CN106397484A - 用于烷氧基羰基化的丁基‑桥连的二膦配体 - Google Patents
用于烷氧基羰基化的丁基‑桥连的二膦配体 Download PDFInfo
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- CN106397484A CN106397484A CN201610782022.7A CN201610782022A CN106397484A CN 106397484 A CN106397484 A CN 106397484A CN 201610782022 A CN201610782022 A CN 201610782022A CN 106397484 A CN106397484 A CN 106397484A
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- Prior art keywords
- alkyl
- heteroaryl
- aryl
- cycloalkyl
- group
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 79
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 39
- 229910052763 palladium Inorganic materials 0.000 title claims description 15
- 238000007083 alkoxycarbonylation reaction Methods 0.000 title abstract description 16
- 239000003054 catalyst Substances 0.000 title description 11
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title 1
- 125000001424 substituent group Chemical group 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 229910006069 SO3H Inorganic materials 0.000 claims abstract description 4
- -1 pyrrole radicals Chemical class 0.000 claims description 90
- 238000000034 method Methods 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 22
- 125000001072 heteroaryl group Chemical group 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 12
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 10
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 7
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002541 furyl group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical group CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 claims description 3
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 claims description 3
- 229940044613 1-propanol Drugs 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003838 furazanyl group Chemical group 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 claims description 3
- 125000001786 isothiazolyl group Chemical group 0.000 claims description 3
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 claims description 3
- 125000002971 oxazolyl group Chemical group 0.000 claims description 3
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 3
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 3
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 3
- 125000005493 quinolyl group Chemical group 0.000 claims description 3
- 238000006884 silylation reaction Methods 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- RRHPTXZOMDSKRS-PHFPKPIQSA-L (1z,5z)-cycloocta-1,5-diene;dichloropalladium Chemical compound Cl[Pd]Cl.C\1C\C=C/CC\C=C/1 RRHPTXZOMDSKRS-PHFPKPIQSA-L 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- 229960004592 isopropanol Drugs 0.000 claims description 2
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims 1
- 238000006206 glycosylation reaction Methods 0.000 claims 1
- 125000003386 piperidinyl group Chemical group 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 7
- 125000006413 ring segment Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 23
- 150000001336 alkenes Chemical class 0.000 description 21
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 14
- 239000007818 Grignard reagent Substances 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 12
- 150000004795 grignard reagents Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000003446 ligand Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 229910000085 borane Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000004679 31P NMR spectroscopy Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000001273 butane Substances 0.000 description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000006315 carbonylation Effects 0.000 description 6
- 238000005810 carbonylation reaction Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 238000005352 clarification Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 239000007848 Bronsted acid Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010413 mother solution Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 3
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 3
- UPSVYNDQEVZTMB-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene;1,3,5,7-tetranitro-1,3,5,7-tetrazocane Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O.[O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UPSVYNDQEVZTMB-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 241001024304 Mino Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 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 description 3
- 239000002244 precipitate Substances 0.000 description 3
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
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- 239000002841 Lewis acid Substances 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
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- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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Abstract
本发明涉及用于烷氧基羰基化的丁基‑桥连的二膦配体。具体地,本发明涉及式(I)的化合物其中R1、R2、R3、R4分别彼此独立地选自‑(C1‑C12)‑烷基、‑(C3‑C12)‑环烷基、‑(C3‑C12)‑杂环烷基、‑(C6‑C20)‑芳基、‑(C3‑C20)‑杂芳基;所述R1、R2、R3、R4基团的至少一个是‑(C3‑C20)‑杂芳基;以及它们作为配体在烷氧基羰基化中的用途。
Description
技术领域
本发明涉及丁基-桥连的二膦化合物、这些化合物的金属配合物和其用于烷氧基羰基化的用途。
背景技术
烯属不饱和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属不饱和化合物(烯烃)与一氧化碳和醇在金属配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烷氧基羰基化的一般反应方程式:
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的制备的中间步骤具有重要意义(S.G.Khokarale,E.J.García-Suárez,J.Xiong,U.V.Mentzel,R.Fehrmann,A.Riisager,Catalysis Communications2014,44,73-75)。乙烯-甲氧基羰基化在作为溶剂的甲醇中在温和的条件下使用被膦配体改性的钯催化剂而进行。
通常地,使用二齿的二膦化合物作为配体。Lucite(现在是Mitsubishi Rayon)开发了非常好的催化体系,其中使用了基于1,2-双(二叔丁基膦基甲基)苯(DTBPMB)的配体(W.Clegg,G.R.Eastham,M.R.J.Elsegood,R.P.Tooze,X.L.Wang,K.Whiston,Chem.Commun.1999,1877-1878)。
EP 0975574 A1公开了3-甲氧基-1-丁烯在例如1,4-双(二苯基膦基)-丁烷和1,4-双(二环己基膦基)-丁烷存在的情况下进行羰基化反应形成3-戊烯酸甲酯。没有研究长链烯属不饱和化合物(例如辛烯)的羰基化反应。
1,4-双(二烷基膦基)-丁烷化合物也可在其它领域用作钯催化剂的配体。例如WO02/10178就公开了使用1,4-双(二金刚烷基膦基)-丁烷作为用于加工卤代芳烃和生产芳基烯烃、二烯、二芳烃、苯甲酸-和丙烯酸衍生物、芳基烷烃和胺的配体。然而没有描述将这些配体用于烷氧基羰基化。
本发明的目的在于提供用于烷氧基羰基化的新型配体,使用其可以实现好的酯产率。特别地,本发明的配体应当适用于长链烯属不饱和化合物,例如C8烯烃和烯属不饱和化合物混合物的烷氧基羰基化。
所述目的通过在至少一个磷原子上被至少一个杂芳基取代的丁基-桥连的二膦化合物而实现。这些化合物特别地适合用作钯配合物的双齿配体和在烯属不饱和化合物(特别是C8-烯烃)的烷氧基羰基化中产生提高的产率。
发明内容
本发明的二膦化合物是式(I)的化合物
其中
R1、R2、R3、R4分别彼此独立地选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基、-(C3-C20)-杂芳基;
所述R1、R2、R3、R4基团的至少一个是-(C3-C20)-杂芳基;
和
R1、R2、R3、R4,如果它们是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C3-C20)-杂芳基,
可以分别彼此独立地被选自下列的一个或多个取代基取代:
-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-O-(C1-C12)-烷基、-O-(C1-C12)-烷基-(C6-C20)-芳基、-O-(C3-C12)-环烷基、-S-(C1-C12)-烷基、-S-(C3-C12)-环烷基、-COO-(C1-C12)-烷基、-COO-(C3-C12)-环烷基、-CONH-(C1-C12)-烷基、-CONH-(C3-C12)-环烷基、-CO-(C1-C12)-烷基、-CO-(C3-C12)-环烷基、-N-[(C1-C12)-烷基]2、-(C6-C20)-芳基、-(C6-C20)-芳基-(C1-C12)-烷基、-(C6-C20)-芳基-O-(C1-C12)-烷基、-(C3-C20)-杂芳基、-(C3-C20)-杂芳基-(C1-C12)-烷基、-(C3-C20)-杂芳基-O-(C1-C12)-烷基、-COOH、-OH、-SO3H、-NH2、卤素。
术语(C1-C12)-烷基包括具有1至12个碳原子的直链和支化的烷基。优选的是(C1-C8)-烷基,更优选(C1-C6)-烷基,最优选(C1-C4)-烷基。
合适的(C1-C12)-烷基特别是甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、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、正己基、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、正庚基、2-庚基、3-庚基、2-乙基戊基、1-丙基丁基、正辛基、2-乙基己基、2-丙基庚基、壬基、癸基。
术语(C1-C12)-烷基的解释也特别适用于在-O-(C1-C12)-烷基、-S-(C1-C12)-烷基、-COO-(C1-C12)-烷基、-CONH-(C1-C12)-烷基、-CO-(C1-C12)-烷基和-N-[(C1-C12)-烷基]2中的烷基。
术语(C3-C12)-环烷基包括具有3至12个碳原子的单环、双环或三环的烃基。优选的是(C5-C12)-环烷基。
所述(C3-C12)-环烷基优选具有3至8,更优选5或6个环原子。
合适的(C3-C12)-环烷基特别是环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环十二烷基、环十五烷基、降冰片基、金刚烷基。
术语(C3-C12)-环烷基的解释也特别适用于在-O-(C3-C12)-环烷基、-S-(C3-C12)-环烷基、-COO-(C3-C12)-环烷基、-CONH-(C3-C12)-环烷基、-CO-(C3-C12)-环烷基中的环烷基。
术语(C3-C12)-杂环烷基包括具有3至12个碳原子的非芳族的、饱和的或部分饱和的环脂族基团,其中环碳原子中的一个或多个被杂原子替代。所述(C3-C12)-杂环烷基具有优选3至8,更优选5或6个环原子和任选地被脂族侧链取代。不同于环烷基,在所述杂环烷基中,一个或多个环碳原子被杂原子或含杂原子的基团替代。所述杂原子或含杂原子的基团优选选自O、S、N、N(=O)、C(=O)、S(=O)。在本发明中,(C3-C12)-杂环烷基因此也是环氧乙烷。
合适的(C3-C12)-杂环烷基特别是四氢硫代苯基、四氢呋喃基、四氢吡喃基和二噁烷基。
术语(C6-C20)-芳基包括具有6至20个碳原子的单环或多环的芳族烃基。优选的是(C6-C14)-芳基,更优选(C6-C10)-芳基。
合适的(C6-C20)-芳基特别是苯基、萘基、茚基、芴基、蒽基、菲基、稠四苯基(naphthacenyl)、基(chrysenyl)、芘基、晕苯基(coronenyl)。优选的(C6-C20)-芳基是苯基、萘基和蒽基。
术语(C3-C20)-杂芳基包括具有3至20个碳原子的单环或多环的芳族烃基,其中一个或多个碳原子被杂原子替代。优选的杂原子是N、O和S。所述(C3-C20)-杂芳基具有3至20,优选6至14和更优选6至10个环原子。因此,例如吡啶基在本发明中是C6-杂芳基;呋喃基是C5-杂芳基。
合适的(C3-C20)-杂芳基特别是呋喃基、噻吩基、吡咯基、噁唑基、异噁唑基、噻唑基、异噻唑基、咪唑基、吡唑基、呋咱基、四唑基、吡啶基、哒嗪基、嘧啶基、吡嗪基、苯并呋喃基、吲哚基、异吲哚基、苯并咪唑基、喹啉基、异喹啉基。
术语卤素特别包括氟、氯、溴和碘。特别优选的是氟和氯。
在一个实施方案中,所述R1、R2、R3、R4基团,如果它们是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C3-C20)-杂芳基,则可以分别彼此独立地被选自下列的一个或多个取代基取代:-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-O-(C1-C12)-烷基、-O-(C1-C12)-烷基-(C6-C20)-芳基、-O-(C3-C12)-环烷基、-S-(C1-C12)-烷基、-S-(C3-C12)-环烷基、-(C6-C20)-芳基、-(C6-C20)-芳基-(C1-C12)-烷基、-(C6-C20)-芳基-O-(C1-C12)-烷基、-(C3-C20)-杂芳基、-(C3-C20)-杂芳基-(C1-C12)-烷基、-(C3-C20)-杂芳基-O-(C1-C12)-烷基、-COOH、-OH、-SO3H、-NH2、卤素。
在一个实施方案中,所述R1、R2、R3、R4基团,如果它们是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C3-C20)-杂芳基,则可以分别彼此独立地被选自下列的一个或多个取代基取代:-(C1-C12)-烷基、-(C3-C12)-环烷基、-O-(C1-C12)-烷基、-O-(C1-C12)-烷基-(C6-C20)-芳基、-O-(C3-C12)-环烷基、-(C6-C20)-芳基、-(C6-C20)-芳基-(C1-C12)-烷基、-(C6-C20)-芳基-O-(C1-C12)-烷基、-(C3-C20)-杂芳基、-(C3-C20)-杂芳基-(C1-C12)-烷基、-(C3-C20)-杂芳基-O-(C1-C12)-烷基。
在一个实施方案中,所述R1、R2、R3、R4基团,如果它们是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C3-C20)-杂芳基,则可以分别彼此独立地被选自下列的一个或多个取代基取代:-(C1-C12)-烷基、-O-(C1-C12)-烷基-(C6-C20)-芳基、-(C3-C20)-杂芳基、-(C3-C20)-杂芳基-(C1-C12)-烷基、-(C3-C20)-杂芳基-O-(C1-C12)-烷基。
在一个实施方案中,所述R1、R2、R3、R4基团,如果它们是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C3-C20)-杂芳基,则可以分别彼此独立地被选自下列的一个或多个取代基取代:-(C1-C12)-烷基和-(C3-C20)-杂芳基。
在一个实施方案中,所述R1、R2、R3、R4基团,如果它们是-(C1-C12)-烷基、-(C3-C12)-环烷基或-(C3-C12)-杂环烷基,则是未取代的,并且如果它们是-(C6-C20)-芳基或-(C3-C20)-杂芳基,则可以如上所述被取代。
在一个实施方案中,所述R1、R2、R3、R4基团,如果它们是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C3-C20)-杂芳基,则是未取代的。
在一个实施方案中,R1、R2、R3、R4分别彼此独立地选自-(C1-C12)-烷基、-(C6-C20)-芳基、-(C3-C20)-杂芳基;
其中所述R1、R2、R3、R4基团的至少一个是-(C3-C20)-杂芳基;
和R1、R2、R3、R4,如果它们是-(C1-C12)-烷基、-(C6-C20)-芳基或-(C3-C20)-杂芳基,则可以分别彼此独立地被上述的一个或多个取代基取代。
在一个优选实施方案中,R1、R2、R3、R4分别彼此独立地选自-(C1-C12)-烷基和-(C3-C20)-杂芳基;
其中所述R1、R2、R3、R4基团的至少一个是-(C3-C20)-杂芳基;
和R1、R2、R3、R4可以分别彼此独立地被上述的一个或多个取代基取代。
在一个实施方案中,所述R1、R2、R3、R4基团的至少两个是-(C3-C20)-杂芳基。
在一个实施方案中,所述R1和R3基团分别是-(C3-C20)-杂芳基和可以分别彼此独立地被上述的一个或多个取代基取代。优选地,R2和R4彼此独立地选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基,更优选-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C6-C20)-芳基,最优选-(C1-C12)-烷基。R2和R4可以彼此独立地被上述的一个或多个取代基取代。
在一个实施方案中,所述R1、R2、R3和R4基团是-(C6-C20)-杂芳基和可以分别彼此独立地被上述的一个或多个取代基取代。
在一个实施方案中,所述R1、R2、R3和R4基团,如果它们是杂芳基,则分别彼此独立地选自具有5至10个环原子,优选5或6个环原子的杂芳基。
在一个实施方案中,所述R1、R2、R3和R4基团,如果它们是杂芳基,则是具有5个环原子的杂芳基。
在一个实施方案中,所述R1、R2、R3和R4基团,如果它们是杂芳基,则分别彼此独立地选自具有6至10个环原子的杂芳基。
在一个实施方案中,所述R1、R2、R3和R4基团,如果它们是杂芳基,则是具有6个环原子的杂芳基。
在一个实施方案中,所述R1、R2、R3和R4基团,如果它们是杂芳基,则选自呋喃基、噻吩基、吡咯基、噁唑基、异噁唑基、噻唑基、异噻唑基、咪唑基、吡唑基、呋咱基、四唑基、吡啶基、哒嗪基、嘧啶基、吡嗪基、苯并呋喃基、吲哚基、异吲哚基、苯并咪唑基、喹啉基、异喹啉基,其中所述的杂芳基可以如上所述地被取代。
在一个实施方案中,所述R1、R2、R3和R4基团,如果它们是杂芳基,则选自呋喃基、噻吩基、吡咯基、咪唑基、吡啶基、嘧啶基、吲哚基,其中所述的杂芳基可以如上所述地被取代。
在一个实施方案中,所述R1、R2、R3和R4基团,如果它们是杂芳基,则选自2-呋喃基、2-噻吩基、2-吡咯基、2-咪唑基、2-吡啶基、2-嘧啶基、2-吲哚基,其中所述的杂芳基可以如上所述地被取代。
在一个实施方案中,所述R1、R2、R3和R4基团,如果它们是杂芳基,则选自2-呋喃基、2-噻吩基、N-甲基-2-吡咯基、N-苯基-2-吡咯基、N-(2-甲氧基苯基)-2-吡咯基、2-吡咯基、N-甲基-2-咪唑基、2-咪唑基、2-吡啶基、2-嘧啶基、N-苯基-2-吲哚基、2-吲哚基,其中所述的杂芳基没有被进一步地取代。
更优选地,所述R1、R2、R3和R4基团,如果它们是杂芳基,则是吡啶基,特别是2-吡啶基。
在一个实施方案中,R1和R3是吡啶基,优选2-吡啶基,和R2和R4是-(C1-C12)-烷基,其中R1、R2、R3和R4可以分别如上所述地被取代。
在一个实施方案中,本发明的二膦化合物是指根据式(1)的化合物:
本发明还涉及包含Pd和本发明的二膦化合物的配合物。在这些配合物中,本发明的二膦化合物用作金属原子的二齿配体。所述配合物例如用作烷氧基羰基化的催化剂。使用本发明的配合物可以在大量不同的烯属不饱和化合物的烷氧基羰基化中实现高的产率。
本发明的配合物另外可以包含在金属原子上配位的配体。其例如是烯属不饱和化合物或阴离子。合适的额外的配体例如是苯乙烯、乙酸根阴离子、马来酰亚胺(例如N-甲基马来酰亚胺)、1,4-萘醌、三氟乙酸根阴离子或氯阴离子。
本发明还涉及本发明的二膦化合物用于催化烷氧基羰基化反应的用途。在此,本发明的化合物特别可以用作本发明的金属配合物。
此外,本发明涉及包含下列方法步骤的方法:
a)首先添加烯属不饱和化合物;
b)添加本发明的二膦化合物和包含Pd的化合物,
或者添加包含Pd和本发明的二膦化合物的本发明配合物;
c)添加醇;
d)导入CO;
e)加热所述反应混合物,其中所述烯属不饱和化合物反应生成酯。
在此,所述方法步骤a)、b)、c)和d)可以以任意顺序进行。然而,通常在步骤a)至c)中预先加入反应物质之后添加CO。步骤d)和e)可以同时或相继地进行。此外,也可以在多个步骤中导入CO,从而例如首先导入一部分CO,然后加热和接着导入另一部分CO。
在本发明的方法中用作反应物的烯属不饱和化合物包含一个或多个碳碳双键。这些化合物在下文中为了简单起见也称为烯烃。所述双键可以是末端的或内部的。
优选地,所述烯属不饱和化合物具有2至30个碳原子,优选2至22个碳原子,更优选2至12个碳原子。
在一个实施方案中,所述烯属不饱和化合物包含4至30个碳原子,优选6至22个碳原子,更优选8至12个碳原子。在一个特别优选的实施方案中,所述烯属不饱和化合物包含8个碳原子。
除了一个或多个双键,所述烯属不饱和化合物还可以包含其它的官能团。优选地,所述烯属不饱和化合物包含选自下列的一个或多个官能团:羧基、硫代羧基、磺基、亚磺酰基、羧酸酐、酰亚胺、羧酸酯、磺酸酯、氨基甲酰基、氨磺酰基、氰基、羰基、硫代羰基、羟基、氢硫基、氨基、醚、硫代醚、芳基、杂芳基或硅烷基和/或卤素取代基。其中,所述烯属不饱和化合物优选总共包含2至30个碳原子,优选2至22个碳原子,更优选2至12个碳原子。
在一个实施方案中,所述烯属不饱和化合物不包含除了碳碳双键之外的其它官能团。
在一个特别优选的实施方案中,所述烯属不饱和化合物是具有至少一个双键和2至30个碳原子,优选6至22个碳原子,还优选8至12个碳原子,最优选8个碳原子的非官能化的烯烃。
合适的烯属不饱和化合物例如是:
乙烯;
丙烯;
C4烯烃,例如1-丁烯、顺式-2-丁烯、反式-2-丁烯、顺式-和反式-2-丁烯的混合物、异丁烯、1,3-丁二烯;萃余液I至III、裂解物-C4
C5烯烃,例如1-戊烯、2-戊烯、2-甲基-1-丁烯、2-甲基-2-丁烯、2-甲基-1,3-丁二烯(异戊二烯)、1,3-戊二烯;
C6烯烃,例如四甲基乙烯、1,3-己二烯、1,3-环己二烯;
C7烯烃,例如1-甲基环己烯、2,4-庚二烯、降冰片二烯;
C8烯烃,例如1-辛烯、2-辛烯、环辛烯、二正丁烯、二异丁烯、1,5-环辛二烯、1,7-辛二烯;
C9烯烃,例如三丙烯;
C10烯烃,例如二环戊二烯;
十一烯;
十二烯;
内部C14烯烃;
内部C15至C18烯烃;
直链或支化的,环状、非环状或部分环状的,内部C15至C30烯烃;
三异丁烯、三正丁烯;
萜,例如柠檬烯、香叶醇、金合欢醇、蒎烯、月桂烯、香芹酮、3-蒈烯;
具有18个碳原子的多重不饱和化合物,例如亚油酸或亚麻酸;
不饱和羧酸的酯,例如乙酸或丙酸的乙烯基酯、不饱和羧酸的烷基酯、丙烯酸或甲基丙烯酸的甲基酯或乙基酯、油酸酯(例如油酸甲酯或油酸乙酯)、亚油酸或亚麻酸的酯;
乙烯基化合物,例如乙酸乙烯酯、乙烯基环己烯、苯乙烯、α-甲基苯乙烯、2-异丙烯基萘;
2-甲基-2-戊醛、甲基-3-戊烯酸酯、甲基丙烯酸酐。
在所述方法的一个变型方案中,所述烯属不饱和化合物选自丙烯、1-丁烯、顺式-和/或反式-2-丁烯,或者它们的混合物。
在所述方法的一个变型方案中,所述烯属不饱和化合物选自1-戊烯、顺式-和/或反式-2-戊烯、2-甲基-1-丁烯、2-甲基-2-丁烯、3-甲基-1-丁烯,或者它们的混合物。
在一个优选的实施方案中,所述烯属不饱和化合物选自乙烯、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、正辛烯、1-辛烯、2-辛烯,或者它们的混合物。
在一个变型方案中,使用烯属不饱和化合物的混合物。在本发明中,所述混合物是指包含至少两种不同的烯属不饱和化合物的组合物,其中每种烯属不饱和化合物的含量为优选至少5重量%,基于所述混合物的总重量。
优选使用分别具有2至30个碳原子,优选4至22个碳原子,更优选6至12个碳原子,最优选8至10个碳原子的烯属不饱和化合物的混合物。
合适的烯属不饱和化合物的混合物是所谓的萃余液I至III。萃余液I包含40%至50%异丁烯、20%至30%1-丁烯、10%至20%顺式-和反式-2-丁烯、最多1%1,3-丁二烯和10%至20%正丁烷和异丁烷。萃余液II是在石脑油裂解中生成的C4级分的一部分和基本上由从萃余液I除去异丁烯之后的正丁烯异构体、异丁烷和正丁烷组成。萃余液III是在石脑油裂解中生成的C4级分的一部分和基本上由正丁烯异构体和正丁烷组成。
另外合适的混合物是二正丁烯,也称为二丁烯、DNB或DnB。二正丁烯是C8烯烃的异构体混合物,其由1-丁烯、顺式-2-丁烯和反式-2-丁烯的混合物的二聚化而生成。在工业中,萃余液II或萃余液III料流通常经受催化低聚化,其中所包含的丁烷(n/iso)未改变地出现和所包含的烯烃完全或部分地反应。除了二聚的二正丁烯,通常也生成更高级的低聚物(三丁烯C12、四丁烯C16),其在反应之后通过蒸馏而分离。这些同样可以用作反应物。
在一个优选的变型方案中,使用包含异丁烯、1-丁烯、顺式-和反式-2-丁烯的混合物。优选地,所述混合物包含1-丁烯、顺式-和反式-2-丁烯。
本发明的烷氧基羰基化通过本发明的Pd配合物催化。在此,在方法步骤b)中可以将Pd配合物作为包含Pd和本发明的膦配体的预成型的配合物添加,或者所述Pd配合物原位地由包含Pd的化合物和游离的膦配体而形成。其中,包含Pd的化合物也称为催化剂前体。
在原位形成催化剂的情况下,可以加入过量的配体,从而在反应混合物中也存在未结合的配体。
在一个变型方案中,包含Pd的化合物选自二氯化钯(PdCl2)、乙酰基丙酮化钯(II)[Pd(acac)2]、乙酸钯(II)[Pd(OAc)2]、二氯(1,5-环辛二烯)钯(II)[Pd(cod)2Cl2]、双(二苯亚甲基丙酮)钯[Pd(dba)2]、双(乙腈)二氯钯(II)[Pd(CH3CN)2Cl2]、(肉桂基)二氯化钯[Pd(肉桂基)Cl2]。
优选地,包含Pd的化合物是PdCl2、Pd(acac)2或Pd(OAc)2。特别合适的是PdCl2。
在方法步骤c)中的醇可以是支化的或直链的,环状的、脂环族的、部分环状或脂环族的,和特别是C1-至C30-烷醇。可以使用一元醇或多元醇。
在方法步骤c)中的醇包含优选1至30个碳原子,更优选1至22个碳原子,特别优选1至12个碳原子。它们可以是一元醇或多元醇。
除了一个或多个羟基之外,所述醇可以包含另外的官能团。优选地,所述醇还包含选自下列的一个或多个官能团:羧基、硫代羧基、磺基、亚磺酰基、羧酸酐、酰亚胺、羧酸酯、磺酸酯、氨基甲酰基、氨磺酰基、氰基、羰基、硫代羰基、氢硫基、氨基、醚、硫代醚、芳基、杂芳基或硅烷基和/或卤素取代基。
在一个实施方案中,所述醇除了羟基之外不包含另外的官能团。
所述醇可以包含不饱和的和芳族的基团。然而,优选的是脂族的醇。
在本发明中,脂族的醇是指不包含芳族基团的醇,例如烷醇、烯醇或炔醇。因此也允许不饱和的、非芳族的醇。
在一个实施方案中,所述醇是具有一个或多个羟基和1至30个碳原子,优选1至22个碳原子,更优选1至12个碳原子,最优选1至6个碳原子的烷醇。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自一元醇的类型。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自: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、苯酚、2-乙基己醇、异壬醇、2-丙基庚醇。
在一个优选的变型方案中,在方法步骤c)中的醇选自甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、2-丙醇、叔丁醇、3-戊醇、环己醇、苯酚,或其混合物。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自多元醇的类型。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自:二元醇、三元醇、四元醇。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自: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、1,2,6-三羟基己烷、季戊四醇、1,1,1-三(羟基甲基)乙烷、儿茶酚、雷琐酚和羟基氢醌。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自:蔗糖、果糖、甘露糖、山梨糖、半乳糖和葡萄糖。
在所述方法的一个优选的变型方案中,在方法步骤c)中的醇选自甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇。
在所述方法的一个特别优选的变型方案中,在方法步骤c)中的醇选自:甲醇、乙醇。
在所述方法的一个特别优选的变型方案中,在方法步骤c)中的醇是甲醇。
在所述方法的一个变型方案中,在方法步骤c)中的醇过量使用。
在所述方法的一个变型方案中,在方法步骤c)中的醇同时作为溶剂使用。
在所述方法的一个变型方案中,使用另一种选自下列的溶剂:甲苯、二甲苯、四氢呋喃(THF)和二氯甲烷(CH2Cl2)。
在步骤d)中,优选在0.1至10MPa(1至100bar),优选1至8MPa(10至80bar),更优选2至4MPa(20至40bar)的CO分压下导入CO。
在本发明的方法步骤e)中,将所述反应混合物优选加热到10℃至180℃,优选20至160℃,更优选40至120℃的温度,从而使所述烯属不饱和化合物反应生成酯。
在步骤a)中预先添加的烯属不饱和化合物与在步骤c)中添加的醇的摩尔比为优选1∶1至1∶20,更优选1∶2至1∶10,更优选1∶3至1∶4。
Pd与在步骤a)中预先添加的烯属不饱和化合物的质量比为优选0.001至0.5重量%,优选0.01至0.1重量%,更优选0.01至0.05重量%。
本发明的二膦化合物与Pd的摩尔比为优选0.1∶1至400∶1,优选0.5∶1至400∶1,更优选1∶1至100∶1,最优选2∶1至50∶1。
优选地,所述方法在添加酸的情况下进行。在一个变型方案中,所述方法因此另外包括步骤c′):将酸添加到反应混合物中。在此,优选的是布朗斯特酸或路易斯酸。
合适的布朗斯特酸的酸强度优选为pKa≤5,优选pKa≤3。所给出的酸强度pKa基于标准条件(25℃,1.01325bar)下测定的pKa值。在本发明中,对于多质子酸,所述酸强度pKa基于第一个质子迁移步骤的pKa值。
优选地,所述酸不是羧酸。
合适的布朗斯特酸例如是高氯酸、硫酸、磷酸、甲基膦酸和磺酸。优选地,所述酸是硫酸或磺酸。合适的磺酸例如是甲磺酸、三氟甲磺酸、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。特别优选的酸是硫酸、甲磺酸、三氟甲磺酸和对甲苯磺酸。
使用的路易斯酸例如可以是三氟甲磺酸铝。
在一个实施方案中,在步骤c′)中添加的酸的量为0.3至40mol%,优选0.4至15mol%,更优选0.5至5mol%,最优选0.6至3mol%,基于在步骤a)中使用的烯属不饱和化合物的物质的量。
具体实施方式
下面的实施例具体阐述本发明。
通用操作说明
所有下列的制备使用标准Schlenk技术在保护气体下进行。溶剂在使用前通过合适的干燥剂干燥(Purification of Laboratory Chemicals,W.L.F.Armarego(作者),Christina Chai(作者),Butterworth Heinemann(Elsevier),第六版,Oxford 2009)。
三氯化磷(Aldrich)在使用前在氩气下蒸馏。所有制备工作在预热过的容器中进行。产物的表征通过NMR光谱法进行。化学位移(δ)以ppm为单位给出。31P NMR信号参照如下:SR31P=SR1H*(BF31P/BF1H)=SR1H*0.4048(Robin K.Harris,Edwin D.Becker,SoniaM.Cabral de Menezes,Robin Goodfellow,和Pierre Granger,Pure Appl.Chem.,2001,73,1795-1818;Robin K.Harris,Edwin D.Becker,Sonia M.Cabral de Menezes,PierreGranger,Roy E.Hoffman和Kurt W.Zilm,Pure Appl.Chem.,2008,80,59-84)。
核磁共振谱的记录在Bruker Avance 300或Bruker Avance 400上完成,气相色谱分析在Agilent GC 7890A上进行,元素分析在Leco TruSpec CHNS和Varian ICP-OES 715上进行,和ESI-TOF质谱法在Thermo Electron Finnigan MAT 95-XP和Agilent 6890 N/5973仪器上进行。
氯-2-吡啶基-叔丁基膦(前体A)的制备
用于合成氯-2-吡啶基-叔丁基膦的格氏试剂根据″Knochel方法″使用异丙基氯化镁制备(Angew.Chem.2004,43,2222-2226)。后处理根据Budzelaar方法进行(Organometallics 1990,9,1222-1227)。
示意图1:前体A的合成。
将8.07ml的1.3M异丙基氯化镁溶液(Knochel试剂)在氩气下加入到50ml圆底烧瓶(带有磁搅拌器和隔膜),并且冷却到-15℃。然后,快速滴加953.5μl(10mmol)的2-溴吡啶。该溶液立即变黄。使其温热到-10℃。如下确定反应的转化:取出大约100μl溶液并且将其加入到1ml的饱和氯化铵溶液。如果该溶液“冒泡”,则还没有形成太多的格氏试剂。将水溶液使用一吸管的***萃取和将有机相通过Na2SO4干燥。记录下该***溶液的GC。当相比于2-溴吡啶形成了大量的吡啶,则获得高的转化率。在-10℃下,仅有很少的转化。在温热到室温和搅拌1-2小时之后,该反应溶液变成棕黄色。GC测试表明完全的转化。这时,可以将格氏试剂的溶液使用注射器泵缓慢地滴加到1.748g(11mmol)的二氯-叔丁基膦在10ml THF中的溶液(该溶液预先冷却到-15℃)中。重要的是需要冷却二氯-叔丁基膦溶液。在室温下,会获得大量的二吡啶基-叔丁基膦。起始形成了澄清的黄色溶液,其然后变浑浊。将该混合物然后温热到室温和过夜搅拌。根据GC-MS,形成了大量的产物。在高真空下除去溶剂和获得发白色并且带有棕色斑点的固体。将该固体悬浮在20ml的庚烷中,并且在超声浴中粉碎。在使白色固体沉淀之后,倾析该溶液。每次使用10-20ml的庚烷重复该操作两次。在高真空下浓缩该庚烷溶液之后,在减压下蒸馏。在4.6mbar、120℃油浴和98℃蒸馏温度下,可以蒸馏出产物。获得1.08g的无色油状物(50%)。
分析数据:1H NMR(300MHz,C6D6):δ8.36(m,1H,Py),7.67(m,1H,Py),7.03-6.93(m,1H,Py),6.55-6.46(m,1H,Py),1.07(d,J=13.3Hz,9H,t-Bu)。
13C NMR(75MHz,C6D6):δ162.9,162.6,148.8,135.5,125.8,125.7,122.8,35.3,34.8,25.9和25.8。
31P NMR(121MHz,C6D6)δ97.9。
MS(EI)m:z(相对强度)201(M+,2),147(32),145(100),109(17),78(8),57.1(17)。
化合物1的制备
(文献:Graham Eastham等,专利US 6335471)。
将675mg(27.8mmol,4eq)的镁粉在手套箱中在250ml圆底烧瓶(带有氮气阀和磁搅拌子)中称重和用隔膜密封。在所述圆底烧瓶中施加高真空(大约5x10-2mbar)和加热45分钟至90℃。在冷却到室温之后,将2小粒碘加入和溶解在20ml的THF中。搅拌该悬浮液大约10分钟,直至碘的黄色消失。在镁粉沉淀之后,倾析该浑浊的THF溶液和将活化的镁粉用1-2ml的THF洗涤两次。然后重新加入20ml新鲜的THF。在室温下,用注射器泵缓慢地滴加755.5μl(6.9mmol)的1,4-二氯丁烷在70ml的THF中的溶液。该THF溶液呈澄清的和浅黄色。第二天,生成深灰色但澄清的溶液,将其通过硅藻土过滤。将格氏试剂溶液的样品如下淬灭和在GC中分析:
将300μl的格氏试剂溶液用1ml的饱和NH4Cl水溶液淬灭和用***萃取。在通过Na2SO4干燥之后,记录***溶液的GC。无法检测到1,4-二氯丁烷,但在GC中没有观察到丁烷的存在。
如下测定格氏试剂化合物的含量:
将1ml的格氏试剂溶液用3ml的0.1M HCl淬灭和用0.1M NaOH滴定过量的酸。合适的指示剂为0.04%溴甲酚水溶液。颜色从黄色变为蓝色。消耗了1.70ml的0.1M NaOH。3ml-1.70ml=1.3ml,这对应于0.13mmol的格氏试剂化合物。由于存在二格氏试剂,该格氏试剂溶液为0.065M。这对应于85%的格式试剂溶液,基于90ml溶液。此时可以将该格氏试剂与氯代膦反应:
在带有回流冷凝器、搅拌磁子和氮气阀的250ml三颈烧瓶中,在氩气下将1.94g(9.75mmol,2.5eq)的氯-2-吡啶基-叔丁基膦(前体A)溶解在10ml的THF中和冷却到-60℃。然后,在该温度下用注射器泵缓慢地滴加60ml的上述测定的格氏试剂溶液(0.065M,3.9mmol)。该溶液首先保持澄清和然后变为深黄色。将其过夜温热到室温和获得澄清的黄色溶液。为了完成所述反应,将其加热回流2小时。在冷却之后,加入1ml的H2O和溶液的颜色消失,并且产生白色的沉淀物。在高真空下除去THF之后,获得粘性的亮黄色固体。加入15ml的水和20ml的***,获得两个均匀的澄清相,它们可以很好地分离开。将水相用***萃取两次。在用Na2SO4干燥有机相之后,在高真空下除去***和获得粘性的几乎无色的油状物。将其在水浴的温热下溶解在4ml的MeOH中和通过硅藻土过滤。在-28℃下,过夜获得白色粘性晶体形式的660mg产物(44%)。
1H NMR(300MHz,C6D6):δ8.54(m,2H,py),7.37(m,2H,py),6.96(m,2H,Py),6.58(m,2H,Py),2.68(m,2H,CH2),1.74(m,4H,CH2),1.52(m;2H,CH2),1.03(d,J=11.5Hz,18H,tBu)。
13C NMR(75MHz,C6D6):δ162.8,162.5(q),149.9,134.3,134.1,132.0,131.5和122.4(py),29.4,29.3,29.1,29.0,20.7,20.5(CH2),28.1和27.9(tBu)。
31P NMR(121MHz,C6D6)δ8.2。
HRMS(ESI) m/z+计算值:C22H34N2P2(M+H)+389.227;测量值:389.2273。
EA计算值:C22H34N2P2:C,68.02;H,8.82;N,7.21;P,15.95.测量值:C,68.16;H,8.97;N,7.07;P,15.91。
双(二金刚烷基膦丁烷硼烷加合物)(前体B)的制备
示意图14:前体B的合成
在配有氮气阀和磁搅拌子的100ml圆底烧瓶中称量加入214.7mg(0.679mmol)二金刚烷基膦硼烷加合物。使用隔膜封闭该烧瓶,使用氩气保护之后加入10ml THF。该硼烷加合物很容易溶解于THF之中,得到澄清无色的溶液,使用干冰将其冷却到-78℃。经过15分钟搅拌之后,缓慢滴加0.5ml(0.70mmol) 1.4M仲丁基锂溶液。完成滴加之后得到浅黄色澄清溶液,在3小时之内使其达到室温。将仍然呈浅黄色的溶液在室温继续搅拌一小时,并且将该溶液重新冷却到-78℃。现在向该溶液缓慢滴加使用5ml THF稀释后的42.6μl(0.323mmol)二碘丁烷。黄色溶液此时退色。加热过夜,从溶液中析出很多白色沉淀物。加入8ml水并且强力搅拌20分钟。白色固体物质悬浮在溶液上面。倾析该溶液,并且使用MeOH将该白色固体物质洗涤三次,以便去除还存在的水。在真空中干燥之后,得到210mg白色固体物质(产率95%)。
1H NMR(300MHz,CDCl3):δ2,11-1,89(m,36H,Ad),1,79-1,68(m,24H,Ad),1,67-1,49(m,8H,CH2),1,03-(-0,51)(m,宽),6H,BH3)。
13C NMR(75MHz,CDCl3):δ37.8和36.6(Ad),36.5和36.4(C),28.1和28.0(Ad),27.9,27.7,15.1和14.7((CH2)4)。
31P NMR(121MHz,CDCl3)δ36.6-33.4(m)。
二金刚烷基膦硼烷加合物(前体C)的制备
示意图15:前体C的合成
在配有氮气阀和椭圆形磁搅拌子的100ml圆底烧瓶中称量加入4.0g(13.22mmol)二金刚烷基膦,使用隔膜将其封闭和保护。将固体物质悬浮于9ml THF之中,并且向该悬浮液连续加入18.9ml(18.9mmol,1M)BH3THF加合物。该悬浮液起初开始溶解,但经过一些时间之后析出白色的沉淀物。搅拌过夜,并且在高真空中去除THF。在水浴上加热(60℃),将白色残留物加入到250ml乙酸乙酯中。硼烷加合物在温热的乙酸乙酯中很容易溶解。加入6勺硅胶60(大约12g)之后,在旋转蒸发仪上完全去除溶剂,并且使用Combi-Flash设备对附着在硅胶上的产物进行色谱分析。使用1∶10(乙酸乙酯/庚烷)作为洗脱液。得到3.1g(74%)二金刚烷基膦硼烷加合物。
1H NMR(300MHz,CDCl3):δ3.71(dq,350.8Hz和6.6Hz,1H,PH),2.01-1.94(m,18H,Ad),1.74(m,12H,Ad),1.05-(-0.35)(m,3H,BH3)。
13C NMR(75MHz,CDCl3):δ37.9和36.4(CH2),34.8和34.4(C),28.1和28.0(CH)。
31P NMR(121MHz,CDCl3)δ42.8-40.0(m)。
制备配体2:双(二金刚烷基膦基)丁烷(对比配体)
示意图16:化合物2的合成
在配有氮气阀的25ml圆底烧瓶中称量加入500mg(0.728mmol)硼烷加合物,并且加入10ml纯净吡咯烷。回流加热该悬浮液,直至溶液无色并且澄清(大约2小时)。冷却之后在高真空中去除吡咯烷,得到白色的残留物。将其加入到15ml甲苯中并且加热到90℃。几乎澄清的溶液不好过滤,因为在冷却时会重新析出产物。在冰箱中(3℃)从滤液析出白色结晶固体物质。使用甲苯将晶体洗涤两次,并且在高真空中将其干燥。得到300mg(62%)白色晶体。
由于室温下的溶解度很差,在苯-d6中在323K温度下记录1H、13C和31P-NMR。
1H NMR(323K,400MHz,C6D6):δ2.12-1.92(m,16H,CH2,Ad),1.92-1.79(m,11H,CH2,Ad),1.75-1.64(m,16H,CH2,Ad),1.64-1.47(m,6H,CH2,Ad),1.45-1-23(m,18H,CH2,Ad)。
13C NMR(323K,100MHz,C6DS):δ41.5和41.4(Ad),37.5(Ad),36.5和36.3(C),30.1(CH2),29.3和29.2(Ad,17.5和17.3(CH2)。
31PNMR(323K,162MHz,C6D6)δ25.71。
高压实验
原料:
二正丁烯在下文也称为:二丁烯、DNB或DnB。
二正丁烯是C8烯烃的异构体混合物,其由1-丁烯,顺式-2-丁烯和反式-2-丁烯的混合物的二聚化而生成。在工业中,萃余液II或萃余液III料流通常经受催化低聚化,其中所包含的丁烷(n/iso)未改变地出现和所包含的烯烃完全或部分地反应。除了二聚的二正丁烯,通常也生成更高级的低聚物(三丁烯C12、四丁烯C16),其在反应之后通过蒸馏而分离。
用于C4烯烃低聚化的工业实践化的方法是所谓的″OCTOL方法″。
在专利文献中,例如DE102008007081A1描述了基于OCTOL方法的低聚化。EP1029839A1涉及在OCTOL方法中生成的C8烯烃的分馏。
工业的二正丁烯通常由5%至30%的正辛烯,45%至75%的3-甲基庚烯和10%至35%的3,4-二甲基己烯组成。优选的料流包含10%至20%正辛烯,55%至65%3-甲基庚烯和15%至25%3,4-二甲基己烯。
对甲苯磺酸缩写为:pTSA、PTSA或p-TSA。在本文中,PTSA总是表示对甲苯磺酸一水合物。
用于实施高压实验的通用说明
用于玻璃瓶中的高压釜试验的通用试验说明:
使用300ml Parr反应器。与之相匹配的是相应尺寸的自造的铝模块,其适合于通过市购可得的磁搅拌器(例如Heidolph公司的)加热。对于高压釜的内部,制成厚度大约1.5cm的圆形金属板,其包括相应于玻璃瓶外周长的6个孔。为了匹配这些玻璃瓶,它们配备有小的磁搅拌器。这些玻璃瓶配备有螺旋盖和合适的隔膜,并且使用在玻璃吹制间制成的特殊装置在氩气下填充相应的反应物、溶剂和催化剂和添加剂。为此,同时填充6个容器,这可以在相同的温度和相同的压力下在一个实验中进行6个反应。然后,将该玻璃容器使用螺旋盖和隔膜密闭和分别通过隔膜***合适大小的小的注射针管。这样可以以后在反应中实现气体交换。将这些瓶放置在金属板中和将其在氩气下转移到高压釜中。该高压釜用CO吹扫和在室温下以预定的CO压力填充。然后,借助磁搅拌器在磁搅拌下加热到反应温度和将该反应进行相应的时间。然后,冷却到室温和缓慢地释放压力。然后,将高压釜用氮气吹扫。将所述瓶从高压釜中取出和加入确定量的合适标准物。进行GC分析,由其结果确定产率和选择性。
分析
二正丁烯的GC分析:使用具有30m HP5-柱的色谱仪(Agilent GC公司,Agilent7890A)用于GC分析。温度变化:35℃,10min;10℃/min至200℃;注射体积为1μl,分割为50∶1。
保留时间(二正丁烯和产物):10.784-13.502min。
由二正丁烯形成的酯在下文中称为MINO(异壬酸甲酯)。
保留时间(未知异构体分布的醚产物):15.312,17.042,17.244,17.417min。
保留时间(异-C9酯):19.502-20.439min(主峰:19.990min)。
保留时间(正-C9酯):20.669,20.730,20.884,21.266min。
试验的评估
为了评估催化试验,使用下面测定的用于比较不同催化剂体系的特征值。
TON:转化数,定义为每摩尔催化剂金属的产物摩尔数,其是所述催化配合物的生产率的量度。
TOF:转化频率,定义为为了实现特定转化率(例如50%)的每单位时间的TON。TOF是催化体系的活性的量度。
在下文中给出的n-选择性是指末端甲氧基羰基化基于甲氧基羰基化产物的总产率的比例。
n/iso-比例说明了末端转化为酯的烯烃与内部转化为酯的烯烃的比例。
二正丁烯的甲氧基羰基化
配体2(对比例):在25ml Schlenk容器中装入由[Pd(acac)2](1.95mg,6.4μmol)、p-甲苯磺酸(PTSA)(18.24mg,95.89μmol)和MeOH(10ml)构成的母液。在4ml小瓶中加入2(2.11mg,0.16mol%,基于二正丁烯的物质的量)和加入磁搅拌子。然后,通过注射器注入1.25ml的该澄清黄色母液和二正丁烯(315μl,2mmol)。因此,基于二正丁烯的物质的量的摩尔含量,Pd(acac)2为0.04mol%和PTSA为0.6mol%。将该小瓶放置在样品架上,其进而在氩气气氛下放入到300ml Parr高压釜中。在用氮气吹扫该高压釜三次之后,将CO压力调节到40bar。所述反应在120℃下进行20小时。在完成反应之后,将高压釜冷却到室温和小心地减压。加入异辛烷作为内部GC标准物。通过GC测定产率和区域选择性。没有观察到MINO的形成。
配体1:在25ml Schlenk容器中装入由[Pd(acac)2](1.95mg,6.4μmol)、p-甲苯磺酸(PTSA)(18.24mg,95.89μmol)和MeOH(10ml)构成的母液。在4ml小瓶中加入1(1.24mg,0.16mol%,基于二正丁烯的物质的量)和加入磁搅拌子。然后,通过注射器注入1.25ml的该澄清黄色母液和二正丁烯(315μl,2mmol)。因此,基于二正丁烯的物质的量的摩尔含量,Pd(acac)2为0.04mol%和PTSA为0.6mol%。将该小瓶放置在样品架上,其进而在氩气气氛下放入到300ml Parr高压釜中。在用氮气吹扫该高压釜三次之后,将CO压力调节到40bar。所述反应在120℃下进行20小时。在完成反应之后,将高压釜冷却到室温和小心地减压。加入异辛烷作为内部GC标准物。通过GC测定产率和区域选择性(产率MINO:13%,区域选择性n/iso:59/41)。
该试验证明了,本发明所述的配体1可形成能催化二正丁烯进行烷氧基羰基化的催化活性钯配合物。而结构类似的配体2则相反地不适合催化所述烷氧基羰基化。
Claims (15)
1.式(I)的化合物
其中
R1、R2、R3、R4分别彼此独立地选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基、-(C3-C20)-杂芳基;
所述R1、R2、R3、R4基团的至少一个是-(C3-C20)-杂芳基;
和
R1、R2、R3、R4,如果它们是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C3-C20)-杂芳基,
可以分别彼此独立地被选自下列的一个或多个取代基取代:
-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-O-(C1-C12)-烷基、-O-(C1-C12)-烷基-(C6-C20)-芳基、-O-(C3-C12)-环烷基、-S-(C1-C12)-烷基、-S-(C3-C12)-环烷基、-COO-(C1-C12)-烷基、-COO-(C3-C12)-环烷基、-CONH-(C1-C12)-烷基、-CONH-(C3-C12)-环烷基、-CO-(C1-C12)-烷基、-CO-(C3-C12)-环烷基、-N-[(C1-C12)-烷基]2、-(C6-C20)-芳基、-(C6-C20)-芳基(C1-C12)-烷基、-(C6-C20)-芳基-O-(C1-C12)-烷基、-(C3-C20)-杂芳基、-(C3-C20)-杂芳基-(C1-C12)-烷基、-(C3-C20)-杂芳基-O-(C1-C12)-烷基、-COOH、-OH、-SO3H、-NH2、卤素。
2.根据权利要求1的化合物,
其中所述R1、R2、R3、R4基团的至少两个是-(C3-C20)-杂芳基。
3.根据权利要求1至2任一项的化合物,
其中所述R1和R3基团分别是-(C3-C20)-杂芳基。
4.根据权利要求1至3任一项的化合物,
其中所述R1和R3基团分别是-(C3-C20)-杂芳基;
和R2和R4分别彼此独立地选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基。
5.根据权利要求1至4任一项的化合物,
其中所述R1和R3基团分别是-(C3-C20)-杂芳基;
和R2和R4分别是-(C1-C12)-烷基。
6.根据权利要求1至5任一项的化合物,
其中R1、R2、R3、R4,如果它们是杂芳基,则分别彼此独立地选自呋喃基、噻吩基、吡咯基、噁唑基、异噁唑基、噻唑基、异噻唑基、咪唑基、吡唑基、呋咱基、四唑基、吡啶基、哒嗪基、嘧啶基、吡嗪基、苯并呋喃基、吲哚基、异吲哚基、苯并咪唑基、喹啉基、异喹啉基。
7.根据权利要求1至6任一项的化合物,
其具有式(1)
8.配合物,其包含Pd和根据权利要求1至7任一项的化合物。
9.包括下列方法步骤的方法:
a)首先添加烯属不饱和化合物;
b)添加根据权利要求1至7任一项的化合物和包含Pd的化合物,
或添加根据权利要求8的配合物;
c)添加醇;
d)导入CO;
e)加热所述反应混合物,其中所述烯属不饱和化合物反应生成酯。
10.根据权利要求9的方法,
其中所述烯属不饱和化合物包含2至30个碳原子和任选具有选自下列的一个或多个官能团:羧基、硫代羧基、磺基、亚磺酰基、羧酸酐、酰亚胺、羧酸酯、磺酸酯、氨基甲酰基、氨磺酰基、氰基、羰基、硫代羰基、羟基、氢硫基、氨基、醚、硫代醚、芳基、杂芳基或硅烷基和/或卤素取代基。
11.根据权利要求9至10任一项的方法,
其中所述烯属不饱和化合物选自乙烯、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,或其混合物。
12.根据权利要求9至11任一项的方法,
其中所述烯属不饱和化合物包含6至22个碳原子。
13.根据权利要求9至12任一项的方法,
其中在方法步骤b)中包含Pd的化合物选自二氯化钯、乙酰基丙酮化钯(II)、乙酸钯(II)、二氯(1,5-环辛二烯)钯(II)、双(二苯亚甲基丙酮)钯、双(乙腈)二氯钯(II)、(肉桂基)二氯化钯。
14.根据权利要求9至13任一项的方法,
其中在方法步骤c)中的醇选自甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、2-丙醇、叔丁醇、3-戊醇、环己醇、苯酚,或其混合物。
15.根据权利要求1至7任一项的化合物或根据权利要求8的配合物用于催化烷氧基羰基化反应的用途。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110156837A (zh) * | 2018-02-14 | 2019-08-23 | 赢创德固赛有限公司 | 用于烷氧羰基化的丙基桥联的二膦配体 |
Families Citing this family (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL3121184T3 (pl) * | 2015-07-23 | 2019-03-29 | Evonik Degussa Gmbh | Oparte na benzenie ligandy difosfinowe do alkoksykarbonylowania |
PT3272759T (pt) | 2016-07-19 | 2019-07-17 | Evonik Degussa Gmbh | Ligandos de 1,1¿-bis(fosfino)ferroceno para a alcoxicarbonilação |
ES2740998T3 (es) | 2016-07-19 | 2020-02-07 | Evonik Operations Gmbh | Ligandos de 1,1'-bis(fosfino)ferroceno para alcoxicarbonilación |
ES2722052T3 (es) | 2016-07-19 | 2019-08-07 | Evonik Degussa Gmbh | Procedimiento para la alcoxicarbonilación de olefinas en un medio con baja concentración de ácidos de Brønsted |
ES2718747T3 (es) | 2016-07-19 | 2019-07-04 | Evonik Degussa Gmbh | Procedimiento para la alcoxicarbonilación de éteres |
ES2734383T3 (es) | 2016-07-19 | 2019-12-05 | Procedimiento para la producción de di- o tricarboxilatos mediante alcoxicarbonilación de dienos con dobles enlaces conjugados | |
PL3272732T3 (pl) | 2016-07-19 | 2020-03-31 | Evonik Degussa Gmbh | Sposób alkoksykarbonylowania etylenowo nienasyconych związków za pomocą ligandów monofosfinowych |
ES2750837T3 (es) | 2016-07-19 | 2020-03-27 | Evonik Operations Gmbh | Procedimiento para la preparación de ésteres mediante carbonilación de éteres |
EP3272728B1 (de) | 2016-07-19 | 2019-06-19 | Evonik Degussa GmbH | Verfahren zur alkoxycarbonylierung von alkoholen |
RU2732499C1 (ru) * | 2017-03-18 | 2020-09-18 | Катарский Фонд Образования, Науки И Общественного Развития | Катализируемое металлом алкоксикарбонилирование лактона |
EP3421478B1 (en) | 2017-06-29 | 2020-03-25 | Evonik Operations GmbH | Markovnikov-selective palladium catalyst for carbonylation of alkynes with heteroarenes |
EP3441137B1 (de) * | 2017-08-08 | 2019-12-25 | Evonik Operations GmbH | Pd-katalysierten zersetzung von ameisensäure |
EP3441383B1 (de) | 2017-08-08 | 2019-12-25 | Evonik Operations GmbH | Methoxycarbonylierung mit ameisensäure als co-quelle |
EP3441384B1 (de) * | 2017-08-08 | 2019-12-25 | Evonik Operations GmbH | Methoxycarbonylierung mit ameisensäure und methanol |
ES2807998T3 (es) * | 2017-12-21 | 2021-02-25 | Evonik Operations Gmbh | Procedimiento para la hidroxicarbonilación de diisobuteno catalizada con Pd: proporción ligando/Pd |
ES2807544T3 (es) * | 2017-12-21 | 2021-02-23 | Evonik Operations Gmbh | Procedimiento para la hidroxicarbonilación de diisobuteno catalizada con Pd: proporción ácido sulfúrico/ligando |
ES2787299T3 (es) * | 2017-12-21 | 2020-10-15 | Evonik Degussa Gmbh | Proceso para la conversión directa de alquenos en ácidos carboxílicos |
PL3502084T3 (pl) * | 2017-12-21 | 2020-07-13 | Evonik Operations Gmbh | Sposób bezpośredniej przemiany diizobutenu w kwas karboksylowy |
EP3502087B1 (de) * | 2017-12-21 | 2020-06-24 | Evonik Operations GmbH | Verfahren zur pd-katalysierten hydroxycarbonylierung von diisobuten: verhältnis essigsäure/diisobuten |
EP3502082B1 (de) * | 2017-12-21 | 2020-02-12 | Evonik Operations GmbH | Verfahren zur pd-katalysierten hydroxycarbonylierung von diisobuten: einfluss des lösungsmittels |
ES2807542T3 (es) * | 2017-12-21 | 2021-02-23 | Evonik Operations Gmbh | Procedimiento para la hidroxicarbonilación de diisobuteno catalizada con Pd: proporción ácido 3,5,5-trimetilhexanoico/H2O |
US10710956B2 (en) * | 2018-02-08 | 2020-07-14 | Regents Of The University Of Minnesota | Process for the preparation of acrylate esters from alkyl lactates |
US11008275B2 (en) * | 2019-06-12 | 2021-05-18 | Evonik Operations Gmbh | Process for preparing carboxylic acids or salts thereof from hydrocarbons |
US20200391194A1 (en) * | 2019-06-12 | 2020-12-17 | Evonik Operations Gmbh | Process for separating one or more components from a mixture |
US11440863B2 (en) | 2019-06-12 | 2022-09-13 | Evonik Operations Gmbh | Process for preparing an alcohol from hydrocarbons |
US11365171B2 (en) | 2019-06-12 | 2022-06-21 | Evonik Operations Gmbh | Process for preparing an ester by alkoxycarbonylation |
ES2953067T3 (es) | 2019-12-17 | 2023-11-07 | Evonik Oxeno Gmbh & Co Kg | Alcoxicarbonilación de trivinilciclohexano |
CN111087306B (zh) | 2019-12-27 | 2021-08-03 | 南京诚志清洁能源有限公司 | 芳基双齿膦配体组合催化制备有机羧酸酯的方法 |
CN111253258A (zh) * | 2020-03-13 | 2020-06-09 | 华东理工大学 | 一种乙烯均相氢酯基化合成丙酸甲酯的方法 |
EP3889163B1 (de) * | 2020-03-30 | 2023-07-19 | Evonik Operations GmbH | Platin-komplexe mit ferrocen-liganden für die katalyse der alkoxycarbonylierung ethylenisch ungesättigter verbindungen |
EP3889161B1 (de) * | 2020-03-30 | 2022-06-08 | Evonik Operations GmbH | Platin-komplexe mit benzylbasierten diphosphinliganden für die katalyse der alkoxycarbonylierung ethylenisch ungesättigter verbindungen |
CN113801161A (zh) * | 2020-06-15 | 2021-12-17 | 华东师范大学 | 咪唑类配体衍生物及其制备和在丁二烯调聚反应中的应用 |
CN111686818B (zh) * | 2020-07-10 | 2022-08-02 | 万华化学集团股份有限公司 | 一种催化剂组合物及其在丙烯氢甲酰化反应中的应用 |
CN112094294A (zh) * | 2020-11-10 | 2020-12-18 | 江苏欣诺科催化剂有限公司 | 双(二环己基膦)烷烃的合成方法 |
EP4001252A1 (de) | 2020-11-12 | 2022-05-25 | Evonik Operations GmbH | Doppelte alkoxycarbonylierung von dienen |
EP4001256A1 (de) | 2020-11-24 | 2022-05-25 | Evonik Operations GmbH | Verfahren zur alkoxycarbonylierung von ethylenisch ungesättigter verbindungen unter einsatz von benzolbasierte diphosphinliganden und aluminiumtriflat |
CN112480170B (zh) * | 2020-12-02 | 2023-03-14 | 中国海洋石油集团有限公司 | 一种双膦化合物、包含其的催化剂体系及其应用 |
EP4011892A1 (de) | 2020-12-09 | 2022-06-15 | Evonik Operations GmbH | Platin-komplexe mit ferrocen-diphosphin-liganden für die katalyse der hydroxycarbonylierung ethylenisch ungesättigter verbindungen |
CN114805434B (zh) * | 2021-01-18 | 2024-07-05 | 广东欧凯新材料有限公司 | 一种新型四齿膦配体化合物及其合成方法与应用 |
CN114835746A (zh) * | 2021-02-01 | 2022-08-02 | 惠州凯特立斯科技有限公司 | 一种新型四齿膦配体化合物及其合成方法与应用 |
CN113620990B (zh) * | 2021-08-30 | 2022-11-08 | 万华化学集团股份有限公司 | 一种硫脲型氮膦配体及其制备方法和应用 |
CN113788748A (zh) * | 2021-09-15 | 2021-12-14 | 华东师范大学 | 多齿膦配体修饰的钯组合催化剂催化不饱和烃制备直链羰基化合物的方法 |
CN113969188B (zh) * | 2021-10-21 | 2022-10-28 | 青岛科技大学 | 一种新型松节油基生物质高能量密度混合燃料 |
CN114014895A (zh) * | 2021-10-26 | 2022-02-08 | 浙江大学 | 一种二茂铁基膦配体化合物及其合成方法 |
CN113999261B (zh) * | 2021-10-26 | 2023-06-06 | 浙江大学 | 一种邻二甲基芳香环类二膦基配体化合物及其合成方法 |
CN114308129B (zh) * | 2021-11-24 | 2022-12-06 | 中国科学院兰州化学物理研究所 | 用于烯烃烷氧羰基化的催化剂组合物及其制备方法与应用 |
EP4197992A1 (de) | 2021-12-20 | 2023-06-21 | Evonik Operations GmbH | Verfahren zur herstellung eines alkohols und abtrennung des homogenen katalysatorsystems unter verwendung einer membran umfassend eine trennaktive schicht aus paek und einer unterstruktur, die paek umfasst |
EP4197623A1 (de) | 2021-12-20 | 2023-06-21 | Evonik Operations GmbH | Verfahren zur herstellung eines esters und abtrennung des homogenen katalysatorsystems unter verwendung einer membran umfassend eine trennaktive schicht aus paek und einer unterstruktur, die paek umfasst |
US20230192486A1 (en) | 2021-12-20 | 2023-06-22 | Evonik Operations Gmbh | Process for producing carbon monoxide-containing streams |
EP4198014A1 (de) | 2021-12-20 | 2023-06-21 | Evonik Operations GmbH | Verfahren zur herstellung von carbonsäuren oder deren salzen und abtrennung des homogenen katalysatorsystems unter verwendung einer membran umfassend eine trennaktive schicht aus paek und einer unterstruktur, die paek umfasst |
WO2023222359A1 (de) | 2022-05-18 | 2023-11-23 | Evonik Oxeno Gmbh & Co. Kg | Verfahren zur aufreinigung von kohlenwasserstoffströmen inklusive heterogen und homogen katalysierter reaktionen |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3213093A (en) * | 1963-12-12 | 1965-10-19 | American Cyanamid Co | Phosphino-s-triazines |
Family Cites Families (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1029839B (de) | 1953-05-07 | 1958-05-14 | Tosaku Yoshioka | Mittel zur Verbesserung und Regelung der Duengerwirkung auf landwirtschaftlichen Kulturboeden |
US5166330A (en) * | 1983-09-06 | 1992-11-24 | Hoechst Aktiengesellschaft | Process for the preparation of nucleoside alkyl-aralkyl- and aryl-phosphonites and -phosphonates |
DK166686A (da) * | 1985-04-16 | 1986-10-17 | Smithkline Beckman Corp | Phosphinforbindelser, fremgangsmaade til fremstilling heraf samt farmaceutiske midler indeholdende disse forbindelser |
GB8705699D0 (en) * | 1987-03-11 | 1987-04-15 | Shell Int Research | Carbonylation of olefinically unsaturated compounds |
US4880902A (en) * | 1987-08-27 | 1989-11-14 | Shell Oil Company | Copolymerization of carbon monoxide and olefin with diphosphine having heterocyclic substituents as catalyst |
CN1024635C (zh) * | 1989-03-03 | 1994-05-25 | 国际壳牌研究有限公司 | 羰基化催化剂及其应用 |
KR0148012B1 (ko) * | 1989-03-03 | 1998-08-17 | 오노 알버어스 | 신규한 포스핀으로 구성되는 촉매시스템 및 이를 이용한 아세틸렌형 또는 올레핀형 불포화화합물의 카르보닐화방법 |
GB9002521D0 (en) * | 1990-02-05 | 1990-04-04 | Shell Int Research | Carbonylation catalyst system |
CA2034971A1 (en) * | 1990-02-05 | 1991-08-06 | Eit Drent | Carbonylation catalyst system |
DE69204691T2 (de) * | 1991-01-15 | 1996-04-11 | Shell Int Research | Verfahren zur Karbonylierung von Olefin. |
DE4141299C2 (de) * | 1991-12-14 | 2000-09-21 | Celanese Chem Europe Gmbh | Verfahren zur Herstellung von tertiären Phosphanen |
EP0577205B1 (en) * | 1992-06-29 | 1997-10-08 | Shell Internationale Researchmaatschappij B.V. | Carbonylation of conjugated dienes |
BE1007422A3 (nl) * | 1993-08-23 | 1995-06-13 | Dsm Nv | Werkwijze voor de bereiding van een mengsel van penteenzure alkylesters. |
BE1008018A3 (nl) * | 1994-01-06 | 1995-12-12 | Dsm Nv | Werkwijze voor de bereiding van een ester. |
TW272949B (zh) * | 1994-07-22 | 1996-03-21 | Taishal Kagaku Kogyo Kk | |
EP0975574A1 (en) | 1997-02-26 | 2000-02-02 | Dsm N.V. | Process to prepare a pentenoic acid derivative |
GB9717059D0 (en) | 1997-08-13 | 1997-10-15 | Ici Plc | Method of manufacturing phosphine compound |
DE19906518A1 (de) | 1999-02-17 | 2000-08-31 | Oxeno Olefinchemie Gmbh | Verfahren zur Fraktionierung von Dibuten |
DE10037961A1 (de) | 2000-07-27 | 2002-02-07 | Aventis Res & Tech Gmbh & Co | Neue Phosphanliganden, deren Herstellung und ihre Verwendung in katalytischen Reaktionen |
JP4467935B2 (ja) * | 2002-10-03 | 2010-05-26 | キヤノン株式会社 | ハロゲン化芳香族アミン化合物の製造法 |
EP1692149B1 (de) * | 2003-12-12 | 2009-07-22 | Solvias AG | Verfahren zur herstellung von orthometallierten und orthosubstituierten aromatischen verbindungen |
GB0400720D0 (en) * | 2004-01-14 | 2004-02-18 | Stylacats Ltd | Novel ferrocene-based phosphorus chiral phosphines |
JP5015451B2 (ja) * | 2005-04-18 | 2012-08-29 | 日本化学工業株式会社 | ホスフィン遷移金属錯体、その製造方法およびそれを含有する抗癌剤 |
CN101235052A (zh) * | 2007-09-30 | 2008-08-06 | 赢创德固赛有限责任公司 | 不对称手性二膦配体 |
DE102008007081B4 (de) | 2008-01-31 | 2018-12-06 | Evonik Degussa Gmbh | Verfahren zur Herstellung von n-Buten-Oligomeren und 1-Buten aus technischen Mischungen I von C4-Kohlenwasserstoffen |
GB0915946D0 (en) | 2009-09-11 | 2009-10-28 | Univ St Andrews | Metal-catalysed carbonylation of unsaturated compounds |
GB201000078D0 (en) * | 2010-01-05 | 2010-02-17 | Lucite Int Uk Ltd | Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporatng such ligands |
WO2011152358A1 (ja) * | 2010-05-31 | 2011-12-08 | 住友化学株式会社 | 銀錯体を含む膜 |
CN102531890A (zh) | 2010-12-18 | 2012-07-04 | 中国科学院兰州化学物理研究所 | 由烯烃氢酯基化反应制备有机羧酸酯的方法 |
WO2012111737A1 (ja) * | 2011-02-17 | 2012-08-23 | 国立大学法人岡山大学 | 新規化合物、新規配位子、新規遷移金属錯体および新規遷移金属錯体からなる触媒 |
DE102011089008B4 (de) | 2011-12-19 | 2017-08-24 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Estern aus Formiaten und olefinisch ungesättigten Verbindungen |
DE102013201669B4 (de) * | 2013-02-01 | 2017-02-09 | Evonik Degussa Gmbh | Verfahren zur Carbonylierung von Olefinen |
KR102205983B1 (ko) * | 2014-10-13 | 2021-01-22 | 덕산네오룩스 주식회사 | 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치 |
PL3121184T3 (pl) | 2015-07-23 | 2019-03-29 | Evonik Degussa Gmbh | Oparte na benzenie ligandy difosfinowe do alkoksykarbonylowania |
ES2834092T3 (es) * | 2018-02-14 | 2021-06-16 | Evonik Degussa Gmbh | Ligandos difosfina puenteados con propilo para la alcoxicarbonilación |
-
2016
- 2016-07-19 PL PL16180045T patent/PL3121184T3/pl unknown
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Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3213093A (en) * | 1963-12-12 | 1965-10-19 | American Cyanamid Co | Phosphino-s-triazines |
Non-Patent Citations (3)
Title |
---|
I. E. NIFANT’EV ET AL.: ""Steric and Electronic Factors in the Promoting Activity of Diphosphine Ligands in Cyclohexene Hydrocarbomethoxylation Catalyzed by Palladium Acetate"", 《KINETICS AND CATALYSIS》 * |
TATYANA I. FESENKO,ET AL.: ""SYNTHESIS OF BIS(2-PYRIDYLPHOSPHINO)ALKANES IN SUPERBASIC MEDIUM AND THEIR HYDROXYMETHYL DERIVATIVES"", 《PHOSPHORUS, SULFUR, AND SILICON》 * |
美国化学会: ""CAS登记号"", 《STN》 * |
Cited By (2)
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---|---|---|---|---|
CN110156837A (zh) * | 2018-02-14 | 2019-08-23 | 赢创德固赛有限公司 | 用于烷氧羰基化的丙基桥联的二膦配体 |
CN110156837B (zh) * | 2018-02-14 | 2023-05-23 | 赢创运营有限公司 | 用于烷氧羰基化的丙基桥联的二膦配体 |
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