CN111116542A - 一种苯并氧杂*类化合物的合成方法 - Google Patents
一种苯并氧杂*类化合物的合成方法 Download PDFInfo
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- CN111116542A CN111116542A CN201911392362.9A CN201911392362A CN111116542A CN 111116542 A CN111116542 A CN 111116542A CN 201911392362 A CN201911392362 A CN 201911392362A CN 111116542 A CN111116542 A CN 111116542A
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- diaryl
- alkyl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- -1 diaryl ether compounds Chemical class 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- PAGZTSLSNQZYEV-UHFFFAOYSA-L 2,2-dimethylpropanoate;palladium(2+) Chemical compound [Pd+2].CC(C)(C)C([O-])=O.CC(C)(C)C([O-])=O PAGZTSLSNQZYEV-UHFFFAOYSA-L 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011056 potassium acetate Nutrition 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 4
- 125000006528 (C2-C6) alkyl group Chemical group 0.000 claims description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- BNBQRQQYDMDJAH-UHFFFAOYSA-N benzodioxan Chemical class C1=CC=C2OCCOC2=C1 BNBQRQQYDMDJAH-UHFFFAOYSA-N 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000758 substrate Substances 0.000 abstract description 19
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 46
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 150000008378 aryl ethers Chemical class 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229930014626 natural product Natural products 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 150000001987 diarylethers Chemical class 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- LWZYUACNWRVDDJ-UHFFFAOYSA-N 1-benzoxepine Chemical compound O1C=CC=CC2=CC=CC=C12 LWZYUACNWRVDDJ-UHFFFAOYSA-N 0.000 description 2
- PSQAVFMIQPKSFW-UHFFFAOYSA-N 1-iodo-2-(2-phenoxyphenyl)benzene Chemical group IC1=CC=CC=C1C1=CC=CC=C1OC1=CC=CC=C1 PSQAVFMIQPKSFW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000006887 Ullmann reaction Methods 0.000 description 2
- 238000006254 arylation reaction Methods 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- CSFWPUWCSPOLJW-UHFFFAOYSA-N lawsone Chemical compound C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000007344 nucleophilic reaction Methods 0.000 description 2
- 150000002920 oxepines Chemical class 0.000 description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- CGPAGJVSYOFHOV-UHFFFAOYSA-N 1-(2-iodophenyl)-2-(4-nitrophenoxy)benzene Chemical group C1=CC=C(C(=C1)C2=CC=CC=C2I)OC3=CC=C(C=C3)[N+](=O)[O-] CGPAGJVSYOFHOV-UHFFFAOYSA-N 0.000 description 1
- ZVWFIPVBOKIRFI-UHFFFAOYSA-N 1-iodo-2-[2-(3-methylphenoxy)phenyl]benzene Chemical group CC1=CC(=CC=C1)OC2=CC=CC=C2C3=CC=CC=C3I ZVWFIPVBOKIRFI-UHFFFAOYSA-N 0.000 description 1
- LGSQZKQYNJWJTA-UHFFFAOYSA-N 1-iodo-2-[2-(4-methoxyphenoxy)phenyl]benzene Chemical group COC1=CC=C(C=C1)OC2=CC=CC=C2C3=CC=CC=C3I LGSQZKQYNJWJTA-UHFFFAOYSA-N 0.000 description 1
- GJJBLGFPCFPWQZ-UHFFFAOYSA-N 1-iodo-2-[2-[4-(trifluoromethyl)phenoxy]phenyl]benzene Chemical group C1=CC=C(C(=C1)C2=CC=CC=C2I)OC3=CC=C(C=C3)C(F)(F)F GJJBLGFPCFPWQZ-UHFFFAOYSA-N 0.000 description 1
- KZKWLWRXNMIAEW-UHFFFAOYSA-N 2-[2-(2-iodophenyl)phenoxy]naphthalene-1,4-dione Chemical compound C1=CC=C2C(=C1)C(=O)C=C(C2=O)OC3=CC=CC=C3C4=CC=CC=C4I KZKWLWRXNMIAEW-UHFFFAOYSA-N 0.000 description 1
- JDSACKZEVUMFNP-UHFFFAOYSA-N 2-[2-(2-iodophenyl)phenoxy]pyridine Chemical compound C1=CC=C(C(=C1)C2=CC=CC=C2I)OC3=CC=CC=N3 JDSACKZEVUMFNP-UHFFFAOYSA-N 0.000 description 1
- HLRRYAAUQSNIII-UHFFFAOYSA-N 2-[2-iodo-4-(trifluoromethyl)phenyl]-3-phenoxythiophene Chemical compound C1=CC=C(C=C1)OC2=C(SC=C2)C3=C(C=C(C=C3)C(F)(F)F)I HLRRYAAUQSNIII-UHFFFAOYSA-N 0.000 description 1
- MDYWLBWXDNLPFN-UHFFFAOYSA-N 2-iodo-1-(4-methoxy-2-phenoxyphenyl)-3,5-dimethylbenzene Chemical group CC1=CC(=C(C(=C1)C2=C(C=C(C=C2)OC)OC3=CC=CC=C3)I)C MDYWLBWXDNLPFN-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- FBCLXMZMPJALGI-UHFFFAOYSA-N COC1=CC2=C(C=C1)OC3=CC=CC=C3C4=CC=CC=C42 Chemical compound COC1=CC2=C(C=C1)OC3=CC=CC=C3C4=CC=CC=C42 FBCLXMZMPJALGI-UHFFFAOYSA-N 0.000 description 1
- 229930195510 Chloropeptin Natural products 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 108010059993 Vancomycin Proteins 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000002259 anti human immunodeficiency virus agent Substances 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- 230000000949 anxiolytic effect Effects 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- RPMDQAYGQBREBS-LPHOPBHVSA-N beloxepin Chemical compound O1C2=CC=CC=C2[C@@]2(O)CCN(C)C[C@H]2C2=CC=CC(C)=C21 RPMDQAYGQBREBS-LPHOPBHVSA-N 0.000 description 1
- 229950003852 beloxepin Drugs 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- FRRCHJPQSWYJSH-OZICGBTHSA-N chloropeptin I Chemical compound N([C@@H]1CC=2C=3C=CC=C(C=3NC=2)C=2C=C3C=C(C=2O)OC2=CC=C(C=C2)C[C@H](N(C([C@@H](C=2C=C(Cl)C(O)=C(Cl)C=2)NC(=O)[C@@H]3NC(=O)[C@@H](C=2C=C(Cl)C(O)=C(Cl)C=2)NC1=O)=O)C)C(=O)N[C@@H](C(O)=O)C=1C=CC(O)=CC=1)C(=O)C(=O)C1=CC(Cl)=C(O)C(Cl)=C1 FRRCHJPQSWYJSH-OZICGBTHSA-N 0.000 description 1
- 108010004919 chloropeptin I Proteins 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- ATYBXHSAIOKLMG-UHFFFAOYSA-N oxepin Chemical compound O1C=CC=CC=C1 ATYBXHSAIOKLMG-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003910 polypeptide antibiotic agent Substances 0.000 description 1
- 208000020016 psychiatric disease Diseases 0.000 description 1
- 229940001470 psychoactive drug Drugs 0.000 description 1
- 239000004089 psychotropic agent Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- MUAHMQUPOQGKOQ-UHFFFAOYSA-N savoxepin Chemical compound C12=CC(C#N)=CC=C2OC2=CC=CC=C2C(CC2)=C1CCN2CC1CCCC1 MUAHMQUPOQGKOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 229960003165 vancomycin Drugs 0.000 description 1
- MYPYJXKWCTUITO-UHFFFAOYSA-N vancomycin Natural products O1C(C(=C2)Cl)=CC=C2C(O)C(C(NC(C2=CC(O)=CC(O)=C2C=2C(O)=CC=C3C=2)C(O)=O)=O)NC(=O)C3NC(=O)C2NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(CC(C)C)NC)C(O)C(C=C3Cl)=CC=C3OC3=CC2=CC1=C3OC1OC(CO)C(O)C(O)C1OC1CC(C)(N)C(O)C(C)O1 MYPYJXKWCTUITO-UHFFFAOYSA-N 0.000 description 1
- MYPYJXKWCTUITO-LYRMYLQWSA-O vancomycin(1+) Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C2C=C3C=C1OC1=CC=C(C=C1Cl)[C@@H](O)[C@H](C(N[C@@H](CC(N)=O)C(=O)N[C@H]3C(=O)N[C@H]1C(=O)N[C@H](C(N[C@@H](C3=CC(O)=CC(O)=C3C=3C(O)=CC=C1C=3)C([O-])=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)O2)=O)NC(=O)[C@@H](CC(C)C)[NH2+]C)[C@H]1C[C@](C)([NH3+])[C@H](O)[C@H](C)O1 MYPYJXKWCTUITO-LYRMYLQWSA-O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/06—Seven-membered rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
技术领域
背景技术
芳基醚是许多天然产物和药物中的重要结构,并且杂原子芳基化和烷基化是候选药物合成中最常见的转化(J.Med.Chem.2011,54,3451–3479;Org.Biomol.Chem.2006,4,2337–2347)。二芳基醚是许多天然产物和生物活性化合物中的常见结构特征(Chem.Rev.2008,108,3054;Angew.Chem.Int.Ed.2003,42,5400)。万古霉素、糖肽类抗生素、抗HIV药物(如chloropeptin)等的全合成中都包含了二芳基醚的结构,并且是农药、香料和颜料等许多化工材料的重要组成部分,在这些领域中有着广泛的应用,因此该结构受到了关注(J.Am.Chem.Soc.2001,123,12411;J.Am.Chem.Soc.2003,125,9032;J.Am.Chem.Soc.1997,119,3421;Angew.Chem.Int.Ed.2010,49,2018;J.Am.Chem.Soc.1999,121,10004)。
苯并氧杂类化合物由于其特殊的化学结构,在天然产物、生物活性分子、药物分子中广泛存在(Drug Res.1996,46,243;Drugs Today 1997,33,95;Pure Appl.Chem.1999,71,2039;RSC Adv.2014,4,60473;Tetrahedron Lett.2001,42,5269;Helv.Chim.Acta2003,86,2566)。作为生物活性分子,苯并氧杂类化合物在治疗焦虑症、抑郁症等精神疾病中发挥了重要作用,例如Maroxepine、Savoxepine、Beloxepin等苯并氧杂衍生物被证明是一类新兴的潜在抗焦虑和抗抑郁药,显示出改善的活性,和现有的经典精神活性药物相比具有耐受性。
目前,二芳基醚类化合物的合成主要有以下二种方法,(1)金属催化的Ullmann反应得到;(2)通过链状碘鎓盐与酚羟基在碱性条件下发生亲核反应(Org.Lett.2013,15,6070-6073;Chem.Sci.2015,6,1277-1281;Org.Lett.2011,13,1552-1555)。从合成角度上讲,Ullmann反应条件苟刻,Cu催化的反应条件温度高,Pd、Ni催化的反应条件温和,但毒性较大价格较高;通过链状碘鎓盐的亲核反应有一分子的碘苯脱去,反应底物的原子经济性不高。
本合成方法以二芳基环状碘鎓盐和含有羟基的底物为原料,在三氟甲磺酸铜的催化下充分的利用底物原子经济性生成二芳基醚。该二芳基醚类化合物可经简单步骤转化成苯并氧杂类化合物,而目前合成该骨架的苯并氧杂类化合物,主要通过Suzuki–Miyaura偶联环化(Org.Biomol.Chem.2014,12(9),1391-1394)、脱水环化(RSC Adv.2014,4,60473-60477)。有文献报道使用C-H键活化环合成环的策略,都是环合成五、六元环,并没有报道过使用该策略合成该类骨架的化合物。因此,无论是从原料来源的丰富性,反应的原子经济性,合成方法的简捷性还是从合成产物广泛的应用性上来讲,都是对以往合成方法的一个比较大的突破,具有一定的应用价值。
发明内容
本发明目的是提供一种苯并氧杂类化合物的合成方法,该法通过二芳基环状碘鎓盐类化合物与含有羟基的底物反应高效的合成二芳基醚类化合物,并通过分子内环化得到苯并氧杂类化合物。该反应操作简单,后处理方便,解决以往合成方法效率低下、反应条件苛刻等问题。
本发明苯并氧杂类化合物属于有机π共轭材料,由于其独特的光学和电荷传输特性,它们在有机半导体的开发中发挥了重要作用,苯稠合的氧杂环庚三烯能在OLED中用作主体材料或发光材料(RSC Adv.2014,4,60473-60477);同时,含有苯并氧杂环庚三烯的结构广泛存在于天然产物中,具有广泛的生物活性,具有抗炎等作用,特别是在精神药物(Tetrahedron 2007,63,10067–10076)。
本发明的技术方案如下:
(a)将二芳基环状碘鎓盐类化合物(I)、含有羟基的化合物(II)、三氟甲磺酸铜、碳酸钾和溶剂二氯甲烷混合,升温至80~120℃搅拌反应6~24h,之后反应液经后处理,得到二芳基醚类化合物(III);
所述二芳基环状碘鎓盐类化合物(I)、含有羟基的化合物(II)、三氟甲磺酸铜、碳酸钾的物质的量之比为1:1~1.5:0.05~0.2:1~3;
所述溶剂二氯甲烷的体积用量以二芳基环状碘鎓盐类化合物(I)的物质的量计为2~10mL/mmol;
所述反应液后处理的方法为:反应结束后,待反应液降至室温(20~30℃),浓缩,进行柱层析,以石油醚与乙酸乙酯体积比为150~1:1的混合液或二氯甲烷与甲醇体积比为100:1的混合液作为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂并干燥,得到二芳基醚类化合物(III);
(b)将二芳基醚类化合物(III)、三苯基膦、新戊酸钯、醋酸钾、特戊酸与溶剂N-甲基吡咯烷酮混合,在氮气保护下,于110~150℃搅拌反应6~10h,之后反应液经后处理,得到产物苯并氧杂类化合物(IV);
所述二芳基醚类化合物(III)、三苯基膦、新戊酸钯、醋酸钾、特戊酸的物质的量之比为1:0.05~0.2:0.02~0.1:1~3:0.3~1;
所述溶剂N-甲基吡咯烷酮的体积用量以二芳基醚类化合物(III)的物质的量计为10mL/mmol;
所述反应液后处理的方法为:反应结束后,待反应液降至室温(20~30℃),然后经乙酸乙酯萃取,萃取液浓缩,进行柱层析,以石油醚与乙酸乙酯体积比为100~10:1的混合液或二氯甲烷与甲醇体积比为100:1的混合液作为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂并干燥,得到苯并氧杂类化合物(IV);
反应通式如下:
式(I)、(II)、(III)或(IV)中,
A处芳香环为苯环;B处芳香环为苯环或噻吩环;C处芳香环为苯环、吡啶环或醌;
R1、R2各自独立为:氢、C1~C6直链烷基、C3~C6支链烷基、C3~C6环状烷基、含杂C2~C6烷基、不饱和C2~C6烷基、C1~C6烷氧基、硝基、氰基、三氟甲基、酯基或卤素(氟、氯、溴);优选例如:氢、甲基、硝基、甲氧基或三氟甲基;
R3为:氢、C1~C6直链烷基、C3~C6支链烷基、C3~C6环状烷基、含杂C2~C6烷基、不饱和C2~C6烷基、C1~C6烷氧基、硝基、氰基、三氟甲基、酯基或卤素(氟、氯、溴);优选例如:氢、甲基、硝基、甲氧基或三氟甲基。
本发明具有以下优点:反应体系简单,原料特别是含有羟基的化合物容易得到,底物无需多步制备,后处理简单,总收率较高。
本发明的创新点在于,充分的利用了底物原子经济性,使用廉价金属铜的催化在一定温度下使用含有羟基的化合物和二芳基环状碘鎓盐高效的得到二芳基醚类化合物,并且通过进一步反应能发生分子内的环化。本发明所得二芳基醚类化合物收率最高为99%,苯并氧杂类化合物收率最高为95%。
具体实施方式
下面通过具体实施例对本发明作进一步的说明,但本发明的保护范围并不仅限于此。
实施例1:
2-碘-2'-苯氧基-1,1'-联苯的合成
将苯酚(45.2mg,0.48mmol),[1,1'-联苯]-环状三氟甲磺酸碘鎓盐(171.1mg,0.4mmol)、三氟甲磺酸铜(14.5mg,0.04mmol)、碳酸钾(110.5mg,0.8mmol)溶解在2mL二氯甲烷置于35mL耐压管中,该溶液在100℃搅拌反应18h。浓缩,经硅胶柱层析,石油醚/乙酸乙酯=100:1洗脱,浓缩得到产物139.5mg,收率为94%。1H NMR(500MHz,CDCl3)δ7.91(dd,J=8.0,1.1Hz,1H),7.40–7.32(m,2H),7.31(dd,J=7.6,2.1Hz,1H),7.29–7.25(m,3H),7.20(td,J=7.5,1.2Hz,1H),7.05(tt,J=7.3,1.1Hz,1H),7.03–7.00(m,1H),7.00–6.97(m,3H)ppm;13C NMR(126MHz,CDCl3)δ157.0,154.1,143.0,138.9,135.8,131.7,130.6,129.5,129.4,128.9,127.7,123.1,123.0,119.1,118.7,100.1ppm;HRMS m/z(EI)calcd forC18H13IO[M]+372.0011,found:371.9994.产物结构式为:
实施例2
三苯并[b,d,f]氧杂环庚三烯的合成
将2-碘-2'-苯氧基-1,1'-联苯(74.4mg,0.2mmol),三苯基膦(5.2mg,0.02mmol)、新戊酸钯(3.1mg,0.01mmol)、醋酸钾(58.8mg,0.6mmol)、特戊酸(12.3mg,0.12mmol)溶解在2mL N-甲基吡咯烷酮中,在氮气保护下130℃搅拌反应8h。萃取、浓缩,经硅胶柱层析,石油醚/乙酸乙酯=100:1洗脱,浓缩得到产物43.2mg,收率为88%。1H NMR(500MHz,CDCl3)δ7.67(dd,J=5.8,3.4Hz,2H),7.60(dd,J=7.7,1.5Hz,2H),7.52(dd,J=5.8,3.3Hz,2H),7.40–7.33(m,4H),7.27(ddd,J=7.7,6.6,2.0Hz,2H)ppm;13C NMR(126MHz,CDCl3)δ160.2,136.6,132.9,129.7,129.4,129.3,128.1,125.5,120.9ppm.产物结构式为:
实施例3
2-碘-2'-(间甲苯氧基)-1,1'-联苯的合成
按实施例1所述的方法,不同的是所使用的羟基底物为间甲基苯酚(52.0mg,0.48mmol),得到产物150.6mg,收率为97%。1H NMR(500MHz,CDCl3)δ7.92(dd,J=7.9,1.1Hz,1H),7.41–7.31(m,3H),7.31–7.27(m,1H),7.23–7.13(m,2H),7.04–6.97(m,2H),6.87(ddt,J=7.5,1.7,0.9Hz,1H),6.83–6.78(m,2H),2.31(s,3H)ppm;13C NMR(126MHz,CDCl3)δ156.9,154.2,143.0,139.6,138.9,135.7,131.6,130.6,129.3,129.2,128.8,127.7,123.9,122.8,119.8,118.6,116.1,100.0,21.3ppm;HRMS m/z(EI)calcd forC19H15IO[M]+386.0168,found:386.0158.产物结构式为:
实施例4
2-碘-2'-(4-硝基苯氧基)-1,1'-联苯的合成
按实施例1所述的方法,不同的是所使用的羟基底物为对硝基苯酚(66.8mg,0.48mmol),得到产物152.8mg,收率为92%。1H NMR(500MHz,CDCl3)δ8.12–8.06(m,2H),7.85(dd,J=8.0,1.2Hz,1H),7.50(dt,J=8.1,4.7Hz,1H),7.40–7.35(m,2H),7.31–7.25(m,1H),7.22(dd,J=7.7,1.8Hz,1H),7.17(dt,J=8.2,0.8Hz,1H),6.97(ddd,J=7.9,7.3,1.8Hz,1H),6.94–6.88(m,2H)ppm;13C NMR(126MHz,CDCl3)δ162.8,151.5,142.5,141.7,139.2,136.9,132.4,130.5,130.0,129.3,127.8,125.6,125.4,121.2,117.1,99.5ppm;HRMS m/z(EI)calcd for C18H12INO3[M]+416.9862,found:416.9883.产物结构式为:
实施例5
2-((2'-碘-[1,1'-联苯]-2-基)氧基)吡啶的合成
按实施例1所述的方法,不同的是所使用的羟基底物为2-羟基吡啶(45.7mg,0.48mmol),得到产物140.0mg,收率为94%。1H NMR(500MHz,CDCl3)δ8.12(ddd,J=5.0,2.0,0.8Hz,1H),7.85(dd,J=7.9,1.0Hz,1H),7.56–7.44(m,2H),7.36–7.29(m,2H),7.28–7.19(m,3H),6.92(ddd,J=8.0,6.7,2.4Hz,1H),6.88(ddd,J=7.2,5.0,0.9Hz,1H),6.72(dt,J=8.3,0.9Hz,1H)ppm;13C NMR(126MHz,CDCl3)δ163.4,151.0,147.3,142.6,139.1,138.8,137.0,131.6,130.7,129.5,128.8,127.5,124.7,122.1,118.1,111.4,99.7ppm;HRMS m/z(ESI)calcd for C17H12INO[M+H]+374.0036,found:374.0036.产物结构式为:
实施例6
2-((2'-碘-[1,1'-联苯]-2-基)氧基)萘-1,4-二酮的合成
按实施例1所述的方法,不同的是所使用的羟基底物为2-羟基萘醌(83.6mg,0.48mmol),得到产物154.1mg,收率为85%。1H NMR(500MHz,CDCl3)δ8.08–8.03(m,1H),8.03–7.99(m,1H),7.84(dd,J=7.9,1.2Hz,1H),7.75–7.65(m,2H),7.52(ddd,J=8.1,5.9,3.3Hz,1H),7.45–7.38(m,2H),7.34(dd,J=7.7,1.8Hz,1H),7.30(td,J=7.5,1.2Hz,1H),7.23(dd,J=7.9,1.0Hz,1H),6.94(ddd,J=8.0,7.2,1.9Hz,1H),6.04(s,1H)ppm;13C NMR(126MHz,CDCl3)δ184.7,179.1,159.3,149.7,140.9,139.5,136.8,134.2,133.3,132.7,131.9,130.9,130.6,130.1,129.4,127.9,126.6,126.5,126.1,121.7,114.4,99.2ppm;HRMS m/z(ESI)calcd for C22H13IO3[M+H]+452.9982,found:452.9985.产物结构式为:
实施例7
2-碘-4'-甲氧基-3,5-二甲基-2'-苯氧基-1,1'-联苯的合成
按实施例1所述的方法,不同的是所使用的碘鎓盐底物为7-甲氧基-2,4-二甲基二苯并[b,d]碘醇-5-三氟甲磺酸盐(194.5mg,0.40mmol),得到产物151.0mg,收率为88%。1HNMR(500MHz,CDCl3)δ7.31–7.26(m,2H),7.15(d,J=8.4Hz,1H),7.09–6.99(m,4H),6.94–6.91(m,1H),6.73(dd,J=8.4,2.5Hz,1H),6.48(d,J=2.5Hz,1H),3.79(s,3H),2.49(s,3H),2.27(s,3H)ppm;13C NMR(126MHz,CDCl3)δ160.2,156.7,155.3,143.7,141.6,137.0,132.0,129.5,129.4,128.9,123.3,119.7,115.3,107.8,104.2,104.1,55.4,29.7,20.7ppm;HRMS m/z(EI)calcd for C21H19IO2[M]+430.0430,found:430.0439.产物结构式为:
实施例8
2-(2-碘-4-(三氟甲基)苯基)-3-苯氧基噻吩的合成
按实施例1所述的方法,不同的是所使用的碘鎓盐底物为6-(三氟甲基)苯并[b]噻吩并[2,3-d]碘醇-4-三氟甲磺酸盐(200.9mg,0.40mmol),得到产物120.0mg,收率为67%。1H NMR(500MHz,Chloroform-d)δ8.16(s,1H),7.60(dd,J=8.0,1.8Hz,1H),7.52(d,J=8.0Hz,1H),7.37(d,J=5.5Hz,1H),7.32–7.24(m,2H),7.09–6.99(m,3H),6.83(d,J=5.5Hz,1H)ppm;13C NMR(126MHz,CDCl3)δ157.7,149.9,141.0,136.3(q,JC-F=3.9Hz),132.3,131.4(q,JC-F=32.9Hz),129.5,126.3,124.7(q,JC-F=3.6Hz),124.7,123.1,122.8(q,JC-F=273.3Hz),120.6,117.6,100.9ppm;HRMS m/z(EI)calcd for C17H10F3IOS[M]+445.9449,found:445.9445.产物结构式为:
实施例9
6-甲氧基三苯并[b,d,f]氧杂环庚三烯的合成
按实施例2所述的方法,不同的是所使用的芳基醚底物为2-碘-2'-(4-甲氧基苯氧基)-1,1'-联苯(80.4mg,0.20mmol),得到产物44.8mg,收率为82%。1H NMR(500MHz,CDCl3)δ7.69–7.63(m,2H),7.58(dd,J=7.7,1.7Hz,1H),7.53–7.49(m,2H),7.38–7.30(m,2H),7.28–7.23(m,2H),7.09(d,J=3.0Hz,1H),6.89(dd,J=8.8,3.0Hz,1H),3.83(s,3H)ppm;13CNMR(126MHz,CDCl3)δ160.5,157.0,154.2,136.7,136.6,133.5,132.8,129.7,129.4,129.3,129.2,128.2,128.1,125.4,121.4,120.6,114.5,114.4,55.7ppm;HRMS m/z(EI)calcd for C19H14O2[M]+274.0994,found:274.1003.产物结构式为:
实施例10
6-(三氟甲基)三苯并[b,d,f]氧杂环庚三烯的合成
按实施例2所述的方法,不同的是所使用的芳基醚底物为2-碘-2'-(4-(三氟甲基)苯氧基)-1,1'-联苯(88.0mg,0.20mmol),得到产物57.5mg,收率为92%。1H NMR(500MHz,Chloroform-d)δ7.88(d,J=2.2Hz,1H),7.71–7.63(m,3H),7.62(dd,J=7.7,1.6Hz,1H),7.59–7.52(m,2H),7.48–7.43(m,1H),7.43–7.34(m,2H),7.31(td,J=7.4,1.6Hz,1H)ppm;13C NMR(126MHz,CDCl3)δ162.4,159.6,136.6,135.3,133.6,132.5,129.8,129.6,129.5,129.4,128.9,128.4,128.0(q,JC-F=32.7Hz),127.0(q,JC-F=3.8Hz),126.3(q,JC-F=3.7Hz),126.0,124.0(q,JC-F=272.3Hz),121.5,120.9ppm;HRMS m/z(EI)calcd forC19H11F3O[M]+312.0762,found:312.0758.产物结构式为:
实施例11
二苯并[4,5:6,7]氧庚啶[2,3-b]吡啶的合成
按实施例2所述的方法,不同的是所使用的芳基醚底物为2-((2'-碘-[1,1'-联苯]-2-基)氧基)吡啶(74.6mg,0.20mmol),得到产物42.0mg,收率为86%。1H NMR(500MHz,CDCl3)δ8.35(dd,J=4.8,1.9Hz,1H),7.97(dd,J=7.5,1.9Hz,1H),7.71–7.66(m,1H),7.62–7.49(m,5H),7.41(td,J=7.7,1.7Hz,1H),7.32–7.26(m,2H)ppm;13C NMR(126MHz,CDCl3)δ164.0,158.1,147.7,139.1,136.5,134.4,132.0,129.7,129.5,129.4,129.4,128.8,128.3,127.4,126.0,122.2,122.0ppm;HRMS m/z(ESI)calcd for C17H11NO[M+H]+246.0913,found:246.0917.产物结构式为:
实施例12
二苯并[b,d]萘并[2,3-f]氧杂环庚三烯-10,15-二酮的合成
按实施例2所述的方法,不同的是所使用的芳基醚底物为2-((2'-碘-[1,1'-联苯]-2-基)氧基)萘-1,4-二酮(90.4mg,0.20mmol),得到产物19.0mg,收率为29%。1H NMR(500MHz,CDCl3)δ8.23–8.15(m,2H),7.80–7.75(m,2H),7.73(dd,J=7.9,1.4Hz,1H),7.69(dd,J=7.8,1.4Hz,1H),7.64–7.57(m,2H),7.52(ddd,J=15.5,7.9,1.4Hz,2H),7.42(td,J=7.8,1.7Hz,1H),7.33(td,J=7.5,1.3Hz,1H)ppm;13C NMR(126MHz,CDCl3)δ184.7,179.4,159.4,157.9,138.7,134.1,133.9,133.2,132.5,132.4,132.3,131.1,129.9,129.8,129.6,129.4,129.0,127.1,127.0,126.4,126.3,121.6ppm;HRMS m/z(ESI)calcd forC22H12O3[M+H]+325.0859,found:325.0864.产物结构式为:
Claims (5)
(a)将二芳基环状碘鎓盐类化合物(I)、含有羟基的化合物(II)、三氟甲磺酸铜、碳酸钾和溶剂二氯甲烷混合,升温至80~120℃搅拌反应6~24h,之后反应液经后处理,得到二芳基醚类化合物(III);
所述二芳基环状碘鎓盐类化合物(I)、含有羟基的化合物(II)、三氟甲磺酸铜、碳酸钾的物质的量之比为1:1~1.5:0.05~0.2:1~3;
(b)将二芳基醚类化合物(III)、三苯基膦、新戊酸钯、醋酸钾、特戊酸与溶剂N-甲基吡咯烷酮混合,在氮气保护下,于110~150℃搅拌反应6~10h,之后反应液经后处理,得到产物苯并氧杂类化合物(IV);
所述二芳基醚类化合物(III)、三苯基膦、新戊酸钯、醋酸钾、特戊酸的物质的量之比为1:0.05~0.2:0.02~0.1:1~3:0.3~1;
反应通式如下:
式(I)、(II)、(III)或(IV)中,
A处芳香环为苯环;B处芳香环为苯环或噻吩环;C处芳香环为苯环、吡啶环或醌;
R1、R2各自独立为:氢、C1~C6直链烷基、C3~C6支链烷基、C3~C6环状烷基、含杂C2~C6烷基、不饱和C2~C6烷基、C1~C6烷氧基、硝基、氰基、三氟甲基、酯基或卤素;
R3为:氢、C1~C6直链烷基、C3~C6支链烷基、C3~C6环状烷基、含杂C2~C6烷基、不饱和C2~C6烷基、C1~C6烷氧基、硝基、氰基、三氟甲基、酯基或卤素。
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