CN1243516A - 鈲膦、其制备方法及其应用 - Google Patents
鈲膦、其制备方法及其应用 Download PDFInfo
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- CN1243516A CN1243516A CN98801885A CN98801885A CN1243516A CN 1243516 A CN1243516 A CN 1243516A CN 98801885 A CN98801885 A CN 98801885A CN 98801885 A CN98801885 A CN 98801885A CN 1243516 A CN1243516 A CN 1243516A
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- phosphine
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- guanidinium
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- FWRSQHWGVGNBTF-UHFFFAOYSA-N P.NC(=N)N Chemical class P.NC(=N)N FWRSQHWGVGNBTF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical group NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 21
- -1 dimethylamino cyanogen Chemical compound 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical group NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 7
- 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 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims description 2
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000000605 extraction Methods 0.000 description 6
- 150000002382 heptanals Chemical class 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 238000007341 Heck reaction Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N caproic aldehyde Natural products CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000003642 hunger Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 230000037351 starvation Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- BHVGMUDWABJNRC-UHFFFAOYSA-N (±)-2-methylhexanal Chemical compound CCCCC(C)C=O BHVGMUDWABJNRC-UHFFFAOYSA-N 0.000 description 1
- BKILWHYRLBCASZ-UHFFFAOYSA-M 2-[bis(2-hydroxyethyl)amino]ethanol;2-hydroxypropanoate;phenylmercury(1+) Chemical class CC(O)C([O-])=O.[Hg+]C1=CC=CC=C1.OCCN(CCO)CCO BKILWHYRLBCASZ-UHFFFAOYSA-M 0.000 description 1
- DQZWMOWSTWWMPP-UHFFFAOYSA-N 3-diphenylphosphanylpropan-1-amine Chemical compound C=1C=CC=CC=1P(CCCN)C1=CC=CC=C1 DQZWMOWSTWWMPP-UHFFFAOYSA-N 0.000 description 1
- FCJNITIJYWQFCM-UHFFFAOYSA-N 3-fluoro-5-iodobenzonitrile Chemical compound FC1=CC(I)=CC(C#N)=C1 FCJNITIJYWQFCM-UHFFFAOYSA-N 0.000 description 1
- FFCSRWGYGMRBGD-UHFFFAOYSA-N 3-iodoaniline Chemical compound NC1=CC=CC(I)=C1 FFCSRWGYGMRBGD-UHFFFAOYSA-N 0.000 description 1
- SHSNFMVCWZIDKX-UHFFFAOYSA-N 3-phenylphosphanylpropan-1-amine Chemical compound NCCCPC1=CC=CC=C1 SHSNFMVCWZIDKX-UHFFFAOYSA-N 0.000 description 1
- BAPSVHDREAOALN-UHFFFAOYSA-N 3-phosphanylaniline Chemical compound NC1=CC=CC(P)=C1 BAPSVHDREAOALN-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 description 1
- LOWZXSYJBACBTH-UHFFFAOYSA-N PC1=CC=CC=C1.I.I Chemical compound PC1=CC=CC=C1.I.I LOWZXSYJBACBTH-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- JYJSYIZVXUVISP-UHFFFAOYSA-N azane;iodobenzene Chemical compound N.IC1=CC=CC=C1 JYJSYIZVXUVISP-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- ZFJMTDFOGDGPTF-UHFFFAOYSA-N phosphanium;chloride;hydrochloride Chemical compound P.Cl.Cl ZFJMTDFOGDGPTF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical group [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
-
- 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
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明涉及式Ⅰ的鈲膦,其中,n是1至3的整数,X是Cl、Br、Ⅰ或PF6,R1、R2、R3、R4相同或不同,且各是C1－C6－烷基或氢,和R5是苯基,且鈲—取代基位于P原子的间位或对位。
Description
本发明涉及鈲膦(guanidinium phosphanes)、其制备方法及其应用
对于化学工业中的许多化学反应而言，水作为溶剂非常有价值。然而，在含水体系中有机反应通常具有不进行反应或只进行到不能令人满意的程度的缺点。然而，借助如含三(间磺基苯基)膦的三钠盐的配合物，使得制备可以用于烯烃的加氢甲酰化反应中的催化剂体系(DE-OS-38 40 600)成为可能。与其它的用于上述反应的已知催化剂相比，它们具有在水中溶解的优点。因此，此加氢甲酰化反应可以在由水相和有机相组成的多相反应体系(二相体系)中进行，如DE-A-38 40 600中描述的那样。
此方法的优点是，终产物可以通常简单的相分离与水溶性催化剂相分离。再者，贵金属催化剂实际上可以回收，用这种方式不会有损失，或可以再循环至合成步骤中(DE-A-26 27 354)。
制备水溶性催化剂体系时，含有磷的化合物特别有价值。催化剂的实例包含含有阴离子膦类作为配位体的钯配合物。
含有阳离子膦类的配位体在过去几乎未曾有人研究，虽然它们应当同样对上述反应具有有利的作用。
有时，某些鈲膦也曾用作钯催化的C-C耦合反应(例如Heck反应中)的催化剂配位体。因此，这些反应在含水体系中进行会是有利的。
鈲膦的合成，例如，是通过将3-氨基丙基二苯基膦或双(3-氨基丙基)苯基膦与1-H-吡唑-1-甲脒(carboxamidine)盐酸盐反应来进行的[H. Dibowski等，《四面体》第51卷，第8期(1995)2325-2330]。
此方法给出3-胍基丙基二苯基膦和双(3-胍基丙基)苯基膦。上述化合物可以用作C-C耦合反应(例如Heck反应中)的催化剂配位体。
因此存在着进一步开发其它含磷配位体的需要，这些配位体可用在Heck-反应和其它有机金属合成或反应中。
在此有感兴趣的特别是鈲膦，其中鈲取代基直接结合到苯基上。这些化合物预期对C-C耦合反应等具有特别有利的作用。
因此，本发明的目的是，提供鈲取代基直接结合到苯基上且可以特别成功地用在C-C耦合反应例如Heck反应中的鈲取代的化合物。
此目的通过式I的鈲膦实现：
其中
n是1至3的整数，
X是Cl、Br、I或PF6，
R1、R2、R3、R4相同或不同，且各是C1-C6-烷基或氢，和
R5是苯基，且鈲取代基位于P-原子的间位或对位。
优选的是，R1与R2相同且R3与R4相同。
优选的是，R1和R2同是H或甲基。
优选的是，R3和R4同是H或甲基。
本发明同样提供一种制备通式I的鈲膦的方法，其特征在于，使式II的N-氨基苯基膦
其中n和R5如式I中所定义，与二甲基氨基氰反应，给出式I的鈲膦。
优选的是，使式II的N-氨基苯基膦首先与等摩尔量的HCl的醚-或水溶液反应，形成式III的HCl的加合物，
其中n和R5与式I中的定义相同，且之后进行与二甲基氨基氰的反应步骤。
本发明同样提供一种制备式I的鈲膦的方法，其特征在于，使伯-和仲膦R5 3-nPHn(n＝1或2)与式IV的间-或对-碘苯基胍反应，
其中
R1、R2、R3、R4与式I中的定义相同，且碘原子位于P-原子的间位或对位。
优选的是使用乙腈、二甲基乙酰胺、醚和/或烃类作为溶剂。
至于此反应的催化剂，优选的是使用乙酸钯(II)、卤化钯(II)-膦配合物、钯(O)-烯烃配合物、钯(O)-膦配合物和细分散的金属钯。
本发明同样提供式I化合物在制备碳-碳耦合反应的催化剂配位体中的应用。
本发明通过下列实施例来示例说明，在这些实施例中，本发明化合物制备成其氯化物、溴化物、碘化物和六氟磷酸盐形式。
实施例1
在搅拌下，将3.5ml的HCl在醚中的溶液(1.65N)加入到2.25g(8.1mmol)二苯基(3-氨基苯基)膦在20ml二氯甲烷中的溶液中。蒸馏掉溶剂，并将残留物通过加入少量乙醚来结晶，随后减压干燥。
由此给出2.48g二苯基(3-铵苯基)膦氯化物，相应于收率为98％。
上述产物(2.48g；7.9mmol)加入到过量的二甲基氨基氰(2.90g；41.1mmol)中，并在110℃下搅拌12小时。为除去过量的二甲基氨基氰，将高粘度的反应混合物用30ml醚萃取，给出2.78g二苯基-(3-(N，N-二甲基鈲)苯基)膦氯化物，为奶油色固体(收率：92％)。
实施例2
在搅拌下，将5.1ml的HCl在醚中的溶液(1.65N)加入到1.26g(4.3mmol)苯基-双-(3-氨基苯基)膦在20ml四氢呋喃中的溶液中。沉淀出1.53g苯基-双-(3-氨基苯基)膦二氯化物，为白色产物(收率：97％)。
上述产物(1.53g；4.2mmol)加入到过量的二甲基氨基氰(1.20g；17.1mmol)中，并在110℃下搅拌4小时。为除去过量的二甲基氨基氰，将高粘度的反应混合物用30ml醚萃取，给出1.96g苯基-双-(3-(N，N-二甲基胍基)苯基)膦二氯化物，为奶油色固体(收率：92％)。
实施例3
将3.04g(9.90mmol)三-(3-氨基苯基)膦在100ml水中的水溶液用13.5ml盐酸(2N)处理，并将清澈的溶液在室温下搅拌30分钟。在60℃、减压下蒸馏掉溶剂，给出3.21g三-(3-氨基苯基)膦三氯化物，为无色固体(收率：78％)。
上述产物(1.90g；4.6mmol)加入到过量的二甲基氨基氰(4.36g；61.4mmol)中，并在110℃下搅拌12小时。为除去过量的二甲基氨基氰，将高粘度的反应混合物用30ml醚萃取，给出2.79g三-[3-(N，N-二甲基鈲)苯基)膦三氯化物，为奶油色固体(收率：97％)。
实施例4
将46.00g(0.21mol)的3-碘苯胺与100ml浓度为15％的盐酸混合。将形成的3-碘苯铵盐酸盐抽吸滤出，由水中重结晶，并减压干燥(收率：52.57g＝98％)。将此苯铵盐的总量与14.42g(0.205mol)二甲基氨基氰混合，并在130℃油浴下加热10分钟。在反应中止后，将反应混合物冷却，将与100ml水混合，并将水溶性组分滤出。此水溶液用每次100ml乙醚萃取二次，用KOH调节至pH为10-12，并随后用100ml二氯甲烷萃取三次。用硫酸镁干燥后的此二氯甲烷萃取液减压去除溶剂。余下48.2g N’-(3-碘苯基)-N，N-二甲基胍，为无色固体(收率：81％)。
上述产物的溶液(32.10g；0.111mol)和6.16g(0.056mol)的PhPH2在150ml乙腈中的溶液仔细地脱气，并用氮气饱和，并在剧烈搅拌下，加入0.25g(0.225mol)Pd(Ph3P)4(0.2mol％)。将反应混合物回流加热40小时，随后减压(20℃，0.2毫巴)除去溶剂。由此余下37.6g苯基-双-(N，N’-二甲基鈲)苯基膦二碘化物，为奶油色残留物(收率：97％)。
实施例5
将20.0g 4-碘苯胺盐酸盐(78.3mmol)和3.29g(78.3mmol)氨基氰细细研磨，并相互彻底混合。混合物在140℃下共熔融，并在此温度下保持3分钟。混合物起泡并变为深色，形成鈲盐[4-I-C6H4-NH-C(NH2)2]Cl。将此黑色的熔融体饼冷却，之后用200ml热(大约80℃)水冷却，获得的溶液用每次各50ml醚萃取5次。随后将水相用浓KOH调节到pH为10-11。将结晶出的4-碘苯基胍(16.7g)抽滤出来，用总量为200ml的水洗涤，并减压干燥(20℃，0.01毫巴)(收率：16.7g；82％)。
将上述产物(5.00g；19.2mmol)溶解于30ml二甲基乙酰胺(DMA)中，并将溶液仔细脱气。随后，在隔绝空气的条件下，加入3.57g(19.2mmol)Ph2PH和1.9ml的一种乙酸钯(II)(0.05％mol％)在DMA中的5×10-3摩尔的溶液，并将反应混合物在130℃下加热6小时。反应完毕后，将反应混合物倒入100ml水中，并与4.60g(25.0mmol)KPF6混合，并加热到50℃。滤出形成的沉淀物(六氟磷酸盐)，用每次20ml水洗涤数次，随后溶解于20ml乙醇中。通过加入2.8g KOH(大约88％，43.9mmol)，将鈲碱释放，并用30ml二氯甲烷萃取。有机相用每次10ml水洗涤三次，用Na2SO4干燥并真空浓缩。残留物用20ml 1.0M HBr在80℃下吸收，过滤并将滤液减压蒸发(30℃，0.02毫巴)。由此给出5.0g二苯基-(4-鈲苯基)膦溴化物，为奶油色固体(收率：65％)。
实施例6：正-己烯-1的批量加氢甲酰化
将105g含有以乙酸铑形式存在的335ppm Ph(33mg)和32mmolTPP-三鈲盐(697mmol的P+++/kg)的一种催化剂溶液放置入0.2升严格隔绝氧气的反应釜中。在25巴的合成气压(CO∶H2＝1∶1)下、在125℃下将催化剂预生成3小时。冷却后，将反应釜卸压，取出催化剂溶液。取一部分催化剂溶液进行分析：335ppm的Rh；293mmolP+++/kg；319mmol的总P/kg。
在严格隔绝氧气下，将79.5g预生成的催化剂溶液与40.0g正己烯-1(水相与有机相的比率＝2∶1)引入反应釜中。让混合物在上述条件下反应3小时，之后将反应釜冷却至室温，随后卸压。根据气相色谱分析，反应混合物的有机相含有63％己烯、35％的庚醛类和0.7％的其它组分。庚醛类由89％的正庚醛和11％的2-甲基-己醛组成。
之后向催化剂溶液中加入按重量计为4％的PEG 400，并在相同的条件下重复上述步骤。根据气相色谱分析，反应混合物的有机相含有66％的己烯、33％的庚醛类和0.1％的其它组分。庚醛类由90％的正庚醛和10％的2-甲基己醛组成。
与鈲配位体相比，在相同的实验条件下，使用所说的TPPTS-Na盐溶液的实验得到的有机相具有下列数值：75％的己烯，25％的庚醛类和0.3％的其它组分。庚醛类由98％的正庚醛和2％的2-甲基己醛组成。
Claims (10)
1.式I的鈲膦，
其中
n是1至3的整数，
X是Cl、Br、I或PF6，
R1、R2、R3、R4相同或不同，且各是C1-C6-烷基或氢，和
R5是苯基，
且鈲取代基位于P原子的间位或对位。
2.根据权利要求1的鈲膦，其特征在于，R1与R2相同且R3与R4相同。
3.根据权利要求1或2的鈲膦，其特征在于，R1和R2同是H或甲基。
4.根据权利要求1至3之一或多项的鈲膦，其特征在于，R3和R4同是H或甲基。
5.制备式I的鈲膦的方法，其特征在于，使式II的N-氨基苯基膦
其中n和R5如式I中所定义，
与二甲基氨基氰反应，给出式I的鈲膦。
6.根据权利要求5的方法，其特征在于，使式II的N-氨基苯基膦首先与等摩尔量的HCl的醚-或水溶液反应，形成式III的HCl-加合物，
其中n和R5与式I中的定义相同，且之后进行与二甲基氨基氰的反应步骤。
7.制备式I的鈲膦的方法，其特征在于，使伯-和仲膦R5 3-nPHn(n＝1或2)与式IV的间-或对-碘苯基胍反应，
其中
R1、R2、R3、R4与式I中的定义相同，且碘原子位于P原子的间位或对位。
8.根据权利要求5至7之一或多项的方法，其特征在于，使用乙腈、二甲基乙酰胺、醚和/或烃类作为溶剂。
9.根据权利要求5至8之一或多项的方法，其中优选的是使用乙酸钯(II)、卤化钯(II)-膦配合物、钯(O)-烯烃配合物、钯(O)-膦配合物和细分散的金属钯作为催化剂。
10.式I化合物在制备碳-碳耦合反应的催化剂配位体中的应用。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19701245A DE19701245C1 (de) | 1997-01-16 | 1997-01-16 | Guanidiniumphosphane, ein Verfahren zu ihrer Herstellung und ihre Verwendung |
| DE19701245.0 | 1997-01-16 |
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| Publication Number | Publication Date |
|---|---|
| CN1243516A true CN1243516A (zh) | 2000-02-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98801885A Pending CN1243516A (zh) | 1997-01-16 | 1998-01-14 | 鈲膦、其制备方法及其应用 |
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| Country | Link |
|---|---|
| US (1) | US6187953B1 (zh) |
| EP (1) | EP0968219B1 (zh) |
| JP (1) | JP2001512427A (zh) |
| KR (1) | KR20000070173A (zh) |
| CN (1) | CN1243516A (zh) |
| AT (1) | ATE220683T1 (zh) |
| DE (2) | DE19701245C1 (zh) |
| DK (1) | DK0968219T3 (zh) |
| ES (1) | ES2178160T3 (zh) |
| PT (1) | PT968219E (zh) |
| WO (1) | WO1998031694A1 (zh) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4248802A (en) * | 1975-06-20 | 1981-02-03 | Rhone-Poulenc Industries | Catalytic hydroformylation of olefins |
| DE3840600A1 (de) * | 1988-12-02 | 1990-06-07 | Hoechst Ag | Sulfonierte phenylphosphane enthaltende komplexverbindungen |
| EP0372313B1 (de) | 1988-12-02 | 1997-03-05 | Hoechst Aktiengesellschaft | Sulfonierte Phenylphosphane enthaltende Komplexverbindungen |
-
1997
- 1997-01-16 DE DE19701245A patent/DE19701245C1/de not_active Expired - Fee Related
-
1998
- 1998-01-14 AT AT98905294T patent/ATE220683T1/de not_active IP Right Cessation
- 1998-01-14 DE DE59804803T patent/DE59804803D1/de not_active Expired - Fee Related
- 1998-01-14 DK DK98905294T patent/DK0968219T3/da active
- 1998-01-14 CN CN98801885A patent/CN1243516A/zh active Pending
- 1998-01-14 WO PCT/EP1998/000181 patent/WO1998031694A1/de not_active Application Discontinuation
- 1998-01-14 KR KR1019997006399A patent/KR20000070173A/ko not_active Application Discontinuation
- 1998-01-14 ES ES98905294T patent/ES2178160T3/es not_active Expired - Lifetime
- 1998-01-14 US US09/341,834 patent/US6187953B1/en not_active Expired - Fee Related
- 1998-01-14 PT PT98905294T patent/PT968219E/pt unknown
- 1998-01-14 EP EP98905294A patent/EP0968219B1/de not_active Expired - Lifetime
- 1998-01-14 JP JP53365098A patent/JP2001512427A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE19701245C1 (de) | 1998-07-23 |
| ES2178160T3 (es) | 2002-12-16 |
| ATE220683T1 (de) | 2002-08-15 |
| WO1998031694A1 (de) | 1998-07-23 |
| EP0968219A1 (de) | 2000-01-05 |
| DK0968219T3 (da) | 2002-11-11 |
| PT968219E (pt) | 2002-12-31 |
| US6187953B1 (en) | 2001-02-13 |
| EP0968219B1 (de) | 2002-07-17 |
| JP2001512427A (ja) | 2001-08-21 |
| DE59804803D1 (de) | 2002-08-22 |
| KR20000070173A (ko) | 2000-11-25 |
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