CN116947586A - 一种高效的多取代丙烯基芳香化合物的制备方法 - Google Patents
一种高效的多取代丙烯基芳香化合物的制备方法 Download PDFInfo
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- CN116947586A CN116947586A CN202310649148.7A CN202310649148A CN116947586A CN 116947586 A CN116947586 A CN 116947586A CN 202310649148 A CN202310649148 A CN 202310649148A CN 116947586 A CN116947586 A CN 116947586A
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- palladium
- propenyl
- acid
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- -1 polysubstituted propenyl aromatic compound Chemical class 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- YLGRTLMDMVAFNI-UHFFFAOYSA-N tributyl(prop-2-enyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)CC=C YLGRTLMDMVAFNI-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 claims description 4
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 claims description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- QZUPHAGRBBOLTB-UHFFFAOYSA-N NSC 244302 Chemical compound C=1C=CC=CC=1P(C(C)(C)C)C1=CC=CC=C1 QZUPHAGRBBOLTB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- PAGZTSLSNQZYEV-UHFFFAOYSA-L 2,2-dimethylpropanoate;palladium(2+) Chemical compound [Pd+2].CC(C)(C)C([O-])=O.CC(C)(C)C([O-])=O PAGZTSLSNQZYEV-UHFFFAOYSA-L 0.000 claims description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 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
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- JGBZTJWQMWZVNX-UHFFFAOYSA-N palladium;tricyclohexylphosphane Chemical compound [Pd].C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 JGBZTJWQMWZVNX-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 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
- DLQYXUGCCKQSRJ-UHFFFAOYSA-N tris(furan-2-yl)phosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2OC=CC=2)=C1 DLQYXUGCCKQSRJ-UHFFFAOYSA-N 0.000 claims description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims 2
- UKSZBOKPHAQOMP-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 UKSZBOKPHAQOMP-UHFFFAOYSA-N 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 claims 1
- 239000012847 fine chemical Substances 0.000 abstract description 4
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 229930014626 natural product Natural products 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 9
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- BETNPSBTDMBHCZ-UHFFFAOYSA-N 1-(chloromethyl)-2,4-dimethylbenzene Chemical compound CC1=CC=C(CCl)C(C)=C1 BETNPSBTDMBHCZ-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- IIEJGTQVBJHMDL-UHFFFAOYSA-N 2-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-[2-oxo-2-[3-(sulfamoylamino)pyrrolidin-1-yl]ethyl]-1,3,4-oxadiazole Chemical compound C1CN(CC1NS(=O)(=O)N)C(=O)CC2=NN=C(O2)C3=CN=C(N=C3)NC4CC5=CC=CC=C5C4 IIEJGTQVBJHMDL-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- ZAZGIJXLYNDFGQ-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical compound C(C)(=O)O.C(C)(=O)O.C1(=CC=CC=C1)PC1=CC=CC=C1 ZAZGIJXLYNDFGQ-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical group C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical class CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 1
- AHEHMEDQTGXXRH-UHFFFAOYSA-N prop-1-enoxyboronic acid Chemical class CC=COB(O)O AHEHMEDQTGXXRH-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- 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
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于精细化学品及相关化学技术领域，提供了一种高效的多取代丙烯基芳香化合物的制备方法，以含卤甲基芳烃及烯丙基三丁基锡为原料，在钯和膦催化剂存在的情况下，于无水有机溶剂中，在室温下反应12小时后，加入酸，在40℃反应12小时，即可得到相应的多取代丙烯基芳香化合物。本发明的制备方法为一锅法，反应条件温和、操作简便、收率高、区域选择性好。利用该方法所合成的多取代丙烯基芳香化合物可以进一步官能化得到各类化合物，应用于天然产物、功能材料及精细化学品的开发与研究。
Description
技术领域
本发明属于精细化学品及相关化学技术领域，提供了一种高效的多取代丙烯基芳香化合物的制备方法。
背景技术
丙烯基芳香化合物广泛存在于天然产物、医药和农药中间体中。此外，丙烯基中的甲基以及碳碳双键部分也易于进行官能化，为其进一步修饰提供了可能。因此，开发一种简便有效的合成方法，来得到多取代的丙烯基芳香化合物越来越受到人们重视。
传统的多取代丙烯基芳香化合物的合成方法主要是在化合物的原有结构基础上进行化学修饰。除了常见的芳香卤化物与丙烯基硼酸频哪醇酯的Suzuki-Miyaura偶联反应外(Tetrahedron Lett.,2008,49,5605-5607)，还包括芳香炔烃的半还原(J.Am.Chem.Soc.,2016,138,8588-94)、苯甲醛与乙基三苯基溴化鏻的Wittig反应(J.Org.Chem.,2008,73,801-812)、芳香醇的脱水(Eur.J.Org.Chem.,2008,2008,5577-5582)、烯丙基苯的双键异构化(Org.Lett.,2012,14,3716-3719)等一系列将丙烯基引入芳香化合物的方法。然而，这些方法受到官能团兼容性差、需要进行预官能化以及苛刻的反应条件的限制。
相比之下，由过渡金属催化的直接C-H丙烯基化反应是一种更理想的方法。到目前为止，共有两种类型的底物可用于直接C-H丙烯基化反应。一种是含有导向基团的芳香化合物(Adv.Synth.Catal.,2016,358,3932-3937)，另一种是含有多个吸电子基团的芳香化合物(Angew.Chem.Int.Ed.,2016,55,1876-1880)。然而，这些方法有时会得到烯丙基产物和丙烯基产物的混合物，而且大多需要在高温(超过100℃)下生成。
因此，为了得到种类更丰富的多取代丙烯基芳香化合物，需要开发一种底物适用性广、反应条件温和、官能团相容性良好和高区域选择性的合成方法。
发明内容
本发明提供了一种多取代丙烯基芳香化合物的新颖制备方法，该合成方法为一锅法，反应条件温和、操作简便、收率高、区域选择性好。
本发明的技术方案：
一种高效的多取代丙烯基芳香化合物的制备方法，以含卤甲基芳烃及其衍生物、烯丙基三丁基锡为原料，在钯和膦催化剂存在的情况下，于无水有机溶剂中，在室温下反应12小时后，加入酸，在40℃反应12小时，即得到相应的多取代丙烯基芳香化合物，合成路线如下：
式中，R1选芳基、甲基、2-萘基、杂芳基；
含卤甲基芳烃及其衍生物与烯丙基三丁基锡的摩尔比为1:1；
含卤甲基芳烃及其衍生物与催化剂的摩尔比为1:0.05；
含卤甲基芳烃及其衍生物与酸的摩尔比为1:2；
含卤甲基芳烃及其衍生物与钯的摩尔比为1:0.05；
含卤甲基芳烃及其衍生物在体系中的摩尔浓度为0.15mmol/mL。
所述的钯为三二亚苄基丙酮二钯、醋酸钯、氯化钯、双乙酰丙酮钯、双(二苄叉丙酮)钯、特戊酸钯、乙酰丙酮钯、二三苯基膦二醋酸钯、乙二胺氯化钯、双(三环己基膦)二氯化钯、三氟乙酸钯中的一种或两种以上混合。优选为三二亚苄基丙酮二钯、醋酸钯、氯化钯中的一种或两种以上混合。
所述的膦催化剂为三苯基膦、三对甲苯基膦、三对甲氧基苯基膦、三对氟苯基膦、叔丁基二苯基膦、三环己基膦、三(2-呋喃基)膦、1,4-双(二苯膦)丁烷、1,1'-双(二苯基膦)二茂铁。优选为三苯基膦、三对甲苯基膦、叔丁基二苯基磷；
所述的无水有机溶剂为二氯甲烷、四氢呋喃、1,4-二氧六环、乙醚、甲基叔丁基醚、甲苯、乙腈、甲基环戊基醚、1,2-二氯乙烷中的一种或两种以上混合，优选二氯甲烷、四氢呋喃、1,4-二氧六环。
所述的酸为对甲苯磺酸一水合物、三氟乙酸、乙酸、氟硼酸、甲磺酸、三氟甲磺酸的一种或两种以上混合，优选对甲苯磺酸一水合物、三氟乙酸、乙酸。
分离方法为柱层析。
用柱层析方法进行产物分离时，可以使用硅胶或者中性氧化铝作为固定相，展开剂一般为极性与非极性的混合溶剂，如乙酸乙酯-石油醚、乙酸乙酯-正己烷、二氯甲烷-石油醚、甲醇-石油醚。
本发明的有益效果是该合成方法为一锅法、反应条件温和、操作简便、收率和区域选择性高；利用该方法所合成的多取代丙烯基芳香化合物可以进一步官能化得到各类化合物，应用于天然产物、功能材料及精细化学品的开发与研究。
附图说明
图1是实施例1(E)-2,5-二甲基-4-丙烯基-1,1'-联苯的1H核磁谱图。
图2是实施例1中(E)-2,5-二甲基-4-丙烯基-1,1'-联苯的13C核磁谱图。
图3是实施例2中(E)-4'-氟-2,5-二甲基-4-丙烯基-1,1'-联苯的1H核磁谱图。
图4是实施例2中(E)-4'-氟-2,5-二甲基-4-丙烯基-1,1'-联苯的13C核磁谱图。
图5是实施例3中(E)-4'-氯-2,5-二甲基-4-丙烯基-1,1'-联苯的1H核磁谱图。
图6是实施例3中(E)-4'-氯-2,5-二甲基-4-丙烯基-1,1'-联苯的13C核磁谱图。
图7是实施例4中(E)-4'-溴-2,5-二甲基-4-丙烯基-1,1'-联苯的1H核磁谱图。
图8是实施例4中(E)-4'-溴-2,5-二甲基-4-丙烯基-1,1'-联苯的13C核磁谱图。
图9是实施例5中(E)-2,4',5-三甲基-4-丙烯基-1,1'-联苯的1H核磁谱图。
图10是实施例5中(E)-2,4',5-三甲基-4-丙烯基-1,1'-联苯的13C核磁谱图。
图11是实施例6中(E)-2,5-二甲基-4-丙烯基-4'-三氟甲氧基-1,1'-联苯的1H核磁谱图。
图12是实施例6中(E)-2,5-二甲基-4-丙烯基-4'-三氟甲氧基-1,1'-联苯的13C核磁谱图。
图13是实施例7中(E)-1,2,4-三甲基-5-丙烯基苯的1H核磁谱图。
图14是实施例7中(E)-1,2,4-三甲基-5-丙烯基苯的13C核磁谱图。
图15是实施例8中(E)-2-(2,5-二甲基-4-丙烯基苯基)萘的1H核磁谱图。
图16是实施例8中(E)-2-(2,5-二甲基-4-丙烯基苯基)萘的13C核磁谱图。
图17是实施例9中(E)-2-(2,5-二甲基-4-丙烯基苯基)噻吩的1H核磁谱图。
图18是实施例9中(E)-2-(2,5-二甲基-4-丙烯基苯基)噻吩的13C核磁谱图。
具体实施方式
本发明所述的多取代丙烯基芳香化合物的制备方法，具有一锅法、反应条件温和、操作简便、收率和区域选择性高等优点。
下面结合具体实施例，进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。在本领域内的技术人员对本发明所做的简单替换或改进均属于本发明所保护的技术方案之内。
实施例1：(E)-2,5-二甲基-4-丙烯基-1,1'-联苯的合成
在25mL反应器中，加入2-苯基-4-甲基苄氯(0.064g,0.3mmol)，烯丙基三丁基锡(0.100mg)，三二亚苄基丙酮二钯(0.014g,0.015mmol)，三苯基膦(0.016g,0.06mmol)，加入无水二氯甲烷2mL，室温、氮气条件下搅拌24h；加入对甲苯磺酸一水合物(0.142mg，0.6mmol)，40℃下搅拌12h。柱层析分离(碱性氧化铝，200-300目；展开剂，石油醚)得到(E)-2,5-二甲基-4-丙烯基-1,1'-联苯0.040g，产率60％。
-2,5-二甲基-4-丙烯基-1,1'-联苯
黄色固体；熔点59-60℃；1H NMR(400MHz,CDCl3)δ7.48–7.39(m,2H),7.37–7.33(m,4H),7.05(s,1H),6.63(dd,J＝15.8,2.0Hz,1H),6.19(dq,J＝15.4,6.5Hz,1H),2.36(s,3H),2.28(s,3H),1.96(dd,J＝6.7,1.7Hz,3H)；13C{1H}NMR(100MHz,CDCl3)δ141.9,140.4,136.0,132.7,132.2,131.7,129.2,128.6,128.1,127.4,126.9,126.7,20.1,19.3,18.9；IR(KBr):νmax 2925,1618,1447,1325,1166,1127,1068,963,847,696cm-1；HRMS(EI)m/z:[M]+Calcd forC17H18 222.1409；Found 222.1402.
实施例2：(E)-4'-氟-2,5-二甲基-4-丙烯基-1,1'-联苯的合成
在25mL反应器中，加入2-(氯甲基)-4'-氟-5-甲基-1,1'-联苯(0.072g,0.3mmol)，烯丙基三丁基锡(0.100mg)，醋酸钯(0.004g,0.015mmol)，三对甲苯基膦(0.018g,0.06mmol)，加入无水四氢呋喃2mL，室温、氮气条件下搅拌24h；加入三氟乙酸(0.068mg，0.6mmol)，40℃下搅拌12h。柱层析分离(硅胶，200-300目；展开剂，石油醚)得到(E)-4'-氟-2,5-二甲基-4-丙烯基-1,1'-联苯0.043g，产率60％。
-4'-氟-2,5-二甲基-4-丙烯基-1,1'-联苯棕色油状液体；1H NMR(400MHz,CDCl3)δ7.39–7.27(m,3H),7.18–7.07(m,2H),7.01(s,1H),6.63(dd,J＝15.6,1.8Hz,1H),6.19(dq,J＝15.6,6.6Hz,1H),2.36(s,3H),2.25(s,3H),1.96(dd,J＝6.6,1.8Hz,3H)；13C{1H}NMR(100MHz,CDCl3)δ161.9(d,J＝245.2Hz),139.3,137.8(d,J＝3.2Hz),136.1,132.7,132.3,131.7,130.7(d,J＝7.9Hz),128.4,127.4,127.0,114.9(d,J＝21.2Hz),20.0,19.3,18.9；19FNMR(376MHz,CDCl3)δ-116.34；IR(neat):νmax 2925,1652,1605,1509,1489,1447,1222,1157,963,839,699cm-1；HRMS(EI)m/z:[M]+CalcdforC17H17F240.1314；Found 240.1308.
实施例3：(E)-4'-氯-2,5-二甲基-4-丙烯基-1,1'-联苯的合成
操作同实施例1，由2-(氯甲基)-4'-氯-5-甲基-1,1'-联苯得到(E)-4'-氯-2,5-二甲基-4-丙烯基-1,1'-联苯0.045g，产率58％。
-4'-氯-2,5-二甲基-4-丙烯基-1,1'-联苯白色固体；熔点60-61℃；1H NMR(400MHz,CDCl3)δ7.38–7.33(m,2H),7.29(s,1H),7.26–7.20(m,2H),6.96(s,1H),6.58(dd,J＝15.7,1.9Hz,1H),6.15(dq,J＝15.6,6.6Hz,1H),2.31(s,3H),2.21(s,3H),1.92(dd,J＝6.6,1.8Hz,3H)；13C{1H}NMR(100MHz,CDCl3)δ140.3,139.1,136.3,132.7,132.6,132.3,131.5,130.5,128.5,128.2,127.5,127.1,20.0,19.2,18.8；IR(KBr):νmax 2922,2069,1652,1483,1445,1266,1090,1013,962,834,747,692cm-1；HRMS(EI)m/z:[M]+Calcd forC17H17Cl256.1019；Found 256.1012.
实施例4：反-4,4'-二甲酸二甲酯-1,2-二苯乙烯的合成
操作同实施例2，由2-(氯甲基)-4'-溴-5-甲基-1,1'-联苯得到(E)-4'-溴-2,5-二甲基-4-丙烯基-1,1'-联苯0.051g，产率57％。
-4'-溴-2,5-二甲基-4-丙烯基-1,1'-联苯白色固体；熔点73-74℃；1H NMR(400MHz,CDCl3)δ7.58–7.51(m,2H),7.33(s,1H),7.24–7.18(m,2H),6.99(s,1H),6.61(dd,J＝15.6,1.8Hz,1H),6.19(dq,J＝15.6,6.6Hz,1H),2.34(s,3H),2.25(s,3H),1.95(dd,J＝6.6,1.8Hz,3H)；13C{1H}NMR(100MHz,CDCl3)δ140.7,139.0,136.3,132.5,132.3,131.4,131.2,130.9,128.4,127.5,127.2,120.8,20.0,19.2,18.9；IR(KBr):νmax 2925,1646,1480,1442,1267,1070,1011,962,698cm-1；HRMS(EI)m/z:[M]+CalcdforC17H17 79Br,C17H17 81Br300.0514,302.0493；Found 300.0506,302.0485.
实施例5：(E)-2,4',5-三甲基-4-丙烯基-1,1'-联苯的合成
在25mL反应器中，加入2-(氯甲基)-4',5-二甲基-1,1'-联苯(0.069g,0.3mmol)，氯化钯(0.003g,0.015mmol)，叔丁基二苯基膦(0.015g,0.06mmol)，加入无水1,4-二氧六环2mL，室温、氮气条件下搅拌24h。加入乙酸(0.036mg，0.6mmol)，40℃下搅拌12h。柱层析分离(硅胶，200-300目；展开剂，石油醚)，得到(E)-2,4',5-三甲基-4-丙烯基-1,1'-联苯0.062g，产率54％。
-2,4',5-三甲基-4-丙烯基-1,1'-联苯白色固体；熔点59-60℃；1H NMR(400MHz,CDCl3)δ7.32(s,1H),7.25–7.19(m,4H),7.02(s,1H),6.62(dd,J＝15.7,2.0Hz,1H),6.17(dq,J＝15.6,6.6Hz,1H),2.41(s,3H),2.34(s,3H),2.26(s,3H),1.94(dd,J＝6.6,1.8Hz,3H)；13C{1H}NMR(100MHz,CDCl3)δ140.3,138.9,136.2,135.8,132.7,132.1,131.7,129.1,128.7,128.6,127.4,126.8,21.2,20.1,19.3,18.9；IR(KBr):νmax 3020,2922,2853,1650,1489,1446,1377,962,889,815cm-1；HRMS(EI)m/z:[M]+CalcdforC18H20236.1565；Found 236.1556.
实施例6：(E)-2,5-二甲基-4-丙烯基-4'-三氟甲氧基-1,1'-联苯的合成
操作同实施例5，由2-(氯甲基)-5-甲基-4'-(三氟甲氧基)-1,1'-联苯反应得到(E)-2,5-二甲基-4-丙烯基-4'-三氟甲氧基-1,1'-联苯0.051g，产率55％。
-2,5-二甲基-4-丙烯基-4'-三氟甲氧基-1,1'-联苯棕色油状液体；1H NMR(400MHz,CDCl3)δ7.37–7.29(m,3H),7.25–7.21(m,2H),6.98(s,1H),6.59(dd,J＝15.6,1.9Hz,1H),6.16(dq,J＝15.6,6.6Hz,1H),2.32(s,3H),2.22(s,3H),1.92(dd,J＝6.6,1.8Hz,3H)；13C{1H}NMR(100MHz,CDCl3)δ148.1,140.6,138.9,136.4,132.6,132.3,131.6,130.5,128.4,127.5,127.2,120.5,19.9,19.2,18.8；19F NMR(376MHz,CDCl3)δ-57.79；IR(neat):νmax 2923,2855,1636,1490,1444,1258,1222,1165,964,750,696cm-1；HRMS(EI)m/z:[M]+Calcd forC18H17F3O306.1231；Found 306.1222.
实施例7：(E)-1,2,4-三甲基-5-丙烯基苯的合成
操作同实施例5，由1-(氯甲基)-2,4-二甲基苯反应得到(E)-1,2,4-三甲基-5-丙烯基苯0.027g，产率56％。
-1,2,4-三甲基-5-丙烯基苯棕色油状液体；1H NMR(400MHz,CDCl3)δ7.17(s,1H),6.89(s,1H),6.53(dd,J＝15.6,1.9Hz,1H),6.06(dq,J＝15.6,6.6Hz,1H),2.26(s,3H),2.21(s,3H),2.20(s,3H),1.88(dd,J＝6.6,1.8Hz,3H)；13C{1H}NMR(100MHz,CDCl3)δ135.0,134.4,133.9,132.1,131.5,128.7,126.7,125.8,19.31,19.27,19.1,18.8.IR(neat):νmax 2919,2862,1647,1502,1459,1377,963,870,840,803cm-1；HRMS(EI)m/z:[M]+Calcd forC12H16 160.1252；Found 160.1243.
实施例8：(E)-2-(2,5-二甲基-4-丙烯基苯基)萘的合成
操作同实施例5，由2-(2-(氯甲基)-5-甲基苯基)萘反应得到(E)-2-(2,5-二甲基-4-丙烯基苯基)萘0.051g，产率62％。
-2-(2,5-二甲基-4-丙烯基苯基)萘
棕色油状液体；1H NMR(400MHz,CDCl3)δ7.89–7.82(m,3H),7.76(s,1H),7.50–7.44(m,3H),7.34(s,1H),7.10(s,1H),6.62(dd,J＝15.6,1.8Hz,1H),6.17(dq,J＝15.6,6.6Hz,1H),2.34(s,3H),2.27(s,3H),1.93(dd,J＝6.6,1.8Hz,3H)；13C{1H}NMR(100MHz,CDCl3)δ140.3,139.5,136.1,133.4,132.9,132.3,131.9,128.6,128.0,127.8,127.73,127.69,127.5,127.4,127.0,126.1,125.8,77.3,20.1,19.3,18.9；IR(neat):νmax 3053,3016,2923,2852,1631,1495,1445,1377,1267,1131,963,857,820,749cm-1；HRMS(EI)m/z:[M]+Calcd forC21H20 272.1565；Found 272.1558.
实施例9：((E)-2-(2,5-二甲基-4-丙烯基苯基)噻吩的合成
操作同实施例5，由2-(2-(氯甲基)-5-甲基苯基)噻吩反应得到(E)-2-(2,5-二甲基-4-丙烯基苯基)噻吩0.039g，产率57％。
-2-(2,5-二甲基-4-丙烯基苯基)噻吩棕色油状液体；1HNMR(400MHz,CDCl3)δ7.28–7.25(m,1H),7.22(s,1H),7.14–7.10(m,1H),7.09–7.06(m,1H),7.01(s,1H),6.50(dd,J＝15.6,1.8Hz,1H),6.07(dq,J＝15.8,6.7Hz,1H),2.23(d,J＝3.2Hz,6H),1.84(dd,J＝6.6,1.8Hz,3H)；13C{1H}NMR(100MHz,CDCl3)δ142.1,136.0,134.9,133.0,132.2,131.5,129.0,128.5,127.5,126.9,124.8,122.3,20.4,19.2,18.9；IR(neat):νmax 2923,1691,1607,1448,1377,1080,1035,964,889,857,789,723cm-1；HRMS(EI)m/z:[M]+Calcd forC15H16S228.0973；Found 228.0966。
Claims (5)
1.一种高效的多取代丙烯基芳香化合物的制备方法，其特征在于，以含卤甲基芳烃及其衍生物、烯丙基三丁基锡为原料，在钯和膦催化剂存在的情况下，于无水有机溶剂中，在室温下反应12小时后，加入酸，在40℃反应12小时，即得到相应的多取代丙烯基芳香化合物，合成路线如下：
式中，R1选芳基、甲基、2-萘基、杂芳基；
含卤甲基芳烃及其衍生物与烯丙基三丁基锡的摩尔比为1:1；
含卤甲基芳烃及其衍生物与催化剂的摩尔比为1:0.05；
含卤甲基芳烃及其衍生物与酸的摩尔比为1:2；
含卤甲基芳烃及其衍生物与钯的摩尔比为1:0.05；
含卤甲基芳烃及其衍生物在体系中的摩尔浓度为0.15mmol/mL。
2.根据权利要求1所述的制备方法，其特征在于，所述的钯为三二亚苄基丙酮二钯、醋酸钯、氯化钯、双乙酰丙酮钯、双(二苄叉丙酮)钯、特戊酸钯、乙酰丙酮钯、二三苯基膦二醋酸钯、乙二胺氯化钯、双(三环己基膦)二氯化钯、三氟乙酸钯中的一种或两种以上混合。
3.根据权利要求1所述的制备方法，其特征在于，所述的膦催化剂为三苯基膦、三对甲苯基膦、三对甲氧基苯基膦、三对氟苯基膦、叔丁基二苯基膦、三环己基膦、三(2-呋喃基)膦、1,4-双(二苯膦)丁烷、1,1'-双(二苯基膦)二茂铁。
4.根据权利要求1所述的制备方法，其特征在于，所述的无水有机溶剂为二氯甲烷、四氢呋喃、1,4-二氧六环、乙醚、甲基叔丁基醚、甲苯、乙腈、甲基环戊基醚、1,2-二氯乙烷中的一种或两种以上混合。
5.根据权利要求1所述的制备方法，其特征在于，所述的酸为对甲苯磺酸一水合物、三氟乙酸、乙酸、氟硼酸、甲磺酸、三氟甲磺酸的一种或两种以上混合。
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