CN116265424A - 使用铂和碘或溴对烯烃进行加氢甲酰化的方法 - Google Patents
使用铂和碘或溴对烯烃进行加氢甲酰化的方法 Download PDFInfo
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- CN116265424A CN116265424A CN202211612393.2A CN202211612393A CN116265424A CN 116265424 A CN116265424 A CN 116265424A CN 202211612393 A CN202211612393 A CN 202211612393A CN 116265424 A CN116265424 A CN 116265424A
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- compound
- alkyl
- aryl
- bromine
- iodine
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- 238000000034 method Methods 0.000 title claims abstract description 63
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 9
- 238000007037 hydroformylation reaction Methods 0.000 title abstract description 6
- 229910052697 platinum Inorganic materials 0.000 title abstract description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910052740 iodine Inorganic materials 0.000 title abstract description 4
- 239000011630 iodine Substances 0.000 title abstract description 4
- -1 bromine compound Chemical class 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000002497 iodine compounds Chemical class 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical class C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- HOAGXXFHJQRWMT-UHFFFAOYSA-N (2-ethenylphenyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=CC=C1C=C HOAGXXFHJQRWMT-UHFFFAOYSA-N 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 description 1
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 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
- 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
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 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
- 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
- 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
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 125000001725 pyrenyl group Chemical group 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
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2247—At least one oxygen and one phosphorous atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
- B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
-
- 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
- C07F15/0086—Platinum compounds
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- 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
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Abstract
本发明涉及使用铂和碘或溴对烯烃进行加氢甲酰化的方法。
Description
技术领域
本发明涉及使用铂和碘或溴对烯烃进行加氢甲酰化的方法。
背景技术
C. Botteghi 等人,Journal of Molecular Catalysis A: Chemical 200,(2003), 147-156 描述了Pt(4,5-双(二苯基膦基)-9,9-二甲基氧杂蒽(Xantphos))Cl2用于2-甲苯磺酰氧基苯乙烯的加氢甲酰化的用途。
发明内容
本发明要解决的问题是提供一种新的加氢甲酰化方法。与使用Pt与Cl2的现有技术已知的方法相比,该方法在此应提供提高的产率。
该目的通过根据权利要求1所述的方法实现。
方法,包括以下方法步骤:
a) 预先加入烯烃;
b) 添加式(I)的化合物:
其中R1、R2、R3、R4、R5、R6、R7、R8选自:-H、-(C1-C12)-烷基、-(C6-C20)-芳基,而R9、R10选自(C1-C12)-烷基、(C6-C20)-芳基; 和,如果 R1、R2、R3、R4、R5、R6、R7、R8、R9、R10是-(C6-C20)-芳基,那么芳环可以具有选自-(C1-C12)-烷基、-O-(C1-C12)-烷基的取代基;
c) 添加能够形成配合物的Pt化合物;
d) 添加碘化合物或溴化合物;
e) 引入CO和H2;
f) 加热由步骤a)至e)获得的反应混合物,其中将烯烃转化为醛。
在此,方法步骤a)至e)可以按任何所需顺序进行。然而,通常情况下,CO和H2在预先加入步骤a)至d)中的反应参与物之后加入。
本文可以通过添加 PtI2或PtBr2在一个步骤中实施方法步骤c)和d)。
在该方法的一个优选的变化中,通过添加PtI2或PtBr2在一个步骤中添加Pt化合物和碘化合物或溴化合物。
术语(C1-C12)-烷基包括具有1至12个碳原子的直链和支链烷基。这些优选(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(C6-C20)-芳基包括具有6至20个碳原子的单环或多环芳族烃基。这些优选(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、并四苯基、䓛基、芘基、蒄基。优选的(C6-C20)-芳基是苯基、萘基和蒽基。
在该方法的一个变化中,R2、R3、R5、R6、R7、R8选自:-(C1-C12)-烷基、-(C6-C20)-芳基。
在该方法的一个变化中,R5、R6、R7、R8是-(C6-C20)-芳基。
在该方法的一个变化中,R5和 R6是不同的基团以及R7和R8 是不同的基团。
在该方法的一个变化中,R2和 R3是-(C1-C12)-烷基。
在该方法的一个变化中,R2和 R3是-CH3。
在该方法的一个变化中,R1和 R4是-H。
在该方法的一个变化中,R9和 R10是-(C1-C12)-烷基。
在该方法的一个变化中,化合物(I)具有结构(1):
在该方法的一个变化中,Pt化合物选自:Pt(II)I2、Pt(II)Br2、Pt(IV)I4、Pt(IV)Br4、二苯基(1,5-COD)Pt(II)、Pt(II)(acac)2、Pt(0)(PPh3)4、Pt(0)(DVTS) 溶液 (CAS:68478-92-2)、Pt(0)(乙烯)(PPh3)2、Pt(II)Br2(COD)、三(亚苄基丙酮)Pt(0)、Pt(II)(OAC)2溶液、Pt(0)(t-Bu)2、Pt(II)(COD)Me2、Pt(II)(COD)I2、Pt(IV)IMe3、Pt(II)(六氟乙酰丙酮合物)2。
在该方法的一个变化中,Pt化合物选自:Pt(II)I2、Pt(II)Br2。
在该方法的一个变化中,碘化合物或溴化合物选自:碱金属卤化物、碱土金属卤化物、NH4X、烷基卤化铵、二烷基卤化物(Dialkylhalogenid)、三烷基卤化物(Trialkylhalogenid)、四烷基卤化物(Tetraalkylhalogenid)和环烷基卤化铵。
在该方法的一个变化中,在方法步骤d)添加碘化合物。
在该方法的一个变化中,碘化合物是 Pt(II)I2。
在该方法的一个变化中,碘化合物的加入量为0.1至10,基于Pt以当量测得。
在该方法的一个变化中,在方法步骤d)添加溴化合物。
在该方法的一个变化中,溴化合物是 Pt(II)Br2。
在该方法的一个变化中,溴化合物的加入量为0.1至10,基于Pt以当量测得。
在该方法的一个变化中,该方法包括附加方法步骤e'):
e') 添加溶剂。
在该方法的一个变化中,溶剂选自:THF、DCM、ACN、庚烷、DMF、甲苯、Texanol、戊烷、己烷、辛烷、异辛烷、癸烷、十二烷、环己烷、苯、二甲苯、 Marlotherm、碳酸亚丙酯、MTBE、二甘醇二甲醚、三甘醇二甲醚、***、二噁烷、异丙醇、叔丁醇、异壬醇、异丁醇、异戊醇、乙酸乙酯。
在该方法的一个变化中,溶剂选自:THF、DCM、ACN、庚烷、DMF、甲苯、Texanol。
在该方法的一个变化中,CO和H2在1 MPa(10巴)至6 MPa(60巴)的压力下引入。
在该方法的一个变化中,CO和H2在2 MPa (20 巴)至5 MPa(50 巴)的压力下引入。
在该方法的一个变化中,加热至25℃至150℃的温度。
在该方法的一个变化中,加热至30℃至130℃的温度。
在该方法的一个变化中,烯烃选自: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。
具体实施方式
本发明将在下文中通过工作实施例进行详细说明。
实验描述
向小瓶中装入PtX2 (X=卤素)、配体和烘箱干燥的搅拌棒。然后用隔膜(PTFE涂覆的丁苯橡胶)和酚醛树脂盖密封小瓶。将小瓶抽真空并重新填充氩气三次。使用注射器将甲苯和1-辛烯添加到小瓶中。将小瓶置于合金板(Legierungsplatte)中,在氩气气氛下将其转移至Parr Instruments的4560系列高压釜中。用CO/H2吹扫高压釜三次后,在室温下将合成气压力增加至40巴。反应在80℃下进行18 h。反应结束后,将高压釜冷却至室温并小心减压。通过GC分析确定产率和选择性。
卤素的变化
反应条件:
20 mmol的1-辛烯,0.5 mol% PtX2,2.0 当量的配体 (1),溶剂:甲苯,p(CO/H2):40巴,T:80℃,t:18 h。
产率:
如实验结果所示,该目的通过根据本发明的方法得以实现。
Claims (15)
1.方法,包括以下方法步骤:
a) 预先加入烯烃;
b) 添加式(I)的化合物:
其中R1、R2、R3、R4、R5、R6、R7、R8选自:-H、-(C1-C12)-烷基、-(C6-C20)-芳基,而R9、R10选自(C1-C12)-烷基、(C6-C20)-芳基; 和如果 R1、R2、R3、R4、R5、R6、R7、R8、R9、R10是-(C6-C20)-芳基,那么芳环可以具有选自-(C1-C12)-烷基、-O-(C1-C12)-烷基的取代基;
c) 添加能够形成配合物的Pt化合物;
d) 添加碘化合物或溴化合物;
e) 引入CO和H2;
f) 加热由步骤a)至e)获得的反应混合物,其中将所述烯烃转化为醛。
2.根据权利要求1所述的方法,
其中R2、R3、R5、R6、R7、R8选自:-(C1-C12)-烷基、-(C6-C20)-芳基。
3.根据权利要求1或2任一项所述的方法,
其中R5、R6、R7、R8 是-(C6-C20)-芳基。
4.根据权利要求1至3中任一项所述的方法,
其中R2和R3是-(C1-C12)-烷基。
5.根据权利要求1至4中任一项所述的方法,
其中R1和R4是-H。
6.根据权利要求1至5中任一项所述的方法,
其中R9和R10是-(C1-C12)-烷基。
8.根据权利要求1至7中任一项所述的方法,
其中所述Pt化合物选自:Pt(II)I2、Pt(II)Br2、Pt(IV)I4、Pt(IV)Br4、二苯基(1,5-COD)Pt(II)、Pt(II)(acac)2、Pt(0)(PPh3)4、Pt(0)(DVTS)溶液(CAS: 68478-92-2)、Pt(0)(乙烯)(PPh3)2、Pt(II)Br2(COD)、三(亚苄基丙酮)Pt(0)、Pt(II)(OAC)2溶液、Pt(0)(t-Bu)2、Pt(II)(COD)Me2、Pt(II)(COD)I2、Pt(IV)IMe3、Pt(II)(六氟乙酰丙酮合物)2。
9.根据权利要求1至8中任一项所述的方法,
其中在方法步骤d)添加碘化合物。
10.根据权利要求9所述的方法,
其中所述碘化合物的加入量为0.1至10,基于Pt以当量测得。
11.根据权利要求1至8中任一项所述的方法,
其中在方法步骤d)添加溴化合物。
12.根据权利要求11所述的方法,
其中所述溴化合物的加入量为0.1至10,基于Pt以当量测得。
13.根据权利要求1至12中任一项所述的方法,
其包括附加方法步骤e'):
e') 添加溶剂。
14.根据权利要求1至13中任一项所述的方法,
其中CO和H2在1 MPa(10巴)至6 MPa(60巴)的压力下引入。
15.根据权利要求1至14中任一项所述的方法,
其中加热至25℃至150℃的温度。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105017317A (zh) * | 2014-12-25 | 2015-11-04 | 青岛科技大学 | 一种基于膦功能化聚醚烷基胍盐离子液体的烯烃两相氢甲酰化的方法 |
CN105175447A (zh) * | 2014-05-20 | 2015-12-23 | 赢创工业集团股份有限公司 | 单亚磷酸酯配体的混合物及其用于催化加氢甲酰基化反应的用途 |
CN116265422A (zh) * | 2021-12-17 | 2023-06-20 | 赢创运营有限公司 | 使用铂和溴对烯烃进行加氢甲酰化的方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105175447A (zh) * | 2014-05-20 | 2015-12-23 | 赢创工业集团股份有限公司 | 单亚磷酸酯配体的混合物及其用于催化加氢甲酰基化反应的用途 |
CN105017317A (zh) * | 2014-12-25 | 2015-11-04 | 青岛科技大学 | 一种基于膦功能化聚醚烷基胍盐离子液体的烯烃两相氢甲酰化的方法 |
CN116265422A (zh) * | 2021-12-17 | 2023-06-20 | 赢创运营有限公司 | 使用铂和溴对烯烃进行加氢甲酰化的方法 |
Non-Patent Citations (1)
Title |
---|
刘雯静;袁茂林;付海燕;李瑞祥;陈华;: "铑/双膦配体催化均相内烯烃氢甲酰化反应的研究进展", 催化学报, no. 06, 15 June 2009 (2009-06-15), pages 577 - 586 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116265422A (zh) * | 2021-12-17 | 2023-06-20 | 赢创运营有限公司 | 使用铂和溴对烯烃进行加氢甲酰化的方法 |
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