CN106632476A - 单膦化合物和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂 - Google Patents
单膦化合物和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂 Download PDFInfo
- Publication number
- CN106632476A CN106632476A CN201610826942.4A CN201610826942A CN106632476A CN 106632476 A CN106632476 A CN 106632476A CN 201610826942 A CN201610826942 A CN 201610826942A CN 106632476 A CN106632476 A CN 106632476A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- compound
- heteroaryl
- cycloalkyl
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 61
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 38
- 229910052763 palladium Inorganic materials 0.000 title claims description 15
- 238000007083 alkoxycarbonylation reaction Methods 0.000 title abstract description 20
- 239000003054 catalyst Substances 0.000 title description 8
- 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 10
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 229910006069 SO3H Inorganic materials 0.000 claims abstract description 3
- -1 pyrimidine radicals Chemical class 0.000 claims description 84
- 238000000034 method Methods 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 36
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 28
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 9
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 9
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- 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 class CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 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
- 238000006206 glycosylation reaction Methods 0.000 claims description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 2
- 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 1
- 241000522254 Cassia Species 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
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 4
- 125000006413 ring segment Chemical group 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 26
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 19
- 150000001336 alkenes Chemical class 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 125000004429 atom Chemical group 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 125000002971 oxazolyl group Chemical group 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 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 6
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 6
- 125000002541 furyl group Chemical group 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000001544 thienyl group Chemical group 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 5
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 125000005842 heteroatom Chemical group 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
- 238000012360 testing method Methods 0.000 description 5
- 239000007848 Bronsted acid Substances 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
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 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
- 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 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000003838 furazanyl group Chemical group 0.000 description 3
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000005956 isoquinolyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000003226 pyrazolyl group Chemical group 0.000 description 3
- 125000002098 pyridazinyl group Chemical group 0.000 description 3
- 125000005493 quinolyl group Chemical group 0.000 description 3
- 239000012925 reference material Substances 0.000 description 3
- 239000007787 solid Substances 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
- 125000000335 thiazolyl group Chemical group 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- HEVGGTGPGPKZHF-UHFFFAOYSA-N 1-(1,2-dimethyl-3-methylidenecyclopentyl)-4-methylbenzene Chemical compound CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical group CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical class CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 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
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000003109 Karl Fischer titration Methods 0.000 description 2
- 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001786 isothiazolyl group Chemical group 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- QYYZXEPEVBXNNA-QGZVFWFLSA-N (1R)-2-acetyl-N-[4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)phenyl]-5-methylsulfonyl-1,3-dihydroisoindole-1-carboxamide Chemical compound C(C)(=O)N1[C@H](C2=CC=C(C=C2C1)S(=O)(=O)C)C(=O)NC1=CC=C(C=C1)C(C(F)(F)F)(C(F)(F)F)O QYYZXEPEVBXNNA-QGZVFWFLSA-N 0.000 description 1
- XTJLXXCARCJVPJ-TWTPFVCWSA-N (2e,4e)-hepta-2,4-diene Chemical compound CC\C=C\C=C\C XTJLXXCARCJVPJ-TWTPFVCWSA-N 0.000 description 1
- RRHPTXZOMDSKRS-PGUQZTAYSA-L (5z)-cycloocta-1,5-diene;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1C\C=C/CCC=C1 RRHPTXZOMDSKRS-PGUQZTAYSA-L 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- ULDHMXUKGWMISQ-VIFPVBQESA-N (S)-(+)-Carvone Natural products CC(=C)[C@H]1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-VIFPVBQESA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-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
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical class CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 1
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000005762 2-bromopyridine Chemical class 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical class CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- WXZUOZKCKRDMCI-UHFFFAOYSA-N 3-benzylbut-3-en-2-one Chemical compound CC(=O)C(=C)CC1=CC=CC=C1 WXZUOZKCKRDMCI-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
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical class CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010020466 Hunger Diseases 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 241000286819 Malo Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical group CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001712 car-3-ene derivatives Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000001816 cooling Methods 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
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 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
- SRONXYPFSAKOGH-UHFFFAOYSA-N cyclopentadecane Chemical compound C1CCCCCCCCCCCCCC1 SRONXYPFSAKOGH-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- LWNLXVXSCCLRRZ-UHFFFAOYSA-N dichlorophosphane Chemical compound ClPCl LWNLXVXSCCLRRZ-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- GZFMLMHXSPPWRN-UHFFFAOYSA-N diphenyl-(1-phenylpyrrol-2-yl)phosphane Chemical class C=1C=CC=CC=1N1C=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 GZFMLMHXSPPWRN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 229940093471 ethyl oleate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007511 glassblowing Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004415 heterocyclylalkyl group Chemical group 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical class CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- 238000006317 isomerization reaction Methods 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
- 239000003041 laboratory chemical Substances 0.000 description 1
- 150000002617 leukotrienes Chemical class 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- KJALUUCEMMPKAC-ONEGZZNKSA-N methyl (e)-pent-3-enoate Chemical compound COC(=O)C\C=C\C KJALUUCEMMPKAC-ONEGZZNKSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-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
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 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
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 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 1
- 235000021017 pears Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 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
- 239000012071 phase Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- QPUMEZIFDXYGPG-UHFFFAOYSA-N piperazine 1H-pyrrole Chemical compound N1CCNCC1.N1C=CC=C1 QPUMEZIFDXYGPG-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005070 sampling Methods 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
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- 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
- C07F15/006—Palladium compounds
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
-
- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
-
- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
-
- 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
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6503—Five-membered rings
- C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
-
- 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
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
-
- 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
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0208—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Peptides Or Proteins (AREA)
Abstract
本发明涉及单膦化合物和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂。具体地,本发明涉及式(I)所示的化合物其中R1选自‑(C1‑C12)‑烷基、‑(C3‑C12)‑环烷基、‑(C3‑C12)‑杂环烷基;R2选自‑(C3‑C12)‑杂环烷基、‑(C6‑C20)‑芳基、‑(C3‑C20)‑杂芳基;R3是‑(C3‑C20)‑杂芳基;并且R1、R2和R3可以是各自相互独立地被选自‑(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、卤素的一个或多个取代基取代的。本发明还涉及包含本发明所述化合物的钯配合物及其在烷氧基羰基化反应中的用途。
Description
技术领域
本发明涉及新型的单膦化合物及其在烷氧基羰基化反应中的用途。
背景技术
烯属不饱和化合物的烷氧基羰基化反应是一种越来越重要的工艺。所谓烷氧基羰基化反应指的是烯烃之类的烯属不饱和化合物与一氧化碳和醇在一种金属或金属配合物和配体存在的情况下转化成相应的酯的反应:
示意图1:通用的烯属不饱和化合物的烷氧基羰基化反应方程式
在烷氧基羰基化反应中,乙烯-甲氧基羰基化反应形成3-甲基丙酸酯是制备甲基丙烯酸甲酯的重要中间步骤(S.G.Khokarale,E.J.García-Suárez,J.Xiong,U.V.Mentzel,R.Fehrmann,A.Riisager,Catalysis Communications 2014,44,73-75)。以甲醇作为溶剂,使用一种膦配体改性的钯催化剂在温和条件下进行乙烯-甲氧基羰基化反应。
烷氧基羰基化反应可以产生支化(iso-)或者直链(n-)的产物。因此除了产率之外,n-/iso-选择性也是为烷氧基羰基化反应开发新型催化体系时要考虑的重要参数。
已知可使用单膦化合物作为烷氧基羰基化反应的配体。例如异戊二烯与苄醇在钯配合物存在的情况下进行的烷氧基羰基化反应。例如使用商品名为cataCXium PtB的配体N-苯基-2-(二叔丁基膦基)吡咯,该反应实现了良好的产率(Fang X.et al.,Angew.Chem.Int.Ed.,2014,53,9030-9034)。然而,该配体只能实现很小的选择性。同样研究了类似的杂芳基取代的单膦化合物,即N-苯基-2-(二苯基膦基)吡咯和N-苯基2-(二环己基膦基)吡咯,但是异戊二烯与苄醇的烷氧基羰基化反应只能实现很小的产率(Fang X.etal.,见上)。
发明内容
本发明的任务在于提供用于烷氧基羰基化反应的新型配体,可将其用来实现很高的产率和很高的n/iso-选择性。这些配体尤其适合于长链烯属不饱和化合物(例如C8烯烃)的烷氧基羰基化反应。
可通过式(I)所示的单膦化合物解决这一任务,
其中
R1选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基;
R2选自-(C3-C12)-杂环烷基、-(C6-C20)-芳基、-(C3-C20)-杂芳基;
R3是-(C3-C20)-杂芳基;
并且R1、R2和R3可以是各自相互独立地被选自-(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、卤素的一个或多个取代基取代的。
本发明所述的单膦化合物适合作为钯配合物的配体,可将其用来在多种烯属不饱和化合物的烷氧基羰基化反应过程中实现很高的产率。本发明所述的化合物尤其适用于乙烯和1-辛烯之类的长链烯烃的烷氧基羰基化反应。
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、四氢吡喃基和二嗯烷基。
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、嗯唑基、异嗯唑基、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,基团R1、R2和R3可以是各自相互独立地被选自-(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、-SC3H、-NH2、卤素的一个或多个取代基取代的。
在一个实施方案中,基团R1、R2和R3可以是各自相互独立地被选自-(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)-烷基的一个或多个取代基取代的。
在一个实施方案中,基团R1、R2和R3可以是各自相互独立地被选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-O-(C1-C12)-烷基、-O-(C3-C12)-环烷基、-(C6-C20)-芳基的一个或多个取代基取代的。
在一个实施方案中,基团R1、R2和R3可以是各自相互独立地被选自-(C1-C12)-烷基的一个或多个取代基取代的。
在一个实施方案中,基团R1、R2和R3是未取代的。
在一个优选的实施方案中,R1表示-(C1-C12)-烷基,优选表示-(C1-C6)-烷基,尤其优选表示-(C1-C4)-烷基。
在一个优选的实施方案中,R2表示-(C6-C20)-芳基或者-(C3-C20)-杂芳基。
在一个实施方案中,如果R2表示杂芳基,则R2选自具有五到十个环原子、优选具有五个或者六个环原子的杂芳基。
在一个实施方案中,如果R2表示杂芳基,则R2选自具有六到十个环原子、优选具有六个环原子的杂芳基。
在一个实施方案中,如果R2表示杂芳基,则R2选自呋喃基、噻吩基、吡咯基、嗯唑基、异嗯唑基、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是如上所述取代的。
在一个实施方案中,如果R2表示杂芳基,则R2选自呋喃基、噻吩基、吡咯基、咪唑基、吡啶基、嘧啶基、吲哚基;尤其是嘧啶基和咪唑基;其中所述杂芳基可以是如上所述取代的。
在一个实施方案中,如果R2表示杂芳基,则R2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;尤其是2-嘧啶基和2-咪唑基;其中所述杂芳基可以是如上所述取代的。
在一个实施方案中,R2选自苯基、嘧啶基和咪唑基,优选苯基、2-嘧啶基和2-咪唑基,其中所述基团可以是如上所述取代的。R2优选选自苯基、2-嘧啶基和N-甲基-咪唑-2-基,其中所述基团没有进一步取代。
在一个实施方案中,R3选自具有五到十个环原子、优选具有五个或者六个环原子的杂芳基。
在一个实施方案中,R3选自具有六到十个环原子、优选具有六个环原子的杂芳基。
在一个实施方案中,R3选自呋喃基、噻吩基、吡咯基、嗯唑基、异嗯唑基、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是如上所述取代的。
在一个实施方案中,R3选自呋喃基、噻吩基、吡咯基、咪唑基、吡啶基、嘧啶基、吲哚基,其中所述杂芳基可以是如上所述取代的。
在一个实施方案中,R3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,其中所述杂芳基可以是如上所述取代的。
在一种特别优选的实施方案中,R3表示嘧啶基或者咪唑基,优选2-嘧啶基和2-咪唑基,其中所述基团可以是如上所述取代的。R3尤其表示2-嘧啶基或者N-甲基-咪唑-2-基,其中所述基团没有进一步取代。
在一个实施方案中,R1选自(C1-C12)-烷基;R2选自苯基、2-嘧啶基和2-咪唑基;并且R3选自2-嘧啶基和2-咪唑基;其中所述基团R1、R2和R3各自可以是如上所述取代的。
在一个实施方案中,所述化合物具有式(1)和(2)所示的结构:
本发明还涉及包含Pd和本发明的单膦化合物的配合物。在这些配合物中,本发明的单膦化合物用作金属原子的配体。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单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)添加本发明的单膦化合物和包含Pd的化合物,
或者添加包含Pd和本发明的单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2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,最优选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。
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。
在开始时才添加配合物的情况下,也可以添加另外的配体,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(bda)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。
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%。
本发明的单膦化合物与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,Oxford2009)。
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 6890N/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乙醚萃取和将有机相通过Na2SO4干燥。记录下该乙醚溶液的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。起始形成了透明的黄色溶液,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。
31PNMR(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
在氩气氛围下在配有温度计和滴液漏斗的50ml三颈烧瓶中称量加入0.78g(9.5mmol)1-甲基咪唑,并且溶解于10ml THF之中。然后将1.6mlTMEDA加入到溶液中。然后将混合物冷却到-78℃。然后利用滴液漏斗滴加6ml 1.6N正丁基锂的己烷溶液。将装有反应混合物的50ml烧瓶在室温下搅拌30分钟。接着将1.5g叔丁基二氯膦溶解于20ml THF之中。然后在-78°下将1-甲基咪唑-丁基锂混合物滴加到叔丁基二氯膦中。然后加热到室温。析出产物。过滤悬浮液,将残留物溶解于水中,接着使用二氯甲烷洗涤三次。使用Na2SO4干燥有机相,然后在真空中去除溶剂。使用5ml二氯甲烷溶解残留物,并且用20ml乙醚覆盖(ueberschichten)。产物结晶出来。可以得到0.8g产物。
纯度(NMR)=98%,
31P NMR(CD2Cl2,121MHz)=-32.25ppm,
13C NMR(CD2Cl2,75MHz)=144s,130.2d(JPC=3.7Hz),123.8s,34.2d,(JPC=11.7Hz),25.9d,(JPC=14.3Hz)
1H NMR(CD2Cl2,300MHz,):7.04,d,(J=1Hz,1H),6.94dd(J=1Hz,J=1.5Hz,1H),3.4s(6H),1.2d(J=14.6Hz,9H)
HRMS:计算值C12H19N4P:251.14201,实测值:251.14206。
2-(叔丁基(苯基)膦基)吡啶(化合物2)的制备
在氩气氛围下在配有低温温度计和磁搅拌器的100ml三颈烧瓶中将3.4g(16.8mmoL)2-(叔丁基氯膦基)吡啶(前体A)溶解于50ml纯净乙醚中。冷却到-78℃。在该温度下在10分种之内利用滴液漏斗加入10ml 1.8N苯基锂溶液(在二丁基醚中)。在该温度下搅拌10分钟,接着加热到室温,并且继续搅拌半小时。然后用10ml脱气水将该溶液洗涤三次。现在在10-1 Torr的高真空中蒸馏有机相。在该压力和130℃温度下得到产物作为高于97%(NMR)的高纯度的透明液体。产率为3.85g(93%)。
分析:
31P(丙酮-d6,121MHz),16.31s,
13C(75MHz,丙酮-d6,165.1(d,JPC=10.5Hz),150.3(d,JPC=5Hz),137.3s,137.0s,136.7s,135.9d,135.9(d,JPC=7.6Hz),131.1s,130.6s,130.2s,128.9(d,JPC=8Hz),122.9s,32.1(d,JPC=13.1Hz),28.5(d,JPC=13.7Hz),
1H(丙酮-d6,300MHz):
8.74(dm,J=4.7Hz),7.7-7.6m(2H),7.4-7.3(m,3H),7.28-7.23(m,1H),1.2(d,J=12.6Hz,9H)
MS(EI,70eV):m/z(%),243(M+,17),203(65),187(78),156(6),126(8),109(100),78(11),57(11)
HRMS(EI),计算值C15H18N1P1:243.11714,实测值:243.11753。
其它配体
以下对比化合物均可在市面上买到。
VB:对比实施例
烷氧基羰基化试验
用于分批试验中的反应的通用试验描述:
将相应量的基料、钯盐、酸和醇在氩气和磁搅拌下在50ml Schlenk容器中混合。
将100ml钢制高压釜(出自Parr公司,配备有气体进口和气体出口阀、数字压力记录器、温度感应器和球阀以及用于取样的嵌入毛细管)通过三次抽真空和氮气吹扫而除去氧气。然后将Schlenk容器中的反应溶液借助毛细管以氩气的逆流通过球阀而填充到高压釜中。然后在室温下压入相应量的CO和再加热到反应温度(不在恒压下进行的反应),或者首先加热到反应温度和再通过量管(借助减压装置与高压釜相连)压入CO。然后将该量管再用CO填充至大约100bar和在反应过程中在恒定压力下提供所需的CO。该量管的死容积为大约30ml和配备有数字压力记录器。然后,将该反应在所需的温度下在搅拌的情况下实施相应的时间。在此,借助软件(SpecView公司的Specview)和Parr公司的4870过程控制器和4875功率控制器记录在高压釜中和在玻璃量管中的压力变化数据。由这些生成Excel表格,从而以后可以制成图表,该图表可以描绘气体消耗(和因此转化率)随时间的变化。如果需要,可以通过毛细管收集GC样品并且分析。为此,在反应之前向Schlenk容器中一起加入合适的准确量(2-10ml)的异辛烷作为内部标准物。由此也可以获知反应进程。在反应结束时,将高压釜冷却至室温,小心地释放压力,如果需要的话加入异辛烷作为内部标准物和进行GC分析或者对于新的产物也进行GC-MS分析。
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插入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:
分析甲醇
在溶剂干燥设备中预处理甲醇:Pure Solv MD-/溶剂净化系统,InnovativeTechnology Inc.公司,One Industrial Way,Amesbury MA 01013
水值:
使用Karl Fischer滴定法测定:TitraLab 580-TIM580,Radiometer AnalyticalSAS公司(Karl-Fischer滴定法),水含量:测量范围,0.1至100%w/w,测定的水含量:0.13889%
使用了:
Applichem的工业用甲醇:编号A2954,5000,批号:LOT:3L005446最大水含量1%
Acros Organics的甲醇(通过分子筛):水含量0.005%,代号:364390010,批号:LOT 1370321
乙烯的甲氧基羰基化反应
向50ml Schlenk容器加入Pd(acac)2(6.53mg,0.04mol%)、配体(0.16mol%)、乙烯(1.5g,53mmol)、20ml甲醇和对甲苯磺酸(PTSA,61mg,0.6mol%)。如上所述利用毛细管在氩气逆流中将反应混合物转移到100ml钢制高压釜之中。将CO压力调整到40bar。反应在80℃温度下进行3小时。在反应结束之后,将高压釜冷却到室温并且小心卸压。加入异辛烷(100μl)作为内部GC标准物。利用GC确定产率和区域选择性。
下表所示为测量结果。
配体 | 产率 |
1 | 30% |
2 | 14% |
3(VB) | 3% |
10(VB) | 0% |
VB:对比实施例
该实施例证明本发明所述的配体1、2与对比配体3和10相比能够在乙烯的甲氧基羰基化反应过程中实现明显更好的产率。
1-辛烯的异构化区域选择性甲氧基羰基化反应
示意图8:1-辛烯的区域选择性甲氧基羰基化;除了末端甲氧基羰基化之外,反应主要会在2-位置(称作major)引起副反应。
以下所述的iso/n比例表示内部转化成酯的烯烃与末端转化成酯的烯烃之比。
a)使用PdCl2的变型方案
向4mL瓶加入PdCl2(1.77mg,1.0mol%)和配体(4.0mol%)并且放入磁搅拌子。然后用注射器注入甲苯(2ml)、1-辛烯(157μl,1mmol)和MeOH(40.5μl,1mmol)。将该瓶放在样品架上,在氩气氛围下再将其放入300ml Parr高压釜之中。用氮气将高压釜吹扫三次之后,将CO压力调整到40bar。反应在120℃温度下进行20小时。在反应结束之后,将高压釜冷却到室温并且小心卸压。加入异辛烷(100μl)作为内部GC标准物。利用GC确定产率和区域选择性。
下表所示为测量结果。
配体 | 产率 | iso/n |
2 | 75% | 28/72 |
3(VB) | 87% | 55/45 |
10(VB) | 10% | 45/55 |
VB:对比实施例;Cy:环己基;o-tol:邻甲苯基;Ph:苯基;tBu:叔丁基。
本发明所述的配体2不仅有产率高、而且也有n/iso选择性高的特征。现有技术所公开的配体10则只有很低的产率,并且没有区域选择性。对比配体3尽管能实现很高的产率,然而同样没有区域选择性。
b)使用Pd(acac)22的变型方案
向25mL Schlenk容器装入[Pd(acac)2](1.95mg,0.04mol%)、对甲苯磺酸(PTSA)(18.24μL,0.6mol%)和MeOH(10mL)。将配体(0.16mol%)装入4mL小瓶并且加入磁搅拌子。然后用注射器注入Schlenk容器中的1.25mL透明黄色溶液和1-辛烯(315μL,2mmol)。将小瓶放在样品架上,在氩气氛围下再将其放入300ml Parr高压釜之中。用氮气将高压釜吹扫三次之后,将CO压力调整到40bar。反应在120℃温度下进行20小时。在反应结束之后,将高压釜冷却到室温并且小心卸压。加入异辛烷(100μl)作为内部GC标准物。利用GC确定产率和区域选择性。
下表所示为测量结果。
VB:对比实施例
本发明所述的配体2在这里也表现出很高的iso/n选择性,并且产率高于对比配体3和10。
Claims (15)
1.式(I)所示的化合物
其中
R1选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基;
R2选自-(C3-C12)-杂环烷基、-(C6-C20)-芳基、-(C3-C20)-杂芳基;
R3是-(C3-C20)-杂芳基;
并且R1、R2和R3可以是各自相互独立地被选自-(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、卤素的一个或多个取代基取代的。
2.根据权利要求1的化合物,其中R1表示-(C1-C12)-烷基。
3.根据权利要求1至2任一项的化合物,其中R2选自-(C6-C20)-芳基和-(C3-C20)-杂芳基。
4.根据权利要求1至3任一项的化合物,其中R2选自苯基、嘧啶基和咪唑基。
5.根据权利要求1至4任一项的化合物,其中R3选自具有五个或者六个环原子的杂芳基基团。
6.根据权利要求1至5任一项的化合物,其中R2选自嘧啶基和咪唑基。
7.根据权利要求1至6任一项的化合物,其中R1、R2和R3可以是各自相互独立地被选自-(C1-C12)-烷基的一个或多个取代基取代的。
8.根据权利要求1至7任一项的化合物,
其具有式(1)和(2)任一项
9.配合物,其包含Pd和根据权利要求1至8任一项的化合物。
10.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8任一项的化合物和包含Pd的化合物,
或添加根据权利要求9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。
11.根据权利要求10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10至11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。
13.根据权利要求10至12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。
14.根据权利要求10至13任一项的方法,
其中在方法步骤c)中的醇是脂族醇。
15.根据权利要求1至8任一项的化合物或根据权利要求9的配合物用于催化烷氧基羰基化反应的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102015213918.2 | 2015-07-23 | ||
DE102015213918 | 2015-07-23 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106632476A true CN106632476A (zh) | 2017-05-10 |
CN106632476B CN106632476B (zh) | 2020-11-20 |
Family
ID=56497599
Family Applications (7)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610567559.1A Active CN106366126B (zh) | 2015-07-23 | 2016-07-19 | 用于烷氧基羰基化的基于苯的二膦配体 |
CN201610826942.4A Active CN106632476B (zh) | 2015-07-23 | 2016-07-19 | 单膦化合物和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂 |
CN202111116065.9A Pending CN113845545A (zh) | 2015-07-23 | 2016-07-19 | 用于烷氧基羰基化的丁基-桥连的二膦配体 |
CN201610782022.7A Pending CN106397484A (zh) | 2015-07-23 | 2016-07-19 | 用于烷氧基羰基化的丁基‑桥连的二膦配体 |
CN201610781379.3A Active CN106432365B (zh) | 2015-07-23 | 2016-07-19 | 二茂铁基化合物和以此为基础用于烯属不饱和化合物烷氧基羰基化的钯催化剂 |
CN201610781876.3A Active CN106432364B (zh) | 2015-07-23 | 2016-07-19 | 二茂铁基化合物和以此为基础用于烯属不饱和化合物烷氧基羰基化的钯催化剂 |
CN201610826997.5A Active CN106632509B (zh) | 2015-07-23 | 2016-07-19 | 膦配体和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610567559.1A Active CN106366126B (zh) | 2015-07-23 | 2016-07-19 | 用于烷氧基羰基化的基于苯的二膦配体 |
Family Applications After (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111116065.9A Pending CN113845545A (zh) | 2015-07-23 | 2016-07-19 | 用于烷氧基羰基化的丁基-桥连的二膦配体 |
CN201610782022.7A Pending CN106397484A (zh) | 2015-07-23 | 2016-07-19 | 用于烷氧基羰基化的丁基‑桥连的二膦配体 |
CN201610781379.3A Active CN106432365B (zh) | 2015-07-23 | 2016-07-19 | 二茂铁基化合物和以此为基础用于烯属不饱和化合物烷氧基羰基化的钯催化剂 |
CN201610781876.3A Active CN106432364B (zh) | 2015-07-23 | 2016-07-19 | 二茂铁基化合物和以此为基础用于烯属不饱和化合物烷氧基羰基化的钯催化剂 |
CN201610826997.5A Active CN106632509B (zh) | 2015-07-23 | 2016-07-19 | 膦配体和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂 |
Country Status (15)
Country | Link |
---|---|
US (8) | US9688604B2 (zh) |
EP (6) | EP3121186B1 (zh) |
JP (2) | JP6714459B2 (zh) |
KR (2) | KR101878043B1 (zh) |
CN (7) | CN106366126B (zh) |
AR (2) | AR105389A1 (zh) |
BR (2) | BR102016016724B1 (zh) |
CA (2) | CA2936723C (zh) |
ES (6) | ES2711749T3 (zh) |
MX (2) | MX2016009398A (zh) |
MY (1) | MY172677A (zh) |
PL (3) | PL3121181T4 (zh) |
SG (3) | SG10201605921SA (zh) |
TW (2) | TWI634947B (zh) |
ZA (2) | ZA201605001B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Families Citing this family (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR105389A1 (es) | 2015-07-23 | 2017-09-27 | Evonik Degussa Gmbh | Compuestos basados en ferroceno y catalizadores de paladio basados en los mismos para la alcoxicarbonilación de compuestos etilénicamente instaurados |
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 |
EP3272730B1 (de) | 2016-07-19 | 2019-01-02 | Evonik Degussa GmbH | Verfahren zur alkoxycarbonylierung von ethern |
EP3272760B1 (de) | 2016-07-19 | 2019-05-15 | Evonik Degussa GmbH | 1,1'-bis(phosphino)ferrocenliganden für die alkoxycarbonylierung |
EP3272759B1 (de) | 2016-07-19 | 2019-05-08 | Evonik Degussa GmbH | 1,1'-bis(phosphino)ferrocenliganden für die alkoxycarbonylierung |
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 |
EP3272729B1 (de) | 2016-07-19 | 2019-09-04 | Evonik Degussa GmbH | Verfahren zur herstellung von estern durch carbonylierung von ethern |
EP3272728B1 (de) | 2016-07-19 | 2019-06-19 | Evonik Degussa GmbH | Verfahren zur alkoxycarbonylierung von alkoholen |
WO2018175332A1 (en) * | 2017-03-18 | 2018-09-27 | Qatar Foundation For Education, Science And Community Development | Metal-catalyzed alkoxycarbonylation of a lactone |
EP3421478B1 (en) | 2017-06-29 | 2020-03-25 | Evonik Operations GmbH | Markovnikov-selective palladium catalyst for carbonylation of alkynes with heteroarenes |
EP3441384B1 (de) * | 2017-08-08 | 2019-12-25 | Evonik Operations GmbH | Methoxycarbonylierung mit ameisensäure und methanol |
EP3441383B1 (de) * | 2017-08-08 | 2019-12-25 | Evonik Operations GmbH | Methoxycarbonylierung mit ameisensäure als co-quelle |
EP3441137B1 (de) * | 2017-08-08 | 2019-12-25 | Evonik Operations GmbH | Pd-katalysierten zersetzung von ameisensäure |
PL3502082T3 (pl) * | 2017-12-21 | 2020-07-27 | Evonik Operations Gmbh | Sposób katalizowanej Pd hydroksykarbonylacji diizobutenów: wpływ rozpuszczalnika |
EP3502081B1 (de) * | 2017-12-21 | 2020-07-01 | Evonik Operations GmbH | Verfahren zur pd-katalysierten hydroxycarbonylierung von diisobuten: verhältnis 3,5,5-trimethylhexansäure/h2o |
ES2807998T3 (es) * | 2017-12-21 | 2021-02-25 | Evonik Operations Gmbh | Procedimiento para la hidroxicarbonilación de diisobuteno catalizada con Pd: proporción ligando/Pd |
EP3502084B1 (de) * | 2017-12-21 | 2020-02-12 | Evonik Operations GmbH | Verfahren zur direkten umsetzung von diisobuten zu einer carbonsäure |
EP3502085B1 (de) * | 2017-12-21 | 2020-03-11 | Evonik Operations GmbH | Verfahren zur direkten umsetzung von alkenen zu carbonsäuren |
EP3502087B1 (de) * | 2017-12-21 | 2020-06-24 | Evonik Operations GmbH | Verfahren zur pd-katalysierten hydroxycarbonylierung von diisobuten: verhältnis essigsäure/diisobuten |
EP3502086B1 (de) * | 2017-12-21 | 2020-07-08 | Evonik Operations GmbH | Verfahren zur pd-katalysierten hydroxycarbonylierung von diisobuten: verhältnis schwefelsäure/ligand |
US10710956B2 (en) * | 2018-02-08 | 2020-07-14 | Regents Of The University Of Minnesota | Process for the preparation of acrylate esters from alkyl lactates |
ES2834092T3 (es) * | 2018-02-14 | 2021-06-16 | Evonik Degussa Gmbh | Ligandos difosfina puenteados con propilo para la alcoxicarbonilación |
US11365171B2 (en) | 2019-06-12 | 2022-06-21 | Evonik Operations Gmbh | Process for preparing an ester by alkoxycarbonylation |
US11440863B2 (en) | 2019-06-12 | 2022-09-13 | Evonik Operations Gmbh | Process for preparing an alcohol from hydrocarbons |
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 |
PL3842411T3 (pl) * | 2019-12-17 | 2023-10-02 | Evonik Operations Gmbh | Ester trimetylowy kwasu 3,3',3''-(cykloheksano-1,2,4-triylo)tripropionowego |
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 |
EP3889161B1 (de) * | 2020-03-30 | 2022-06-08 | Evonik Operations GmbH | Platin-komplexe mit benzylbasierten diphosphinliganden für die katalyse der alkoxycarbonylierung ethylenisch ungesättigter verbindungen |
EP3889163B1 (de) * | 2020-03-30 | 2023-07-19 | Evonik Operations GmbH | Platin-komplexe mit ferrocen-liganden für die katalyse der alkoxycarbonylierung ethylenisch ungesättigter verbindungen |
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 |
CN114805434A (zh) * | 2021-01-18 | 2022-07-29 | 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 |
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 |
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 |
US20230192486A1 (en) | 2021-12-20 | 2023-06-22 | Evonik Operations Gmbh | Process for producing carbon monoxide-containing streams |
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 (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN88101206A (zh) * | 1987-03-11 | 1988-09-28 | 国际壳牌研究有限公司 | 在钯催化剂下烯属不饱和化合物羰基化的方法 |
CN1049462A (zh) * | 1989-03-03 | 1991-02-27 | 国际壳牌研究有限公司 | 羰基化催化剂 |
EP0441446A1 (en) * | 1990-02-05 | 1991-08-14 | Shell Internationale Researchmaatschappij B.V. | Carbonylation catalyst system |
EP0441447A1 (en) * | 1990-02-05 | 1991-08-14 | Shell Internationale Researchmaatschappij B.V. | Carbonylation catalyst process |
US5268479A (en) * | 1991-12-14 | 1993-12-07 | Hoechst Aktiengesellschaft | Process for the preparation of tertiary phosphines |
CN1127245A (zh) * | 1994-07-22 | 1996-07-24 | 大世吕化学工业株式会社 | 用于羰基化作用的催化系统和方法 |
TW201434532A (zh) * | 2013-02-01 | 2014-09-16 | Evonik Industries Ag | 使烯烴類羰基化之方法 |
Family Cites Families (27)
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 |
US3213093A (en) * | 1963-12-12 | 1965-10-19 | American Cyanamid Co | Phosphino-s-triazines |
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 |
US4880902A (en) * | 1987-08-27 | 1989-11-14 | Shell Oil Company | Copolymerization of carbon monoxide and olefin with diphosphine having heterocyclic substituents as catalyst |
KR0148012B1 (ko) * | 1989-03-03 | 1998-08-17 | 오노 알버어스 | 신규한 포스핀으로 구성되는 촉매시스템 및 이를 이용한 아세틸렌형 또는 올레핀형 불포화화합물의 카르보닐화방법 |
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. |
AU5579598A (en) | 1997-02-26 | 1998-09-18 | 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 |
WO2005056566A2 (de) * | 2003-12-12 | 2005-06-23 | 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 |
JP6011798B2 (ja) | 2011-02-17 | 2016-10-19 | 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 |
KR102205983B1 (ko) * | 2014-10-13 | 2021-01-22 | 덕산네오룩스 주식회사 | 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치 |
AR105389A1 (es) | 2015-07-23 | 2017-09-27 | Evonik Degussa Gmbh | Compuestos basados en ferroceno y catalizadores de paladio basados en los mismos para la alcoxicarbonilación de compuestos etilénicamente instaurados |
ES2834092T3 (es) * | 2018-02-14 | 2021-06-16 | Evonik Degussa Gmbh | Ligandos difosfina puenteados con propilo para la alcoxicarbonilación |
-
2016
- 2016-07-19 AR ARP160102179A patent/AR105389A1/es unknown
- 2016-07-19 US US15/213,435 patent/US9688604B2/en active Active
- 2016-07-19 TW TW105122754A patent/TWI634947B/zh active
- 2016-07-19 EP EP16180047.9A patent/EP3121186B1/de active Active
- 2016-07-19 TW TW105122755A patent/TWI648283B/zh active
- 2016-07-19 US US15/213,441 patent/US9725398B2/en active Active
- 2016-07-19 CN CN201610567559.1A patent/CN106366126B/zh active Active
- 2016-07-19 CN CN201610826942.4A patent/CN106632476B/zh active Active
- 2016-07-19 SG SG10201605921SA patent/SG10201605921SA/en unknown
- 2016-07-19 US US15/213,453 patent/US10202329B2/en active Active
- 2016-07-19 CN CN202111116065.9A patent/CN113845545A/zh active Pending
- 2016-07-19 ES ES16180046T patent/ES2711749T3/es active Active
- 2016-07-19 US US15/213,456 patent/US10077228B2/en active Active
- 2016-07-19 KR KR1020160091333A patent/KR101878043B1/ko active IP Right Grant
- 2016-07-19 AR ARP160102178A patent/AR105388A1/es active IP Right Grant
- 2016-07-19 US US15/213,444 patent/US20170022138A1/en not_active Abandoned
- 2016-07-19 JP JP2016141023A patent/JP6714459B2/ja active Active
- 2016-07-19 BR BR102016016724-8A patent/BR102016016724B1/pt active IP Right Grant
- 2016-07-19 BR BR102016016726-4A patent/BR102016016726B1/pt active IP Right Grant
- 2016-07-19 CN CN201610782022.7A patent/CN106397484A/zh active Pending
- 2016-07-19 KR KR1020160091335A patent/KR101828687B1/ko active IP Right Grant
- 2016-07-19 EP EP16180044.6A patent/EP3121180B1/de active Active
- 2016-07-19 SG SG10201806584VA patent/SG10201806584VA/en unknown
- 2016-07-19 EP EP16180042.0A patent/EP3121179B1/de active Active
- 2016-07-19 ES ES16180044T patent/ES2702924T3/es active Active
- 2016-07-19 ZA ZA2016/05001A patent/ZA201605001B/en unknown
- 2016-07-19 CA CA2936723A patent/CA2936723C/en active Active
- 2016-07-19 ZA ZA2016/05000A patent/ZA201605000B/en unknown
- 2016-07-19 CN CN201610781379.3A patent/CN106432365B/zh active Active
- 2016-07-19 PL PL16180043.8T patent/PL3121181T4/pl unknown
- 2016-07-19 CN CN201610781876.3A patent/CN106432364B/zh active Active
- 2016-07-19 CA CA2936724A patent/CA2936724C/en active Active
- 2016-07-19 EP EP16180045.3A patent/EP3121184B1/de active Active
- 2016-07-19 MX MX2016009398A patent/MX2016009398A/es unknown
- 2016-07-19 EP EP16180046.1A patent/EP3121185B1/de active Active
- 2016-07-19 PL PL16180044T patent/PL3121180T3/pl unknown
- 2016-07-19 EP EP16180043.8A patent/EP3121181B1/de active Active
- 2016-07-19 MY MYPI2016001351A patent/MY172677A/en unknown
- 2016-07-19 US US15/213,449 patent/US10294191B2/en active Active
- 2016-07-19 CN CN201610826997.5A patent/CN106632509B/zh active Active
- 2016-07-19 PL PL16180045T patent/PL3121184T3/pl unknown
- 2016-07-19 ES ES16180045T patent/ES2705723T3/es active Active
- 2016-07-19 MX MX2016009397A patent/MX2016009397A/es unknown
- 2016-07-19 JP JP2016141022A patent/JP6840480B2/ja active Active
- 2016-07-19 ES ES16180047T patent/ES2703563T3/es active Active
- 2016-07-19 ES ES16180042T patent/ES2705078T3/es active Active
- 2016-07-19 SG SG10201605918UA patent/SG10201605918UA/en unknown
- 2016-07-19 ES ES16180043T patent/ES2714150T3/es active Active
-
2021
- 2021-05-21 US US17/326,738 patent/US20210276939A1/en not_active Abandoned
-
2023
- 2023-07-07 US US18/348,913 patent/US20230348356A1/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN88101206A (zh) * | 1987-03-11 | 1988-09-28 | 国际壳牌研究有限公司 | 在钯催化剂下烯属不饱和化合物羰基化的方法 |
CN1049462A (zh) * | 1989-03-03 | 1991-02-27 | 国际壳牌研究有限公司 | 羰基化催化剂 |
EP0441446A1 (en) * | 1990-02-05 | 1991-08-14 | Shell Internationale Researchmaatschappij B.V. | Carbonylation catalyst system |
EP0441447A1 (en) * | 1990-02-05 | 1991-08-14 | Shell Internationale Researchmaatschappij B.V. | Carbonylation catalyst process |
US5268479A (en) * | 1991-12-14 | 1993-12-07 | Hoechst Aktiengesellschaft | Process for the preparation of tertiary phosphines |
CN1127245A (zh) * | 1994-07-22 | 1996-07-24 | 大世吕化学工业株式会社 | 用于羰基化作用的催化系统和方法 |
TW201434532A (zh) * | 2013-02-01 | 2014-09-16 | Evonik Industries Ag | 使烯烴類羰基化之方法 |
Non-Patent Citations (6)
Title |
---|
ANNE BRENNFUHRER等: "Palladium-Catalyzed Carbonylation Reactions of Alkenes and Alkynes", 《CHEMCATCHEM》 * |
COLUMBUS, OHIO: "STN检索报告", 《STN REGISTRY》 * |
MELINDA J. GREEN等: "Palladium(II) complexes of new OPN phosphine ligands and their application in homogeneously catalysed reactions of CO with alkenes or alkynes", 《DALTON TRANS.》 * |
P. ELSBETH GOUDRIAAN等: "Synthesis of Building Blocks for the Development of the SUPRAPhos Ligand Library and Examples of Their Application in Catalysis", 《EUR. J. ORG. CHEM.》 * |
SHAN-MING KUANG等: "Formation of donor-acceptor Fe(0)-Hg(II) bond in separation and stabilization of optically active iron(0) phosphine complexes.Absolute configuration of (+)-(R)-(CO)4Fe(µ-EtPhPpy)HgCl2", 《INORGANICA CHIMICA ACTA》 * |
XIANJIE FANG等: "Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes under Acid-Free Conditions: Atom-Economic Synthesis of β,γ-Unsaturated Esters", 《ANGEW. CHEM.》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106632476A (zh) | 单膦化合物和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂 | |
JP6467004B2 (ja) | モノホスフィンリガンドを有するエチレン性不飽和化合物のアルコキシカルボニル化方法 | |
CN107629093B (zh) | 用于烷氧基羰基化的1,1'-双(膦基)二茂铁配体 | |
TWI691482B (zh) | 在布氏酸(Bronsted acid)濃度低的介質中使烯烴類烷氧羰基化的方法 | |
CN107629092B (zh) | 用于烷氧羰基化的1,1’-双(膦基)二茂铁配体 | |
CN107628949A (zh) | 用于使醚烷氧基羰基化的方法 | |
JP2018058817A (ja) | アルコールのアルコキシカルボニル化方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information |
Address after: Essen, Germany Applicant after: Evonik Operations Ltd. Address before: Essen, Germany Applicant before: EVONIK DEGUSSA GmbH |
|
CB02 | Change of applicant information | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20231120 Address after: mAhR Patentee after: Evonik Oxenor Co.,Ltd. Address before: essen Patentee before: Evonik Operations Ltd. |
|
TR01 | Transfer of patent right |