CN1140531C - 膦化合物的生产方法 - Google Patents
膦化合物的生产方法 Download PDFInfo
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- CN1140531C CN1140531C CNB988080192A CN98808019A CN1140531C CN 1140531 C CN1140531 C CN 1140531C CN B988080192 A CNB988080192 A CN B988080192A CN 98808019 A CN98808019 A CN 98808019A CN 1140531 C CN1140531 C CN 1140531C
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- 238000004519 manufacturing process Methods 0.000 title claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title description 25
- -1 phosphine compound Chemical class 0.000 title description 25
- 229910000073 phosphorus hydride Inorganic materials 0.000 title description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 125000000962 organic group Chemical group 0.000 claims abstract description 9
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 125000005647 linker group Chemical group 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 9
- NVLHGZIXTRYOKT-UHFFFAOYSA-N 1-chloro-2,3-dimethylbenzene Chemical compound CC1=CC=CC(Cl)=C1C NVLHGZIXTRYOKT-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- ULNVTMFBEVVUMH-UHFFFAOYSA-N P.[Cl] Chemical compound P.[Cl] ULNVTMFBEVVUMH-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- DIHZKHJDWYVEEE-UHFFFAOYSA-N P.[Br] Chemical compound P.[Br] DIHZKHJDWYVEEE-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000003747 Grignard reaction Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001721 carbon Chemical group 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
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JNFBOWNNNAHVNZ-UHFFFAOYSA-N 1,2-dibromoethyne Chemical group BrC#CBr JNFBOWNNNAHVNZ-UHFFFAOYSA-N 0.000 description 1
- WLPXNBYWDDYJTN-UHFFFAOYSA-N 1-bromo-2,3-dimethylbenzene Chemical compound CC1=CC=CC(Br)=C1C WLPXNBYWDDYJTN-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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000008232 de-aerated water Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HHDLJTLPOGOXLR-UHFFFAOYSA-N propan-2-ylphosphane Chemical compound CC(C)P HHDLJTLPOGOXLR-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- 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
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- 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
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
通式(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物(I)的制备方法，其中各个R独立地为与叔碳原子C相连的可任选被取代的侧有机基团；L1、L2独立地为连接各磷原子与X基的选自可任选被取代的低级亚烷基链的连接基，以及X为桥连基，该桥连基包括可任选被取代的芳基部分，并且所述磷原子在可用的相邻碳原子上与之相连，包括以下步骤：(i)使式A-L1-X-L2-A的化合物(II)与金属M在适合的溶剂中一起反应生成式A-M-L1-X-L2-M-A的中间化合物(III)，其中A为卤原子；(ii)使所述中间化合物(III)与式(R3-C)2P-A1的化合物(IV)反应生成所述化合物(I)，其中A1为卤原子，并且可与A相同或不同。所述化合物(I)可用于形成烯烃羰基化作用的催化剂体系。
Description
本发明涉及一种膦化合物，它适合作为可用于烯烃羰基化作用的催化剂体系的组分，特别涉及这种膦化合物的生产方法。
WO96/19434公开了一种乙烯的羰基化方法及用于其中的催化剂体系。该文献中所述催化剂体系包括二齿膦配体和第VIII族金属或其化合物，所述二齿膦配体具有以下通式：(R3-C)2P-L1-X-L2-P-(C-R3)2，其中各个R独立地为与叔碳原子C相连的可任选取代的侧有机基团；L1、L2独立地为连接各磷原子与X基的选自可任选取代的低级亚烷基链的连接基，以及X为桥连基，包括可任选取代的芳基部分，所述磷原子在可用的相邻碳原子上与之相连。这种二齿膦配体的一个例子是双(二-叔丁膦基)-邻二甲苯。
这种催化剂可通过混合所述膦配体与适合的钯源如乙酸钯制备。WO96/19434描述通过适合的仲膦与相应的芳族二卤化物反应产生的磷鎓盐制备一种形式的所述配体。在WO96/19434的优选膦配体形式中，R为低级烷基，特别是甲基。通过所述途径生产此配体的问题是所用的仲膦(例如二叔丁基膦)是有毒、高活性、有臭味且是可燃的。我们还发现所述反应的产率低，一些二叔丁基膦转化成不能再生的废品而必须处理掉。
Zvezdina等(VINITI3581-80，化学文摘《Chemical Abstracts》第96卷(1992)52409)描述了通过二溴化乙炔基二镁与二异丙基氯膦反应形成1，2-亚乙炔基双[二(1-甲基乙基)膦]，来生产用于加氢甲酰化作用催化剂的配体的方法。
M.F.LaPpert和T.R.Martin(J.Chem.Soc.，Dalton Trans.，1982第1952页)描述了通过二-格利雅合成途径制备各种金属环化合物的方法。
现在我们已发现WO96/19434中所述类型的膦配体可通过一种高产率的途径制备，使用更有益于健康的原料并且产生的废品少于WO96/19434中所述途径。
根据本发明，通式(R3-C)2P-L1-X-L2-P-(C-R3)2(I)化合物的生产方法，其中各个R独立地为与叔碳原子C相连的可任选取代的侧有机基团；L1、L2独立地为连接各磷原子与X基的选自可任选取代的低级亚烷基链的连接基，以及X为桥连基，包括可任选取代的芳基部分，所述磷原子在可用的相邻碳原子上与之相连，包括以下步骤：
i)使式A-L1-X-L2-A(II)的化合物与金属M在适合的溶剂中一起反应生成式A-M-L1-X-L2-M-A(III)的中间化合物，其中A为卤原子，
ii)使所述中间化合物(III)与式(R3-C)2P-A1(IV)的化合物反应生成所述化合物(I)，其中A1为卤原子，并且可与A相同或不同。
通式(R3-C)2P-L1-X-L2-P-(C-R3)2的化合物(I)可用作催化剂复合物的组分。特别是WO96/19434描述了用这种化合物作二齿配体，与第VIII族金属如钯一起使用时是用于烯烃羰基化作用的有效催化剂。
所述可任选取代的侧有机基团R可独立地选自宽范围的基团。优选地，所述侧基是可任选取代的低级烷基，例如C1-8，可以是支链或直链的。每个R基可与其它R基相同或不同。优选(R3-C)2P-L1-X-L2-P-(C-R3)2是对称的，其中两个(C-R3)2基团相同。
特别优选的是，当所述有机基团R与它们各自的碳原子相连时，形成空间位阻至少和叔丁基一样的复合基团。本文中空间位阻如C.Masters，《均相过渡金属催化-一种温和的技术》“HomogeneousTransition Metal Catalysis-A Gentle Art”，Chapman and Hall出版(1981)，第14-所述。
连接基L1和L2独立地选自可任选取代的(特别是低级烷基如C1至C4取代的)低级亚烷基，例如C1至C4链。特别优选两个L1和L2均为亚甲基。
桥连基X为芳基部分，例如苯基，它可任选地被取代，条件是两个磷原子与相邻碳原子相连，例如在所述苯基上的1和2位上相连。芳基部分可任选被其它有机基团例如烷基，特别是C1-8、芳基、烷氧基、烷氧羰基、卤素、硝基、三卤甲基和氰基取代。此外，所述芳基部分可以是稠合多环基团例如萘、亚联苯基或茚。
利于通过本发明方法制备的化合物(I)的例子描述在WO96/19434中，该文献引入本文作为参考，包括双(二叔丁膦基)-邻二甲苯(也称为1，2-双(二叔丁膦基甲基)苯)、双(二-t-新戊膦基)-邻二甲苯和双-1，2-(二叔丁膦基)萘。
M可以是与烷基卤反应生成极性金属有机基团的任何适合的金属。适合的金属包括第II族和第IIB族金属例如镁、钙、锌、镉、汞、铝、镓、铟、锡和铅。优选的金属是镁。使用镁时，所述化合物(III)称为二-格利雅化合物。所述镁可为任何常见的形式如切屑、碎片、颗粒、条等，但优选使用镁粉。
化合物(II)的性质取决于所要产品化合物(I)的性质。当L1和L2均为亚甲基和X为未取代的苯基时，优选的起始原料是α，α＇-二氯-邻二甲苯。A为卤原子。优选的卤素是氯，但其它卤素如溴也可以有效。
我们已发现化合物(II)逐渐地加入所述金属中，例如滴加或利用其它手段(例如可控制的泵)实现缓慢加入比较有利。
M.F.Lappert等，J.Chem.Soc.Dalton Trans.(1982)第1959页描述了二-格利雅化合物例如邻-C6h4(CH2MgCl)2的制备。该文献描述了通过二-格利雅反应制备金属环化合物的方法，但详细描述了二-格利雅化合物的制备，这可用于制备本发明化合物(III)。因此，按照该文献的教导(引入本文供参考)，如果用THF作为溶剂，且当化合物(II)和所得二-格利雅化合物(III)在该溶剂中的浓度较低例如低于约0.1mol/l、优选约0.075mol/l时，可提高二-格利雅化合物的产率。
膦化合物(IV)的性质取决于欲制备的产品化合物。可任选取代的侧有机基团R可独立地选自宽范围的基团。优选地，所述侧基为可任选取代的低级烷基例如C1-8，可以是支链的或直链的。每个R基可与其它R基相同或不同。优选(R3-C)2P-L1-X-L2-P-(C-R3)2是对称的，其中两个(C-R3)2基团相同。A1优选为氯或溴或碘原子。例如，当每个R基均为甲基时，即当(C-R3)2为叔丁基时，所述膦化合物(IV)可为二-叔丁基氯膦。通过合成，例如利用格利雅反应(其中(R3-C)MgCl与PCl3反应)或通过本领域已知的其它合成方法可获得化合物(IV)。一些适用的原料也可商购得到。
膦化合物(IV)可以超过化学计量的量加入到化合物(III)中。优选化合物(IV)与化合物(III)的比率为至少2∶1，不过该比值如果更大例如至少4∶1，可取得更快的反应速率。然而，在这些较高比例下取得的反应速率增加必须以使用更多膦化合物为代价。通常化合物(IV)与化合物(III)的比率低于20∶1，优选低于约10∶1。
所用溶剂不得含有与所述中间化合物反应的任何组分，适合的此类溶剂为本领域技术人员所公知。有利的溶剂包括无水醚类溶剂如四氢呋喃(THF)、二噁烷和二甲氧基乙烷。优选的溶剂是THF。二-格利雅化合物的制备必须在无水条件下进行，因为水与所述格利雅化合物发生副反应产生H-L1-X-L2-H。
如需要，化合物(III)和化合物(IV)之间的反应可被加热以提高反应速率。然而，如果反应特别快，在无附加热量或在冷却的情况下可能更易控制反应。以此方式降低反应速率可能有利于减少某些体系中的副反应。例如，我们发现当化合物(IV)为氯膦时，如果稍微加热例如在约50℃的温度下进行反应，可易于控制反应并取得令人满意的速率。然而，用相应的溴膦代替所述氯膦时，反应在室温下将会非常迅速，因此不需附加热量，冷却反应混合物将会有利。
可通过蒸出过量的溶剂和过量的反应物(如果存在的话)，优选在真空下进行，然后将产品化合物萃取至溶剂例如己烷或甲醇(优选热的)中，并从所述溶剂中沉淀或重结晶，使化合物(I)从反应混合物中分离出来。有机化学领域的技术人员亦可采用其它技术和试剂来分离所述产品。
下面通过实施例进一步描述本发明。
实施例1化合物(III)的制备
将1.35g(55mmol)镁粉在90℃真空下加热30分钟使之活化，然后冷却并在约40ml THF(预先已在N2保护下用钠进行蒸馏)中与单晶碘一起搅拌直至碘斑消失。滤出碘化镁，并使所述金属再悬浮于约40ml蒸馏过的THF中。历经3-4小时向其中加入2.42g(13.8mmol)升华α，α′-二氯-邻二甲苯的THF(140ml)溶液，将反应混合物搅拌过夜。将所得二格利雅化合物溶液过滤，用2ml脱气水处理(quench)产生邻二甲苯。然后通过气相色谱法分析所得到的邻二甲苯，与实验室中配制的标准溶液对比确定产率。产率基于α，α′-二氯-邻二甲苯起始原料大概为91％，证明该反应可得到高产率的二-格利雅化合物。
实施例2
重复实施例1，但用α，α′-二溴-邻二甲苯代替实施例1的二氯化合物。测定产率为15％。与实施例1相比，此产率下降可能是由于所述二-格利雅溴化物的反应性增加促使所述格利雅分子迅速偶合所导致的。
实施例3化合物(I)的制备
如实施例1中所述，由α，α′-二氯-邻二甲苯和镁粉制备二-格利雅化合物。通过滤出的反应混合物的水处理试样的GC分析测定二-格利雅的产率为94％。将所得二-格利雅滴加至剧烈搅拌的过量二倍的二叔丁基氯膦(由Aldrich提供)的THF溶液中，加完后使之回流8小时，从而使所滤出的二-格利雅化合物官能化。通过31P核磁共振测定：双(二叔丁膦基)-邻二甲苯的产率为55％(基于所存在的二-格利雅化合物)。该反应混合物中还发现一些其它未确定的含磷化合物。
实施例4化合物(IV)：化合物(III)之比的变化
在125ml蒸馏过的THF中，用单晶碘使6.73g(0.277mol)镁粉活化。用Gilson泵控制添加速度，将12.11g(0.069mol)α，α′-二氯-邻二甲苯在875ml蒸馏过的THF中的溶液经大约4小时滴加至所述镁混合物中，将混合物搅拌过夜。将所得的二-格利雅溶液过滤，用水处理少量试样以便通过气相色谱分析确定邻二甲苯的产率。然后将所述二-格利雅化合物以表1中所示不同比例加至二-叔丁基氯膦中，并在50℃下搅拌至多约24小时。通过31P NMR监视产品的形成以确定反应终点。在真空下除去溶剂，并将所得蜡状固体用热甲醇重结晶。基于二-格利雅计算产率，示于表1中。
表1
| 膦∶二格利雅2∶1 | 膦∶二格利雅4∶1 | 膦∶二格利雅8∶1 | |
| 双(二叔丁膦基)-邻二甲苯的产率 | 42.8 | 55.3 | 61.8 |
实施例5
如实施例1中所述，由α，α′-二氯-邻二甲苯和镁粉制备二-格利雅化合物，并加入到含80％w/w二叔丁基溴膦和20％w/w二叔丁基氯膦的混合溶液中。随着反应的进行，通过取自该混合物的试样的31P NMR分析监视产品的形成来跟踪反应。随着迅速形成双(二叔丁膦基)-邻二甲苯产品，混合物中溴膦的量非常迅速地下降，而氯膦含量下降的要慢得多。因此所述溴膦与氯膦相比可更迅速地反应得到所需的产品。约8小时后，在混合物中未检测到溴膦，而24小时后仍残留有一些氯膦。基于所述二-格利雅反应物，产品的产率为23％。
Claims (7)
1.一种通式(R3-C)2P-L1-X-L2-p-(C-R3)2的化合物(I)的生产方法，其中各个R独立地为与叔碳原子C相连的可任选被取代的侧有机基团；L1、L2独立地为连接各磷原子与X基的选自可任选被取代的C1-C4亚烷基链的连接基，以及X为桥连基，该桥连基包括可任选被取代的芳基部分，并且所述磷原子在可用的相邻碳原子上与之相连，包括以下步骤：
i)使式A-L1-X-L2-A的化合物(II)与金属M在适合的溶剂中反应生成式A-M-L1-X-L2-M-A的中间化合物(III)，其中A为卤原子，
ii)使所述中间化合物(III)与式(R3-C)2P-A1的化合物(IV)反应生成所述化合物(I)，其中A1为卤原子，并且可与A相同或不同。
2.根据权利要求1的方法，其中M为镁。
3.根据权利要求1的方法，其中A为氯。
4.根据权利要求2的方法，其中A为氯。
5.根据权利要求3或4的方法，其中A1为氯、溴或碘原子。
6.根据权利要求1，2，3或4任一项的方法，其中各R基包括可任选被取代的C1-8烷基，并且各个R与其它R基相同或不同。
7.根据权利要求1的方法，其中化合物(I)包括双(二叔丁膦基)-邻二甲苯、双(二-t-新戊膦基)-邻二甲苯和双-1，2-(二叔丁膦基)萘。
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| MY121701A (en) | 2006-02-28 |
| AU741245B2 (en) | 2001-11-29 |
| CN1266436A (zh) | 2000-09-13 |
| KR100581624B1 (ko) | 2006-05-23 |
| US6335471B1 (en) | 2002-01-01 |
| ES2212329T3 (es) | 2004-07-16 |
| CA2297838A1 (en) | 1999-02-25 |
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