CN113045530A - 一种钌催化制备萘并吡喃类化合物的方法 - Google Patents
一种钌催化制备萘并吡喃类化合物的方法 Download PDFInfo
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- CN113045530A CN113045530A CN202110309305.0A CN202110309305A CN113045530A CN 113045530 A CN113045530 A CN 113045530A CN 202110309305 A CN202110309305 A CN 202110309305A CN 113045530 A CN113045530 A CN 113045530A
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- unsubstituted
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- 238000000034 method Methods 0.000 title claims abstract description 23
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 18
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical class C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 title abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 125000002252 acyl group Chemical group 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229940125782 compound 2 Drugs 0.000 claims abstract description 6
- 229940125904 compound 1 Drugs 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 125000003368 amide group Chemical group 0.000 claims description 10
- -1 nitro, hydroxyl Chemical group 0.000 claims description 10
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 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 8
- 229940126214 compound 3 Drugs 0.000 claims description 7
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- 125000001544 thienyl group Chemical group 0.000 claims description 5
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical group [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 125000006163 5-membered heteroaryl group Chemical group 0.000 claims description 2
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 239000007836 KH2PO4 Substances 0.000 claims description 2
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- 150000003304 ruthenium compounds Chemical group 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 16
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 abstract description 12
- 238000007363 ring formation reaction Methods 0.000 abstract description 8
- 230000011987 methylation Effects 0.000 abstract description 4
- 238000007069 methylation reaction Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 66
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 46
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 45
- 238000005160 1H NMR spectroscopy Methods 0.000 description 45
- 239000007787 solid Substances 0.000 description 44
- YVNQSWMQEGGLDD-UHFFFAOYSA-N 1-oxaphenalene Chemical compound O1C=CC2=CC=CC3=CC=CC1=C32 YVNQSWMQEGGLDD-UHFFFAOYSA-N 0.000 description 18
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000004293 19F NMR spectroscopy Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 150000001345 alkine derivatives Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052805 deuterium Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000004780 naphthols Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- JFGQHAHJWJBOPD-UHFFFAOYSA-N 3-hydroxy-n-phenylnaphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=CC=C1 JFGQHAHJWJBOPD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 125000002751 aliphatic alkane group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- KIHBJERLDDVXHD-UHFFFAOYSA-N s-benzoyl benzenecarbothioate Chemical compound C=1C=CC=CC=1C(=O)SC(=O)C1=CC=CC=C1 KIHBJERLDDVXHD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000004001 thioalkyl group Chemical group 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明公开了一种钌催化制备萘并吡喃类化合物的方法，在惰性气体和/或氮气气氛下，将化合物1、化合物2、钌催化剂、添加剂、碱、溶剂混合反应后，直接反应体系中添加三氟甲磺酸酐反应后即得。本发明方法通过一锅法制备萘并吡喃类化合物反应步骤短，操作简单，高效快捷，同时反应条件缓和，底物耐受性较好，适用范围广泛，解决了传统反应条件苛刻，操作复杂，底物局限，步骤繁琐，底物的官能团不耐受等不足，实现了萘酚C8位选择性酰甲基化以及环化反应制备萘并吡喃类化合物，为药物以及光电材料的开发奠定基础。
Description
技术领域
本发明涉及有机合成领域，特别是涉及一种钌催化制备萘并吡喃类化合物的方法。
背景技术
萘并吡喃类结构广泛的存在于具有生物活性的天然产物，药物分子或者光电子能性材料中。因此对于此类化合物的合成与结构修饰一直是化学工作者关注的重点。传统的合成方法大都以预官能化的萘酚为起始原料，经过氧化，还原，环合等反应，反应路线较长反应条件苛刻官能团耐受性较差，产物的多样性极大的受到了限制。
近年来，过渡金属催化的选择性C-H官能团化已经成为生物活性分子合成或结构修饰的重要策略。然而，关于过渡金属催化的合成萘酚合成芳并吡喃类化合物的研究仅仅局限于萘酚与炔类底物的环合反应。在2010年，Miura课题组报道了第一例Rh(III)催化的萘酚与炔类化合物的环化反应，此反应催化剂过渡金属铑价格昂贵。在此基础上，Ackermann和Sen课题组利用廉价的钌或者钴作为催化剂也顺利实现了萘酚类化合物与炔的环化反应。虽然这些反应为萘并吡喃类化合物的提供了一条经济便捷的合成路线，但是该类反应涉及使用加化学当量的金属铜盐作为氧化剂，对环境造成一定的重金属污染。最近Ackermann课题组在过渡金属钌催化下利用电合成技术实现了萘酚与炔的环化反应，此反应避免使用化学当量的铜盐作为氧化剂，更加符合绿色化学要求。
过渡金属催化萘酚与炔环化反应制备萘并吡喃类化合物取得了一定的进展，但是这些反应涉及的底物炔类化合物制备繁琐价格普遍昂贵，并且当反应底物为不对称炔时，反应的区域选择性较差，生成异构体难以分离。尤其是对于端炔类底物不适用，极大的限制了产物的多样性。
因此，发展一种反应条件缓和，高效便捷，底物耐受性较好，能够解决上述技术问题的的新合成方法显得十分必要。
发明内容
本发明解决的主要技术问题是提供一种钌催化制备萘并吡喃类化合物的方法，操作简单，底物范围广，实现了一系列萘并吡喃类化合物的高效合成。
为了解决上述的技术问题，本发明所采用的技术方案是：
本发明提供化合物3的制备方法，包含以下内容：在惰性气体和/或氮气气氛下，将化合物1、化合物2、钌催化剂、添加剂、碱、溶剂混合：
所述钌催化剂选自钌化合物和/或钌络合物；
所述添加剂选自铜盐或铜的氧化物；
R1选自非取代或取代的烷基、非取代或取代的杂烷基、非取代或取代的环烷基、非取代或取代的杂环烷基、非取代或取代的芳基、非取代或取代的杂芳基；
R3选自卤素、硝基、羟基、巯基、氨基、氰基、酰胺基、酰基、酯基、磺酰基、非取代或取代的烷基、非取代或取代的杂烷基、非取代或取代的环烷基、非取代或取代的杂环烷基、非取代或取代的芳基、非取代或取代的杂芳基；
R1、R3中的取代基选自卤素、硝基、羟基、巯基、氨基、氰基、酰胺基、酰基、酯基、磺酰基、烷基、杂烷基、环烷基、杂环烷基、芳基、杂芳基，或两个相邻的取代基共同组成非取代或取代的烷基、非取代或取代的杂烷基；
n选自0、1、2、3、4。
反应完后，通过本领域常规的后处理方法(过滤、浓缩、柱层析等)即可得到化合物3。
结构中虚线表示该部分结构可不存在。
进一步地，所述钌催化剂选自为[RuCl2(p-cymene)]2、CpRuCl(PPh3)2、RuCl3、RuCl2(PPh3)3中的一种或几种，优选[RuCl2(p-cymene)]2。
进一步地，所述钌催化剂的摩尔用量为化合物1摩尔用量的1.0％～20.0％，优选1.0％～10.0％，优选2.0％～7.0％，更优选为5.0％。
进一步地，所述添加剂选自Cu(OAc)2、Cu(OAc)2·H2O、CuCl2、CuO、Cu2O中的一种或几种，优选Cu(OAc)2和/或Cu(OAc)2·H2O。
进一步地，所述添加剂的摩尔用量为化合物1摩尔用量的1.0％～20.0％，优选1.0％～10.0％，优选2.0％～7.0％，更优选为5.0％。
进一步地，所述碱选自无机碱；进一步地，所述碱选自KOAc、NaOAc、K2CO3、Na2CO3、Cs2CO3、KHCO3、NaHCO3、K3PO4、Na3PO4、K2HPO4、Na2HPO4、KH2PO4、NaH2PO4中的一种或几种，优选KOAc。
进一步地，所述碱的摩尔用量为化合物1摩尔用量的1～5倍，优选1～3倍，更优选为2倍。
进一步地，所述溶剂选自二氯甲烷、二氯乙烷、四氢呋喃、甲苯、三氟甲苯中的一种或几种，优选二氯甲烷。
进一步地，所述溶剂的用量为，化合物1：溶剂的料液比为1mmol：5～15mL，优选为1mmol：5～10mL，更优选为1mmol：8mL。
进一步地，所述反应的温度为80℃～120℃，优选100℃。
进一步地，所述化合物2的摩尔用量为化合物1摩尔用量的1～5倍，优选1～3倍，更优选为1.5倍。
进一步地，R1选自非取代或取代的C1～C12烷基、非取代或取代的2～11元杂烷基、非取代或取代的C1～C12环烷基、非取代或取代的2～11元杂环烷基、非取代或取代的6～10元芳基、非取代或取代的5～10元杂芳基；
R3选自卤素、硝基、羟基、氰基、酰胺基、酰基、酯基、非取代或取代的烷基、非取代或取代的杂烷基、非取代或取代的环烷基、非取代或取代的杂环烷基、非取代或取代的芳基、非取代或取代的杂芳基；
R1、R3中的取代基选自卤素、硝基、羟基、氨基、氰基、酰胺基、酰基、酯基、烷基、杂烷基、环烷基、杂环烷基、芳基、杂芳基，或两个相邻的取代基共同组成非取代或取代的烷基、非取代或取代的杂烷基；
进一步地，R1选自非取代或取代的C1～C6烷基、非取代或取代的2～5元杂烷基、非取代或取代的C1～C12环烷基、非取代或取代的2～11元杂环烷基、非取代或取代的6～10元芳基、非取代或取代的5元杂芳基；
R3选自卤素、非取代或取代的C1～C6烷基、非取代或取代的2～5元杂烷基、非取代或取代的C1～C6环烷基、非取代或取代的2～5元杂环烷基；
R1、R3中的取代基选自卤素、硝基、羟基、氨基、氰基、酰胺基、酰基、酯基、烷基、杂烷基、环烷基、杂环烷基、芳基、杂芳基，或两个相邻的取代基共同组成非取代或取代的烷基、非取代或取代的杂烷基；
进一步地，R1选自非取代或取代的C1～C6烷基、非取代或取代的C1～C12环烷基、非取代或取代的苯基、非取代或取代的萘基、非取代或取代的噻吩基、非取代或取代的呋喃基；
R3选自卤素、非取代或取代的C1～C6烷基；
R1、R3中的取代基选自卤素、硝基、氰基、烷基、烷氧基、芳基、烯基，或两个相邻的取代基共同组成非取代或取代的氧杂烷基；n选自0、1、2；
进一步地，R1选自非取代或取代的C1～C6烷基、非取代或取代的C1～C12环烷基、非取代或取代的苯基、非取代或取代的萘基、非取代或取代的噻吩基、非取代或取代的呋喃基；
R3选自卤素、非取代或取代的C1～C3烷基；
R1、R3中的取代基选自卤素、硝基、氰基、烷基、三氟甲基、烷氧基、苯基、乙烯基，或两个相邻的取代基共同组成非取代或取代的
n选自0、1；
更进一步地，所述R1选自如下基团：
R3选自Br、甲基。
本发明还提供了一种化合物4的制备方法：向上述任一化合物3的制备方法反应后的反应体系中加入三氟甲磺酸酐：
当需要制备化合物4时，可在制备化合物3的反应体系反应完后，直接加入三氟甲磺酸酐，无需单独分离纯化出化合物3，操作方便，简化了生产步骤。
进一步地，所述三氟甲磺酸酐的摩尔用量为化合物1摩尔用量的0.2～2倍，优选0.2～1倍，更优选为0.3～0.5倍。
在本发明中：
“取代”是指分子中的氢原子被其它不同的原子或分子所替换。
“元”是表示构成取代基主链的原子个数或构成环的骨架原子的个数。
“烷基”，是指脂肪族烷烃基团，是饱和烃基。其中，烷基可以是直链烷基或支链烷基。典型的烷基包括但不限于甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、己基等等。
本发明中所使用的C1～Cn烷基包括C1～C2、C1～C3……C1～Cn。n是大于或等于一的整数，表示主链上的碳原子数，例如，“C1～C6烷基”是指含有1个至6个碳原子的烷基。
“烯基”，是指具有至少一个碳-碳双键的脂肪族碳氢基团。所述烯基可以是直链或支链的。
“氨基”，是指-NH3。
“酰胺”是具有式-C(O)NHR或-NHC(O)R的化学结构，其中R选自烷基、杂烷基、环烷基、杂环烷基、芳基、杂芳基等。
“酰基”是具有式-C(O)R的化学结构，其中R选自烷基、杂烷基、环烷基、杂环烷基、芳基、杂芳基等。
“磺酰基”是指具有式-SO2R的化学结构，其中R选自烷基、杂烷基、环烷基、杂环烷基、芳基、杂芳基等。
“环”是指任意的共价封闭结构，其中包括如下结构：碳环(如环烷基或芳基)、杂环(如杂环烷基或杂芳基)。环可以是单环、多环或任意取代的环。典型的多环一般有二环、三环(或桥环、螺环)。
“杂烷基”是指含有杂原子的烷基，其中，杂原子包括但不限于N、O、S、P等；氨烷基、硫烷基、烷氧基等都属于杂烷基。
“杂原子”是指除了碳或氢以外的其它原子。杂原子可独立地选自于N、O、S、P或Si，但不限于此。
“芳香基”是指平面环具有离域的π电子系统且含有4n+2个π电子，n为整数。芳香基环可以由五、六、七、八、九或九个以上的原子构成，芳香基包括但不限于噻吩基、苯基、萘基、菲基等等。
“环烷基”是指单环或多环的烃基，其结构式中只含有原子和氢原子，可以是饱和的也可以是不饱和的。
“卤素”是指氟、氯、溴或碘。
本发明所述基团和化合物中所涉及的碳、氢、氧、硫、氮或F、Cl、Br、I均包括它们的同位素情况，及本发明所述基团和化合物中所涉及的碳、氢、氧、硫或氮任选进一步被一个或多个它们对应的同位素所替代，其中碳的同位素包括12C、13C和14C，氢的同位素包括氕(H)、氘(D，又叫重氢)、氚(T，又叫超重氢)，氧的同位素包括16O、17O和18O，硫的同位素包括32S、33S、34S和36S，氮的同位素包括14N和15N，氟的同位素包括17F和19F，氯的同位素包括35Cl和37Cl，溴的同位素包括79Br和81Br。
在本发明中部分缩写表示的含义如下：
Me：甲基；
tBu：叔丁基。
本发明的有益效果是：
(1)本发明以萘酚和酰化的硫叶立德作为反应试剂，通过钌催化实现了萘酚C8位选择性酰甲基化以及环化反应制备萘并吡喃类化合物，为药物以及光电材料的开发奠定基础。
(2)本发明中酰化的硫叶立德结构简单易制备，价格便宜，衍生范围广，可更好地丰富萘并吡喃类化合物的结构多样性。
(3)本发明方法可通过一锅法制备，反应步骤短，操作简单，高效快捷，同时反应条件缓和，底物耐受性较好，适用范围广泛，解决了传统反应条件苛刻，操作复杂，底物局限，步骤繁琐，底物的官能团不耐受等不足。
具体实施方式
以下对本发明的技术方案进行清晰、完整地描述，显然，此处所描述的实施例仅是本发明中的一部分，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明的保护范围。
本发明实施例中所使用的化合物2(酰化硫叶立德)可通过市售购买，也可通过现有技术合成，参考文献：
[1]S.Zhu,K.Shi,H.Zhu,Org.Lett.2020,22,1504–1509.
本发明实施例中所用的钌催化剂、碱、溶剂等都可通过商业购买获得。
本发明系列萘并吡喃类化合物的合成通式如下：
实施例1萘酚C8位选择性酰甲基化
一种钌催化萘酚C8位选择性酰甲基化合成方法，包括以下步骤：
将0.25mmol萘酚类底物和1.5equiv酰化硫叶立德混合，加入5mol％催化剂和2equiv碱到反应管中，20mmol％Cu(OAc)2.H2O为添加剂，在氩气保护下加入干燥二氯甲烷(2mL)，100℃反应16h得混合液体。反应结束后添加水和乙酸乙酯萃取三次，合并有机层，无水Na2SO4干燥有机层，过滤，浓缩，硅胶柱层析(石油醚/乙酸乙酯＝30/1～5/1)分离纯化得到C8位酰甲基萘酚类化合物3。
通过本实施例方法，用带有萘酚与不同取代基的底物2a～2x制得化合物3aa～3ax，化合物后对应的百分数为产率：
实施例2一锅法制备萘并吡喃类化合物
将0.25mmol萘酚类底物和1.5equiv苯酰基硫叶立德混合，加入5mol％催化剂和2equiv碱到反应管中，20mmol％Cu(OAc)2.H2O为添加剂，在氩气保护下加入干燥二氯甲烷(2mL)，100℃反应16h得混合液体。然后向反应体系中加入三氟甲磺酸酐(17ul)，室温下继续反应6小时，反应结束后添加水和乙酸乙酯萃取三次，合并有机层，无水Na2SO4干燥有机层，过滤，浓缩，硅胶柱层析(石油醚/乙酸乙酯＝30/1～5/1)分离纯化得到萘并吡喃类化合物4。
通过本实施例方法，用带有萘酚与不同取代基的底物2a～2x制得如下化合物，化合物后对应的百分数为产率：
2-(8-hydroxynaphthalen-1-yl)-1-(4-methoxyphenyl)ethan-1-one(3aa).white solid.M.p＝122–123℃.1H NMR(600MHz,CDCl3)δ＝7.73(d,J＝8.3Hz,1H),7.72–7.68(m,2H),7.50(d,J＝8.1Hz,1H),7.43(t,J＝7.4Hz,2H),7.21(d,J＝6.9Hz,1H),7.05(d,J＝7.6Hz,1H),6.99–6.94(m,2H),3.84(s,3H),3.48(q,J＝16.3Hz,2H).13C NMR(150MHz)δ＝159.94,150.60,135.87,133.81,128.49,127.02,126.83,126.45,126.21,123.71,120.87,120.78,113.88,111.46,97.85,55.46,41.93.
2-(8-hydroxynaphthalen-1-yl)-1-phenylethan-1-one(3ab).white solid.M.p＝177–178℃.1H NMR(600MHz,DMSO)δ＝7.71(d,J＝8.2Hz,1H),7.67(d,J＝7.4Hz,2H),7.46(d,J＝8.1Hz,1H),7.43–7.37(m,4H),7.36–7.32(m,1H),7.20(d,J＝7.2Hz,2H),6.95(d,J＝7.3Hz,1H),3.38(q,J＝16.3Hz,2H).13C NMR(150MHz)δ＝151.79,144.74,133.77,130.42,128.62,128.59,127.34,126.83,126.25,125.83,123.68,121.32,120.40,111.18,98.43,41.91.
1-(4-(tert-butyl)phenyl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3ac).white solid.M.p＝103–104℃.1H NMR(600MHz,DMSO)δ＝7.71(d,J＝8.3Hz,1H),7.58(d,J＝8.4Hz,2H),7.45(d,J＝8.0Hz,1H),7.43–7.38(m,4H),7.20(d,J＝7.0Hz,1H),7.10(d,J＝1.5Hz,1H),6.93(d,J＝7.4Hz,1H),3.47(q,J＝16.1Hz,2H),1.27(s,9H).13CNMR(150MHz)δ＝151.90,150.98,141.82,133.76,130.53,127.34,126.82,126.00,125.80,125.31,123.63,121.33,120.32,111.12,98.42,41.81,34.81,31.67.
1-(4-fluorophenyl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3ad).whitesolid.M.p＝140–141℃.1H NMR(600MHz,DMSO)δ＝7.73–7.69(m,3H),7.47(d,J＝8.1Hz,1H),7.41(q,J＝8.0Hz,2H),7.26(d,J＝1.6Hz,1H),7.26–7.19(m,3H),6.96(d,J＝7.4Hz,1H),3.38(q,J＝16.2Hz,2H).13C NMR(150MHz)δ＝159.94,150.60,135.87,133.81,128.49,127.02,126.83,126.45,126.21,123.71,120.87,113.88,111.46,97.85,55.46,41.93.19FNMR(565MHz)δ＝-113.16–-115.98(m).
1-(4-bromophenyl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3ae).whitesolid.M.p＝160–161℃.1H NMR(600MHz,CDCl3)δ＝7.75(d,J＝8.3Hz,2H),7.64(s,4H),7.52–7.48(m,1H),7.44(q,J＝7.8Hz,2H),7.32(d,J＝1.7Hz,1H),7.24(d,J＝6.9Hz,1H),6.98(dd,J＝7.4,0.9Hz,1H),3.40(q,J＝16.3Hz,2H).13C NMR(150MHz)δ＝153.00,151.77,140.45,137.72,133.76,130.53,127.29,126.84,125.77,123.60,121.30,120.43,111.27,103.81,98.40,41.80.
2-(8-hydroxynaphthalen-1-yl)-1-(4-iodophenyl)ethan-1-one(3af).whitesolid.M.p＝177–178℃.1H NMR(600MHz,DMSO)δ＝7.80(d,J＝8.4Hz,2H),7.74(d,J＝8.3Hz,1H),7.50–7.48(m,3H),7.43(q,J＝8.4Hz,2H),7.31(d,J＝1.8Hz,1H),7.23(d,J＝7.0Hz,1H),6.98(d,J＝7.3Hz,1H).3.39(q,J＝16.2Hz,2H).13C NMR(150MHz)δ＝151.52,144.47,137.42,133.74,130.15,128.70,127.34,126.87,125.90,123.76,121.21,120.56,111.22,98.18,95.13,41.58.
2-(8-hydroxynaphthalen-1-yl)-1-(4-nitrophenyl)ethan-1-one(3ag).whitesolid.M.p＝145–146℃.1H NMR(600MHz,DMSO)δ＝8.32–8.22(m,2H),7.97–7.90(m,2H),7.73(d,J＝8.3Hz,1H),7.54(d,J＝1.8Hz,1H),7.49(d,J＝8.1Hz,1H),7.46–7.38(m,2H),7.22(d,J＝6.9Hz,1H),6.99(d,J＝7.5Hz,1H),3.41(q,J＝16.2Hz,2H).13C NMR(150MHz)δ＝151.54,151.14,147.85,133.74,129.69,127.87,127.36,126.93,126.02,123.94,121.10,120.81,111.35,97.88,41.33.
4-(2-(8-hydroxynaphthalen-1-yl)acetyl)benzonitrile(3ah).whitesolid.M.p＝177–178℃.1H NMR(600MHz,DMSO)δ＝7.90–7.84(m,4H),7.73(d,J＝8.3Hz,1H),7.49–7.46(m,2H),7.42(q,J＝8.4Hz,2H),7.21(d,J＝6.9Hz,1H),6.98(d,J＝7.5Hz,1H).3.39(q,J＝16.2Hz,2H).13C NMR(150MHz)δ＝151.52,144.47,137.42,133.74,130.15,128.70,127.34,126.87,125.90,124.95,123.76,121.21,120.56,111.22,98.18,95.13,41.58.
2-(8-hydroxynaphthalen-1-yl)-1-(4-(trifluoromethyl)phenyl)ethan-1-one(3ai).whitesolid.M.p＝103–104℃.1H NMR(600MHz,DMSO)δ＝7.92(d,J＝8.1Hz,2H),7.82(d,J＝8.3Hz,2H),7.76(d,J＝8.3Hz,1H),7.52(d,J＝8.1Hz,1H),7.48–7.43(m,3H),7.25(d,J＝6.9Hz,1H),7.01(d,J＝7.5Hz,1H),3.44(q,J＝16.2Hz,2H).13C NMR(150MHz)δ＝151.33,149.04,133.74,129.93,129.34,129.13,127.35,127.26,126.90,125.95,125.67–125.64(d,J＝3.8Hz),123.85,121.16,120.69,111.29,97.97,41.49.19F NMR(565MHz)δ＝-106.97–-107.03(m).
2-(8-hydroxynaphthalen-1-yl)-1-(3-methoxyphenyl)ethan-1-one(3aj).white solid.M.p＝131–132℃.1H NMR(600MHz,DMSO)δ＝7.71(d,J＝8.3Hz,1H),7.46(d,J＝8.0Hz,1H),7.40(q,J＝8.0Hz,2H),7.31(t,J＝7.9Hz,1H),7.24(d,J＝7.9Hz,1H),7.20–7.18(m,3H),6.95(d,J＝6.9Hz,1H),6.91(dd,J＝8.1,2.4Hz,1H),3.75(s,3H),3.38(q,J＝16.1Hz,2H).13C NMR(150MHz)δ＝159.56,151.77,146.33,133.76,130.43,129.74,127.33,126.84,125.81,123.67,121.30,120.42,118.53,113.92,112.15,111.19,98.32,55.62,41.78.
1-(3-fluorophenyl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3ak).whitesolid.M.p＝138–139℃.1H NMR(600MHz,DMSO)δ＝7.82(s,1H),7.72(d,J＝8.3Hz,1H),7.66(d,J＝7.8Hz,1H),7.58–7.52(m,1H),7.47(d,J＝8.2Hz,1H),7.44–7.35(m,3H),7.33(d,J＝1.7Hz,1H),7.20(d,J＝6.9Hz,1H),6.97(d,J＝7.3Hz,1H),3.38(q,J＝16.1Hz,2H).13C NMR(150MHz)δ＝151.40,147.30,133.73,131.54,130.99,130.08,129.13,127.34,126.88,125.90,125.49,123.79,121.97,121.18,120.63,111.28,41.52.19F NMR(565MHz)δ＝-116.06(s).
1-(3-chlorophenyl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3al).whitesolid.M.p＝177–178℃.1H NMR(600MHz,DMSO)δ＝7.82(d,J＝1.8Hz,1H),7.72(d,J＝8.3Hz,1H),7.67(d,J＝7.8Hz,1H),7.58–7.54(m,1H),7.47(d,J＝8.1Hz,1H),7.41(q,J＝8.0Hz,2H),7.37(d,J＝7.9Hz,1H),7.33(d,J＝1.7Hz,1H),7.20(d,J＝6.9Hz,1H),6.97(d,J＝7.3Hz,1H),3.36(q,J＝16.1Hz,2H).13C NMR(150MHz)δ＝151.40,147.31,133.73,131.54,130.97,130.07,129.14,127.33,126.88,125.90,125.48,123.79,121.97,121.18,120.63,111.28,97.77,41.54.
1-(3-bromophenyl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3am).whitesolid.M.p＝106–107℃.1H NMR(600MHz,DMSO)δ＝7.83(d,J＝1.7Hz,1H),7.69(dd,J＝29.6,8.0Hz,2H),7.58–7.54(m,1H),7.47(d,J＝8.1Hz,1H),7.40(dt,J＝15.8,8.1Hz,3H),7.34(d,J＝1.7Hz,1H),7.20(d,J＝6.8Hz,1H),6.97(d,J＝7.5Hz,1H),3.39(q,J＝16.1Hz,2H).13C NMR(150MHz)δ＝151.41,147.32,133.74,131.54,130.98,130.08,129.14,127.34,126.88,125.91,125.49,123.80,121.98,121.19,120.64,111.29,97.78,41.54.
1-(3,4-dimethoxyphenyl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3an).white solid.M.p＝134–135℃.1H NMR(600MHz,DMSO)δ＝7.70(d,J＝8.3Hz,1H),7.44(d,J＝8.1Hz,1H),7.40(dt,J＝11.0,7.7Hz,2H),7.22(d,J＝1.9Hz,1H),7.18(m,2H),7.08(s,1H),6.94(d,J＝8.2Hz,2H),3.39(q,J＝16.1Hz,2H).13C NMR(150MHz)δ＝161.91,156.28,155.59,152.18,139.28,135.59,132.28,129.17,125.55,126.55,123.86,120.15,118.05,118.38,115.92,110.29,43.29.
1-(3-bromo-4-methoxyphenyl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3ao).white solid.M.p＝148–149℃.1H NMR(600MHz,DMSO)δ＝7.80(d,J＝2.4Hz,1H),7.70(d,J＝8.3Hz,1H),7.60(dd,J＝8.4,2.1Hz,1H),7.45(d,J＝8.1Hz,1H),7.37–7.36(m,2H),7.22(d,J＝1.8Hz,1H),7.19(d,J＝6.9Hz,1H),7.12(d,J＝8.8Hz,1H),6.94(d,J＝7.6Hz,1H),3.83(s,3H).2.94(q,J＝16.2Hz,2H).13C NMR(150MHz)δ＝155.95,152.89,139.57,138.45,131.29,128.17,125.22,123.43,122.44,120.19,119.96,115.67,114.29,112.81,111.19,110.73,98.29,56.99,43.42.
1-(2-fluoro-4-methoxyphenyl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3ap).white solid.M.p＝140–141℃.1H NMR(600MHz,DMSO)δ＝7.70(d,J＝8.3Hz,1H),7.62(t,J＝9.1Hz,1H),7.45(d,J＝8.0Hz,1H),7.42–7.36(m,2H),7.29(d,J＝1.9Hz,1H),7.22–7.19(m,1H),6.93(d,J＝7.6Hz,1H),6.83(dd,J＝13.4,2.4Hz,1H),6.78(dd,J＝8.8,2.5Hz,1H),3.75(s,3H),3.38(q,J＝16.1Hz,2H).13C NMR(150MHz)δ＝158.26,159.18,155.28,149.87,136.66,132.01,129.19,128.63,127.59,126.39,124.95,122.28,119.87,111.74,110.95,101.28,98.36,57.21,45.19.19F NMR(565MHz)δ＝-110.42(s).
1-(benzo[d][1,3]dioxol-5-yl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3aq).white solid.M.p＝159–160℃.1H NMR(600MHz,DMSO)δ＝7.69(d,J＝8.3Hz,1H),7.44(d,J＝8.1Hz,1H),7.42–7.36(m,1H),7.19–7.17(m,1H),7.15(t,J＝2.2Hz,2H),7.10(d,J＝1.9Hz,1H),6.92(d,J＝7.6Hz,1H),6.90(d,J＝8.0Hz,1H),6.00(d,J＝2.7Hz,2H),3.21(q,J＝16.1Hz,2H).13C NMR(150MHz)δ＝160.55,155.69,151.85,149.84,136.85,132.10,131.58,129.18,126.54,125.96,124.16,122.83,120.85,115.36,110.26,109.54,100.69,45.22.
2-(8-hydroxynaphthalen-1-yl)-1-(3,4,5-trimethoxyphenyl)ethan-1-one(3ar).white solid.M.p＝139–140℃.1H NMR(600MHz,DMSO)δ＝7.71(d,J＝8.3Hz,1H),7.46(d,J＝8.1Hz,1H),7.44–7.38(m,2H),7.19(d,J＝6.6Hz,1H),7.13(d,J＝1.9Hz,1H),6.98–6.92(m,3H),3.78(s,6H),3.66(s,3H),3.34(q,J＝16.3Hz,2H).13C NMR(150MHz)δ＝160.29,158.19,155.63,145.27,138.74,135.49,132.46,131.28,128.25,125.66,123.40,122.50,120.98,111.44,108.29,61.80,58.42,45.19.
2-(8-hydroxynaphthalen-1-yl)-1-(naphthalen-1-yl)ethan-1-one(3as).white solid.M.p＝209–210℃.1H NMR(600MHz,DMSO)δ＝8.81(dd,J＝7.5,1.4Hz,1H),8.35(s,1H),8.26(dd,J＝7.5,1.3Hz,1H),7.93(d,J＝7.7Hz,2H),7.85–7.59(m,3H),7.56–7.14(m,4H),6.92(dd,J＝7.4,1.5Hz,1H),6.28(dd,J＝7.5,1.4Hz,1H),3.12(q,J＝16.2Hz,2H).13C NMR(150MHz)δ＝162.18,154.47,136.58,135.08,133.28,132.67,132.00,131.44,130.46,128.50,127.52,126.85,124.40,120.50,112.29,48.34.
1-(furan-2-yl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3at).whitesolid.M.p＝118–119℃.1H NMR(600MHz,DMSO)δ＝7.96(s,1H),7.63(s,1H),7.46–7.42(m,1H),7.34–7.27(m,2H),7.23(d,J＝6.9Hz,1H),6.91(d,J＝7.4Hz,1H),6.74–6.66(m,2H),6.45(d,J＝3.2Hz,1H),3.15(q,J＝16.2Hz,2H).13C NMR(150MHz)δ＝159.72,156.18,156.09,149.28,139.56,135.07,136.17,128.15,127.29,126.18,126.06,121.15,114.22,110.84,106.18,46.28.
2-(8-hydroxynaphthalen-1-yl)-1-(thiophen-2-yl)ethan-1-one(3au).whitesolid.M.p＝132–133℃.1H NMR(600MHz,DMSO)δ＝8.04(d,J＝4.3Hz,1H),7.93(d,J＝4.7Hz,1H),7.68(d,J＝8.1Hz,1H),7.58(d,J＝0.9Hz,1H),7.46(dd,J＝8.5,4.3Hz,2H),7.27–7.21(m,1H),6.92(d,J＝7.3Hz,1H),6.69(d,J＝7.5Hz,1H).3.25(q,J＝16.1Hz,2H).13C NMR(150MHz)δ＝159.58,154.37,153.29,148.17,139.38,133.16,131.46,130.29,129.89,127.59,126.14,125.75,124.19,123.55,45.19.
1-(8-hydroxynaphthalen-1-yl)-3-methyl-3-phenylbutan-2-one(3av).whitesolid.M.p＝73–74℃.1H NMR(600MHz,DMSO)δ＝7.64–7.57(m,3H),7.37(d,J＝7.2Hz,1H),7.33(q,J＝7.8Hz,2H),7.27(t,J＝7.7Hz,2H),7.16(t,J＝7.3Hz,2H),7.05(d,J＝6.9Hz,1H),6.89–6.85(m,1H),6.06(d,J＝1.2Hz,1H),2.94(q,J＝16.2Hz,2H),1.55(d,J＝18.5Hz,6H).13C NMR(150MHz)δ＝151.29,146.15,133.61,130.16,128.79,127.95,127.18,126.75,126.47,125.43,124.08,121.10,120.02,110.90,100.92,46.72,34.41,24.30,24.11.
1-(8-hydroxynaphthalen-1-yl)-3,3-dimethylbutan-2-one(3aw).whitesolid.M.p＝112–113℃.1H NMR(600MHz,DMSO)δ＝7.66(d,J＝8.3Hz,1H),7.43–7.36(m,2H),7.34(t,J＝7.8Hz,1H),7.18(d,J＝6.8Hz,1H),6.82(d,J＝7.4Hz,1H),5.76(s,1H),3.21(q,J＝16.1Hz,2H),1.11(s,9H).13C NMR(150MHz)δ＝151.71,133.70,130.68,127.18,126.75,125.40,124.15,121.42,119.87,110.82,101.54,39.38,33.57,25.44.
1-(adamantan-2-yl)-2-(8-hydroxynaphthalen-1-yl)ethan-1-one(3ax).whitesolid.M.p＝153–154℃.1H NMR(600MHz,DMSO)δ＝7.70(d,J＝8.3Hz,1H),7.42(t,J＝7.3Hz,2H),7.37(t,J＝7.8Hz,1H),7.21(d,J＝6.9Hz,1H),6.85(d,J＝7.5Hz,1H),5.72(d,J＝1.2Hz,1H),3.19(q,J＝16.1Hz,2H),1.88(s,7H),1.71(q,J＝12Hz,7H).13C NMR(150MHz)δ＝151.73,133.69,130.78,127.16,126.72,125.34,124.20,121.54,119.80,110.81,101.08,40.55,37.25,36.01,32.71,28.39.
2-(4-methoxyphenyl)benzo[de]chromene(4aa).yellow solid.M.p＝120–121℃.1H NMR(600MHz,CDCl3)δ＝7.75–7.67(m,2H),δ7.32(d,J＝8.3Hz,1H),7.28(t,J＝7.9Hz,1H),7.24–7.18(m,2H),6.99–6.90(m,2H),6.85(d,J＝7.5Hz,1H),6.75(d,J＝6.9Hz,1H),6.39(s,1H),3.85(s,3H).13C NMR(150MHz)δ＝160.35,152.98,151.99,134.77,130.26,127.86,127.41,126.08,125.70,123.02,122.96,119.30,115.41,113.83,106.97,101.41,55.31.
2-(4-fluorophenyl)benzo[de]chromene(4ab).yellow solid.M.p＝91–92℃.1HNMR(600MHz,CDCl3)δ＝7.75(dd,J＝8.7,5.4Hz,2H),7.34(d,J＝8.4Hz,1H),7.28(t,J＝7.9Hz,1H),7.22(dd,J＝14.3,7.4Hz,2H),7.11(t,J＝8.6Hz,2H),6.84(d,J＝7.5Hz,1H),6.76(d,J＝7.0Hz,1H),6.42(s,1H).13C NMR(150MHz)δ＝164.03,162.38,152.80,151.19,134.75,129.77,129.31,127.86,127.49,126.53(d,J＝8.1Hz),123.51,123.06,119.52,115.91,115.58,115.44,107.11,102.77.19F NMR(565MHz)δ＝-110.09(s).
2-(4-chlorophenyl)benzo[de]chromene(4ac).yellow solid.M.p＝126–127℃.1H NMR(600MHz,CDCl3)δ＝7.68(d,J＝8.5Hz,2H),7.38(d,J＝8.5Hz,2H),7.34(d,J＝8.4Hz,1H),7.28(t,J＝7.9Hz,1H),7.22(m,2H),6.83(d,J＝7.5Hz,1H),6.76(d,J＝7.0Hz,1H),6.45(s,1H).13C NMR(150MHz)δ＝152.85,151.10,135.03,134.87,131.66,129.73,128.82,127.98,127.66,125.97,123.86,123.26,119.70,116.28,107.30,103.49.
2-(4-iodophenyl)benzo[de]chromene(4ad).yellow solid.M.p＝129–130℃.1HNMR(600MHz,CDCl3)δ＝7.75(d,J＝8.4Hz,2H),7.49(d,J＝8.4Hz,2H),7.34(d,J＝8.4Hz,1H),7.28(t,J＝7.9Hz,1H),7.24–7.19(m,2H),6.83(d,J＝7.6Hz,1H),6.77(d,J＝7.0Hz,1H),6.49(s,1H).13C NMR(150MHz)δ＝152.83,151.24,137.72,134.87,132.71,129.67,127.98,127.66,126.32,123.94,123.30,119.70,116.35,107.32,103.61,95.07.
4-(benzo[de]chromen-2-yl)benzonitrile(4ae).yellow solid.M.p＝165–166℃.1H NMR(600MHz,CDCl3)δ＝7.84(d,J＝8.3Hz,2H),7.68(d,J＝8.3Hz,2H),7.39(d,J＝8.4Hz,1H),7.30(t,J＝7.9Hz,1H),7.26–7.21(m,2H),6.85(d,J＝7.5Hz,1H),6.82(d,J＝7.0Hz,1H),6.59(s,1H).13C NMR(150MHz)δ＝152.42,149.95,137.11,134.69,132.27,128.92,127.86,127.66,124.86,124.62,123.19,119.85,118.64,117.03,112.14,107.38,105.84.
2-(4-(trifluoromethyl)phenyl)benzo[de]chromene(4af).yellow solid.M.p＝84–85℃.1H NMR(600MHz,CDCl3)δ＝7.87(d,J＝8.1Hz,2H),7.67(d,J＝8.1Hz,2H),7.37(d,J＝8.4Hz,1H),7.30(t,J＝7.9Hz,1H),7.24–7.20(m,2H),6.86(d,J＝7.5Hz,1H),6.81(d,J＝7.0Hz,1H),6.58(s,1H).13C NMR(150MHz)δ＝152.75,150.69,136.52,134.86,131.37–130.14(m),129.38,127.98,127.73,125.58,124.88,124.34,123.35,123.27–123.04(m),119.84,116.74,107.43,104.96.19F NMR(565MHz)δ＝-62.51(s).
2-([1,1'-biphenyl]-4-yl)benzo[de]chromene(4ag).yellow solid.M.p＝158–159℃.1H NMR(600MHz,CDCl3)δ＝7.85(d,J＝8.3Hz,2H),7.67(d,J＝8.3 Hz,2H),7.65(d,J＝7.5Hz,2H),7.48(t,J＝7.6Hz,2H),7.42–7.34(m,2H),7.31(t,J＝7.9Hz,1H),7.26–7.22(m,2H),6.89(d,J＝7.5Hz,1H),6.79(d,J＝6.9Hz,1H),6.55(s,1H).13C NMR(150MHz)δ＝153.09,151.93,141.93,140.44,134.94,132.10,130.12,129.00,128.02,127.77,127.68,127.27,127.15,125.17,123.64,123.38,119.58,116.10,107.30,103.23.
2-(m-tolyl)benzo[de]chromene(4ah).yellow solid.M.p＝92–93℃.1H NMR(600MHz,CDCl3)δ＝7.62–7.56(m,2H),7.36–7.31(m,2H),7.30(t,J＝7.9Hz,1H),7.24(d,J＝2.9Hz,1H),7.23–7.20(m,2H),6.87(d,J＝7.6Hz,1H),6.78(d,J＝7.0 Hz,1H),6.50(s,1H),2.44(s,3H).13C NMR(150MHz)δ＝153.16,152.38,138.27,134.94,133.21,130.22,130.10,128.54,128.00,127.64,125.39,123.50,123.38,121.98,119.49,115.94,107.24,103.10,21.68.
2-(3-methoxyphenyl)benzo[de]chromene(4ai).yellow solid.M.p＝131–132℃.1H NMR(600MHz,CDCl3)δ＝7.35(m,4H),7.29(t,J＝7.9Hz,1H),7.22(m,2H),6.94(d,J＝6.6Hz,1H),6.86(d,J＝7.6Hz,1H),6.78(d,J＝7.0Hz,1H),6.50(s,1H),3.88(s,3H).13CNMR(150MHz)δ＝159.84,153.06,151.99,134.91,134.68,130.04,129.65,127.99,127.65,123.65,123.38,119.54,117.30,116.08,114.78,110.42,107.27,103.50,55.49.
2-(3-bromophenyl)benzo[de]chromene(4aj).yellow solid.M.p＝88–89℃.1HNMR(600MHz,CDCl3)δ＝7.91(s,1H),7.68(d,J＝7.8Hz,1H),7.50(d,J＝7.8Hz,1H),7.35(d,J＝8.4Hz,1H),7.28(t,J＝7.2Hz,2H),7.22(m,2H),6.85(d,J＝7.6Hz,1H),6.78(d,J＝7.0Hz,1H),6.48(s,1H).13C NMR(150MHz)δ＝152.79,150.60,135.23,134.85,132.06,130.11,129.55,127.96,127.70,124.06,123.32,123.22,122.88,119.74,116.49,107.39,104.17.
2-(2-fluorophenyl)benzo[de]chromene(4ak).yellow solid.M.p＝74–75℃.1HNMR(600MHz,CDCl3)δ＝7.86(td,J＝7.9,1.4Hz,1H),7.38–7.31(m,2H),7.28(t,J＝7.9Hz,1H),7.22(m,3H),7.14(dd,J＝12.1,8.2Hz,1H),6.81(dd,J＝17.1,7.3Hz,2H),6.72(s,1H).13C NMR(150MHz)δ＝160.93,159.26,152.94,146.89,134.83,130.31(d,J＝8.8Hz),129.78,127.96(d,J＝12.6Hz),127.61,124.33(d,J＝3.5Hz),124.00,123.27,121.46(d,J＝10.0Hz),119.54,116.67,116.37(d,J＝23.0Hz),108.55(d,J＝14.3Hz),107.14.19F NMR(565MHz)δ＝-111.748(s).
2-(o-tolyl)benzo[de]chromene(4al).yellow solid.M.p＝112–113℃.1H NMR(600MHz,CDCl3)δ＝7.48(d,J＝7.5Hz,1H),7.35(d,J＝8.4Hz,1H),7.31(d,J＝7.2Hz,1H),7.27(d,J＝7.8Hz,2H),7.24–7.19(m,3H),6.74(dd,J＝21.1,7.2Hz,2H),6.09(s,1H),2.52(s,3H).13C NMR(150MHz)δ＝154.45,153.34,136.75,134.98,134.21,130.97,130.26,129.43,128.81,127.98,127.65,126.01,123.58,123.24,119.55,115.68,107.17,106.87,20.74.
2-(4-bromo-3-methoxyphenyl)benzo[de]chromene(4am).yellow solid.M.p＝124–125℃.1H NMR(600MHz,CDCl3)δ＝7.96(d,J＝1.8Hz,1H),7.68(dd,J＝8.6,1.8Hz,1H),7.32(d,J＝8.4Hz,1H),7.28(t,J＝7.9Hz,1H),7.24–7.18(m,2H),6.92(d,J＝8.7Hz,1H),6.84(d,J＝7.6Hz,1H),6.75(d,J＝6.9Hz,1H),6.38(s,1H),3.93(s,3H).13C NMR(150MHz)δ＝156.56,152.89,150.68,134.87,129.93,129.76,127.99,127.61,127.17,125.08,123.53,123.15,119.64,115.95,111.94,111.63,107.26,102.42,56.46.
2-(3,4-dimethoxyphenyl)benzo[de]chromene(4an).yellow solid.M.p＝99–100℃.1H NMR(600MHz,CDCl3)δ＝7.37(dd,J＝8.3,1.9Hz,1H),7.32(d,J＝8.4Hz,1H),7.30–7.25(m,2H),7.24–7.17(m,2H),6.90(d,J＝8.4Hz,1H),6.85(d,J＝7.5Hz,1H),6.75(d,J＝7.0Hz,1H),6.39(s,1H),3.97(s,3H),3.92(s,3H).13C NMR(150MHz)δ＝152.95,151.96,149.94,148.80,134.78,130.16,127.88,127.42,126.01,123.07,123.03,119.37,117.74,115.48,110.82,107.65,107.01,101.80,55.93(d,J＝2.8Hz).
2-(3,4,5-trimethoxyphenyl)benzo[de]chromene(4ao).yellow solid.M.p＝135–136℃.1H NMR(600MHz,CDCl3)δ＝7.33(d,J＝8.4Hz,1H),7.28(t,J＝7.9Hz,1H),7.24–7.19(m,2H),6.98(s,2H),6.86(d,J＝7.5Hz,1H),6.77(d,J＝6.9Hz,1H),6.41(s,1H),3.94(s,6H),3.90(s,3H).13C NMR(150MHz)δ＝153.35,153.01,152.03,139.20,134.91,130.03,128.90,128.02,127.60,123.55,123.22,119.63,115.93,107.25,103.00,102.17,61.10,56.34.
2-(furan-2-yl)benzo[de]chromene(4ap).yellow solid.M.p＝89–90℃.1H NMR(600MHz,CDCl3)δ＝7.46(s,1H),7.33(d,J＝8.4Hz,1H),7.27(d,J＝7.9Hz,1H),7.21(dd,J＝14.3,7.4Hz,2H),6.79(dd,J＝20.0,7.2Hz,2H),6.74(d,J＝3.3Hz,1H),6.50(dd,J＝3.2,1.5Hz,1H),6.46(s,1H).13C NMR(150MHz)δ＝152.48,148.08,144.93,143.22,134.90,129.35,127.94,127.54,123.67,123.22,119.78,116.33,111.76,108.29,107.37,101.80.
2-(octahydro-2,5-methanopentalen-7-yl)benzo[de]chromene(4aq).yellowsolid.M.p＝110–111℃.1H NMR(600MHz,CDCl3)δ＝7.26(d,J＝8.2Hz,1H),7.24–7.21(m,1H),7.18–7.14(m,2H),5.75(s,1H),2.07(s,3H),1.90(m,6H),1.76(q,J＝12.1Hz,6H).13CNMR(150MHz)δ＝163.69,153.62,134.95,130.75,127.94,127.43,123.23,122.59,118.91,114.88,106.63,99.86,39.73,36.97,36.85,28.28.
2-(4-methoxyphenyl)-9-methylbenzo[de]chromene(4ba).yellow solid.M.p＝80–81℃.1H NMR(600MHz,CDCl3)δ＝7.74(d,J＝8.7Hz,2H),7.28(d,J＝8.3Hz,1H),7.16(dt,J＝15.5,8.1Hz,3H),6.96(d,J＝8.7Hz,2H),6.73(d,J＝6.9Hz,1H),6.41(s,1H),3.86(s,3H),2.36(s,3H).13C NMR(150MHz)δ＝160.45,151.91,149.99,133.31,130.33,129.98,126.92,126.19,126.05,123.12,122.98,118.79,116.17,115.47,114.03,101.45,55.48,15.38.
7-bromo-2-(4-methoxyphenyl)benzo[de]chromene(4ca).yellow solid.M.p＝159–160℃.1H NMR(600MHz,CDCl3)δ＝7.70(d,J＝8.8Hz,2H),7.59(d,J＝8.6Hz,1H),7.55(d,J＝8.2Hz,1H),7.34(dd,J＝8.3,7.3Hz,1H),6.94(d,J＝8.8Hz,2H),6.83(d,J＝7.1Hz,1H),6.75(d,J＝8.2Hz,1H),6.44(s,1H),3.85(s,3H).13C NMR(150MHz)δ＝160.73,152.69,152.25,133.03,131.01,130.75,129.39,126.31,125.39,123.91,122.52,116.51,114.07,112.12,107.99,101.26,55.48.
5-bromo-2-(4-methoxyphenyl)benzo[de]chromene(4da).yellow solid.M.p＝137–138℃.1H NMR(600MHz,CDCl3)δ＝7.71(d,J＝8.8Hz,2H),7.44(d,J＝1.6Hz,1H),7.29(t,J＝7.9Hz,1H),7.12(d,J＝8.2Hz,1H),6.95(d,J＝8.9Hz,2H),6.86(d,J＝7.6Hz,1H),6.83(d,J＝1.4Hz,1H),6.33(s,1H),3.86(s,3H).13C NMR(150MHz)δ＝161.89,153.43,153.00,135.94,132.57,128.64,126.46,125.37,124.71,122.45,121.57,118.68,118.29,114.09,107.70,100.42,55.49.
4-(4-methoxyphenyl)phenanthro[3,4,5-defg]chromene(4ea).yellowsolid.M.p＝150–151℃.1H NMR(600MHz,CDCl3)δ＝7.91(d,J＝8.4Hz,1H),7.79–7.72(m,7H),7.70(d,J＝7.4Hz,1H),7.44(d,J＝8.3Hz,1H),7.10(s,1H),6.96(d,J＝8.7Hz,2H),6.53(s,1H),3.85(s,3H).13C NMR(150MHz)δ＝160.59,152.50,150.46,134.06,132.41,128.95,126.85,126.66,126.56,126.31,126.04,125.99,125.87,125.62,125.27,122.14,121.92,118.45,114.12,114.04,112.34,102.50,102.50,55.47.
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (10)
1.化合物3的制备方法，其特征在于，包含以下内容：在惰性气体和/或氮气气氛下，将化合物1、化合物2、钌催化剂、添加剂、碱、溶剂混合：
所述钌催化剂选自钌化合物和/或钌络合物；
所述添加剂选自铜盐或铜的氧化物；
R1选自非取代或取代的烷基、非取代或取代的杂烷基、非取代或取代的环烷基、非取代或取代的杂环烷基、非取代或取代的芳基、非取代或取代的杂芳基；
R3选自卤素、硝基、羟基、巯基、氨基、氰基、酰胺基、酰基、酯基、磺酰基、非取代或取代的烷基、非取代或取代的杂烷基、非取代或取代的环烷基、非取代或取代的杂环烷基、非取代或取代的芳基、非取代或取代的杂芳基；
R1、R3中的取代基选自卤素、硝基、羟基、巯基、氨基、氰基、酰胺基、酰基、酯基、磺酰基、烷基、杂烷基、环烷基、杂环烷基、芳基、杂芳基，或两个相邻的取代基共同组成非取代或取代的烷基、非取代或取代的杂烷基；
n选自0、1、2、3、4。
2.根据权利要求1所述制备方法，其特征在于，所述钌催化剂选自为[RuCl2(p-cymene)]2、CpRuCl(PPh3)2、RuCl3、RuCl2(PPh3)3中的一种或几种，优选[RuCl2(p-cymene)]2；
进一步地，所述钌催化剂的摩尔用量为化合物1摩尔用量的1.0％～20.0％，优选1.0％～10.0％，优选2.0％～7.0％，更优选为5.0％。
3.根据权利要求1所述制备方法，其特征在于，所述添加剂选自Cu(OAc)2、Cu(OAc)2·H2O、Cu(OAc)、CuCl2、CuO、Cu2O中的一种或几种，优选Cu(OAc)2和/或Cu(OAc)2·H2O；
进一步地，所述添加剂的摩尔用量为化合物1摩尔用量的1.0％～20.0％，优选1.0％～10.0％，优选2.0％～7.0％，更优选为5.0％。
4.根据权利要求1所述制备方法，其特征在于，所述碱选自无机碱；进一步地，所述碱选自KOAc、NaOAc、K2CO3、Na2CO3、Cs2CO3、KHCO3、NaHCO3、K3PO4、Na3PO4、K2HPO4、Na2HPO4、KH2PO4、NaH2PO4中的一种或几种，优选KOAc；
进一步地，所述碱的摩尔用量为化合物1摩尔用量的1～5倍，优选1～3倍，更优选为2倍。
5.根据权利要求1所述制备方法，其特征在于，所述溶剂选自二氯甲烷、二氯乙烷、四氢呋喃、甲苯、三氟甲苯中的一种或几种，优选二氯甲烷；
进一步地，所述溶剂的用量为，化合物1：溶剂的料液比为1mmol：5～15mL，优选为1mmol：5～10mL，更优选为1mmol：8mL。
6.根据权利要求1所述制备方法，其特征在于，所述反应的温度为80℃～120℃，优选100℃。
7.根据权利要求1所述制备方法，其特征在于，所述化合物2的摩尔用量为化合物1摩尔用量的1～5倍，优选1～3倍，更优选为1.5倍。
8.根据权利要求1所述制备方法，其特征在于，R1选自非取代或取代的C1～C12烷基、非取代或取代的2～11元杂烷基、非取代或取代的C1～C12环烷基、非取代或取代的2～11元杂环烷基、非取代或取代的6～10元芳基、非取代或取代的5～10元杂芳基；
R3选自卤素、硝基、羟基、氰基、酰胺基、酰基、酯基、非取代或取代的烷基、非取代或取代的杂烷基、非取代或取代的环烷基、非取代或取代的杂环烷基、非取代或取代的芳基、非取代或取代的杂芳基；
R1、R3中的取代基选自卤素、硝基、羟基、氨基、氰基、酰胺基、酰基、酯基、烷基、杂烷基、环烷基、杂环烷基、芳基、杂芳基，或两个相邻的取代基共同组成非取代或取代的烷基、非取代或取代的杂烷基；
进一步地，R1选自非取代或取代的C1～C6烷基、非取代或取代的2～5元杂烷基、非取代或取代的C1～C12环烷基、非取代或取代的2～11元杂环烷基、非取代或取代的6～10元芳基、非取代或取代的5元杂芳基；
R3选自卤素、非取代或取代的C1～C6烷基、非取代或取代的2～5元杂烷基、非取代或取代的C1～C6环烷基、非取代或取代的2～5元杂环烷基；
R1、R3中的取代基选自卤素、硝基、羟基、氨基、氰基、酰胺基、酰基、酯基、烷基、杂烷基、环烷基、杂环烷基、芳基、杂芳基，或两个相邻的取代基共同组成非取代或取代的烷基、非取代或取代的杂烷基；
进一步地，R1选自非取代或取代的C1～C6烷基、非取代或取代的C1～C12环烷基、非取代或取代的苯基、非取代或取代的萘基、非取代或取代的噻吩基、非取代或取代的呋喃基；
R3选自卤素、非取代或取代的C1～C6烷基；
R1、R3中的取代基选自卤素、硝基、氰基、烷基、烷氧基、芳基，或两个相邻的取代基共同组成非取代或取代的氧杂烷基；n选自0、1、2；
进一步地，R1选自非取代或取代的C1～C6烷基、非取代或取代的C1～C12环烷基、非取代或取代的苯基、非取代或取代的萘基、非取代或取代的噻吩基、非取代或取代的呋喃基；
R3选自卤素、非取代或取代的C1～C3烷基；
R1、R3中的取代基选自卤素、硝基、氰基、烷基、三氟甲基、烷氧基、苯基、乙烯基，或两个相邻的取代基共同组成非取代或取代的
n选自0、1；
更进一步地，所述R1选自如下基团：
R3选自Br、甲基。
9.一种化合物4的制备方法，其特征在于，向权利要求1～8任一项所述方法反应后的反应体系中加入三氟甲磺酸酐：
10.根据权利要求9所述制备方法，其特征在于，所述三氟甲磺酸酐的摩尔用量为化合物1摩尔用量的0.2～2倍，优选0.2～1倍，更优选为0.3～0.5倍。
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| CN115286609A (zh) * | 2022-08-09 | 2022-11-04 | 浙江理工大学 | 一种2-三氟甲基取代的二氢苯并色烯的制备方法 |
| CN115286609B (zh) * | 2022-08-09 | 2023-12-19 | 浙江理工大学 | 一种2-三氟甲基取代的二氢苯并色烯的制备方法 |
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