CN1293675A - 二膦的制备方法 - Google Patents
二膦的制备方法 Download PDFInfo
- Publication number
- CN1293675A CN1293675A CN99804030A CN99804030A CN1293675A CN 1293675 A CN1293675 A CN 1293675A CN 99804030 A CN99804030 A CN 99804030A CN 99804030 A CN99804030 A CN 99804030A CN 1293675 A CN1293675 A CN 1293675A
- Authority
- CN
- China
- Prior art keywords
- compound
- reaction
- formula
- group
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000000962 organic group Chemical group 0.000 claims abstract description 9
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 125000005647 linker group Chemical group 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 17
- -1 sodium alkoxide Chemical class 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 10
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 238000005810 carbonylation reaction Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- OPDOJCUOMZNPIT-UHFFFAOYSA-N CC1=CC=CC=C1.C(C)(C)(C)PC(C)(C)C Chemical compound CC1=CC=CC=C1.C(C)(C)(C)PC(C)(C)C OPDOJCUOMZNPIT-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 abstract description 4
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 23
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- DOWCWUCBOQRQJE-UHFFFAOYSA-N ditert-butylphosphane;hydrochloride Chemical compound Cl.CC(C)(C)PC(C)(C)C DOWCWUCBOQRQJE-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 5
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 5
- 238000006366 phosphorylation reaction Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000972773 Aulopiformes Species 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- CRHWEIDCXNDTMO-UHFFFAOYSA-N ditert-butylphosphane Chemical compound CC(C)(C)PC(C)(C)C CRHWEIDCXNDTMO-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000026731 phosphorylation Effects 0.000 description 2
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000019515 salmon Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010572 single replacement reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LVRVASUUGVLEHQ-UHFFFAOYSA-N C=1(C(=CC=CC1)C)C.C(C)(C)(C)PC(C)(C)C Chemical class C=1(C(=CC=CC1)C)C.C(C)(C)(C)PC(C)(C)C LVRVASUUGVLEHQ-UHFFFAOYSA-N 0.000 description 1
- KCMZYCFSSYXEQR-UHFFFAOYSA-N CCCC[K] Chemical compound CCCC[K] KCMZYCFSSYXEQR-UHFFFAOYSA-N 0.000 description 1
- IRDQNLLVRXMERV-UHFFFAOYSA-N CCCC[Na] Chemical compound CCCC[Na] IRDQNLLVRXMERV-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000008232 de-aerated water Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HYYBABOKPJLUIN-UHFFFAOYSA-N mefenamic acid Chemical compound CC1=CC=CC(NC=2C(=CC=CC=2)C(O)=O)=C1C HYYBABOKPJLUIN-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- CAZCDFBHRPRTNN-UHFFFAOYSA-N potassium;1,2-xylene Chemical compound [K].CC1=CC=CC=C1C CAZCDFBHRPRTNN-UHFFFAOYSA-N 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5068—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure >P-Hal
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种制备通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物的方法,其中每个R独立地为任选取代的侧有机基团,通过它该基团与叔碳原子C连接;L1、L2独立地为连接基团,选自将各自的磷原子与基团X连接的任选取代的低级亚烷基链,X为包括任选取代的芳基部分的桥连基,该芳基部分通过可得到的相邻碳原子与磷原子连接,该方法包括:i)将式H-L1-X-L2-H所示的化合物与有机金属化合物一起反应,生成式M-L1-X-L2-M所示的中间体化合物,其中M为碱金属原子,ii)将所述中间体化合物与式(R3-C)2P-A所示的化合物反应,其中A为卤原子,形成所述通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物。M优选为锂、钾或钠。中间体化合物可以分离或不分离。反应(i)可在诸如四甲基乙二胺的络合剂存在下有利地进行。
Description
本发明涉及用作催化剂体系组分的膦化合物,该催化剂体系可用于烯烃羰基化,本发明尤其涉及制备这样的膦化合物的方法。
WO96/19434公开了一种用于乙烯羰基化的方法以及其中使用的催化剂体系。在该文献中描述的催化剂体系包含通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的二齿膦,其中每个R独立地为任选取代的侧有机基团,通过它该基团与叔碳原子C连接;L1、L2独立地为连接基团,选自将各自的磷原子与基团X连接的任选取代的低级亚烷基链,X为包括任选取代的芳基部分的桥连基,该芳基部分通过可得到的相邻碳原子与磷原子连接。这样的二齿膦的一个例子是双(二-叔丁基膦基)-邻二甲苯(也称作1,2-双(二叔丁基膦甲基)苯)。
这样的催化剂可通过将膦配体与诸如乙酸钯的适宜钯源混合来制备。WO96/19434描述了经从合适的仲膦与相应的芳族二卤化物的反应制备的鏻盐制备一种形式的配体。在WO96/19434优选的膦配体形式中,R为低级烷基,特别是甲基。通过所述路线制备这种配体的问题在于所用的仲膦(如二叔丁基膦)有毒、活性高、有味而且易燃。我们还发现该反应是低收率的,而且一部分二叔丁基膦转化为必须除去的不可回收的废产物。
Al-Salem等在Journal of the Chemical Society(Dalton)1979页1980描述了通过将锂金属与1,5-二溴戊烷反应,然后用叔丁基氯化膦磷酸化得到的锂化中间体制备1,5-双(二叔丁基膦基)戊烷。为形成烷基化合物的膦,该方法从卤代烷基化合物开始。烷基卤化物一般要求在贮存和使用期间非常小心,而且使用起来可能很不合意。因此,采用这种以非卤代烷基化合物作为原材料制备膦的方法需要首先转化为烷基卤化物的额外步骤。
我们现已发现,在WO96/19434中所述类型的膦配体可通过采用更温和的材料的高收率路线制备,该路线比WO96/19434中所述路线产生更少的磷废产物。
根据本发明,一种制备通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物的方法,其中每个R独立地为任选取代的侧有机基团,通过它该基团与叔碳原子C连接;L1、L2独立地为连接基团,选自将各自的磷原子与基团X连接的任选取代的低级亚烷基链,X为包括任选取代的芳基部分的桥连基,该芳基部分通过可得到的相邻碳原子与磷原子连接,该方法包括下列步骤:ⅰ)将式H-L1-X-L2-H所示的化合物与有机金属化合物一起反应,生成式M-L1-X-L2-M所示的中间体化合物,其中M为碱金属原子,ⅱ)将所述中间体化合物与式(R3-C)2P-A所示的化合物反应,其中A为卤原子,形成所述的通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物。
通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物可用作催化剂化合物的组分。特别是WO96/19434描述了这样的化合物作为二齿配体的应用,该二齿配体在与诸如钯的VⅢ族金属一起使用时,是用于烯烃羰基化的有效催化剂。
任选取代的侧有机基团R可独立地选自宽范围的组分。侧基优选为任选取代的低级烷基,如C1-8,可为支链或直链的。
特别优选的是,当有机基团R在与它们各自的碳原子结合时,形成至少象叔丁基一样的空间位阻的复合基团。本文中的空间位阻如CMasters,在Chapman and Hall,1981年出版的“HomogeneousTransition Metal Catalysis-A Gentle Art”第14页以及下列等页中所讨论的。在一个优选实施方案中,有机基团R均为甲基,即R3-C基团的优选形式为叔丁基。
连接基团L1和L2独立地选自任选取代的、特别是低级烷基,如C1~C4,取代的低级亚烷基,如C1~C4链。尤其优选L1和L2均为亚甲基。
桥连基X为芳基部分,例如苯基,其可以是任选取代的,只要两个磷原子连在相邻的碳原子上,例如在苯基的1和2位上。芳基部分的任选取代可以是被其它的有机基团,如烷基,特别是C1-8、芳基、烷氧基、烷氧羰基、卤素、硝基、三卤甲基和氰基。此外,芳基部分可为稠合多环基,如萘基、亚联苯基或茚基。
可有利地通过根据本发明的方法制备的化合物的例子为双(二叔丁基膦)-邻二甲苯(也称作1,2-双(二叔丁基膦甲基)苯)、双(二叔新戊基膦基)-邻二甲苯和双1,2-(二叔丁基膦基)萘。
式H-L1-X-L2-H所示的化合物与式RmM所示的碱性有机金属化合物生成式M-L1-X-L2-M所示的中间体化合物的反应,其中M为碱金属原子,可通过有机金属化学领域已知的各种方法进行。例如,Wilkinson等在“Comprehensive Organometallic Chemistry”,54页;以及Lambert等在“Preparative Polar Organometallic Chemistry”中描述了这种金属化方法。
有机金属化合物可包括式Rm-M所示的化合物,其中Rm为趋向于从金属原子M中取出电子的有机基团。合适的有机基团包括芳族或脂族基团,尤其是烷基,该烷基可以是取代的。已经发现低级烷基特别合适,例如优选的Rm化合物包括正丁基、叔丁基、仲丁基、甲基或戊基。M可为与Rm形成极性有机金属基团的任何合适的碱金属。合适的金属包括IA族金属,如钠、钾或锂。当M包括K或Na时,Rm-M金属化试剂优选通过交换机理在原位产生,例如通过Lochman等在Tetrahedron Letters第2期,257-262页(1966)所述的Rm-Li和叔丁醇钾或叔丁醇钠之间的反应。优选的金属化化合物为丁基锂、丁基钠和丁基钾,后面的化合物优选通过丁基锂与叔丁醇钾或叔丁醇钠的反应在原位形成。
其它有机金属化合物也是本领域已知的,可包括Me3SiCH2K,优选用于液氨中的氨基碱金属MNH2,二烷氨基锂(lithiumdialkylamide),如二异丙氨基锂(lithium diisopropylamide)(LDA),锂、钠或钾金属,金属氢化物,如在配位化合物存在下的KH。
RmM和H-L1-X-L2-H之间的反应可在溶剂存在下进行。所用的任何溶剂必须不含有任何与中间体化合物反应的组分,合适的这样的溶剂对于熟练的化学工作者是熟知的。有利的溶剂包括干烷基醚,如乙醚、甲基叔丁基醚、二(正丙基)醚、四氢呋喃(THF)和诸如己烷和庚烷的烃类。
RmM和H-L1-X-L2-H之间的反应可在能与金属形成络合物的碱性化合物存在下有利地进行。优选的络合剂为四甲基乙二胺(TMEDA)。当金属化剂为烷基锂或烷基钠时,TMEDA的存在是大大优选的。当使用烷基钾(或烷基锂/叔丁醇钾混合物)时,我们已经发现反应在没有TMEDA存在下令人满意地进行。
金属化剂∶H-L1-X-L2-H的摩尔比优选在1∶1~10∶1范围内,更优选至少为1.5∶1。优选的比率取决于所用金属化剂的性质,例如当使用烷基锂时,可优选R-Li∶H-L1-X-L2-H的比为3∶1。可优选更高的比率以促进二取代产物而不是单取代化合物的形成。
RmM∶络合剂的优选比率在1∶1~4∶1范围内,尤其优选约1∶1~约2∶1的比率。
优选在-20~150℃范围内的温度下,更优选在室温或高于室温进行RmM和H-L1-X-L2-H之间的金属化反应。最优温度和反应时间取决于反应物的本性,特别取决于所用的碱金属。例如,我们已经发现,以邻二甲苯作为将要进行金属化的化合物,当使用烷基锂时,反应在室温(即约20~22℃)下进行得很好,而使用烷基钠和烷基钾的反应优选分别在约60(如50~70℃)和约80℃(如70~90℃)下进行。
中间体化合物M-L1-X-L2-M可在进行M-L1-X-L2-M和式(R3-C)2P-A所示化合物之间的反应之前从反应混合物中分离出来。但是中间体的分离可以不是必要的,已经发现当不分离中间体时反应非常令人满意地进行。当中间体产物M-L1-X-L2-M可相当容易地分离时,例如如果它处于不同于原材料的物理形式,则从反应混合物中分离中间体以促进更多中间体的形成可能是有利的。我们已经发现,反应混合物可含有式M-L1-X-L2-H所示的部分反应的化合物,通过加入更多量的RmM和络合剂(如果使用的话)可使该化合物反应至完全。
中间体产物M-L1-X-L2-M和卤代膦(R3-C)2P-A之间的磷酸化反应也在溶剂存在下进行,与那些用于金属化的溶剂类似的溶剂是合适的,例如醚类、C5+烷烃和石油醚类。我们已经发现,当所用金属为钾时,当用乙醚作为磷酸化反应的溶剂,有利于反应,尽管烷烃,如庚烷可优选用于金属化反应。而且,甚至当用钠或锂作为金属物质时,使用与用于金属化的溶剂不同的溶剂用于磷酸化可能是有利的,例如为了使在一个反应中能够使用较高的温度此外还使溶剂与第二反应的产物容易分离。
磷酸化反应可在高温下进行,如在60℃或更高温度,但优选在室温或低于室温的温度下进行反应,如在-20~25℃。
通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物可通过馏去过量溶剂,优选在真空下,然后将产物化合物萃取至溶剂如甲醇中(从中它可沉淀出来)而从反应混合物中分离。
本发明通过下列仅有的实施例将得到进一步的描述。在所有反应中,准备了所用的反应物和装置以使反应在无水和无氧反应条件下进行。实施例1
在氮气气氛下,将N,N,N’,N’-四甲基乙二胺(0.79cm3,5.25mmol)加至搅拌的正丁基锂(2.10cm3,2.5M在己烷中,5.25mmol)的庚烷(15cm3)溶液中。五分钟后,缓慢加入邻二甲苯(0.26cm3,2.10mmol)。将溶液在室温下搅拌96小时后,形成橙棕色沉淀。
加入二叔丁基氯化膦(1.40cm3,7.37mmol),然后在室温下搅拌溶液直至颜色消失。
通过31P{1H}NMR分析了反应混合物的样品,并测定了双(二叔丁基膦基)-邻二甲苯和单取代类似物的转化率。结果如表1所示。实施例2-8
重复实施例1的实验步骤,但如表1所示改变反应物比率和反应条件。实施例9
重复上述实验步骤,采用丁基锂∶TMEDA∶邻二甲苯的比率为4∶4∶1,温度为25℃以及反应时间为48小时,但过滤丁基锂和邻二甲苯/TMEDA之间反应的产物以从红色液体中分离棕色固体。然后将每个分别与二叔丁基氯化膦反应,测定双(二叔丁基膦基)-邻二甲苯和单取代类似物的转化率。结果如表2所示。实施例10-13
将正丁基锂(11mmol)滴加至搅拌良好的邻二甲苯(0.6ml,5mmol)和叔丁醇钾(1.2g,11mmol)的庚烷(25ml)溶液中。搅拌(有时加热)反应至预定的一段时间(见表3)。
通过将体系置于冰浴中而使其冷却,然后向烧瓶中慢慢加入二叔丁基氯化膦(1.87ml,11mmol)。搅拌体系直至颜色全部消失。向烧瓶中加入乙醚(50cm3)以确保所有生成的膦溶解。所得溶液的样品收集在密封的NMR管中,并用31P{1H}NMR分析。
表1
表2
%转化率(单取代) | %转化率(二取代) | |
固体 | 5 | 38 |
液体 | 30 | 8 |
表3
实施例14
实施例 | 比:BuLi/BuOK/二甲苯 | 钾化反应时间和温度(℃) | %二取代产物的转化率 |
10 | 2.2∶2.2∶1 | 1小时,室温(RT) | 40 |
11 | 3∶3∶1 | RT1小时+60℃1小时 | 45 |
12 | 2.2∶2.2∶1 | 80℃1小时 | 44 |
13 | 3∶3∶1 | 80℃1小时 | 49 |
通过注射器将邻二甲苯(3.3cm3,270×10-2mol)加入至叔丁醇钾(6.6g,5.88×10-2mol)的40/60石油醚(150cm3)悬浮体中。冷却下将42cm31.4M的丁基锂的己烷溶液加入到醚混合物中。混合物搅拌过夜以完成反应,得到橙红色固体二钾代邻二甲苯。过滤混合物,并进一步用石油醚洗涤固体。
然后将二钾代衍生物在-78℃下悬浮于乙醚(150cm3)中,并通过注射器加入二叔丁基氯化膦(10g,5.54×10-2mol)。混合物搅拌一小时,慢慢至室温,然后过滤。滤液通过加入1cm3脱气水水解并干燥。收率(以邻二甲苯计)为94%。通过31P{1H}NMR分析表明,α,α’-双(二叔丁基膦基)邻二甲苯的收率为80%,而单膦的收率为10%。实施例15
将叔丁醇钾(3.99g,35.6mmol)、庚烷(150cm3)和邻二甲苯(1.47cm3,12mmol)加至500ml圆底烧瓶中。向该搅拌的溶液中缓慢加入正丁基锂(14.45cm3,36.1mmol,2.5M在己烷中),将烧瓶加热至80℃1小时。形成橙/红色沉淀,通过过滤将该沉淀分离并用戊烷(3×100cm3)洗涤,然后再悬浮于已预冷却至-20℃的乙醚(100cm3)中。向保持在-20℃的该溶液中加入二叔丁基氯化膦(4.58cm3,24.1mmol),并使反应加热至室温,然后搅拌过夜。经31PNMR测定,α,α’-双(二叔丁基膦基)邻二甲苯的原位反应收率为64%。实施例16
重复实施例15中所述反应,除了将橙红色沉淀二钾代邻二甲苯再悬浮于100cm3已预冷却至0℃的乙醚中,以及溶液保持在0℃的同时加入二叔丁基氯化膦(4.58cm3,24.1mmol)。使反应加热至室温,然后搅拌过夜。经31PNMR测定,α,α’-双(二叔丁基膦基)邻二甲苯的原位反应收率为74.9%。实施例17
重复实施例15中所述反应,除了将橙红色沉淀二钾代邻二甲苯再悬浮于100cm3室温下的乙醚中,以及溶液保持在室温的同时加入二叔丁基氯化膦(4.58cm3,24.1mmol)。搅拌反应过夜,经31PNMR测定,α,α’-双(二叔丁基膦基)邻二甲苯的原位反应收率为75.5%。实施例18
将叔丁醇钠(17.29g,180mmol)、N,N,N’,N’-四甲基乙二胺(27.1cm3,180mmol)、庚烷(100cm3)和邻二甲苯(7.32cm3,60mmol)加至1升圆底烧瓶中。向该搅拌的溶液中缓慢加入正丁基锂(72.0cm3,180mmol,2.5M在己烷中),将烧瓶加热至60℃2小时。形成橙色沉淀,通过过滤将该沉淀分离并用戊烷(100cm3)洗涤,然后再悬浮于戊烷(100cm3)中。向其中加入二叔丁基氯化膦(22.75cm3,120mmol),在室温下搅拌反应过夜。当形成清晰的两层时通过加入脱气/去离子水(50cm3)猝灭反应,然后分离戊烷层(上层)。在真空中除去溶剂,并通过用冷甲醇(-10C)洗涤而纯化产物。收率(20.0g,84.6%)。
Claims (7)
1.一种制备通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物的方法,其中每个R独立地为任选取代的侧有机基团,通过它该基团与叔碳原子C连接;L1、L2独立地为连接基团,选自将各自的磷原子与基团X连接的任选取代的低级亚烷基链,X为包括任选取代的芳基部分的桥连基,该芳基部分通过可得到的相邻碳原子与磷原子连接,该方法包括:
ⅰ)将式H-L1-X-L2-H所示的化合物与有机金属化合物一起反应,生成式M-L1-X-L2-M所示的中间体化合物,其中M为碱金属原子,
ⅱ)将所述中间体化合物与式(R3-C)2P-A所示的化合物反应,其中A为卤原子,形成所述通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物。
2.权利要求1所述的方法,其中M为选自钠、钾或锂的ⅠA族金属。
3.权利要求1或2所述的方法,其中Rm-M通过Rm-Li和烷醇钾或烷醇钠之间的交换反应在原位产生。
4.权利要求1-3中任一项所述的方法,其中RmM与H-L1-X-L2-H的反应在能与金属形成络合物的碱性化合物存在下进行。
5.权利要求4所述的方法,其中所述碱性化合物包括四甲基乙二胺。
6.前述权利要求中任一项所述的方法,其中所述通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物选自α,α’-双(二叔丁基膦基)邻二甲苯(也称作1,2-双(二叔丁基膦甲基)苯)、双(二叔新戊基膦基)-邻二甲苯或双1,2(二叔丁基膦基)萘。
7.一种适于催化乙烯羰基化反应的催化剂,该催化剂包括通过权利要求1所述方法制备的通式为(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物以及钯或其化合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9805348.1 | 1998-03-16 | ||
GBGB9805348.1A GB9805348D0 (en) | 1998-03-16 | 1998-03-16 | Compound |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1293675A true CN1293675A (zh) | 2001-05-02 |
CN1140532C CN1140532C (zh) | 2004-03-03 |
Family
ID=10828473
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB998040304A Expired - Fee Related CN1140532C (zh) | 1998-03-16 | 1999-03-16 | 二膦的制备方法 |
Country Status (14)
Country | Link |
---|---|
US (1) | US6376715B1 (zh) |
EP (1) | EP1064288B1 (zh) |
JP (1) | JP4283443B2 (zh) |
KR (1) | KR100421627B1 (zh) |
CN (1) | CN1140532C (zh) |
AU (1) | AU742029B2 (zh) |
CA (1) | CA2323906C (zh) |
DE (1) | DE69907433T2 (zh) |
ES (1) | ES2195544T3 (zh) |
GB (1) | GB9805348D0 (zh) |
MY (1) | MY120565A (zh) |
TW (1) | TWI249534B (zh) |
WO (1) | WO1999047528A1 (zh) |
ZA (1) | ZA200004914B (zh) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102341405A (zh) * | 2009-01-26 | 2012-02-01 | 罗地亚运作公司 | 配体 |
CN103687842A (zh) * | 2011-07-22 | 2014-03-26 | 帝斯曼知识产权资产管理有限公司 | 取代烯烃的异构化的方法 |
CN107098932A (zh) * | 2017-06-29 | 2017-08-29 | 管德新 | 一种可用于氢甲酰化反应的苄基类配体的合成方法 |
CN109476680A (zh) * | 2016-07-04 | 2019-03-15 | 北兴化学工业株式会社 | 有机磷化镁及制造方法、其络合物及制造方法及使用该磷化物的有机磷化合物的制造方法 |
CN114805434A (zh) * | 2021-01-18 | 2022-07-29 | 惠州凯特立斯科技有限公司 | 一种新型四齿膦配体化合物及其合成方法与应用 |
CN114835746A (zh) * | 2021-02-01 | 2022-08-02 | 惠州凯特立斯科技有限公司 | 一种新型四齿膦配体化合物及其合成方法与应用 |
CN114805434B (zh) * | 2021-01-18 | 2024-07-05 | 广东欧凯新材料有限公司 | 一种新型四齿膦配体化合物及其合成方法与应用 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6743911B2 (en) † | 2000-03-14 | 2004-06-01 | Shell Oil Company | Process for the carbonylation of pentenenitrile |
MXPA02001147A (es) * | 2001-03-19 | 2004-04-21 | Warner Lambert Co | Sintesis de ligandos bisfosina no-c2-simetricos como catalizadores para la hidrogenacion asimetrica. |
TWI301481B (en) | 2002-08-10 | 2008-10-01 | Lucite Int Uk Ltd | A catalyst system |
JP4599169B2 (ja) * | 2002-12-04 | 2010-12-15 | チバ ホールディング インコーポレーテッド | シクロオルガニルホスファンおよびジ(アルカリ金属/アルカリ土類金属)オリゴホスファンジイドの合成方法 |
WO2005003070A1 (en) | 2003-07-03 | 2005-01-13 | Lucite International Uk Limited | Process for the hydroformylation of ethylenically unsaturated compounds |
GB0403592D0 (en) | 2004-02-18 | 2004-03-24 | Lucite Int Uk Ltd | A catalyst system |
GB0516556D0 (en) | 2005-08-12 | 2005-09-21 | Lucite Int Uk Ltd | Improved catalyst system |
JP2009515936A (ja) | 2005-11-17 | 2009-04-16 | ルーサイト インターナショナル ユーケー リミテッド | エチレン性不飽和化合物のカルボニル化 |
CA2671409C (en) | 2006-12-02 | 2016-07-26 | Lucite International Uk Limited | Novel carbonylation ligands and their use in the carbonylation of ethylenically unsaturated compounds |
GB201000078D0 (en) | 2010-01-05 | 2010-02-17 | Lucite Int Uk Ltd | Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporatng such ligands |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB877592A (en) * | 1959-03-26 | 1961-09-13 | Ici Ltd | Preparation of diphosphines |
US4879008A (en) * | 1987-11-09 | 1989-11-07 | Eastman Kodak Company | Preparation of bidentate ligands |
DE4134772A1 (de) * | 1990-10-31 | 1992-05-07 | Basf Ag | Verfahren zur herstellung von bis(di-tert.-butylphosphino)methan |
WO1996017855A1 (en) * | 1994-12-09 | 1996-06-13 | Griffith University | Anti-tumour agents |
GB9425911D0 (en) * | 1994-12-22 | 1995-02-22 | Ici Plc | Process for the carbonylation of olefins and catalyst system for use therein |
GB9717059D0 (en) * | 1997-08-13 | 1997-10-15 | Ici Plc | Method of manufacturing phosphine compound |
-
1998
- 1998-03-16 GB GBGB9805348.1A patent/GB9805348D0/en not_active Ceased
-
1999
- 1999-03-16 JP JP2000536723A patent/JP4283443B2/ja not_active Expired - Fee Related
- 1999-03-16 DE DE69907433T patent/DE69907433T2/de not_active Expired - Lifetime
- 1999-03-16 ES ES99909108T patent/ES2195544T3/es not_active Expired - Lifetime
- 1999-03-16 KR KR10-2000-7010184A patent/KR100421627B1/ko not_active IP Right Cessation
- 1999-03-16 AU AU28475/99A patent/AU742029B2/en not_active Ceased
- 1999-03-16 CN CNB998040304A patent/CN1140532C/zh not_active Expired - Fee Related
- 1999-03-16 WO PCT/GB1999/000797 patent/WO1999047528A1/en active IP Right Grant
- 1999-03-16 CA CA002323906A patent/CA2323906C/en not_active Expired - Fee Related
- 1999-03-16 EP EP99909108A patent/EP1064288B1/en not_active Expired - Lifetime
- 1999-03-16 MY MYPI99000973A patent/MY120565A/en unknown
- 1999-03-16 US US09/646,049 patent/US6376715B1/en not_active Expired - Lifetime
- 1999-04-14 TW TW088105944A patent/TWI249534B/zh not_active IP Right Cessation
-
2000
- 2000-09-14 ZA ZA200004914A patent/ZA200004914B/xx unknown
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102341405A (zh) * | 2009-01-26 | 2012-02-01 | 罗地亚运作公司 | 配体 |
CN103687842A (zh) * | 2011-07-22 | 2014-03-26 | 帝斯曼知识产权资产管理有限公司 | 取代烯烃的异构化的方法 |
CN109476680A (zh) * | 2016-07-04 | 2019-03-15 | 北兴化学工业株式会社 | 有机磷化镁及制造方法、其络合物及制造方法及使用该磷化物的有机磷化合物的制造方法 |
CN107098932A (zh) * | 2017-06-29 | 2017-08-29 | 管德新 | 一种可用于氢甲酰化反应的苄基类配体的合成方法 |
CN114805434A (zh) * | 2021-01-18 | 2022-07-29 | 惠州凯特立斯科技有限公司 | 一种新型四齿膦配体化合物及其合成方法与应用 |
CN114805434B (zh) * | 2021-01-18 | 2024-07-05 | 广东欧凯新材料有限公司 | 一种新型四齿膦配体化合物及其合成方法与应用 |
CN114835746A (zh) * | 2021-02-01 | 2022-08-02 | 惠州凯特立斯科技有限公司 | 一种新型四齿膦配体化合物及其合成方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
EP1064288A1 (en) | 2001-01-03 |
US6376715B1 (en) | 2002-04-23 |
AU742029B2 (en) | 2001-12-13 |
ZA200004914B (en) | 2001-08-10 |
ES2195544T3 (es) | 2003-12-01 |
CN1140532C (zh) | 2004-03-03 |
AU2847599A (en) | 1999-10-11 |
CA2323906C (en) | 2009-02-17 |
WO1999047528A1 (en) | 1999-09-23 |
TWI249534B (en) | 2006-02-21 |
DE69907433D1 (de) | 2003-06-05 |
CA2323906A1 (en) | 1999-09-23 |
JP4283443B2 (ja) | 2009-06-24 |
JP2002506872A (ja) | 2002-03-05 |
DE69907433T2 (de) | 2004-05-06 |
KR100421627B1 (ko) | 2004-03-10 |
EP1064288B1 (en) | 2003-05-02 |
KR20010041885A (ko) | 2001-05-25 |
MY120565A (en) | 2005-11-30 |
GB9805348D0 (en) | 1998-05-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1140532C (zh) | 二膦的制备方法 | |
US6124476A (en) | Catalyst ligands, catalyst compositions, catalyst metal complexes and processes for cross-coupling aromatic boron compounds with aromatic halogens or perfluoroalkylsulfonates | |
KR100581624B1 (ko) | 포스핀 화합물의 제조 방법 | |
CN101200476B (zh) | 用于过渡金属催化的加氢甲酰化的双亚磷酸酯配体 | |
CN101990543B (zh) | 制备钌卡宾络合物的方法 | |
JPH08231571A (ja) | 複素環式カルベンとの金属錯体 | |
Falloon et al. | Attaching Metal‐Capped sp Carbon Chains to Metal Clusters: Synthesis, Structure, and Reactivity of Rhenium/Triosmium Complexes of Formula [(η5‐C5Me5) Re (NO)(PPh3)(CC) nOs3 (CO) y (X) z] m+, Including Carbon Geometries More Distorted than Planar Tetracoordinate | |
JPH06506485A (ja) | 燐化合物 | |
Durran et al. | The synthesis and co-ordination chemistry of new functionalised pyridylphosphines derived from Ph 2 PCH 2 OH | |
Rickard et al. | Synthesis and Structures of cis‐and trans‐[Os (Bcat)(aryl)(CO) 2 (PPh3) 2]: Compounds of Relevance to the Metal‐Catalyzed Hydroboration Reaction and the Metal‐Mediated Borylation of Arenes | |
KR100350814B1 (ko) | 3가인의사이클릭화합물,이의제조방법및이를포함하는균질가용성촉매시스템 | |
JP4298505B2 (ja) | 不斉反応のためのリガンド | |
Shiu et al. | Conditioned P− CH2 Bond Cleavage of a μ-DPPM Ligand in a Cationic Diruthenium System | |
US4661608A (en) | Process for the manufacture of silylmetallocene compounds | |
Arena et al. | Chiral rhodium complexes containing bidentate ligands derived from (R, R)-1, 2-diaminocyclohexane for catalytic enantioselective hydrosilylation of acetophenone | |
JPH09241276A (ja) | アルケニルホスフィンオキシド化合物の製造法 | |
Kasani et al. | Chromium bis (phosphoranimine) complexes; bridging chromium carbenes with no CO or Cp supporting ligands | |
JP2560246B2 (ja) | 有機白金ポリマーおよびその製造法 | |
JP2003190806A (ja) | アルキン二量化触媒 | |
Tanski et al. | The synthesis and molecular structures of 2, 5-diarylpyrroles, H (Ar= Ph, 2, 4-Xyl) | |
김용주 et al. | A Facile Preparation, Structure, and Some Reactions of trans-PdPHI $(PMe_3) _2$ | |
WO2006095476A1 (ja) | 多座ホスフィン配位子を有する遷移金属含有デンドリマー及び触媒 | |
Bailey et al. | Synthesis of acylphosphine complexes by controllable migration of acyl groups from molybdenum to phosphido ligands |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040303 Termination date: 20170316 |
|
CF01 | Termination of patent right due to non-payment of annual fee |