CN114805434A - 一种新型四齿膦配体化合物及其合成方法与应用 - Google Patents
一种新型四齿膦配体化合物及其合成方法与应用 Download PDFInfo
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- CN114805434A CN114805434A CN202110064661.0A CN202110064661A CN114805434A CN 114805434 A CN114805434 A CN 114805434A CN 202110064661 A CN202110064661 A CN 202110064661A CN 114805434 A CN114805434 A CN 114805434A
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- Prior art keywords
- acid
- compound
- palladium
- methyl
- reaction
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- 239000003446 ligand Substances 0.000 title claims abstract description 42
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 title claims description 30
- 238000010189 synthetic method Methods 0.000 title description 2
- 150000001336 alkenes Chemical class 0.000 claims abstract description 29
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000007083 alkoxycarbonylation reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 5
- 125000005647 linker group Chemical group 0.000 claims abstract description 5
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 238000005930 hydroaminomethylation reaction Methods 0.000 claims abstract description 4
- 239000012696 Pd precursors Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 45
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 150000002941 palladium compounds Chemical class 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 229960001701 chloroform Drugs 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical compound CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000007039 two-step reaction Methods 0.000 claims description 5
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 claims description 4
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 4
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- LXFQSRIDYRFTJW-UHFFFAOYSA-N 2,4,6-trimethylbenzenesulfonic acid Chemical compound CC1=CC(C)=C(S(O)(=O)=O)C(C)=C1 LXFQSRIDYRFTJW-UHFFFAOYSA-N 0.000 claims description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 4
- XCJGLBWDZKLQCY-UHFFFAOYSA-N 2-methylpropane-2-sulfonic acid Chemical compound CC(C)(C)S(O)(=O)=O XCJGLBWDZKLQCY-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- TWKVUTXHANJYGH-UHFFFAOYSA-L allyl palladium chloride Chemical compound Cl[Pd]CC=C.Cl[Pd]CC=C TWKVUTXHANJYGH-UHFFFAOYSA-L 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007514 bases Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 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 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000006063 methoxycarbonylation reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[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.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims 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 claims description 2
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 claims description 2
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 claims description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 claims description 2
- WCBWZBSYSCYPTM-UHFFFAOYSA-N 2-hydroxypropane-2-sulfonic acid Chemical compound CC(C)(O)S(O)(=O)=O WCBWZBSYSCYPTM-UHFFFAOYSA-N 0.000 claims description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 2
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- CMWINYFJZCARON-UHFFFAOYSA-N 6-chloro-2-(4-iodophenyl)imidazo[1,2-b]pyridazine Chemical compound C=1N2N=C(Cl)C=CC2=NC=1C1=CC=C(I)C=C1 CMWINYFJZCARON-UHFFFAOYSA-N 0.000 claims description 2
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
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- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
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- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 2
- PFURGBBHAOXLIO-WDSKDSINSA-N cyclohexane-1,2-diol Chemical compound O[C@H]1CCCC[C@@H]1O PFURGBBHAOXLIO-WDSKDSINSA-N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
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- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
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- XEAIHUDTEINXFG-SNAWJCMRSA-N methyl (e)-hex-3-enoate Chemical compound CC\C=C\CC(=O)OC XEAIHUDTEINXFG-SNAWJCMRSA-N 0.000 claims description 2
- XEAIHUDTEINXFG-UHFFFAOYSA-N methyl cis-3-hexenoate Natural products CCC=CCC(=O)OC XEAIHUDTEINXFG-UHFFFAOYSA-N 0.000 claims description 2
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- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 2
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical class P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 claims description 2
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- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 claims description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 239000002243 precursor Substances 0.000 claims 2
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- IQQDLHGWGKEQDS-VOTSOKGWSA-N Methyl 2-heptenoate Chemical compound CCCC\C=C\C(=O)OC IQQDLHGWGKEQDS-VOTSOKGWSA-N 0.000 claims 1
- CJBQSBZJDJHMLF-BQYQJAHWSA-N Methyl 2-octenoate Chemical compound CCCCC\C=C\C(=O)OC CJBQSBZJDJHMLF-BQYQJAHWSA-N 0.000 claims 1
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- ASKDFGVMJZMYEM-UHFFFAOYSA-N methyl hex-5-enoate Chemical compound COC(=O)CCCC=C ASKDFGVMJZMYEM-UHFFFAOYSA-N 0.000 claims 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims 1
- NHOPGDPSLMBDQD-UHFFFAOYSA-N tert-butyl 2-(methylaminomethyl)pyrrolidine-1-carboxylate Chemical compound CNCC1CCCN1C(=O)OC(C)(C)C NHOPGDPSLMBDQD-UHFFFAOYSA-N 0.000 claims 1
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- DOWCWUCBOQRQJE-UHFFFAOYSA-N ditert-butylphosphane;hydrochloride Chemical compound Cl.CC(C)(C)PC(C)(C)C DOWCWUCBOQRQJE-UHFFFAOYSA-N 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
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- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- FOGHPENQGFYWSI-UHFFFAOYSA-N methyl 4-oxohexanoate Chemical compound CCC(=O)CCC(=O)OC FOGHPENQGFYWSI-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- AWDMDDKZURRKFG-UHFFFAOYSA-N potassium;propan-1-olate Chemical compound [K+].CCC[O-] AWDMDDKZURRKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
Description
技术领域
本发明涉及化学合成技术领域,一种新型四齿膦配体及其合成方法与在烯烃烷氧羰基化反应中的应用。
背景技术
烯烃的氢酯基化反应是在金属化合物/膦配体作用下,烯烃与一氧化碳和醇反应得到比烯烃多一个碳原子的酯。在众多合成有机羧酸酯的方法中,这是一种最原子经济、简便的方法。以下方案显示了烯烃氢酯基化反应的通用反应方程式:烯烃化合物的烷氧基羰基化是具有越来越重要的意义的工艺过程。烷氧基羰基化是指烯烃与一氧化碳和醇在金属体配合物的存在下反应生成相应的酯。通常地,使用钯作为金属。下面的示意图显示了氧基羰基化的一般反应方程式:
有机羧酸酯是一类重要的含氧化合物,广泛应用于精细化工产品、医药、农药、食品添加剂、香料、涂料、油漆等领域。例如,丙酸甲酯作为溶剂、添加剂、防腐剂或香料,广泛应用于食品、饲料、化妆品行业。此外,它还是重要的化工中间体,它是生产聚甲基丙烯酸甲酯(PMMA)关键的原料。PMMA拥有良好的耐候性,适中的密度,刚性,稳定性,透明性等优点而广泛应用于汽车、led核心原件材料、建筑、航空等领域。因此,开发有机羧酸酯高效合成方法具有重要的意义。
目前,已报道的催化剂体系主要是由中心金属、相关膦配体、酸添加剂组成。中心金属是viii、x副族过渡金属如Rh、Pd、Ni、Co、Cu等,其中研究最多的就是金属Pd。相关膦配体如烷基膦、环烷基膦、二齿膦等的研究已经在许多专利中进行了描述,例如EPA04489472、EPA0499329、EPA0495547、US2005085671A1、US6284919B1、US2001051745A1、US6476255B1等。尤其是璐彩特(Lucite)公司公开了一组具有取代芳基桥的二齿膦化物,1,2-双(二叔丁基膦基甲基)苯(dtbpx)可以提供显著得高于先前公开的那些催化剂的反应速率和产生少许或不产生杂质,且具有高转化率(Chem.Commun.,1999,1877-1878;WO96/19434;WO2004/014552A1)。此外,赢创德固赛(Evonik-Degusa)公司也公开了1,1’-双(叔丁基苯基膦基)-二茂铁配体,对于烯烃的烷氧羰基化反应具有高的催化性能(Angew.Chem.Int.Ed.,2017,56(19),5267-5271;US2017/0022234Al)。
这两个配体是目前烯烃氢酯基化反应中最高效的配体。这些案例指出高活性的重要因素来源于叔碳烷基膦配体结构。虽然这两个配体在氢酯基化反应中表现出良好的性能,在烷氧基羰基化反应中,特别是乙烯与甲醇反应生成3-甲基丙酸酯(乙烯-甲氧基羰基化)作为甲基丙烯酸甲酯(MMA)的制备的中间步骤具有重要意义(Cata.Comun.,2014,44,73-75)。乙烯甲氧基羰基化反应是在温和的条件下以甲醇作为溶剂使用被配体改性的钯催化剂而进行。
本发明的目的在于提供了用于烷氧基羰基化的新型体,使用其可以实现更好的l/b选择性,更高的酯收率,更温和的反应条件。特别地,本发明的配体应当还适用于烯烃化合物的氢甲酰化反应、氢胺甲基化反应。烯烃存在其他官能团的情况也适用。
发明内容
鉴于现有技术存在的问题及困难,本发明提供了一种配体化合物,具有以下式(I)的结构:
其中,结构中R1、R2表示各自独立地任选取代的有机基团,X表示任选取代的从C1到C7直链亚烷基连接基团。
优选化合物如下式(Ia)所示:
作为本发明的一种优选技术方案,所述配体化合物除通式I所表示的结构外,该类新型四膦配体的结构还可以有以下取代基扩展,所代表的具体结构包括如下化合物:
本发明另一目的在于提供了一种合成前述配体化合物的方法,通过下面的路线合成得到:
其中,R1、R2表示各自独立地任选取代的有机基团,X表示任选取代的从C1到C7直链亚烷基连接基团,M为碱金属原子,R3为烷基。
作为本发明的一种优选技术方案,合成过程分两步,第一步是将路线中化合物a与有机金属化合物R3M一起反应,生成金属有机化合物的中间体,第二步是将第一步生成的中间体再与二取的氯化膦b反应,形成所述通式为I的化合物,包括:
(a)第一步所述的反应在能与金属形成络合物的碱性化合物存在下进行,其中所述碱性化合物包括四甲基乙二胺、三乙胺、乙二胺等。
(b)有机溶剂选自氯仿、二氯甲烷、1,2-二氯乙烷、乙醚、四氢呋喃、甲基叔丁基醚、2-甲基四氢呋喃、环戊烷、正戊烷、正己烷、环己烷、正庚烷的一种或多种的混合;
(c)式a化合物与有机溶剂的摩尔体积比mol/L为1:1~1:10;
(d)两步反应中,第一步所述反应的温度为-30–150℃;第二步所述反应的温度为0–180℃;
(e)两步反应中,第一步的反应时间为1~6小时;第二步的反应时间为8~72小时。
或者,本发明化合物通过以下路线合成:
作为本发明的一种优选技术方案,所述合成方法进一步包括,所使用的锂试剂可以是但不限于:甲基锂、乙基锂、正丁基锂、叔丁基锂、二异丙基胺基锂、戊基锂、苯基锂等;所使用的醇类有机碱包括但不限于:甲醇钾、甲醇钠、乙醇钾、乙醇钠、丙醇钾、丙醇钠、丁醇钾、丁醇钠、叔丁醇钾、叔丁醇钠、六甲基二硅基胺基钾、六甲基二硅基胺基钠等;所使用的胺类碱性化合物可以是但不限于:碱性化合物可以为甲胺、乙胺、二甲胺、二乙胺、三甲胺、三乙胺、N,N’-二甲基苯胺、N-甲基苯胺、苯胺、二苯胺、乙二胺(EDA)、N-甲基乙二胺、N,N-二甲基乙二胺(DMAEA)、N,N’-二甲基乙二胺、N,N,N’-三甲基乙二胺、N,N,N’,N’-四甲基乙二胺(TMEDA)、N-乙基乙二胺(EAEA)、N,N’-二乙基乙二胺(DEEN)、N,N-二乙基乙二胺(DEAEA)、N,N,N’-三乙基乙二胺、N,N,N’,N’-四二乙基乙二胺(TEEDA)、N,N-二叔丁基乙二胺、N,N,N’,N’-四甲基丙二胺(TMPDA)中的任意一种;第一步所述反应的温度为-30–150℃,优选10℃;第二步所述反应的温度为0–180℃,优选160℃。两步反应中,第一步的反应时间为1~12小时,优选4小时;第二步的反应时间为8~72小时,优选48小时。有机溶剂选自氯仿、二氯甲烷、1,2-二氯乙烷、乙醚、四氢呋喃、甲基叔丁基醚、2-甲基四氢呋喃、环戊烷、正戊烷、正己烷、环己烷、正庚烷、辛烷、壬烷、癸烷、十一烷、十二烷或十三烷的一种或多种的混合。
本发明进一步提供了所述配合化合物与金属钯前体的络合物在催化烯烃烷氧基羰基化反应中的应用,所述烯烃羰基化反应包括烷氧基羰基化反应,氢甲酰化反应、氢胺甲基化反应。
所述配体化合物在烷氧羰基化反应中的应用,包括但不限于:氢化反应,氢甲酰化反应,硅氢化反应,硼氢化反应,氢羟基化反应,氢氨化反应,氢氰基化反应,异构化甲酰基化反应,氢氨甲基化反应,转移氢化反应,烯丙基化反应,烯烃复分解反应,环异构化反应,Diels-Alder反应,不对称偶联反应,Aldol反应,Michael加成反应,不对称环氧化反应,动力学拆分和[m+n]环化反应。
例如,烯烃氢酯基化反应路线如下:
例如,催化不对称反应,使用所述的化合物作为催化剂,反应路线如下:
作为本发明的一种优选技术方案,烯烃氢酯基化反应制备有机羧酸酯的方法,是在钯化合物/四齿膦配体/酸性添加剂组合催化剂作用下,在有机溶剂中,末端烯烃、一氧化碳和醇进行氢酯基化反应生成较烯烃多一个碳的有机羧酸酯。
氢酯基化反应压力控制在1~15.0MPa(优选4~10MPa),反应温度控制在40~200℃(优选60~140℃)。
钯化合物/四齿膦配体/酸性添加剂组合催化剂中,四齿膦配体与钯化合物的摩尔比为0.2:1~120:1(优选1:1~20:1);酸性添加剂与钯化合物的摩尔比为0.2:1~200:1(优选1:1~50:1)。组合催化剂的用量以钯化合物相对烯烃的用量计:钯化合物的摩尔量为末端烯烃摩尔量的0.000001~1%(优选0.00005~0.001%)。
所述钯化合物选自醋酸钯、氯化钯、双(三苯基膦)二氯化钯、双(乙腈)二氯化钯、(1,5-环辛二烯)二氯化钯、烯丙基氯化钯、四三苯基膦钯、乙酰丙酮钯、双(二亚苄基丙酮)钯以及三(二亚苄基丙酮)二钯中的一种。优选PdCl2、Pd(acac)2,双(乙腈)二氯化钯、(1,5-环辛二烯)二氯化钯、烯丙基氯化钯、碘化钯、溴化钯。
所述酸性添加剂选自高氯酸、硫酸、磷酸、盐酸、甲酸、乙酸、草酸、甲磺酸(MsOH)、三氟甲磺酸(TfOH)、叔丁烷磺酸、对甲苯磺酸(PTSA)、2-羟-基丙烷-2-磺酸、2,4,6-三甲基苯磺酸和十二烷基磺酸、三氟甲磺酸铝的一种。优选对甲苯磺酸、甲磺酸、三氟甲磺酸、叔丁烷磺酸、2,4,6-三甲基苯磺酸、十二烷基磺酸。
所述末端烯烃为碳原子数为2~10的烯烃。如乙烯、丙烯、1-丁烯、顺式-和/或反式-2-丁烯、异丁烯、1,3-丁二烯、1-戊烯、顺式-和/或反式-2-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、己烯、四甲基乙烯、庚烯、1-辛烯、2-辛烯、二正丁烯、二异丁烯、正癸烯的一种或其混合物。
所述醇为含1-20个碳原子的脂肪族醇化合物或环脂族醇化合物。如自甲醇、乙醇、1-丙醇、异丙醇、异丁醇、叔丁醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、1-己醇、环己醇、2-乙基己醇、异壬醇、2-丙基庚醇、环己烷-1,2-二醇、1,2-乙二醇、1,3-丙二醇、丙三醇、1,2,4-丁三醇、2-羟基甲基-1,3-丙二醇、季戊四醇、1,2,6-三羟基己烷、1,1,1-三(羟基甲基)乙烷一种或其混合物。
所述反应溶剂为醇、二氧六环、四氢呋喃、乙二醇二甲醚、四甘醇二甲醚、1,2-二乙氧基乙烷醚、乙酸乙酯、乙酸丁酯、苯、甲苯、苯甲醚、二甲苯、二氯甲烷、三氯甲烷以及氯仿中的一种。
本发明相对于现有技术的有益效果包括:
(1)高反应选择性和转化数,TON>10000,选择性>99%;
(2)高反应活性,反应时间1~8小时,TOF>10000s-1;
(3)配体合成和后处理方法简单,容易放大且后处理产生的三废较少。
附图说明
图1,本发明配体化合物L1的1H NMR(400MHz,CDCl3)示意图;
图2,本发明配体化合物L1的31P NMR(400MHz,CDCl3)示意图;
图3,本发明配体化合物L1的13C NMR(400MHz,CDCl3)示意图。
具体实施方式
下面通过实施例和附图对本发明加以说明,但本发明并不仅限于以下实施例。
实施例1:1,2,4,5-四(二叔丁基膦甲基)苯(dttpx)的制备
合成路线如下:
工艺参数及条件如下:
在惰性气体保护下,1L的反应瓶中先后加入17.29g(180mmol)叔丁醇钠、27.1ml(180mmol)四甲基乙二胺、200ml辛烷和4.03g(30mmol)均四甲苯。搅拌并向反应体系中缓慢加入72.0ml(2.5M)正丁基锂,将温度升至100℃反应6小时。形成灰红色沉淀,通过过滤将该沉淀分离并用100ml辛烷洗涤,然后再悬浮于200ml辛烷中,向其中加入30.33ml(120mol)二叔丁基氯化膦,60℃搅拌反应过夜。次日加入50ml脱气蒸馏水猝灭反应,然后分离有机相,旋蒸除去溶剂,用冷甲醇在-20℃重结晶,收率(16.64g,78%)。
其中,L1的1H NMR(400MHz,CDCl3),31P NMR(400MHz,CDCl3),13C NMR(400MHz,CDCl3)示意图分别如图1、2和3所示。
除了L1配体,配体L20可通过下面路线合成得到:
除了直链或支链烯烃以外,配体L20还可应用于3-己烯酸甲酯、环辛烯等带酯基取代或环状烯烃的烷氧羰基化反应中
对比实施例1:烷氧羰基化反应对比试验
新型四膦配体dttpx,即:(1,2,4,5-四(二叔丁基膦甲基)苯)为实施例1的配体化合物,璐彩特公司商业化配体dtbpx做为对比配体,即:1,2-双(二叔丁基磷甲基)苯。在氩气氛围下,向200ml装有压力传感器、温度探针、在线取样口和安全泄压阀等装置的不锈钢高压反应釜中加入一定量的Pd(OAc)2(0.26μmol,0.06mg)、一定量的配体dttpx或dtbpx(0.52-2.08μmol)和过量的甲基磺酸(2.6-5.2μmol),加入一定体积的甲醇和内标物甲苯,用磁子搅拌络合30分钟,生成钯与配体的催化络合物。随后,连接气体管线并充分置换后,在两位四通阀的切换下,用带计量功能的柱塞泵向反应釜内加入一定比例液态化的乙烯(26mmol)。向反应装置内充入一氧化碳与至4.5MPa。将反应釜升至所需温度80℃,反应中持续补充一氧化碳保持总压力恒定在4.5MPa左右。反应8个小时后,将反应釜接入-40℃冷套降温,待釜温降至常温后,在不开釜的情况下,打开在线取样口取样,用色谱级的乙酸乙酯稀释后,气相色谱仪(GC)测定正异比(丙酸甲酯/丁二酸二甲酯/4-氧代己酸甲酯/4-氧代庚二酸二甲酯的比例)。开釜后,在通风橱内将高压反应釜内的气体释放完全,取样称重。结果如表1所示。
*Reacion conaitions:45 par,8n.
[b]Conversion andl/b ratio is determined by GC.
[c]TON is calculated by conversion×100000.
从上述实验结果可见,采用本发明配体,在S/C=100000,反应时间8小时,TON高达92600,TOF近12000s-1,比商业化的配体dtbpx高出近一倍的活性,且正异比比dtbpx更好。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单推演或替换,都应当视为属于本发明的保护范围。
Claims (10)
4.根据权利要求3所述的方法,其特征在于:
合成过程分两步,第一步是将路线中化合物a与有机金属化合物R3M一起反应,生成金属有机化合物的中间体,第二步是将第一步生成的中间体再与二取的氯化膦b反应,形成所述通式为I的化合物,包括:
(a)第一步所述的反应在能与金属形成络合物的碱性化合物存在下进行,其中所述碱性化合物包括四甲基乙二胺、三乙胺、乙二胺等。
(b)有机溶剂选自氯仿、二氯甲烷、1,2-二氯乙烷、乙醚、四氢呋喃、甲基叔丁基醚、2-甲基四氢呋喃、环戊烷、正戊烷、正己烷、环己烷、正庚烷的一种或多种的混合;
(c)式a化合物与有机溶剂的摩尔体积比mol/L为1:1~1:10;
(d)两步反应中,第一步所述反应的温度为-30–150℃;第二步所述反应的温度为0–180℃;
(e)两步反应中,第一步的反应时间为1~6小时;第二步的反应时间为8~72小时。
5.权利要求1或2所述化合物与金属钯前体的络合物在催化烯烃烷氧基羰基化反应中的应用,其特征在于,所述烯烃羰基化反应包括烷氧基羰基化反应,氢甲酰化反应、氢胺甲基化反应。
6.一种催化乙烯甲氧基羰基化反应,其特征在于,使用权利要求1或2所述化合物与金属钯前体的络合物作为催化剂,在有机溶剂中,末端烯烃、一氧化碳和醇进行氢酯基化反应生成较烯烃多一个碳的有机羧酸酯。
7.根据权利要求6所述的方法,其特征在于,金属钯前体的络合物在催化烯烃烷氧基羰基化反应,反应压力控制在1~15.0MPa(优选4~10MPa),反应温度控制在40~200℃(优选60~140℃)。
8.根据权利要求6所述的方法,其特征在于,钯化合物/四齿膦配体/酸性添加剂组合催化剂中,四齿膦配体与钯化合物的摩尔比为0.2:1~120:1(优选1:1~20:1);酸性添加剂与钯化合物的摩尔比为0.2:1~200:1(优选1:1~50:1);组合催化剂的用量以钯化合物相对烯烃的用量计:钯化合物的摩尔量为末端烯烃摩尔量的0.000001~1%(优选0.00005~0.001%)。
9.根据权利要求8所述的方法,其特征在于,所述钯化合物选自醋酸钯、氯化钯、双(三苯基膦)二氯化钯、双(乙腈)二氯化钯、(1,5-环辛二烯)二氯化钯、烯丙基氯化钯、四三苯基膦钯、乙酰丙酮钯、双(二亚苄基丙酮)钯以及三(二亚苄基丙酮)二钯中的一种。优选PdCl2、Pd(acac)2,双(乙腈)二氯化钯、(1,5-环辛二烯)二氯化钯、烯丙基氯化钯、碘化钯、溴化钯;
所述酸性添加剂选自高氯酸、硫酸、磷酸、盐酸、甲酸、乙酸、草酸、甲磺酸(MsOH)、三氟甲磺酸(TfOH)、叔丁烷磺酸、对甲苯磺酸(PTSA)、2-羟-基丙烷-2-磺酸、2,4,6-三甲基苯磺酸和十二烷基磺酸、三氟甲磺酸铝的一种。优选对甲苯磺酸、甲磺酸、三氟甲磺酸、叔丁烷磺酸、2,4,6-三甲基苯磺酸、十二烷基磺酸。
10.根据权利要求6所述的方法,其特征在于,所述末端烯烃为碳原子数为2~10的烯烃,如乙烯、丙烯、1-丁烯、顺式-和/或反式-2-丁烯、异丁烯、1,3-丁二烯、1-戊烯、顺式-和/或反式-2-戊烯、2,4,4-三甲基-1-戊烯、2,4,4-三甲基-2-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、3,3-二甲基-1-丁烯、2,3,3-三甲基-1-丁烯\2,3-二甲基-2-丁烯、己烯、四甲基乙烯、庚烯、1-辛烯、2-辛烯、二正丁烯、二异丁烯、正癸烯、环己烯、环庚烯、环辛烯、3-戊烯酸甲酯、4-戊烯酸甲酯、2-己烯酸甲酯、3-己烯酸甲酯、5-己烯酸甲酯、2-庚烯酸甲酯、(E)-2-辛烯酸甲酯、(E)-2-壬烯酸甲酯、10-烯酸甲酯、11-烯酸甲酯、(Z)-油酸甲酯、(E)-油酸甲酯中的一种或其混合物;
所述醇为含1-20个碳原子的脂肪族醇化合物或环脂族醇化合物,如自甲醇、乙醇、1-丙醇、异丙醇、异丁醇、叔丁醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、1-己醇、环己醇、2-乙基己醇、异壬醇、2-丙基庚醇、环己烷-1,2-二醇、1,2-乙二醇、1,3-丙二醇、丙三醇、1,2,4-丁三醇、2-羟基甲基-1,3-丙二醇、季戊四醇、1,2,6-三羟基己烷、1,1,1-三(羟基甲基)乙烷一种或其混合物;
所述反应溶剂为醇、二氧六环、四氢呋喃、乙二醇二甲醚、四甘醇二甲醚、1,2-二乙氧基乙烷醚、乙酸乙酯、乙酸丁酯、苯、甲苯、苯甲醚、二甲苯、二氯甲烷、三氯甲烷以及氯仿中的一种。
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