CN108892604A - 一种制备卤代苯并[b]芴酮系列化合物的方法 - Google Patents
一种制备卤代苯并[b]芴酮系列化合物的方法 Download PDFInfo
- Publication number
- CN108892604A CN108892604A CN201810926535.XA CN201810926535A CN108892604A CN 108892604 A CN108892604 A CN 108892604A CN 201810926535 A CN201810926535 A CN 201810926535A CN 108892604 A CN108892604 A CN 108892604A
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- China
- Prior art keywords
- benzo
- phenyl
- catalyst
- ketone
- series compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 halogenated benzo [b] Fluorenone series compound Chemical class 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 10
- 125000005605 benzo group Chemical group 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000003814 drug Substances 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 69
- 239000003921 oil Substances 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 150000002240 furans Chemical class 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical group 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical compound [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052740 iodine Chemical group 0.000 claims description 3
- 239000011630 iodine Chemical group 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- CISNNLXXANUBPI-UHFFFAOYSA-N cyano(nitro)azanide Chemical group [O-][N+](=O)[N-]C#N CISNNLXXANUBPI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- VJGJZVCKMKGZKS-UHFFFAOYSA-N iron;oxalic acid;hydrate Chemical compound O.[Fe].OC(=O)C(O)=O VJGJZVCKMKGZKS-UHFFFAOYSA-N 0.000 claims description 2
- QZLVALRWETVYSE-UHFFFAOYSA-N iron;trifluoromethanesulfonic acid Chemical compound [Fe].OS(=O)(=O)C(F)(F)F QZLVALRWETVYSE-UHFFFAOYSA-N 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- NGOCMUBXJDDBLB-UHFFFAOYSA-N trifluoromethanesulfonic acid;zinc Chemical compound [Zn].OS(=O)(=O)C(F)(F)F NGOCMUBXJDDBLB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 229930194224 Kinamycin Natural products 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 125000005843 halogen group Chemical group 0.000 abstract description 5
- 238000002512 chemotherapy Methods 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- WVXMLBXFHITUIT-UHFFFAOYSA-N benzo[a]fluoren-1-one Chemical compound C1=CC=CC2=CC3=C4C(=O)C=CC=C4C=CC3=C21 WVXMLBXFHITUIT-UHFFFAOYSA-N 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 125000002524 organometallic group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 84
- 239000000047 product Substances 0.000 description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- 238000005481 NMR spectroscopy Methods 0.000 description 22
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 21
- 239000012295 chemical reaction liquid Substances 0.000 description 21
- 238000002474 experimental method Methods 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 238000004440 column chromatography Methods 0.000 description 17
- 238000012805 post-processing Methods 0.000 description 17
- 239000000741 silica gel Substances 0.000 description 17
- 229910002027 silica gel Inorganic materials 0.000 description 17
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 16
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 150000002220 fluorenes Chemical class 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HKMTVMBEALTRRR-UHFFFAOYSA-N Benzo[a]fluorene Chemical class C1=CC=CC2=C3CC4=CC=CC=C4C3=CC=C21 HKMTVMBEALTRRR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- HAPOJKSPCGLOOD-UHFFFAOYSA-N Benzo[b]fluorene Chemical class C1=CC=C2C=C3CC4=CC=CC=C4C3=CC2=C1 HAPOJKSPCGLOOD-UHFFFAOYSA-N 0.000 description 2
- FRIJWEQBTIZQMD-UHFFFAOYSA-N Benzo[c]fluorene Chemical compound C1=CC2=CC=CC=C2C2=C1CC1=CC=CC=C12 FRIJWEQBTIZQMD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N benzofuran Natural products C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 238000007154 radical cyclization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- LDCVEPMPZLHMMK-UHFFFAOYSA-N 11h-benzo[a]fluoren-1-ol Chemical class C1=CC=C2CC3=C4C(O)=CC=CC4=CC=C3C2=C1 LDCVEPMPZLHMMK-UHFFFAOYSA-N 0.000 description 1
- ZKOORZPQGPMQPC-UHFFFAOYSA-N COc(cc1)ccc1-c(c1c2-c3ccccc3C1=O)c(cccc1)c1c2Br Chemical compound COc(cc1)ccc1-c(c1c2-c3ccccc3C1=O)c(cccc1)c1c2Br ZKOORZPQGPMQPC-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- BMXFEOSAVZSEOZ-UHFFFAOYSA-N Ninamycin D Natural products O=C1C2=CC=CC(O)=C2C(=O)C(N2C#N)=C1C1=C2C(OC(C)=O)C(O)(C)C(OC(=O)C)C1O BMXFEOSAVZSEOZ-UHFFFAOYSA-N 0.000 description 1
- 241000187747 Streptomyces Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229940045799 anthracyclines and related substance Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007366 cycloisomerization reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 229930186097 fluostatin Natural products 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- KPVVXTRWIKTJBS-DXBBTUNJSA-N kinamycin D Chemical compound O=C1C2=CC=CC(O)=C2C(=O)C(C2=[N+]=[N-])=C1C1=C2[C@@H](OC(C)=O)[C@](O)(C)[C@H](OC(=O)C)[C@H]1O KPVVXTRWIKTJBS-DXBBTUNJSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000007832 transition metal-catalyzed coupling reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
一种制备卤代苯并[b]芴酮系列化合物的方法,该方法采1‑(2‑(芳乙炔基)苯基)丙‑2‑炔‑1‑酮类化合物作为反应底物,在催化剂的辅助下与N‑卤代丁二酰亚胺发生反应,高效制得苯并芴酮结构骨架的5‑位具有一个卤素原子的5‑卤代苯并[b]芴酮系列化合物。所得产物分子骨架上引入的卤素原子可以作为多功能合成子,从而通过有机偶联反应在该位置引入其他各种官能团。所得产物具有醌那霉素类药物的核心骨架结构,可望作为该类药物合成的重要中间体。同时由于产物具有大π共轭平面结构,因此可望用于光电功能材料或电致发光材料领域。本方法化学选择性高,底物适用性广,操作简便、反应时间短,产率高、便于分离提纯、可适用于较大规模的制备。
Description
技术领域
本发明属有机化学技术领域,具体涉及一种制备5-卤代苯并[b]芴酮系列化合物的方法。
背景技术
苯并芴类化合物广泛应用于药物及药物合成中。例如,醌那霉素(Kinamycin)类抗生素具有显著的抑菌以及抗肿瘤活性,最早由Omura等人于1970年从链霉菌Streptomyces发酵液中分离得到一种角蒽环类聚酮,该物质分子所具有的苯并[b]芴结构在自然界中是被首次发现。醌那霉素类天然产物主要包括:醌那霉素(Gould,S.Chem.Rev.1997,97,2499.),抗生素Fluostatins(HerzonS.B.2012,Natural Product Reports,29(1):87-118)和化疗药物Lomaiviticins(KerstenR.D.,2013,Hembiochem,14(8):955-962)。醌那霉素D分子含有苯并[b]芴四元并环以及一个重氮结构,该物质具有强效的抗革兰氏阳性菌活性((a)Gould,S.;J.Am.Chem.Soc.1994,116,2207.(b)Mithani,S.;J.Am.Chem.Soc.1994,116,2209.(c)Gould,S.;Bioorg.Med.Chem.Lett.1995,5,51)。Lomaiviticin作为醌那霉素类化合物的新近成员,其由两个类似醌那霉素的结构单体通过C-C键交联而成,研究表明其在n M-p M浓度级别已具有显著生物活性(Woo,C.M.Angew.Chem.2014,53(35):9325-9328)。醌那霉素类化合物因其良好的生物活性,独特的苯并芴结构引起了各方持续的研究兴趣。
此外,由于芴化合物本身具有的大π共轭的平面结构,以及非常高的荧光量子效率,因此在光电功能材料领域具有十分重要的用途。目前,含芴结构的小分子化合物或聚合物已被广泛用作光电功能材料领域((a)Shimizu,A.;Angew.Chem.Int.Ed.2011,50,6906;(b)Allard,S.;Angew.Chem.Int.Ed.2008,47,4070;(c)Anthony,J.E.Chem.Rev.2006,106,5028;(d)Anthony,J.E.Angew.Chem.Int.Ed.2008,47,452.)。苯并芴结构增大了芴环的平面面积,用做光电功能材料时,分子内的官能团例如叔丁基能有效防止芳香环之间的π-π堆积,因此能够有效地抑制荧光猝灭,保证发光的颜色单纯性,同时有效地延长器件的寿命。最近,苯并芴衍生物已经成功地应用于光学器件((a)Karolis,K.;Appl.Phys.Lett.2015,107,43301.(b)Karolis,K.;J.Phys.Chem.Chem.Phys.2015,17,12935.)。
文献报道的合成此类化合物的方法却十分有限,并且反应都存在着一些局限性。早期的自由基热芳构化反应需要将反应原料加热到140℃以上发生反应才能得到预期的苯并[b]芴类化合物,此方法效率低,对于官能团兼容性差,并且构造异构体难以分离((a)Rodríguez,D.;Org.Lett.2000,2,1497.(b)Rodríguez,D.;Tetrahedron Lett.2002,43,2717)。利用1-(2-(苯基乙炔基)苯基)-3-(三甲基甲硅烷)丙-2-炔-1-酮类化合物在甲苯中发生分子内的脱氢自由基环合反应,可用于合成苯并[b]芴和苯并[c]芴类衍生物,然而此方法仍需要的反应温度高达150度(Rodríguez,D.J.Org.Chem.2004,69,3842.);改进的方法利用芳香的乙醛肟醚类和芳基卤代物在甲苯中回流温度下,通过钯催化双碳氢键活化Heck环化反应直接构建芴酮类衍生物(Thirunavukkarasu,V.;Angew.Chem.Int.Ed.2008,47,9462)。此几种方法需要将反应物加热到比较高的温度才能发生转化,条件比较苛刻,并且反应时间较长,高温下对官能团的兼容性比较差,难以大规模地生产和应用。
最近我们小组发展了新的方法,在温和的条件下可以快速合成苯并芴类化合物。采用3-芳基基-1-(2-(2-芳乙炔基)苯基)炔丙基-2-醇作为反应底物,使其在过渡金属银盐作为催化剂的条件下,可与卤素亲电试剂在10度至室温的条件下发生反应,一锅法高效率、高化学选择性地制得含卤素的苯并[a]芴醇衍生物(陈知远,贾学功等,中国专利,ZL201210144087.0)。此外,我们还成功发展了利用非金属氧化剂DDQ诱导串联环异构化反应,利用1,1-二芳基-3-(2-(对甲苯基乙炔基)苯基)丙-2-炔-1-醇作为反应底物,无需任何金属元素参与,即可高效地合成苯并[b]芴酮系列化合物(陈知远,朱辉等,中国专利,ZL201510700797.0)。此两种反应对于合成苯并芴骨架的系列化合物具有十分重要的意义。然而,反应所得的四元环系骨架上直接引入了多个芳基或烷基基团,而对于可作为合成子的官能团如卤素则需要在反应底物设计时预先引入才能得到保留,此举无疑增加了合成了步骤,降低了合成效率。中国专利CN106278856A报道了一种合成取代苯并芴酮类化合物的合成方法,然而由于所用的原料包含硅乙炔基,因此利用该方法所得的苯并[b]芴酮产物骨架的5-位只能是氢原子,意味着无法通过化学反应在此位置引入其他的官能团。
发明内容
为了解决背景技术中提到问题,最近,我们通过研究发现,利用1-(2-(芳乙炔基)苯基)丙-2-炔-1-酮类化合物作为反应底物,可在微量路易斯酸催化剂的催化作用下与N-卤代丁二酰亚胺发生自由基环化反应,一锅法高效率地合成苯并芴产物,同时更重要的是在其核心骨架上引入了卤素。卤素原子的存在意味着在该位置可通过过渡金属催化的偶联反应引入多种有机官能团,因此具有重要的合成意义和应用价值。
根据研究成果,我们总结出以下技术方案:
一种制备卤代苯并[b]芴酮系列化合物的方法,其特征在于:在有机溶剂中,采用1-(2-(芳乙炔基)苯基)丙-2-炔-1-酮类化合物作为反应底物,使其在路易斯酸的催化作用下,于一定温度下与N-卤代丁酰亚胺发生分子内的自由基串联环异构化反应,高效制得卤代苯并[b]芴酮系列化合物。反应通式如下:
式中,R1、R2、R3分别为H或烷基、烷氧基、环烷基、烷氨基、二烷氨基等各种供电子基团,或卤素(氟、氯、溴、碘)、酯基、硝基、氰基、酰胺基等各种吸电子基团,或呋喃基、噻吩基、吡啶基、烯基、炔基、硅基。X为卤素原子,包括氟、氯、溴、碘。
所述的有机溶剂为四氢呋喃、乙醚、乙酸乙酯、甲苯、乙腈、1,2-二氯乙烷或二氯甲烷。
所述的路易斯酸为硫酸铜、三氟甲磺酸镁、醋酸镁、醋酸锌、醋酸亚铁、三氟甲磺酸锌、三氟甲磺酸镁、硫酸亚铁、三氟甲磺酸亚铁、三氟甲磺酸铁、醋酸亚铁、六水合草酸铁或七水硫酸亚铁。
所述的N-卤代丁酰亚胺为N-氟代丁酰亚胺、N-氯代丁酰亚胺、N-溴代丁酰亚胺或N-碘代丁酰亚胺。
反应温度的控制可以采用油浴锅等加热模式,反应温度为50~120℃,优选为80℃;反应时长为2~12小时。
在本发明中,反应的原子经济性很高,反应物1-(2-(芳乙炔基)苯基)丙-2-炔-1-酮与N-卤代丁酰亚胺的比例为1:1.05~1:3.0就能非常顺利地进行,由此反应体现出良好的绿色化。本发明的方法化学选择性高、反应条件温和、操作简便、成本较低、副反应少、产品纯度高、便于分离提纯,可适合于较大规模的制备。
本发明的产品卤代苯并[b]芴酮系列化合物具有抗生素醌那霉素类药物的核心结构骨架,具有潜在的生物或药物活性;此外,产品所具有的大π共轭的平面结构以及芴衍生物高的荧光量子效率,使其具有良好的光电功能特性,因此也是一类潜在的荧光发射材料。所得产品分子骨架上5-位引入的卤素原子,可以作为多功能合成子,通过产品分子中的卤素原子能方便地进一步修饰,引入其他的各种官能团。产品可以应用于生物医药或农药光电功能材料、电致发光材料等领域,具有非常好的应用前景。
附图说明
图1是根据本发明方法所得产物5-卤代-11H-苯并[b]芴-11-酮系列化合物的结构通式。
图2是本发明实施例六的产物5-溴-8-正丁基-10-苯基-11H-苯并[b]芴-11-酮化合物的单晶结构示意图。
图3是本发明实施例六的产物5-溴-8-正丁基-10-苯基-11H-苯并[b]芴-11-酮化合物的结构式。
具体实施方式
下面的实施例是对本发明的进一步说明,而不是限制本发明的范围。
实施例一:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(176mg,1.0mmol)、3-苯基-1-(2-(p-甲苯基乙炔基)苯基)丙-2-炔基-1-酮(160mg,0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全。反应完毕,将反应液冷却至室温,碳酸钠稀溶液洗涤除掉催化剂,有机相浓缩后过柱分离得纯净的产品5-溴-8-甲基-10-芳基(烷基)-11H-苯并[b]呋喃-11-酮,产品重量178mg,产率89%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.74(d,J=7.6Hz,1H),8.31(d,J=8.4Hz,1H),7.65(d,J=7.6Hz,1H),7.61(td,J=1.0Hz,7.8Hz,1H),7.55(dd,J=3.5Hz,6.8Hz,3H),7.48(d,J=8.4Hz,1H),7.39-7.30(m,4H),2.39(s,3H).
13C NMR(100MHz,CDCl3)δ191.2,144.0,140.2,137.8,136.7,136.2,135.4,134.8,134.6,133.9,132.0,130.1,129.4,128.6,128.1,127.80(s),124.7,124.1,117.8,21.5
实施例二:
在一个装有磁力搅拌子的500mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(775mg,5mmol)、N-溴代丁酰亚胺(17.6g,100mmol)、3-苯基-1-(2-(p-甲苯基乙炔基)苯基)丙-2-炔基-1-酮(16.0g,50mmol)和乙酸乙酯(250mL),氮气保护。将反应液置于80℃的油浴锅中反应约4h,TLC检测至反应完全,然后将反应液冷却至室温,碳酸钠稀溶液洗涤除掉催化剂,有机浓缩后用石油醚洗涤除掉丁二酰亚胺副产物,乙醇重结晶得纯净的产品5-溴-8-甲基-10-芳基(烷基)-11H-苯并[b]呋喃-11-酮,产品重量16.7g,产率84%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.74(d,J=7.6Hz,1H),8.31(d,J=8.4Hz,1H),7.65(d,J=7.6Hz,1H),7.61(td,J=1.0Hz,7.8Hz,1H),7.55(dd,J=3.5Hz,6.8Hz,3H),7.48(d,J=8.4Hz,1H),7.39-7.30(m,4H),2.39(s,3H).
13C NMR(100MHz,CDCl3)δ191.2,144.0,140.2,137.8,136.7,136.2,135.4,134.8,134.6,133.9,132.0,130.1,129.4,128.6,128.1,127.80(s),124.7,124.1,117.8,21.5
实施例三:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂醋酸铜(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、3-苯基-1-(2-(苯基乙炔基)苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-10-苯基-11H-苯并[b]呋喃-11-酮,产率84%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.78(s,1H),8.43(d,J=6.8Hz,1H),7.64(d,J=16.3Hz,4H),7.54(s,3H),7.47-7.37(m,2H),7.33(s,2H).
13C NMR(100MHz,CDCl3)δ191.1,143.9,141.3,140.7,137.1,136.7,135.7,135.2,134.68,130.0,129.7,129.4,128.2,127.9,127.6,124.9 124.2,117.9.
实施例四:
在一个装有机械搅拌子的3000mL耐压反应瓶中,加入催化剂三氟甲磺酸镁(16.1g,5mol%)、N-溴代丁酰亚胺(354g,1.5mol)、3-苯基-1-(2-(苯基乙炔基)苯基)丙-2-炔基-1-酮(306g,1mol)和乙酸乙酯(1500mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温,碳酸钠稀溶液洗涤除掉催化剂,有机浓缩后用石油醚洗涤除掉丁二酰亚胺副产物,乙醇重结晶得纯净的产品5-溴-10-苯基-11H-苯并[b]呋喃-11-酮。产品称重307g,产率80%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.78(s,1H),8.43(d,J=6.8Hz,1H),7.64(d,J=16.3Hz,4H),7.54(s,3H),7.47-7.37(m,2H),7.33(s,2H).
13C NMR(100MHz,CDCl3)δ191.1,143.9,141.3,140.7,137.1,136.7,135.7,135.2,134.68,130.0,129.7,129.4,128.2,127.9,127.6,124.9 124.2,117.9.
实施例五:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、1-(2((4-甲氧基苯基)乙炔基)苯基)-3-苯基丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,碳酸钠稀溶液洗涤除掉催化剂,有机浓缩后用石油醚洗涤除掉丁二酰亚胺副产物,乙醇重结晶分离得纯净的产品5-溴-8-甲氧基-10-苯基-11H-苯并[b]呋喃-11-酮,产率82%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.69(d,J=8.0Hz,1H),8.32(d,J=9.2Hz,1H),7.63(d,J=7.6Hz,1H),7.59(t,J=7.6Hz,1H),7.55–7.50(m,3H),7.36-7.30(m,3H),7.28(dd,J=2.5Hz,9.3Hz,1H),6.91(d,J=2.4Hz,1H),3.69(s,3H).
13C NMR(100MHz,CDCl3)δ191.3,159.0,144.2,139.5,136.3,135.4,135.1,134.6,130.6,129.3,128.2,124.4,124.1,121.0,117.7,108.9,55.32.
实施例六:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、1-(2((4-正丁基苯基)乙炔基)苯基)-3-苯基丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-8-正丁基-10-苯基-11H-苯并[b]呋喃-11-酮,产率91%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.74(d,J=7.6Hz,1H),8.33(d,J=8.4Hz,1H),7.65(d,J=7.6Hz,1H),7.61(t,J=7.6Hz,1H),7.55-7.54(m,3H),7.51(d,J=8.8Hz,1H),7.39-7.30(m,4H),2.64(t,J=7.6Hz,2H),1.60-1.49(m,2H),1.37-1.24(m,2H),0.88(t,J=7.2Hz,3H).
13C NMR(100MHz,CDCl3)δ191.2,144.0,142.7,140.3,136.7,136.2,135.4,134.8,134.5,134.1,131.3,130.1,129.4,128.3,128.0,127.9,124.7,124.1,117.8,35.5,33.3,22.3,13.9.
实施例七:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、1-(2((4-氟苯基)乙炔基)苯基)-3-苯基丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-8-氟-10-苯基-11H-苯并[b]呋喃-11-酮,产率83%。以下是产物核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.71(d,J=8.0Hz,1H),8.41(dd,J=5.5Hz,9.3Hz,1H),7.65(d,J=7.6Hz,1H),7.61(t,J=7.6Hz,1H),7.57–7.52(m,3H),7.42–7.35(m,2H),7.30(dd,J=2.9Hz,6.4Hz,2H),7.23(dd,J=2.9Hz,10.7Hz,1H).
13C NMR(100MHz,CDCl3)δ190.8,163.1,160.6,143.8,139.8,136.4,134.7,132.5,130.9,130.5,129.7,129.3,128.4,124.7,124.3,119.5,119.3,117.5,113.4,113.2.
实施例八:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、1-(2((4-氯苯基)乙炔基)苯基)-3-苯基丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-8-氯-10-苯基-11H-苯并[b]呋喃-11-酮,产率87%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.72(d,J=7.8Hz,1H),8.34(d,J=8.8Hz,1H),7.66(d,J=7.2Hz,1H),7.61(t,J=7.8Hz,1H),7.56(dd,J=2.1Hz,11.3Hz,5H),7.38(t,J=7.4Hz,1H),7.30(dd,J=2.8Hz,6.2Hz,2H).
13C NMR(100MHz,CDCl3)δ190.7,143.6,139.6,137.4,136.6,135.6,134.7,134.5,134.2,134.0,130.9,130.5,129.9,129.5,129.4,128.5,128.4,128.1,124.8,124.3,117.4.
实施例九:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、1-(2((4-溴苯基)乙炔基)苯基)-3-苯基丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5,8-二溴-10-苯基-11H-苯并[b]呋喃-11-酮,产率83%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.72(d,J=7.6Hz,1H),8.27(d,J=8.4Hz,1H),7.71(d,J=7.6Hz,2H),7.66(d,J=7.6Hz,1H),7.61(t,J=7.6Hz,1H),7.55(s,3H),7.39(t,J=7.2Hz,1H),7.31(s,2H).
13C NMR(100MHz,CDCl3)δ190.6,143.6,139.6,137.5,136.6,135.9,134.8,134.4,134.3,133.1,131.3,130.9,129.9,129.5,129.4,128.5,128.4,124.9,124.3,122.5,117.5.
实施例十:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、1-(2-(苯乙炔基)苯基-3-(p-甲苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-10-(p-甲苯基)-11H-苯并[b]呋喃-11-酮,产率80%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.74(d,J=8.0Hz,1H),8.40(d,J=8.8Hz,1H),7.66-7.47(m,4H),7.44–7.38(m,1H),7.38–7.32(m,3H),7.21(d,J=8.0Hz,2H),2.49(s,3H).
13C NMR(100MHz,CDCl3)δ191.1,143.8,140.9,137.9,137.1,136.8,135.7,134.9,134.5,132.1,130.1,129.8,129.6,129.5,129.4,129.0,127.9,127.5,124.8,124.2,117.7.
实施例十一:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、3-(4-甲氧基苯基)-1-(2-(苯乙炔基)苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-10-(4-甲氧基苯基)-11H-苯并[b]呋喃-11-酮,产率73%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.76(d,J=7.6Hz,1H),8.42(d,J=8.4Hz,1H),7.69–7.66(m,2H),7.65-7.59(m,2H),7.46-7.40(m,1H),7.38(t,J=7.3Hz,1H),7.28-7.24(m,2H),7.07(d,J=8.6Hz,2H),3.92(s,3H).
13C NMR(100MHz,CDCl3)δ191.2,159.6,143.8,140.7,137.2,136.8,135.7,135.1,134.5,130.8,130.1,129.9,129.6,127.9,127.6,127.1,124.9,124.2,117.7,113.7,55.3
实施例十二:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、3-(4-正丁基苯基)-1-(2-(苯乙炔基)苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-10-(4-正丁基苯基)-11H-苯并[b]呋喃-11-酮,产率78%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.68(d,J=8.0Hz,1H),8.36–8.31(m,1H),7.60–7.50(m,4H),7.37–7.32(m,1H),7.28(dd,J=7.7Hz,12.9Hz,3H),7.16(t,J=5.6Hz,2H),2.71–2.64(m,2H),1.70–1.61(m,2H),1.44–1.32(m,2H),0.92(t,J=7.3Hz,3H).
13C NMR(100MHz,CDCl3)δ191.2,143.9,142.8,141.0,137.1,136.8,135.7,135.0,134.5,132.3,130.0,129.9,129.6,129.5,129.3,128.2,127.9,127.5,124.9,124.2,117.7,35.7,33.5,22.6,14.1.
实施例十三:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、3-(4-氟苯基)-1-(2-(苯乙炔基)苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-10-(4-氟苯基)-11H-苯并[b]呋喃-11-酮,产率84%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.76(d,J=7.6Hz,1H),8.43(d,J=8.4Hz,1H),7.69–7.64(m,2H),7.60(dd,J=8.0Hz,14.6Hz,2H),7.45(t,J=7.6Hz,1H),7.39(t,J=7.6Hz,1H),7.32–7.27(m,2H),7.24(d,J=8.8Hz,2H).
13C NMR(100MHz,CDCl3)δ191.1,143.8,139.5,137.1,136.7,135.77,134.77,131.3,130.91,130.1,129.8,129.18,128.08,127.78,124.98,124.28,118.1,115.5,115.2.
实施例十四:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、3-(4-氯苯基)-1-(2-(苯乙炔基)苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-10-(4-氯苯基)-11H-苯并[b]呋喃-11-酮,产率83%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.68(d,J=8.0Hz,1H),8.35(d,J=8.4Hz,1H),7.59(d,J=6.4Hz,2H),7.54(d,J=7.6Hz,1H),7.48(d,J=8.4Hz,1H),7.43(d,J=8.0Hz,2H),7.39–7.34(m,1H),7.31(t,J=7.2Hz,1H),7.18(d,J=8.0Hz,2H).
13C NMR(100MHz,CDCl3)δ191.0,143.8,139.2,137.1,136.6,135.7,134.7,134.5,134.3,133.8,133.6,130.9,130.1,129.8,129.0,128.6,128.0,127.8,124.9,124.2,118.2.
实施例十五:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、3-(4-溴苯基)-1-(2-(苯乙炔基)苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约2h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-10-(4-溴苯基)-11H-苯并[b]呋喃-11-酮,产率80%。以下是产物的核磁共振实验数据:
H NMR(400MHz,CDCl3)δ8.68(d,J=8.0Hz,1H),8.35(d,J=8.4Hz,1H),7.59(d,J=7.6Hz,4H),7.54(d,J=7.6Hz,1H),7.48(d,J=8.4Hz,1H),7.41–7.34(m,1H),7.31(t,J=7.2Hz,1H),7.13(d,J=8.0Hz,2H).
13C NMR(100MHz,CDCl3)δ191.0,143.8,139.1,137.1,136.6),135.7,134.8,134.4,134.1,131.5,131.2,130.1,129.8,129.0,128.0,127.8,124.9,124.2,122.5,118.2.
实施例十六:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、3-环丙基-1-(2-(苯乙炔基)苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于100℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-10-环丙基-11H-苯并[b]呋喃-11-酮,产率71%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.60(dd,J=8.1Hz,15.9Hz,2H),8.26(d,J=8.4Hz,1H),7.69(d,J=7.2Hz,1H),7.58–7.43(m,3H),7.31(t,J=7.2Hz,1H),2.17–2.06(m,1H),1.31(d,J=8.0Hz,2H),0.58(d,J=5.2Hz,2H).
13C NMR(100MHz,CDCl3)δ191.56,143.5,142.7,137.2,136.9,135.7,135.4,134.3,132.9,129.6,129.5,128.4,128.1,127.2,124.8,124.0,117.3,10.0,9.8.
实施例十七:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、1-(2-(苯乙炔基)苯基)-3-(噻吩-2-基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-10-(噻吩-2-基)-11H-苯并[b]呋喃-11-酮,产率69%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ7.59(t,J=6.6Hz,2H),7.53–7.47(m,3H),7.40(dd,J=3.1Hz,6.9Hz,3H),7.15–7.04(m,2H),6.38(d,J=7.5Hz,1H).
13C NMR(100MHz,CDCl3)δ190.9,148.1,142.8,140.7,137.7,136.8,135.8,134.4,131.3,129.5,129.2,129.0,128.9,128.8,128.7,126.1,124.4,123.0,115.6.
实施例十八:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、3-(p-甲苯基)-1-(2-(p-甲苯基乙炔基)苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-8-甲基-10-(p-甲苯基)-11H-苯并[b]呋喃-11-酮,产率82%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.72(d,J=7.6Hz,1H),8.29(d,J=8.8Hz,1H),7.64(d,J=7.2Hz,1H),7.59(t,J=7.6Hz,1H),7.46(d,J=8.4Hz,1H),7.39(s,1H),7.35(d,J=7.6Hz,3H),7.21(d,J=7.6Hz,2H),2.50(s,3H),2.39(s,3H).
13C NMR(100MHz,CDCl3)δ191.2,144.0,140.4,137.7,136.7,136.3,135.0,134.5,133.9,132.3,131.9,130.2,129.4,129.4,129.0,128.7,127.8,124.7,124.1,117.7,21.5,21.4.
实施例十九:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、3-(4-氯苯基)-1-(2-(p-甲苯基乙炔基)苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-10-(4-氯苯基)-8-甲基-11H-苯并[b]呋喃-11-酮,产率94%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.71(d,J=8.0Hz,1H),8.29(d,J=8.4Hz,1H),7.64(d,J=7.2Hz,1H),7.60(t,J=7.6Hz,1H),7.51(d,J=8.0Hz,2H),7.48(d,J=8.8Hz,1H),7.36(t,J=7.4Hz,1H),7.30(s,1H),7.25(d,J=8.0Hz,2H),2.40(s,3H).
13C NMR(100MHz,CDCl3)δ191.1,144.0,138.7,138.1,136.5,136.2,134.7,134.5,134.2,133.9,133.8,132.1,130.9,130.2,129.5,128.6,128.2,127.9,124.7,124.2118.1,21.5.
实施例二十:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、3-(4-氯苯基)-1-((2-(4-氯苯基)乙炔基)苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5-溴-8-氯-10-(4-氯苯基)-11H-苯并[b]呋喃-11-酮,产率96%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.71(d,J=7.8Hz,1H),8.34(d,J=8.8Hz,1H),7.66(d,J=7.6Hz,1H),7.62(dd,J=4.5Hz,12.1Hz,1H),7.58(dd,J=1.9Hz,9.1Hz,1H),7.53(d,J=8.4Hz,2H),7.50(d,J=1.8Hz,1H),7.39(t,J=7.4Hz,1H),7.24(d,J=8.4Hz,2H).
13C NMR(101MHz,CDCl3)δ190.6,143.6,138.1,137.3,136.4,135.3,134.9,134.7,134.4,134.0,132.8,131.0,130.9,130.6,130.0(s),129.6,128.8,127.7,124.9,124.4,117.8.
实施例二十一:
在一个装有磁力搅拌子的25mL耐压反应管中,加入催化剂Fe(C2O4)·6H2O(0.05mmol)、N-溴代丁酰亚胺(0.1mmol)、1-(2-((4-溴苯基)乙炔基)苯基)-3-(p-甲苯基)丙-2-炔基-1-酮(0.5mmol)和乙酸乙酯(10mL),氮气保护。将反应液置于80℃的油浴锅中反应约3h,TLC检测至反应完全,然后将反应液冷却至室温。后处理时先通过装有硅胶的砂芯漏斗抽滤除掉催化剂,所得滤液通过快速柱层析分离得纯净的产品5,8-二溴-10-(p-甲苯基)-11H-苯并[b]呋喃-11-酮,产率96%。以下是产物的核磁共振实验数据:
1H NMR(400MHz,CDCl3)δ8.72(d,J=7.6Hz,1H),8.26(d,J=9.2Hz,1H),7.76(d,J=1.8Hz,1H),7.70(dd,J=1.3Hz,9.0Hz,1H),7.66(d,J=7.6Hz,1H),7.61(t,J=7.6Hz,1H),7.39(d,J=7.6Hz,1H),7.36(d,J=7.6Hz,2H),7.19(d,J=8.0Hz,2H),2.51(s,3H).
13C NMR(100MHz,CDCl3)δ190.7,143.6,139.9,138.2,137.5,136.7,136.1,134.7,134.3,133.1,131.3,130.9,129.9,129.5,129.2,124.9,124.3,122.4,117.4,21.5.
Claims (11)
1.一种制备卤代苯并[b]芴酮系列化合物的方法,其特征在于:在有机溶剂中,以路易斯酸为催化剂,使结构如式I所示的1-(2-(芳乙炔基)苯基)丙-2-炔-1-酮类化合物与N-卤代丁酰亚胺发生反应,得到结构如式II所示的卤代苯并[b]芴酮系列化合物;
式中,X为卤素;
R1、R2、R3独立地选自H、烷基、烷氧基、环烷基、烷氨基、二烷氨基,或者独立地选自氟、氯、溴、碘、酯基、硝基、氰基、酰胺基,或者独立地选自呋喃基、噻吩基、吡啶基、烯基、炔基、硅基。
2.根据权利要求1所述的方法,其特征在于:所述的催化剂选自硫酸铜、三氟甲磺酸镁、醋酸镁、醋酸锌、醋酸亚铁、三氟甲磺酸锌、三氟甲磺酸镁、硫酸亚铁、三氟甲磺酸亚铁、三氟甲磺酸铁、醋酸亚铁、六水合草酸铁、七水硫酸亚铁。
3.根据权利要求1所述的方法,其特征在于:所述的有机溶剂选自乙醚、乙酸乙酯、四氢呋喃、二氧六环、甲苯、乙腈、1,2-二氯乙烷、二氯甲烷、氯仿。
4.根据权利要求1所述的方法,其特征在于:所述的N-卤代丁酰亚胺为N-氟代丁酰亚胺、N-氯代丁酰亚胺、N-溴代丁酰亚胺或N-碘代丁酰亚胺,式中X为氟、氯、溴或碘。
5.根据权利要求1所述的方法,其特征在于:1-(2-(芳乙炔基)苯基)丙-2-炔-1-酮与N-卤代丁酰亚胺的摩尔数比例为1:1.2至1:3.0。
6.根据权利要求1所述的方法,其特征在于:反应的温度采用油浴加热控制,反应温度为50~120℃。
7.根据权利要求6所述的方法,其特征在于:反应温度为80℃。
8.根据权利要求1所述的方法,其特征在于:反应时间为2~12小时。
9.卤代苯并[b]芴酮系列化合物,其特征在于:根据权利要求1~8任一权利要求所述的方法制备得到。
10.根据权利要求9所述的卤代苯并[b]芴酮系列化合物作为荧光发射材料的应用。
11.根据权利要求9所述的卤代苯并[b]芴酮系列化合物在医药或农药领域中的应用。
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