CN113976173A - 一种含p骨架结构单元的有机分子笼非均相催化剂及其制备方法和用途 - Google Patents
一种含p骨架结构单元的有机分子笼非均相催化剂及其制备方法和用途 Download PDFInfo
- Publication number
- CN113976173A CN113976173A CN202111169177.0A CN202111169177A CN113976173A CN 113976173 A CN113976173 A CN 113976173A CN 202111169177 A CN202111169177 A CN 202111169177A CN 113976173 A CN113976173 A CN 113976173A
- Authority
- CN
- China
- Prior art keywords
- substituted
- aryl
- solvent
- acid
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 29
- 239000002091 nanocage Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 150000001408 amides Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 12
- 238000005910 aminocarbonylation reaction Methods 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 62
- 239000002904 solvent Substances 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 125000005842 heteroatom Chemical group 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 125000003282 alkyl amino group Chemical group 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 11
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 230000001737 promoting effect Effects 0.000 claims description 6
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 6
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 claims description 5
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 229940125773 compound 10 Drugs 0.000 claims description 5
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 125000006528 (C2-C6) alkyl group Chemical group 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 125000005157 alkyl carboxy group Chemical group 0.000 claims description 4
- 125000005189 alkyl hydroxy group Chemical group 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 4
- 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 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- SFLXUZPXEWWQNH-UHFFFAOYSA-K tetrabutylazanium;tribromide Chemical compound [Br-].[Br-].[Br-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC SFLXUZPXEWWQNH-UHFFFAOYSA-K 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- ZIIGSRYPZWDGBT-UHFFFAOYSA-N 610-30-0 Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O ZIIGSRYPZWDGBT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 2
- 239000005456 alcohol based solvent Substances 0.000 claims description 2
- -1 aliphatic amines Chemical class 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 150000004982 aromatic amines Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000005605 benzo group Chemical group 0.000 claims description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 150000007522 mineralic acids Chemical group 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims description 2
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 2
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-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
- 239000008096 xylene Substances 0.000 claims description 2
- 125000006559 (C1-C3) alkylamino group Chemical group 0.000 claims 1
- 239000000460 chlorine Chemical group 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Chemical group 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 70
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- LJIOTBMDLVHTBO-CUYJMHBOSA-N (2s)-2-amino-n-[(1r,2r)-1-cyano-2-[4-[4-(4-methylpiperazin-1-yl)sulfonylphenyl]phenyl]cyclopropyl]butanamide Chemical compound CC[C@H](N)C(=O)N[C@]1(C#N)C[C@@H]1C1=CC=C(C=2C=CC(=CC=2)S(=O)(=O)N2CCN(C)CC2)C=C1 LJIOTBMDLVHTBO-CUYJMHBOSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- HPKJGHVHQWJOOT-ZJOUEHCJSA-N N-[(2S)-3-cyclohexyl-1-oxo-1-({(2S)-1-oxo-3-[(3S)-2-oxopyrrolidin-3-yl]propan-2-yl}amino)propan-2-yl]-1H-indole-2-carboxamide Chemical compound C1C(CCCC1)C[C@H](NC(=O)C=1NC2=CC=CC=C2C=1)C(=O)N[C@@H](C[C@H]1C(=O)NCC1)C=O HPKJGHVHQWJOOT-ZJOUEHCJSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UZVNCLCLJHPHIF-NOJKMYKQSA-J zinc;(1e)-2-(ethylcarbamoylamino)-n-methoxy-2-oxoethanimidoyl cyanide;manganese(2+);n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[Zn+2].[S-]C(=S)NCCNC([S-])=S.[S-]C(=S)NCCNC([S-])=S.CCNC(=O)NC(=O)C(\C#N)=N\OC UZVNCLCLJHPHIF-NOJKMYKQSA-J 0.000 description 2
- UVNPEUJXKZFWSJ-LMTQTHQJSA-N (R)-N-[(4S)-8-[6-amino-5-[(3,3-difluoro-2-oxo-1H-pyrrolo[2,3-b]pyridin-4-yl)sulfanyl]pyrazin-2-yl]-2-oxa-8-azaspiro[4.5]decan-4-yl]-2-methylpropane-2-sulfinamide Chemical compound CC(C)(C)[S@@](=O)N[C@@H]1COCC11CCN(CC1)c1cnc(Sc2ccnc3NC(=O)C(F)(F)c23)c(N)n1 UVNPEUJXKZFWSJ-LMTQTHQJSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- TZKBVRDEOITLRB-UHFFFAOYSA-N 4-methyl-n-[4-[(4-methylpiperazin-1-yl)methyl]-3-(trifluoromethyl)phenyl]-3-[2-(1h-pyrazolo[3,4-b]pyridin-5-yl)ethynyl]benzamide Chemical compound C1CN(C)CCN1CC(C(=C1)C(F)(F)F)=CC=C1NC(=O)C1=CC=C(C)C(C#CC=2C=C3C=NNC3=NC=2)=C1 TZKBVRDEOITLRB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000007825 activation reagent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- NLEUXPOVZGDKJI-UHFFFAOYSA-N nickel(2+);dicyanide Chemical compound [Ni+2].N#[C-].N#[C-] NLEUXPOVZGDKJI-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- JQSHBVHOMNKWFT-DTORHVGOSA-N varenicline Chemical compound C12=CC3=NC=CN=C3C=C2[C@H]2C[C@@H]1CNC2 JQSHBVHOMNKWFT-DTORHVGOSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0269—Phosphorus containing compounds on mineral substrates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/06—Formation or introduction of functional groups containing nitrogen of amide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/38—Nitrogen atoms
- C07D215/40—Nitrogen atoms attached in position 8
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/192—Radicals derived from carboxylic acids from aromatic carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
技术领域
本发明属于催化和精细化工领域,具体而言,涉及一类含P骨架结构单元的有机分子笼负载Pd纳米颗粒的非均相催化剂及其合成方法,以及该类非均相催化剂在促进烯炔氢氨基羰基化反应中的应用。
背景技术
酰胺作为各种有机转化的关键中间体,可直接用于合成含有该类基团的天然产物、药物、功能材料和农用化学品。酰胺分子中的氮原子为sp2杂化,孤对电子所在的p轨道和羰基形成p-π共轭,导致C-N键具有部分双键性质而不能自由旋转,这种特殊的构象显著影响酰胺的理化性质以及蛋白质构象,因此酰胺结构广泛存在于活性天然产物、药物分子、功能材料和农用化学品中。
经典的酰胺合成主要通过羧酸与胺的缩合反应而制得,但该类方法需要使用大量的缩合试剂和活化试剂,且生成的副产物难于处理;使用羧酸衍生物可以显著提高酰胺的合成效率,但需要预先将酰胺制备成活性物质再与胺反应生成酰胺,同时产生化学计量的副产物,原子经济性较低。
近几十年来,烯炔氢氨基羰基化反应成为酰胺合成最具前景的方法,是一条具有100%原子效率的途径。在氨基羰基化的早期研究中,羰基钴配合物(Chem.Abstr.1975,83,205731)或氰化镍(Chem.Abstr.1953,47,5428)被用作催化剂。铁羰基配合物(J.Prakt.Chem.1965,29,281)和氯化钌(J.Org.Chem.1961,26,3126)也显示出一些催化活性。然而,这些反应都是在非常剧烈的反应条件下进行(>200℃;>150atm)。自20世纪80年代以来,不同有效的催化剂,如钌羰基配合物(J.Organomet.Chem.1986,309,333)和碳化钴(Chem.Commun.2002,1310)被开发出来;然而,反应底物范围有限,反应条件仍较苛刻(150℃;70atm)。此外,铑基催化剂(Org.Lett.2007,9,2465;Adv.Synth.Catal.2007,349,849)也应用于炔烃的氢氨基羰基化,但仍需较高的反应温度和较长的反应时间。
烯炔氢氨基羰基化技术突破的关键在于催化剂的开发,具体来说,在于新型结构膦配体的设计合成。膦配体结构对催化反应的活性和产物的选择性起着决定性的作用。在过去几十年中,Beller(Angew.Chem.Int.Ed.2013,52,14089;Angew.Chem.Int.Ed.2015,54,10239;J.Am.Chem.Soc.2015,137,6053;Angew.Chem.Int.Ed.2016,55,13544;)、Cole-Hamilton(Catal.Sci.Technol.2014,4,2332)、Huang(Angew.Chem.Int.Ed.2015,54,7657;ACS Catal.2016,6,6785;Org.Biomol.Chem.2017,15,2910;Chem.Sci.2018,9,380;Org.Lett.2018,20,2208;Commun.Chem.2019,20,14)、Alper(J.Am.Chem.Soc.2016,138,6629)、Liu(Chem.Commun.2014,50,7848)、Wu(Angew.Chem.Int.Ed.2020,59,22441)和Guan(J.Am.Chem.Soc.2021,143,85;J.Am.Chem.Soc.2021,143,7298)等人通过有机膦配体调控Pd催化烯烃的氢氨基羰基化巧妙地开发了合成线性或支链酰胺的方法;此外,Ali(Tetrahedron Lett.2000,41,5761;Appl.Organometal.Chem.2002,16,369;J.Mol.Catal.A Chem.2002,187,17;Appl.Organometal.Chem.2003,17,921;Appl.Organometal.Chem.2010,24,38)、Matteoli(J.Mol.Catal.A Chem.2004,213,183)、Alper(J.Am.Chem.Soc.2008,130,6451;ACS.Catal.2017,7,2220)、Beller(Angew.Chem.Int.Ed.2011,50,537)、Dyson(J.Org.Chem.2015,80,386)、Huang(Org.Lett.2017,9,6260;J.Org.Chem.2018,83,10134)、Liu(ChemCatChem 2018,10,4264;Catal.Sci.Technol.2019,9,1334)、Lei(Nat.Catal.2020,3,438)以及离子液体Yu(Org.Lett.2006,8,5199)和自由基Ryu(Angew.Chem.Int.Ed.2005,44,1075)介导的炔烃与胺的氢氨基羰基化合成线性或支链酰胺的方法。尽管该类钯催化的氢氨基羰基化已取得了巨大的成功,但均相催化过程中催化剂和产物的分离以及过渡金属的回收利用问题仍是制约烯炔氢氨基羰基化反应工业化应用的关键问题。
解决上述问题的可行技术之一是新型的非均相催化技术的研发。传统的非均相催化剂是将有机配体经化学手段形成难溶或不溶的有机高分子聚合物,通过与金属前驱体的配位形成非均相催化剂,该类催化剂可以很好的实现产物与催化剂的分离,但仍然无法保证金属的流失问题。与之不同的是,具有纳米结构的非均相催化剂可以很好的改善这一状况。2018年,Shi等(Green Chem.2018,20,3457)通过使用148nm的钯粉实现了非均相钯催化的烯烃氢氨基羰基化,但该方法中产物的选择性较差,直/支链比约为2:1-1:1,仍然无法满足工业化生产的需要。随后,该课题组通过POPs负载的钯纳米催化剂实现了炔烃的氢氨基羰基化(Adv.Synth.Catal.2020,362,2348)。
尽管经过几十年的探索研究,目前烯炔氢氨基羰基化仍然无法满足工业化生产的需要。进一步解决催化过程中催化剂和产物的分离以及过渡金属的回收利用问题是该工艺路线早日实现突破的关键。显而易见,多相催化剂的开发将是实现烯炔氢氨基羰基化制酰胺的关键,直接关系到该反应路线能否迈向工业化。
发明内容
针对上述现有技术中的问题,本发明的一个目的在于提供一种含P架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂,其具有通式1的结构,
其中,R1和R2各自独立地选自以下结构:氢、C1-C6烷基、C1-C6烷氧基、C1-C6烷基羟基、C2-C6烷基羧基、C2-C6烷基酯基、C1-C6烷基酰胺基,或者
R1和R2彼此连接与它们相连的苯环一起形成含有1至3个杂原子的八至十元并环结构,所述1至3个杂原子选自O、S或N;
R3和R4各自独立地选自氢、C1-C6烷基,C1-C6烷氧基,C2-C6烷基胺基、C6-C10芳基、C1-C6烷氧基取代的C6-C10芳基、C1-C6烷基取代的C6-C10芳基、C2-C6烯基取代的C6-C10芳基或C2-C6烷基胺基取代的C6-C10芳基,或者
R3和R4彼此连接与它们相连的碳原子一起形成C6-C10芳基、C1-C6烷氧基取代的C6-C10芳基、C1-C6烷基取代的C6-C10芳基、C2-C6烯基取代的C6-C10芳基或C2-C6烷基胺基取代的C6-C10芳基、卤素取代的C6-C10芳基、羟基取代的C6-C10芳基、硝基取代的C6-C10芳基、酰胺基取代的C6-C10芳基、C1-C6烷基胺基取代的C6-C10芳基、含有1至3个杂原子的八至十元并环结构,所述1至3个杂原子选自O、S或N。
优选地,R1和R2各自独立地选自以下结构:氢、C1-C3烷基、C1-C3烷氧基、C1-C3烷基羟基、C2-C4烷基羧基、C2-C6烷基酯基、C1-C4烷基酰胺基,或者
R1和R2彼此连接与它们相连的苯环一起形成含有1至3个杂原子的八至十元并环结构,所述1至3个杂原子选自O、S或N;
R3和R4各自独立地选自氢、C1-C3烷基,C1-C3烷氧基,C2-C4烷基胺基、C6-C10芳基、C1-C3烷氧基取代的C6-C10芳基、C1-C3烷基取代的C6-C10芳基、C2-C4烯基取代的C6-C10芳基或C2-C4烷基胺基取代的C6-C10芳基、氟取代的C6-C10芳基、氯取代的C6-C10芳基、羟基取代的C6-C10芳基、酰胺基取代的C6-C10芳基、C1-C3烷基胺基取代的C6-C10芳基,或者
R3和R4彼此连接与它们相连的碳原子一起形成C6-C10芳基、C1-C3烷氧基取代的C6-C10芳基、C1-C3烷基取代的C6-C10芳基、C2-C4烯基取代的C6-C10芳基或C2-C4烷基胺基取代的C6-C10芳基、硝基取代的C6-C10芳基,含有1至3个杂原子的八至十元并环结构,所述1至3个杂原子选自O、S或N。
优选地,R1和R2各自独立地选自以下结构:-H、-Me、-OMe、-OEt、-OAc、-COOMe、-NHAc、-CONH2,或者
R3和R4各自独立地选自氢、C1-C3烷基,C1-C3烷氧基,C2-C4烷基胺基、苯基,或者
R3和R4彼此连接与它们相连的碳原子一起形成苯基、C1-C3烷氧基取代的苯基、C1-C3烷基取代的苯基、C2-C4烯基取代的苯基或C2-C4烷基胺基取代的苯基、硝基取代的苯基,含有1至3个杂原子的八至十元苯并结构,所述1至3个杂原子选自O、S或N。
优选地,R1选自-H、-Me或-OMe;
R2选自-H、-Me、-OMe、-OEt、-OAc、-COOMe、-NHAc、-CONH2,或者
优选地,R3和R4各自独立地选自以下结构:
优选地,所述含P骨架结构单元有机分子笼负载Pd纳米颗粒催化剂结构选自如下1至6中:
根据本发明的另一个方面,本发明的另一个目的在于提供所述含P骨架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂(Pd@PPOC)的制备方法,所述方法包括惰性气体保护下在溶剂中在还原剂的存在下将二齿膦配体化合物8(以下简称PPOC)与金属前驱体反应得到,如下反应式1所示:
其中,金属前驱体与二齿膦配体化合物8的摩尔比为2:1-1:10,优选1:1-1:5,更优选1:1-1:3;
惰性气体选自氮气或氩气;
反应温度为-78℃-150℃,优选为0℃-室温;
反应时间为0.5h-24h;
所述溶剂选自二氯甲烷、四氢呋喃、二氧六环、吡啶、己烷、甲醇、乙醇、乙酸乙酯、乙醚和丙酮中的一种或者多种;更优选为二氯甲烷和甲醇;
所述金属前驱体选自醋酸钯、硫酸钯、碘化钯、溴化钯、氯化钯、乙二胺氯化钯、硝酸钯、四氯钯酸钠和三氟乙酸钯中的一种或者多种;更优选为醋酸钯和三氟乙酸钯;
所述还原剂选自硼氢化钠、氰基硼氢化钠、三乙酰基硼氢化钠、硼氢化镍、硼氢化氢化铝锂、红铝、二异丁基氢化铝、Schwartz试剂、三丁基氢化锡。
其中,有机膦P骨架结构单元有机分子笼中的取代基R1、R2和R3的定义与通式1中的相同。
优选地,所述二齿膦配体化合物8按照以下方法制备:
1)在溶剂中以四丁基三溴化铵为催化剂,化合物9与原甲酸三甲酯在60℃反应得到化合物10,其中取代基R1和R2的定义与通式1中的相同;
2)在0℃的溶剂中,化合物10与正丁基锂发生锂-卤交换所得的碳负离子与三氯化磷反应得到化合物11;
3)化合物11在溶剂中经酸水解反应得到化合物7,温度为0℃-60℃,时间为1h-12h;
4)在惰性气体保护下将化合物7与包含R3和R4的对应1,2-二胺化合物加入溶剂中,温度控制为0℃-100℃;时间为1天-7天,反应完成后减压蒸馏除去溶剂,得到二齿膦配体化合物8,其中取代基R3和R4的定义与通式1中的相同。
优选地,步骤1)中所述溶剂为醇类溶剂或酮类溶剂,优选为甲醇、乙醇或者丙酮。
优选地,步骤2)中所述溶剂为醚类溶剂或烃类溶剂,优选为乙醚、四氢呋喃、二正丁基醚、1,4-二氧六环、正己烷、环己烷或者甲苯。
优选地,步骤3)中所述溶剂为醇类溶剂或醚类溶剂,优选为乙醚、四氢呋喃、二正丁基醚、1,4-二氧六环、甲醇或者乙醇;根据本发明的另一个目的在于提供所述含P骨架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂在促进金属催化烯炔的氢氨基羰基化反应中的用途。
根据本发明的另一个目的在于提供一种由烯烃和炔烃的氨基羰基化反应制备支链酰胺的方法,包括以下步骤:
取适量根据本发明所述含P骨架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂加入反应釜中,然后加入溶剂、添加剂、胺和烯烃或炔烃,封闭反应釜,充入一定压力的CO气体,在设定的温度下反应一定时间。
优选地,所述溶剂选自脂肪烃类溶剂,芳香烃类溶剂,醇类溶剂,酰胺类溶剂或者醚类溶剂;
更优选地,所述溶剂选自正己烷、环己烷、辛烷、苯、甲苯、二甲苯、甲醇、乙醇、异丙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、乙醚、四氢呋喃和二氧六环中的一种或多种,更优选为N-甲基吡咯烷酮;
优选地,所述添加剂选自无机酸类或者有机酸类,该类添加剂的作用是促进催化剂活性物种的生成,进而促进反应的进行。
更优选地,所述添加剂选自氢氟酸、盐酸、氢溴酸、氢碘酸、硫酸、亚硫酸、硼酸、硝酸、磷酸、草酸、三氟乙酸、甲磺酸、三氟甲磺酸、对甲苯磺酸、樟脑磺酸、2,4-二硝基苯甲酸;
优选地,所述胺选自芳香胺和脂肪胺;
优选地,含P骨架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂与烯烃或炔烃的摩尔比为1/50-1/5000,优选为1/100-1/1000;
优选地,气体的压力为1MPa-10MPa,优选为2MPa-5MPa;
优选地,反应温度为50℃-200℃,优选为80℃-120℃;
优选地,反应时间为5h-24h,优选为6h-16h;
优选地,烯烃或炔烃的反应浓度为0.1mol/L-10mol/L,优选为0.5mol/L-3mol/L。
有益效果
本发明中制备的含P骨架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂可以催化烯炔的氢氨基羰基化反应制备酰胺,与现有技术文献报道催化剂相比产物中酰胺的分离收率最高可达98%,支链/支链比为77:1,几乎无副产物生成,同时本发明的催化剂为非均相催化剂,因此,根据本发明的催化剂有很好的催化效果并且易于分离回收再利用,为进一步工业化打下了基础。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单的介绍,显而易见地,下面描述中的附图是本发明的一些实施方式,对本领域普通技术人员而言,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为根据本发明的通式1表示的含P架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂(Pd@PPOC)的立体结构示意图,其中通式1中的元素符号Pd代表钯原子构成的纳米颗粒,而不是单独一个钯原子。
图2为制备实施例1中的化合物PPOC(化合物8a)的液体核磁氢谱。
图3为制备实施例1中的化合物PPOC(化合物8a)的液体核磁碳谱。
图4为制备实施例1中的化合物PPOC(化合物8a)的液体核磁磷谱。
图5为制备实施例1中的化合物Pd@PPOC(化合物1)的HR-TEM图像和粒度分布。
图6为制备实施例1中的化合物Pd@PPOC(化合物1)的液态核磁磷谱。
图7为测试实施例2中采用制备实施例1中的化合物Pd@PPOC(化合物1)催化苯乙烯与苯胺的循环实验结果图。
具体实施方式
为了更好的理解本发明,下面结合实施例进一步阐明本发明的内容,以下实施例仅是列举本发明实施方案的部分例子,并不对本发明构成任何限制,本领域技术人员可以理解在不偏离本发明的实质和构思的范围内的修改均落入本发明的保护范围。除非特别说明,以下实施例中使用的试剂和仪器均为市售可得产品。
根据本发明的由通式1表示的含P架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂(Pd@PPOC)具有立体结构,其中两个三苯基膦分子通过三个1,2-二胺类连接键彼此连接形成笼形结构,并且通过适当选择R1至R4可以方便地控制该分子结构的空间位阻和电子效应。通过钯金属前驱体与二齿膦配体化合物(PPOC)在还原剂的存在下反应,使钯金属元素在该分子笼形结构中原位生长,形成钯金属纳米团簇(纳米颗粒),参考图1,示例性的展示了根据本发明的所述Pd@PPOC催化剂的结构,其中钯金属纳米团簇位于笼形分子内部并受到配体PPOC的空间限制,这种结构便于保持钯金属作为催化活性位点的同时,由于颗粒较大,实现了非均相催化的目的。
在本文中,用语“包含”、“包括”、“具有”、“含有”或其他任何类似用语均属于开放性连接词(open-ended transitional phrase),其意欲涵盖非排他性的包括物。举例而言,含有复数要素的一组合物或制品并不仅限于本文所列出的这些要素而已,而是还可包括未明确列出但却是该组合物或制品通常固有的其他要素。除此之外,除非有相反的明确说明,否则用语“或”是指涵盖性的“或”,而不是指排他性的“或”。例如,以下任何一种情况均满足条件“A或B”:A为真(或存在)且B为伪(或不存在)、A为伪(或不存在)且B为真(或存在)、A和B均为真(或存在)。此外,在本文中,用语“包含”、“包括”、“具有”、“含有”的解读应视为已具体公开并同时涵盖“由…所组成”及“实质上由…所组成”等封闭式或半封闭式连接词。
在本文中,所有以数值范围或百分比范围形式界定的特征或条件仅是为了简洁及方便。据此,数值范围或百分比范围的描述应视为已涵盖且具体公开所有可能的次级范围及范围内的个别数值,特别是整数数值。举例而言,“1至8”的范围描述应视为已经具体公开如1至7、2至8、2至6、3至6、4至8、3至8等等所有次级范围,特别是由所有整数数值所界定的次级范围,且应视为已经具体公开范围内如1、2、3、4、5、6、7、8等个别数值。除非另有指明,否则前述解释方法适用于本发明全文的所有内容,不论范围广泛与否。
若数量或其他数值或参数是以范围、较佳范围或一系列上限与下限表示,则其应理解成是本文已特定公开了由任一对该范围的上限或较佳值与该范围的下限或较佳值构成的所有范围,不论这些范围是否有分别公开。此外,本文中若提到数值的范围时,除非另有说明,否则该范围应包括其端点以及范围内的所有整数与分数。
在本文中,在可实现发明目的的前提下,数值应理解成具有该数值有效位数的精确度。举例来说,数字40.0则应理解成涵盖从39.50至40.49的范围。
在本文中,对于使用马库什群组(Markush group)或选项式用语以描述本发明特征或实例的情形,本领域技术人员应了解马库什群组或选项列表内所有要素的次级群组或任何个别要素亦可用于描述本发明。举例而言,若X描述成“选自于由X1、X2及X3所组成的群组”,亦表示已经完全描述出X为X1的主张与X为X1及/或X2的主张。再者,对于使用马库什群组或选项式用语以描述本发明的特征或实例的情况,本领域技术人员应了解马库什群组或选项列表内所有要素的次级群组或个别要素的任何组合亦可用于描述本发明。据此,举例而言,若X描述成“选自于由X1、X2及X3所组成的群组”,且Y描述成“选自于由Y1、Y2及Y3所组成的群组”,则表示已经完全描述出X为X1或X2或X3而Y为Y1或Y2或Y3的主张。
本发明中的取代基中的缩写“Me”为甲基,“Et”为乙基,“Ac”为乙酰基,“NHAc”为乙酰氨基。
材料表征所用仪器:
(1)气相色谱仪:型号为GC-2010,生产厂家为日本SHIMADZU
(2)气相色谱质谱联用仪:型号为GCMS-QP2010,生产厂家为日本SHIMADZU
(3)液相色谱质谱联用仪:型号为Agilent1290-6430,生产厂家为美国Agilent
(4)核磁共振波谱仪:型号为ASCEND 400MHz和AVANCE-III 600MHz,生产厂家为瑞士布鲁克公司。
在随后的具体实施例中,催化体系选用的金属前驱体为Pd(OAc)2,所用的有机P骨架结构单元有机分子笼结构如下:
制备实施例1:配体8a的合成
步骤1:化合物10a的合成:
取10g 4-溴苯甲醛(化合物9a)加入反应器中,加20mL甲醇溶解,之后加7.1mL原甲酸三甲酯(CH(OCH3)3)和2.61g四丁基三溴化铵(Bu4NBr3),80℃反应过夜。冷却至室温,将反应液减压蒸馏,以石油醚:乙酸乙酯=20:1进行柱层析纯化,60℃真空干燥,得到化合物10a。
步骤2:化合物11a的合成:
取6.5g化合物10a加入反应器中,加50mL四氢呋喃(THF)溶解,然后冷却到-78℃,缓慢滴加17.6mL正丁基锂(n-BuLi),室温反应2h。将反应冷却至-78℃,缓慢滴加615μL三氯化磷(PCl3),室温反应过夜。加20mL 2N HCl淬灭反应,水相用50mL乙酸乙酯萃取3次,有机相用无水硫酸钠干燥,过滤减压蒸干溶剂得到化合物11a粗品。
步骤3:化合物7a的合成:
将上述所得化合物11a粗品溶解于50mL四氢呋喃中,加入20mL 1N HCl室温搅拌反应1h。加20mL饱和NaHCO3溶液淬灭反应,水相用50ml*3乙酸乙酯萃取,有机相用无水硫酸钠干燥,过滤减压蒸干溶剂,随后以石油醚:乙酸乙酯=4:1进行柱层析纯化,得到化合物7a纯品。核磁数据如下:1H NMR(400MHz,CDCl3)δ9.97(s,3H),7.81(dd,J=8.2,1.4Hz,6H),7.40(t,J=7.7Hz,6H).31P NMR(162MHz,CDCl3)δ-3.96。
步骤4:化合物8a的合成:
氩气保护下,将1.24g 7a溶于300mL二氯甲烷中,随后加入300mL甲醇,搅拌状态下缓慢滴加615μL 1,2-环己二胺,40℃下搅拌反应5天。减压蒸除2/3的溶剂,溶液中有白色沉淀析出,过滤,5mL甲醇洗涤3次,干燥得化合物8a。核磁数据如下:1HNMR(400MHz,CDCl3)δ7.67(s,6H),7.31(d,J=6.9Hz,12H),6.99(t,J=7.5Hz,12H),3.19(s,6H),2.14(d,J=11.7Hz,6H),1.92(d,J=7.0Hz,12H),1.51(t,J=9.8Hz,6H).13CNMR(101MHz,CDCl3)δ163.06,139.13,139.01,136.75,136.65,133.23,133.04,127.66,127.60,73.20,31.98,24.38.31P NMR(162MHz,CDCl3)δ-7.85.HR-MS(ESI):m/z for C60H60N6P2,[M+H]+927.4431(calcd 927.4433);[M+2H]2+464.2234(calcd 464.2255)。
制备实施例2:催化剂Pd@PPOC(化合物1)的合成:
氩气保护下将413mg PPOC(化合物8a)溶于50mL二氯甲烷中,随后加入50mL甲醇,搅拌状态下加入302mg醋酸钯(Pd(OAc)2),室温搅拌反应4h。0℃下加入599mg硼氢化钠(NaBH4),室温搅拌过夜。减压蒸除溶剂,过滤并用5mL水洗涤3次,干燥得到催化剂Pd@PPOC(结构1)。
测试实施例1:
将4.0mg制备实施例1制备得到的含P骨架结构单元有机分子笼负载Pd纳米颗粒催化剂加入到25ml的高压釜内,加3ml N-甲基吡咯烷酮溶解,然后依次加入烯烃或炔烃(0.5mmol),胺(0.6mmol),盐酸(0.6mmol),封闭反应釜,通入一定压力的CO(4.0MPa),反应16h。降温,过滤回收催化剂(水洗干燥后用于下一催化),并用5mL甲醇洗涤3次,采用GC-2010检测产物的支链/支链的选择性,减压蒸干溶剂,柱层析得到目标产物。实验条件及结果见下表1。
表1:
从表1的数据可以看出,根据本发明制备的含P骨架结构单元有机分子笼负载Pd纳米颗粒催化剂可以有效催化烯炔转化为酰胺。酰胺的收率最高可以达到98%以上,支链选择性可达77:1。
产物核磁数据如下:
表1中生成的产物的核磁数据如下:
编号1:1H NMR(400MHz,CDCl3)δ7.48–7.20(m,10H),7.13–6.97(m,2H),3.72(q,J=7.1Hz,1H),1.61(d,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ172.2,140.9,137.8,129.2,128.9,127.7,127.6,124.3,119.7,48.2,18.6.
编号2:1H NMR(400MHz,CDCl3)δ7.41–7.27(m,7H),7.14(s,1H),6.84–6.76(m,2H),3.75(s,3H),3.70(q,J=7.1Hz,1H),1.59(d,J=7.2Hz,3H).13C NMR(101MHz,CDCl3)δ172.4,156.5,141.2,131.1,129.2,127.8,127.6,121.8,114.1,55.6,47.9,18.7.
编号3:1H NMR(400MHz,CDCl3)δ7.42–7.27(m,6H),7.17(dt,J=15.4,8.2Hz,3H),6.89(d,J=7.3Hz,1H),3.71(q,J=7.1Hz,1H),2.29(s,3H),1.60(d,J=7.1Hz,3H).13CNMR(101MHz,CDCl3)δ172.4,141.0,138.9,137.8,129.2,128.7,127.7,127.6,125.1,120.4,116.8,48.1,21.5,18.6.
编号4:1H NMR(400MHz,CDCl3)δ7.66(d,J=8.2Hz,1H),7.44–7.29(m,5H),6.97(d,J=8.2Hz,1H),6.90(s,1H),6.81(s,1H),3.77(q,J=7.2Hz,1H),2.25(s,3H),1.87(s,3H),1.64(d,J=7.2Hz,3H).13C NMR(101MHz,CDCl3)δ172.3,141.1,134.6,133.1,131.0,129.2,128.6,127.9,127.7,127.2,122.5,48.0,20.8,18.1,17.1.
编号5:1H NMR(400MHz,CDCl3)δ7.44–7.20(m,8H),6.99–6.90(m,2H),3.71(q,J=7.1Hz,1H),1.59(d,J=7.2Hz,3H).13C NMR(101MHz,CDCl3)δ172.5,160.6,158.1,140.9,133.9,133.8,129.2,127.7,127.6,121.7,121.7,115.6,115.4,47.9,18.6.
编号6:1H NMR(400MHz,CDCl3)δ7.94(s,2H),7.56(s,1H),7.49–7.30(m,6H),3.75(q,J=7.1Hz,1H),1.61(d,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ173.0,140.2,139.3,132.9,132.6,132.3,131.9,129.6,128.2,127.8,127.2,124.5,121.8,119.5,119.5,119.1,117.7,117.7,117.6,117.6,117.6,48.3,18.6.
编号7:1H NMR(400MHz,DMSO-d6)δ10.26(s,1H),7.81(d,J=8.7Hz,3H),7.65(d,J=8.7Hz,2H),7.39(d,J=7.3Hz,2H),7.33(t,J=7.6Hz,2H),7.28–7.17(m,2H),3.85(q,J=6.9Hz,1H),1.42(d,J=7.0Hz,3H).13C NMR(101MHz,DMSO-d6)δ172.6,167.3,141.8,141.7,128.7,128.4,128.3,127.3,118.2,46.0,18.6.
编号8:1H NMR(400MHz,CDCl3)δ9.89(s,1H),8.76(dd,J=7.5,1.5Hz,1H),8.69(dd,J=4.2,1.7Hz,1H),8.08(dd,J=8.3,1.7Hz,1H),7.52–7.42(m,4H),7.41–7.35(m,3H),7.31–7.26(m,1H),3.93(q,J=7.1Hz,1H),1.69(d,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ172.7,148.1,141.1,138.5,136.2,134.5,128.9,127.9,127.7,127.3,121.5,121.4,116.3,48.7,18.6.
编号9:1H NMR(400MHz,CDCl3)δ7.31(t,J=7.2Hz,2H),7.25-7.18(m,3H),3.83(q,J=6.8Hz,1H),3.86-3.22(m,7H),3.08(ddd,J=11.2,7.1,3.2Hz,1H),1.44(d,J=6.9Hz,3H).13C NMR(101MHz,CDCl3)δ172.4,142.1,129.2,127.4,127.1,67.0,66.5,46.2,43.5,42.6,20.9.
编号10:1H NMR(400MHz,CDCl3)δ7.52(d,J=7.9Hz,2H),7.42(s,1H),7.33–7.25(m,2H),7.07(t,J=7.4Hz,1H),2.49(d,J=3.6Hz,1H),2.37–2.22(m,2H),1.98(dtd,J=9.2,4.7,2.5Hz,1H),1.70–1.43(m,4H),1.30–1.13(m,3H).13C NMR(101MHz,CDCl3)δ174.3,138.4,129.0,124.0,119.8,49.1,41.8,36.6,36.1,34.3,29.9,28.8.
编号11:1H NMR(400MHz,DMSO-d6):δ9.79(s,1H),7.59(d,J=7.8Hz,2H),7.27(t,J=7.8Hz,2H),7.00(d,J=7.2Hz,1H),2.32(t,J=11.4Hz,1H),1.77-1.64(m,5H),1.46-1.15(m,5H);13C NMR(101MHz,DMSO-d6):δ174.2,139.4,128.5,122.7,118.9,44.8,29.1,25.3,25.2;
编号12:1H NMR(400MHz,CDCl3)δ7.52(d,J=8.0Hz,2H),7.43(s,1H),7.37(d,J=8.0Hz,2H),7.32(t,J=7.9Hz,2H),7.29–7.23(m,2H),7.12(t,J=7.4Hz,1H),2.70(q,J=7.6Hz,2H),1.28(t,J=7.6Hz,3H).13C NMR(101MHz,CDCl3)δ165.5,145.3,145.1,137.8,134.1,129.1,128.6,128.4,124.7,123.0,120.1,28.7,15.6.
编号13:1H NMR(400MHz,CDCl3)δ7.48(d,J=8.0Hz,3H),7.42–7.27(m,5H),7.20(s,1H),7.11(t,J=7.4Hz,1H),6.54(s,1H),5.68(s,1H).13C NMR(101MHz,CDCl3)δ163.8,143.1,137.7,136.1,133.7,131.7,130.5,130.1,129.1,127.6,126.8,124.8,120.4.
编号14:1H NMR(400MHz,CDCl3)δ7.53(d,J=7.8Hz,2H),7.46(s,2H),7.35(dt,J=15.8,6.4Hz,5H),7.14(t,J=7.3Hz,1H),6.21(s,1H),5.75(s,1H).13C NMR(101MHz,CDCl3)δ165.1,144.3,138.4,137.6,135.0,130.2,129.2,129.1,128.4,126.4,124.9,123.4,120.2.
编号15:1H NMR(400MHz,CDCl3)δ7.51(t,J=11.1Hz,3H),7.39(s,4H),7.32(t,J=7.8Hz,2H),7.13(t,J=7.4Hz,1H),6.18(s,1H),5.73(s,1H).13C NMR(101MHz,CDCl3)δ165.3,144.4,137.6,135.1,135.0,129.6,129.2,129.2,124.9,122.8,120.1.
编号16:1H NMR(400MHz,CDCl3)δ7.52(t,J=9.4Hz,3H),7.43(d,J=8.0Hz,0H),7.38–7.29(m,4H),7.24(d,J=7.9Hz,2H),7.18(d,J=7.9Hz,0H),7.12(t,J=7.4Hz,1H),7.04(d,J=7.4Hz,0H),6.24(s,1H),5.69(s,1H),2.40(s,3H).13C NMR(101MHz,CDCl3)δ165.6,145.1,139.0,137.8,133.8,129.7,129.1,128.3,124.6,122.8,120.0,21.3.
编号17:1H NMR(400MHz,CDCl3)δ7.53(d,J=7.9Hz,2H),7.46(s,1H),7.39–7.29(m,4H),7.24(d,J=8.0Hz,2H),7.12(t,J=7.4Hz,1H),6.29–6.20(m,1H),5.70(d,J=1.2Hz,1H),2.67–2.60(m,2H),1.72–1.64(m,2H),0.98(t,J=7.3Hz,3H).13C NMR(101MHz,CDCl3)δ165.5,145.0,143.7,137.7,134.0,129.1,129.0,128.2,124.6,122.7,120.0,37.8,24.5,13.9.
测试实施例2:
随后,以苯乙烯和苯胺为底物在最优反应条件下对制备实施例1制备得到的含P骨架结构单元有机分子笼负载Pd纳米颗粒催化剂的稳定性和循环使用性进行了测试。每次反应完成之后,通过离心收集催化剂,并用水和乙醇冲洗,在65℃下真空干燥后,无需再次活化直接应用于下一催化循环。催化剂循环使用10次,不会造成明显的产率和选择性损失。图7为循环实验结果图,从图中可以看出,随着循环次数的增加,产率从近100%逐步降低,但即使循环10次,产率依然接近90%,同时选择性,除了第10次循环时略低以外,其余9次循环都保持高的选择性。这表明催化剂制备的催化剂具有良好的可重复使用性和稳定性。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应所述以权利要求的保护范围为准。
Claims (10)
1.一种含P架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂,其具有通式1的结构,
其中,R1和R2各自独立地选自以下结构:氢、C1-C6烷基、C1-C6烷氧基、C1-C6烷基羟基、C2-C6烷基羧基、C2-C6烷基酯基、C1-C6烷基酰胺基,或者
R1和R2彼此连接与它们相连的苯环一起形成含有1至3个杂原子的八至十元并环结构,所述1至3个杂原子选自O、S或N;
R3和R4各自独立地选自氢、C1-C6烷基,C1-C6烷氧基,C2-C6烷基胺基、C6-C10芳基、C1-C6烷氧基取代的C6-C10芳基、C1-C6烷基取代的C6-C10芳基、C2-C6烯基取代的C6-C10芳基或C2-C6烷基胺基取代的C6-C10芳基,或者
R3和R4彼此连接与它们相连的碳原子一起形成C6-C10芳基、C1-C6烷氧基取代的C6-C10芳基、C1-C6烷基取代的C6-C10芳基、C2-C6烯基取代的C6-C10芳基或C2-C6烷基胺基取代的C6-C10芳基、卤素取代的C6-C10芳基、羟基取代的C6-C10芳基、硝基取代的C6-C10芳基、酰胺基取代的C6-C10芳基、C1-C6烷基胺基取代的C6-C10芳基、含有1至3个杂原子的八至十元并环结构,所述1至3个杂原子选自O、S或N。
2.根据权利要求1所述的非均相催化剂,其特征在于,
R1和R2各自独立地选自以下结构:氢、C1-C3烷基、C1-C3烷氧基、C1-C3烷基羟基、C2-C4烷基羧基、C2-C6烷基酯基、C1-C4烷基酰胺基,或者
R1和R2彼此连接与它们相连的苯环一起形成含有1至3个杂原子的八至十元并环结构,所述1至3个杂原子选自O、S或N;
R3和R4各自独立地选自氢、C1-C3烷基,C1-C3烷氧基,C2-C4烷基胺基、C6-C10芳基、C1-C3烷氧基取代的C6-C10芳基、C1-C3烷基取代的C6-C10芳基、C2-C4烯基取代的C6-C10芳基或C2-C4烷基胺基取代的C6-C10芳基、氟取代的C6-C10芳基、氯取代的C6-C10芳基、羟基取代的C6-C10芳基、酰胺基取代的C6-C10芳基、C1-C3烷基胺基取代的C6-C10芳基,或者
R3和R4彼此连接与它们相连的碳原子一起形成C6-C10芳基、C1-C3烷氧基取代的C6-C10芳基、C1-C3烷基取代的C6-C10芳基、C2-C4烯基取代的C6-C10芳基或C2-C4烷基胺基取代的C6-C10芳基、硝基取代的C6-C10芳基,含有1至3个杂原子的八至十元并环结构,所述1至3个杂原子选自O、S或N。
3.根据权利要求1所述的非均相催化剂,其特征在于,R1和R2各自独立地选自以下结构:-H、-Me、-OMe、-OEt、-OAc、-COOMe、-NHAc、-CONH2,或者
R3和R4各自独立地选自氢、C1-C3烷基,C1-C3烷氧基,C2-C4烷基胺基、苯基,或者
R3和R4彼此连接与它们相连的碳原子一起形成苯基、C1-C3烷氧基取代的苯基、C1-C3烷基取代的苯基、C2-C4烯基取代的苯基或C2-C4烷基胺基取代的苯基、硝基取代的苯基,含有1至3个杂原子的八至十元苯并结构,所述1至3个杂原子选自O、S或N。
6.根据权利要求1至5中任意一项所述含P骨架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂(Pd@PPOC)的制备方法,所述方法包括惰性气体保护下在溶剂中在还原剂的存在下将二齿膦配体化合物8(PPOC)与金属前驱体反应得到,如下反应式1所示:
其中,金属前驱体与二齿膦配体化合物8的摩尔比为2:1-1:10,优选1:1-1:5,更优选1:1-1:3;
惰性气体选自氮气或氩气;
反应温度为-78℃-150℃,优选为0℃-室温;
反应时间为0.5h-24h;
所述溶剂选自二氯甲烷、四氢呋喃、二氧六环、吡啶、己烷、甲醇、乙醇、乙酸乙酯、乙醚和丙酮中的一种或者多种;更优选为二氯甲烷和甲醇;
所述金属前驱体选自醋酸钯、硫酸钯、碘化钯、溴化钯、氯化钯、乙二胺氯化钯、硝酸钯、四氯钯酸钠和三氟乙酸钯中的一种或者多种;更优选为醋酸钯和三氟乙酸钯;
所述还原剂选自硼氢化钠、氰基硼氢化钠、三乙酰基硼氢化钠、硼氢化镍、硼氢化氢化铝锂、红铝、二异丁基氢化铝、Schwartz试剂、三丁基氢化锡;
其中,有机膦P骨架结构单元有机分子笼中的取代基R1、R2和R3的定义与权利要求1的通式1中的相同。
7.根据权利要求6所述的制备方法,其特征在于,所述二齿膦配体化合物8按照以下方法制备:
1)在溶剂中以四丁基三溴化铵为催化剂,化合物9与原甲酸三甲酯在60℃反应得到化合物10,其中取代基R1和R2的定义与通式1中的相同;
2)在0℃的溶剂中,化合物10与正丁基锂发生锂-卤交换所得的碳负离子与三氯化磷反应得到化合物11;
3)化合物11在溶剂中经酸水解反应得到化合物7,温度为0℃-60℃,时间为1h-12h;
4)在惰性气体保护下将化合物7与包含R3和R4的对应1,2-二胺化合物加入溶剂中,温度控制为0℃-100℃;时间为1天-7天,反应完成后减压蒸馏除去溶剂,得到二齿膦配体化合物8,其中取代基R3和R4的定义与权利要求1的通式1中的相同。
8.根据权利要求7所述的制备方法,其特征在于,步骤1)中所述溶剂为醇类溶剂或酮类溶剂,优选为甲醇、乙醇或者丙酮;
优选地,步骤2)中所述溶剂为醚类溶剂或烃类溶剂,优选为乙醚、四氢呋喃、二正丁基醚、1,4-二氧六环、正己烷、环己烷或者甲苯;
优选地,步骤3)中所述溶剂为醇类溶剂或醚类溶剂,优选为乙醚、四氢呋喃、二正丁基醚、1,4-二氧六环、甲醇或者乙醇;根据本发明的另一个目的在于提供所述含P骨架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂在促进金属催化烯炔的氢氨基羰基化反应中的用途。
9.一种由烯烃和炔烃的氨基羰基化反应制备支链酰胺的方法,包括以下步骤:
取适量根据权利要求1至5中任意一项所述含P骨架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂加入反应釜中,然后加入溶剂、添加剂、胺和烯烃或炔烃,封闭反应釜,充入一定压力的CO气体,在设定的温度下反应一定时间。
10.根据权利要求9所述的方法,其特征在于,所述溶剂选自脂肪烃类溶剂,芳香烃类溶剂,醇类溶剂,酰胺类溶剂或者醚类溶剂;
更优选地,所述溶剂选自正己烷、环己烷、辛烷、苯、甲苯、二甲苯、甲醇、乙醇、异丙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、乙醚、四氢呋喃和二氧六环中的一种或多种,更优选为N-甲基吡咯烷酮;
优选地,所述添加剂选自无机酸类或者有机酸类,该类添加剂的作用是促进催化剂活性物种的生成,进而促进反应的进行;
更优选地,所述添加剂选自氢氟酸、盐酸、氢溴酸、氢碘酸、硫酸、亚硫酸、硼酸、硝酸、磷酸、草酸、三氟乙酸、甲磺酸、三氟甲磺酸、对甲苯磺酸、樟脑磺酸、2,4-二硝基苯甲酸;
优选地,所述胺选自芳香胺和脂肪胺;
优选地,含P骨架结构单元有机分子笼负载Pd纳米颗粒的非均相催化剂与烯烃或炔烃的摩尔比为1/50-1/5000,优选为1/100-1/1000;
优选地,气体的压力为1MPa-10MPa,优选为2MPa-5MPa;
优选地,反应温度为50℃-200℃,优选为80℃-120℃;
优选地,反应时间为5h-24h,优选为6h-16h;
优选地,烯烃或炔烃的反应浓度为0.1mol/L-10mol/L,优选为0.5mol/L-3mol/L。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111169177.0A CN113976173B (zh) | 2021-10-08 | 2021-10-08 | 一种含p骨架结构单元的有机分子笼非均相催化剂及其制备方法和用途 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111169177.0A CN113976173B (zh) | 2021-10-08 | 2021-10-08 | 一种含p骨架结构单元的有机分子笼非均相催化剂及其制备方法和用途 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113976173A true CN113976173A (zh) | 2022-01-28 |
CN113976173B CN113976173B (zh) | 2024-02-06 |
Family
ID=79737716
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111169177.0A Active CN113976173B (zh) | 2021-10-08 | 2021-10-08 | 一种含p骨架结构单元的有机分子笼非均相催化剂及其制备方法和用途 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113976173B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115448812A (zh) * | 2022-09-16 | 2022-12-09 | 中国科学院青岛生物能源与过程研究所 | 一种由环氧化合物还原开环制备醇的方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110835343A (zh) * | 2018-08-17 | 2020-02-25 | 中国科学院大连化学物理研究所 | 一种含p、n多孔有机笼配体及其制备和应用 |
CN110835359A (zh) * | 2018-08-17 | 2020-02-25 | 中国科学院大连化学物理研究所 | 一种含p、n多孔有机笼配体及络合物催化剂和应用 |
-
2021
- 2021-10-08 CN CN202111169177.0A patent/CN113976173B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110835343A (zh) * | 2018-08-17 | 2020-02-25 | 中国科学院大连化学物理研究所 | 一种含p、n多孔有机笼配体及其制备和应用 |
CN110835359A (zh) * | 2018-08-17 | 2020-02-25 | 中国科学院大连化学物理研究所 | 一种含p、n多孔有机笼配体及络合物催化剂和应用 |
Non-Patent Citations (1)
Title |
---|
ZHAOZHAN WANG等: "Phosphine-Built-in Porous Organic Cage for Stabilization and Boosting the Catalytic Performance of Palladium Nanoparticles in Cross-Coupling of Aryl Halides", ACS APPL. MATER. INTERFACES, vol. 12, pages 53141 - 53149 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115448812A (zh) * | 2022-09-16 | 2022-12-09 | 中国科学院青岛生物能源与过程研究所 | 一种由环氧化合物还原开环制备醇的方法 |
Also Published As
Publication number | Publication date |
---|---|
CN113976173B (zh) | 2024-02-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhang et al. | Forging C− heteroatom bonds by transition-metal-catalyzed enantioselective C–H functionalization | |
Wu et al. | Cobalt (II) coordination polymer as a precatalyst for selective hydroboration of aldehydes, ketones, and imines | |
Cai et al. | A phosphine-free carbonylative cross-coupling reaction of aryl iodides with arylboronic acids catalyzed by immobilization of palladium in MCM-41 | |
Jin et al. | Highly Active, Well‐Defined (Cyclopentadiene)(N‐heterocyclic carbene) palladium Chloride Complexes for Room‐Temperature Suzuki–Miyaura and Buchwald–Hartwig Cross‐Coupling Reactions of Aryl Chlorides and Deboronation Homocoupling of Arylboronic Acids | |
Mohan et al. | Superparamagnetic copper ferrite nanoparticles catalyzed aerobic, ligand-free, regioselective hydroboration of alkynes: influence of synergistic effect | |
CN106513048A (zh) | 用于内烯烃氢甲酰化反应的催化剂及其制备方法和应用 | |
Wei et al. | Efficient synthesis of (S, R)-Bn-Yanphos and Rh/(S, R)-Bn-Yanphos catalyzed asymmetric hydroformylation of vinyl heteroarenes | |
Salvio et al. | Sustainable hydration of alkynes promoted by first row transition metal complexes. Background, highlights and perspectives | |
CN113976173B (zh) | 一种含p骨架结构单元的有机分子笼非均相催化剂及其制备方法和用途 | |
CN104098607B (zh) | 含三环己基膦的单膦单氮杂环卡宾镍(ii)配合物及其应用 | |
CN109810147B (zh) | 芘标记的苯并咪唑氮杂环卡宾钯金属配合物及制备和应用 | |
CN104311424A (zh) | 一种光学纯β-硝基醇类衍生物及合成方法 | |
Iranpoor et al. | 1, 3, 2, 4-Diazadiphosphetidines as ligand and base for palladium-catalyzed Suzuki–Miyaura, Sonogashira–Hagihara, and homocoupling reactions of aryl halides under heterogeneous conditions in water | |
CN113620878B (zh) | 一种Ni的金属-有机骨架材料及其制备方法和用途 | |
CN113024611B (zh) | 一种氮杂环卡宾环钯化合物及其制备方法和应用 | |
CN103788130A (zh) | 一种新型含磷有机配体1-(9-蒽基)-2-二苯基膦-咪唑的合成方法及应用 | |
Liu et al. | Heterogeneous gold-catalyzed oxidative cross-coupling of propargylic acetates with arylboronic acids leading to (E)-α-arylenones | |
CN109867699B (zh) | 一种联吡啶基桥联双三嗪钌配合物及其制备和应用 | |
CN109651421B (zh) | 一种2-芳基邻位取代三乙基硅吡啶类化合物的合成方法 | |
CN114907404A (zh) | 5-(2-(二取代膦基)苯基)-1-烷基-1h-吡唑膦配体及其制备方法和应用 | |
CN108164561B (zh) | 一种手性薄荷基苯基膦酰胺类化合物及制备方法 | |
CN111909217A (zh) | 一种双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(ⅱ)化合物及其制备方法和用途 | |
CN114632552B (zh) | Buchwald预催化剂及其制备方法与应用 | |
CN113861237B (zh) | 有机磷配体及其制备方法和应用 | |
CN103467323B (zh) | 一种制备β-不饱和烯胺酯衍生物的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |