CN115925527B - Method for preparing alpha-diaryl methyl substituted ketone compound - Google Patents
Method for preparing alpha-diaryl methyl substituted ketone compound Download PDFInfo
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- CN115925527B CN115925527B CN202310019132.8A CN202310019132A CN115925527B CN 115925527 B CN115925527 B CN 115925527B CN 202310019132 A CN202310019132 A CN 202310019132A CN 115925527 B CN115925527 B CN 115925527B
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- mmol
- tert
- butyl
- cyclohexadien
- methylene
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- -1 ketone compound Chemical class 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 157
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 152
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 76
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 239000013110 organic ligand Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 162
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 144
- 229910052757 nitrogen Inorganic materials 0.000 claims description 98
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 62
- HCUWXYBKPSKTAB-UHFFFAOYSA-N 4-benzylidene-2,6-ditert-butylcyclohexa-2,5-dien-1-one Chemical compound C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=CC1=CC1=CC=CC=C1 HCUWXYBKPSKTAB-UHFFFAOYSA-N 0.000 claims description 46
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 claims description 6
- BMHMKWXYXFBWMI-UHFFFAOYSA-N 3,4-Methylenedioxyacetophenone Chemical compound CC(=O)C1=CC=C2OCOC2=C1 BMHMKWXYXFBWMI-UHFFFAOYSA-N 0.000 claims description 6
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 claims description 6
- ZAJNGDIORYACQU-UHFFFAOYSA-N decan-2-one Chemical compound CCCCCCCCC(C)=O ZAJNGDIORYACQU-UHFFFAOYSA-N 0.000 claims description 6
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 6
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 claims description 5
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 5
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 4
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 4
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 claims description 4
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 4
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims description 4
- UMTUIVWGEMXRKH-UHFFFAOYSA-N C(C)C1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound C(C)C1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C UMTUIVWGEMXRKH-UHFFFAOYSA-N 0.000 claims description 4
- PZSYEZUGGGAMTF-UHFFFAOYSA-N CC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound CC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C PZSYEZUGGGAMTF-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 4
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- HSDSKVWQTONQBJ-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C)C=C1C HSDSKVWQTONQBJ-UHFFFAOYSA-N 0.000 claims description 3
- PIMNFNXBTGPCIL-UHFFFAOYSA-N 1-(2-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1Br PIMNFNXBTGPCIL-UHFFFAOYSA-N 0.000 claims description 3
- XDXCBCXNCQGZPG-UHFFFAOYSA-N 1-(2-iodophenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1I XDXCBCXNCQGZPG-UHFFFAOYSA-N 0.000 claims description 3
- DWPLEOPKBWNPQV-UHFFFAOYSA-N 1-(2-methoxyphenyl)ethanone Chemical compound COC1=CC=CC=C1C(C)=O DWPLEOPKBWNPQV-UHFFFAOYSA-N 0.000 claims description 3
- HCEKGPAHZCYRBZ-UHFFFAOYSA-N 1-(3-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1 HCEKGPAHZCYRBZ-UHFFFAOYSA-N 0.000 claims description 3
- BAYUSCHCCGXLAY-UHFFFAOYSA-N 1-(3-methoxyphenyl)ethanone Chemical compound COC1=CC=CC(C(C)=O)=C1 BAYUSCHCCGXLAY-UHFFFAOYSA-N 0.000 claims description 3
- ARKIFHPFTHVKDT-UHFFFAOYSA-N 1-(3-nitrophenyl)ethanone Chemical compound CC(=O)C1=CC=CC([N+]([O-])=O)=C1 ARKIFHPFTHVKDT-UHFFFAOYSA-N 0.000 claims description 3
- YJFNFQHMQJCPRG-UHFFFAOYSA-N 1-(4-ethoxyphenyl)ethanone Chemical compound CCOC1=CC=C(C(C)=O)C=C1 YJFNFQHMQJCPRG-UHFFFAOYSA-N 0.000 claims description 3
- ZDPAWHACYDRYIW-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1 ZDPAWHACYDRYIW-UHFFFAOYSA-N 0.000 claims description 3
- JZJWCDQGIPQBAO-UHFFFAOYSA-N 1-(4-iodophenyl)ethanone Chemical compound CC(=O)C1=CC=C(I)C=C1 JZJWCDQGIPQBAO-UHFFFAOYSA-N 0.000 claims description 3
- JECUZQLBQKNEMW-UHFFFAOYSA-N 1-(4-methylsulfanylphenyl)ethanone Chemical compound CSC1=CC=C(C(C)=O)C=C1 JECUZQLBQKNEMW-UHFFFAOYSA-N 0.000 claims description 3
- DJNIFZYQFLFGDT-UHFFFAOYSA-N 1-(4-phenoxyphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1OC1=CC=CC=C1 DJNIFZYQFLFGDT-UHFFFAOYSA-N 0.000 claims description 3
- QCZZSANNLWPGEA-UHFFFAOYSA-N 1-(4-phenylphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1C1=CC=CC=C1 QCZZSANNLWPGEA-UHFFFAOYSA-N 0.000 claims description 3
- UYFJYGWNYQCHOB-UHFFFAOYSA-N 1-(4-tert-butylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)(C)C)C=C1 UYFJYGWNYQCHOB-UHFFFAOYSA-N 0.000 claims description 3
- ABXGMGUHGLQMAW-UHFFFAOYSA-N 1-[3-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=CC(C(F)(F)F)=C1 ABXGMGUHGLQMAW-UHFFFAOYSA-N 0.000 claims description 3
- KEAGRYYGYWZVPC-UHFFFAOYSA-N 1-[4-(2-methylpropyl)phenyl]ethanone Chemical compound CC(C)CC1=CC=C(C(C)=O)C=C1 KEAGRYYGYWZVPC-UHFFFAOYSA-N 0.000 claims description 3
- HHAISVSEJFEWBZ-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=C(C(F)(F)F)C=C1 HHAISVSEJFEWBZ-UHFFFAOYSA-N 0.000 claims description 3
- HVCFCNAITDHQFX-UHFFFAOYSA-N 1-cyclopropylethanone Chemical compound CC(=O)C1CC1 HVCFCNAITDHQFX-UHFFFAOYSA-N 0.000 claims description 3
- GKDLTXYXODKDEA-UHFFFAOYSA-N 1-phenylbutan-2-one Chemical compound CCC(=O)CC1=CC=CC=C1 GKDLTXYXODKDEA-UHFFFAOYSA-N 0.000 claims description 3
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 claims description 3
- YXWWHNCQZBVZPV-UHFFFAOYSA-N 2'-methylacetophenone Chemical compound CC(=O)C1=CC=CC=C1C YXWWHNCQZBVZPV-UHFFFAOYSA-N 0.000 claims description 3
- JJQCWPWUHZFKBN-UHFFFAOYSA-N 2,6-ditert-butyl-4-methylidenecyclohexa-2,5-dien-1-one Chemical compound CC(C)(C)C1=CC(=C)C=C(C(C)(C)C)C1=O JJQCWPWUHZFKBN-UHFFFAOYSA-N 0.000 claims description 3
- IDYKOCGYJGNSFV-UHFFFAOYSA-N 2-tert-butyl-6-(2-methylbut-3-en-2-yl)-4-(4-propan-2-yloxyphenyl)cyclohexa-2,5-dien-1-one Chemical compound C(C)(C)OC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C IDYKOCGYJGNSFV-UHFFFAOYSA-N 0.000 claims description 3
- SBCFGFDAZCTSRH-UHFFFAOYSA-N 3-acetylbenzonitrile Chemical compound CC(=O)C1=CC=CC(C#N)=C1 SBCFGFDAZCTSRH-UHFFFAOYSA-N 0.000 claims description 3
- NLPHXWGWBKZSJC-UHFFFAOYSA-N 4-acetylbenzonitrile Chemical compound CC(=O)C1=CC=C(C#N)C=C1 NLPHXWGWBKZSJC-UHFFFAOYSA-N 0.000 claims description 3
- KWVFKUXYRNZFCX-UHFFFAOYSA-N 4-benzylidene-2,6-di(propan-2-yl)cyclohexa-2,5-dien-1-one Chemical compound C1=C(C(C)C)C(=O)C(C(C)C)=CC1=CC1=CC=CC=C1 KWVFKUXYRNZFCX-UHFFFAOYSA-N 0.000 claims description 3
- AIJTYOKWWVAWQF-UHFFFAOYSA-N 4-benzylidene-2,6-dimethylcyclohexa-2,5-dien-1-one Chemical compound C1=C(C)C(=O)C(C)=CC1=CC1=CC=CC=C1 AIJTYOKWWVAWQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- UFASLVBSTHYMOQ-UHFFFAOYSA-N BrC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound BrC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C UFASLVBSTHYMOQ-UHFFFAOYSA-N 0.000 claims description 3
- FOYOLGQCSRMMGN-UHFFFAOYSA-N BrC=1C=C(C=CC1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound BrC=1C=C(C=CC1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C FOYOLGQCSRMMGN-UHFFFAOYSA-N 0.000 claims description 3
- JPIKDXYCLZLSKD-UHFFFAOYSA-N C(#N)C1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound C(#N)C1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C JPIKDXYCLZLSKD-UHFFFAOYSA-N 0.000 claims description 3
- RXKXAMTZWIXEJY-UHFFFAOYSA-N C(#N)C=1C=C(C=CC=1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound C(#N)C=1C=C(C=CC=1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C RXKXAMTZWIXEJY-UHFFFAOYSA-N 0.000 claims description 3
- MMYSVIOYLIFESQ-UHFFFAOYSA-N C(C)(C)(C)C1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound C(C)(C)(C)C1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C MMYSVIOYLIFESQ-UHFFFAOYSA-N 0.000 claims description 3
- PLPHFNBDZUFZQV-UHFFFAOYSA-N FC(C1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C)(F)F Chemical compound FC(C1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C)(F)F PLPHFNBDZUFZQV-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- QPYFYAPCDWUQMG-UHFFFAOYSA-N N1=C(C=CC=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound N1=C(C=CC=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C QPYFYAPCDWUQMG-UHFFFAOYSA-N 0.000 claims description 3
- CXUIMVCDHRBLIQ-UHFFFAOYSA-N S1C(=CC=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound S1C(=CC=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C CXUIMVCDHRBLIQ-UHFFFAOYSA-N 0.000 claims description 3
- MACBYTMGNQXAQR-UHFFFAOYSA-N S1C=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound S1C=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C MACBYTMGNQXAQR-UHFFFAOYSA-N 0.000 claims description 3
- MRUWHZNISRHISQ-UHFFFAOYSA-N [N+](=O)([O-])C=1C=C(C=CC1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound [N+](=O)([O-])C=1C=C(C=CC1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C MRUWHZNISRHISQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- DYQAZJQDLPPHNB-UHFFFAOYSA-N 1-phenyl-2-hexanone Chemical compound CCCCC(=O)CC1=CC=CC=C1 DYQAZJQDLPPHNB-UHFFFAOYSA-N 0.000 claims description 2
- NFKAWBGFIMBUMB-UHFFFAOYSA-N 1-phenylpentan-2-one Chemical compound CCCC(=O)CC1=CC=CC=C1 NFKAWBGFIMBUMB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000006304 2-iodophenyl group Chemical group [H]C1=C([H])C(I)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 claims description 2
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 claims description 2
- JJLREPHQBMFHAN-UHFFFAOYSA-N BrC1=C(C=CC=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound BrC1=C(C=CC=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C JJLREPHQBMFHAN-UHFFFAOYSA-N 0.000 claims description 2
- BZUPZCPIHHCSKH-UHFFFAOYSA-N C(C1=CC=CC=C1)OC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound C(C1=CC=CC=C1)OC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C BZUPZCPIHHCSKH-UHFFFAOYSA-N 0.000 claims description 2
- IRQVWMIDIRCWGB-UHFFFAOYSA-N COC=1C=C(C=CC1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound COC=1C=C(C=CC1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C IRQVWMIDIRCWGB-UHFFFAOYSA-N 0.000 claims description 2
- DPJSGLFZRXSVBQ-UHFFFAOYSA-N FC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound FC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C DPJSGLFZRXSVBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000005605 benzo group Chemical group 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- NODGRWCMFMEGJH-UHFFFAOYSA-N p-ethylacetophenone Chemical compound CCC1=CC=C(C(C)=O)C=C1 NODGRWCMFMEGJH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- JZGBFLPDWLTZHJ-UHFFFAOYSA-N 4-benzylidenecyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=CC1=CC=CC=C1 JZGBFLPDWLTZHJ-UHFFFAOYSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for efficiently and selectively synthesizing alpha-diaryl methyl substituted ketone compounds containing different substituted functional groups, which adopts ruthenium trichloride as a catalyst, adopts potassium carbonate as alkali, adopts 1, 10-phenanthroline as an organic ligand, adopts 4-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compounds and ketone compounds as reaction substrates, and adds an organic solvent into a reaction system. The method has the advantages that: the catalyst, the alkali and the organic ligand are cheap and easy to obtain; the applicability of the substrate is high; the reaction condition is mild, safe and reliable; the selectivity of the obtained target product is close to 100%, and the yield is high. The method solves the defects of poor reaction selectivity, complicated reaction steps, low yield, requirement of using reagents harmful to the environment and the like in the traditional synthesis of the alpha-diaryl methyl substituted ketone compound, and has good industrial application prospect. The invention also provides corresponding alpha-diaryl methyl substituted ketone derivatives containing different substituted functional groups.
Description
Technical Field
The invention relates to the field of catalytic synthesis of ketone compounds, in particular to a synthesis method for preparing alpha-diaryl methyl substituted ketone compounds by using 4-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compounds and ketone compounds through a hydroarylation reaction.
Background
The alpha-diaryl methyl substituted ketone compound is an important organic synthesis intermediate, and has wide application in the fields of medicine intermediate, pesticide, biological preparation, photoelectric material, catalyst ligand and the like.
P-methylene quinonep-QMs) is a special dienone system, twoα，βUnsaturated carbonyl groups make them very electrophilic. Its specific structural units are not only an important component of many acid-base indicators and cationic dyes, but are also widely found in natural products and active drug molecules. In addition, due to its own electron-deficient nature, the product exhibits unique electrophilic activity in organic synthesis reactions, such as lignin synthesis, enzyme inhibition studies, DNA alkylation and cross-couplingp-QMs as starting material for the synthesis.
The method for synthesizing the alpha-diaryl methyl substituted ketone compound reported in the current literature mainly comprises the following steps: (1) Cross-coupling reaction: diphenylethanone compounds are used as starting materials, and cross-coupling reaction of the diphenylethanone compounds with iodo-aromatic hydrocarbon or aryl boric acid is catalyzed in the presence of transition metals (copper, nickel, palladium and the like) and reagents such as alkali and the like; (2) 1, 6-conjugate addition reaction: at low temperature (-40) with (chiral) Bronsted acid as catalyst and p-methylenequinone ketone and diphenyl malonate as reactants o C) The target product is prepared by 1, 6-conjugate addition reaction in the environment. However, the above-mentioned method has a large limitation, such as in the method (1), due to the absence of a phenyl groupThe influence of steric hindrance and electronic effect generally reduces the yield and selectivity in the process of carrying out the bisphenylation reaction; the substrate limitation in the method (2) is also larger, and only ketone compounds containing strong electron withdrawing group (ester group) substitution have better expansibility in the system. In addition, the method has the defects of complicated experimental steps (a pre-functionalization strategy of a substrate and the like), harsh reaction conditions, cross substrate applicability, low yield, large pollution to the environment and the like.
To date, the high-efficiency synthesis of alpha-diaryl methyl substituted ketone compounds has the problems of raw material quality, production safety, product stability, product purity and the like, the synthesis technology has great difficulty, only few companies such as the United states and Germany are producing at present, and the current situation of high-end or special alpha-diaryl methyl substituted ketone compounds in China mainly depends on import.
Aiming at the defects of the existing synthesis process of alpha-diaryl methyl substituted ketone compounds, the industry is focused on developing a high-efficiency and high-atom-economy catalytic system, and developing a novel method for synthesizing corresponding alpha-diaryl methyl substituted ketone compounds by taking stable, low-cost and easily-obtained ketone compounds as starting raw materials through a C-H activation strategy.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing corresponding alpha-diaryl methyl substituted ketone compounds with high efficiency and high selectivity by taking 4-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compounds and ketone compounds which are cheap and easy to obtain as raw materials through hydroalkylation reaction, so as to overcome the defects in the prior art.
The invention comprises the following steps: taking the reaction amount of 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compound, catalyst, alkali, organic ligand and organic solvent, putting the mixture in a reaction vessel under nitrogen environment, mixing the mixture under stirring at 25-100 o And C, reacting for 1-12 hours to obtain the corresponding alpha-diaryl methyl substituted ketone compound containing different substituted functional groups. The specific reaction formula is as follows:
（I）
wherein,
the catalyst is ruthenium trichloride, the alkali is potassium carbonate, the organic ligand is 1, 10-phenanthroline, and the organic solvent isN, N-dimethylformamide;
ar is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-isopropoxyphenyl, 4-benzyloxyphenyl, 3-methoxyphenyl, 2-methylphenyl, 2, 5-dimethoxyphenyl, 3-cyanophenyl, 4-cyanophenyl, 3-nitrophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 2-fluorophenyl, 4-fluorophenyl, 2-bromophenyl, 4-bromophenyl, 3-bromophenyl, 2-pyridyl, 6-benzo-2, 3-dihydrofuryl, 2-thienyl, 3-thienyl, 9-anthracenyl;
R 1 is selected from methyl, isopropyl, tert-butyl and phenyl;
R 2 is selected from hydrogen, methyl, ethyl, pentyl, heptyl, acetyl, isopropyl, propyl, butyl, phenyl;
R 3 is selected from methyl, ethyl, cyclopropyl, benzo [ d ]][1,3]Dioxin-5-yl, phenyl, 2-phenyl-1-ethyl, 4-methylphenyl, 4-methoxyphenyl, 4-bromophenyl, 4-chlorophenyl, 2-methylphenyl, 3-methylphenyl, 4-ethylphenyl, 4-t-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-ethoxyphenyl, 4-phenoxyphenyl, 2, 4-dimethylphenyl, 4-isobutylphenyl, 4-methylthiophenyl, 3-cyanophenyl, 4-cyanophenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 4-fluorophenyl, 3-nitrophenyl, 2-iodophenyl, 4-iodophenyl, 2-bromophenyl, 4-phenylphenyl, benzoyl, 2-naphthyl, 1-naphthyl.
In the above method for synthesizing an alpha-diarylmethyl-substituted ketone compound from a 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one compound and a ketone compound, the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one is selected from the group consisting of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-isopropoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-methylphenyl) methylene-1-one, 4-tert-butyl-2, 6-cyclohexadien-5-cyclohexadien-1-one, 5-cyclohexadien-1-one, 4- (2, 5-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-nitrophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-trifluoromethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-bromophenyl) 2-di-tert-butyl-1-2, 5-cyclohexadien-1-one, 4- (3-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-pyridinyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (6-benzo-2, 3-dihydrofuranyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-thienyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-thienyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (9-anthracenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-dimethyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-diisopropyl-2, 5-cyclohexadien-1-one, 4-phenyldiene-1-one.
In the above method for synthesizing an alpha-diarylmethyl substituted ketone compound from a 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one compound and a ketone compound, the ketone compound is selected from the group consisting of acetone, 3-pentanone, 2-octanone, 2-decanone, 4-methylpentan-2-one, cyclopropylmethyl ketone, 3',4' - (methylenedioxy) acetophenone, phenylbutanone, phenylpentanone, phenylhexanone, benzyl acetone, 4' -methylphenylacetone, 4' -methoxyphenylacetone, 4' -bromophenylacetone, 4' -chlorophenyl acetone, 2' -methylacetophenone, 3' -methylacetophenone, 4' -ethylacetophenone, 4' -tert-butylacetophenone, 2' -methoxyacetophenone, 3' -methoxyacetophenone, 4' -ethoxyacetophenone, 4' -phenoxyacetophenone, 2',4' -dimethyl acetophenone, 4' -isobutyl acetophenone, 4' -methylthioacetophenone, 3' -cyano acetophenone, 4' -cyano acetophenone, 3' -trifluoromethyl acetophenone, 4' -trifluoromethyl acetophenone, 3' -fluoro acetophenone, 4' -fluoro acetophenone, 3' -nitro acetophenone, 2' -iodo acetophenone, 4' -iodo acetophenone, 2' -bromo acetophenone, 4' -phenyl acetophenone, benzoyl acetone, diphenylethanone, 2-naphthaleneethanone, 1-naphthaleneethanone.
In the above method for synthesizing the alpha-diarylmethyl substituted ketone compound from the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one compound and the ketone compound, the molar ratio of the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one compound to the ketone compound is 1: [1.0 to 1.2], most preferably 1:1, a step of; the molar ratio of the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compound to the ruthenium trichloride to the 1, 10-phenanthroline is 1: [0.01 to 0.2]: [0.01 to 0.2], most preferably 1:0.05:0.1; the molar ratio of the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one compound to the potassium carbonate is 1: [0.5 to 2.0], most preferably 1:1.
the method for synthesizing the alpha-diaryl methyl substituted ketone compound by the-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compound and the ketone compound is efficient and highly selective, and the reaction process is mild and easy to control. The method is simple and feasible while obtaining higher yield and 100% selectivity, and the used raw materials are cheap and easy to obtain, so that the method is simple to prepare and has good industrial application prospect.
[ detailed description ] of the invention
The invention is further illustrated by the following examples in connection with the invention:
1. testing and analysis
Structural analysis of the reaction products in the following examples of the present invention was performed by using a gas-mass spectrometer combined with GC/MS (6890N/5973N) equipped with HP-5MS capillary chromatography column (30 m. Times.0.45 mm. Times.0.8 μm) manufactured by Agilent corporation, and Bruker Avance-III 500 nuclear magnetic resonance analyzer manufactured by Bruker corporation. The selectivity and yield of the target product were analyzed using a Bruker Avance-III 500 Nuclear magnetic resonance Analyzer manufactured by Bruker Corp.
2. Examples
Example 1
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 97%.
Example 2
154 mg (0.5 mmol) of 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 3
161 mg (0.5 mmol) of 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol)1, 10-phenanthroline of 9 mg (0.05 mmol) and potassium carbonate of 69 mg (0.5 mmol) are introduced into a Schlenk tube under nitrogen, and 1.0 mL is introduced under nitrogenN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 4
175 mg (0.5 mmol) of 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate were introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL was additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 5
176 mg (0.5 mmol) of 4- (4-isopropoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 6
200 mg (0.5 mmol) of 4- (4-benzyloxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate were introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL was additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 7
162 mg (0.5 mmol) of 4- (3-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate were introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL was additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 8
154 mg (0.5 mmol) of 4- (2-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 9
177 mg (0.5 mmol) of 4- (2, 5-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate were introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL was additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
Example 10
159.5 mg (0.5 mmol) of 4- (3-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, N-dimethylformamideAt 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 11
159.5 mg (0.5 mmol) of 4- (4-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 12
169.5 mg (0.5 mmol) of 4- (3-nitrophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate were introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL was additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 13
181 mg (0.5 mmol) of 4- (4-trifluoromethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere, and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 82%.
Example 14
156 mg (0.5 mmol) of 4- (3-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride9. 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen, and 1.0 mL is introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 15
156 mg (0.5 mmol) of 4- (2-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 96%.
Example 16
156 mg (0.5 mmol) of 4- (4-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 17
186.5 mg (0.5 mmol) of 4- (2-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 18
186.5 mg (0.5 mmol) of 4- (4-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 19
186.5 mg (0.5 mmol) of 4- (3-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 96%.
Example 20
147.5 mg (0.5 mmol) of 4- (2-pyridyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 21
168 mg (0.5 mmol) of 4- (6-benzo-2, 3-dihydrofuranyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate were introduced into a Schlenk tube under nitrogen atmosphere, and 1.0 mL was further introduced under nitrogen protectionN, NDimethylformamide, at 100 o C stirring reverselyShould be 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 22
150 mg (0.5 mmol) of 4- (2-thienyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 23
150 mg (0.5 mmol) of 4- (3-thienyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 24
197 mg (0.5 mmol) of 4- (9-anthryl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 25
105 mg (0.5 mmol) of 4-phenylmethylene-2, 6-dimethyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonateAdding into Schlenk tube under nitrogen atmosphere, and adding 1.0. 1.0 mL under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 85%.
Example 26
133 mg (0.5 mmol) of 4-phenylmethylene-2, 6-diisopropyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 27
167. 167 mg (0.5 mmol) of 4-phenylmethylene-2, 6-diphenyl-2, 5-cyclohexadien-1-one, 29 mg (0.5 mmol) of acetone, 5.2. 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69. 69 mg (0.5 mmol) of potassium carbonate were introduced into a Schlenk tube under nitrogen atmosphere, and 1.0. 1.0 mL was additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 67%.
Example 28
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 43 mg (0.5 mmol) of 3-pentanone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 82%.
Example 29
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 43 mg (0.5 mmol)2-pentanone, 5.2 mg (0.025 mmol) ruthenium trichloride, 9 mg (0.05 mmol) 1, 10-phenanthroline and 69 mg (0.5 mmol) potassium carbonate are introduced into a Schlenk tube under nitrogen, and 1.0 mL under nitrogenN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 30
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 64 mg (0.5 mmol) of 2-octanone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 31
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 78 mg (0.5 mmol) of 2-decanone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 72%.
Example 32
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 50 mg (0.5 mmol) of 4-methylpentan-2-one, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 33
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 42 mg (0.5 mmol) of cyclopropylmethyl ketone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 66%.
Example 34
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 82 mg (0.5 mmol) of 3',4' - (methylenedioxy) acetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 35
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 74 mg (0.5 mmol) of phenylbutanone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere, and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 36
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 81 mg (0.5 mmol) of benzopentanone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o C stirringThe reaction was carried out for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 96%.
Example 37
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 88 mg (0.5 mmol) of cyclohexanone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere, and 1.0 mL is additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
Example 38
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 74 mg (0.5 mmol) of benzyl acetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 74%.
Example 39
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 74 mg (0.5 mmol) of 4' -methylbenzophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 79%.
Example 40
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 82 mg (0.5 mmol) of 4' -methoxyphenylacetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 m)mol) Potassium carbonate was charged into a Schlenk tube under nitrogen atmosphere, and 1.0. 1.0 mL was further charged under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the target product is separated and purified by column chromatography, and the yield of the target product is 81%.
Example 41
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 106.5 mg (0.5 mmol) of 4' -bromophenylacetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 42
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 84 mg (0.5 mmol) of 4' -propiophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 43
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 67 mg (0.5 mmol) of 2' -methylacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
Example 44
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl1, 10-phenanthroline and 69 mg (0.5 mmol) potassium carbonate were introduced into a Schlenk tube under nitrogen, 67. 67 mg (0.5 mmol) of 3' -methylacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate were introduced into a tube under nitrogen, and under nitrogen again 1.0 mLN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 45
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 67 mg (0.5 mmol) of 4' -methylacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 46
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 74 mg (0.5 mmol) of 4' -methylacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 47
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 88 mg (0.5 mmol) of 4' -tert-butylacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, and obtainingThe yield of the target product was 92%.
Example 48
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 75 mg (0.5 mmol) of 2' -methoxyacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 79%.
Example 49
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 75 mg (0.5 mmol) of 3' -methoxyacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 50
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 75 mg (0.5 mmol) of 4' -methoxyacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 51
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 82 mg (0.5 mmol) of 4' -ethoxyacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen,adding 1.0. 1.0 mL under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 76%.
Example 52
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 106 mg (0.5 mmol) of 4' -phenoxyacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 53
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 74 mg (0.5 mmol) of 2',4' -dimethyl acetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 54
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 88 mg (0.5 mmol) of 4' -isobutylacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 55
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one and 83 mg%0.5 mmol) of 4' -methylthioacetophenone, 5.2. 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69. 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen, and 1.0. 1.0 mL is additionally introduced under nitrogenN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 56
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 72.5 mg (0.5 mmol) of 3' -cyanoacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 77%.
Example 57
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 72.5 mg (0.5 mmol) of 4' -cyanoacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 82%.
Example 58
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 94 mg (0.5 mmol) of 3' -trifluoromethyl acetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 81 percent。
Example 59
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 94 mg (0.5 mmol) of 4' -trifluoromethyl acetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 75%.
Example 60
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 69 mg (0.5 mmol) of 3' -fluoroacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 61
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 69 mg (0.5 mmol) of 4' -fluoroacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 76%.
Example 62
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 82.5 mg (0.5 mmol) of 3' -nitroacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and under nitrogen protection 1.0 mL N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 72%.
Example 63
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 123 mg (0.5 mmol) of 2' -iodoacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
Example 64
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 123 mg (0.5 mmol) of 4' -iodoacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 65
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 99.5 mg (0.5 mmol) of 2' -bromoacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 66%.
Example 66
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 99.5 mg (0.5 mmol) of 4' -bromoacetophenone, 5.2 mg (0.025 mmol)) 1, 10-phenanthroline of 9 mg (0.05 mmol) and potassium carbonate of 69 mg (0.5 mmol) are introduced into a Schlenk tube under nitrogen, and 1.0 mL is introduced under nitrogenN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 96%.
Example 67
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 98 mg (0.5 mmol) of 4' -phenylacetophenone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protection N, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 68
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 81 mg (0.5 mmol) of benzoylacetone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere, and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 77%.
Example 69
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 98 mg (0.5 mmol) of diphenylethanone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 70
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 85 mg (0.5 mmol) of 2-naphthaleneethanone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 95%.
Example 71
147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 85 mg (0.5 mmol) of 1-naphthaleneethanone, 5.2 mg (0.025 mmol) of ruthenium trichloride, 9 mg (0.05 mmol) of 1, 10-phenanthroline and 69 mg (0.5 mmol) of potassium carbonate are introduced into a Schlenk tube under nitrogen atmosphere and 1.0 mL is additionally introduced under nitrogen protectionN, NDimethylformamide, at 100 o The reaction was stirred for 2 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
As can be seen from the above examples, the method for preparing the corresponding alpha-diarylmethyl substituted ketone compound containing different substituted functional groups by using the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compound and the ketone compound through efficient reaction has the advantages of mild reaction conditions, low price and easiness in obtaining a catalyst, simplicity in preparation and the like. In addition, the method has the advantages of wide substrate applicability, high yield and the like, and provides a method for efficiently synthesizing the alpha-diaryl methyl substituted ketone compound containing different substituted functional groups.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (4)
1. A structural formula is prepared by reacting 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compound with ketone compound（I）The specific reaction formula of the preparation method of the alpha-diaryl methyl substituted ketone compound is as follows:
（I）
the method is characterized by comprising the following steps of:
taking the reaction amount of 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compound, catalyst, alkali, organic ligand and organic solvent, putting the mixture in a reaction vessel under nitrogen environment, mixing the mixture under stirring at 25-100 o C, reacting for 1-12 hours to obtain corresponding alpha-diaryl methyl substituted ketone compounds containing different substituted functional groups;
wherein,
The catalyst is ruthenium trichloride, the alkali is potassium carbonate, the organic ligand is 1, 10-phenanthroline, and the organic solvent isN, N-dimethylformamide;
ar is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-isopropoxyphenyl, 4-benzyloxyphenyl, 3-methoxyphenyl, 2-methylphenyl, 2, 5-dimethoxyphenyl, 3-cyanophenyl, 4-cyanophenyl, 3-nitrophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 2-fluorophenyl, 4-fluorophenyl, 2-bromophenyl, 4-bromophenyl, 3-bromophenyl, 2-pyridyl, 6-benzo-2, 3-dihydrofuryl, 2-thienyl, 3-thienyl, 9-anthracenyl;
R 1 is selected from methyl, isopropyl, tert-butyl and phenyl;
R 2 is selected from hydrogen, methyl, ethyl, pentyl, heptyl, acetyl, isopropyl, propyl, butyl, phenyl;
R 3 is selected from methyl, ethyl, cyclopropyl, benzo [ d ]][1,3]Dioxin-5-yl, phenyl, 2-phenyl-1-ethyl, 4-methylPhenyl, 4-methoxyphenyl, 4-bromophenyl, 4-chlorophenyl, 2-methylphenyl, 3-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-ethoxyphenyl, 4-phenoxyphenyl, 2, 4-dimethylphenyl, 4-isobutylphenyl, 4-methylthiophenyl, 3-cyanophenyl, 4-cyanophenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 4-fluorophenyl, 3-nitrophenyl, 2-iodophenyl, 4-iodophenyl, 2-bromophenyl, 4-phenylphenyl, benzoyl, 2-naphthyl, 1-naphthyl.
2. The process according to claim 1, wherein the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one is selected from the group consisting of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-isopropoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-benzyloxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (3-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-methoxyphenyl) methylene-2, 6-di-tert-butyl-1-one, 5-cyclohexadiene-1-one, 4- (3-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-nitrophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-trifluoromethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one 4- (2-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-pyridinyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (6-benzo-2, 3-dihydrofuranyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-thienyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-thienyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (9-anthryl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-dimethyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-diisopropyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 5-cyclohexadien-1-one.
3. The process according to claim 1, wherein the ketone compound is selected from the group consisting of acetone, 3-pentanone, 2-octanone, 2-decanone, 4-methylpentan-2-one, cyclopropylmethyl ketone, 3',4' - (methylenedioxy) acetophenone, phenylbutanone, phenylpentanone, phenylhexanone, benzyl acetone, 4' -methylphenylacetone, 4' -methoxyphenylacetone, 4' -bromophenylacetone, 4' -chlorophenyl acetone, 2' -methylacetophenone, 3' -methylacetophenone, 4' -ethylacetophenone, 4' -tert-butylacetophenone, 2' -methoxyacetophenone, 3' -methoxyacetophenone, 4' -ethoxyacetophenone, 4' -phenoxyacetophenone, 2',4' -dimethyl acetophenone, 4' -isobutyl acetophenone, 4' -methylthioacetophenone, 3' -cyano acetophenone, 4' -cyano acetophenone, 3' -trifluoromethyl acetophenone, 4' -trifluoromethyl acetophenone, 3' -fluoro acetophenone, 4' -fluoro acetophenone, 3' -nitro acetophenone, 2' -iodo acetophenone, 4' -iodo acetophenone, 2' -bromo acetophenone, 4' -phenyl acetophenone, benzoyl acetone, diphenyl ethanone, 2-naphtalenethanone, 1-naphtalenethanone.
4. The method according to claim 1, wherein the molar ratio of the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one compound to the ketone compound is 1: [1.0 to 1.2]; the molar ratio of the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compound to the ruthenium trichloride to the 1, 10-phenanthroline is 1: [0.01 to 0.2]: [0.01 to 0.2]; the molar ratio of the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one compound to the potassium carbonate is 1: [0.5 to 2.0].
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| CN112574093A (en) * | 2021-01-29 | 2021-03-30 | 湖南理工学院 | Novel green method for preparing 3-diaryl methyl substituted indole compound |
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