CN107866282A - A kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction - Google Patents
A kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction Download PDFInfo
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- CN107866282A CN107866282A CN201610847024.XA CN201610847024A CN107866282A CN 107866282 A CN107866282 A CN 107866282A CN 201610847024 A CN201610847024 A CN 201610847024A CN 107866282 A CN107866282 A CN 107866282A
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- China
- Prior art keywords
- reaction
- hydroformylation
- alkene
- aminophosphine ligand
- cascade
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 80
- 239000003446 ligand Substances 0.000 title claims abstract description 75
- 238000010523 cascade reaction Methods 0.000 title claims abstract description 61
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical compound PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 title claims abstract description 60
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010948 rhodium Substances 0.000 claims abstract description 16
- 239000007848 Bronsted acid Substances 0.000 claims abstract description 14
- 238000005576 amination reaction Methods 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 11
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 150000002466 imines Chemical class 0.000 claims abstract description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 14
- -1 1- normal-butyl -3- methyl imidazolium tetrafluoroborates Chemical group 0.000 claims description 13
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 11
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 3
- 239000000758 substrate Substances 0.000 claims 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims 2
- GDCCFQMGFUZVKK-UHFFFAOYSA-N 1-butyl-2h-pyridine Chemical class CCCCN1CC=CC=C1 GDCCFQMGFUZVKK-UHFFFAOYSA-N 0.000 claims 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- ALTVCFKRYOLNPF-UHFFFAOYSA-N imino(trifluoromethyl)sulfanium Chemical compound FC(F)(F)[S+]=N ALTVCFKRYOLNPF-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 15
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 14
- 238000010189 synthetic method Methods 0.000 description 14
- 229910004039 HBF4 Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000004679 31P NMR spectroscopy Methods 0.000 description 9
- 230000005311 nuclear magnetism Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 7
- 230000000977 initiatory effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 229910019891 RuCl3 Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 150000003284 rhodium compounds Chemical class 0.000 description 3
- 150000003304 ruthenium compounds Chemical class 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 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
- 125000004429 atom Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical compound [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 241000894007 species Species 0.000 description 2
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical class C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 description 1
- REGFWZVTTFGQOJ-UHFFFAOYSA-N 4,5-dihydro-1,3-thiazol-2-amine Chemical compound NC1=NCCS1 REGFWZVTTFGQOJ-UHFFFAOYSA-N 0.000 description 1
- ODOFVTXHRCTYBS-UHFFFAOYSA-N C/N=C(/NP(c1ccccc1)c1ccccc1)\SCCC#C Chemical compound C/N=C(/NP(c1ccccc1)c1ccccc1)\SCCC#C ODOFVTXHRCTYBS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HGKBLGIPFLBAJL-UHFFFAOYSA-N c(cc1)ccc1P(c1ccccc1)Nc1nc2ccccc2[nH]1 Chemical compound c(cc1)ccc1P(c1ccccc1)Nc1nc2ccccc2[nH]1 HGKBLGIPFLBAJL-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical class NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J31/2414—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 comprising aliphatic or saturated rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/54—Preparation of compounds having groups by reactions producing groups by addition of compounds to unsaturated carbon-to-carbon bonds
-
- 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
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon 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
- 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
- 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
- B01J2531/821—Ruthenium
-
- 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
- B01J2531/822—Rhodium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses application of the one kind containing aminophosphine ligand in olefin hydroformylation cascade reaction; it is alkene " hydroformylation acetalation " reaction, alkene " hydroformylation hydrogenation " reaction and alkene " hydroformylation reduction amination " reaction respectively including 3 class cascade reactions.Described possesses double function characteristic containing aminophosphine ligand, the existing Phosphine ligands group being coordinated with transition metal rhodium or ruthenium, there is the secondary amine (NH) or imines (C=N) with Bronsted acid effect again) nitrogen-containing group.It is this kind of that there is catalytic activity height containing aminophosphine ligand; long lifespan and the advantages of can be recycled; and 3 class olefin hydroformylation cascade reactions being catalyzed improve Atom economy; the generation of accessory substance can be reduced; separation and the purification step of intermediate product are avoided, so as to reach the synthesis technique of the simplification of green high-efficient.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, is connected more particularly to one kind containing aminophosphine ligand in olefin hydroformylation
Application in reaction.
Background technology
Hydroformylation of olefin is alkene and synthesis gas (CO and H2Mixed gas) in transition metal complex catalysts
The lower reaction generation of effect course of reaction of the aldehyde of carbon atom or alcohol more than former alkene, the aldehyde thus produced, alcohol and its derivative
Thing, plasticizer, surfactant, solvent and spices etc. are widely used as, and in most cases, product aldehyde is frequently not final
Product, more valuable fine chemicals is further converted to using the activity of aldehyde radical.Based on Atom economy and low
The principle of energy consumption, hydroformylation of olefin can be combined into cascade reaction one pot process with many organic reactions and go out target production
Product, wherein what is received much concern mainly has olefin hydroformylation-acetalation, olefin hydroformylation-reduction hydrogenation, alkene hydrogen formyl
Change-reduction amination cascade reaction, target product acetal, alkohol and amine can be directly obtained in " one pot " reaction, and can reduced
The generation of accessory substance, separation and the purification step of intermediate product are avoided, so as to reach the building-up process of the simplification of green high-efficient.
The research for having much three class olefin hydroformylation cascade reactions on more than at present is reported (Appl.Catal.A:
Gen.2006,303,213；Chem.Rev.1999,99,3329；Green Chem.2013,15,3236；
J.Am.Chem.Soc.2013,135,3989；Tetrahedron Lett.2013,54,5998；J.Am.Chem.Soc.2013,
135,17393；Angew.Chem.Int.Ed.2014,53,7320；J.Mol.Catal.A.2005,230,9；
Adv.Synth.Catal.2012,354,670), what document above disclosed is mainly with transition metal Rh or Ru compound and phosphine
The catalyst of part composition carries out single catalysis to olefin hydroformylation cascade reaction, finally only obtains acetal, alcohol or amine production
Product, and also without a kind of Phosphine ligands, the three class alkene cascade reactions to more than are equal with the catalyst that transition metal forms in the prior art
There is the report of catalytic action.
In view of the shortcomings of the prior art, being badly in need of a kind of three class cascade reactions to more than has the catalyst system and catalyzing of catalytic effect.
In view of the characteristics of olefin hydroformylation cascade reaction is the coupling of two chemical reaction processes, connects to catalyzed alkene hydroformylation
The part in catalyst system and catalyzing needed for reaction requires it to possess double function characteristic, could efficiently realize that olefin hydroformylation is connected
Reaction.This kind of Phosphine ligands disclosed by the invention have concurrently high activity and it is longer use mission, and be provided simultaneously with above-mentioned double function characteristic,
Wherein Phosphine ligands are combined in metal Rh or Ru by coordination and prepare aldehyde for the hydroformylation reaction of catalyzed alkene, therein
The imines salt ion that nitrogenous group (- NH or-C=N) combines to form with Bronsted acid, can be by back hydroformylation cascade reaction
Product aldehyde be successfully catalytically conveted to acetal (" olefin hydroformylation-acetalation " cascade reaction), alcohol (" olefin hydroformylation-
Hydrogenation " cascade reaction) or amine (" olefin hydroformylation-reduction amination " cascade reaction), and then realize that one pot process is high additional
It is worth the purpose of fine chemicals.
The content of the invention
It is such it is an object of the invention to provide application of the one kind containing aminophosphine ligand in olefin hydroformylation cascade reaction
Phosphine ligands possess double function characteristic, and wherein Phosphine ligands combine the hydrogen first for catalyzed alkene by coordination in metal Rh or Ru
Acylation reaction prepares aldehyde, and the imines that nitrogenous group (- NH or-C=N) therein combines to form with Bronsted acid can be by back hydrogen
Formylated cascade reaction product aldehyde is successfully catalytically conveted to acetal (alkene " hydroformylation-acetalation " cascade reaction), alcohol (alkene
Hydrocarbon " hydroformylation-hydrogenation " cascade reaction) or amine (alkene " hydroformylation-reduction amination " cascade reaction), and it is this kind of nitrogenous
Phosphine ligands and Rh or Ru compound groups into catalyst can be recycled in ion liquid solvent.
It is disclosed by the invention it is this kind of containing aminophosphine ligand both containing the Phosphine ligands that can be coordinated with transition metal rhodium or ruthenium, contain again
The nitrogen-containing group (secondary amine (- NH) or imines (- C=N)) that can be neutralized with Bronsted acid.Wherein described has such as containing aminophosphine ligand
Lower structural formula：
It is this kind of to form the present invention with transition metal Rh or Ru compound, Bronsted acid, reaction dissolvent and alkene containing aminophosphine ligand
The catalyst system and catalyzing of olefin hydroformylation cascade reaction, wherein the ratio used containing aminophosphine ligand, Rh or Ru compounds, Bronsted acid three
Example is 1:1:1~20:1:20 (mol ratios).
Olefin hydroformylation cascade reaction involved in the present invention is three class cascade reactions, be respectively alkene " hydroformylation-
Acetalation " cascade reaction, alkene " hydroformylation-hydrogenation " cascade reaction, alkene " hydroformylation-reduction amination " cascade reaction.
Reaction dissolvent involved by invention olefin hydroformylation cascade reaction system is that one kind by organic matter is medium
Solvent, have no particular limits, be organic solvent well known to those skilled in the art, specifically may be selected from methanol, ethanol, two
Chloromethanes, chloroform, carbon tetrachloride, tetrahydrofuran etc., preferred solvent are methanol.
Bronsted acid involved by invention olefin hydroformylation cascade reaction system is a kind of all molecules that can provide proton
Or ion, have no particular limits, preferably Bronsted acid is HBF4。
Alkene involved by invention olefin hydroformylation cascade reaction system is a kind of nytron containing C=C keys
Thing, its species is unrestricted, may be selected from C3-C12Linear alpha-olefin.Preferred alkenes are 1- propylene, 1- butylene and 1- octenes.
Transition metal Rh or Ru classes of compounds involved by invention olefin hydroformylation cascade reaction system does not limit
System, may be selected from Ru3(CO)12、RuCl3 3H2O or Rh (acac) (CO)2, acac represents acetylacetone,2,4-pentanedione.
Further, invention olefin hydroformylation cascade reaction system further relates to ion liquid solvent, for one kind all
By from molecular liquid, its species is unrestricted, may be selected from 1- normal-butyl -3- methyl imidazolium tetrafluoroborates ([Bmim]
BF4), 1- normal-butyl -3- methylimidazoles hexafluorophosphates ([Bmim] PF6), 1- normal-butyl -3- methylimidazole bis trifluoromethyl sulphurs
Acid imide ([Bmim] NTf2), 1- normal-butyl pyridinium tetrafluoroborates salt ([Bpy] BF4) or 1- normal-butyl pyridine hexafluorophosphates
([Bpy]PF6)。
It is disclosed by the invention this kind of to be prepared containing aminophosphine ligand by following scheme：In inert gas such as Ar gas or N2Gas
Under atmosphere, containing amino agents (- NH2) with Chlorodiphenylphosphine in organic solvent stirring at normal temperature can uniformly obtain it is of the invention in
Such contains aminophosphine ligand, wherein containing amino agents (- NH2) with the mol ratio of Chlorodiphenylphosphine it is 1:1.
Involved organic solvent is a kind of by the solvent that organic matter is medium in preparation process containing aminophosphine ligand, is not had
Special limitation, is organic solvent well known to those skilled in the art, specifically may be selected from methanol, ethanol, chloroform, dichloromethane
Alkane, carbon tetrachloride, tetrahydrofuran etc., preferred solvent are dichloromethane.
Above-mentioned preparation can be used for catalyzed alkene " hydroformylation-acetalation " cascade reaction containing aminophosphine ligand, generate acetal
Compound, the reaction condition that the catalytic process is recommended are as follows：
Alcohol, alkene, ruthenium compound, nitrogenous phosphine is sequentially added in the stainless steel autoclave of polytetrafluoroethyllining lining to match somebody with somebody
(mol ratio of alkene and rhodium compound is 200 for body and Bronsted acid:1~2000:1, the volume ratio of alcohol and alkene is 1:1~20:
1) CO and H, are filled with2Volume ratio is 1 synthesis gas, and in the case where 2.0~8.0MPa synthesizes atmospheric pressure, reaction temperature is room temperature~150
DEG C, after reacting 1~10 hour, room temperature is cooled to, organic phase is separated, ether extraction organic products, obtains olefin conversion as 98
~99% and acetal yield be 36~89%.
Above-mentioned preparation can be used for catalyzed alkene " hydroformylation-hydrogenation " cascade reaction containing aminophosphine ligand, generate alcohol compound
Thing, the reaction condition that the catalytic process is recommended are as follows：
Methanol solvate, alkene are sequentially added in the stainless steel autoclave of polytetrafluoroethyllining lining, ruthenium compound, is contained
(mol ratio of alkene and ruthenium compound is 50 for aminophosphine ligand and Bronsted acid:1~1000:1, the volume ratio of methanol and alkene is 1:1
~20:1) CO and H, are filled with2Volume ratio is 1 synthesis gas, and in the case where 2.0~8.0MPa synthesizes atmospheric pressure, reaction temperature is room temperature
~150 DEG C, after reacting 1~10 hour, room temperature is cooled to, organic phase is separated, ether extraction organic products, obtains olefin conversion
Rate for 97~99% and alcohol is 14~60%.
Above-mentioned preparation can be used for catalyzed alkene " hydroformylation-reduction amination " cascade reaction, generation two containing aminophosphine ligand
Level amines, the reaction condition that the catalytic process is recommended are as follows：
Sequentially added in the stainless steel autoclave of polytetrafluoroethyllining lining tetrahydrofuran solvent, alkene, one-level amine,
Rhodium compound, containing aminophosphine ligand and Bronsted acid, be filled with CO and H2Volume ratio is 1 synthesis gas, and air pressure is synthesized in 2.0~8.0MPa
Under power, reaction temperature is room temperature~150 DEG C, after reacting 1~10 hour, is cooled to room temperature, separates organic phase, entered with gas-chromatography
Row analysis, obtains that olefin conversion is 99% and the yield of secondary amine is 8~61%.Wherein：Mole of alkene and rhodium compound
Than for 200:1~2000:1；The volume ratio of tetrahydrofuran solvent and alkene is 1:1~10:1.
The present invention uses " one kettle way " acetal processed, alcohol or amine containing aminophosphine ligand in catalyzed alkene hydroformylation cascade reaction
During, have the following advantages that：
1st, Atom economy is improved, and reduces energy consumption of reaction.
2nd, the generation of accessory substance can be reduced, separation and the purification step of intermediate product are avoided, so as to reach green high-efficient
Simplification building-up process.
3rd, such has double function characteristic concurrently containing aminophosphine ligand, can be recycled in ionic liquid, and catalytic activity is high, the life-span
It is long.
4th, such wide adaptability containing aminophosphine ligand in olefin hydroformylation cascade reaction, to three class olefin hydroformylations
Cascade reaction is applicable.
Embodiment
The present invention does finer description with the following Examples.But these embodiments are only limitted to the explanation present invention, and
Any type of limitation is not formed to the present invention.The reaction reagent being related in embodiment is conventional commercially available prod.Embodiment
The middle device information that uses is as follows：
GC conditions：Shimadzu SHIMADZU-2014 gas chromatographs, DM-Wax capillary chromatographic columns (30m ×
0.25mm × 0.25 μm), column temperature：50 DEG C of holding 5min；10 DEG C/min rises to 200 DEG C, keeps 30min.
Nuclear magnetic resonance chemical analyser model：(the tests of Bruker Avance 40031During P H NMR spectroscopies, to be sealed in capillary
85% phosphoric acid be internal standard).
Embodiment 1：The synthesis of the L1 containing aminophosphine ligand
In N2Or under Ar gas shieldeds, anhydrous methylene chloride (45mL), aniline are sequentially added into 100mL three-necked flasks
(5mmol) and triethylamine (15mmol).After stirring, the anhydrous of Chlorodiphenylphosphine (5mmol) is slowly added dropwise at room temperature
Dichloromethane solution (20mL).There are a large amount of white precipitates to generate.Continue to stir 24h at room temperature.After TLC shows reaction completely,
It is evaporated under reduced pressure and removes solvent and excessive triethylamine, then adds tetrahydrofuran (100mL) and be sufficiently stirred, make the salt of triethylamine
Hydrochlorate separates out completely.Filter 2 times, and washed with tetrahydrofuran.Merging filtrate, it is evaporated under reduced pressure after removing tetrahydrofuran, adds nothing
Water dichloromethane (50mL), crude product is dissolved, then filtered with 3cm neutral aluminas aluminium lamination, and washed with dichloromethane (50mL)
Neutral alumina aluminium lamination.Merging filtrate, it is evaporated under reduced pressure and removes dichloromethane, is then crystallized with dichloromethane and absolute ether, vacuum
Dry, it is ligand L 1 to obtain white solid, yield 85%.Nuclear-magnetism characterize data：1H NMR(δ,ppm,CDCl3):8.25(d,1H,
), J=12.0Hz 7.80-7.77 (m, 4H), 7.56-7.50 (m, 6H), 7.10-7.04 (m, 4H), 6.79 (t, 1H, J=
8.0Hz)；31P NMR(δ,ppm,CDCl3):18.69(s)。
Embodiment 2：The synthesis of the L2 containing aminophosphine ligand
L2 synthetic method is identical with L1 synthetic method, and initiation material is replaced by benzene methanamine.It is white solid to obtain L2,
Yield 80%.Nuclear-magnetism table data：1H NMR(δ,ppm,CDCl3):7.80 (s, 1H), 7.36-7.26 (m, 10H), 7.10-7.07
(m,3H),6.76-6.74(m,2H),2.01-1.96(m,2H)；31P NMR(δ,ppm,CDCl3):17.21(s)。
Embodiment 3：The synthesis of the L3 containing aminophosphine ligand
L3 synthetic method is identical with L1 synthetic method, and initiation material is replaced by phenyl ethylamine.It is white solid to obtain L3,
Yield 91%.Nuclear-magnetism characterize data：1H NMR(δ,ppm,CDCl3):7.68(s,1H),7.59-7.54(6H,m),7.52-7.47
(4H,m),7.09-7.08(3H,m),6.37-6.35(2H,m),3.48-3.40(2H,m),2.01-1.96(2H,m)；31P NMR
(δ,ppm,CDCl3):25.43(s)。
Embodiment 4：The synthesis of the L4 containing aminophosphine ligand
L4 synthetic method is identical with L1 synthetic method, and initiation material is replaced by PA.L4 is obtained as white
Solid, yield 42%.Nuclear-magnetism characterize data：1H NMR(δ,ppm,CDCl3):7.97 (d, 1H, J=9.0Hz), 7.45-7.43
(m,3H),7.34-7.30(m,8H),7.04-7.02(m,2H),6.66-6.64(m,1H)；31P NMR(δ,ppm,CDCl3):
35.23(s)。
Embodiment 5：The synthesis of the L5 containing aminophosphine ligand
L5 synthetic method is identical with L1 synthetic method, and initiation material is replaced by thiazolamine.L5 is obtained as white
Solid, yield 89%.Nuclear-magnetism characterize data：1H NMR(δ,ppm,CDCl3):8.97 (d, 1H, J=4.0Hz), 7.49-7.39
(m, 4H), 7.41-7.39 (m, 6H), 7.11 (t, 1H, J=4.0Hz), 6.82 (d, 1H, J=4.0Hz)；31P NMR(δ,ppm,
CDCl3):41.14(s)。
Embodiment 6：The synthesis of the L6 containing aminophosphine ligand
L6 synthetic method is identical with L1 synthetic method, and initiation material is replaced by 2-Aminothiazoline.It is white to obtain L6
Color solid, yield 71%.Nuclear-magnetism characterize data：1H NMR(δ,ppm,CDCl3):7.85-7.80(m,4H),7.44-7.39(m,
6H), 3.74 (t, 2H, J=8.0Hz), 3.28 (t, 2H, J=8.0Hz)；31P NMR(δ,ppm,CDCl3):25.26(s)。
Embodiment 7：The synthesis of the L7 containing aminophosphine ligand
L7 synthetic method is identical with L1 synthetic method, and initiation material is replaced by 2- aminobenzimidazoles.Obtaining L7 is
White solid, yield 52%.Nuclear-magnetism characterize data：1H NMR(δ,ppm,CDCl3):8.43 (d, 1H, J=5.4Hz), 7.79-
7.75 (m, 4H), 7.65-7.63 (m, 6H), 7.51 (dd, 2H, J=7.8Hz), 7.35 (dd, 2H, J=6.9Hz), 6.50 (d,
1H, J=3.9Hz),31P NMR(δ,ppm,CDCl3):33.41(s)。
Embodiment 8：The synthesis of the L8 containing aminophosphine ligand
L8 synthetic method is identical with L1 synthetic method, and initiation material is 2- (1H- benzimidazolyl-2 radicals-yl) aniline.
The L8 arrived is white solid, yield 41%.Nuclear-magnetism characterize data：1H NMR(δ,ppm,CDCl3):8.03 (d, 1H, J=
7.6Hz), 7.74-7.69 (m, 4H), 7.21-7.19 (m, 6H), 6.86-7.27 (dd, 2H, J=7.6Hz), 6.84 (dd, 2H, J
=4.8Hz), 6.69 (d, 1H, J=6.5Hz), 6.59-6.619 (m, 4H)；31P NMR(δ,ppm,CDCl3):29.53(s)。
Embodiment 9：The synthesis of the L9 containing aminophosphine ligand
In N2Or under Ar gas shieldeds, anhydrous methylene chloride (45mL), 2- amino thiophenes are sequentially added into 100mL three-necked flasks
Oxazoline (5mmol) and triethylamine (15mmol).After stirring, Chlorodiphenylphosphine (22mmol) is slowly added dropwise at room temperature.
There are a large amount of white precipitates to generate.Continue to stir 48h at room temperature, after TLC shows reaction completely, be evaporated under reduced pressure and remove solvent and mistake
The triethylamine of amount, then add tetrahydrofuran (100mL) and be sufficiently stirred, so that the hydrochloride of triethylamine separates out completely.Filter 2
It is secondary, and washed with tetrahydrofuran.Merging filtrate, it is evaporated under reduced pressure after removing tetrahydrofuran, adds absolute methanol (50mL), dissolving is thick
Product, then absolute ether crystallize, vacuum drying, it is ligand L 9 to obtain white solid, yield 9%.Nuclear-magnetism characterize data：1H
NMR(δ,ppm,CDCl3):7.86-7.27(m,20H),3.89-3.81(m,2H),3.49-3.42(m,2H)；31P NMR(δ,
ppm,CDCl3):33.54(s),21.82(s)。
Embodiment 10~18：L1~L9 and Ru3(CO)12The catalyst 1- octenes " hydroformylation-acetalation " of composition
Cascade reaction
1- octenes (10mmol), Ru are sequentially added in the stainless steel autoclave for having polytetrafluoroethyllining lining3(CO)12
(1mmol), 0.2mmol are containing aminophosphine ligand (L1~L9), HBF4(0.2mmol) and methanol (3mL), is filled with CO and H2Volume ratio is 1
Synthesis gas to 4.0MPa, reacted 20 hours at 120 DEG C after sealing.After reaction terminates, room temperature is cooled to, pressure release, takes upper strata to have
Machine phase, is analyzed with gas-chromatography, it is determined that the yield to product acetal.Table 1 is provided using difference L1 containing aminophosphine ligand~L9
And Ru3(CO)12Catalyst 1- octenes " hydroformylation-acetalation " cascade reaction of composition prepares the experimental result of acetal.
Table 1：L1 containing aminophosphine ligand~L9 and Ru3(CO)12The catalyst of composition is gone here and there to 1- octenes " hydroformylation-acetalation "
Connection reaction prepares the catalytic reaction result of acetala
a Ru3(CO)121mol% (0.1mmol), 0.2mmol containing aminophosphine ligand, 1- octenes 10.0mmol, HBF4
0.2mmol, methanol 3mL, CO/H2(1:1) 4.0MPa, 120 DEG C, 20 hours.
bGas chromatographic analysis.
Embodiment 19~24：Ligand L 6 and Ru in different ionic liquid at room temperature solvents3(CO)12The catalyst 1- of composition
Octene " hydroformylation-acetalation " cascade reaction
1- octenes (10mmol), Ru are sequentially added in the stainless steel autoclave for having polytetrafluoroethyllining lining3(CO)12
(1mmol), L6 containing aminophosphine ligand (0.2mmol), HBF4(0.2mmol), ionic liquid at room temperature (3mL) and methanol (3mL), are filled with
CO and H2The synthesis gas that volume ratio is 1 reacts 20 hours to 4.0MPa after sealing at 120 DEG C.After reaction terminates, room is cooled to
Temperature, pressure release, upper organic phase is taken, analyzed with gas-chromatography, it is determined that the yield to product acetal.Table 2 provides different room temperatures
Ligand L 6 and Ru in ion liquid solvent3(CO)121- octenes " hydroformylation-acetalation " series connection of the catalyst of composition is anti-
The experimental result of acetal should be prepared.
Table 2：Ligand L 6 and Ru in different ionic liquid at room temperature solvents3(CO)12The catalyst of composition is to 1- octenes " hydrogen formyl
Change-acetalation " cascade reaction prepares the catalytic reaction result of acetala
a Ru3(CO)121.0mol% (1mmol), L6 0.2mmol, 1- octene 10.0mmol, HBF40.2mmol, methanol
3mL, ionic liquid at room temperature 3mL, CO/H2(1:1) 4.0MPa, 120 DEG C, 20 hours.
bGas chromatographic analysis.
Embodiment 24~28：L6 and Ru3(CO)12The catalyst of composition is in [Bmim] PF6In 1- octenes " hydroformylation-
Cycle applications in acetalation " cascade reaction
1- octenes (10mmol), Ru are sequentially added in the stainless steel autoclave for having polytetrafluoroethyllining lining3(CO)12
(1mmol), L6 containing aminophosphine ligand (0.2mmol), HBF4(0.2mmol)、[Bmim]PF6(3mL) and methanol (3mL), be filled with CO and
H2The synthesis gas that volume ratio is 1 reacts 20 hours to 4.0MPa after sealing at 120 DEG C.After reaction terminates, room temperature is cooled to, is let out
Pressure takes upper organic phase, is analyzed with gas-chromatography, it is determined that the yield to product acetal.Table 3 provide L6 containing aminophosphine ligand and
Ru3(CO)12The catalyst of composition is in [Bmim] PF61- octenes " hydroformylation-acetalation " cascade reaction follows in ionic liquid
Ring uses result.Catalyst recycles 5 times and still keeps certain activity and stability, but catalyst also has stream in organic phase
Lose.
Table 3：L6 and Ru3(CO)12The catalyst of composition is in [Bmim] PF6In 1- octenes " hydroformylation-acetalation " string
Connection reaction cycle uses resulta
a Ru3(CO)121.0mol% (0.1mmol), L6 0.2mmol, 1- octene 10.0mmol, HBF40.2mmol, first
Alcohol 3mL, [Bmim] PF63mL, CO/H2(1:1) 4.0MPa, 120 DEG C, 20 hours.
bGas chromatographic analysis.
Embodiment 29~33：L6 and Ru3(CO)12" hydroformylation-acetalation " of the catalyst of composition to different alpha-olefins
The catalytic reaction of cascade reaction
Alpha-olefin (10mmol), Ru are sequentially added in the stainless steel autoclave for having polytetrafluoroethyllining lining3(CO)12
(1mmol), L6 containing aminophosphine ligand (0.2mmol), HBF4(0.2mmol) and methanol (3mL), is filled with CO and H2Volume ratio is 1 conjunction
Into gas to 4.0MPa, reacted 20 hours at 120 DEG C after sealing.After reaction terminates, room temperature is cooled to, pressure release, is extracted reaction solution, uses gas
Phase chromatogram is analyzed, it is determined that the yield to product acetal.Table 4 provides L6 and Ru3(CO)12The catalyst of composition is to different α-alkene
" hydroformylation-acetalation " cascade reaction catalytic reaction result of hydrocarbon.
Table 4：Ligand L 6 and Ru3(CO)12The catalyst of composition is connected anti-to " hydroformylation-acetalation " of different alpha-olefins
Answer catalytic reaction resulta
a Ru3(CO)121.0mol% (1mmol), L6 0.2mmol, alpha-olefin 10.0mmol, HBF4 0.2mmol, first
Alcohol 3mL, CO/H2(1:1) 4.0MPa, 120 DEG C, 20 hours.
bGas chromatographic analysis.
Embodiment 34~38：L1~L9 and RuCl3·3H2The catalyst 1- octenes " hydroformylation-hydrogenation " of O compositions
Cascade reaction
1- octenes (10mmol), RuCl are sequentially added in the stainless steel autoclave for having polytetrafluoroethyllining lining3·
3H2O (1mmol), 0.2mmol are containing aminophosphine ligand (L1~L9), HBF4(0.2mmol) and methanol (3mL), is filled with CO and H2Volume
Than the synthesis gas for 1 to 4.0MPa, reacted 20 hours at 120 DEG C after sealing.After reaction terminates, room temperature is cooled to, pressure release, is taken
Layer organic phase, is analyzed with gas-chromatography, it is determined that the yield to product alcohol.Table 5 provide using difference L1 containing aminophosphine ligand~
L9 and RuCl3·3H21- octenes " hydroformylation-hydrogenation " cascade reaction of the catalyst of O compositions prepares the experiment knot of alcohol
Fruit.
Table 5：L5 containing aminophosphine ligand~L9 and RuCl3·3H2The catalyst of O compositions is gone here and there to 1- octenes " hydroformylation-hydrogenation "
Connection reaction prepares the catalytic reaction result of alcohola
a RuCl3·3H2O 1mol% (1mmol), 0.2mmol containing aminophosphine ligand, 1- octenes 10.0mmol, HBF4
0.2mmol, methanol 3mL, CO/H2(1:1) 4.0MPa, 120 DEG C, 20 hours.
bGas chromatographic analysis.
Embodiment 39~44：L1~L9 and Rh (acac) (CO)2The catalyst 1- octenes " hydroformylation-go back of composition
Former amination " cascade reaction
1- octenes (10mmol), Rh (acac) are sequentially added in the stainless steel autoclave for having polytetrafluoroethyllining lining
(CO)2(0.1mmol), 0.1mmol are containing aminophosphine ligand (L1~L9), HBF4(0.1mmol), aniline (10mmol) and tetrahydrofuran
(3mL), is filled with CO and H2The synthesis gas that volume ratio is 1 reacts 20 hours to 4.0MPa after sealing at 120 DEG C.After reaction terminates,
Room temperature is cooled to, pressure release, takes upper organic phase, is analyzed with gas-chromatography, it is determined that the yield to product secondary amine.Table 6 is given
Go out to use difference L1 containing aminophosphine ligand~L9 and Rh (acac) (CO)21- octenes " the hydroformylation-go back of the catalyst of composition
Former amination " cascade reaction prepares the experimental result of secondary amine.
Table 6：L1 containing aminophosphine ligand~L9 and Rh (acac) (CO)2The catalyst of composition is to 1- octenes " hydroformylation-reduction
Amination " cascade reaction prepares the catalytic reaction result of secondary aminea
a Rh(acac)(CO)20.1mol% (0.1mmol), 0.1mmol containing aminophosphine ligand, 1- octene 10.0mmol, benzene
Amine 10.0mmol, HBF40.1mmol, tetrahydrofuran 3mL, CO/H2(1:1) 4.0MPa, 120 DEG C, 20 hours.
bGas chromatographic analysis.
Claims (9)
1. a kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction, it is characterised in that：It is described to contain aminophosphine ligand
The existing Phosphine ligands group being coordinated with transition metal rhodium or ruthenium, again containing the secondary amine (- NH) or imines that can be neutralized with Bronsted acid
(- C=N) nitrogen-containing group, its structural formula are as follows：
2. a kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction as claimed in claim 1, its feature exist
In：The olefin hydroformylation cascade reaction includes alkene " hydroformylation-acetalation " reaction, alkene " hydroformylation-hydrogenation "
Reaction, alkene " hydroformylation-reduction amination " reaction.
3. a kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction as claimed in claim 2, its feature exist
In：Alkene " hydroformylation-acetalation " reaction is with alkene and synthesis gas (CO and H2) it is substrate, synthesis gas volume ratio is 1:
1, pressure is 2.0~8.0MPa, and with Ru3(CO)12For catalyst, L1~L9 is containing aminophosphine ligand, in reaction dissolvent and proton
In the presence of acid, controlling reaction temperature is room temperature~150 DEG C, 1~10 hour reaction time.
4. a kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction as claimed in claim 2, its feature exist
In：Alkene " hydroformylation-hydrogenation " reaction is with alkene and synthesis gas (CO and H2) it is substrate, synthesis gas volume ratio is 1:1,
Pressure is 2.0~8.0MPa, and with RuCl3.3H2O is catalyst, and L1~L9 is containing aminophosphine ligand, in reaction dissolvent and Bronsted acid
In the presence of, controlling reaction temperature is room temperature~150 DEG C, 1~10 hour reaction time.
5. a kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction as claimed in claim 2, its feature exist
In：Alkene " hydroformylation-reduction amination " reaction is with alkene and synthesis gas (CO and H2) it is substrate, synthesis gas volume ratio is
1:1, pressure is 2.0~8.0MPa, and with Rh (acac) (CO)2For catalyst, L1~L9 is containing aminophosphine ligand, in reaction dissolvent
In the presence of Bronsted acid, controlling reaction temperature is room temperature~150 DEG C, 1~10 hour reaction time.
6. a kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction as described in any one of claim 2~5,
It is characterized in that：Described reaction dissolvent still further comprises ion solvent.
7. a kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction as claimed in claim 6, its feature exist
In：Described ion solvent is selected from 1- normal-butyl -3- methyl imidazolium tetrafluoroborates ([Bmim] BF4), 1- normal-butyl -3- methyl
Limidazolium hexafluorophosphate ([Bmim] PF6), 1- normal-butyl -3- methylimidazole bis trifluoromethyls sulfimides ([Bmim] NTf2)、1-
Normal-butyl pyridinium tetrafluoroborate salt ([Bpy] BF4), 1- normal-butyl pyridines hexafluorophosphate ([Bpy] PF6) or 1- normal-butyl pyridines
Bis trifluoromethyl sulfimide ([Bpy] NTf2)。
8. a kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction as claimed in claim 7, its feature exist
In：Alkene in the reaction is selected from C3~C12Linear alpha-olefin.
9. a kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction as claimed in claim 8, its feature exist
In：The alkene is selected from 1- propylene, 1- butylene, 1- hexenes, 1- octenes, 1- decene and 1- laurylenes.
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| CN109453816A (en) * | 2018-12-12 | 2019-03-12 | 四川大学 | A kind of catalyst and its preparation method and application for hydroformylation of olefin |
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| CN109453816A (en) * | 2018-12-12 | 2019-03-12 | 四川大学 | A kind of catalyst and its preparation method and application for hydroformylation of olefin |
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