺才能完成,还需要过渡金属催化剂、化学当量的金属氧化剂等困难;本发明可广泛用于光电,印染,医药,超分子识别等多个领域;无金属催化,多组分一锅法选择性合成多取代咔唑及衍生物的方法,它极大限度地保持了原子经济性;它具有分子结构稳定、化学性质优良,分子切块和化合物片段包含丰富的生物活性和药理活性内容;它还具有反应体系简单、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;本发明方法比已有方法更安全、更经济有效,所用的催化剂也更廉价易得;同时此反应体系简单,易于实现工业化生产。
结合附图,一种多取代咔唑及衍生物,它的通式为式Ⅰ;一种合成多取代咔唑及衍生物的方法,所述吲哚类化合物,选自C8-C20芳香类吲哚,其通式为式Ⅱ;所述酮(醛)类化合物的通式为式Ⅲ;所述烯烃类化合物的通式为式Ⅳ。
结合附图,一种合成多取代咔唑及衍生物的方法,所述的碘类化合物选自:碘化铵、碘化钾、碘化钠、碘化亚铜、碘化钯、碘酸钾、碘酸钠、高碘酸钠、单质碘、碘苯、碘苯二乙酯、双(三氟乙酰氧基)碘苯中的一种或数种;优选碘化铵。结合附图,一种合成多取代咔唑及衍生物的方法,所述的反应氛围为:氮气、空气、氧气、惰性气体;优选惰性气体;保护气为1atm的惰性气体。结合附图,一种合成多取代咔唑及衍生物的方法,所述的有机溶剂为:乙腈,二氯乙烷,四氢呋喃,N,N-二甲基乙酰,苯,氯苯,环己烷,1,4-二氧六环,苯甲醚,苯甲腈,二甲苯,三氟甲苯,甲苯,三甲苯;优选甲苯。结合附图,一种合成多取代咔唑及衍生物的方法,吲哚类化合物与酮(醛)类化合物与烯烃类化合物与催化剂的摩尔比为1:0.5-10.0:0.5-6.0:0.01-1.0;最佳方案的摩尔比为1:3:1:0.2。同时,反应温度为20℃-200℃;更优选160℃。结合附图,一种合成多取代咔唑及衍生物的方法,由上述式Ⅰ、式Ⅱ、式Ⅲ和式Ⅳ构成本发明的反应体系及通式如附图1。包括以下步骤:
(Ⅰ)加入吲哚类化合物和酮(醛)类、烯烃类化合物和有机溶剂;
(Ⅱ)将反应物充分混合,充入1atm反应氛围,加热反应;
(Ⅲ)纯化得到产物。
从上述本发明化合物的合成反应体系过程中合成的多取代咔唑类化合物,首次以吲哚,酮(醛)类,烯烃类化合物三组分一锅法选择性合成多取代咔唑,同时不需要金属催化。
总之,本发明化合物具有反应原料廉价易得且不需要进行预处理;反应不需要使用昂贵催化剂以及金属氧化剂或过氧化物;只使用绿色廉价的碘试剂;反应为一锅直接选择性合成等特点;它解决了现有采用多步合成方法带来的成本较高等难题;它反应条件简单,合成的一系列多取代咔唑类化合物具有相当高的潜在应用价值。
按照上述实施方式中的操作方法,本发明合成了以下各实施例并汇总如附图2中的对应化合物。
参照附图,实施例1-54如下:
实施例1:9-甲基-2,4-二苯基-9-氢咔唑的合成
取一反应管,氩气保护下加入0.2mmol(25.0μL)1-甲基吲哚、0.2mmol(29.8mg)反式硝基苯乙烯、0.6mmol(70.4μL)苯乙酮、0.04mmol(5.8mg)碘化铵、0.5mL甲苯,160℃下反应30小时,常规处理得到纯品56.0mg,产率84%。
实施例1产物的核磁及高分辨质谱数据如下:
1H NMR(400MHz,CDCl3,ppm)δ7.76-7.74(m,2H),7.69-7.66(m,2H),7.57(d,J=1.6Hz,1H),7.55-7.44(m,6H),7.41-7.33(m,4H),7.00-6.96(m,1H),3.87(s,3H);13C NMR(100MHz,CDCl3,ppm)δ141.8,141.7,141.6,141.2,138.7,137.8,129.2,128.7,128.4,127.5,127.5,127.1,125.5,122.2,122.1,120.2,119.4,118.6,108.2,105.8,28.9;HRMScalcd.for C25H19N[M+H]+334.1590,found 334.1592.
实施例2:7-甲基-5-苯基-2,3,4,7-四氢-1-氢苯并[c]咔唑的合成
取一反应管,氩气保护下加入0.2mmol(25.0μL)1-甲基吲哚、0.2mmol(29.8mg)反式硝基苯乙烯、0.6mmol(62.0μL)环己酮、0.04mmol(5.8mg)碘化铵、0.5mL甲苯,160℃下反应30小时,常规处理得到纯品55.4mg,产率89%。
实施例2产物的核磁及高分辨质谱数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.21(d,J=8.0Hz,1H),7.48-7.34(m,7H),7.23-7.34(m,1H),7.15(s,1H),3.81(s,3H),3.46(t,J=6.4Hz,2H),2.72(t,J=6.2Hz,2H),2.05-1.93(m,2H),1.84-1.78(m,2H);13C NMR(100MHz,CDCl3,ppm)δ143.1,141.2,140.4,138.9,132.7,129.5,127.9,126.6,125.4,124.7,123.2,123.0,120.1,118.6,108.0,107.4,28.9,28.9,28.6,23.5,23.0;HRMS calcd.for C23H21N[M+H]+312.1747,found 312.1746.
实施例3:1,9-二甲基-2,4-苯基-9-氢咔唑的合成
取一反应管,氩气保护下加入0.2mmol(25.0μL)1-甲基吲哚、0.2mmol(36.2mg)1-苯基-2硝基丙烯、0.6mmol(70.4μL)苯乙酮、0.04mmol(5.8mg)碘化铵、0.5mL甲苯,160℃下反应30小时,常规处理得到纯品53.5mg,产率77%。
实施例3产物的核磁及高分辨质谱数据如下:
1H NMR(400MHz,CDCl3,ppm)δ7.62-7.60(m,2H),7.51-7.43(m,7H),7.40-7.33(m,4H),7.03(s,1H),6.97-6.93(m,1H),4.18(s,3H),2.77(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.8,142.4,141.2,141.1,140.8,134.9,130.0,129.3,128.3,128.0,127.3,126.7,125.4,123.7,122.5,122.2,120.3,118.7,116.9,108.6,33.3,17.5;HRMS calcd.forC26H21N[M+H]+348.1747,found 348.1731.
实施例4:1,3,9-三甲基-4-乙基--2-苯基-9氢咔唑的合成
取一反应管,氩气保护下加入0.2mmol(25.0μL)1-甲基吲哚、0.2mmol(29.8mg)反式硝基苯乙烯、0.6mmol(63.0μL)3-戊酮、0.04mmol(5.8mg)碘化铵、0.5mL甲苯,160℃下反应30小时,常规处理得到纯品41.4mg,产率66%。
实施例4产物的核磁及高分辨质谱数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.21(d,J=8.0Hz,1H),7.47-7.43(m,3H),7.40-7.36(m,2H),7.25-7.20(m,3H),4.09(s,3H),3.32(q,J=7.5Hz,2H),2.46(s,3H),2.09(s,3H),1.40(t,J=7.6Hz,3H);13C NMR(100MHz,CDCl3,ppm)δ143.0,142.8,141.6,139.1,135.0,129.8,128.3,126.4,125.0,124.8,122.7,122.5,120.9,118.9,116.2,108.6,33.3,23.5,17.7,16.6,13.2;HRMS calcd.for C23H23N[M+H]+314.1903,found 314.1914.
实施例5:6-氯-2-(4-氟苯基)-4-(4-甲氧基苯基)-9-甲基-9氢咔唑的合成
取一反应管,氩气保护下加入0.2mmol(33.1mg)5-氯-1-甲基吲哚、0.2mmol(33.4mg)反式-4-氟硝基苯乙烯、0.6mmol(90.1mg)4-甲氧基苯乙酮、0.04mmol(5.8mg)碘化铵、0.5mL甲苯,160℃下反应30小时,常规处理得到纯品49.9mg,产率60%。
实施例5产物的核磁及高分辨质谱数据如下:
1H NMR(400MHz,CDCl3,ppm)δ7.71-7.68(m,2H),7.58(s,1H),7.56-7.55(m,2H),7.48(d,J=1.2Hz,1H),7.38-7.35(m,1H),7.31-7.28(m,2H),7.16(t,J=8.6Hz,2H),7.09(d,J=8.4Hz,2H),3.94(s,3H),3.89(s,3H);13C NMR(100MHz,CDCl3,ppm)δ162.5(d,J=245.2Hz),159.5,142.4,140.0,138.6,138.0,137.8(d,J=3.1Hz),132.9,130.1,129.1(d,J=7.9Hz),125.6,124.1,123.3,121.8,120.7,118.7,115.7(d,J=21.3Hz),114.0,109.2,105.6,55.4,29.3;HRMS calcd.for C26H19ClFNO[M+H]+416.1212,found 416.1206.
按照实施例1所述的操作方法,本发明合成的化合物汇总如图2。
下面给出了本发明部分实施例化合物的核磁、高分辨质谱等表征数据。
实施例6:6-甲基-4-苯基-1,2,3,6-四氢环戊并[c]咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.08(d,J=7.6Hz,1H),7.57(d,J=7.6Hz,2H),7.46(t,J=7.2Hz,3H),7.40-7.34(m,2H),7.23-7.22(m,2H),3.84(s,3H),3.49(t,J=7.4Hz,2H),3.10(t,J=7.2Hz,2H),2.30-2.23(m,2H);13C NMR(100MHz,CDCl3,ppm)δ142.6,141.6,140.8,138.1,136.2,133.0,128.9,128.2,126.7,125.1,122.7,121.8,118.7,118.4,108.1,106.6,32.3,32.3,29.3,26.0;HRMS calcd.for C22H19N[M+H]+298.1590,found298.1588.
实施例7:8-甲基-6-苯基-1,2,3,4,5,8-六氢环庚并[c]咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.34(d,J=8.4Hz,1H),7.48-7.35(m,7H),7.24-7.20(m,1H),7.11(s,1H),3.160(s,3H),3.60(t,J=4.6Hz,2H),2.90(t,J=5.4Hz,2H),1.91-1.90(m,4H),1.66-164(m,2H);13C NMR(100MHz,CDCl3,ppm)δ143.9,141.7,139.7,139.4,139.3,132.4,129.7,127.8,126.5,124.9,123.0,122.5,120.0,118.5,108.2,107.1,32.1,30.8,30.3,28.9,28.5,26.7;HRMS calcd.for C24H23N[M+H]+326.1903,found 326.1903.
实施例8:9-甲基-7-苯基-2,3,4,5,6,9-六氢-1-氢环辛并[c]咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.23(d,J=8.4Hz,1H),7.49-7.38(m,7H),7.25-7.23(m,1H),7.12(s,1H),3.160(s,1H),3.51(t,J=5.4Hz,2H),2.88(t,J=6.0Hz,2H),2.01-1.99(m,2H),1.50-1.39(m,6H);13C NMR(100MHz,CDCl3,ppm)δ144.1,141.4,140.5,139.2,136.5,129.6,129.5,127.7,126.5,124.8,122.8,122.5,119.8,118.7,108.2,107.9,32.1,29.1,28.9,28.6,27.6,26.7,26.2;HRMS calcd.for C25H25N[M+H]+340.2060,found340.2052.
实施例9:4,9-甲基-2-苯基-9氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.20(d,J=8.0Hz,1H),7.75-7.73(m,2H),7.51-7.42(m,5H),7.38-7.35(m,1H),7.29-7.27(m,2H),3.90(s,3H),2.94(s,3H); 13C NMR(100MHz,CDCl3,ppm)δ142.2,141.6,141.4,138.9,133.5,128.7,127.6,127.0,125.1,123.2,122.5,120.6,120.2,118.9,108.2,104.6,29.1,20.9;HRMS calcd.for C20H17N[M+H]+272.1434,found 272.1433.
实施例10:3,9-二甲基-4-乙基-2-苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.22(d,J=8.0Hz,1H),7.49-7.36(m,7H),7.27-7.23(m,1H),7.15(s,1H),3.160(s,3H),3.37(q,J=7.6Hz,2H),2.35(s,3H),1.43(t,J=7.6Hz,3H);13C NMR(100MHz,CDCl3,ppm)δ143.9,141.5,140.9,139.4,138.1,129.6,127.9,126.5,124.9,123.5,122.5,120.0,118.8,108.2,107.6,28.9,23.8,15.8,13.2;HRMS calcd.forC22H21N[M+H]+300.1747,found 300.1742.
实施例11:9-甲基-4-丙基-2-苯基-9-氢咔唑的合成
实施例11′:4,9-二甲基-3-乙基-2-苯基-9-咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.28(d,J=8.0Hz,1H),8.12(d,J=7.6Hz,0.66H),7.75-7.73(m,1.32H),7.48-7.34(m,11H),7.28-7.22(m,2.64H),7.10(s, 1H),3.87(s,2H),3.77(s,3H),3.26(t,J=7.8Hz,1.32H),2.93(s,3H),2.75(q,J=7.5Hz,2H),1.97-1.88(m,1.32H),1.14-1.01(m,5H);13C NMR(100MHz,CDCl3,ppm)δ144.0,142.2,141.9,141.4,140.5,138.8,138.3,131.4,130.9,129.5,128.7,127.8,127.6,127.0,126.6,125.0,124.9,123.5,122.8,122.5,122.5,121.2,119.5,119.0,118.6,108.3,108.0,107.6,104.7,36.6,29.1,28.9,22.9,22.7,16.8,15.9,14.3;HRMS calcd.for C22H21N[M+H]+300.1747,found 300.1750.
实施例12:9-甲基-3-辛基-2-苯基-9-氢咔唑的合成
实施例12′:4,9-二甲基-3-庚基-2-苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.28(d,J=7.6Hz,1H),8.12(d,J=8.0Hz,0.67H),7.74(d,J=7.2Hz,1.32H),7.50-7.37(m,10.6H),7.28-7.23(m,3H),7.11(s,1H),3.89(s,2H),3.79(s,3H),3.27(t,J=7.8Hz,1.32H),2.92(s,3H),2.70(t,J=8.2Hz,2H),1.92-1.85(m,1.32H),1.57-1.50(m,2.63H),1.44-1.17(m,16.6H),0.88-0.83(m,5.29H);13C NMR(100MHz,CDCl3,ppm)δ144.0,142.2,141.9,141.4,140.7,138.9,138.8,138.6,131.5,129.8,129.6,128.7,127.7,127.6,126.9,126.5,125.0,124.8,123.5,122.8,122.5,122.5,121.2,119.9,119.4,119.0,118.6,108.2,108.0,107.6,104.7,34.6,31.9,31.7,31.4,29.9,29.8,29.7,29.6,29.3,29.0,28.8,22.7,22.6,16.9,14.1,14.1;HRMScalcd.for C27H31N[M+H]+370.2529,found 370.2521.
实施例13:9-甲基-4-([1,1'-二苯基]-4-基)-2-苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.79-7.75(m,8H),7.66-7.62(m,2H),7.51-7.48(m,4H),7.43-7.38(m,5H),7.02(s,1H),3.95(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.0,141.8,141.7,140.8,140.3,140.2,138.9,137.4,129.7,128.8,128.8,127.6,127.4,127.2,127.1,127.1,125.6,122.4,122.2,120.4,119.4,118.7,108.3,106.0,28.2;HRMScalcd.for C31H23N[M+H]+410.1903,found 410.1903.
实施例14:9-甲基-2-苯基-4-(对甲苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.77(d,J=6.8Hz,2H),7.59-7.57(m,4H),7.48(t,J=6.8Hz,2H),7.41-7.37(m,6H),7.00(s,1H),3.94(s,3H),2.50(s,3H); 13C NMR(100MHz,CDCl3,ppm)δ142.0,141.9,141.7,138.9,138.3,137.9,137.2,129.1,129.1,128.8,127.6,127.1,125.5,122.4,122.3,120.4,119.5,118.6,108.2,105.7,29.2,21.4;HRMScalcd.for C26H21N[M+H]+348.1747,found 348.1749.
实施例15:9-甲基-2-苯基-4-(4-(叔丁基)苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.76(d,J=6.8Hz,2H),7.64-7.55(m,6H),7.47(t,J=7.2Hz,2H),7.41-7.35(m,4H),7.01(t,J=6.4Hz,1H),3.92(s,3H),1.45(s,9H);13C NMR(100MHz,CDCl3,ppm)δ150.5,142.0,141.9,141.7,138.8,138.2,137.9,128.9,128.7,127.6,127.1,125.5,125.3,122.4,122.3,120.5,119.5,118.6,108.2,105.7,34.7,31.5,29.2;HRMS calcd.for C29H27N[M+H]+390.2216,found 390.2218.
实施例16:9-甲基-2-苯基-4-(4-甲氧基苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.77(d,J=7.2Hz,2H),7.62-7.58(m,4H),7.48(t,J=7.2Hz,2H),7.41-7.35(m,4H),7.08(d,J=7.6Hz,2H),7.01(t,J=6.6Hz,1H),3.93(s,6H);13C NMR(100MHz,CDCl3,ppm)δ159.2,142.0,141.9,141.7,138.9,137.6,137.6,133.6,130.3,128.8,127.6,127.1,125.5,122.3,120.5,119.6,118.7,113.8,108.2,105.6,55.4,29.2;HRMS calcd.for C26H21NO[M+H]+364.1696,found 364.1696.
实施例17:9-甲基-2-苯基-4-(4-甲砜基苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.13(d,J=7.6Hz,2H),7.91(d,J=7.6Hz,2H),7.76(d,J=7.2Hz,2H),7.66(s,1H),7.52-7.38(m,6H),7.33(s,1H),7.04(t,J=6.6Hz,1H),3.96(s,3H),3.20(s,3H);13C NMR(100MHz,CDCl3,ppm)δ147.1,141.9,141.7,141.4,139.5,139.0,135.4,130.3,128.9,127.6,127.5,127.4,126.0,121.9,121.5,120.2,119.0,118.9,108.6,106.9,44.6,29.2;HRMS calcd.for C26H21NO2S[M+H]+412.1366,found412.1368.
实施例18:4-(9-甲基-2-苯基-9氢咔唑-4-基)苯甲腈的合成
1H NMR(400MHz,CDCl3,ppm)δ7.85-7.160(m,4H),7.75(d,J=6.8Hz,2H),7.66(s,1H),7.52-7.40(m,6H),7.32(s,1H),7.05-7.04(m,1H),3.96(s,3H);13C NMR(100MHz,CDCl3,ppm)δ146.1,141.9,141.7,141.4,139.1,135.6,132.3,130.1,128.9,127.5,127.4,126.0,121.8,121.5,120.1,119.0,119.0,118.9,111.4,108.6,106.9,29.2;HRMScalcd.for C26H18N2[M+H]+359.1543,found 359.1543.
实施例19:9-甲基-2-苯基-4-(4-氟苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.76(d,J=7.2Hz,2H),7.66-7.61(m,3H),7.49-7.38(m,6H),7.33(s,1H),7.26-7.22(m,2H),7.02(m,1H),3.94(s,3H);13C NMR(100MHz,CDCl3,ppm)δ162.5(d,J=244.4Hz),141.9,141.7,141.7,138.9,137.2(d,J=3.3Hz),136.7,130.8(d,J=7.9Hz),128.8,127.6,127.2,125.7,122.1,122.0,120.3,119.5,118.8,115.4(d,J=21.2Hz),108.4,106.0,29.2;HRMS calcd.for C25H18FN[M+H]+352.1496,found352.1497.
实施例20:9-甲基-2-苯基-4-(4-氯苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.75(d,J=7.2Hz,2H),7.62-7.60(m,3H),7.52-7.46(m,5H),7.43-7.35(m,3H),7.32(s,1H),7.02(t,J=7.2Hz,1H),3.91(s,3H);13C NMR(100MHz,CDCl3,ppm)δ141.9,141.7,141.7,139.7,138.9,136.5,133.6,130.6,128.8,128.6,127.6,127.3,125.7,122.1,121.9,120.2,119.3,118.8,108.4,106.2,29.2;HRMScalcd.for C25H18ClN[M+H]+368.1201,found 368.1203.
实施例21:9-甲基-2-苯基-4-(4-溴苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.76(d,J=7.2Hz,2H),7.68(d,J=7.2Hz,2H),7.61(s,1H),7.56-7.37(m,8H),7.32(s,1H),7.03(t,J=6.4Hz,1H),3.94(s,3H);13C NMR(100MHz,CDCl3,ppm)δ141.9,141.7,141.7,140.2,139.0,136.4,131.6,131.0,128.8,127.6,127.3,125.7,122.1,121.9,121.7,120.2,119.2,118.8,108.4,106.2,29.2;HRMScalcd.for C25H18BrN[M+H]+412.0695,found 412.0692.
实施例22:9-甲基-2-苯基-4-(4-碘苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.87(d,J=7.6Hz,2H),7.75(d,J=7.2Hz,2H),7.60(s,1H),7.55-7.38(m,8H),7.31(s,1H),7.03(t,J=6.6Hz,1H),3.93(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.0,141.7,141.7,140.8,139.0,137.6,136.5,131.2,128.8,127.6,127.3,125.7,122.1,122.0,120.1,119.2,118.8,108.4,106.2,93.3,29.2;HRMScalcd.for C25H18IN[M+H]+460.0557,found 460.0559.
实施例23:9-甲基-2-苯基-4-(3-甲氧基苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.76(d,J=7.6Hz,2H),7.59-7.57(m,2H),7.49-7.34(m,7H),7.28-7.26(m,1H),7.23-7.21(m,1H),7.05-6.99(m,2H),3.90(s,3H),3.84(s,3H);13C NMR(100MHz,CDCl3,ppm)δ159.6,142.6,141.9,141.8,141.7,138.8,137.7,129.4,128.8,127.6,127.2,125.6,122.4,122.1,121.7,120.2,119.4,118.7,114.4,113.5,108.2,105.9,55.3,29.2;HRMS calcd.for C26H21NO[M+H]+364.1696,found 364.1693.
实施例24:9-甲基-2-苯基-4-(3-溴苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.84(s,1H),7.76(d,J=7.2Hz,2H),7.64-7.62(m,3H),7.53-7.36(m,7H),7.34(s,1H),7.04(t,J=6.8Hz,1H),3.94(s,3H); 13C NMR(100MHz,CDCl3,ppm)δ143.3,141.9,141.7,141.6,138.9,136.1,132.2,130.6,129.9,128.8,128.0,127.6,127.3,125.8,122.5,122.1,121.9,120.2,119.2,118.9,108.4,106.4,29.2;HRMScalcd.for C25H18BrN[M+H]+412.0695,found 412.0693.
实施例25:9-甲基-2-苯基-4-(3-硝基苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.56(s,1H),8.37(d,J=7.6Hz,1H),8.05(d,J=7.2Hz,1H),7.78-7.71(m,3H),7.67(s,1H),7.52-7.36(m,7H),7.02(s,1H),3.97(s,3H);13CNMR(100MHz,CDCl3,ppm)δ148.4,142.9,142.0,141.7,141.4,139.1,135.5,134.9,129.3,128.9,127.5,127.4,126.0,124.1,122.5,121.6,121.5,120.3,119.0,119.0,108.6,106.9,29.2;HRMS calcd.for C25H18N2O2[M+H]+379.1441,found 379.1438.
实施例26:9-甲基-2-苯基-4-(2-氯苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.78(d,J=7.6Hz,2H),7.65-7.61(m,2H),7.51-7.36(m,9H),7.09-7.07(m,1H),7.01-6.97(m,1H),3.93(s,3H);13C NMR(100 MHz,CDCl3,ppm)δ141.7,141.6,141.5,139.8,138.7,134.4,133.7,131.4,129.7,129.2,129.1,128.8,127.6,127.2,126.9,125.7,122.1,121.8,120.1,119.0,108.3,106.4,29.2;HRMScalcd.for C25H18ClN[M+H]+368.1201,found 368.1199.
实施例27:9-甲基-2-苯基-4-(3,4-二氯苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.78-7.74(m,3H),7.63-7.61(m,2H),7.54-7.37(m,7H),7.31(s,1H),7.04(t,J=6.8Hz,1H),3.94(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.0,141.8,141.5,141.3,139.0,135.1,132.6,131.7,131.1,130.4,128.8,128.7,127.6,127.4,125.9,122.0,121.7,120.1,119.1,119.0,108.5,106.6,29.2;HRMS calcd.forC25H17Cl2N[M+H]+402.0811,found 402.0814.
实施例28:9-甲基-2-苯基-4-(2-噻吩基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.76(d,J=8.0Hz,3H),7.61(s,1H),7.51-7.36(m,8H),7.25-7.23(m,1H),7.07(t,J=7.2Hz,1H),3.93(s,3H);13C NMR(100MHz,CDCl3,ppm)δ144.9,142.2,141.9,141.7,141.6,138.7,129.9,128.8,127.6,127.2,126.8,125.8,125.6,122.3,122.0,121.6,120.3,118.9,108.3,106.7,29.2;HRMS calcd.for C23H17NS[M+H]+340.1155,found 340.1157.
实施例29 6,9-二甲基-2,4-苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.77-7.7(m,2H),7.70-7.65(m,2H),7.57-7.46(m,7H),7.38-7.35(m,2H),7.31-7.29(m,2H),3.90(s,3H),2.33(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.2,141.9,141.3,140.0,138.6,137.8,129.3,129.0,128.7,128.6,128.3,127.8,127.6,127.1,126.9,122.3,120.1,119.2,107.9,105.8,29.2,21.5;HRMScalcd.for C26H21N[M+H]+348.1747,found 348.1736.
实施例30:9-甲基-6-甲氧基-2,4-二苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.78-7.76(m,2H),7.70-7.67(m,2H),7.57-7.53(m,3H),7.50-7.46(m,3H),7.39-7.37(m,1H),7.35(d,J=1.6Hz,1H),7.31-7.29(m,1H),7.08-7.05(m,1H),6.98(d,J=2.4Hz,1H),3.91(s,3H),3.63(s,3H); 13C NMR(100MHz,CDCl3,ppm)δ153.0,142.3,141.9,141.0,138.8,137.8,136.8,129.3,128.8,128.3,127.6,127.6,127.1,122.4,119.7,119.2,114.5,108.8,106.0,105.3,55.6,29.3;HRMS calcd.forC26H21NO[M+H]+364.1696,found 364.1700.
实施例31:6-氟-9-甲基-2,4-二苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.77-7.75(m,2H),7.66-7.64(m,2H),7.58-7.47(m,6H),7.40-7.36(m,2H),7.32-7.29(m,1H),7.19-7.13(m,2H),3.91(s,3H);13C NMR(100MHz,CDCl3,ppm)δ156.7(d,J=232.4Hz),142.6,141.6,140.6,139.4,138.0,129.1,128.8,128.6,127.8,127.6,127.3,122.5,122.4,120.2,119.0,113.2(d,J=25.7Hz),108.6(d,J=9.3Hz),107.9(d,J=24.6Hz),106.1,29.3;HRMS calcd.for C25H18FN[M+H]+352.1496,found 352.1486.
实施例32:6-氯-9-甲基-2,4-二苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.75(d,J=7.6Hz,2H),7.64(d,J=7.6Hz,2H),7.56-7.46(m,7H),7.39-7.34(m,3H),7.29-7.23(m,1H),3.87(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.3,141.5,140.6,139.9,139.5,138.1,129.0,128.8,128.6,127.9,127.6,127.3,125.5,124.0,123.2,121.8,120.7,118.5,109.2,106.1,29.3;HRMS calcd.for C25H18ClN[M+H]+368.1200,found 368.1214.
实施例33:6-溴-9-甲基-2,4-二苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.76(d,J=7.6Hz,2H),7.66(d,J=1.2Hz,1H),7.65(s,1H),7.62(d,J=2.0Hz,1H),7.59-7.47(m,7H),7.40-7.37(m,2H),7.28-7.26(m,1H),3.94(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.2,141.6,140.6,140.3,139.6,138.1,129.0,128.8,128.6,128.2,128.0,127.6,127.4,124.8,123.9,120.7,118.5,111.5,109.7,106.1,29.3;HRMS calcd.for C25H18BrN[M+H]+412.0695,found 412.0697.
实施例34:9-甲基-5,7-苯基9-氢咔唑-2-羧酸甲酯的合成
1H NMR(400MHz,CDCl3,ppm)δ8.14(s,1H),7.76(d,J=7.6Hz,2H),7.69-7.66(m,3H),7.62(s,1H),7.57-7.47(m,6H),7.41-7.37(m,2H),3.98(s,3H),3.95(s,3H);13C NMR(100MHz,CDCl3,ppm)δ167.8,1431,141.4,141.0,140.7,140.2,138.6,129.1,128.8,128.5,127.8,127.6,127.4,126.7,125.9,121.8,120.8,119.8,118.8,110.0,106.1,52.2,29.3;HRMS calcd.for C27H21NO2[M+H]+392.1645,found 392.1654.
实施例35:7-氟-9-甲基-2,4-二苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.76-7.74(m,2H),7.66-7.64(m,2H),7.57-7.35(m,9H),7.05-7.02(m,1H),6.73-6.68(m,1H),3.86(s,3H);13C NMR(100MHz,CDCl3,ppm)δ161.9(d,J=240.9Hz),142.5,142.4,141.6,140.9,138.6,137.4,129.1,128.8,128.5,127.7,127.5,127.2,123.2(d,J=10.1Hz),120.7,119.2,118.6,106.7(d,J=23.6Hz),105.9,95.1(d,J=26.4Hz),29.2;HRMS calcd.for C25H18FN[M+H]+352.1496,found 352.1495.
实施例36:7-氯-9-甲基-2,4-二苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.75(d,J=7.2Hz,2H),7.66-7.64(m,2H),7.58(d,J=1.2Hz,1H),7.56-7.46(m,5H),7.04-7.36(m,4H),6.96-6.93(m,1H),3.90(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.2,141.6,140.8,139.2,137.8,135.9, 131.4,129.1,128.8,128.5,127.7,127.5,127.5,127.3,123.0,120.8,120.7,119.1,108.4,106.0,29.2;HRMScalcd.for C25H18ClN[M+H]+368.1201,found 368.1199.
实施例37:1,9-二甲基-5,7-苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.76(d,J=7.6Hz,2H),7.64(d,J=7.2Hz,2H),7.57(s,1H),7.55-7.46(m,5H),7.38-7.29(m,3H),7.10(d,J=6.8Hz,1H),6.84(d,J=7.6Hz,1H),4.20(s,3H),2.87(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.6,141.9,141.3,140.4,138.5,137.6,129.3,128.7,128.4,127.6,127.5,127.1,123.0,120.5,120.3,120.0,119.5,118.8,106.1,32.5,20.7;HRMS calcd.for C26H21N[M+H]+348.1747,found348.1747.
实施例38 9-苄基-2,4-苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.72-7.68(m,4H),7.57-7.49(m,5H),7.44(t,J=7.6Hz,2H),7.39(s,1H),7.37-7.34(m,3H),7.31-7.26(m,3H),7.21(d,J=7.2Hz,2H),7.04-6.97(m,1H),5.61(s,2H);13C NMR(100MHz,CDCl3,ppm)δ141.7,141.6,141.3,141.2,139.0,138.0,137.0,129.3,128.8,128.7,128.4,127.6,127.6,127.5,127.2,126.4,125.7,122.4,122.4,120.7,119.7,119.0,108.7,106.2,46.6;HRMS calcd.for C31H23N[M+H]+410.1903,found 410.1903.
实施例39:2,4-二苯基-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.18(s,1H),7.73-7.67(m,4H),7.61(d,J=1.6Hz,1H),7.56-7.44(m,6H),7.42-7.33(m,4H),7.01-6.98(m,1H);13C NMR(100MHz,CDCl3,ppm)δ141.5,141.1,140.4,140.1,138.9,137.8,129.2,128.8,128.4,127.6,127.5,127.2,125.7,122.7,122.3,120.8,120.0,119.2,110.4,107.9;HRMS calcd.for C24H17N[M+H]+320.1434,found 320.1432.
实施例40:9-甲基-4-苯基-2-(4-甲氧基苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.71-7.67(m,4H),7.56-7.49(m,5H),7.40-7.33(m,2H),7.33(d,J=1.6Hz,1H),7.02-6.97(m,3H),3.91(s,3H),3.86(s,3H);13C NMR(100MHz,CDCl3,ppm)δ159.0,141.9,141.6,141.3,138.5,137.8,134.3,129.2,128.5,128.4,127.5,125.4,122.2,122.2,120.0,119.0,118.6,114.2,108.2,105.3,55.3,29.1;HRMScalcd.for C26H21NO[M+H]+364.1696,found 364.1694.
实施例41:9-甲基-4-苯基-2-(4-氟苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.73-7.66(m,4H),7.56-7.47(m,5H),7.44-7.39(m,2H),7.30(s,1H),7.16(t,J=8.6Hz,2H),7.01-6.97(m,1H),3.92(s,3H);13C NMR(100MHz,CDCl3,ppm)δ162.4(d,J=244.9Hz),141.8,141.6,141.1,137.9,137.8,129.2,129.1,129.0,128.4,127.6,125.6,122.3,122.1,120.1,119.4,118.7,115.6(d,J=21.2Hz),108.3,105.7,29.1;HRMS calcd.for C25H18FN[M+H]+352.1496,found352.1499.
实施例42:9-甲基-4-苯基-2-(4-氯苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.69-7.66(m,4H),7.56-7.48(m,5H),7.45-7.39(m,4H),7.31(s,1H),7.00(t,J=8.2Hz,1H),3.92(s,3H);13C NMR(100MHz,CDCl3,ppm)δ141.9,141.7,141.0,140.2,138.0,137.5,133.2,129.2,128.9,128.8,128.5,127.7,125.7,122.3,122.1,120.0,119.7,118.8,108.3,105.7,29.2;HRMS calcd.for C25H18ClN[M+H]+368.1200,found 368.1203.
实施例43:9-甲基-4-苯基-2-(4-溴苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.67-7.49(m,11H),7.43-7.39(m,2H),7.31(s,1H),7.00(t,J=7.0Hz,1H),3.92(s,3H);13C NMR(100MHz,CDCl3,ppm)δ141.9, 141.7,141.0,140.7,138.0,137.5,131.8,129.2,129.1,128.5,127.7,125.7,122.3,122.1,121.4,120.0,119.7,118.8,108.3,105.6,29.2;HRMS calcd.for C25H18BrN[M+H]+412.0695,found412.0694.
实施例44:9-甲基-4-苯基-2-(3-甲基苯基)-9-咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.68(d,J=6.8Hz,2H),7.59-7.47(m,7H),7.44-7.35(m,4H),7.19(d,J=7.6Hz,1H),7.01-6.97(m,1H),3.93(s,3H),2.45(s,3H);13C NMR(100MHz,CDCl3,ppm)δ141.9,141.8,141.6,141.3,139.0,138.4,137.8,129.2,128.7,128.4,128.4,127.9,127.5,125.5,124.7,122.3,122.2,120.4,119.4,118.6,108.2,105.9,29.2,21.6;HRMS calcd.for:C26H21N[M+H]+348.1747,found 348.1743.
实施例45:9-甲基-4-苯基-2-(2-氯苯基)-9-咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.70-7.68(m,2H),7.57-7.47(m,7H),7.44-7.40(m,2H),7.36-7.28(m,2H),7.21(d,J=1.2Hz,1H),7.02-6.98(m,1H),3.90(s,3H); 13C NMR(100MHz,CDCl3,ppm)δ141.7,141.2,141.1,141.0,137.2,136.7,132.7,131.8,130.0,129.3,128.4,127.5,126.8,125.7,122.4,122.4,122.2,119.5,118.7,108.4,108.3,29.2;HRMS calcd.for:C25H18ClN[M+H]+368.1200,found 368.1183.
实施例46:9-甲基-4-苯基-2-(2-萘基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.21(s,1H),7.97-7.87(m,4H),7.73-7.71(m,3H),7.58-7.48(m,7H),7.43-7.42(m,2H),7.03-6.99(m,1H),3.96(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.0,141.7,141.2,139.1,138.6,138.0,133.7,132.6,129.3,128.5,128.4,128.2,127.6,127.6,126.2,126.1,126.0,125.8,125.6,122.3,122.2,120.5,119.6,118.7,108.3,106.1,29.2;HRMS calcd.for C29H21N[M+H]+384.1747,found 384.1749.
实施例47:9-甲基-4-苯基-2-(2-噻吩基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.67-7.65(m,2H),7.60(d,J=1.6Hz,1H),7.56-7.49(m,3H),7.46-7.43(m,2H),7.40-7.36(m,3H),7.31-7.30(m,1H),7.12-7.10(m,1H),7.00-6.96(m,1H),3.90(s,3H);13C NMR(100MHz,CDCl3,ppm)δ145.2,141.8,141.7,140.9,138.0,131.8,129.2,128.4,128.0,127.7,125.6,124.7,123.2,122.2,122.2,119.7,119.2,118.8,108.3,104.6,29.2;HRMS calcd.for:C23H17NS[M+H]+340.1155,found 340.1152.
实施例48:6,7-二甲基-5-苯基-2,3,4,7-四氢-1-氢苯并[c]咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.22(d,J=8.0Hz,1H),7.48-7.35(m,5H),7.25-7.20(m,3H),4.11(s,3H),3.41(t,J=6.4Hz,2H),2.48(s,3H),2.39(t,J=6.2Hz,2H).1.97-1.91(m,2H),1.77-1.74(m,2H);13C NMR(100MHz,CDCl3,ppm)δ142.5,142.1,141.0,138.5,130.1,129.7,128.3,126.5,126.4,124.6,123.5,123.0,121.0,118.6,106.1,108.4,33.2,29.5,28.6,23.4,23.0,17.4;HRMS calcd.for:C24H23N[M+H]+326.1903,found 326.1905.
实施例49:5,6-二甲基-4-苯基-1,2,3,6-四氢环戊并[c]咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ8.06(d,J=7.6Hz,1H),7.48-7.43(m,3H),7.40-7.34(m,2H),7.29-7.27(m,2H),7.24-7.21(m,1H),4.14(s,3H),3.47(t,J=7.6Hz,2H),2.72(t,J=7.4Hz,2H),2.59(s,3H),2.23-2.15(m,2H);13C NMR(100MHz,CDCl3,ppm)δ142.6,141.7,139.7,137.4,134.6,134.5,129.6,128.1,126.5,125.0,123.1,121.6,119.2,118.8,116.0,108.5,33.1,32.6,32.5,25.2,16.9;HRMS calcd.for:C23H21N[M+H]+312.1747,found312.1745.
实施例50:6-氯-9-甲基-2-苯基-4-(4-甲氧基苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.74(d,J=7.2Hz,2H),7.58-7.54(m,4H),7.48(t,J=7.6Hz,2H),7.39-7.34(m,3H),7.30-7.27(m,1H),7.09(d,J=8.4Hz,2H),3.93(s,3H),3.88(s,3H);13C NMR(100MHz,CDCl3,ppm)δ159.4,142.4,141.6,140.0,139.6,137.8,133.0,130.2,128.8,127.6,127.3,125.5,124.0,123.4,121.8,120.8,118.7,114.0,109.1,105.8,55.4,29.3;HRMS calcd.for:C26H20ClNO[M+H]+398.1306,found 398.1300.
实施例51:6-溴-9-甲基-2-苯基-4-(4-甲氧基苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.73-7.70(m,3H),7.54(d,J=8.8Hz,2H),7.49-7.43(m,4H),7.38-7.33(m,2H),7.21-7.16(m,1H),7.05(d,J=8.8Hz,2H),3.90(s,3H),3.79(s,3H);13C NMR(100MHz,CDCl3,ppm)δ159.4,142.2,141.6,140.2,139.6,137.8,132.9,130.2,128.8,128.1,127.6,127.3,124.7,124.0,120.8,118.5,114.0,111.4,109.6,105.7,55.4,29.3;HRMS calcd.for:C26H20BrNO[M+H]+442.0801,found 442.0799.
实施例52:6-氯-9-甲基-2-苯基-4-(4-溴苯基)-9-氢咔唑的合成
1H NMR(400MHz,CDCl3,ppm)δ7.73(d,J=7.2Hz,2H),7.69-7.66(m,2H),7.58(d,J=1.2Hz,1H),7.54-7.53(m,1H),7.52-7.47(m,4H),7.41-7.36(m,2H),7.31-7.29(m,2H),3.90(s,3H);13C NMR(100MHz,CDCl3,ppm)δ142.4,141.4,140.0,139.7,139.5,136.7,131.7,130.7,128.8,127.5,127.4,125.7,124.2,123.0,122.1,121.5,120.6,118.2,109.3,106.4,29.3;HRMS calcd.for:C25H17BrClN[M+H]+448.0286,found 448.0274.
实施例53:6,9-二甲基-2-(2-萘基)-4-(3-溴苯基)--9-氢咔唑
1H NMR(400MHz,CDCl3,ppm)δ8.20(s,1H),7.97-7.89(m,5H),7.71(d,J=1.2Hz,1H),7.68-7.64(m,2H),7.55-7.48(m,2H),7.45-7.41(m,2H),7.34-7.27(m,3H),3.95(s,3H),2.38(s,3H);13C NMR(100MHz,CDCl3,ppm)δ143.4,142.2,140.1,139.0,138.5,136.7,133.7,132.6,132.3,130.6,129.9,128.4,128.2,128.1,128.1,127.7,127.2,126.3,126.1,126.0,125.9,122.4,122.2,121.9,120.2,119.1,108.1,106.6,29.3,21.5;HRMScalcd.for C30H22BrN[M+H]+476.1008,found 476.1005.
实施例54:9-甲基-3-己基--2-苯基-9-氢咔唑
1H NMR(400MHz,CDCl3,ppm)δ8.10(d,J=8.0Hz,1H),7.98(s,1H),7.48-7.37(m,7H),7.25-7.21(m,2H),3.81(s,3H),2.72(t,J=8.0Hz,2H),1.56-1.48(m,2H),1.26-1.13(m,6H),0.82(t,J=7.0Hz,3H);13C NMR(100MHz,CDCl3,ppm)δ143.1,141.5,140.1,139.3,131.3,129.6,127.9,126.6,125.5,122.5,122.1,120.4,120.2,118.7,109.7,108.3,33.2,32.0,31.6,29.1,29.0,22.5,14.1;HRMS calcd.for:C25H27N[M+H]+342.2216,found342.2210。
Claims (3)
1.一种合成多取代咔唑及衍生物的方法,其特征在于以碘类化合物作催化剂、惰性气体的保护下,将吲哚类、醛(酮)类和烯烃类化合物与有机溶剂进行混合,经加热反应、纯化得到产物;
所述吲哚类化合物选自;吲哚,1-甲基吲哚 ,1-苄基吲哚,1,5-二甲基吲哚,1 ,7-二甲基吲哚,1-甲基-5-甲氧基吲哚,5-氟-1-甲基吲哚,5-氯-1-甲基吲哚,5-溴-1-甲基吲哚,6-甲酯基-1-甲基吲哚,6-氟-1-甲基吲哚,6-氯-1-甲基吲哚;
所述醛(酮)类化合物选自;环己酮,环庚酮,环戊酮,环辛酮,3-戊酮,2-戊酮,2-癸酮,苯乙酮,4-甲基苯乙酮,4-甲氧基苯乙酮,4-叔丁基苯乙酮,4-苯基苯乙酮,4-甲砜基苯乙酮,4-氰基苯乙酮,4-氟苯乙酮,4-氯苯乙酮,4-溴苯乙酮,4-碘苯乙酮,3-甲氧基苯乙酮,3-溴苯乙酮,3-硝基苯乙酮,2-氯苯乙酮,3,4-二氯苯乙酮,2-乙酰噻吩,正辛醛;
所述烯烃类化合物选自:反式硝基苯乙烯,反-4-甲氧基-β-硝基苯乙烯,反-4-氟-β-硝基苯乙烯,反-4-氯-β-硝基苯乙烯,反-4-溴-β-硝基苯乙烯,反-3-甲基-β-硝基苯乙烯,反-2-氯-β-硝基苯乙烯,1-苯基-2-硝基丙烯,反式-2-(2-硝基乙烯基)萘,反式-2-(2-硝基乙烯基)噻吩;
所述催化剂为碘化铵;
所述有机溶剂为甲苯。
2.根据权利要求1所述的合成方法,其特征在于所述吲哚类化合物与醛(酮)类化合物与烯烃类化合物与催化剂的摩尔比为1:0.5~10.0:0.5~6.0:0.01~1.0。
3.根据权利要求1所述的合成方法,其特征在于反应温度为20℃-200℃。
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