CN114736239A - 一种双齿膦配体及其制备方法、应用 - Google Patents
一种双齿膦配体及其制备方法、应用 Download PDFInfo
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- CN114736239A CN114736239A CN202210581669.9A CN202210581669A CN114736239A CN 114736239 A CN114736239 A CN 114736239A CN 202210581669 A CN202210581669 A CN 202210581669A CN 114736239 A CN114736239 A CN 114736239A
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- Prior art keywords
- formula
- phosphine ligand
- bidentate phosphine
- compound
- reaction
- Prior art date
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000003446 ligand Substances 0.000 title claims abstract description 89
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 48
- 150000001336 alkenes Chemical class 0.000 claims abstract description 35
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 57
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- 239000010948 rhodium Substances 0.000 claims description 28
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052703 rhodium Inorganic materials 0.000 claims description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 15
- -1 diaryl phosphine derivative Chemical class 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- RHKGZYVYKXVQSD-MECAPONASA-N [Rh].[O+]#[C-].C\C(O)=C\C(C)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [Rh].[O+]#[C-].C\C(O)=C\C(C)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RHKGZYVYKXVQSD-MECAPONASA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 2
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical group [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 23
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 76
- 150000001299 aldehydes Chemical class 0.000 description 30
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 20
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 239000012300 argon atmosphere Substances 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 13
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000012043 crude product Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical class CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BWRRWBIBNBVHQF-UHFFFAOYSA-N 4-(3-pyridin-2-yl-1,2,4-oxadiazol-5-yl)butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2N=CC=CC=2)=N1 BWRRWBIBNBVHQF-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
本发明公开了一种双齿膦配体及其制备方法、应用,该双齿膦配体在呋喃环上稠合的七元环或八元环不仅增大了催化剂中心金属周围的空间位阻,同时显著地提升了骨架的旋转能垒,使得骨架中的两个苯环不易产生相对旋转,进而确保两个苯环上的P大部分时间处于同侧,确保基于该类骨架衍生的双齿膦配体具有优异的螯合配位能力,可以在少量配体存在下,显著地提升催化剂的选择性;此外,七元环、八元环相较于六元环或苯环更强的供电性,对于烯烃氢甲酰化氢甲酰化反应展现出相对更弱的异构化能力,对于端烯烃为原料的氢甲酰化反应,有利于进一步提高成醛率,在相对现有技术更低的压力、温度条件下正构醛的选择性稳定在97%以上。
Description
技术领域
本发明涉及氢甲酰化反应催化剂领域,具体涉及一类大位阻双齿膦配体及其制备方法、以及该双齿膦配体在提高烯烃氢甲酰化的反应速率以及产物中直链醛的选择性中的应用。
背景技术
氢甲酰化反应是指烯烃与合成气在过渡金属络合催化剂作用下反应生成醛的反应过程,其产生的醛及其衍生物被广泛地用作合成增塑剂、表面活性剂、溶剂和香料等的原料。目前,氢甲酰化反应已成为工业应用中最重要的化学反应之一。
膦配体在氢甲酰化反应的催化剂体系中发挥着重要作用,通过空间效应和电荷效应影响氢甲酰化反应的活性和选择性。因此,近年来开展了大量的双齿膦配体的研究。
发明人在专利CN113583046A中公开了一种双齿膦配体,该双齿膦配体采用的骨架不仅具有C2对称性和适当的刚性,而且该双齿膦配体可以通过在催化剂中心金属周围提供有效的空间位阻以提高催化剂的选择性。
在持续研发过程中,发明人通过对机理的研究发现在双齿膦配体配位过程中,专利 CN113583046A公开的双齿膦配体的两个苯环容易相对旋转导致两个苯环上的P位于不同侧,而双齿膦配体与铑络合物配合时,位于不同侧的P相较于两个苯环上的P旋转至同侧时更加困难。此外,稠合在呋喃环上的六元环或苯环较强的吸电子能力将一定程度上抑制氢甲酰化反应的成醛率,因此,有必要优化现有的双齿膦配体,以进一步提高氢甲酰化反应的成醛率或正构醛的选择性。
发明内容
本发明的一个目的在于提供一种双齿膦配体,以解决现有技术中双齿膦配体类与铑络合物配合过程中,两个苯环相对旋转至P位于不同侧而造成的配位困难、以及呋喃环上稠合的六元环、苯环由于吸电子能力而一定程度上抑制氢甲酰化反应的成醛率的问题,以提高氢甲酰化反应的反应活性、成醛率或正构醛的选择性。
本目的通过下述技术方案实现:
一种双齿膦配体,所述双齿膦配体为式I或式II所示的化合物,或者所述化合物的对映体、消旋体或非对映异构体:
式I、式II中,R3和R4各自独立地选自氢或者C1~C8的烷基,R1和R2各自独立地选自取代或未取代的以下基团中的任一种:
其中,Y为O、S、亚甲基或者亚氨基。
在前期研发中,发明人于专利CN113583046A中公开的双齿膦配体的骨架结构能够有效地提升有效地提升催化活性、成醛率,发明人认为该技术效果的产生机理在于骨架具有C2对称性和适当的刚性,并且该双齿膦配体能够通过在催化剂中心金属周围提供有效的空间位阻。但是,这类空间位阻不宜更大,否则将抑制氢甲酰化反应的活性和成醛率。因此,在双齿膦配体的骨架的呋喃环上稠合的六元环、苯环均能提供适宜的空间位阻。
随着研究的深入,发明人发现在将呋喃环上稠合的六元环、苯环替换为七元环或八元环后,虽然进一步增大了催化剂中心金属周围的空间位阻,但是氢甲酰化反应的反应活性,特别是成醛率以及正构醛的选择性却能够显著提升。这是因为,两个苯环易相对旋转,当两个苯环上的P转动至不同侧时,相较于两个苯环上的P位于同侧的情况,其与铑络合物配合的难度将明显提升,而呋喃环上稠合的七元环或八元环能够增大骨架的旋转能垒,使得双齿膦配体骨架具有更大的刚性,两个苯环之间不易旋转,确保基于该类骨架衍生的双齿膦配体具有优异的螯合配位能力,可以在少量配体存在下,显著地提升催化剂的选择性和反应活性。不仅如此,相较于六元环或苯环,七元环或八元环的供电性更强,对于烯烃氢甲酰化反应能够展现出相对更弱的异构化能力,提高正构醛的选择性,对于端烯烃为原料的氢甲酰化反应,有利于进一步提高成醛率。
因此,本技术方案中,与现有技术不同的是,双齿膦配体采用的骨架的呋喃环上稠合的是如式I所示的七元环,或者如式II所示的八元环,以进一步提高氢甲酰化反应的反应活性,并显著提高成醛率和正构醛的选择性。
在式I、式II中,R3和R4各自独立地选择氢或者C1~C8的烷基,优选地,R3和R4各自独立地氢或者C1~C4的烷基,进一步优选地,R3和R4各自独立地氢、甲基或乙基。
在部分实施例中,基团R1和基团R2为未被取代基取代的基团。
在部分实施例中,所述基团R1和/或基团R2被卤素、磺酸基、C1~C6的烷基、C1~C6的卤代烷基、C1~C6的烷氧基、C1~C6的烷酰基、C1~C6的酯基、腈基、C1~C6的磺酸酯基取代。在一个或多个实施例中,所述取代可以是部分取代,也可以是一取代、二取代、三取代、四取代、五取代、六取代、七取代或八取代。
作为本发明中双齿膦配体的优选化学结构式,所述双齿膦配体具有以下任一种化学结构式:
通过合成上述双齿膦配体1~4,并将其与铑络合物构成用于氢甲酰化反应的催化剂组合物,在1-己烯、2-戊烯、2-辛烯、丙烯酸甲酯等烯烃的氢甲酰化反应中表现十分优异,在相对现有技术更低的压力、温度条件下正构醛的选择性稳定在90%以上,相较于现有的稠合六元环或苯环的双齿膦配体,显著地提高了氢甲酰化反应的反应活性、成醛率和正构醛的选择性。
本发明的另一个目的在于提供前述任一种双齿膦配体的制备方法,该制备方法合成路线简单、反应条件温和,能够进行放大生产并用于工业化生产。
本目的通过下述技术方案实现:
一种用于制备前述任一种双齿膦配体的制备方法,该制备方法具体包括以下步骤:
式III的化合物、式IV的化合物、铜盐、碱性试剂、第一溶剂混合后在氧气氛下反应得到式V的化合物,将式V的化合物、二芳基膦衍生物或环状二芳基膦衍生物、第二溶剂混合后在惰性气氛下反应得到式I的化合物;或者
式VI的化合物、式VII的化合物、铜盐、碱性试剂、第一溶剂混合后在氧气氛下反应得到式VIII的化合物,将式VIII的化合物、二芳基膦衍生物或环状二芳基膦衍生物、第二溶剂混合后在惰性气氛下反应得到式II的化合物;
本技术方案中,式I的化合物的合成路线为:
具体地,将式III的化合物和式IV的化合物与铜盐、碱性试剂、第一溶剂混合均匀后优选在室温下于氧气氛中反应数小时,反应完毕后停止反应,调节反应体系的pH至6~7,之后分层获得有机相,浓缩有机相后重结晶得到式V的化合物,用于后续反应。之后将式V的化合物与二芳基膦衍生物或环状二芳基膦衍生物,以及第二溶剂混合后在惰性气氛下低温反应数小时候,得到式I的化合物。
类似地,将式VI的化合物和式VII的化合物与铜盐、碱性试剂、第一溶剂混合均匀后优选在室温下于氧气氛中反应数小时,反应完毕后停止反应,调节反应体系的pH至6~7,之后分层获得有机相,浓缩有机相后重结晶得到式VIII的化合物,用于后续反应。之后将式VIII 的化合物与二芳基膦衍生物或环状二芳基膦衍生物,以及第二溶剂混合后在惰性气氛下低温反应数小时候,得到式II的化合物。
在部分实施例中,所述铜盐为氯化亚铜、溴化亚铜、碘化亚铜、氧化亚铜、乙酸亚铜、氰化亚铜、硫氰酸亚铜、硫化亚铜、三氟甲磺酸亚铜、硝酸铜、硫酸铜、醋酸铜、草酸酮、氯化铜、氧化铜中的至少一种。
在部分实施例中,所述碱性试剂为碳酸氢钠、碳酸氢铵、苄胺、碳酸钠、碳酸钾、碳酸铯、硫代硫酸钠、氢氧化钠、氢氧化锂、氢氧化钾中的至少一种。
在部分实施例中,所述第一溶剂、第二溶剂各自独立地选自苯、甲苯、二甲苯、三甲苯、氯仿、二氯甲烷、四氢呋喃、二甲基亚砜、乙腈、乙醚、乙二醇二甲醚、甲醇、乙醇、异丙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮中的一种或多种。
本发明的又一个目的在于提供前述任一种双齿膦配体在氢甲酰化反应的催化剂体系中的应用,该双齿膦配体能够与铑络合物构成催化剂组合物,该催化剂组合物能够用于烯烃氢甲酰化反应合成醛,与现有催化剂体系相比,对于不同结构的原料烯烃都能获得突出的反应速率和正构醛选择性,且反应活性更高。
本目的通过下述技术方案实现:
所述双齿膦配体与铑络合物构成催化剂组合物,所述催化剂组合物、原料烯烃、第三溶剂混合均匀后形成混合物,所述混合物与一氧化碳和氢气构成的合成气进行氢甲酰化反应或者异构化氢甲酰化反应,其中,所述氢甲酰化反应的原料烯烃为C2~C18烯烃,所述异构化氢甲酰化反应的原料烯烃为C4~C18烯烃。
本技术方案中,原料烯烃、双齿膦配体、铑络合物和第三溶剂混合均匀后形成混合物,所述混合物与一氧化碳和氢气构成的合成气反应直至反应完成。向反应器中加入铑催化剂、膦配体、原料烯烃和溶剂,利用合成气置换掉反应器中的空气,再将合成气通入至反应器中达到预设的压力,之后在加热至预设的温度,搅拌反应,直至反应结束。反应结束后,冷却至室温取出反应液分析原料烯烃的转化率、成醛率以及正构醛选择性。
在一个或多个实施例中,所述原料烯烃可以为C2~C18烯烃中的链状端烯烃或中间烯烃中的一种或多种混合,如乙烯、丙烯、1-丁烯、2-丁烯、1,3-丁二烯、异丁烯、1-戊烯、2-戊烯、 1-己烯、2-己烯、1-庚烯、1-辛烯、2-辛烯、1-壬烯、1-癸烯、1-十一烯、1-十二烯等。在一个或多个实施例中,所述原料烯烃还可以为其他含官能团或取代基的烯烃中的一种或多种混合,如丙烯酸甲酯、乙酸乙烯酯、苯乙烯、双环戊二烯、异戊二烯、降冰片二烯、油酸、油酸甲酯等。
在部分实施例中,所述铑络合物为Rh(acac)(CO)2、Rh(acac)(CO)(PPh3)、HRh(CO)(PPh3)3、 RhCl3、[Rh(cod)Cl]2、[Rh(CO)2Cl]2、Rh(acac)(C2H4)、Rh(C2H4)2Cl]2中的至少一种,其中,acac 为乙酰丙酮,cod为1,5-环辛二烯。
在部分实施例中,所述溶剂为苯、甲苯、二甲苯、三甲苯、丁醛、戊醛、己醛、庚醛、辛醛、壬醛、癸醛、氯仿、二氯甲烷、四氢呋喃、二甲基亚砜、乙腈、乙醚、乙二醇二甲醚、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、无溶剂中的至少一种。
进一步地,所述催化剂组合物中,双齿膦配体与铑络合物的摩尔比为2:1~20:1。优选地,所述摩尔比为2:1~8:1,进一步优选地,所述摩尔比为4:1~8:1。
进一步地,所述氢甲酰化反应或者异构化氢甲酰化反应的反应温度为70~90℃,反应压力为1~2MPa。本发明提供的双齿膦配体与铑络合物构成的催化剂组合物能够提高反应活性,使反应条件更加温和,通过降低反应温度和反应压力,以有利于工业化应用。
本发明与现有技术相比,具有如下的优点和有益效果:
1、本发明提供的双齿膦配体在呋喃环上稠合的七元环或八元环不仅增大了催化剂中心金属周围的空间位阻,同时显著地提升了骨架的旋转能垒,使得骨架中的两个苯环不易产生相对旋转,进而确保两个苯环上的P大部分时间处于同侧,确保基于该类骨架衍生的双齿膦配体具有优异的螯合配位能力,可以在少量配体存在下,显著地提升催化剂的选择性和反应活性;
2、本发明提供的双齿膦配体利用呋喃环上稠合的七元环、八元环相较于六元环或苯环更强的供电性,对于烯烃氢甲酰化氢甲酰化反应展现出相对更弱的异构化能力,对于端烯烃为原料的氢甲酰化反应,有利于进一步提高成醛率,在1-己烯、2-戊烯、2-辛烯、丙烯酸甲酯等烯烃的氢甲酰化反应中表现十分优异,在相对现有技术更低的压力、温度条件下正构醛的选择性稳定在90%以上;
3、本发明的双齿膦配体的合成路线简单,反应条件更加温和,有利于工业化生产;
4、本发明的双齿膦配体与铑络合物构成的催化剂组合物能够用于烯烃氢甲酰化反应合成醛,与现有催化剂体系相比,对于不同结构的原料烯烃都能获得突出的反应速率和正构醛选择性,此外,氢甲酰化反应或者异构化氢甲酰化反应的反应温度、反应压力能够进一步降低,降低了工业生产的成本、提高了生产的安全性,适合工业上推广应用。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,下面结合实施例,对本发明作进一步的详细说明,本发明的示意性实施方式及其说明仅用于解释本发明,并不作为对本发明的限定。在本发明中使用的术语“连接”在不进行特别说明的情况下,可以是直接相连,也可以使经由其他基团间接相连。
本发明所有原料,对其来源没有特别限制,在市场上购买的或按照本领域技术人员熟知的常规方法即可制备;本发明所有原料,对其纯度没有特别限制,本发明优选采用分析纯或催化剂领域常规的纯度要求;本发明所有原料,其牌号和简称均属于本领域常规牌号和简称,每个牌号和简称在其相关用途的领域内均是清楚明确的,本领域技术人员根据牌号、简称以及相应的用途,能够从市售中购买得到或者通过常规方法制备得到。
本发明对所述取代基的表达方式没有特别限制,均采用本领域技术人员熟知的表达方式,本领域技术人员基于常识,可根据其表达方式正确理解其含义。
实施例1:
配体骨架a的制备:
在500mL三颈烧瓶中加入化合物a’(50mmol),碘化亚铜(5mmol),碳酸铯(10mmol),二氯甲烷(200mL),氧气氛下,室温下反应10小时。停止反应,加入稀盐酸调节pH至6~7,分层获得有机相,浓缩,经无水乙醇重结晶得白色固体的化合物a,收率62%。用于后续反应。
化合物a的核磁共振波谱法结构表征:1H NMR(400MHz,氘代二甲基亚砜)δ8.47(2H), 7.18(2H),6.73(2H),2.78(4H),1.97–1.74(4H),1.62(8H),1.36–1.26(4H).
双齿膦配体1的制备:
在氩气氛下,在250mL三颈烧瓶中加入三氯化磷(60mmol)和四氢呋喃(120mL),0~5℃下,滴加吡咯(120mmol)、三乙胺(200mmol)以及四氢呋喃(20ml)混合溶液,滴加完毕后,升至室温下反应8小时。在氩气氛下,过滤除去不溶物,所得溶液经减压蒸馏,收集高沸点馏分为产品二吡咯基氯化膦,用于后续反应。
在氩气氛下,在50mL的三颈烧瓶中,加入二吡咯基氯化膦(16mmol)的四氢呋喃溶液 (5mL),0~5℃下,缓慢滴加a(6mmol)、三乙胺(30mmol)以及四氢呋喃(20ml)的混合溶液。滴加结束后,升至室温下反应8小时,停止反应,氩气氛下,过滤除去不溶物,所得溶液经减压除去低沸点化合物,得到油状粗产物,经乙醇重结晶得到白色固体的双齿膦配体 1,收率66%。
双齿膦配体1的核磁共振波谱法结构表征:31P NMR(162MHz,氘代氯仿)δ109.25。
实施例2:
双齿膦配体2的制备:
在氩气氛下,在100mL三颈烧瓶中加入三氯化磷(10mol)和四氢呋喃(10mL),0~5℃下,滴加吲哚(20mmol)、三乙胺(60mmol)以及四氢呋喃(10ml)的混合溶液,滴加完毕后,升至室温下反应8小时。0~5℃下,向反应液中缓慢滴加化合物a(3mmol)的四氢呋喃(20ml)的混合溶液。滴加结束后,升至室温下反应8小时,停止反应,氩气氛下,过滤除去不溶物,所得溶液经减压除去低沸点化合物,得到油状粗产物,经柱层析分离得到白色固体的双齿膦配体2,收率78%。
双齿膦配体2的核磁共振波谱法结构表征:31P NMR(162MHz,氘代氯仿)δ105.73。
实施例3:
双齿膦配体3的制备:
在氩气氛下,在50mL的三颈烧瓶中,加入二苯基氯化膦(12mmol)的四氢呋喃溶液(5mL),0~5℃下,缓慢滴加a(6mmol)、三乙胺(30mmol)以及四氢呋喃(20ml)的混合溶液。滴加结束后,升至室温下反应8小时,停止反应,氩气氛下,过滤除去不溶物,所得溶液经减压除去低沸点化合物,得到油状粗产物,经乙醇重结晶得到白色固体的双齿膦配体 3,收率46%。
双齿膦配体3的核磁共振波谱法结构表征:31P NMR(162MHz,氘代氯仿)δ111.73。
实施例4:
双齿膦配体4的制备:
在氩气氛下,在100mL三颈烧瓶中加入联苯酚(10mmol)和四氢呋喃(10mL),0~5℃下,滴加三氯化磷(10mmol)、三乙胺(60mmol)以及四氢呋喃(10ml)的混合溶液,滴加完毕后,升至室温下反应8小时。0~5℃下,向反应液中缓慢滴加化合物a(3mmol)的四氢呋喃(20ml)的混合溶液。滴加结束后,升至室温下反应8小时,停止反应,氩气氛下,过滤除去不溶物,所得溶液经减压除去低沸点化合物,得到油状粗产物,经柱层析分离得到白色固体的双齿膦配体4,收率55%。
双齿膦配体4的核磁共振波谱法结构表征:31P NMR(162MHz,氘代氯仿)δ144.13。
实施例5:
双齿膦配体5的制备:
在氩气氛下,在100mL三颈烧瓶中加入四甲基乙二胺(20mmol)、正丁基锂(15mmol)和四氢呋喃(5mL),0~5℃下,滴加二苯醚(6mmol)和四氢呋喃(10ml)的混合溶液,滴加完毕后,升至室温下反应2小时。0~5℃下,向反应液中缓慢滴加三氯化磷(6mmol)和四氢呋喃(10ml)的混合溶液,滴加完毕后,升至室温下反应8小时。0~5℃下,向反应液中缓慢滴加化合物a(1mmol)的四氢呋喃(10ml)的混合溶液。滴加结束后,升至室温下反应8 小时,停止反应,氩气氛下,过滤除去不溶物,所得溶液经减压除去低沸点化合物,得到油状粗产物,经柱层析分离得到白色固体的双齿膦配体5,收率33%。
双齿膦配体5的核磁共振波谱法结构表征:31P NMR(162MHz,氘代氯仿)δ32.64。
实施例6:
配体骨架b的制备:
在500mL三颈烧瓶中加入化合物b’(50mmol),碘化亚铜(5mmol),碳酸铯(10mmol),二氯甲烷(200mL),氧气氛下,室温下反应10小时。停止反应,加入稀盐酸调节pH至6~7,分层获得有机相,浓缩,经无水乙醇重结晶得白色固体的化合物b,收率64%,用于后续反应。
化合物b的核磁共振波谱法结构表征:1H NMR(400MHz,氘代二甲基亚砜)δ8.52(2H), 7.22(2H),6.74(2H),2.73(4H),1.97(4H),1.74–1.50(4H),1.33(4H),1.20(4H),0.98(4H).
根据实施例1所示方法获得二吡咯基氯化膦,用于后续反应。
在氩气氛下,在100mL三颈烧瓶中,加入二吡咯基氯化膦(16mmol)的四氢呋喃溶液(5mL),0~5℃下,缓慢滴加化合物b(6mmol)、三乙胺(30mmol)以及四氢呋喃(10ml) 的混合溶液。滴加结束后,升至室温下反应8小时,停止反应,氩气氛下,过滤除去不溶物,所得溶液经减压除去低沸点化合物,得到油状粗产物,经乙醇重结晶得到白色固体的双齿膦配体6,收率57%。
双齿膦配体6的核磁共振波谱法结构表征:31P NMR(162MHz,氘代氯仿)δ108.98。
实施例7:
双齿膦配体7的制备:
在氩气氛下,在100mL三颈烧瓶中加入三氯化磷(0.01mol)和四氢呋喃(10mL),0~5℃下,滴加吲哚(0.02mol)、三乙胺(0.06mol)以及四氢呋喃(10ml)的混合溶液,滴加完毕后,升至室温下反应8小时。0~5℃下,向反应液中缓慢滴加化合物b(3mmol)的四氢呋喃(20ml)的混合溶液。滴加结束后,升至室温下反应8小时,停止反应,氩气氛下,过滤除去不溶物,所得溶液经减压除去低沸点化合物,得到油状粗产物,经柱层析分离得到白色固体的双齿膦配体4,收率71%。
双齿膦配体4的核磁共振波谱法结构表征:31P NMR(162MHz,氘代氯仿)δ105.12。
实施例8~13:
双齿膦配体1~6分别用于1-己烯氢甲酰化反应:
在50ml高压反应釜中,加入0.05mmol双齿膦配体,0.025mmol Rh(acac)(CO)2,250mmol 1-己烯,5ml甲苯,随后充入合成气(CO:H2=1:1)置换反应釜三次,再次充入合成气,保持反应釜内总压为2MPa,迅速升温至70℃并开始搅拌,反应2h后停止搅拌,并迅速冷却至室温,取出反应液分析。
实施例14~18:
双齿膦配体3~7分别用于2-戊烯氢甲酰化反应:
在50ml高压反应釜中,加入0.16mmol双齿膦配体,0.04mmol Rh(acac)(CO)2,20mmol 2-戊烯,5ml甲苯,随后充入合成气(CO:H2=1:1)置换反应釜三次,再次充入合成气,保持反应釜内总压为1MPa,迅速升温至90℃并开始搅拌,反应2h后停止搅拌,并迅速冷却至室温,取出反应液分析。
实施例19~25:
双齿膦配体1~7分别用于2-辛烯氢甲酰化反应:
在50ml高压反应釜中,加入0.16mmol双齿膦配体,0.04mmol Rh(acac)(CO)2,20mmol 2-辛烯,5ml甲苯,随后充入合成气(CO:H2=1:1)置换反应釜三次,再次充入合成气,保持反应釜内总压为2MPa,迅速升温至90℃并开始搅拌,反应2h后停止搅拌,并迅速冷却至室温,取出反应液分析。
实施例26~30:
双齿膦配体1、3-6分别用于丙烯酸甲酯氢甲酰化反应:
在50ml高压反应釜中,加入0.16mmol双齿膦配体,0.04mmol Rh(acac)(CO)2,20mmol 丙烯酸甲酯,5ml甲苯,随后充入合成气(CO:H2=1:1)置换反应釜三次,再次充入合成气,保持反应釜内总压为1MPa,迅速升温至90℃并开始搅拌,反应2h后停止搅拌,并迅速冷却至室温,取出反应液分析。
实施例8~30的反应结果详见表1:
表1:
实施例 | 底物烯烃 | 膦配体 | 转化率 | 正构醛选择性 |
8 | 1-己烯 | 1 | >99% | >99% |
9 | 1-己烯 | 2 | >99% | >99% |
10 | 1-己烯 | 3 | >99% | 97% |
11 | 1-己烯 | 4 | >99% | 98% |
12 | 1-己烯 | 5 | >99% | >99% |
13 | 1-己烯 | 6 | >99% | >99% |
14 | 2-戊烯 | 3 | >99% | 91% |
15 | 2-戊烯 | 4 | >99% | 94% |
16 | 2-戊烯 | 5 | >99% | 96% |
17 | 2-戊烯 | 6 | >99% | 98% |
18 | 2-戊烯 | 7 | >99% | 98% |
19 | 2-辛烯 | 1 | >99% | 98% |
20 | 2-辛烯 | 2 | >99% | 98% |
21 | 2-辛烯 | 3 | >99% | 90% |
22 | 2-辛烯 | 4 | >99% | 92% |
23 | 2-辛烯 | 5 | >99% | 95% |
24 | 2-辛烯 | 6 | >99% | 98% |
25 | 2-辛烯 | 7 | >99% | 98% |
26 | 丙烯酸甲酯 | 1 | >99% | 97% |
27 | 丙烯酸甲酯 | 3 | >99% | 97% |
28 | 丙烯酸甲酯 | 4 | >99% | 97% |
29 | 丙烯酸甲酯 | 5 | >99% | 97% |
30 | 丙烯酸甲酯 | 6 | >99% | 98% |
通过表1可以看出,包含双齿膦配体1~7的催化剂体系在进行烯烃氢甲酰化反应时具有高转化率,并且,呋喃环上稠合的七元环或八元环不仅通过在催化剂中心金属周围提供有效的空间位阻,而且显著地提升了骨架的旋转能垒,使得骨架中的两个苯环不易产生相对旋转,确保双齿膦配体具有优异的螯合配位能力,反应活性更强,反应压力和温度更低,此外,七元环、八元环相较于六元环或苯环更强的供电性对于烯烃氢甲酰化氢甲酰化反应展现出相对更弱的异构化能力,对于端烯烃为原料的氢甲酰化反应,有利于进一步提高成醛率,正构醛选择性稳定在90%以上,在用于部分烯烃的氢甲酰化反应时,正构醛选择性可高达99%。
以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
4.根据权利要求3所述的一种双齿膦配体的制备方法,其特征在于,所述铜盐为氯化亚铜、溴化亚铜、碘化亚铜、氧化亚铜、乙酸亚铜、氰化亚铜、硫氰酸亚铜、硫化亚铜、三氟甲磺酸亚铜、硝酸铜、硫酸铜、醋酸铜、草酸酮、氯化铜、氧化铜中的至少一种。
5.根据权利要求3所述的一种双齿膦配体的制备方法,其特征在于,所述碱性试剂为碳酸氢钠、碳酸氢铵、苄胺、碳酸钠、碳酸钾、碳酸铯、硫代硫酸钠、氢氧化钠、氢氧化锂、氢氧化钾中的至少一种。
6.根据权利要求3所述的一种双齿膦配体的制备方法,其特征在于,所述第一溶剂、第二溶剂各自独立地选自苯、甲苯、二甲苯、三甲苯、氯仿、二氯甲烷、四氢呋喃、二甲基亚砜、乙腈、乙醚、乙二醇二甲醚、甲醇、乙醇、异丙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮中的一种或多种。
7.如权利要求1或2所述的一种双齿膦配体的应用,其特征在于,所述双齿膦配体与铑络合物构成催化剂组合物,所述催化剂组合物、原料烯烃、第三溶剂混合均匀后形成混合物,所述混合物与一氧化碳和氢气构成的合成气进行氢甲酰化反应或者异构化氢甲酰化反应,其中,所述氢甲酰化反应的原料烯烃为C2~C18烯烃,所述异构化氢甲酰化反应的原料烯烃为C4~C18烯烃。
8.根据权利要求7所述的一种双齿膦配体的应用,其特征在于,所述催化剂组合物中,双齿膦配体与铑络合物的摩尔比为2:1~20:1。
9.根据权利要求7所述的一种双齿膦配体的应用,其特征在于,所述铑络合物为Rh(acac)(CO)2、Rh(acac)(CO)(PPh3)、HRh(CO)(PPh3)3、RhCl3、[Rh(cod)Cl]2、[Rh(CO)2Cl]2、Rh(acac)(C2H4)、Rh(C2H4)2Cl]2中的至少一种,其中,acac为乙酰丙酮,cod为1,5-环辛二烯。
10.根据权利要求7所述的一种双齿膦配体的应用,其特征在于,所述氢甲酰化反应或者异构化氢甲酰化反应的反应温度为70~90℃,反应压力为1~2MPa。
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