TW201634469A - 包括蔥酚之單亞磷酸酯 - Google Patents
包括蔥酚之單亞磷酸酯 Download PDFInfo
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- TW201634469A TW201634469A TW104140153A TW104140153A TW201634469A TW 201634469 A TW201634469 A TW 201634469A TW 104140153 A TW104140153 A TW 104140153A TW 104140153 A TW104140153 A TW 104140153A TW 201634469 A TW201634469 A TW 201634469A
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- Prior art keywords
- alkyl
- aryl
- arom
- group
- compound
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- MUVQKFGNPGZBII-UHFFFAOYSA-N 1-anthrol Chemical compound C1=CC=C2C=C3C(O)=CC=CC3=CC2=C1 MUVQKFGNPGZBII-UHFFFAOYSA-N 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 27
- 150000001336 alkenes Chemical class 0.000 claims description 20
- 239000011541 reaction mixture Substances 0.000 claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 93
- 239000013256 coordination polymer Substances 0.000 description 54
- 239000000460 chlorine Substances 0.000 description 37
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- -1 olefin compound Chemical class 0.000 description 30
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 238000000921 elemental analysis Methods 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 239000003446 ligand Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 229940086542 triethylamine Drugs 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000007037 hydroformylation reaction Methods 0.000 description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- LWNLXVXSCCLRRZ-UHFFFAOYSA-N dichlorophosphane Chemical compound ClPCl LWNLXVXSCCLRRZ-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- OHRBIPDRQWZHPM-UHFFFAOYSA-N 5H-dioxaphosphole Chemical compound P=1OOCC1 OHRBIPDRQWZHPM-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000006413 ring segment Chemical group 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- DTFBPBSAXIOREZ-UHFFFAOYSA-N 3H-dioxaphosphole Chemical compound P1OOC=C1 DTFBPBSAXIOREZ-UHFFFAOYSA-N 0.000 description 3
- AUKRYONWZHRJRE-UHFFFAOYSA-N 9-anthrol Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=CC2=C1 AUKRYONWZHRJRE-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- PKAUJJPTOIWMDM-UHFFFAOYSA-N 3h-dioxaphosphepine Chemical compound C=1C=CPOOC=1 PKAUJJPTOIWMDM-UHFFFAOYSA-N 0.000 description 2
- RKNWJMHQLOIGIH-UHFFFAOYSA-N 6-chlorobenzo[d][1,3,2]benzodioxaphosphepine Chemical compound C12=CC=CC=C2OP(Cl)OC2=C1C=CC=C2 RKNWJMHQLOIGIH-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 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 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- ATCZEXMBDMWINW-UHFFFAOYSA-N anthracen-9-yloxy(dichloro)phosphane Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)OP(Cl)Cl ATCZEXMBDMWINW-UHFFFAOYSA-N 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- DQTRYXANLKJLPK-UHFFFAOYSA-N chlorophosphonous acid Chemical compound OP(O)Cl DQTRYXANLKJLPK-UHFFFAOYSA-N 0.000 description 2
- KGQCLZJFUIPDGS-UHFFFAOYSA-N dioxaphospholane Chemical compound C1CPOO1 KGQCLZJFUIPDGS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 1
- 125000006707 (C3-C12) heterocycloalkyl group Chemical group 0.000 description 1
- ILPBINAXDRFYPL-HWKANZROSA-N (E)-2-octene Chemical compound CCCCC\C=C\C ILPBINAXDRFYPL-HWKANZROSA-N 0.000 description 1
- YCTDZYMMFQCTEO-FNORWQNLSA-N (E)-3-octene Chemical compound CCCC\C=C\CC YCTDZYMMFQCTEO-FNORWQNLSA-N 0.000 description 1
- POILWHVDKZOXJZ-ONEGZZNKSA-M (E)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C/C(C)=O POILWHVDKZOXJZ-ONEGZZNKSA-M 0.000 description 1
- VIHUHUGDEZCPDK-GQCTYLIASA-N (e)-5-methylhept-2-ene Chemical compound CCC(C)C\C=C\C VIHUHUGDEZCPDK-GQCTYLIASA-N 0.000 description 1
- IRUCBBFNLDIMIK-BQYQJAHWSA-N (e)-oct-4-ene Chemical compound CCC\C=C\CCC IRUCBBFNLDIMIK-BQYQJAHWSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- ARLUCNJVCSOZQH-UHFFFAOYSA-N 1-(2-hydroxy-3-methoxy-5-methylphenyl)naphthalen-2-ol Chemical compound COC1=CC(C)=CC(C=2C3=CC=CC=C3C=CC=2O)=C1O ARLUCNJVCSOZQH-UHFFFAOYSA-N 0.000 description 1
- BIECTBHJVOPVCQ-UHFFFAOYSA-N 1-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)naphthalen-2-ol Chemical compound CC(C)(C)C1=CC(OC)=CC(C=2C3=CC=CC=C3C=CC=2O)=C1O BIECTBHJVOPVCQ-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- ROJXZLIBZOQRSS-UHFFFAOYSA-N 2,4,8,10-tetratert-butyl-6-(2,6-diphenylphenoxy)benzo[d][1,3,2]benzodioxaphosphepine Chemical compound C1(=CC=CC=C1)C1=C(C(=CC=C1)C1=CC=CC=C1)OP1OC2=C(C3=C(O1)C(=CC(=C3)C(C)(C)C)C(C)(C)C)C=C(C=C2C(C)(C)C)C(C)(C)C ROJXZLIBZOQRSS-UHFFFAOYSA-N 0.000 description 1
- SMPZKBDUWHMMLO-UHFFFAOYSA-N 2,4,8,10-tetratert-butyl-6-chlorobenzo[d][1,3,2]benzodioxaphosphepine Chemical compound O1P(Cl)OC2=C(C(C)(C)C)C=C(C(C)(C)C)C=C2C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C21 SMPZKBDUWHMMLO-UHFFFAOYSA-N 0.000 description 1
- GDGDLBOVIAWEAD-UHFFFAOYSA-N 2,4-ditert-butyl-6-(3,5-ditert-butyl-2-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O GDGDLBOVIAWEAD-UHFFFAOYSA-N 0.000 description 1
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 description 1
- AYXPLDQLAJRYDF-UHFFFAOYSA-N 2-(2-hydroxy-3-methoxy-5-methylphenyl)-4,6-dimethylphenol Chemical compound COC1=CC(C)=CC(C=2C(=C(C)C=C(C)C=2)O)=C1O AYXPLDQLAJRYDF-UHFFFAOYSA-N 0.000 description 1
- CMQNHFCKHHLJHC-UHFFFAOYSA-N 2-(2-hydroxy-4,5-dimethylphenyl)-6-methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC(C=2C(=CC(C)=C(C)C=2)O)=C1O CMQNHFCKHHLJHC-UHFFFAOYSA-N 0.000 description 1
- PAJXXTNETDHJMD-UHFFFAOYSA-N 2-(2-hydroxy-4-methyl-5-propan-2-ylphenyl)-6-methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC(C=2C(=CC(C)=C(C(C)C)C=2)O)=C1O PAJXXTNETDHJMD-UHFFFAOYSA-N 0.000 description 1
- BHUDRMUALYDWTK-UHFFFAOYSA-N 2-(2-hydroxy-5-methylphenyl)-6-methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC(C=2C(=CC=C(C)C=2)O)=C1O BHUDRMUALYDWTK-UHFFFAOYSA-N 0.000 description 1
- UKHDFPAHOWKZNY-UHFFFAOYSA-N 2-(4-tert-butyl-2-hydroxyphenyl)-6-methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC(C=2C(=CC(=CC=2)C(C)(C)C)O)=C1O UKHDFPAHOWKZNY-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- RCBGGJURENJHKV-UHFFFAOYSA-N 2-methylhept-1-ene Chemical compound CCCCCC(C)=C RCBGGJURENJHKV-UHFFFAOYSA-N 0.000 description 1
- IRUDSQHLKGNCGF-UHFFFAOYSA-N 2-methylhex-1-ene Chemical compound CCCCC(C)=C IRUDSQHLKGNCGF-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- QDMFTFWKTYXBIW-UHFFFAOYSA-N 3-Methyl-1-heptene Chemical compound CCCCC(C)C=C QDMFTFWKTYXBIW-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RITONZMLZWYPHW-UHFFFAOYSA-N 3-methylhex-1-ene Chemical compound CCCC(C)C=C RITONZMLZWYPHW-UHFFFAOYSA-N 0.000 description 1
- SLHFFNUTOSKGQG-UHFFFAOYSA-N 3-methylideneoctane Chemical compound CCCCCC(=C)CC SLHFFNUTOSKGQG-UHFFFAOYSA-N 0.000 description 1
- GLUPFQMLFXGTNL-UHFFFAOYSA-N 3-methyloct-1-ene Chemical compound CCCCCC(C)C=C GLUPFQMLFXGTNL-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- YCTDZYMMFQCTEO-UHFFFAOYSA-N 3-octene Chemical compound CCCCC=CCC YCTDZYMMFQCTEO-UHFFFAOYSA-N 0.000 description 1
- DEGKCSWRXAONGH-UHFFFAOYSA-N 4,8-ditert-butyl-6-chloro-2,10-dimethoxybenzo[d][1,3,2]benzodioxaphosphepine Chemical compound O1P(Cl)OC2=C(C(C)(C)C)C=C(OC)C=C2C2=CC(OC)=CC(C(C)(C)C)=C21 DEGKCSWRXAONGH-UHFFFAOYSA-N 0.000 description 1
- HTGWWIYFNRXQBL-UHFFFAOYSA-N 6-anthracen-9-yloxy-2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepine Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)OP1OC2=C(C3=C(O1)C(=CC(=C3)C(C)(C)C)C(C)(C)C)C=C(C=C2C(C)(C)C)C(C)(C)C HTGWWIYFNRXQBL-UHFFFAOYSA-N 0.000 description 1
- FODVJNLWVDRDRM-UHFFFAOYSA-N 6-anthracen-9-yloxy-3-tert-butyl-8-methoxy-10-methylbenzo[d][1,3,2]benzodioxaphosphepine Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)OP1OC2=C(C3=C(O1)C(=CC(=C3)C)OC)C=CC(=C2)C(C)(C)C FODVJNLWVDRDRM-UHFFFAOYSA-N 0.000 description 1
- LMNBMOYEQJJDQF-UHFFFAOYSA-N 6-anthracen-9-yloxy-4-methoxy-2,10-dimethylbenzo[d][1,3,2]benzodioxaphosphepine Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)OP1OC2=C(C3=C(O1)C(=CC(=C3)C)OC)C=C(C=C2)C LMNBMOYEQJJDQF-UHFFFAOYSA-N 0.000 description 1
- ZZOVUAZTJXTDEI-UHFFFAOYSA-N 6-anthracen-9-yloxy-4-methoxy-2,8,10-trimethylbenzo[d][1,3,2]benzodioxaphosphepine Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)OP1OC2=C(C3=C(O1)C(=CC(=C3)C)OC)C=C(C=C2C)C ZZOVUAZTJXTDEI-UHFFFAOYSA-N 0.000 description 1
- JDHQLTDOQHETSB-UHFFFAOYSA-N 6-anthracen-9-yloxy-4-methoxy-2-methylnaphtho[2,1-d][1,3,2]benzodioxaphosphepine Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)OP1OC2=C(C3=C(O1)C(=CC(=C3)C)OC)C1=CC=CC=C1C=C2 JDHQLTDOQHETSB-UHFFFAOYSA-N 0.000 description 1
- SLZWVRRRFPIJHR-UHFFFAOYSA-N 6-anthracen-9-yloxy-4-tert-butyl-2-methoxynaphtho[2,1-d][1,3,2]benzodioxaphosphepine Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)OP1OC2=C(C3=C(O1)C(=CC(=C3)OC)C(C)(C)C)C1=CC=CC=C1C=C2 SLZWVRRRFPIJHR-UHFFFAOYSA-N 0.000 description 1
- OETWMSXQAXWEIU-UHFFFAOYSA-N 6-anthracen-9-yloxy-8-methoxy-2,3,10-trimethylbenzo[d][1,3,2]benzodioxaphosphepine Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)OP1OC2=C(C3=C(O1)C=C(C(=C3)C)C)C=C(C=C2OC)C OETWMSXQAXWEIU-UHFFFAOYSA-N 0.000 description 1
- CGNRLEFDVAFASX-UHFFFAOYSA-N 6-anthracen-9-yloxy-8-methoxy-3,10-dimethyl-2-propan-2-ylbenzo[d][1,3,2]benzodioxaphosphepine Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)OP1OC2=C(C3=C(O1)C=C(C(=C3)C(C)C)C)C=C(C=C2OC)C CGNRLEFDVAFASX-UHFFFAOYSA-N 0.000 description 1
- GJNOHYNMVHVHJA-UHFFFAOYSA-N 6-anthracen-9-yloxybenzo[d][1,3,2]benzodioxaphosphepine Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)OP1OC2=C(C3=C(O1)C=CC=C3)C=CC=C2 GJNOHYNMVHVHJA-UHFFFAOYSA-N 0.000 description 1
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFVKKKJBIUQTNH-UHFFFAOYSA-N N'-amino-N-cyanoiminomethanimidamide Chemical compound NN=CN=NC#N OFVKKKJBIUQTNH-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 125000003336 coronenyl group Chemical group C1(=CC2=CC=C3C=CC4=CC=C5C=CC6=CC=C1C1=C6C5=C4C3=C21)* 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- CNLUIDKVGOQQIJ-UHFFFAOYSA-N dichloro-(2,6-diphenylphenoxy)phosphane Chemical compound C1(=CC=CC=C1)C1=C(OP(Cl)Cl)C(=CC=C1)C1=CC=CC=C1 CNLUIDKVGOQQIJ-UHFFFAOYSA-N 0.000 description 1
- ZDTQJPVEXIUREJ-UHFFFAOYSA-N dichlorophosphinous acid Chemical class OP(Cl)Cl ZDTQJPVEXIUREJ-UHFFFAOYSA-N 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- BAZQYVYVKYOAGO-UHFFFAOYSA-M loxoprofen sodium hydrate Chemical group O.O.[Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 BAZQYVYVKYOAGO-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WHQDPSGUFIHZTE-UHFFFAOYSA-N naphthalen-2-ol Chemical compound C1=CC=CC2=CC(O)=CC=C21.C1=CC=CC2=CC(O)=CC=C21 WHQDPSGUFIHZTE-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N propyl ethylene Natural products CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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- 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
- B01J31/16—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
- B01J31/1845—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 phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
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- 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
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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Abstract
包括蒽酚之單亞磷酸酯。
Description
本發明係關於包括蒽酚之單亞磷酸酯。此外,本發明亦包括其在氫甲醯化(hydroformylation)中作為配體的用途。
在催化劑存在下,烯烴(olefin)化合物、一氧化碳與氫的反應生成包括多一個碳的醛,這是已知的氫甲醯化(hydroformylation)或氧代(oxo)合成。在這些反應中,元素週期表中的VIII族過渡金屬之化合物時常作為催化劑。已知的配體例如來自膦(phosphine)、亞磷酸酯(phosphite)以及膦酸酯(phosphonite)類的化合物,分別具有三價磷(P(III))。1996年在紐約Weinheim,B.CORNILS、W.A.HERRMANN於VCH第1與2冊發表「具有有機金屬化合物之應用的同質催化劑(Applied Homogeneous Catalysis with Organometallic Compounds)」或是2012年R.Franke、D.Selent、A.Börner於Chem.Rev.的DOI:10.1021/cr3001803發表「應用的氫甲醯化
(Applied Hydroformylation)」係烯烴氫甲醯化領域中的技藝狀態之很好的概述。
每一種催化活性組成物具有其專有的益處。因此,根據原料與目標產物,使用不同的催化活性組成物。
EP 0 155 508 A1係揭露在立體障礙的烯烴(olefin)之銠(rhodium)催化的氫甲醯化中,使用經雙伸芳基取代的單亞磷酸酯(bisarylene-substituted monophosphite),其中該烯烴(olefin)係例如異丁烯(isobutene)。然而,此處所使用的銠濃度有時非常高(一例為250ppm),就銠的當前成本而言,這是工業規模製程所無法接受的,並且必須改良。上述揭露的第41頁說明一化合物,其中三個苯基經由C-C橋而彼此相接,而於此例中形成2,6-聯苯基酚單元(2,6-biphenylphenol unit)。
本發明之目的係提供相較於習知的單亞磷酸酯,在氫甲醯化(hydroformylation)反應中具有優點性質的單亞磷酸酯。特別地,該目的包含提供新的配體,其除了聯酚(biphenol)單元之外,另具有芳香族系統(aromatic system),相較於使用結構相關的單亞磷酸酯,其造成產率改良。至少一烯烴(olefin)應達到該改良的產率。金屬濃度(例如銠)低於100ppm亦為所欲。
根據申請專利範圍第1項之化合物達到該目的。
化合物具有通式結構(I)或(II)之一:
(C1-C12)-烷基以及O-(C1-C12)-烷基可各自為未經取代的或是經由一或多個相同或不同的基團取代,該基團係選自於(C3-C12)-環烷基、(C3-C12)-雜環烷基、(C6-C20)-芳基、氟、氯、氰基、甲醯基(formyl)、醯基(acyl)以及烷氧基羰基(alkoxycarbonyl)。
(C6-C20)-芳基與-(C6-C20)-芳基-(C6-C20)-芳基-可各自為未經取代的或是經由一或多個相同或不同的基團取代,該基團係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-鹵素(例如Cl、F、Br、I)、-COO-(C1-C12)-烷基、-CONH-(C1-C12)-烷基、-(C6-C20)-芳基-CON[(C1-C12)-烷基]2、CO-(C1-C12)-烷基、-CO-(C6-C20)-芳基、-COOH、-OH、-SO3H、-SO3Na、-NO2、-CN、-NH2、-N[(C1-C12)-烷基]2。
在本發明的內容中,「-(C1-C12)-烷基」表述包括直鏈與支鏈烷基基團。較佳地,這些基團是未經取代的直鏈或是支鏈的-(C1-C8)-烷基基團,以及最佳係-(C1-C6)-烷基基團。-(C1-C12)-烷基基團的範例特別係甲基、乙基、丙基、異丙基、正丁基、異丁基、第二丁基(sec-butyl)、第三丁基(tert-butyl)、正戊基、2-戊基、2-甲基丁基、3-甲基丁基、1,2-二甲基丙基、1,1-二甲基丙基、2,2-二甲基丙基、1-乙基丙基、n-己基、2-己基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、2,2-二甲基丁基、1,3-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基丁基、1-乙基-2-甲基丙基、n-庚基、2-庚基、3-庚基、2-乙基戊基、1-丙基丁基、n-辛基、2-乙基己基、2-丙基庚基、壬基、癸基。
關於「-(C1-C12)-烷基」表述之說明亦適用於-O-(C1-C12)-烷基的烷基基團,亦即-(C1-C12)-烷氧中的烷基基團。較佳地,這些基團係未經取代的直鏈或是支鏈的-(C1-C6)-烷氧基團。
經取代的(C1-C12)-烷基基團與經取代的-(C1-C12)-烷氧基團可具有一或多個取代基,依其鏈長度而定。該取代基較佳係各自獨立選自於-(C3-C12)-環氧基、-(C3-C12)-雜環烷基、-(C6-C20)-芳基、氟、氯、氰基、甲醯基(formyl)、醯基(acyl)以及烷氧基羰基(alkoxycarbonyl)。
本發明內容中之「-(C3-C12)-環烷基」表述包括單、
二、三環烴基(hydrocarbyl)基團,其具有3至12個碳原子,特別係5至12個碳原子。這些包含環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環十二基(cyclododecyl-)、環十五基(cyclopentadecyl-)、降莰基(norbornyl-)以及金剛烷基(adamantyl)。經取代的環烷基之一範例可為薄荷腦基(menthyl)。
本發明內容中之「-(C3-C12)-雜環烷基基團」表述包括非芳香族飽和的或是部分未飽和的環脂族(cycloaliphatic)基團,其具有3至12個碳原子,特別係具有5至12個碳原子。-(C3-C12)-雜環烷基基團較佳係具有3至8個環原子,更佳係具有5或6個環原子。在雜環烷基基團中,相對於環烷基基團,1、2、3或4該環碳原子係以雜原子或包含雜原子的基團替代。該雜原子或是包含雜原子的基團較佳係選自於-O-、-S-、-N-、-N(=O)-、-C(=O)-以及-S(=O)-。-(C3-C12)-雜環烷基基團的範例係四氫苯硫基(tetrahydrothiophenyl)、四氫呋喃基(tetrahydrofuryl)、四氫哌喃基(tetrahydropyranyl)以及二氧雜環己烷基(dioxanyl)。
在本發明的內容中,「-(C6-C20)-芳基與-(C6-C20)-芳基-(C6-C20)-芳基-」包括單或多環芳香族烴基基團。這些具有6至20個環原子,較佳係具有6至14個環原子,特別係具有6至10個環原子。芳基較佳係-(C6-C10)-芳基以及-(C6-C10)-芳基-(C6-C10)-芳基-。芳基特別係苯基、萘基(naphthyl)、茚基(indenyl)、茀基(fluorenyl)、蔥基
(anthracenyl)、菲基(phenanthrenyl)、萘并萘基(naphthacenyl)、(chrysenyl)、芘基(pyrenyl)、蔻基(coronenyl)。更特別地,芳基係苯基、萘基以及蔥基(anthracenyl)。
經取代的-(C6-C20)-芳基基團與-(C6-C20)-芳基-(C6-C20)-芳基基團可具有一或多個(例如1、2、3、4或5個)取代基,依環的大小而定。這些取代基較佳係各自獨立選自於-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-鹵素(例如Cl、F、Br、I)、-COO-(C1-C12)-烷基、-CONH-(C1-C12)-烷基、-(C6-C20)-芳基-CON[(C1-C12)-烷基]2、-CO-(C1-C12)-烷基、-CO-(C6-C20)-芳基、-COOH、-OH、-SO3H、-SO3Na、-NO2、-CN、-NH2、-N[(C1-C12)-烷基]2。經取代的-(C6-C20)-芳基基團與-(C6-C20)-芳基-(C6-C20)-芳基基團較佳係經取代的-(C6-C10)-芳基基團與-(C6-C10)-芳基-(C6-C10)-芳基基團,特別係經取代的苯基或是經取代的萘基或是經取代的蔥基。經取代的-(C6-C20)-芳基基團較佳係具有一或多個,例如1、2、3、4或5個取代基,其係選自於-(C1-C12)-烷基基團、-(C1-C12)-烷氧基基團。
在一實施例中,R1、R2、R3、R4、R5、R6、R7、R8係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-S-烷基、-S-芳基、鹵素、-CO-(C1-C12)-烷基、-CO-(C6-C20)-芳基、-N[(C1-C12)-烷基]2。
在一實施例中,R9、R10、R11、R12、R13、R14、R15、R16、R17、R18係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-S-烷基、-S-芳基、鹵素、-CO-(C1-C12)-烷基、-CO-(C6-C20)-芳基、-N[(C1-C12)-烷基]2。
在一實施例中,R1、R2、R3、R4、R5、R6、R7、R8係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-S-烷基、-S-芳基、鹵素。
在一實施例中,R9、R10、R11、R12、R13、R14、R15、R16、R17、R18係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-S-烷基、-S-芳基、鹵素。
在一實施例中,R1、R2、R3、R4、R5、R6、R7、R8係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-S-烷基、-S-芳基。
在一實施例中,R9、R10、R11、R12、R13、R14、R15、R16、R17、R18係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-S-烷基、-S-芳基。
在一實施例中,R1、R2、R3、R4、R5、R6、R7、R8係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-
芳基。
在一實施例中,R9、R10、R11、R12、R13、R14、R15、R16、R17、R18係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基。
在一實施例中,R1、R2、R3、R4、R5、R6、R7、R8係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基。
在一實施例中,R9、R10、R11、R12、R13、R14、R15、R16、R17、R18係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基。
在一實施例中,該化合物具有以下結構(1)至(10)其中之一。
在一實施例中,該化合物具有通式結構I。
在一實施例中,該化合物具有通式結構II。
除了主張化合物之外,申請專利範圍亦主張包括這些化合物的錯合物。
錯合物包括:-上述化合物,-金屬原子,其係選自於:Rh、Ru、Co、Ir。
在一較佳實施例中,該金屬係Rh。
在這方面,請參閱2012年R.Franke、D.Selent、A.Börner發表於Chem.Rev.,DOI:10.1021/cr3001803的「Applied Hydroformylation」;第5688頁之方案12「General Method for the Preparation of a P-Modified Rh precatalyst」與本文所引用之參考文獻,以及2000年Dordrecht的出版社Kluwer的P.W.N.M.van Leeuwen,C.Claver(編輯)之P.W.N.M.van Leeuwen所發表的in Rhodium Catalyzed Hydroformylation,包含第48ff、233ff頁與本文所引用的參考文獻,以及2006年K.D.Wiese與
D.Obst所著的Top.Organomet.Chem.第18冊第1-13頁;2006年Heidelberg的出版社Springer Verlag Berlin之第6ff頁與本文所引用的參考文獻。
此外,申請專利範圍主張在用於催化氫甲醯化反應的配體-金屬錯合物中,該化合物作為配體之用途。
上述的化合物於配體-金屬錯合物中的用途,係用於催化氫甲醯化反應。
申請專利範圍亦主張該化合物作為配體-金屬錯合物的配體用於轉換烯烴(olefin)為醛之製程。
製程包括以下製程步驟:a)起初投入烯烴,b)加入上述錯合物,或是上述化合物以及包含金屬原子的物質,該金屬原子係選自於:Rh、Ru、Co、Ir,c)饋入H2與CO,d)加熱該反應混合物,將該烯烴轉換為醛。
在此製程中,可用任何所欲之順序完成製程步驟a)至d)。
在該製程的一較佳變化中,該金屬原子係Rh。
此例子中可使用過量的配體,並且各個配體非必須以配體-金屬錯合物的形式鍵結存在,而是在反應混合物中以游離配體存在。
該反應係在常規條件下進行。
溫度較佳係在80℃至200℃,以及壓力較佳係在1巴
至300巴。
溫度特別較佳係在100℃至160℃,以及壓力特別較佳係在15巴至250巴。
在本發明的製程中,氫甲醯化的反應物係烯烴(olefin)或是烯烴的混合物,特別是具有2至24個碳原子的單烯烴(monoolefin),較佳係具有3至16個碳原子的單烯烴(monoolefin),以及更佳係具有3至12個碳原子的單烯烴(monoolefin),具有終端或是內部C-C雙鍵,例如1-丙烯、1-或2-戊烯、2-甲基-1-丁烯、2-甲基-2-丁烯、3-甲基-1-丁烯、1-、2-或3-己烯、丙烯之二聚合作用所得到的C6烯烴混合物(二丙烯)、庚烯、2-或3-甲基-1-己烯、辛烯、2-甲基庚烯、3-甲基庚烯、5-甲基-2-庚烯、6-甲基-2-庚烯、2-乙基-1-庚烯、丁烯之二聚合作用所得到的C8烯烴混合物(二丁烯)、壬烯、2-或3-甲基辛烯、丙烯之三聚合作用所得到的C9烯烴混合物(三丙烯)、癸烯、2-乙烯-1-辛烯、十二烯、丁烯之四聚合作用或三聚合作用所得到的C12烯烴混合物(四丙烯或三丁烯)、四癸烯、六癸烯、丁烯之四聚合作用所得到的C16烯烴混合物(四丁烷(tetrabutane)),以及由具有不同碳原子數目(較佳為2至4)的烯烴之共寡聚合作用製備而得的烯烴混合物。
藉由以下的工作例說明本發明。
使用標準Schlenk技術在保護氣體下進行以下所有製備。使用前,以合適的乾燥劑乾燥溶劑(2009年在牛津出版的Butterworth Heinemann(Elsevier)(第6版)中W.L.F.Armarego(作者)、Christina Chai(作者)所著之Purification of Laboratory Chemicals)。使用前,在氬氣下稀釋三氯化磷(Aldrich)。在烘烤過的容器中完成所有製備操作。藉由NMR光譜將產物定性。以ppm報導呈現化學偏移(δ)。根據SR31P=SR1H *(BF31P/BF1H)=SR1H * 0.4048而引用31P NMR信號。(2001年Robin K.Harris、Edwin D.Becker、Sonia M.Cabral de Menezes、Robin Goodfellow與Pierre Granger,Pure Appl.Chem.,第73冊第1795-1818頁;2008年Robin K.Harris、Edwin D.Becker、Sonia M.Cabral de Menezes、Pierre Granger、Roy E.Hoffman與Kurt W.Zilm,Pure Appl.Chem.第80冊第59-84頁)。
以Bruker Avance 300或Bruker Avance 400完成核磁共振光譜的記錄,Agilent GC 7890A進行氣相色層分析,以Leco TruSpec CHNS與Varian ICP-OES 715進行元素分析,以及Thermo Electron Finnigan MAT 95-XP與Agilent 6890 N/5973設備進行ESI-TOF質譜分析。
聯酚的合成類似於DE102013203865與DE102013203867。
該技藝中的技術人士已知單-與二氯亞磷酸酯例如(蒽-9-基氧)二氯膦((anthracen-9-yloxy)dichlorophosphine)、2,6-二苯基苯氧基二氯膦(2,6-diphenylphenoxydichlorophosphine)或是6-氯二苯并[d,f][1,3,2]二氧雜磷雜環庚烯(6-chlorodibenzo[d,f][1,3,2]dioxaphosphepine)的合成並且用已知的方式進行。可在鹼的存在中,加入三氯化磷(phosphorus trichloride),而製備氯亞磷酸酯。關於詳細資訊,請參閱2010年John Wiley及Sons所出版的Paul C.J.Kamer與Piet W.N.M.van Leeuwen所著之「Phosphorous(III)Ligands in Homogeneous Catalysis-Design and Synthesis」包含第94 ff頁以及本文所引用的參考文獻。
將三乙基胺(triethylamine)(1.858g;18.36mmol)加入在甲苯(9ml)中的蒽-9-醇(anthracen-9-ol)(0.389g;2.00mmol)之攪拌溶液,並且將所得到的混合物於0℃逐滴加入在甲苯(9ml)中的6-氯二苯并[d,f][1,3,2]二氧雜磷雜環
庚烯(6-chlorodibenzo[d,f][1,3,2]dioxaphosphepine)溶液(0.501g;2.00mmol)。將反應混合物攪拌過夜並且過濾。在真空下,將濾液濃縮至乾燥。將所得到的固體於40℃乾燥2小時,而後自熱的二氯甲烷(3ml)再結晶。產量:0.206g(0.504mmol;25%)。
元素分析(計算C26H17O3P=408.37g/mol)C 76.59(76.47);H 4.14(4.20);P 7.64(7.58)%。
31P-NMR(CD2Cl2):148.4ppm。
1H-NMR(CD2Cl2):7.37-7.72(m,12H);8.10(m,2H);8.40(s,1H);8.56(m,2H)ppm。
13C-NMR(CD2Cl2):122.6;122.9;123.7;125.0;126.1;126.2;126.4;128.6;129.8;130.6;131.5;132.5;143.4(d,J CP=6.0Hz);149.4(d,J CP=5.8Hz)ppm。
ESI-TOF/HRMS:m/e 409.09945(M+H)+。
將三乙基胺(triethylamine)(1.854g;18.33mmol)加入
在甲苯(9ml)中的蒽-9-醇(anthracen-9-ol)(0.388g;2mmol)之攪拌溶液,並且將所得到的混合物於0℃逐滴加入在甲苯(8ml)中的4,8-二-第三丁基-6-氯-2,10-二甲氧基二苯并[d,f][1,3,2]二氧雜磷雜環庚烯(4,8-di-tert-butyl-6-chloro-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepine)溶液(0.845g;2mmol)。將反應混合物攪拌過夜並且過濾。在真空下,將濾液濃縮至乾燥。將所得到的殘留物以己烷攪拌兩次(各次4ml)並且過濾,而後在真空下乾燥。產量:0.206g(0.355mmol;18%)。
元素分析(計算C36H37O5P=580.63g/mol)C 74.28(74.46);H 6.62(6.42);P 5.39(5.33)%。
31P-NMR(CD2Cl2):140.4ppm。
1H-NMR(CD2Cl2):1.39(s,18H);3.92(s,6H);6.93(d,5 J HH=3.1Hz,2H,Harom);7.14(d,5 J HH=3.1Hz,2H,Harom);7.51(m,4H,Harom);8.05(m,2H,Harom);8.34(s,1H,Harom);8.41(m,2H,Harom)ppm。
13C-NMR(CD2Cl2):31.0;35.7;56.0;113.5;114.9;123.2;123.7(d,J CP=5.4Hz);124.8;125.9;126.0;128.4;132.6;134.2(d,J CP=3.9Hz);141.7(d,J CP=6.0Hz);143.4;143.5;156.6ppm。
ESI-TOF/HRMS:m/e 581.24490(M+H)+。
將三乙基胺(triethylamine)(1.344g;13.28mmol)加入在甲苯(7ml)中的蒽-9-醇(anthracen-9-ol)(0.281g;1.45mmol)之攪拌溶液,並且將所得到的混合物於0℃逐滴加入在甲苯(6ml)中的2,4,8,10-四-第三丁基-6-氯二苯并[d,f][1,3,2]二氧雜磷雜環庚烯(2,4,8,10-tetra-tert-butyl-6-chlorodibenzo[d,f][1,3,2]dioxaphosphepine)溶液(0.724g;1.52mmol)。將反應混合物攪拌過夜並且過濾。在真空下,將濾液濃縮至乾燥,並且以己烷(4ml)將所得到的殘留物再結晶。產量:0.559g(0.883mmol;61%)。
元素分析(計算C42H49O3P=632.78g/mol)C 79.83(79.71);H 7.61(7.81);P 5.01(4.89)%。
31P-NMR(CD2Cl2):140.7ppm。
1H-NMR(CD2Cl2):1.41(s,18H,C(CH 3)3);1.50(s,18H,C(CH 3)3);7.40(d,5 J HH=2.4Hz,2H,Harom);7.43-7.56(m,4H,Harom);7.60(d,5 J HH=2.4Hz,2H,Harom);8.05(m,2H,Harom);8..34(s,1H,Harom);8.38(m,2H,Harom)ppm。
13C-NMR(CD2Cl2):31.2;31.2;31.8;35.1;35.7;123.1;123.7(d,J CP=5.3Hz);124.8;125.0;125.8;
126.0;127.2;128.4;132.6;133.3(d,J CP=3.7Hz);141.0;143.5;145.8(d,J CP=6.2Hz);147.7ppm。
ESI-TOF/HRMS:m/e 633.34934(M+H)+。
將吡啶(pyridine)(0.284g;3.596mmol)加入在THF(8ml)中的1-(2-羥基-3-甲氧基-5-甲基苯基)萘-2-酚(1-(2-hydroxy-3-methoxy-5-methylphenyl)naphthalen-2-ol)(0.448g;1.598mmol)溶液。而後,於0℃將在THF(6ml)中的(蒽-9-基氧)二氯膦(anthracen-9-yloxy)dichlorophosphine)(0.472g;1.598mmol)溶液逐滴加入。將反應混合物攪拌過夜、過濾、並且於真空下將濾液濃縮至乾燥。以熱的二氯甲烷(13ml)再結晶所得到的殘留物。產量:0.302g(0.601mmol;38%)。
元素分析(計算C32H23O4P=502.50g/mol)C 76.38(76.49);H 4.68(4.61);P 6.15(6.16)%。
31P-NMR(THF-d8):147.3;152.7ppm。
1H-NMR(THF-d8):29-2.31(2s,3H);3.77-3.87(2s,3H);6.92(m,1H,Harom);7.01(m,1H,Harom);7.34-7.46
(m,7H,Harom);7.47-7.58(m,1H,Harom);7.81-7.95(m,4H,Harom);8.11(m,1H,Harom);8.25(m,1H,Harom);8.47(m,1H,Harom);8.74(m,1H,Harom)ppm。
13C-NMR(THF-d8):20.6;20.7;55.2;55.5;112.4;112.8;121.4;121.6;122.6;123.0;123.0;123.8;124.0;124.6;124.6;124.9;125.1;125.5;125.5;125.6;125.7;125.7;126.2;126.2;126.6;126.7;127.9;128.0;128.4;128.4;128.5;128.5;129.5;130.0;130.2(d,J CP=4.3Hz);132.0;132.3;132.5;134.0;134.8;135.7;137.6;143.2(d,J CP=7.7Hz);143.5(d,J CP=8.3Hz);145.8(d,J CP=2.8Hz);147.2(d,J CP=6.7Hz);152.2;152.5(d,J CP=2.6Hz)ppm。
ESI-TOF/HRMS:m/e 503.14057(M+H)+。
將三乙基胺(triethylamine)(2.277g;22.50mmol)加入在甲苯(7ml)中的4’-(第三丁基)-3-甲氧基-5-甲基-[1,1’-聯苯基]-2,2’-二醇(4’-(tert-butyl)-3-methoxy-5-methyl-[1,1’-biphenyl]-2,2’-diol)(0.703g;2.46mmol)之攪拌懸浮液,
並且將此混合物於0℃逐滴加入在甲苯(13ml)中的(蒽-9-基氧)二氯膦(0.725g;2.46mmol)溶液。將反應混合物攪拌過夜,而後將其過濾。在真空下,將濾液濃縮至乾燥,並且以甲苯(2ml)將所得到的殘留物再結晶。產量:0.320g(0.630mmol;26%)。元素分析(計算C32H29O4P=508.55g/mol)C 75.48(75.58);H 5.86(5.75);P 6.03(6.09)%。
31P-NMR(CD2Cl2):148.4ppm。
1H-NMR(CD2Cl2):44(s,9H);2.49(m,3H);4.00(s,3H);6.94-7.04(m,2H,Harom);7.46(m,2H,Harom);7.56-7.69(m,5H,Harom);8.10(m,2H,Harom);8.39(m,1H,Harom);8.78(m,2H,Harom)ppm。
13C-NMR(CD2Cl2):21.7;31.3;31.4;35.1;56.5;113.0;119.5;121.9;123.2;123.3;123.5;125.2(d,J CP=5.4Hz);126.3(d,J CP=9.5Hz);128.5;129.9;132.0(d,J CP=3.0Hz);132.6;136.1;136.2(d,J CP=6.0Hz);143.9(d,J CP=6.7Hz);149.3(d,J CP=5.7Hz);152.1;153.8ppm。
ESI-TOF/HRMS:m/e 509.18744(M+H)+。
將三乙基胺(triethylamine)(1.161g;11.473mmol)加入在甲苯(7ml)中的5’-異丙基-3-甲氧基-4’,5-二甲基-[1,1’-聯苯基]-2,2’-二醇(5’-isopropyl-3-methoxy-4’,5-dimethyl-[1,1’-biphenyl]-2,2’-diol)(0.359g;1.252mmol)之溶液,冷卻至0℃,並且將在甲苯(9ml)中的(蒽-9-基氧)二氯膦(0.370g;1.252mmol)溶液逐滴加入此混合物。將反應混合物攪拌過夜,而後過濾。在真空下,將濾液濃縮至乾燥。產量:0.594g(1.168mmol;93%)。
元素分析(計算C32H29O4P=508.55g/mol)C 75.46(75.58);H 5.90(5.75);P 6.09(6.09)%。
31P-NMR(CD2Cl2):148.5ppm。
1H-NMR(CD2Cl2):38(d, 2 J HH=6.8Hz,3H);1.39(d,2 J CP=6.8Hz,3H);2.46(s,3H);2.52(s,3H);3.22-3.32(m,1H);3.99(s,3H);6.95(m,1H,Harom);7.07(m,1H,Harom);7.20(m,1H,Harom);7.52(s,1H,Harom);7.57-7.68(m,4H,Harom);8.10(m,2H,Harom);8.39(m,1H,Harom);8.79(m,2H,Harom)ppm。
13C-NMR(CD2Cl2):19.3;21.7;23.6;23.6;29.5;56.5;113.0;121.9;123.4;123.5;123.8;125.2;(d,J CP=3.3Hz);125.7;126.3(d,J CP=3.3Hz);126.7;128.6(d,J CP=8.7Hz);129.4;132.5(d,J CP=3.6Hz);
132.6;136.1;136.2(d,J CP=6.2Hz);137.5;138.4;143.9(d,J CP=6.5Hz);144.8;146.9(d,J CP=5.9Hz);152.1ppm。
ESI-TOF/HRMS:m/e 509.18763(M+H)+。
將三乙基胺(triethylamine)(2.487g;24.58mmol)加入在甲苯(16ml)中的3-甲氧基-5,5’-二甲基-[1,1’-聯苯基]-2,2’-二醇(3-methoxy-5,5’-dimethyl-[1,1’-biphenyl]-2,2’-diol)(0.655g;2.68mmol)之攪拌溶液,並且將混合物冷卻至0℃。將在甲苯(18ml)中的(蒽-9-基氧)二氯膦(0.792g;2.683mmol)溶液逐滴加入此混合物。將反應混合物攪拌過夜,而後過濾。在真空下,將濾液濃縮至乾燥,並且於50℃/0.1毫巴乾燥殘留物3小時。產量:1.020g(2.187mmol;82%)。元素分析(計算C29H23O4P=466.47g/mol)C 74.58(74.67);H 5.19(4.97);P 6.78(6.64)%。
31P-NMR(CD2Cl2):148.6ppm。
1H-NMR(CD2Cl2):2.51(m,6H);3.99(s,3H);6.96(m,1H,Harom);7.06(m,1H,Harom);7.32-7.37(m,2H,
Harom);7.48(m,1H,Harom);7.57-7.69(m,4H,Harom);8.10(m,2H,Harom);8.39(m,1H,Harom);8.79(m,2H,Harom)ppm。
13C-NMR(CD2Cl2):21.1;21.7;56.4;113.2;122.0;122.2;123.3;123.5;125.1(d,J CP=3.7Hz);126.2;126.3;128.5;130.3;130.9;131.3(d,J CP=3.2Hz);132.1(d,J CP=3.3Hz);132.5(d,J CP=2.0Hz);135.7;136.1;136.3(d,J CP=5.8Hz);143.9(d,J CP=7.1Hz);147.3(d,J CP=5.4Hz);152.0(d,J CP=2.0Hz)ppm。
ESI-TOF/HRMS:m/e 467.10093(M+H)+。
將三乙基胺(triethylamine)(2.468g;14.51mmol)加入在甲苯(9ml)中的3-甲氧基-3’,5,5’-三甲基-[1,1’-聯苯基]-2,2’-二醇(3-methoxy-3’,5,5’-trimethyl-[1,1’-biphenyl]-2,2’-diol)(0.409g;1.58mmol)之溶液,冷卻至0℃,並且將在甲苯(11ml)中的(蒽-9-基氧)二氯膦(0.467g;1.584mmol)溶液逐滴加入此混合物。將反應混合物攪拌過夜,而後過濾。在真空下,將濾液濃縮至乾燥,並且以己烷
(17ml)將所得到的殘留物再結晶。產量:0.511g(1.063mmol;67%)。元素分析(計算C30H25O4P=480.50g/mol)C 74.53(74.99);H 5.53(5.24);P 6.48(6.45)%。
31P-NMR(CD2Cl2):147.7ppm。
1H-NMR(CD2Cl2):2.46-2.50(m,9H);4.02(s,3H);6.96(m,1H,Harom);7.05(m,1H,Harom);7.20(m,1H,Harom);7.30(m,1H,Harom);7.56-7.68(m,4H,Harom);8.10(m,2H,Harom);8.40(m,1H,Harom);8.88(m,2H,Harom)ppm。
13C-NMR(CD2Cl2):17.0;21.1;21.7;56.3;113.0;122.2;123.4;123.5;125.3(d,J CP=3.6Hz);125.7;126.3(d,J CP=5.5Hz);128.4;128.5;130.9;131.6(d,J CP=3.7Hz);132.0;132.0;132.5;135.4;135.8;136.8(d,J CP=8.0Hz);143.9(d,J CP=7.4Hz);145.3(d,J CP=4.0Hz);151.9ppm。ESI-TOF/HRMS:m/e 481.15626(M+H)+。
將三乙基胺(triethylamine)(1.857g;18.35mmol)加入
在甲苯(11ml)中的3-甲氧基-4’,5,5’-三甲基-[1,1’-聯苯基]-2,2’-二醇(3-methoxy-4’,5,5’-trimethyl-[1,1’-biphenyl]-2,2’-diol)(0.518g;2.00mmol)之溶液,並且將混合物冷卻至0℃。將在甲苯(8ml)中的(蒽-9-基氧)二氯膦(0.591g;2.00mmol)溶液逐滴加入此混合物。在進一步加入甲苯(30ml)之後,將反應混合物攪拌過夜。而後,將混合物過濾,並且在真空下移除溶劑。將所得到的殘留物置入甲苯(11ml)中,並且將所得到的懸浮液緩和加熱,而後將其過濾。在真空下將濾液濃縮至乾燥,並且於50℃/0.1毫巴將所得到的殘留物乾燥。產量:0.489g(1.018mmol;51%)。
元素分析(計算C30H25O4P=480.50g/mol)C 74.77(74.99);H 5.10(5.24);P 6.47(6.45)%。
31P-NMR(CD2Cl2):148.2ppm。
1H-NMR(CD2Cl2):2.38(m,6H);2.49(m,3H);3.98(s,3H);6.93(m,1H,Harom);7.03(m,1H,Harom);7.19(m,1H,Harom);7.40(m,1H,Harom);7.56-7.68(m,4H,Harom);8.09(m,2H,Harom);8.38(m,1H,Harom);8.76(m,2H,Harom)ppm。
13C-NMR(CD2Cl2):19.4;19.8;21.7;56.4;112.9;121.8;123.3;123.3;123.4;125.1(d,J CP=3.5Hz);125.6(d,J CP=3.5Hz);126.1;126.2;128.4;131.1;132.1(d,J CP=3.1Hz);132.5;134.4;136.0;136.2(d,J CP=6.0Hz);138.8;143.9(d,J CP=6.9Hz);
147.2(d,J CP=5.7Hz);152.0ppm。
ESI-TOF/HRMS:m/e 481.15601(M+H)+。
將三乙基胺(triethylamine)(2.097g;20.73mmol)加入在甲苯(14ml)中的1-(3-(第三丁基)-2-羥基-5-甲氧苯基)萘-2-醇(1-(3-(tert-butyl)-2-hydroxy-5-methoxyphenyl)naphthalen-2-ol)(0.730g;2.26mmol)之溶液,並且於0℃將在甲苯(10ml)中的(蒽-9-基氧)二氯膦(0.668g;2.26mmol)溶液逐滴加入此混合物。將反應混合物攪拌過夜,而後將其過濾。在真空下將濾液濃縮至乾燥,並且以己烷(28ml)將所得到的殘留物再結晶。產量:0.708g(1.30mmol;58%)。元素分析(計算C35H29O4P=544.58g/mol)C 76.96(77.19);H 5.38(5.37);P 5.66(5.69)%。
31P-NMR(CD2Cl2):150.0ppm。
1H-NMR(CD2Cl2):53(s,9H);3.88(s,3H);7.10(d,J HH=3.1Hz,1H,Harom);7.18(d,J HH=3.1Hz,1H,Harom);7.54-7.64(m,6H,Harom);7.78(m,1H,Harom);7.99-8.10
(m,4H,Harom);8.18-8.22(m,1H,Harom);8.38(m,1H,Harom);8.62(m,2H,Harom)ppm。
13C-NMR(CD2Cl2):31.2;35.8;56.1;115.0;115.1;121.7;123.1;123.7;125.0(d,J CP=3.7Hz);125.7;126.0;126.2;126.4;127.3;128.6;128.9;129.4;130.1;130.7(d,J CP=5.0Hz);132.4;132.5;133.0;138.4;142.1;143.7(d,J CP=7.2Hz);144.4;146.8(d,J CP=5.5Hz);156.1ppm。
ESI-TOF/HRMS:m/e 545.18764(M+H)+。
將三乙基胺(triethylamine)(1.529g;15.11mmol)加入在甲苯(8ml)中的2,6-二苯基酚(2,6-diphenylphenol)(0.411g;1.65mmol)之溶液,並且將所得到的混合物於0℃逐滴加入在甲苯(6ml)中的4,8-二-第三丁基-6-氯-2,10-二甲氧基二苯并[d,f][1,3,2]二氧雜磷雜環庚烯(4,8-di-tert-
butyl-6-chloro-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepine)(0.697g;1.65mmol)之溶液。將反應混合物於室溫攪拌過夜,並且於70℃攪拌5小時。而後,將混合物過濾,並且於真空下將濾液濃縮至乾燥。以己烷(4ml)將所得到的殘留物再結晶。產量:0.417g(0.659mmol;40%)。
元素分析(計算C40H41O5P=632.70g/mol)C 75.95(75.93);H 6.52(6.53);P 5.01(5.00)%。
31P-NMR(CD2Cl2):140.9ppm。
1H-NMR(CD2Cl2):1.37(s,18H);3.84(s,6H);6.51(d,5 J HH=3.1Hz,2H,Harom);6.89-7.95(m,br,15H,Harom)ppm。
13C-NMR(CD2Cl2):31.1;35.5;55.9;113.0;114.5;125.2;126.5-131.0(寬的,重疊信號);133.8(d,J CP=4.0Hz);141.5(d,J CP=6.3Hz);142.6;144.8;156.1ppm。
ESI-TOF/HRMS:m/e 633.27654(M+H)+。
將三乙基胺(triethylamine)(1.390g;13.74mmol)加入在甲苯(13ml)中的3,3’,5,5’-四-第三丁基-[1,1’-聯苯基]-2,2’-二醇(3,3’,5,5’-tetra-tert-butyl-[1,1’-biphenyl]-2,2’-diol)(0.616g;1.50mmol)之溶液,並且將混合物冷卻至0℃。將在甲苯(3ml)中的(2,6-二苯基苯氧基)二氯膦((2,6-diphenylphenoxy)dichlorophosphine)(0.521g;1.50mmol)溶液逐滴加入此混合物中。將反應混合物攪拌過夜並且過濾。真空下將濾液濃縮至乾燥,將所得到的殘留物置入二氯甲烷(3ml)並且以矽氧凝膠(silica gel)過濾。在真空下濃縮濾液,在50℃/0.1毫巴乾燥得到固體。產量:0.955g(1.394mmol;93%)。
元素分析(計算C46H53O3P=684.90g/mol)C 80.60(80.67);H 7.71(7.80);P 4.36(4.52)%。
31P-NMR(CD2Cl2):138.7ppm。
1H-NMR(CD2Cl2):1.29-1.46(m,br,36H,C(CH 3)3);6.76-7.13(m,br,4H,Harom);7.30-7.34(m,1H,Harom);7.34-7.40(m,2H,Harom);7.40-7.87(m,br,10H,Harom)ppm。
13C-NMR(CD2Cl2):31.3;31.3;31.7;34.9;35.6;124.6;125.2;125.7;126.7;128.6;129.4;133.0;
137.7;138.4;140.5;143.5;144.9;145.5;146.9;150.2;在127與131ppm之間的其他寬信號。
ESI-TOF/HRMS:m/e 685.38089(M+H)+。
購自瑞士Lengau的Premex Reactor AG之配備壓力維持裝置、氣流計、通氣攪拌器(sparging stirrer)以及壓力吸管的200ml高壓釜(autoclave)中,進行氫甲醯化作用。為了將濕度與氧氣的影響最小化,以鈉酮基(sodium ketyl)乾燥作為溶劑的甲苯並且在氬氣下蒸餾。所使用的烯烴(olefin)係辛烯混合物:正辛烯(Oxeno GmbH,辛烯異構物的混合物為1-辛烯:~3%;順+反-2-辛烯:~49%;順+反-3-辛烯:~29%;順+反-4-辛烯:~16%;結構異構辛烯:~3%,以鈉於回流之下加熱數小時並且於氬氣下蒸餾)。
關於實驗,以下於[(acac)Rh(COD)](acac=acetylacetonate anion(乙醯丙酮酸根陰離子);COD=1,5-環辛二烯(1,5-cyclooctadiene),Umicore)形式的銠溶液作為甲苯中的催化劑前驅物係被導入至在氬氣下的高壓釜中:100ppm的實驗係使用4.31毫莫耳濃度溶液之10ml的銠,40或60ppm的實驗係使用經適當稀釋的溶液之等量的銠。而後,加入溶解於甲苯中的適當量之亞磷酸酯化合物(每個銠5個配體當量)。藉由加入更多甲苯(決定用於GC分析之甲苯的總量,如下所示),催化劑溶液的初始體積調整至41.0ml。在每個例子中,決定所導入的甲苯量。正辛烯的
重量:10.70g(95.35mmol)。將高壓釜加熱至各個例子所稱之溫度,總氣體壓力(合成氣體:Linde;H2(99.999%):CO(99.997%)=1:1)為a)42巴用於最終壓力為50巴或是b)12巴用於最終壓力為20巴,具有攪拌(1500rpm)。在達到反應溫度之後,合成氣體壓力增加至a)48.5巴用於最終壓力為50巴或是b)19.5巴用於最終壓力為20巴以及在壓力吸管中所設定的正壓力約3巴下所導入的反應物。分別於固定壓力為50或20巴(荷蘭,Bronkhorst的封閉迴路壓力控制器),進行反應4小時。在反應時間結束之後,高壓釜冷卻至室溫、解壓,同時攪拌並且以氬氣沖洗。在攪拌器關閉之後,立即移出1ml的各反應混合物,以5ml戊烷稀釋,並且以氣相層析法進行分析:HP 5890 Series II plus,PONA,50m×0.2mm×0.5μm。參考溶劑甲苯作為內部標準,進行殘留的烯烴(olefin)與醛之定量判斷。
催化劑實驗的結果係概括說明於表1與表2。
如表1所示,根據本發明,所有化合物皆達到非常良好的產率。此外,銠濃度從100ppm降低至60ppm與40ppm係由配體的高活性補償,因而達到高於90%的產率。
這扮演了重要角色,特別是在大量生產使用時,因為較佳係盡可能使用小量的昂貴銠金屬而仍得到高產量的所欲產物。
亦於較低壓力(20巴)測試表1所列示的四個化合物。在此例子中,所有四個化合物皆造成非常良好的產率。
相較於比較化合物(A)與(B),本發明的化合物達到顯著改良的產率。
基於上述的實驗可知,本發明的化合物達到所稱之目的。
Claims (15)
- 一種化合物,其具有通式結構I或II:
- 如申請專利範圍第1項之化合物,其中R1、R2、R3、R4、R5、R6、R7、R8係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-S-烷基、-S-芳基、鹵素、-CO-(C1-C12)-烷基、-CO-(C6-C20)-芳基、-N[(C1-C12)-烷基]2。
- 如申請專利範圍第1或2項之化合物,其中R9、R10、R11、R12、R13、R14、R15、R16、R17、R18係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-S-烷基、-S-芳基、鹵素、-CO-(C1-C12)-烷基、-CO-(C6-C20)-芳基、-N[(C1-C12)-烷基]2。
- 如申請專利範圍第1至3項中任一項之化合物, 其中R1、R2、R3、R4、R5、R6、R7、R8係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-S-烷基、-S-芳基、鹵素。
- 如申請專利範圍第1至4項中任一項之化合物,其中R9、R10、R11、R12、R13、R14、R15、R16、R17、R18係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基、-(C6-C20)-芳基、-S-烷基、-S-芳基、鹵素。
- 如申請專利範圍第1至5項中任一項之化合物,其中R1、R2、R3、R4、R5、R6、R7、R8係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基。
- 如申請專利範圍第1至6項中任一項之化合物,其中R9、R10、R11、R12、R13、R14、R15、R16、R17、R18係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-O-(C6-C20)-芳基。
- 如申請專利範圍第1至7項中任一項之化合物,其中R1、R2、R3、R4、R5、R6、R7、R8係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基。
- 如申請專利範圍第1至8項中任一項之化合物,其中R9、R10、R11、R12、R13、R14、R15、R16、R17、R18係選自於:-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基。
- 如申請專利範圍第1至9項中任一項之化合物,具有以下通式結構1至10其中之一:
- 如申請專利範圍第1至10項中任一項之化合物,其中該化合物具有該通式結構I。
- 如申請專利範圍第1至10項中任一項之化合物,其中該化合物具有該通式結構II。
- 一種錯合物,其包括: -如申請專利範圍第1至12項中任一項之化合物,-選自Rh、Ru、Co、Ir的金屬原子。
- 一種如申請專利範圍第1至12項中任一項之化合物的用途,係用於催化氫甲醯化反應。
- 一種製程,其包括以下的製程步驟:a)起初投入烯烴,b)加入如申請專利範圍第13項的錯合物,或是如申請專利範圍第1至12項中任一項的化合物,以及具有選自於Rh、Ru、Co、Ir金屬原子的物質,c)饋入H2與CO,d)加熱該反應混合物,將該烯烴轉換為醛。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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EP14196192.0A EP3029052B1 (de) | 2014-12-04 | 2014-12-04 | 9-Anthrol-monophosphit Ester als Liganden für Hydroformylierungs-Katalysatoren |
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TW201634469A true TW201634469A (zh) | 2016-10-01 |
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TW104140153A TW201634469A (zh) | 2014-12-04 | 2015-12-01 | 包括蔥酚之單亞磷酸酯 |
Country Status (7)
Country | Link |
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US (1) | US20160159718A1 (zh) |
EP (1) | EP3029052B1 (zh) |
KR (1) | KR20160067770A (zh) |
CN (1) | CN105669757A (zh) |
ES (1) | ES2670512T3 (zh) |
SG (1) | SG10201509687SA (zh) |
TW (1) | TW201634469A (zh) |
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ES2670039T3 (es) * | 2014-12-04 | 2018-05-29 | Evonik Degussa Gmbh | Monofosfitos que presentan un componente biarilo asimétrico |
EP3296304B1 (de) | 2016-09-16 | 2018-11-14 | Evonik Degussa GmbH | Monophosphite mit methylenverbrücktem diphenol und anthracenylrest |
EP3388413A1 (de) | 2017-04-11 | 2018-10-17 | Evonik Degussa GmbH | Verfahren zur hydroformylierung von cyclooctadien unter einsatz von 2-(anthracen-9-yloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaphospholan |
EP3388414A1 (de) * | 2017-04-11 | 2018-10-17 | Evonik Degussa GmbH | Verfahren zur hydroformylierung von cyclooctadien unter einsatz von 4-([1,1':3',1''-terphenyl]-2'-yloxy)-s-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin |
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US4599206A (en) * | 1984-02-17 | 1986-07-08 | Union Carbide Corporation | Transition metal complex catalyzed reactions |
US5710306A (en) * | 1996-03-15 | 1998-01-20 | Dsm N.V. | Process to prepare a multidentate phosphite compound |
US7253298B2 (en) * | 2002-07-15 | 2007-08-07 | Rhodia Polyamide Intermediates | Process for preparing nitrile compounds from ethylenically unsaturated compounds |
WO2004078766A1 (en) * | 2003-02-27 | 2004-09-16 | Mitsubishi Chemical Corporation | Optically active phosphites and phosphoramides bearing biphenol skeletons with axial chirality, and their use in catalytic asymmetric reactions |
DE102011085883A1 (de) * | 2011-11-08 | 2013-05-08 | Evonik Oxeno Gmbh | Neue Organophosphorverbindungen auf Basis von Anthracentriol |
DE102013203867A1 (de) | 2013-03-07 | 2014-09-11 | Evonik Industries Ag | Elektrochemische Kupplung von Anilinen |
DE102013203865A1 (de) | 2013-03-07 | 2014-09-11 | Evonik Industries Ag | Elektrochemische Kupplung zweier Phenole, welche sich in ihrem Oxidationspotential unterscheiden |
ES2670039T3 (es) * | 2014-12-04 | 2018-05-29 | Evonik Degussa Gmbh | Monofosfitos que presentan un componente biarilo asimétrico |
-
2014
- 2014-12-04 EP EP14196192.0A patent/EP3029052B1/de not_active Not-in-force
- 2014-12-04 ES ES14196192.0T patent/ES2670512T3/es active Active
-
2015
- 2015-11-25 SG SG10201509687SA patent/SG10201509687SA/en unknown
- 2015-11-27 US US14/953,210 patent/US20160159718A1/en not_active Abandoned
- 2015-12-01 TW TW104140153A patent/TW201634469A/zh unknown
- 2015-12-03 CN CN201510876376.3A patent/CN105669757A/zh active Pending
- 2015-12-03 KR KR1020150171257A patent/KR20160067770A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
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EP3029052A1 (de) | 2016-06-08 |
KR20160067770A (ko) | 2016-06-14 |
SG10201509687SA (en) | 2016-07-28 |
EP3029052B1 (de) | 2018-02-28 |
CN105669757A (zh) | 2016-06-15 |
US20160159718A1 (en) | 2016-06-09 |
ES2670512T3 (es) | 2018-05-30 |
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