CN112442087A - 一种离子型亚膦酰胺类配体的制备方法及其应用 - Google Patents
一种离子型亚膦酰胺类配体的制备方法及其应用 Download PDFInfo
- Publication number
- CN112442087A CN112442087A CN202011342977.3A CN202011342977A CN112442087A CN 112442087 A CN112442087 A CN 112442087A CN 202011342977 A CN202011342977 A CN 202011342977A CN 112442087 A CN112442087 A CN 112442087A
- Authority
- CN
- China
- Prior art keywords
- phosphoramidite
- reaction
- ionic
- solvent
- ligand
- 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.)
- Pending
Links
- 150000008300 phosphoramidites Chemical class 0.000 title claims abstract description 82
- 239000003446 ligand Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000047 product Substances 0.000 claims abstract description 38
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 239000000706 filtrate Substances 0.000 claims abstract description 17
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000005576 amination reaction Methods 0.000 claims abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- 239000010948 rhodium Substances 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- -1 methanesulfonic acid ester Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000008053 sultones Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- VFLQQZCRHPIGJU-UHFFFAOYSA-N 1-(2-chloroethyl)piperidine;hydron;chloride Chemical compound Cl.ClCCN1CCCCC1 VFLQQZCRHPIGJU-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019603 Rh2O3 Inorganic materials 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 claims description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical group [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000005673 monoalkenes Chemical class 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 238000005956 quaternization reaction Methods 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- CCCUVHHPYBWVOW-UHFFFAOYSA-K [Na+].[Na+].[Na+].[O-]S(=O)(=O)c1ccccc1.[O-]S(=O)(=O)c1ccccc1.[O-]S(=O)(=O)c1ccccc1 Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)c1ccccc1.[O-]S(=O)(=O)c1ccccc1.[O-]S(=O)(=O)c1ccccc1 CCCUVHHPYBWVOW-UHFFFAOYSA-K 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 231100000925 very toxic Toxicity 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
-
- 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
- B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
- B01J31/187—Amide 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
- B01J31/18—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
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
- B01J31/188—Amide 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
- B01J31/20—Carbonyls
-
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
-
- 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
-
- 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
- B01J2531/822—Rhodium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域
本发明涉及一种离子型亚膦酰胺类配体的制备方法和应用,该催化剂合成过程简单,物理化学性质独特,在氢甲酰化等反应中具有较高的工业应用前景,属于金属有机及均相催化技术领域。
背景技术
氢甲酰化反应又称oxo反应,是在催化剂作用下,烯烃与合成气(CO+H2)生成醛或醇的催化反应过程。每年通过氢甲酰化反应生产的醛类和醇类化合物产量已超过1000万吨。
早期氢甲酰化反应以Co金属络合物为催化剂,但是反应条件苛刻,产物选择性差,此外Co络合物毒性很大(Angew.Chem.Int.Ed.,1994,33,2144)。随着研究的深入,人们发现Rh金属络合物的催化活性远远高于Co金属络合物,因此Rh金属络合物逐渐成为氢甲酰化反应的主要催化剂。
配体是影响过渡金属催化剂催化活性的一个重要因素,而膦配体因其结构多样性和独特的效果,成为目前为止研究最多,应用最广泛的配体。按照与P相连的原子不同,膦配体又可以分为有机膦配体(P与三个碳原子相连),亚磷酸酯配体(P与一个或多个O原子相连),亚膦酰胺类配体(P与一个或多个N原子相连)三类。亚膦酰胺类配体合成简单,容易修饰,效果独特,相对于叔膦配体和亚磷酸酯类配体,亚膦酰胺是更强的π电子受体,这一特性有利于CO从催化剂上分离,对氢甲酰化的反应速率有利,然而关于亚膦酰胺类配体的研究目前较少。专利CN106000470A设计合成了联萘酚骨架的亚膦酰胺类配体,并用其催化烯烃的氢甲酰化反应,有较高的转化率,但该方法所需配体用量较大,需要达到铑摩尔数的100倍。专利CN102746338A设计合成了螺缩酮骨架的双齿亚膦酰胺类配体,并应用于烯烃的氢甲酰化反应中,具有较好的催化活性,然而配体合成原料成本较高,不利于其工业化应用。
此外,水溶性配体的设计使用可以实现水油两相的氢甲酰化反应,提高催化剂的分离回收效率。该类配体的一大突破是磺化芳基膦TPPTS(3,3’,3”-亚膦基三(苯磺酸)的三钠盐),然而该类配体的制备过程复杂,反应条件苛刻且需要严格地排除氧的存在,因此以简洁高效的方法开发新型的水溶性配体有利于推动氢甲酰化反应的进一步发展,具有良好的工业应用前景。
尽管亚膦酰胺类配体已有报道,但大部分工作集中于以吡咯,吲哚等作为修饰基团,以咪唑为基团的亚膦酰胺类配体的合成方法还有待设计与优化。此外,咪唑基团可以进行季胺化修饰从而改变配体的电子效应,水溶性等特性,从而调控过渡金属催化剂的催化效果,并有潜力实现水油两相氢甲酰化反应。
相对于亚磷酸酯类配体的合成应用来说,亚膦酰胺类配体的研究相对有限,而水溶性亚膦酰胺类配体更是鲜有报道。
发明内容
本发明所要解决的技术问题是:提供一系列咪唑基团修饰的离子型亚膦酰胺类配体,以及如何高效合成它们的方法,并将其应用在氢甲酰化反应中。
为了解决上述技术问题,本发明提供了一种离子型亚膦酰胺类配体,其特征在于,结构通式为:
上式中,R1、R2独立地为氢、C1-C 6烷基或C1-C 6烷氧基,R3独立地为C1-C18烷基或磺酸内酯基。
本发明还提供了上述制备方法,其特征在于,包括以下步骤:
步骤1):将三氯化磷与咪唑溶于溶剂中,搅拌反应后过滤,将取代联苯酚溶于溶剂滴加入上述滤液中反应,得到的产物经纯化后得单齿亚膦酰胺;
步骤2):将单齿亚膦酰胺与季胺化试剂在溶剂中反应,得到的产物经纯化后得式Ⅰ所示的离子型单齿亚膦酰胺类配体;
步骤3):将三氯化磷与咪唑溶于溶剂中,于碱性条件下搅拌反应后过滤,将取代联苯酚溶于溶剂滴加入上述滤液中反应,得到的产物经纯化后得双齿亚膦酰胺。
步骤4):将双齿亚膦酰胺与季胺化试剂在溶剂中反应,得到的产物经纯化后得式Ⅱ所示的离子型双齿亚膦酰胺类配体。
上述步骤1)、2)的原理如下:
上述步骤3)、4)的原理如下:
优选地,所述溶剂为二氯甲烷、四氢呋喃、氯仿、甲苯、二甲亚砜、乙腈和去离子水中的至少一种;所述纯化的方式可以采用本领域内常规使用的各种后处理方法对所得到的产物进行后处理。所述后处理的方法包括但不限于:萃取,重结晶,洗涤,干燥,过滤等。
优选地,所述步骤2)、4)中,季胺化试剂为卤代烃、甲磺酸酯类衍生物和磺酸内酯衍生物中的至少一种;反应的温度为25-150℃,时间为0.5-48h,优选为24h。
更优选地,所述季胺化试剂为氯代正丁烷、氯乙基哌啶盐酸盐、三氟甲磺酸甲酯和1,3-丙磺酸内酯中的至少一种。
优选地,所述步骤1)中三氯化磷与咪唑的摩尔比为1:6-1:10,优选为1:7;所述步骤3)中三氯化磷与咪唑的摩尔比为1:2;碱性条件采用的碱为有机碱或无机碱;三氯化磷与碱的摩尔比为1:2-1:6,优选为1:3。
优选地,其特征在于,所述碱性条件采用的碱为三乙胺、吡啶、4-二甲氨基吡啶、二异丙基乙基胺和碳酸钾中的至少一种,优选为三乙胺和4-二甲氨基吡啶中的任意一种或两种。
优选地,所述步骤1)、3)中反应的温度为0-100℃,优选为25℃,时间为0.5-24h,优选为1h。
本发明还提供了上述离子型亚膦酰胺类配体在氢甲酰化反应中的应用,其特征在于,将铑催化前体、所述离子型亚膦酰胺类配体与有机溶剂加入到反应釜中,并加入烯烃,然后充入气体,将反应釜加热反应。
优选地,所述的铑催化前体为乙酰丙酮二羰基铑、乙酰丙酮三苯基膦羰基铑、三苯基膦氢化铑、Rh(OAc)3、Rh2O3、Rh4(CO)12和Rh6(CO)16中的至少一种;所述的有机溶剂为苯、甲苯、二甲苯、戊醛、二甲亚砜、二氯甲烷、二氯乙烷、乙腈、己烷、乙酸乙酯、二氧六环、四氢呋喃、甲醇、乙醇、正丙醇、异丙醇和正丁醇中的至少一种;所述的烯烃为C2-C18的单烯烃,优选为丙烯、丁烯、辛烯、苯乙烯;所述铑催化前体与离子型亚膦酰胺类配体的摩尔比为1:1-1:50,优选为铑催化前体与单齿亚磷酰胺配体的摩尔比为1:10,铑催化前体与双齿亚磷酰胺配体的摩尔比为1:5;所述铑催化前体与烯烃的摩尔比为1:100-1:10000;所述有机溶剂与烯烃的体积比为1:1-20:1;所述气体为CO与H2以摩尔比1:1混合的混合气,反应釜充入气体后的压力为2-8MPa,优选为3-5MPa。
优选地,所述加热反应的温度为80-180℃,优选为90-120℃,时间为0.5-10h,优选为2h。
通过本发明提供的方法,可以方便的合成一系列中性亚膦酰胺类配体,并通过季胺化方法高效合成一系列具有不同物理化学性质的离子型亚膦酰胺类配体。
与现有技术相比,本发明具有如下优点:
(1)本发明提供的新型离子型亚膦酰胺类配体,其具有高π受电子能力,对氢甲酰化的反应速率有利;
(2)本发明通过简单的季胺化反应,可以改变所得亚膦酰胺类配体的水溶性和油溶性等特性,实现水溶性亚膦酰胺类配体的高效制备与功能化修饰,在氢甲酰化反应中有良好的应用前景。
具体实施方式
为使本发明更明显易懂,兹以优选实施例,作详细说明如下。
实施例1
结构式为A的离子型单齿亚膦酰胺的制备方法及其在丁烯氢甲酰化反应中的应用:
将咪唑2.04g于氮气保护下溶于超干二氯甲烷50mL,冰浴下滴加三氯化磷0.43mL,反应30min后过滤,滤液用氮气保护。将联苯酚0.93g溶于10mL超干二氯甲烷中,将该溶液滴加入上述滤液中,室温反应1h后,过滤,旋干溶剂,所得产物通过柱层析纯化,洗脱剂为乙酸乙酯:正己烷=1:10,得到单齿亚膦酰胺产物。在氮气保护下,将得到的单齿亚磷酰胺1.41g溶于甲苯20mL中,加入氯代正丁烷0.52mL,升温至110℃回流12h,冷却后析出晶体,迅速抽滤并用***洗涤晶体,将所得晶体溶于去离子水中,并加入NaBF4 0.55g室温搅拌24h。反应结束后旋蒸除去水,用二氯甲烷萃取产物,无水硫酸钠干燥后,旋干即得离子型亚膦酰胺产物A,产率85%。
将0.02mmol的Rh(acac)(CO)2,0.2mmol的亚膦酰胺类配体A,加入到100mL的反应釜中,加入40mL甲苯溶剂,随后使用合成气置换三次,加入正丁烯20mmol(1.72g),冲入合成气至4MPa,在120℃条件下进行反应。4h后反应结束,将反应釜进行冷却,用甲苯洗出反应液,加入内标物并进行气相色谱分析,得到正丁烯转化率35%,醛类选择性为91%,正异比为4.5。
实施例2
结构式为B的离子型单齿亚膦酰胺的制备方法及其在丁烯氢甲酰化反应中的应用:
将咪唑2.04g于氮气保护下溶于超干二氯甲烷50mL,冰浴下滴加三氯化磷0.43mL,反应30min后过滤,滤液用氮气保护。将联苯酚0.93g溶于10mL超干二氯甲烷中,将该溶液滴加入上述滤液中,室温反应1h后,过滤,旋干溶剂,所得产物通过柱层析纯化,洗脱剂为乙酸乙酯:正己烷=1:10,得到单齿亚膦酰胺产物。在氮气保护下,将得到的单齿亚磷酰胺1.41g溶于甲苯20mL中,加入1,3-丙磺酸内酯0.61g,升温至110℃回流12h,冷却后析出晶体,迅速抽滤并用***洗涤晶体,干燥即得离子型亚膦酰胺产物B,产率79%。
将0.02mmol的Rh(acac)(CO)2,0.2mmol的亚膦酰胺类配体B,加入到100mL的反应釜中,加入40mL甲苯溶剂,随后使用合成气置换三次,加入正丁烯20mmol(1.72g),冲入合成气至4MPa,在120℃条件下进行反应。4h后反应结束,将反应釜进行冷却,用甲苯洗出反应液,加入内标物并进行气相色谱分析,得到正丁烯转化率70%,醛类选择性为94%,正异比为5.4。
实施例3
结构式为C的离子型单齿亚膦酰胺的制备方法及其在丁烯氢甲酰化反应中的应用:
将咪唑2.04g于氮气保护下溶于超干二氯甲烷50mL,冰浴下滴加三氯化磷0.43mL,反应30min后过滤,滤液用氮气保护。将3,3’-5,5’-四叔丁基-2,2’-联苯酚2.05g溶于10mL超干二氯甲烷中,将该溶液滴加入上述滤液中,室温反应1h后,过滤,旋干溶剂,所得产物通过柱层析纯化,洗脱剂为乙酸乙酯:正己烷=1:10,得到单齿亚膦酰胺产物。在氮气保护下,将得到的单齿亚磷酰胺2.53g溶于甲苯20mL中,加入1,3-丙磺酸内酯0.61g,升温至110℃回流12h,冷却后析出晶体,迅速抽滤并用***洗涤晶体,干燥即得离子型亚膦酰胺产物C,产率75%。
将0.02mmol的Rh(acac)(CO)2,0.1mmol的亚膦酰胺类配体C,加入到100mL的反应釜中,加入40mL甲苯溶剂,随后使用合成气置换三次,加入正丁烯20mmol(1.72g),冲入合成气至4MPa,在120℃条件下进行反应。4h后反应结束,将反应釜进行冷却,用甲苯洗出反应液,加入内标物并进行气相色谱分析,得到正丁烯转化率80%,醛类选择性为94%,正异比为6。
实施例4
结构式为D的双齿亚膦酰胺的制备方法及其在丁烯氢甲酰化反应中的应用
将咪唑2.04g与三乙胺1.39mL于氮气保护下溶于超干二氯甲烷50mL,冰浴下滴加三氯化磷1.29mL,反应30min后过滤,滤液用氮气保护。将联苯酚0.93g溶于10mL超干二氯甲烷中,将该溶液滴加入上述滤液中,室温反应1h后,过滤,旋干溶剂,所得产物通过柱层析纯化,洗脱剂为乙酸乙酯:正己烷=1:6,得到双齿亚膦酰胺产物。将所得双齿亚膦酰胺2.57g溶于甲苯40mL中,加入氯代正丁烷0.52mL,升温至110℃回流12h,冷却后析出晶体,迅速抽滤并用***洗涤晶体,将所得晶体溶于去离子水中,并加入NaBF4 2.20g室温搅拌24h。反应结束后旋蒸除去水,用二氯甲烷萃取产物,无水硫酸钠干燥后,旋干即得离子型亚膦酰胺产物D,产率74%。
将0.02mmol的Rh(acac)(CO)2,0.1mmol的亚膦酰胺类配体D,加入到100mL的反应釜中,加入40mL甲苯溶剂,随后使用合成气置换三次,加入正丁烯20mmol,冲入合成气至4MPa,在120℃条件下进行反应。4h后反应结束,将反应釜进行冷却,用甲苯洗出反应液,加入内标物并进行气相色谱分析,得到正丁烯转化率90%,醛类选择性为97%,正异比为11。
实施例5
结构式为E的离子型双齿亚膦酰胺的制备方法及其在丁烯氢甲酰化反应中的应用:
将咪唑2.04g与三乙胺1.39mL于氮气保护下溶于超干二氯甲烷50mL,冰浴下滴加三氯化磷1.29mL,反应30min后过滤,滤液用氮气保护。将联苯酚0.93g溶于10mL超干二氯甲烷中,将该溶液滴加入上述滤液中,室温反应1h后,过滤,旋干溶剂,所得产物通过柱层析纯化,洗脱剂为乙酸乙酯:正己烷=1:6,得到双齿亚膦酰胺产物。将所得双齿亚膦酰胺2.57g溶于甲苯40mL中,1,3-丙磺酸内酯0.61g,升温至110℃回流12h,冷却后析出晶体,迅速抽滤并用***洗涤晶体,干燥即得离子型亚膦酰胺产物E,产率70%。
将0.02mmol的Rh(acac)(CO)2,0.1mmol的亚膦酰胺类配体E,加入到100mL的反应釜中,加入40mL甲苯溶剂,随后使用合成气置换三次,加入正丁烯20mmol,冲入合成气至4MPa,在120℃条件下进行反应。4h后反应结束,将反应釜进行冷却,用甲苯洗出反应液,加入内标物并进行气相色谱分析,得到正丁烯转化率84%,醛类选择性为95%,正异比为10。
实施例6
结构式为F的离子型双齿亚膦酰胺的制备方法及其在丁烯氢甲酰化反应中的应用:
将咪唑2.04g与三乙胺1.39mL于氮气保护下溶于超干二氯甲烷50mL,冰浴下滴加三氯化磷1.29mL,反应30min后过滤,滤液用氮气保护。将3,3’-5,5’-四叔丁基-2,2’-联苯酚2.05g溶于10mL超干二氯甲烷中,将该溶液滴加入上述滤液中,室温反应1h后,过滤,旋干溶剂,所得产物通过柱层析纯化,洗脱剂为乙酸乙酯:正己烷=1:6,得到双齿亚膦酰胺产物。将所得双齿亚膦酰胺3.69g溶于甲苯40mL中,1,3-丙磺酸内酯0.61g,升温至110℃回流12h,冷却后析出晶体,迅速抽滤并用***洗涤晶体,干燥即得离子型亚膦酰胺产物F,产率65%。
将0.02mmol的Rh(acac)(CO)2,0.1mmol的亚膦酰胺类配体F,加入到100mL的反应釜中,加入40mL甲苯溶剂,随后使用合成气置换三次,加入正丁烯20mmol,冲入合成气至4MPa,在120℃条件下进行反应。4h后反应结束,将反应釜进行冷却,用甲苯洗出反应液,加入内标物并进行气相色谱分析,得到正丁烯转化率95%,醛类选择性为99%,正异比为15。
Claims (11)
2.权利要求1所述的离子型亚膦酰胺类配体的制备方法,其特征在于,包括以下步骤:
步骤1):将三氯化磷与咪唑溶于溶剂中,搅拌反应后过滤,将取代联苯酚溶于溶剂滴加入上述滤液中反应,得到的产物经纯化后得单齿亚膦酰胺;
步骤2):将单齿亚膦酰胺与季胺化试剂在溶剂中反应,得到的产物经纯化后得式Ⅰ所示的离子型单齿亚膦酰胺类配体;
步骤3):将三氯化磷与咪唑溶于溶剂中,于碱性条件下搅拌反应后过滤,将取代联苯酚溶于溶剂滴加入上述滤液中反应,得到的产物经纯化后得双齿亚膦酰胺。
步骤4):将双齿亚膦酰胺与季胺化试剂在溶剂中反应,得到的产物经纯化后得式Ⅱ所示的离子型双齿亚膦酰胺类配体。
3.如权利要求2所述的离子型亚膦酰胺类配体的制备方法,其特征在于,所述溶剂为二氯甲烷、四氢呋喃、氯仿、甲苯、二甲亚砜、乙腈和去离子水中的至少一种。
4.如权利要求2所述的离子型亚膦酰胺类配体的制备方法,其特征在于,所述步骤2)、4)中,季胺化试剂为卤代烃、甲磺酸酯类衍生物和磺酸内酯衍生物中的至少一种;反应的温度为25-150℃,时间为0.5-48h。
5.如权利要求4所述的离子型亚膦酰胺类配体的制备方法,其特征在于,所述季胺化试剂为氯代正丁烷、氯乙基哌啶盐酸盐、三氟甲磺酸甲酯和1,3-丙磺酸内酯中的至少一种。
6.如权利要求2所述的离子型亚膦酰胺类配体的制备方法,其特征在于,所述步骤1)中三氯化磷与咪唑的摩尔比为1:6-1:10;所述步骤3)中三氯化磷与咪唑的摩尔比为1:2;碱性条件采用的碱为有机碱或无机碱;三氯化磷与碱的摩尔比为1:2-1:6。
7.如权利要求6所述的离子型亚膦酰胺类配体的制备方法,其特征在于,所述碱性条件采用的碱为三乙胺、吡啶、4-二甲氨基吡啶、二异丙基乙基胺和碳酸钾中的至少一种。
8.如权利要求2所述的离子型亚膦酰胺类配体的制备方法,其特征在于,所述步骤1)、3)中反应的温度为0-100℃,时间为0.5-24h。
9.一种权利要求1所述的离子型亚膦酰胺类配体在氢甲酰化反应中的应用,其特征在于,将铑催化前体、所述离子型亚膦酰胺类配体与有机溶剂加入到反应釜中,并加入烯烃,然后充入气体,将反应釜加热反应。
10.如权利要求9所述的应用,其特征在于,所述的铑催化前体为乙酰丙酮二羰基铑、乙酰丙酮三苯基膦羰基铑、三苯基膦氢化铑、Rh(OAc)3、Rh2O3、Rh4(CO)12和Rh6(CO)16中的至少一种;所述的有机溶剂为苯、甲苯、二甲苯、戊醛、二甲亚砜、二氯甲烷、二氯乙烷、乙腈、己烷、乙酸乙酯、二氧六环、四氢呋喃、甲醇、乙醇、正丙醇、异丙醇和正丁醇中的至少一种;所述的烯烃为C2-C18的单烯烃;所述铑催化前体与离子型亚膦酰胺类配体的摩尔比为1:1-1:50;所述铑催化前体与烯烃的摩尔比为1:100-1:10000;所述有机溶剂与烯烃的体积比为1:1-20:1;所述气体为CO与H2以摩尔比1:1混合的混合气,反应釜充入气体后的压力为2-8MPa。
11.如权利要求9所述的应用,其特征在于,所述加热反应的温度为80-180℃,时间为0.5-10h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011342977.3A CN112442087A (zh) | 2020-11-26 | 2020-11-26 | 一种离子型亚膦酰胺类配体的制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011342977.3A CN112442087A (zh) | 2020-11-26 | 2020-11-26 | 一种离子型亚膦酰胺类配体的制备方法及其应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112442087A true CN112442087A (zh) | 2021-03-05 |
Family
ID=74737419
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011342977.3A Pending CN112442087A (zh) | 2020-11-26 | 2020-11-26 | 一种离子型亚膦酰胺类配体的制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112442087A (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114456041A (zh) * | 2022-02-21 | 2022-05-10 | 广东仁康达材料科技有限公司 | 一种异构十三醇的制备方法 |
CN114835905A (zh) * | 2022-06-01 | 2022-08-02 | 常州巨德新材料有限公司 | 催化聚合的聚膦酰胺金属配合物催化剂及其制备方法 |
CN115739184A (zh) * | 2022-09-27 | 2023-03-07 | 成都欣华源科技有限责任公司 | 二聚异丁烯氢甲酰化催化剂组合物及其应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108525704A (zh) * | 2018-04-25 | 2018-09-14 | 四川大学 | 用于烯烃氢甲酰化反应的催化剂及其制备方法和应用 |
-
2020
- 2020-11-26 CN CN202011342977.3A patent/CN112442087A/zh active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108525704A (zh) * | 2018-04-25 | 2018-09-14 | 四川大学 | 用于烯烃氢甲酰化反应的催化剂及其制备方法和应用 |
Non-Patent Citations (3)
Title |
---|
ARMIN·BORNER 等 著: "《氢甲酰化反应的原理、过程和工业应用 上》", 30 November 2018, 华东理工大学出版社, pages: 83 * |
LAURENT LEFORT: "Rapid Identification of a Scalable Catalyst for the Asymmetric Hydrogenation of a Sterically Demanding Aryl Enamide", 《ORGANIC PROCESS RESEARCH & DEVELOPMENT》, vol. 14, no. 3, 31 December 2010 (2010-12-31), pages 568 - 573, XP055134224, DOI: 10.1021/op100011y * |
VARINIA BERNALES: "Rhodium catalyzed hydroformylation of olefins", 《JOURNAL OF COMPUTATIONAL CHEMISTRY》, vol. 40, no. 2, 31 December 2019 (2019-12-31), pages 342 - 348 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114456041A (zh) * | 2022-02-21 | 2022-05-10 | 广东仁康达材料科技有限公司 | 一种异构十三醇的制备方法 |
CN114835905A (zh) * | 2022-06-01 | 2022-08-02 | 常州巨德新材料有限公司 | 催化聚合的聚膦酰胺金属配合物催化剂及其制备方法 |
CN115739184A (zh) * | 2022-09-27 | 2023-03-07 | 成都欣华源科技有限责任公司 | 二聚异丁烯氢甲酰化催化剂组合物及其应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112442087A (zh) | 一种离子型亚膦酰胺类配体的制备方法及其应用 | |
CN109453816B (zh) | 一种用于烯烃氢甲酰化反应的催化剂及其制备方法和应用 | |
CN102643175A (zh) | 钌络合物配体、钌络合物、固载钌络合物催化剂及其制备方法和用途 | |
CN113583045B (zh) | 一种含双齿膦配体的催化剂组合物及其应用 | |
CN1907992B (zh) | 钌络合物配体、钌络合物、固载钌络合物催化剂及其制备方法和用途 | |
CN114436949B (zh) | 一种四齿配体及金属络合物及其制备方法和应用 | |
CN110128439B (zh) | 一种氧杂螺环化合物及其合成与拆分方法 | |
CN114315917A (zh) | 手性二茂铁pnno四齿配体及其在不对称氢化反应中的应用 | |
CA2905638C (en) | Complex catalysts based on amino-phosphine ligands for hydrogenation and dehydrogenation processes | |
CN107445999B (zh) | 金属络合物、制备方法和应用及其中间体 | |
CN109593085B (zh) | 吡啶-酰胺-噁唑啉配体、其合成方法及其金属配合物和用途 | |
CN113912646B (zh) | 一种双齿膦配体的制备方法 | |
JP2011507955A (ja) | ヒドロホルミル化方法のためのホスホナイト含有触媒 | |
EP3438113B1 (en) | Tetradentate ligand, and production method therefor, synthetic intermediate thereof, and transition metal complex thereof | |
CN113583046B (zh) | 双齿膦配体及其制备方法、应用 | |
CN101717408B (zh) | 含双磷叶立德茂环卡宾前体的鏻盐化合物及其制备方法和用途 | |
CN116063355A (zh) | 一种手性多齿配体及其在不对称氢化的应用 | |
CN101693727A (zh) | 一种含有半夹心结构铱、铑、钌的四核/六核大环配合物及其制备方法 | |
CN109666044B (zh) | 基于[2.2]对环芳烷骨架的有机磷化合物及其中间体和制备方法与用途 | |
JP4928798B2 (ja) | 不斉合成用触媒およびそれに用いる配位子、並びにこれらを用いた不斉合成反応による光学活性化合物の製造方法 | |
CN111617808A (zh) | 一种用于co2参与炔烃羰化酯化反应的催化剂 | |
CN111389468B (zh) | 一类磺化binap和聚醚功能化离子液体一体化的手性催化剂在不对称氢化反应中的应用 | |
CN114276487B (zh) | 有机膦聚合物、含其的催化剂、其合成方法及应用 | |
CN114736239B (zh) | 一种双齿膦配体及其制备方法、应用 | |
CN114230607B (zh) | 一种轴手性双膦配体及其在不对称催化反应中的应用 |
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 | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210305 |