CN1106816A - 三价磷的环状化合物 - Google Patents
三价磷的环状化合物 Download PDFInfo
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- CN1106816A CN1106816A CN94116587A CN94116587A CN1106816A CN 1106816 A CN1106816 A CN 1106816A CN 94116587 A CN94116587 A CN 94116587A CN 94116587 A CN94116587 A CN 94116587A CN 1106816 A CN1106816 A CN 1106816A
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- 150000001923 cyclic compounds Chemical class 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 10
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000574 NaK Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000002790 naphthalenes Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- NSIKFNOYIGGILA-UHFFFAOYSA-N [Na].[Na].[K] Chemical compound [Na].[Na].[K] NSIKFNOYIGGILA-UHFFFAOYSA-N 0.000 claims 1
- 229910052728 basic metal Inorganic materials 0.000 claims 1
- 150000003818 basic metals Chemical class 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 13
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 14
- 229910052703 rhodium Inorganic materials 0.000 description 14
- 239000010948 rhodium Substances 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 13
- 239000011574 phosphorus Substances 0.000 description 9
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- 239000000047 product Substances 0.000 description 7
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
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- 238000005984 hydrogenation reaction Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000002585 base Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
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- 239000011734 sodium Substances 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 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 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- 239000003643 water by type Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- CMIMBQIBIZZZHQ-UHFFFAOYSA-N 1-bromo-2-methylnaphthalene Chemical class C1=CC=CC2=C(Br)C(C)=CC=C21 CMIMBQIBIZZZHQ-UHFFFAOYSA-N 0.000 description 2
- ABMKWMASVFVTMD-UHFFFAOYSA-N 1-methyl-2-(2-methylphenyl)benzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1C ABMKWMASVFVTMD-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical class CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910000528 Na alloy Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000000706 filtrate Substances 0.000 description 2
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- 239000011491 glass wool Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
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- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
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- 238000006366 phosphorylation reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical class CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical compound C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- SDJKREQSNPYHJT-UHFFFAOYSA-N dibromo(phenyl)phosphane Chemical class BrP(Br)C1=CC=CC=C1 SDJKREQSNPYHJT-UHFFFAOYSA-N 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical class ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- 125000004982 dihaloalkyl group Chemical group 0.000 description 1
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- BJOLKYGKSZKIGU-UHFFFAOYSA-N ecothiopate Chemical compound CCOP(=O)(OCC)SCC[N+](C)(C)C BJOLKYGKSZKIGU-UHFFFAOYSA-N 0.000 description 1
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- 239000013081 microcrystal Substances 0.000 description 1
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- UXIUJWVLLVYKHZ-UHFFFAOYSA-N nickel(2+);triphenylphosphane Chemical compound [Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UXIUJWVLLVYKHZ-UHFFFAOYSA-N 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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Classifications
-
- 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
- B01J31/2461—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 ring members in the condensed ring system or in a further ring
- B01J31/2471—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 ring members in the condensed ring system or in a further 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
-
- 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
- B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
- B01J31/2428—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom
-
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Abstract
本说明书说明了一些新环状碳(III)—化合物及
其制备方法。这些磷化合物作为二齿配位体能与一
些金属、尤其与周期表第八族的一些金属形成配位化
合物。这些配位化合物可用作催化剂体系的成分。
Description
本发明涉及一些新的环状磷-(Ⅲ)-化合物,它们作为二齿配位体可与金属,尤其可与元素周期表第八族的金属生成配位化合物,以及涉及它们的制备方法。可均匀溶解的配位化合物被用作催化剂成分,尤其被用作加氢甲酰催化剂的成分。
含有元素周期表第八族的一种金属作为中心原子和磷-(Ⅲ)-化合物、膦或亚磷酸盐作为配位体、此外必要时还含有其它能生成配合物的一些基团的配位化合物近几年作为催化剂逐渐显得重要。例如,工业上大规模实施的链烯烃与合成气生成醛的反应在由钴,尤其由铑和三苯基膦组成的催化剂体系存在下进行。已证明以含有膦的配位化合物为基础的一些催化剂对于用分子氢来氢化不饱和的碳-碳重键或碳-氧重键也是有效。在上述的这些情况下,通常有过量配位体,以致此催化剂体系由配位化合物和游离的配位体组成。根据这些催化剂在有机介质中的可溶性,反应在均匀的溶液中进行。
已知的这些催化方法已证明在工业规模很有效。尽管如此,人们正努力争取进一步完善这些已知的方法。
例如,人们正试图通过对这些复合配位体的改性来提高这些催化剂的活性和延长其有效性,以减少催化剂需要量。此外还力求研制出解决个别问题的匹配配位体系。作为例子提到了化学合成配向性和立体选择性的控制,目的在于由前手性原料得到纯的对映体。这样一些反应尤其在精细化学品和药物领域赢得了越来越重要的意义。
用单齿配位体不再可能或不大可能影响立体选择性。因此主要用二齿配位体来制备纯对映体产品。在这些产品中,迄今主要是二膦受到重视。例如,为了α、β-不饱和的酯如作为前手性化合物的丙烯酸酯的选择性加氢甲酰化,使用以钴/1,2-双-(二苯基膦基)-乙烷和铑/1,4-双-(二苯基膦基)-丁烷为基础的催化剂体系。这些反应要求强烈的反应条件,就是说温度为120-150℃,压力为5-10MPa(百万帕斯卡)。此外,已证明这些催化剂体系不大稳定。用铑催化剂在温和条件下主要使原料氢化。
因此,本发明的目的是研制出适合作为均匀溶解的催化剂体系的成分的磷化合物,在这些磷化合物的分子中含有尤其能与铑形成配合物的两个磷-(Ⅲ)-原子。这些催化剂体系应具有高活性和高配向性,因此例如使得有可能进行立体选择合成。
因此本发明提供了如下通式所示的一些新的磷化合物:
式中:环状基团
为饱和的或单或多重不饱和的五节环或六节环基,R3和R4相同或不同并表示氢或甲基基团,R1、R2为相同或不同,并代表氢、C1-5烷基、芳烷基或C1-5-烷氧基或代表一个卤素原子,R1和R2也可代表稠合的苯环或萘环。m和n为相同或不同,并代表零或1,s和t为相同或不同,并代表4或5,p、g、r为相同或不同,并代表零、1、2或3、Ar表示一个被取代了的或未被取代的C6-18-芳基。
优选的配位体是那些对应于上述通式的化合物,在这些化合物中,p和r各代表1,q为零或1,而且在这些化合物中R3和R4表示氢。
在上述通式中,以Ar表示的芳族基团可能是未被取代的或被取代了的,也可能是多环系或稠环系。Ar优选为未被取代的或被取代了的一个亚苯基-、亚萘基-、亚联苯基-或亚联萘基基团。
在这些新化合物中包含的磷(Ⅲ)原子是饱和的或不饱和的五环节或六环节的一些杂环化合物的成分。优选的是除磷原子之外还含有四个碳原子的杂环,就是说由被取代了的或未被取代的棉安磷(Phospholanen)、二乙氧膦酰硫胆碱和尤其由二氧磷基酚(Phospholen)衍生的一些化合物。与此相应,在通式中s和t优选代表4。R1和R2为相同或不同,并且最好各表示一个直链的或有分支的、至多有5个碳原子的烷基基团、苄基-、苯乙基-、甲苯基-、二甲苯基-和
基基团。R1和R2也可代表成环的苯环或萘环。符合含磷的这些杂环的基团例如可从2,3-苯并二氧磷基酚(Phospholen)、2,3,4,5-二苯并二氧磷基酚、2,3-茚并二氧磷基酚衍生。
这些新化合物可以用简单方法获得,产率高。一种证明是可靠的合成法是下面通式所示的二卤代烷基化物的磷酸化作用。
式中p、q、r、R3、R4和Ar有上面所述的意义,Hal表示一个卤素原子,最好是氯或溴,尤其是溴。例如从非卤代的基本原料通过N-溴丁二酰亚胺的溴化作用可获得这些溴化合物。
有杂环磷阴离子的碱金属化合物作为有效的磷酸化试剂。这些碱金属化合物的制备是通过在磷原子上的苯基化杂环化合物与金属反应,最好与锂、钠或钾反应,尤其与一种钠-/钾合金反应来实现的。这种金属衍生物与二卤化合物反应,产生所希望的环状磷化合物。
本发明的磷化合物作为二齿配位体与很多金属原子形成配位化合物。在这些配位化合物中,铑的配位化合物作为链烯烃的低压加氢甲酰化生成醛的高活性催化剂有特殊的意义。此反应中直链化合物产量很高;只有少量有分支链的异构体。已证明2,2′-双-(3,4-二甲基二氧磷基酚亚甲基)-1,1′-联苯和2,2′-双-(3,4-二甲基二氧磷基酚亚甲基)-1,1′-联萘这些化合物作为催化剂组分特别有效。
在使用由铑和这些新的磷(Ⅲ)-化合物组成的催化剂体系的烯烃加氢甲酰化反应在约0.1至约6MPa、最好是0.5-3MPa、尤其1.5-2.0MPa的压力下进行。反应温度可为约20至约200℃,优选范围为约50至约170℃,尤其为约80至约150℃。
将催化剂加到反应混合物中,催化剂最好预先溶于溶剂中,甚至由反应混合物中的各组分在加氢甲酰化条件下形成。不仅在预先制备催化剂,而且在就地制备催化剂的情况下,都可将铑作为细粉末形式或作为化合物例如氧化物、无机或有机酸盐或作为羰基铑来使用。
需要的铑量很少,每摩尔链烯烃约1×10-6摩尔铑就有效。但由于经济原因要提高反应速度,优选每摩尔链烯烃使用约1×10-2-1×10-5摩尔铑,尤其使用1×10-2-1×10-4摩尔铑。在反应混合物中铑对配位体的摩尔比为约1∶1-200,最好约1∶2-10,尤其约1∶25-4。
把合成气和链烯烃以其消耗量连续地加到反应器中。合成气中一氧化碳和氢的摩尔比可在宽的范围内变动,约为1∶10至约10∶1,要反应的烯烃种类可影响到所选择的比例。优选含一氧化碳和氢的比为约1∶2至约2∶1,尤其为约1∶1.5至1.5∶1的混合物。按链烯烃计算总是使用过量合成气,按链烯烃计算,合成气(CO+H2)的摩尔过量通常为约0.5至约20,优选为约1至约10。
在反应可在溶剂存在下进行,这些溶剂在反应条件下对反应物和反应产品都是惰性的。属于这些溶剂的例如有:芳族烃和苯、甲苯、二甲苯;脂族烃如戊烷、煤油和矿物油以及醇类、醚类和酯类。
加氢甲酰化反应在常规反应器中进行,可连续地或间歇地进行。反应连续进行时,将产品不断地和未反应的合成气一起抽出,通过冷凝从气相中分离出来,并按常规方法继续处理,例如蒸馏提纯。把合成气送回反应区。为使催化剂体系的活性保持在均匀的高水平上,可取的是间或从反应器中抽取出催化剂,并用新鲜催化剂代替。
这类新的二齿配位体和铑一起可成功地用于各种链烯烃的加氢甲酰化反应。属于这些链烯烃的是含2-20个碳原子的α-链烯烃,它们可含有在反应条件下是惰性的取代基。合适的链烯烃的例子有乙烯、丙烯、丁烯-1、丁烯-2,此外还有戊烯、己烯和庚烯。这些新的配位体由于其立体定向性在前手性的链烯烃加氢甲酰化时特别有意义。
以下实施例说明本发明,而不是把本发明限于这些详细说明的实施方案。
实施例
1)2,2′-双-(3,4-二甲基二氧磷基酚亚甲基)-1,1′-联苯的制备
(a)3,4-二甲基-1-苯基二氧磷基酚(按A.Bregue等,Synth.1981,12,984)
在一个1000毫升的带搅拌的烧瓶中,于氮气保护下将44.7克(250毫摩尔)苯基二氯膦和66.9克(250毫摩尔)苯基二溴膦于室温下一起搅拌30分钟。然后在冰冷却下将42.0克(511毫摩尔)二甲基丁二烯加到这种均匀溶液中,并在继续冷却下搅拌24小时。使产生的这种悬浮体在室温下继续静置10天。在此过程中这种悬浮体完全转变成一种白色结晶块,在烧瓶中将这种结晶块破碎成尽可能小的碎块,然后加入300毫升已烷和200毫升二氯甲烷。
通过吹入氮气30分钟,除去悬浮体中多余的二甲基丁二烯。在强烈搅拌下于室温滴入一种由103克(1094毫摩尔)2-甲基吡啶溶入100毫升二氯甲烷所成的溶液。在24小时中产生一种可分离成两个液相的混合物。用100毫升3N盐酸进行水解之后,分离出有机相,用100升水洗三次直到中性。用硫酸钠进行干燥,然后进行过滤和蒸发。用300毫升已烷萃取留下的液体,萃取物进行过滤和蒸发。如此获得的黄色油不需要进一步精制。
产量:71.17克(378毫摩尔,理论量的74.15%)。
31P-NMR(161.8MHz,DC2Cl2):=-1.3ppm(5.1P)。
(b)2,2′-二甲基-1,1′-联苯(根据C.W.Kohlpaintner,dissertation 1990,Technische Universitat Munchen)
在一个500厘米3的烧瓶中先加有18.59(0.75摩尔)镁刨屑和200毫升四氢呋喃,然后在搅拌下用一小时滴入70毫升(0.6摩尔)2-氯甲苯和2毫升1,2-二溴乙烷,这时混合物变成灰色而且轻微发热。紧接着将混合物回流加热18小时。冷却后用玻璃棉过滤此悬浮体,在室温下用2小时将滤液滴加到由70毫升(0.6摩尔)2-氯甲苯和3.0克(4.5毫摩尔)顺式-二氯-双(三苯基膦)镍(Ⅱ)溶于250毫升四氢呋喃而成的一种溶液中。经过20小时回流加热后,将此液体加到一个1000厘米3的分液漏斗中,通过小心地加入400毫升甲苯和200毫升饱和的氯化铵溶液,使此溶液慢慢冷却。分离出有机相,依次用250毫升10重量%的盐酸洗涤,用水洗三次,每次用水125毫升。在一种油泵抽的真空下除去溶剂,留下一种棕色油。在66.7-133.3帕斯卡(Pa)的压力下进行蒸馏,得到预期的产品,为无色液体,其沸点范围为77-77℃。
产量:77.31克(理论量的70.7%)。
GC(气相色谱法)-质谱(AS(美国标准)60,保留时间12.767分钟):m/z=182(55%,〔(M)+.〕),167(100%,〔(M-CH3)+.〕),152(20%,〔(C12H8)+.〕),128(10%,115(12%),89(18%),76(10%),〔(C6H4)+.〕),63(15%),39(18%),27(12%)。
(c)2,2′-双(溴亚甲基)-1,1′-联苯(根据W.Wenner,J.Org.Chem.1952,17,523-528)
将20.0克(0.11摩尔)N-溴丁二酰亚胺和0.2克偶氮双异丁腈加到7.1克(0.039摩尔)2,2′二甲基-1,1′-联苯溶于15毫升四氯化碳的溶液中并进行缓和的回流加热。经过9小时之后在室温下通过G3玻璃料滤出琥珀酰亚胺,将留下的液体在40℃和油泵抽的真空下浓缩成一种粘性的黄色油。通过在15毫升石油醚中重结晶,得到细粒的白色晶体,用G4玻璃料滤出这些晶体,并在油泵抽的真空下进行干燥。
产量:11.5克(理论量的84%)。
熔点:82℃
GC-质谱:(AS60,保留时间17.273分钟):m/z=340(6%,〔(M)+.〕),259(15%,〔(M-Br)+.〕),179(100%,〔(M-2*Br)+.〕),152(12%,(C12H8)+.〕)。
元素分析:(C14H12Br2;340.07)
计算值:C49.45 H3.55 Br47.00
测定值:C49.20 H3.58 Br46.09
(d)(3,4-二甲基二氧磷基酚基)钠/钾
在室温和强烈搅拌下将0.62克(20毫摩尔)钠/钾合金一份一份地慢慢加到1.88克(10毫摩尔)1-苯基-3,4-二甲基二氧磷基酚溶于40毫升四氢呋喃的溶液中。二小时后用玻璃棉滤出多余的合金,将深棕色的悬浮液冷却到-30℃,加入0.16克(0.19毫升,17毫摩尔)2-氯-2-甲基丙烷。加热1小时变成一种深红色悬浮液,不用分离出产品就可将此悬浮液继续加工。根据31P-NMR这种转化是定量的。
31P-{1H}-NMR(CDCl3):δ=55.40PPm(S,1P),52.36ppm(S,1P)
(e)2,2′-双(3,4-二甲基二氧磷基酚亚甲基)-1,1′-联苯
将12.0克(35毫摩尔)2,2′-双(溴甲基)-1,1′-联苯溶于30毫升四氢呋喃的溶液滴加到悬浮于150毫升四氢呋喃的15.8克(84毫摩尔)(3,4-二甲基二氧磷基酚)-钠/钾中。搅拌12小时之后,此悬浮液由深红色变成淡棕色,然后在油泵抽的真空下除去溶剂,把留下的棕色残留物吸收在甲苯中,这时沉淀出KB和NaBr。将上层的澄清溶液浓缩成一种深棕色油,通过用10毫升乙醇进行重结晶,得到的产品为白色微晶粉末。
产量:8.52克(21毫摩尔,理论值的60%)
熔点:120℃
质谱(CI):m/e=402.2(36.99%,〔(M)+.〕),291.2(14.87%,〔(M-C4H10P)+.〕),179.1(4.14%,〔(M-2*C4H10P)+.〕),154(2.66%,〔(M-2*C5H11P)+.〕)
31P-{1H}-NMR(CDCl3):δ=3.99(S,2P)
1H-NMR(CDCl3):δ=0.89(t,6H,-CH3,2J(H,H)=7.4Hz),1.19(t,6H,C′H3,2J(H,H=7.4Hz),1.54(dd,2H,-CHaHb-,2J(H,H)=14.8Hz,2J(P,H)=6.78Hz),1.97(d,2H,-CHaHb,2J(H,H)=20.34Hz),3.55(7,2H,∶CH-,2J(P,H)=6.78),3,67(t,2H,∶C′H-,2J(P,H)=6.78),8.6(m,8H,Aromat)元素分析(C26H28P2;402.26)
计算值:C77.60 H7.00 P15.39
测定值:C77.08 H7.05 P15.68
2.)2,2′-双(3,4-二甲基二氧磷基酚亚甲基)-1,1′-联萘的制备
(a)2,2′-双甲基-1,1′-联萘
将83.8克(0.379摩尔)1-溴-2-甲基萘溶于150毫升乙醚和150毫升苯中的溶液在室温下慢慢滴加到10克(0.415摩尔)镁刨屑(先加上几滴1,2-二溴乙烷)悬浮在30毫升乙醚中的悬浮液中。用4小时滴入卤代芳香。选择滴入速度使得反应物料一直保持温热。随后将此反应混合物再回流加热一小时,在室温下继续搅拌过夜。从一个滴液漏斗中将此悬浮体一份一份一加到74克(0.335摩尔)1-溴-2-甲基萘溶于250毫升乙醚的溶液中,并加入2.5克(3.8毫摩尔〔(Pph3)2Ni〕Ni〕Cl2(偶合催化剂)。然后将混合物回流加热24小时,冷却到室温,用200毫升水和200毫升20重量%的盐酸进行水解。用200毫升水把从水相中分离出的有机相洗两次,再分离出有机相,然后用硫酸镁进行干燥。在真空下蒸去有机溶剂,用一个小型Vigreux塔在压力<1.3Pa的条件下将剩余物进行蒸馏。在上述条件下,于169-173℃蒸出预期的化合物,为绿色油,用10毫升丙酮在-18℃下使此绿色油重结晶。
产量:74.9克(0.265摩尔,理论值的69%)
(b)2,2′-双溴甲基-1,1′-联萘(按照W.Wenner,J.Org.Chem.1952,17,523-528)
将28.2克(0.1摩尔)2,2′-二甲基-1,1′-联萘和35.6克(0.2摩尔)N-溴丁二酰胺一起悬浮在65毫升四氯化碳中。在回流加热下用4个多小时将0.43克偶氮双异丁腈分多份加入,并且继续回流加热9小时。在过滤出琥珀酰亚胺和将滤液浓缩之后,留下一种粘性的黄色油。用20毫升石油醚(轻汽油混合物)使这种黄色油重结晶,过滤出所要的白色固体物质。
产量:35.55克(0.08摩尔,理论值的80%)
1H-NMR(CDCl3):δ=8.0-9.0(m,芳香物,12H),5.3ppm(S,CH2,4H)
(c)2,2′-双(3,4-二甲基二氧磷基酚亚甲基)-1,1′-联萘
将9.9克(0.022摩尔)-2,2′-双溴甲基-1,1′-联萘溶于20毫升四氢呋喃的溶液滴加到5.0克(0.045摩尔)3,4-二甲基二磷基酚基阴离子在120毫升四氢呋喃中的悬浮液中。在室温下搅拌18小时之后将溶剂完全除去,在一个索格利特抽提器(Soxhlet Apparatur)中用80毫升甲苯萃取淡棕色残留物。紧接着浓缩成一种棕色油,通过用30毫升正已烷重结晶,可从这种棕色油得到淡棕色固体产品。
产量:5.46克(0.01摩尔,理论值的49%)
31P-{1H}-NMR(CDCl3):δ=-5.4ppm(S,2P)
质谱(CI):m/e=503.1(5.6%,〔(M)+.〕),391.1(15.1%,〔(M-C4H10P)+.〕),281.1(15.4%,〔(M-2*C4H10P)+.〕),154(2.66%,〔(M-2*C5H11P)+.〕)。
Claims (12)
2、按权利要求1所述的化合物,其特征在于:R3和R4基团代表氢。
3、按权利要求1或2所述的化合物,其特征在于:R1和R2基团代表氢或甲基基团。
4、按权利要求1至3中的一项或多项所述的化合物,其特征在于:Ar为亚苯基-、亚萘基-、1,1′-亚联苯基-、1,1′-亚联萘基基团。
5、按权利要求1至4中的一项或多项所述的化合物,其特征在于:s和t代表4。
6、按权利要求1至5中的一项或多项所述的化合物,其特征在于:p和r相同或不同,并代表1。
7、按权利要求1至6中的一项或多项所述的化合物,其特征在于:q代表零或1。
8、化合物2,2′-双(3,4-二甲基二氧磷基酚亚甲基)-1,1′-联苯。
9、化合物2,2′-双(3,4-二甲基二氧磷基酚亚甲基)-1,1′-联萘。
11、按权利要求10所述的方法,其特征在于:所用的金属为一种钠-钾合金。
12、按权利要求1至9中的一项或多项所述的化合物的应用,用作可均匀溶解的催化剂体系的成分。
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DE4333307A DE4333307A1 (de) | 1993-09-30 | 1993-09-30 | Cyclische Verbindungen des dreiwertigen Phosphors |
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CN1116265C (zh) * | 1996-05-31 | 2003-07-30 | 巴斯福股份公司 | 加氢甲酰化和适用于此用途的含磷化合物作为配体的催化剂 |
CN106083551A (zh) * | 2016-06-30 | 2016-11-09 | 成都欣华源科技有限责任公司 | 一种丙烯氢甲酰化制备丁醛的方法 |
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DE19702025A1 (de) * | 1997-01-23 | 1998-07-30 | Studiengesellschaft Kohle Mbh | Verwendung perfluoralkylsubstituierter Phosphorverbindungen als Liganden für die homogene Katalyse in überkritischem Kohlendioxid |
US7012162B2 (en) * | 2000-06-26 | 2006-03-14 | Basf Aktiengesellschaft | Phosphacyclohexanes and the use thereof in the hydroformylation of olefins |
WO2002000580A1 (de) * | 2000-06-26 | 2002-01-03 | Basf Aktiengesellschaft | Alkoholgemische mit 13 und 15 kohlenstoffatomen und deren verwendung in der herstellung von oberflächenaktiven substanzen |
DE10106348A1 (de) * | 2001-02-09 | 2002-08-14 | Basf Ag | Als Katalysator oder zur Herstellung eines Katalysatorsystems geeignete Verbindung |
US6794553B2 (en) * | 2001-11-09 | 2004-09-21 | Shell Oil Company | Process for the telomerization of a conjugated diene, catalyst and bidentate ligand useful therein |
DE102008044783B4 (de) | 2008-08-28 | 2012-05-16 | Oxea Gmbh | Verfahren zur Gewinnung von aliphatischen C3- bis C10- Aldehyden aus Hochsiedern durch thermische Behandlung |
DE102009004655B4 (de) | 2009-01-15 | 2013-02-14 | Oxea Gmbh | Verfahren zur Herstellung von Aldehyden |
DE102009016651B4 (de) | 2009-04-07 | 2011-11-17 | Oxea Gmbh | Verfahren zur Herstellung von Aldehyden |
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CA1300164C (en) * | 1986-06-13 | 1992-05-05 | Thomas James Devon | Chelate ligands for low pressure hydroformylation catalyst and process employing same |
US5202493A (en) * | 1991-04-26 | 1993-04-13 | E. I. Du Pont De Nemours And Company | Chiral tridentate bis(phospholane) ligands |
US5171892A (en) * | 1991-07-02 | 1992-12-15 | E. I. Du Pont De Nemours And Company | Chiral phospholanes via chiral 1,4-diol cyclic sulfates |
ATE165361T1 (de) * | 1992-01-31 | 1998-05-15 | Hoffmann La Roche | Diphosphinliganden |
US5332846A (en) * | 1993-06-01 | 1994-07-26 | Eastman Kodak Company | Hydroformylation process using novel phosphine-rhodium catalyst system |
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- 1994-09-23 KR KR1019940023934A patent/KR100350814B1/ko not_active IP Right Cessation
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- 1994-09-27 CN CN94116587A patent/CN1106816A/zh active Pending
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CN1116265C (zh) * | 1996-05-31 | 2003-07-30 | 巴斯福股份公司 | 加氢甲酰化和适用于此用途的含磷化合物作为配体的催化剂 |
CN106083551A (zh) * | 2016-06-30 | 2016-11-09 | 成都欣华源科技有限责任公司 | 一种丙烯氢甲酰化制备丁醛的方法 |
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EP0646588B1 (de) | 2000-01-26 |
JPH07173183A (ja) | 1995-07-11 |
AU7430394A (en) | 1995-04-13 |
CA2132673A1 (en) | 1995-03-31 |
DE59409100D1 (de) | 2000-03-02 |
EP0646588A1 (de) | 1995-04-05 |
ZA947456B (en) | 1995-05-15 |
BR9403827A (pt) | 1995-05-30 |
TW283149B (zh) | 1996-08-11 |
KR950008526A (ko) | 1995-04-19 |
DE4333307A1 (de) | 1995-04-06 |
ES2143515T3 (es) | 2000-05-16 |
KR100350814B1 (ko) | 2002-10-31 |
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PL305159A1 (en) | 1995-04-03 |
ATE189225T1 (de) | 2000-02-15 |
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