CN111068789B - 一种用于co2参与的烯烃羰基酯化反应的催化剂 - Google Patents
一种用于co2参与的烯烃羰基酯化反应的催化剂 Download PDFInfo
- Publication number
- CN111068789B CN111068789B CN201911404892.0A CN201911404892A CN111068789B CN 111068789 B CN111068789 B CN 111068789B CN 201911404892 A CN201911404892 A CN 201911404892A CN 111068789 B CN111068789 B CN 111068789B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrogen
- chem
- olefins
- olefin
- 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.)
- Active
Links
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 5
- 230000006315 carbonylation Effects 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 239000000852 hydrogen donor Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HXVJDHROZFWXHT-UHFFFAOYSA-N 2-diphenylphosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HXVJDHROZFWXHT-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- -1 carboxylic ester compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 description 2
- 229940052810 complex b Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical group 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical class P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical group BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000012826 global research Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—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
- B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
-
- 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
- B01J2531/827—Iridium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种用于CO2参与的烯烃羰基化反应的催化剂及其制备方法,并且涉及用这样的催化剂催化烯烃与CO2的氢酯化反应。本发明开发了一类结构性能稳定的(P、N、carbene)类磺酸根配体的金属有机催化剂,以CO2作为简单的C1源、有机醇作为氢供体,催化烯烃与CO2羰基化反应,将烯烃转化为高附加值的羧酸酯及其衍生物、实现C‑C键的构筑。
Description
技术领域
本发明涉及一种用于CO2参与的烯烃羰基化反应的催化剂及其制备方法,并且涉及用这样的催化剂催化烯烃与CO2的氢酯化反应。属于均相催化领域。
背景技术
温室气体CO2主要由化石燃料的燃烧产生,也是地球上储量极为丰富和廉价的C1资源。化学法固定CO2既可以缓解“温室效应”,又可以将其转化为附加值更高的化学产品,具有很高的原子经济性和环境经济效应,已成为全球重要的研究方向(Nat.Commun.2015,6, 5933;Angew.Chem.Int.Ed.2018,57,15948)。以CO2为C1源的烯烃羰基化是CO2催化转化的重要反应类型之一。已有的报道集中于针对羧酸产物的研究,开发的有机金属催化剂活性中心主要有:镍、铁、钴、钯等(Chem.Rev.2001,101,3435;Org.Lett.2003,5,4329;J.Org.Chem.2003,68,8353;J.Am.Chem.Soc.2008,130,14936;J.Am.Chem.Soc.2012,134,11900;Chem.Lett.2014,43,565);其它羧酸衍生物(如:羧酸酯、醛、醇等)鲜有报道。
羧酸酯类化合物有很多用途,如酒类、食品、化妆品以及重要化工中间体等(Org.Lett. 2011,13,5;J.Am.Chem.Soc.2012,134,11900;Green Chem.2018,20,5533;Nat.Commun. 2014,5,3091)。工业上报道合成羧酸酯类化合物主要是以有毒的CO作为羰基源、有机醇作为溶剂,在高温高压的条件下,对烯烃进行的氢酯化反应;采用Pd、Rh等贵金属催化,昂贵的膦配体(WO2007057640A1,US6476255B1,CN101665432A,US6294687B1);考虑到CO的不安全性,选择CO2替代CO,廉价金属作为金属催化剂,从而使该反应变得简单、安全、经济、易操作。近年来,Beller(ChemCatChem 2014,6,2805;Nat Commun.2014, 5,3091;NatCommun.2015,6,5933;Catal.Sci.Technol.2016,6,4712)、Dupont(ChemSusChem. 2015,8,586)以及夏春谷(Green Chem.2018,20,5533)小组先后报道了以CO2为羰源,Ru 催化的烯烃羰基酯化反应,反应不需要任何敏感的配体,但需要氯代离子液体/盐作为添加剂,同时存在底物范围较小、选择性差、反应温度高、产物难分离等不足。本发明开发了一类结构性能稳定的(P、N、carbene)类磺酸根配体的金属有机催化剂,旨在实现烯烃与CO2及醇的氢酯化反应。
发明内容:
针对现有技术的不足,本发明的目的在于提供一种以CO2为羰源烯烃氢酯化反应的催化剂结构及其制备方法。
第一方面,本发明提供的方法,烯烃与CO2及醇直接氢酯化反应在方案1中示出。
方案1:
其中R1为苯基或含有取代基的苯基、-F、-Cl、-Br、-I、-CF3、-OCH3、C1~C5的烷基或氢;R2为甲基或氢;R3为甲基或氢;R4为甲基或氢;R5为甲基、苯基或含有取代基的苯基、 -F、-Cl、-Br、-I、-CF3、-OCH3、C1~C5的烷基、或带羟基的C1~C5的烷基。
第二方面,本发明涉及的磺酸类配体用M、Y、Z的结构式代表:
其中R7、R8、R9、R10可以独立地为H、C1~C18的烷基、-CF3、-OCH3;R11、R12可以独立为C1~C8烷基、Cy、Ph、Ar;R13、R14、R15可以独立地为C1~C18的烷基、Ph、Ar。
M类磺酸配体的制备参考文献(Chem.Eur.J.2012,18,3277;Angew.Chem.Int.Ed.2012, 51,8876),包括合成步骤如下:
①在惰性气体保护下,将磺酸类化合物溶于无水四氢呋喃(THF)中,冷却到0℃左右;
②按照正丁基锂与磺酸类化合物摩尔比为1.5~2.5:1,用注射器逐滴滴加正丁基锂反应,室温搅拌1~3小时;
③在0℃下,二取代氯化膦的THF溶液滴加到上述溶液中(二取代氯化膦与磺酸类化合物的摩尔比为1:10);
④然后室温搅拌10小时后,用真空泵抽干溶剂,将该固体物质溶解到二氯甲烷溶液中,用5M的盐酸溶液酸化,再用去离子水萃取3次,对有机相部分用无水硫酸钠进行干燥、过滤,真空泵抽干溶剂,最后在二氯甲烷/正己烷中进行重结晶所得。
Y、Z类磺酸配体的制备,参考文献(Organometallics.2009,28,6131;DaltonTrans.2015, 44,17467;Angew.Chem.Int.Ed.2007,46,1097)包括合成步骤如下:
①在惰性气体保护下,按照取代基取代的咪唑盐、二溴甲烷、去离子水的摩尔比为1: 200:400加入到反应管里,在90℃下,剧烈搅拌17小时;
②然后加入Na2SO3(按照Na2SO3与取代基取代咪唑的摩尔比为2:1)到上述溶液中,在85℃下,剧烈搅拌7小时;
③反应结束后,将溶液冷却至室温,用二氯甲烷萃取3次,然后将有机相放到4℃下重结晶得到该配体。
第三方面,本发明涉及的催化剂用配合物A和配合物B的结构式表示:
其中M为Ru、Co、Ir、Ni、Cu、Mn、Zn等金属;
配合物A催化剂的制备参考文献(Chem.Eur.J.2012,18,3277;Angew.Chem.Int.Ed. 2012,51,8876),包括合成步骤如下:
①在惰性气体的保护下,1.2~1.8摩尔份的叔丁醇钾和1摩尔份的配体A或者B溶解于20~60摩尔份脱气的甲醇中,室温搅拌1小时;
②加入1摩尔份(按照金属原子的摩尔数)的前驱体金属盐(Ru(p-cymene)Cl2]2,[Ir(C5Me5)Cl2]2、[Cp*Co(CO)I2]等等)室温搅拌8小时;
③真空泵抽干溶剂,所得固体溶解于无水二氯甲烷,再用活化的硅藻土进行过滤,用真空泵抽干溶剂得到该催化剂。
配合物B催化剂的制备,参考文献(Organometallics.2009,28,6131;DaltonTrans.2015, 44,17467;Angew.Chem.Int.Ed.2007,46,1097)包括合成步骤如下:
①在惰性气体的保护下,1摩尔份的配体C或者D溶解于40~70摩尔份无水的二氯甲烷中,室温搅拌20分钟;
②加入1摩尔份(按照金属原子的摩尔数)的前驱体金属盐(Ru(p-cymene)Cl2]2,
[Ir(C5Me5)Cl2]2、[Cp*Co(CO)I2]等等)45℃下搅拌回流20小时;
③用活化的硅藻土进行过滤,用真空泵抽干溶剂得到该催化剂。
本发明涉及的磺酸配体和催化剂经核磁共振方法检测,证实其为所述的配体和催化剂。
本发明具有以下有益效果:
本发明我们用廉价且更加稳定的(P、N、carbene)类磺酸配体的催化剂实现烯烃与CO2及有机醇的氢酯化反应。
附图说明
图1是本发明实施例1合成的配体(Dppbsa)的核磁图谱。
图2是本发明实施例2合成的配合物1的核磁图谱。
图3是本发明实施例3合成的配合物2的核磁图谱。
图4是本发明实施例4合成的配合物3的核磁图谱。
备注:1H NMR(600MHz,298K,CDCl3),13C NMR(151MHz,298K,CDCl3)and 31P NMR(243MHz,CDCl3,298K)
具体实施方式
为了更好地理解本发明,下面结合实施案例进一步阐明本发明的内容,但本发明的内容不局限于下面的实施案例,也不应视为对本发明的限制。
实施例1
2-二苯基膦苯磺酸(Dppbsa)配体的合成
实施方法:
参考文献(Chem.Eur.J.2012,18,3277;Angew.Chem.Int.Ed.2012,51,8876);在氩气 (Ar)的氛围中,将无水苯磺酸(1.03g,6mmol)加入到无水THF(30mL)中,然后冷却到0℃左右;用注射器取正丁基锂n-BuLi(2.5M in hexanes;4.8mL,12mmol,2equiv.),然后逐滴加入到上述溶液中,然后搅拌1小时;在搅拌1小时后,将二苯基氯化膦(1.32g, 6mmol,1equiv.)溶解到无水THF(20mL),然后将上述溶液缓慢的滴加到上述溶液中;上述溶液的温度从0℃升高到20℃,然后搅拌10小时,直到透明澄清的溶液产生为止;用真空泵抽干溶剂,将该固体物质溶解到二氯甲烷(50mL)中,然后用盐酸溶液(5M,30 mL)酸化,再用30mL的去离子水萃取3次,取有机相。经无水硫酸钠进行干燥,过滤,真空泵抽干溶剂,最后在二氯甲烷/正己烷中进行重结晶,该结晶固体进行干燥所得。1H NMR (600MHz,CDCl3,298K):δ=8.39(m,1H),7.80(m,1H),7.73(m,2H),7.66(m,2H),7.64(m, 2H),7.59(m,4H),7.49(m,1H),7.25(m,1H),N.O.(-SO3H).13C{1H}NMR(151MHz,CDCl3, 298K):δ=152.9(JPC=8.9Hz,i-Ph-SO3H),135.5(JPC=3.2Hz,i-Ph),134.6(JPC=3.0Hz, 2×i-Ph),134.5,134.4,134.0,133.9,130.2,130.1(4),130.1(1),130.0(5),129.4(2),129.3(6),119.1, 118.5,113.7,113.1(Ph).31P{1H}NMR(243MHz,CDCl3,298K):δ=3.8.
实施例2
配合物A1的合成
实施方法:
参考文献(Chem.Eur.J.2012,18,3277;Angew.Chem.Int.Ed.2012,51,8876);在氩气 (Ar)的氛围中,将上述2-二苯基膦苯磺酸(Dppbsa)配体(271mg,0.792mmol,2equiv.)和叔丁醇钾t-BuOK(98mg,0.871mmol,2equiv.)添加到25mL的希拉克管中,加入甲醇(10mL),搅拌30分钟;添加(Ru(p-cymene)Cl2]2)(0.243g,0.396mmol,1equiv.)到上述溶液中,搅拌16小时;溶剂甲醇被真空泵抽干,固体再溶解到二氯甲烷(30mL)中,经过活化的硅藻土进行过滤,用真空泵抽干溶剂得到该催化剂。1H NMR(600MHz,CDCl3, 298K):δ=8.08(m,1H),7.92(m,2H),7.64(m,1H),7.62(m,1H),7.54(m,1H),7.50(m,1H), 7.46(m,4H),7.44(m,1H),7.25(m,1H),6.96(m,1H),5.83(d,3JHH=6.5Hz,1H),5.78(d,3JHH=6.5Hz,1H),5.54(d,3JHH=5.5Hz,1H),5.44(d,3JHH=5.5Hz,1H),2.62(sept,3JHH=6.8Hz, 3JHH=6.8Hz,1H),1.89(s,3H,CH3),1.15(d,3JHH=6.8Hz,3H),0.94(d,3JHH=6.8Hz, 3H).13C{1H}NMR(151MHz,CDCl3,298K):δ=147.2(JPC=12.8Hz,i-Ph-SO3Ru),136.1(JPC= 9.8Hz),134.1(JPC=9.8Hz),133.3,133.0(0),132.9(6),131.8(JPC=2.5Hz),131.5,131.3(JPC=2.0Hz),131.2,131.0(JPC=2.5Hz),129.9(JPC=6.8Hz),128.7(JPC=8.3Hz),128.5(JPC=9.7 Hz),128.4(JPC=10.3Hz),128.2,128.1,108.0,94.4,92.9(JPC=5.3Hz),87.3(JPC=7.7Hz),85.6 (JPC=2.2Hz),83.9(JPC=2.2Hz),30.2,22.9,20.5,17.8.31P{1H}NMR(243MHz,CDCl3,298K): δ=22.9.
实施例3
配合物A2的合成
实施方法:
在氩气(Ar)的氛围中,将无水苯磺酸(0.476g,3mmol)加入到无水THF(30mL) 中,冷却到0℃左右;用注射器取正丁基锂n-BuLi(2.5M in hexanes;2.4mL,6mmol,2equiv.)逐滴加入到上述溶液中,搅拌1小时;再将二-(4-三氟甲基)苯基氯化膦(3mmol,2equiv.)溶解到无水THF(20mL),并缓慢地滴加到上述溶液中;混合溶液的温度从0℃升高到 20℃,然后搅拌10小时,直到透明澄清的溶液产生为止;用真空泵抽干溶剂,将所得固体溶解到二氯甲烷(50mL)中,用盐酸溶液(5M,30mL)酸化,再用30mL的去离子水萃取3次,取有机相,经过无水硫酸钠进行干燥,过滤,真空泵抽干溶剂。称取上述2-二苯基膦苯磺酸(Btmppbsa)配体(379mg,0.792mmol,2equiv.)和叔丁醇钾t-BuOK(98mg,0.871 mmol,2equiv.)添加到25mL的希拉克管中,加入甲醇(10mL),搅拌30分钟;再加入 Ru(p-cymene)Cl2]2(0.243g,0.396mmol,1equiv.),搅拌16小时;溶剂甲醇被真空泵抽干,所得固体溶解到二氯甲烷(30mL)中,再用活化的硅藻土进行过滤,最后真空泵抽干溶剂得到该催化剂。1H NMR(600MHz,CDCl3,298K):δ=8.09(m,1H),8.03(m,2H),7.78(m,2H), 7.73(m,4H),7.52(m,1H),7.33(m,1H),6.98(m,1H),5.84(d,3JHH=6.1Hz,1H),5.81(d,3JHH=6.2Hz,1H),5.65(d,3JHH=6.2Hz,1H),5.53(d,3JHH=6.1Hz,1H),2.57(sept,3JHH=6.8Hz, 3JHH=6.8Hz,1H),1.94(s,3H,CH3),1.13(d,3JHH=6.8Hz,3H),0.97(d,3JHH=6.8Hz,3H). 31P{1H}NMR(243MHz,CDCl3,298K):δ=21.9.19F NMR(565MHz,CDCl3,298K):δ=-63.16,-63.26
实施例4
配合物A3的合成
实施方法:
参考文献(Dalton Trans.2015,44,17467;Angew.Chem.Int.Ed.2007,46,1097);在氩气(Ar)的氛围中,将2-二苯基膦苯磺酸(Dppbsa)配体(271mg,0.792mmol,2equiv.) 和叔丁醇钾t-BuOK(98mg,0.871mmol,2equiv.)添加到25mL的希拉克管中,并加入甲醇(10mL),搅拌30分钟;添加([Ir(C5Me5)Cl2]2)(0.316g,0.396mmol,1equiv.)到上述溶液中,搅拌16小时;溶剂甲醇被真空泵抽干,所得固体溶解到二氯甲烷(30mL)中,再用活化的硅藻土进行过滤,最后用真空泵抽干溶剂得到该催化剂。1H NMR(600MHz, CDCl3,298K):δ=8.12(m,1H),7.83(m,2H),7.74(m,1H),7.49(m,4H),7.41(m,2H),7.36(m, 1H),1.49(d,3JHH=1.8Hz,15H).13C{1H}NMR(151MHz,CDCl3,298K):δ=147.0(JPC=12.4 Hz),134.5(JPC=10.1Hz),135.1(JPC=11.2Hz),133.4(JPC=1.6Hz),131.5,131.4(JPC=2.3Hz), 131.2(JPC=2.2Hz),131.1,131.0(JPC=2.1Hz),129.9(JPC=7.2Hz),129.5,129.2,128.9(JPC=7.6Hz),128.3,128.1(JPC=10.9Hz),127.9(JPC=11.2Hz),92.2(JPC=2.7Hz),8.9.31P{1H}NMR(243MHz,CDCl3,298K):δ=1.7.
实施例5
实施方法:在氩气的氛围下,在50mL的反应釜中加入苯乙烯(2mmol,1equiv.)、甲醇(2mL)、对甲苯磺酸(0~0.8mmol)、催化剂(0~0.1mmol,)、溶剂(2mL)、充入 CO2(0~60bar),该反应在100~150℃的温度下反应12~36小时,冷却至室温,加入内标异辛烷(1mmol,0.5equiv.),使用GC进行分析苯乙烯转化率和羧酸酯收率。
实施例6
实施方法:在氩气的氛围下,在50mL的反应釜中加入环己烯(2mmol)、醇(2mL)、对甲苯磺酸(0~0.8mmol)、催化剂(0~0.1mmol)、甲苯(1mL)、充入CO2(0~60bar),该反应在100~150℃的温度下反应12~36个小时,冷却至室温,加入内标异辛烷(1mmol,0.5equiv.),使用GC进行分析环己烯转化率和羧酸酯收率的结果.
申请人声明,本发明通过上述实施例来说明本发明的详细方法,但本发明并不局限于上述详细方法,即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911404892.0A CN111068789B (zh) | 2019-12-31 | 2019-12-31 | 一种用于co2参与的烯烃羰基酯化反应的催化剂 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911404892.0A CN111068789B (zh) | 2019-12-31 | 2019-12-31 | 一种用于co2参与的烯烃羰基酯化反应的催化剂 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111068789A CN111068789A (zh) | 2020-04-28 |
CN111068789B true CN111068789B (zh) | 2021-10-08 |
Family
ID=70320264
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911404892.0A Active CN111068789B (zh) | 2019-12-31 | 2019-12-31 | 一种用于co2参与的烯烃羰基酯化反应的催化剂 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111068789B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115403465B (zh) * | 2022-05-20 | 2023-08-18 | 湖南工程学院 | 一种二氧化碳和烯烃合成有机羧酸酯的制备方法 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1352648A (zh) * | 1998-12-23 | 2002-06-05 | 罗狄亚聚酰胺中间体公司 | 水溶性磺化有机磷化合物的制备方法 |
CN101514195A (zh) * | 2009-03-11 | 2009-08-26 | 兰州大学 | 一种环碳酸酯的制备方法 |
CN102695559A (zh) * | 2010-01-05 | 2012-09-26 | 璐彩特国际英国有限公司 | 用于烯键式不饱和化合物的羰基化的工艺、新颖的羰基化配体和结合有上述配体的催化剂体系 |
CN103788055A (zh) * | 2012-10-31 | 2014-05-14 | 中国科学院大连化学物理研究所 | 一种由烯烃直接制备环状碳酸酯的方法 |
CN104684885A (zh) * | 2012-09-28 | 2015-06-03 | 吉坤日矿日石能源株式会社 | 酯化合物的制造方法及用于该方法的钯催化剂 |
CN105517986A (zh) * | 2013-06-11 | 2016-04-20 | 赢创德固赛有限公司 | 由烯烃和CO2合成α,β-不饱和羧酸(甲基)丙烯酸盐 |
CN105541610A (zh) * | 2016-01-13 | 2016-05-04 | 河北工业大学 | 一种利用二氧化碳和乙烯合成丙酸甲酯的方法 |
EP3030544A1 (de) * | 2013-08-08 | 2016-06-15 | Evonik Degussa GmbH | Verfahren zur synthese von gesättigten carbonsäureestern |
WO2018087678A1 (en) * | 2016-11-10 | 2018-05-17 | Apeiron Synthesis S.A. | Use of ruthenium complexes in olefin metathesis reaction |
CN108884010A (zh) * | 2016-04-11 | 2018-11-23 | 巴斯夫欧洲公司 | 制备不饱和羧酸盐的方法 |
CN108993602A (zh) * | 2018-07-23 | 2018-12-14 | 河北工业大学 | 一种合成丙酸甲酯的催化体系及其应用方法 |
CN110506041A (zh) * | 2016-12-28 | 2019-11-26 | Ptt全球化学股份有限公司 | 用于由二氧化碳和1,3-丁二烯制造δ-内酯的制造方法的催化剂组合物 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2896500B1 (fr) * | 2006-01-24 | 2010-08-13 | Inst Francais Du Petrole | Procede de co-production d'olefines et de diesters ou de diacides par homometathese de corps gras insatures dans des liquides ioniques non-aqueux. |
-
2019
- 2019-12-31 CN CN201911404892.0A patent/CN111068789B/zh active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1352648A (zh) * | 1998-12-23 | 2002-06-05 | 罗狄亚聚酰胺中间体公司 | 水溶性磺化有机磷化合物的制备方法 |
CN101514195A (zh) * | 2009-03-11 | 2009-08-26 | 兰州大学 | 一种环碳酸酯的制备方法 |
CN102695559A (zh) * | 2010-01-05 | 2012-09-26 | 璐彩特国际英国有限公司 | 用于烯键式不饱和化合物的羰基化的工艺、新颖的羰基化配体和结合有上述配体的催化剂体系 |
CN104684885A (zh) * | 2012-09-28 | 2015-06-03 | 吉坤日矿日石能源株式会社 | 酯化合物的制造方法及用于该方法的钯催化剂 |
CN103788055A (zh) * | 2012-10-31 | 2014-05-14 | 中国科学院大连化学物理研究所 | 一种由烯烃直接制备环状碳酸酯的方法 |
CN105517986A (zh) * | 2013-06-11 | 2016-04-20 | 赢创德固赛有限公司 | 由烯烃和CO2合成α,β-不饱和羧酸(甲基)丙烯酸盐 |
EP3030544A1 (de) * | 2013-08-08 | 2016-06-15 | Evonik Degussa GmbH | Verfahren zur synthese von gesättigten carbonsäureestern |
CN105541610A (zh) * | 2016-01-13 | 2016-05-04 | 河北工业大学 | 一种利用二氧化碳和乙烯合成丙酸甲酯的方法 |
CN108884010A (zh) * | 2016-04-11 | 2018-11-23 | 巴斯夫欧洲公司 | 制备不饱和羧酸盐的方法 |
WO2018087678A1 (en) * | 2016-11-10 | 2018-05-17 | Apeiron Synthesis S.A. | Use of ruthenium complexes in olefin metathesis reaction |
CN110506041A (zh) * | 2016-12-28 | 2019-11-26 | Ptt全球化学股份有限公司 | 用于由二氧化碳和1,3-丁二烯制造δ-内酯的制造方法的催化剂组合物 |
CN108993602A (zh) * | 2018-07-23 | 2018-12-14 | 河北工业大学 | 一种合成丙酸甲酯的催化体系及其应用方法 |
Non-Patent Citations (7)
Also Published As
Publication number | Publication date |
---|---|
CN111068789A (zh) | 2020-04-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109806911B (zh) | 一种高选择性制备直链醛的催化剂及其制备和应用 | |
US5917071A (en) | Synthesis of ruthenium or osmium metathesis catalysts | |
Imlinger et al. | Arylation of Carbonyl Compounds Catalyzed by Rhodium and Iridium 1, 3‐R2‐Tetrahydropyrimidin‐2‐ylidenes: Structure‐Reactivity Correlations | |
US20040127350A1 (en) | Ruthenium complexes as (pre)catalysts for metathesis reactions | |
Aydemir et al. | Novel neutral phosphinite bridged dinuclear ruthenium (II) arene complexes and their catalytic use in transfer hydrogenation of aromatic ketones: X-ray structure of a new Schiff base, N3, N3′-di-2-hydroxybenzylidene-[2, 2′] bipyridinyl-3, 3′-diamine | |
Ahlsten et al. | Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature | |
Dayrit et al. | Electron transfer in nickel-catalyzed addition reactions of organozirconium compounds to unsaturated ketones | |
Aydemir et al. | Ruthenium-catalyzed transfer hydrogenation of aromatic ketones with aminophosphine or bis (phosphino) amine ligands derived from isopropyl substituted anilines | |
Smith et al. | Palladium methoxide and carbomethoxy complexes: synthesis and molecular structure of (bipy) Pd (CO2CH3) 2 | |
KR20090078835A (ko) | 수소 분리 조성물 | |
CN106513048A (zh) | 用于内烯烃氢甲酰化反应的催化剂及其制备方法和应用 | |
CN104220418A (zh) | 钌基复分解催化剂以及用于其制备的前体 | |
How et al. | A modular family of phosphine-phosphoramidite ligands and their hydroformylation catalysts: steric tuning impacts upon the coordination geometry of trigonal bipyramidal complexes of type [Rh (H)(CO) 2 (P^ P*)] | |
US9556211B2 (en) | Metal complex compound, hydrogen production catalyst and hydrogenation reaction catalyst each comprising the metal complex compound, and hydrogen production method and hydrogenation method each using the catalyst | |
CN111068789B (zh) | 一种用于co2参与的烯烃羰基酯化反应的催化剂 | |
CN113004326B (zh) | 一种用于丁二烯氢甲酰化反应的膦配体及其制备方法 | |
WO2007094211A1 (ja) | カルボン酸エステルおよびエーテル化合物の製造方法 | |
Fortea-Pérez et al. | Structurally characterized dipalladium (ii)-oxamate metallacyclophanes as efficient catalysts for sustainable Heck and Suzuki reactions in ionic liquids | |
WO2010038209A1 (en) | Hydrogenation of esters or carbonyl groups with phosphino-oxide based ruthenium complexes | |
Hao et al. | Ruthenium carbonyl complexes with pyridine-alkoxide ligands: synthesis, characterization and catalytic application in dehydrogenative oxidation of alcohols | |
Aydemir et al. | Applications of transition metal complexes containing 3, 3′-bis (diphenylphosphinoamine)-2, 2′-bipyridine ligand to transfer hydrogenation of ketones | |
CN114478362A (zh) | 一种手性吡啶醇衍生物的制备方法 | |
CN105728047B (zh) | 一种氢甲酰化催化剂及其制备方法和应用 | |
CN111217809B (zh) | 一类手性含氮双烯配体及其制备方法和应用 | |
EP2961756A1 (en) | Complex catalysts based on amino-phosphine ligands for hydrogenation and dehydrogenation processes |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |