EP0938490A1 - New dipalladaphosphacyclobutanes and a process for preparing the same - Google Patents
New dipalladaphosphacyclobutanes and a process for preparing the sameInfo
- Publication number
- EP0938490A1 EP0938490A1 EP97950184A EP97950184A EP0938490A1 EP 0938490 A1 EP0938490 A1 EP 0938490A1 EP 97950184 A EP97950184 A EP 97950184A EP 97950184 A EP97950184 A EP 97950184A EP 0938490 A1 EP0938490 A1 EP 0938490A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bis
- dimethylethyl
- methylpropyl
- dipalladium
- phosphino
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 35
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- -1 dimethylethyl Chemical group 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000005922 Phosphane Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910000064 phosphane Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002941 palladium compounds Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052744 lithium Chemical group 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Chemical group 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000003738 xylenes Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract description 3
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 abstract description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 229940071536 silver acetate Drugs 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004651 chloromethoxy group Chemical group ClCO* 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical class C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical class CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- B01J31/2419—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
- B01J31/2423—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 comprising aliphatic or saturated rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
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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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- 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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- 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
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/20—Non-coordinating groups comprising halogens
- B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
- B01J2540/225—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate comprising perfluoroalkyl groups or moieties
Definitions
- the present invention relates to new palladaphosphacyclobutanes and a process for their preparation.
- Palladaphosphacyclobutanes play an important role as catalysts for a number of processes. Examples of such processes are the synthesis of substituted styrenes, stilbenes and cinnamic acids from aryl halides.
- Clark describes in Inorg. Chim. Acta 31, (1978), L441 -L442 the reaction of PdCI 2 (NCPh) 2 with two equivalents of P (t-Bu) 3 to the corresponding palladaphosphacyclobutane in 70% yield.
- the toxicologically questionable solvent methylene chloride is used, in which both the starting material and the product are soluble.
- the solvent is removed, the product is extracted with benzene and then precipitated by adding hexane.
- the process is ecologically and economically disadvantageous due to the use of two equivalents of P (t-Bu) 3 per equivalent of palladium and the use of methylene chloride and benzene.
- Clark describes in Inorg. Chim. Acta 31, (1978), L441 -L442 the reaction of K 2 PdCI 4 with two equivalents of P (t-Bu) 3 to the corresponding palladaphosphacyclobutane in 72% yield. Dimethylformamide is used as the solvent in this process. To isolate this palladaphosphacyclobutane, the solvent is removed and the product is precipitated by adding ethanol. Clark describes an analogous process in Organometallics 1, (1982), 658-666 in which Na 2 PdCI 4 and three equivalents of P (t-Bu) 3 are used as starting materials and the corresponding palladaphosphacyclobutane is obtained in a yield of 75%. Both methods are based on the use of two or three equivalents of P (t-Bu) 3 pro Equivalent palladium ecologically and economically disadvantageous.
- Clark describes in Inorg. Chem. 18, (1979), 2803-2808 the reaction of PdCI 2 (NCPh) 2 with one equivalent of P (t-Bu) 3 to the corresponding palladaphosphacyclobutane without indication of the yield.
- the toxicologically questionable solvent methylene chloride is used in which both the starting material and the product are soluble.
- the solvent is removed, the product is extracted with benzene and then precipitated by adding hexane.
- the process is ecologically and economically disadvantageous due to the use of methylene chloride and benzene.
- the invention relates to palladaphosphacyclobutanes of the formula (I)
- R 1 , R 2 independently of one another are hydrogen, (C 1 -C 4 ) -alkyl, (C 3 -
- R, R 4 , R 5 , R 6 independently of one another (C r C 8 ) alkyl, (C 3 -C 12 ) cycloalkyl, or aryl; or wherein R 1 and R 2 , R 1 or R 2 and R 3 or R 4 , R 3 and R 4 , R 3 or R 4 and R 5 or R 6 , or R 5 and R 6 together form an aliphatic ring with 4 form up to 10 carbon atoms;
- R 5 and R 6 , R 3 or R 4 and R 5 or R 6 together form an aromatic ring having 5 to 9 carbon atoms;
- Y represents an anion of an inorganic or organic acid
- R 1 , R 2 are independently phenyl
- R 5 , R 6 independently of one another are phenyl, naphthyl or anthracenyl, which can be substituted by 1 to 3 (C r C 4 ) -alkyl or 1 to 3 (C r C 4 ) -alkoxy groups.
- Palladaphosphacyclobutanes of the formula (I) are particularly preferred in which R 3 , R 4 independently of one another are phenyl, R 5 , R 6 independently of one another o-trifluoromethylphenyl, o-
- Trifluoromethyl-p-tolyl o-trifluoromethyl-p-methoxy-phenyl, o-methoxy-phenyl, o, p-dimethoxy-phenyl, o, o, p-trimethoxy-phenyl, tert-butyl, n-butyl, isopropyl , Isobutyl, cyclohexyl, 1 - methylcyclohexyl.
- the palladaphosphacyclobutanes according to the invention represent a new class of catalysts. Their catalytic activity in the olefination of aryl halides is exceptional compared to the prior art, so that there is great technical interest in the compounds according to the invention.
- the invention further relates to a process for the preparation of compounds of the formula 1, characterized in that a phosphane of the formula (II)
- R 1 to R 6 have the meanings mentioned above and R 7 is hydrogen or deuterium, with a palladium salt of the formula (IM), a palladium complex of the formula (IV) or an alkali metal palletate of the formula (V)
- M is sodium, potassium or lithium and L is 1, 5-cyclooctadiene, acetonitrile or benzonitrile, in the presence of an organic solvent.
- the phosphane of the formula (II) and the palladium compound of the formula (III), (IV) or (V) are in a molar ratio of phosphine to Pd compound of 0.1 to 20, in particular 0.1 5 to 15, preferably 0.2 to 10, particularly preferably from 0.8 to 1.2.
- Aliphatic hydrocarbons and aromatic hydrocarbons are suitable as solvents. Toluene or xylenes are very suitable.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Palladaphosphacyclobutanes are disclosed having the formula (I), in which R<1>, R<2> independently represent hydrogen, (C1-C4)-alkyl, (C3-C12)-cycloalkyl, (C1-C4)-alkoxy, fluorine, N(alkyl)2-C(C1-C4-alkyl, OCO-alkyl-(C1-C4) or aryl; R<3>, R<4>, R<5>, R<6> independently represent (C1-C8)-alkyl, (C3-C12)-cycloalkyl or aryl; or in which R<1> and R<2>, R<1> or R<2> and R<3> or R<4>, R<3> and R<4>, R<3> or R<4> and R<5> or R<6>, or R<5> and R<6> form together an aliphatic ring; or in which R<5> and R<6>, R<3> or R<4> and R<5> or R<6> form together an aromatic ring; and Y stands for an anion of an inorganic or organic acid, except for the compounds di- mu -chloro-bis[2-[bis(1,1-dimethylethyl)phosphino]-2-methylpropyl-C,P]dipalladium (II), di- mu -bromo-bis[2-[bis(1,1-dimethylethyl)phosphino]-2-methylpropyl-C,P]dipalladium (II), di- mu -trifluoroacetato-bis[2-[bis(1,1-dimethylethyl)phosphino]-2-methylpropyl-C,P]dipalladium (II), di- mu -chloro-bis[2-[(1,1-dimethylethyl)phénylphosphino]-2-methylpropyl-C,P]dipalladium (II), mu -chloro- mu -methoxy-bis[2-[bis(1,1-dimethylethyl)phosphino]-2-methylpropyl-C,P]dipalladium (II).
Description
Neue Palladaphosphacyclobutane sowie ein Verfahren zu ihrer HerstellungNew palladaphosphacyclobutanes and a process for their preparation
Die vorliegende Erfindung betrifft neue Palladaphosphacyclobutane sowie ein Verfahren zu ihrer Herstellung.The present invention relates to new palladaphosphacyclobutanes and a process for their preparation.
Palladaphosphacyclobutane spielen als Katalysatoren für eine Reihe von Verfahren eine wichtige Rolle. Als Beispiele für derartige Verfahren seien die Synthese von substituierten Styrolen, Stilbenen und Zimtsäuren aus Arylhalogeniden genannt.Palladaphosphacyclobutanes play an important role as catalysts for a number of processes. Examples of such processes are the synthesis of substituted styrenes, stilbenes and cinnamic acids from aryl halides.
In der Literatur sind folgende Verbindungen dieser Art offenbart:The following compounds of this type are disclosed in the literature:
1. Di- /-chloro-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl- C,P]dipalladium (II); H.C. Clark et al., Inorg. Chim. Acta 31 , (1978), L441 -L442 ; H.C. Clark et al. J. Organomet. Chem. 166, (1979) C29- C32; H.C. Clark et al., Inorg. Chem. 18, (1979), 2803-28081. di- / chloro-bis [2- [bis (1,1-dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II); H.C. Clark et al., Inorg. Chim. Acta 31, (1978), L441-L442; H.C. Clark et al. J. Organomet. Chem. 166, (1979) C29-C32; H.C. Clark et al., Inorg. Chem. 18, (1979), 2803-2808
2. Di-μ-bromo-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2-methylpropyl- C,P]dipalladium (II); H.C. Clark et al., J. Organomet. Chem. 166, (1979) C29-C32; H.C. Clark et al., Inorg. Chem. 18, (1979), 2803-28082. Di-μ-bromo-bis [2- [bis (1,1, dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II); H.C. Clark et al., J. Organomet. Chem. 166, (1979) C29-C32; H.C. Clark et al., Inorg. Chem. 18, (1979), 2803-2808
3. Di-μ-trif luoroacetato-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2- methylpropyl-C,P]dipalladium (II); H.C. Clark et al., J. Organomet. Chem. 166, (1979) C29-C32; H.C. Clark et al., Inorg. Chem. 18, (1979), 2803- 28083. Di-μ-trif luoroacetato-bis [2- [bis (1,1, dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II); H.C. Clark et al., J. Organomet. Chem. 166, (1979) C29-C32; H.C. Clark et al., Inorg. Chem. 18, (1979), 2803-2808
4. Di- /-chloro-bis[2-[(1 , 1 -dimethylethyl)-phenylphosphino]-2-methylpropyl- C,P]dipalladium (II); H. Werner et al., J. Organomet. Chem. 204, (1980), 415-422
5. /-chloro-μ-methoxy-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2- methylpropyl-C,P]dipalladium (II); A.B. Goel et al., Trans. Met. Chem 5, (1980), 378-3794. di- / chloro-bis [2 - [(1,1-dimethylethyl) phenylphosphino] -2-methylpropyl-C, P] dipalladium (II); H. Werner et al., J. Organomet. Chem. 204, (1980), 415-422 5. / -chloro-μ-methoxy-bis [2- [bis (1,1, dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II); AB Goel et al., Trans. Met. Chem 5, (1980), 378-379
Shaw beschreibt in J. Chem. Soc. (A) (1971 ), 2976-2980 die Addition von tert.-Butylphosphinen der Formel P(f-Bu)nR3_n an Palladium-Il-Verbindungen zu den entsprechenden Komplexen der allgemeinen Formel Pd(P(f-Bu)nR3_n)2X2 sowie Pd2(P(f-Bu)nR3_n)2X4. Bei der Synthese werden nicht die erfindungsgemäßen Palladaphosphacyclobutane erhalten.Shaw describes in J. Chem. Soc. (A) (1971), 2976-2980 the addition of tert-butylphosphines of the formula P (f-Bu) n R 3 _ n to palladium-II compounds to the corresponding complexes of the general formula Pd (P (f-Bu ) n R 3 _ n ) 2 X 2 and Pd 2 (P (f-Bu) n R 3 _ n ) 2 X 4 . The palladaphosphacyclobutanes according to the invention are not obtained in the synthesis.
Clark beschreibt in Inorg. Chim. Acta 31 , (1978), L441 -L442 die Reaktion von PdCI2(NCPh)2 mit zwei Äquivalenten P(t-Bu)3 zu dem entsprechenden Palladaphosphacyclobutan mit 70% Ausbeute. In diesem Verfahren wird das toxikologisch bedenkliche Lösemittel Methylenchlorid verwendeten dem sowohl das Startmaterial als auch das Produkt löslich sind. Zur Isolierung dieses Palladaphosphacyclobutans wird das Lösemittel abgezogen, das Produkt mit Benzol extrahiert und anschließend durch Zugabe von Hexan gefällt. Das Verfahren ist aufgrund des Einsatzes von zwei Äquivalenten P(t-Bu)3 pro Äquivalent Palladium und der Verwendung von Methylenchlorid und Benzol ökologisch und ökonomisch nachteilig.Clark describes in Inorg. Chim. Acta 31, (1978), L441 -L442 the reaction of PdCI 2 (NCPh) 2 with two equivalents of P (t-Bu) 3 to the corresponding palladaphosphacyclobutane in 70% yield. In this process, the toxicologically questionable solvent methylene chloride is used, in which both the starting material and the product are soluble. To isolate this palladaphosphacyclobutane, the solvent is removed, the product is extracted with benzene and then precipitated by adding hexane. The process is ecologically and economically disadvantageous due to the use of two equivalents of P (t-Bu) 3 per equivalent of palladium and the use of methylene chloride and benzene.
Clark beschreibt in Inorg. Chim. Acta 31 , (1978), L441 -L442 die Reaktion von K2PdCI4 mit zwei Äquivalenten P(t-Bu)3 zu dem entsprechenden Palladaphosphacyclobutan mit 72% Ausbeute. In diesem Verfahren wird als Lösemittel Dimethylformamid verwendet. Zur Isolierung dieses Palladaphosphacyclobutans wird das Lösemittel abgezogen und das Produkt durch Zugabe von Ethanol gefällt. Ein analoges Verfahren beschreibt Clark in Organometallics 1 , (1982), 658-666 bei dem Na2PdCI4 und drei Äquivalente P(t-Bu)3 als Startmaterialien eingesetzt werden und das korrespondierende Palladaphosphacyclobutan mit 75% Ausbeute erhalten wird. Beide Verfahren sind aufgund des Einsatzes von zwei bzw. drei Äquivalenten P(t-Bu)3 pro
Äquivalent Palladium ökologisch und ökonomisch nachteilig.Clark describes in Inorg. Chim. Acta 31, (1978), L441 -L442 the reaction of K 2 PdCI 4 with two equivalents of P (t-Bu) 3 to the corresponding palladaphosphacyclobutane in 72% yield. Dimethylformamide is used as the solvent in this process. To isolate this palladaphosphacyclobutane, the solvent is removed and the product is precipitated by adding ethanol. Clark describes an analogous process in Organometallics 1, (1982), 658-666 in which Na 2 PdCI 4 and three equivalents of P (t-Bu) 3 are used as starting materials and the corresponding palladaphosphacyclobutane is obtained in a yield of 75%. Both methods are based on the use of two or three equivalents of P (t-Bu) 3 pro Equivalent palladium ecologically and economically disadvantageous.
Clark beschreibt in Inorg. Chem. 18, (1979), 2803-2808 die Reaktion von PdCI2(NCPh)2 mit einem Äquivalent P(t-Bu)3 zu dem entsprechenden Palladaphosphacyclobutan ohne Angabe der Ausbeute. In diesem Verfahren wird das toxikologisch bedenkliche Lösemittel Methylenchlorid verwendet in dem sowohl das Startmaterial als auch das Produkt löslich sind. Zur Isolierung dieses Palladaphosphacyclobutans wird das Lösemittel abgezogen, das Produkt mit Benzol extrahiert und anschließend durch Zugabe von Hexan gefällt. Das Verfahren ist aufgund der Verwendung von Methylenchlorid und Benzol ökologisch und ökonomisch nachteilig.Clark describes in Inorg. Chem. 18, (1979), 2803-2808 the reaction of PdCI 2 (NCPh) 2 with one equivalent of P (t-Bu) 3 to the corresponding palladaphosphacyclobutane without indication of the yield. In this process, the toxicologically questionable solvent methylene chloride is used in which both the starting material and the product are soluble. To isolate this palladaphosphacyclobutane, the solvent is removed, the product is extracted with benzene and then precipitated by adding hexane. The process is ecologically and economically disadvantageous due to the use of methylene chloride and benzene.
Werner beschreibt in J. Organomet. Chem. 204, (1980) 415-422 die Reaktion von Pd(P(t-Bu)3)2CI2 und Pd(P(t-Bu)2Ph)2CI2 mit Silberacetat zur Darstellung der korrespondierenden Palladaphosphacyclobutane, Di-μ-chloro-bis[2-[bis(1 ,1- dimethylethyl)phosphino]-2-methylpropyI-C,P]dipalladium (II) und Di-μ-chloro- bis[2-[(1 ,1-dimethylethyl)-phenylphosphino]-2-methylpropyl-C,P]dipalladium (II). Dieses Verfahren ist aufgund des Einsatzes von zwei Äquivalenten Phosphin pro Äquivalent Palladium und der Verwendung von Silberacetat in stöchiometrischen Mengen ökologisch sowie ökonomisch sehr nachteilig.Werner describes in J. Organomet. Chem. 204, (1980) 415-422 the reaction of Pd (P (t-Bu) 3 ) 2 CI 2 and Pd (P (t-Bu) 2 Ph) 2 CI 2 with silver acetate to prepare the corresponding palladaphosphacyclobutanes, Di -μ-chloro-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyI-C, P] dipalladium (II) and di-μ-chloro-bis [2 - [(1, 1- dimethylethyl) phenylphosphino] -2-methylpropyl-C, P] dipalladium (II). This method is ecologically and economically disadvantageous due to the use of two equivalents of phosphine per equivalent of palladium and the use of silver acetate in stoichiometric amounts.
Goel beschreibt in Trans. Met. Chem 5, (1980), 378-379 die Reaktion von dem in Methanol unlöslichen Di-μ-chloro-bis[2-[bis(1 , 1-dimethylethyl)phosphino]-2- methylpropyl-C,P]dipalladium (II) zu dem in Methanol löslichen -Chloro-//- methoxy-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-C,P]dipalladium (II) durch Suspendieren des Ausgangsmaterials in Methanol, anschließender Umsetzung mit einem Äquivalent Natriumhydroxid und Einengen des Lösemittels mit einer Ausbeute von 70%. Die Verwendung einer schlecht löslichen Substanz um eine leicht lösliche zu erzeugen ist insofern von Nachteil, als das Lösemittel am Ende abgezogen werden muß, und spiegelt sich in der geringen Ausbeute wieder. Da für diese Reaktion zuerst das Di- -chloro-bis[2-
Ibis{1 ,1-dimethylethyl)phosphino]-2-methylpropyl-C,P]dipalladium (II) dargestellt werden muß, handelt es sich gegenüber den vorher beschriebenen Synthesen um eine zwei-Stufen-Synthese, was einen weiteren Nachteil bedeutet.Goel describes in Trans. Met. Chem 5, (1980), 378-379 the reaction of the di-μ-chloro-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl- insoluble in methanol C, P] dipalladium (II) to the methanol-soluble chloro - // - methoxy bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II) Suspend the starting material in methanol, then react with an equivalent of sodium hydroxide and concentrate the solvent in a yield of 70%. The use of a poorly soluble substance to produce a readily soluble one is disadvantageous in that the solvent has to be stripped off at the end and is reflected in the low yield. Since the di- chloro-bis [2- Ibis {1, 1-dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II) must be prepared, it is a two-step synthesis compared to the previously described syntheses, which means a further disadvantage.
Im Hinblick auf die Vielfalt der Einsatzmöglichkeiten von Palladaphosphacyclobutanen besteht ein Bedarf an neuen Palladaphosphacyclobutanen, um einerseits das Spektrum ihrer Anwendungsmöglichkeiten zu ergänzen und zu erweitern, und andererseits bestimmte Reaktionen besonders günstig durchführen zu können. Ebenso besteht zudem ein hoher Bedarf nach einem einfacheren Verfahren zur Darstellung von Palladaphosphacyclobutanen der Formel (I).In view of the variety of possible uses of palladaphosphacyclobutanes, there is a need for new palladaphosphacyclobutanes in order to supplement and expand the spectrum of their possible uses and to carry out certain reactions particularly cheaply. There is also a great need for a simpler process for the preparation of palladaphosphacyclobutanes of the formula (I).
Diese Aufgabe wird durch die erfindungsgemäßen Palladaphosphacyclobutane gelöst.This object is achieved by the palladaphosphacyclobutanes according to the invention.
Gegenstand der Erfindung sind Palladaphosphacyclobutane der Formel (I)The invention relates to palladaphosphacyclobutanes of the formula (I)
worinwherein
R1, R2 unabhängig voneinander Wasserstoff, (C1-C4)-Alkyl, (C3-R 1 , R 2 independently of one another are hydrogen, (C 1 -C 4 ) -alkyl, (C 3 -
C12)-Cycloalkyl, (CrC4)-Alkoxy, Fluor, N-[(CrC4)-Alkyl]2, CO2-(CrC4)-Alkyl, OCO-(CrC4)-Alkyl, oder Aryl;C 12 ) cycloalkyl, (C r C 4 ) alkoxy, fluorine, N - [(C r C 4 ) alkyl] 2 , CO 2 - (C r C 4 ) alkyl, OCO- (C r C 4 ) Alkyl, or aryl;
R , R4, R5, R6 unabhängig voneinander (CrC8)-Alkyl, (C3-C12)-Cycloalkyl, oder Aryl;
oder worin R1 und R2, R1 oder R2 und R3 oder R4, R3 und R4, R3 oder R4 und R5 oder R6, oder R5 und R6 zusammen einen aliphatischen Ring mit 4 bis 10 Kohlenstoffatomen bilden;R, R 4 , R 5 , R 6 independently of one another (C r C 8 ) alkyl, (C 3 -C 12 ) cycloalkyl, or aryl; or wherein R 1 and R 2 , R 1 or R 2 and R 3 or R 4 , R 3 and R 4 , R 3 or R 4 and R 5 or R 6 , or R 5 and R 6 together form an aliphatic ring with 4 form up to 10 carbon atoms;
oder worin R5 und R6, R3 oder R4 und R5 oder R6 zusammen einen aromatischen Ring mit 5 bis 9 Kohlenstoffatomen bilden;or wherein R 5 and R 6 , R 3 or R 4 and R 5 or R 6 together form an aromatic ring having 5 to 9 carbon atoms;
undand
Y ein Anion einer anorganischen oder organischen Säure darstellt, wobei die VerbindungenY represents an anion of an inorganic or organic acid, the compounds
Di-μ-chloro-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di-μ-chloro-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di- /-bromo-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di- / -bromo-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di- /-trifluoroacetato-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di- / -trifluoroacetato-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di-/y-chloro-bis[2-[( 1 , 1 -dimethylethyl)-phenylphosphino]-2-methylpropyl-Di- / y-chloro-bis [2 - [(1, 1-dimethylethyl) phenylphosphino] -2-methylpropyl-
CPJdipalladium (II)CPJdipalladium (II)
/ -chloro-/ -methoxy-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-/ -chloro- / -methoxy-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II) ausgenommen sind.C, P] dipalladium (II) are excluded.
Bevorzugt sind Palladaphosphacyclobutane der Formel (I), worinPalladaphosphacyclobutanes of the formula (I) are preferred in which
R1 , R2 unabhängig voneinander Phenyl,R 1 , R 2 are independently phenyl,
R5, R6 unabhängig voneinander Phenyl, Naphthyl oder Anthracenyl, die mit 1 bis 3 (CrC4)-Alkyl oder 1 bis 3 (CrC4)-Alkoxy Gruppen substituiert sein können, bedeuten.R 5 , R 6 independently of one another are phenyl, naphthyl or anthracenyl, which can be substituted by 1 to 3 (C r C 4 ) -alkyl or 1 to 3 (C r C 4 ) -alkoxy groups.
Besonders bevorzugt sind Palladaphosphacyclobutane der Formel (I), worin R3, R4 unabhängig voneinander Phenyl,
R5, R6 unabhängig voneinander o-Trifluoromethylphenyl, o-Palladaphosphacyclobutanes of the formula (I) are particularly preferred in which R 3 , R 4 independently of one another are phenyl, R 5 , R 6 independently of one another o-trifluoromethylphenyl, o-
Trifluoromethyl-p-tolyl, o-Trifluoromethyl-p-methoxy-phenyl, o- Methoxy-phenyl, o,p-Dimethoxy-phenyl, o,o,p-Trimethoxy-phenyl, tert.-Butyl, n-Butyl, Isopropyl, Isobutyl, Cyclohexyl, 1 - Methylcyclohexyl bedeuten.Trifluoromethyl-p-tolyl, o-trifluoromethyl-p-methoxy-phenyl, o-methoxy-phenyl, o, p-dimethoxy-phenyl, o, o, p-trimethoxy-phenyl, tert-butyl, n-butyl, isopropyl , Isobutyl, cyclohexyl, 1 - methylcyclohexyl.
Von besonderer Bedeutung sind die VerbindungenThe connections are of particular importance
Di- -acetato-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di- -acetato-bis [2- [bis (1,1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di-μ-acetato-bis[2-[( 1 , 1 -dimethylethyl)-phenylphosphino]-2-methylpropyl-Di-μ-acetato-bis [2 - [(1, 1-dimethylethyl) phenylphosphino] -2-methylpropyl-
C,P]dipaIladium (II)C, P] dipaIladium (II)
Di-μ-chloro-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di-μ-chloro-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di-μ-chloro-bis[2-[( 1 , 1 -dimethylethyl)-phenylphosphino]-2-methylpropyl-Di-μ-chloro-bis [2 - [(1, 1-dimethylethyl) phenylphosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di-//-bromo-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di - // - bromo-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di- -bromo-bis[2-[(1 , 1 -dimethylethyl)-phenylphosphino]-2-methylpropyl-Di- -bromo-bis [2 - [(1, 1-dimethylethyl) phenylphosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Die erfindungsgemäßen Palladaphosphacyclobutane stellen eine neue Klasse von Katalysatoren dar. Ihre katalytische Aktivität bei der Olefinierung von Arylhalogeniden ist im Vergleich zum Stand der Technik außergewöhnlich, so daß ein großes technisches Interesse an den erfindungsgemäßen Verbindungen besteht.The palladaphosphacyclobutanes according to the invention represent a new class of catalysts. Their catalytic activity in the olefination of aryl halides is exceptional compared to the prior art, so that there is great technical interest in the compounds according to the invention.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung von Verbindungen nach Formel 1 , dadurch gekennzeichnet, daß man ein Phosphan der Formel (II)
The invention further relates to a process for the preparation of compounds of the formula 1, characterized in that a phosphane of the formula (II)
worin R1 bis R6 die zuvor genannten Bedeutungen besitzen und R7 Wasserstoff oder Deuterium bedeutet, mit einem Palladiumsalz der Formel (IM), einem Palladiumkomplex der Formel (IV) oder einem Alkalipalladat der Formel (V)wherein R 1 to R 6 have the meanings mentioned above and R 7 is hydrogen or deuterium, with a palladium salt of the formula (IM), a palladium complex of the formula (IV) or an alkali metal palletate of the formula (V)
Pd Y2 (III) Pd Y2L2 (IV) M2[PdY4] (V)Pd Y 2 (III) Pd Y 2 L 2 (IV) M 2 [PdY 4 ] (V)
wobei Y die zuvor genannte Bedeutung besitzt, M für Natrium, Kalium oder Lithium und L für 1 ,5-Cyclooctadien, Acetonitril oder Benzonitril steht, in Gegenwart eines organischen Lösungsmittels umsetzt.where Y is as defined above, M is sodium, potassium or lithium and L is 1, 5-cyclooctadiene, acetonitrile or benzonitrile, in the presence of an organic solvent.
In vielen Fällen hat es sich bewährt die Reaktion bei einer Temperatur von 0° bis 160°C, bevorzugt 0° bis 150°C, insbesondere 5 bis 140°C durchzuführen.In many cases it has proven useful to carry out the reaction at a temperature of 0 ° to 160 ° C., preferably 0 ° to 150 ° C., in particular 5 to 140 ° C.
Das Phosphan der Formel (II) und die Palladiumverbindung der Formel (III), (IV) oder (V) werden in einem molaren Verhältnis von Phosphan zu Pd-Verbindung von 0.1 bis 20, insbesondere 0.1 5 bis 15, bevorzugt 0.2 bis 10, besonders bevorzugt von 0.8 bis 1.2 einzusetzen.The phosphane of the formula (II) and the palladium compound of the formula (III), (IV) or (V) are in a molar ratio of phosphine to Pd compound of 0.1 to 20, in particular 0.1 5 to 15, preferably 0.2 to 10, particularly preferably from 0.8 to 1.2.
Als Lösungsmittel eignen sich aliphatische Kohlenwasserstoffe und aromatische Kohlenwasserstoffe. Sehr geeignet sind Toluol oder Xylole.Aliphatic hydrocarbons and aromatic hydrocarbons are suitable as solvents. Toluene or xylenes are very suitable.
Für die Herstellung von schwerer löslichen Palladaphosphacyclobutanen ist es auch möglich einen leichter löslichen Palladacyclus mit dem entsprechenden Anion einer organischen oder anorganischen Säure umzusetzen.
Die folgenden Beispiele sollen die Erfindung näher erläutern:For the production of poorly soluble palladaphosphacyclobutanes, it is also possible to implement a more soluble palladacycle with the corresponding anion of an organic or inorganic acid. The following examples are intended to illustrate the invention:
Beispiel 1 :Example 1 :
Di-μ-acetato-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di-μ-acetato-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
5,1 g (22,7 mmol) Pd(OAc)2 werden in 200 ml Toluol gelöst. Die Lösung wird mit 5 g (24,7 mmol) Tri-(tert.-butyl)phosphan versetzt. Die sich rasch nach hellorange aufklarende Lösung wird 10 Minuten lang auf 70-80°C erhitzt und dann auf Raumtemperatur abgekühlt. Das Lösungsmittel wird im Vakuum entfernt. Nach Zugabe von 200 ml Hexan kristallisiert nach kurzer Zeit das Produkt, Di-μ-acetato-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2-methylpropyl- C,P]dipalladium, aus und wird abfiltriert. Man erhält 6, 15 g (80 % d. Th.) bezogen auf Pd(OAc)2 als weißen Feststoff. Durch Umkristallisation aus Hexan und Filtration der Lösungen über Celite kann das Produkt in Form weiße Kristallnadeln analysenrein gewonnen werden. Elementaranalyse: C28H58O4P2Pd2 (733,51 ): gef.: C, 45.6 %; H, 7.7 %; ber.: C, 45.85 %; H, 7.97 %; ^-NMR (300 MHz, CDCI3): δ = 1 .88 (3H, s, CH3); 1 .50 (d, 18H, CH3, 4J(PH) = 14 Hz); 1.44 (d, 12H, CH3, 4J(PH) = 15 Hz); 1.07 (2H, sbreit, 4H, CH2); 13C{1 H}-NMR (75.4 MHz, -70 C, CD2CI2): δ = 181.5 (s, CH3CO2); 49.5 (s, PC, J(PC) = 20.1 Hz); 37.5 (s, PC, J(PC) = 10.6 Hz); 32.3 (s, CH3, J(PC) = 2,9 Hz); 31.1 (s, CH3); 24.7 (s, CH3CO2); 7.2 (s, £H2, J(PC) = 33.6 Hz). 31P{1H}-NMR (121.4 MHz, CDCI3): = -8.5 (s).5.1 g (22.7 mmol) of Pd (OAc) 2 are dissolved in 200 ml of toluene. 5 g (24.7 mmol) of tri- (tert-butyl) phosphane are added to the solution. The solution, which quickly clears to light orange, is heated to 70-80 ° C. for 10 minutes and then cooled to room temperature. The solvent is removed in vacuo. After addition of 200 ml of hexane, the product, di-μ-acetato-bis [2- [bis (1,1, dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium, crystallizes out after a short time and is filtered off. 6.15 g (80% of theory), based on Pd (OAc) 2, are obtained as a white solid. By recrystallization from hexane and filtration of the solutions over Celite, the product can be obtained in the form of white crystal needles in a pure analysis. Elemental analysis: C 28 H 58 O 4 P 2 Pd 2 (733.51): found: C, 45.6%; H, 7.7%; calc .: C, 45.85%; H, 7.97%; ^ -NMR (300 MHz, CDCI 3 ): δ = 1.88 (3H, s, CH 3 ); 1 .50 (d, 18H, CH 3, 4 J (PH) = 14 Hz); 1:44 (d, 12H, CH 3, 4 J (PH) = 15 Hz); 1:07 (2H, s broad, 4H, CH 2); 13 C { 1 H} -NMR (75.4 MHz, -70 C, CD 2 CI 2 ): δ = 181.5 (s, CH 3 CO 2 ); 49.5 (s, PC, J (PC) = 20.1 Hz); 37.5 (s, PC, J (PC) = 10.6 Hz); 32.3 (s, CH 3 , J (PC) = 2.9 Hz); 31.1 (s, CH 3); 24.7 (s, CH 3 CO 2); 7.2 (s, £ H 2 , J (PC) = 33.6 Hz). 31 P { 1 H} -NMR (121.4 MHz, CDCI 3 ): = -8.5 (s).
Beispie! 2Example! 2
Di-//-chloro-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl- C,P]dipalladium (II)Di - // - chloro-bis [2- [bis (1,1-dimethylethyl) phosphino] -2-methylpropyl- C, P] dipalladium (II)
50,0 mg Pd2(OAc)2{CH2C(CH3)2P(f-Bu)2}2 werden in 0,5 ml Methanol gelöst,
mit 25 mg Lithiumchlorid in 0,5 ml Methanol versetzt und 5 min bei Raumtemperatur gerührt. Nach Zugabe von 0,2 ml Wasser wird der feine, weiße Niederschlag abfiltriert, dreimal mit 1 ml Methanol/Wasser (1 :1 ) gewaschen und im Vakuum getrocknet (90°C, 100 mbar, 1 h). Man erhält 44,9 mg (98 % d. Th.) Di-μ-chloro-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2- methylpropyl-C,P]dipalladium (II) als weißen Feststoff der Summenformel C24H52CI2P2Pd2 (686.34). 1 H-NMR und 31 P-NMR entsprechen Beispiel 4.50.0 mg Pd 2 (OAc) 2 {CH 2 C (CH 3 ) 2 P (f-Bu) 2 } 2 are dissolved in 0.5 ml methanol, 25 mg of lithium chloride in 0.5 ml of methanol were added and the mixture was stirred at room temperature for 5 min. After adding 0.2 ml of water, the fine, white precipitate is filtered off, washed three times with 1 ml of methanol / water (1: 1) and dried in vacuo (90 ° C., 100 mbar, 1 h). 44.9 mg (98% of theory) of di-μ-chloro-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II) are obtained as white Solid of the empirical formula C 24 H 52 CI 2 P 2 Pd 2 (686.34). 1 H-NMR and 31 P-NMR correspond to Example 4.
Beispiel 3Example 3
Di-μ-bromo-bis[2-[bis(1 ,1 -dimethylethyl)phosphino]-2-methylpropyl- C,P]dipalladium (II)Di-μ-bromo-bis [2- [bis (1,1-dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II)
50,0 mg Pd2(OAc)2{CH2C(CH3)2P(f-Bu)2}2 werden in 0,5 ml Methanol gelöst, mit 30 mg Lithiumbromid im 0,5 ml Methanol versetzt und 5 min bei Raumtemperatur gerührt. Der feine, weiße Niederschlag wird abfiltriert, dreimal mit 1 ml Methanol/Wasser (1 :1 ) gewaschen und im Vakuum getrocknet (90°C, 100 mbar, 1 h). Man erhält 51.8 mg (98 % d. Th.) Di-//-bromo-bis[2-[bis(1 , 1 - dimethylethyl)phosphino]-2-methylpropyl-C,P]dipalladium (II) als weißen Feststoff der Summenformel C24H52Br2P2Pd2 (775.24). 1 H-NMR und 31 P-NMR entsprechen Beispiel 5.50.0 mg Pd 2 (OAc) 2 {CH 2 C (CH 3 ) 2 P (f-Bu) 2 } 2 are dissolved in 0.5 ml methanol, mixed with 30 mg lithium bromide in 0.5 ml methanol and 5 min stirred at room temperature. The fine, white precipitate is filtered off, washed three times with 1 ml of methanol / water (1: 1) and dried in vacuo (90 ° C., 100 mbar, 1 h). 51.8 mg (98% of theory) of di - // - bromo-bis [2- [bis (1,1-dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II) are obtained as a white solid the empirical formula C 24 H 52 Br 2 P 2 Pd 2 (775.24). 1 H-NMR and 31 P-NMR correspond to Example 5.
Beispiel 4Example 4
Di-//-chloro-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di - // - chloro-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
1 ,00 g (1 ,36 mmol) Pd2(OAc)2{CH2C(CH3)2P(f-Bu)2}2 werden in 60 ml Methylenchlorid gelöst, mit 4,00 g (13,6 mmol) [NBu4]CI versetzt und 1 Stunde bei Raumtemperatur gerührt. Das Lösungsmittel wird im Vakuum entfernt und der Rückstand in 50 ml Methanol aufgenommen. Der feine, gelbe Niederschlag wird abfiltriert, dreimal mit 20 ml Methanol und zweimal mit 20 ml Pentan gewaschen und im Vakuum getrocknet. Man erhält 700 mg (75 % d. Th.) Di-//-
chloro-bis[2-[bis(1 ,1-dimethylethyl)phosphino]-2-methylpropyl-C,P]dipalladium (II) als weißen Feststoff.1.00 g (1.36 mmol) Pd 2 (OAc) 2 {CH 2 C (CH 3 ) 2 P (f-Bu) 2 } 2 are dissolved in 60 ml methylene chloride, with 4.00 g (13.6 mmol) [NBu 4 ] CI was added and the mixture was stirred at room temperature for 1 hour. The solvent is removed in vacuo and the residue is taken up in 50 ml of methanol. The fine, yellow precipitate is filtered off, washed three times with 20 ml of methanol and twice with 20 ml of pentane and dried in vacuo. 700 mg (75% of theory) of Di - // - are obtained chloro-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II) as a white solid.
Elementaranalyse: C24H52CI2P2Pd2 (686.34): gef.: C, 41 .8 %; H, 7.4 %; ber.: C, 42.00 %; H, 7.64 %; 1H-NMR (300 MHz, CDCI3): δ = 1.56 (d, 18H, CH3, J(PH) = 14 Hz); 1.47 (d, 12H, CH3, 4J(PH) = 14 Hz); 1.10 (d, 4H, CH2, 4J(PH) = 3 Hz); 13C{1 H}-NMR (75.4 MHz, -70 C, CD2CI2): δ = 49.3 (d, PC, J(PC) = 19.6 Hz); 38.0 (d, PC, J(PC) = 10.0 Hz); 32.1 (d, CH3, J(PC) = 3.2 Hz); 31 .0 (s, CH3); 1 1 .6 (d, CH2, J(PC) = 29.4 Hz). 31 P{1 H}-NMR (121 .4 MHz, CDCI3): = -9.7 (s).Elemental analysis: C 24 H 52 CI 2 P 2 Pd 2 (686.34): found: C, 41.8%; H, 7.4%; calc .: C, 42.00%; H, 7.64%; 1 H NMR (300 MHz, CDCI 3 ): δ = 1.56 (d, 18H, CH 3 , J (PH) = 14 Hz); 1:47 (d, 12H, CH 3, 4 J (PH) = 14 Hz); 1.10 (d, 4H, CH 2 , 4 J (PH) = 3 Hz); 13 C { 1 H} -NMR (75.4 MHz, -70 C, CD 2 CI 2 ): δ = 49.3 (d, PC, J (PC) = 19.6 Hz); 38.0 (d, PC, J (PC) = 10.0 Hz); 32.1 (d, CH 3 , J (PC) = 3.2 Hz); 31. 0 (s, CH 3 ); 1 1 .6 (d, CH 2 , J (PC) = 29.4 Hz). 31 P { 1 H} -NMR (121 .4 MHz, CDCI 3 ): = -9.7 (s).
Beispiel 5Example 5
Di-μ-bromo-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl- C,P]dipalladium (II)Di-μ-bromo-bis [2- [bis (1,1-dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II)
1 ,90 g (2,60 mmol) Pd2(OAc)2{CH2C(CH3)2P(f-Bu)2}2 werden in 60 ml Methylenchlorid gelöst, mit 7,50 g (23,3 mmol) [NBu4]CI versetzt und 1 Stunde bei Raumtemperatur gerührt. Das Lösungsmittel wird im Vakuum entfernt und der Rückstand in 50 ml Methanol aufgenommen. Der feine, gelbe Niederschlag wird abfiltriert, dreimal mit 20 ml Methanol und zweimal mit 20 ml Pentan gewaschen und im Vakuum getrocknet. Man erhält 1 ,20 g (60 % d. Th.) Di-μ- bromo-bis[2-[bis(1 ,1 -dimethylethyl)phosphino]-2-methylpropyl-C,P]dipalladium (II) als weißen Feststoff. C24H52Br2P2Pd2 (775.24): gef.: C, 37.9 %; H, 6.5 %; ber.: C, 37.18 %; H, 6.76 %; ^-NMR (300 MHz, CDCI3): δ = 1.57 (d, 18H, CH3, 4J(PH) = 14 Hz); 1.48 (d, 12H, CH3, 4J(PH) = 14 Hz); 1 .21 (d, 4H, CH2, 4J(PH) = 3 Hz); 13C{1 H}-NMR (75.4 MHz, -70 C, CD2CI2): δ = 49.7 (d, PC, J(PC) = 19.3 Hz);
38.3 (d, PC, J(PC) = 9.0 Hz); 32.1 (d, CH3, J(PC) = 3.5 Hz); 31.2 (s, CH3);1.90 g (2.60 mmol) Pd 2 (OAc) 2 {CH 2 C (CH 3 ) 2 P (f-Bu) 2 } 2 are dissolved in 60 ml methylene chloride, with 7.50 g (23.3 mmol) [NBu 4 ] CI was added and the mixture was stirred at room temperature for 1 hour. The solvent is removed in vacuo and the residue is taken up in 50 ml of methanol. The fine, yellow precipitate is filtered off, washed three times with 20 ml of methanol and twice with 20 ml of pentane and dried in vacuo. 1.20 g (60% of theory) of di-μ-bromo-bis [2- [bis (1,1-dimethylethyl) phosphino] -2-methylpropyl-C, P] dipalladium (II) are obtained as white Solid. C 24 H 52 Br 2 P 2 Pd 2 (775.24): Found: C, 37.9%; H, 6.5%; calc .: C, 37.18%; H, 6.76%; ^ -NMR (300 MHz, CDCI 3 ): δ = 1.57 (d, 18H, CH 3 , 4 J (PH) = 14 Hz); 1:48 (d, 12H, CH 3, 4 J (PH) = 14 Hz); 1 .21 (d, 4H, CH 2, 4 J (PH) = 3 Hz); 13 C { 1 H} -NMR (75.4 MHz, -70 C, CD 2 CI 2 ): δ = 49.7 (d, PC, J (PC) = 19.3 Hz); 38.3 (d, PC, J (PC) = 9.0 Hz); 32.1 (d, CH 3 , J (PC) = 3.5 Hz); 31.2 (s, CH 3);
13.9 (d, CH2, J(PC) = 27.3 Hz).13.9 (d, CH 2 , J (PC) = 27.3 Hz).
31 P{1 H}-NMR (121.4 MHz, CDCI3): = -8.6 (s). 31 P { 1 H} -NMR (121.4 MHz, CDCI 3 ): = -8.6 (s).
Folgende Handelsprodukte wurden verwendet: Celite®/Aldrich Filterhilsmittel auf SiO2-Basis
The following commercial products were used: Celite ® / Aldrich filter aid based on SiO 2
Claims
Patentansprüche:Claims:
1. Palladaphosphacyclobutane der Formel (I)1. Palladaphosphacyclobutanes of the formula (I)
worinwherein
R1 , R2 unabhängig voneinander Wasserstoff, (C,-C4)-Alkyl, (C3-R 1 , R 2 independently of one another are hydrogen, (C, -C 4 ) -alkyl, (C 3 -
C1 2)-Cycloalkyl, (CrC4)-Alkoxy, Fluor, N-[(CrC4)-Alkyl]2, CO2-(CrC4)-Alkyl, OCO-(CrC4)-Alkyl, oder Aryl;C 1 2 ) -cycloalkyl, (C r C 4 ) -alkoxy, fluorine, N - [(C r C 4 ) -alkyl] 2 , CO 2 - (C r C 4 ) -alkyl, OCO- (C r C 4 ) alkyl, or aryl;
R3, R4, R5, R6 unabhängig voneinander (CrC8)-Alkyl, (C3-C1 2)-Cycloalkyl, oder Aryl;R 3 , R 4 , R 5 , R 6 independently of one another (C r C 8 ) alkyl, (C 3 -C 1 2 ) cycloalkyl, or aryl;
oder worin R1 und R2, R1 oder R2 und R3 oder R4, R3 und R4, R3 oder R4 und R5 oder R6, oder R5 und R6 zusammen einen aliphatischen Ring mit 4 bis 10 Kohlenstoffatomen bilden;or wherein R 1 and R 2 , R 1 or R 2 and R 3 or R 4 , R 3 and R 4 , R 3 or R 4 and R 5 or R 6 , or R 5 and R 6 together form an aliphatic ring with 4 form up to 10 carbon atoms;
oder worin R5 und R6, R3 oder R4 und R5 oder R6 zusammen einen aromatischen Ring mit 5 bis 9 Kohlenstoffatomen bilden; undor wherein R 5 and R 6 , R 3 or R 4 and R 5 or R 6 together form an aromatic ring having 5 to 9 carbon atoms; and
Y ein Anion einer anorganischen oder organischen Säure darstellt, wobei die VerbindungenY represents an anion of an inorganic or organic acid, the compounds
Di- /-chloro-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di- / chloro-bis [2- [bis (1,1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di-//-bromo-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di - // - bromo-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)
Di-μ-trifluoroacetato-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-C, P] dipalladium (II) Di-μ-trifluoroacetato-bis [2- [bis (1,1, dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di-μ-chloro-bis[2-[( 1 , 1 -dimethylethyl)-phenylphosphino]-2-methylpropyl-Di-μ-chloro-bis [2 - [(1, 1-dimethylethyl) phenylphosphino] -2-methylpropyl-
C,P]dipalladium (II) μ-chloro-μ-methoxy-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-C, P] dipalladium (II) μ-chloro-μ-methoxy-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II) ausgenommen sind.C, P] dipalladium (II) are excluded.
2. Palladaphosphacyclobutane nach Anspruch 1 , dadurch gekennzeichnet, daß2. Palladaphosphacyclobutane according to claim 1, characterized in that
R1 , R2 unabhängig voneinander Phenyl,R 1 , R 2 are independently phenyl,
R5, R6 unabhängig voneinander Phenyl, Naphthyl oder Anthracenyl, die mit 1 bis 3 (CrC4)-Alkyl oder 1 bis 3 (CrC4)-Alkoxy Gruppen substituiert sein können, bedeuten.R 5 , R 6 independently of one another are phenyl, naphthyl or anthracenyl, which can be substituted by 1 to 3 (C r C 4 ) -alkyl or 1 to 3 (C r C 4 ) -alkoxy groups.
3. Palladaphosphacyclobutane nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß3. Palladaphosphacyclobutane according to claim 1 or 2, characterized in that
R3, R4 unabhängig voneinander Phenyl,R 3 , R 4 are independently phenyl,
R5, R6 unabhängig voneinander o-Trifluoromethylphenyl, o-R 5 , R 6 independently of one another o-trifluoromethylphenyl, o-
Trifluoromethyl-p-tolyl, o-Trifluoromethyl-p-methoxy-phenyl, o- Methoxy-phenyl, o,p-Dimethoxy-phenyl, o,o,p-Trimethoxy-phenyl, tert.-Butyl, n-Butyl, Isopropyl, Isobutyl, Cyclohexyl, 1- Methylcyclohexyl bedeuten.Trifluoromethyl-p-tolyl, o-trifluoromethyl-p-methoxy-phenyl, o-methoxy-phenyl, o, p-dimethoxy-phenyl, o, o, p-trimethoxy-phenyl, tert-butyl, n-butyl, isopropyl , Isobutyl, cyclohexyl, 1-methylcyclohexyl.
4. Palladaphosphacyclobutane nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es sich um Di-μ-acetato-bis[2-[bis(1 ,1 -dimethylethyl)phosphino]-2-methylpropyl- C,P]dipalladium (II)4. Palladaphosphacyclobutane according to one or more of claims 1 to 3, characterized in that it is di-μ-acetato-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl- C, P] dipalladium (II)
Di-/v-acetato-bis[2-[( 1 , 1 -dimethylethyl)-phenylphosphino]-2-methylpropyl-Di- / v-acetato-bis [2 - [(1, 1-dimethylethyl) phenylphosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di-μ-chloro-bis[2-[bis( 1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-
C,P]dipalladium (II)Di-μ-chloro-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl- C, P] dipalladium (II)
Di-//-chloro-bis[2-[( 1 , 1 -dimethylethyl)-phenylphosphino]-2-methylpropyl-Di - // - chloro-bis [2 - [(1, 1-dimethylethyl) phenylphosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di-μ-bromo-bis[2-[bis(1 , 1 -dimethylethyl)phosphino]-2-methylpropyl-Di-μ-bromo-bis [2- [bis (1, 1-dimethylethyl) phosphino] -2-methylpropyl-
C,P]dipalladium (II)C, P] dipalladium (II)
Di-μ-bromo-bis[2-[( 1 , 1 -dimethylethyl)-phenylphosphino]-2-methylpropyl-Di-μ-bromo-bis [2 - [(1, 1-dimethylethyl) phenylphosphino] -2-methylpropyl-
C,P]dipalladium (II) handelt.C, P] dipalladium (II).
Verfahren zur Herstellung von Verbindungen nach Formel 1 , dadurch gekennzeichnet, daß man ein Phosphan der Formel (II)Process for the preparation of compounds according to formula 1, characterized in that a phosphane of formula (II)
worin R1 bis R6 die zuvor genannten Bedeutungen besitzen und R7 Wasserstoff oder Deuterium bedeutet, mit einem Palladiumsalz der Formel (IM), einem Palladiumkomplex der Formel (IV) oder einem Alkalipalladat der Formel (V)wherein R 1 to R 6 have the meanings mentioned above and R 7 is hydrogen or deuterium, with a palladium salt of the formula (IM), a palladium complex of the formula (IV) or an alkali metal palletate of the formula (V)
Pd Y2 (IM) Pd Y2L2 (IV) M2[PdY4] (V)Pd Y 2 (IM) Pd Y 2 L 2 (IV) M 2 [PdY 4 ] (V)
wobei Y die zuvor genannte Bedeutung besitzt, M für Natrium, Kalium oder Lithium und L für 1 ,5-Cyclooctadien, Acetonitril oder Benzonitril steht, in Gegenwart eines organischen Lösungsmittels umsetzt.where Y is as defined above, M is sodium, potassium or lithium and L is 1, 5-cyclooctadiene, acetonitrile or benzonitrile, in the presence of an organic solvent.
Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Reaktion bei 0 bis 160 °C durchgeführt wird.
Process according to claim 5, characterized in that the reaction is carried out at 0 to 160 ° C.
7. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Reaktion bei 10 bis 150 °C durchgeführt wird.7. The method according to claim 5, characterized in that the reaction is carried out at 10 to 150 ° C.
8. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Reaktion bei 15 bis 140 °C durchgeführt wird.8. The method according to claim 5, characterized in that the reaction is carried out at 15 to 140 ° C.
9. Verfahren nach einem oder mehreren der Ansprüche 5 bis 8, dadurch gekennzeichnet, daß das Phosphan der Formel (II) zur Palladiumverbindung der Formeln (IM), (IV) oder (V) im molaren Verhältnis von 0,1 bis 20 eingesetzt wird.9. The method according to one or more of claims 5 to 8, characterized in that the phosphane of the formula (II) for the palladium compound of the formulas (IM), (IV) or (V) is used in a molar ratio of 0.1 to 20 .
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß das Phosphan der Formel (II) zur Palladiumverbindung der Formeln (IM), (IV) oder (V) im molaren Verhältnis von 0, 1 5 bis 15 eingesetzt wird.10. The method according to claim 9, characterized in that the phosphane of the formula (II) for the palladium compound of the formulas (IM), (IV) or (V) is used in a molar ratio of 0.1 to 15.
1 1. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß das Phosphan der Formel (II) zur Palladiumverbindung der Formeln (IM), (IV) oder (V) im molaren Verhältnis von 0,2 bis 10, bevorzugt 0,8 bis 1 ,2 eingesetzt wird.1 1. The method according to claim 9, characterized in that the phosphane of the formula (II) for the palladium compound of the formulas (IM), (IV) or (V) in a molar ratio of 0.2 to 10, preferably 0.8 to 1 , 2 is used.
12. Verfahren nach einem oder mehreren der Ansprüche 5 bis 1 1 , dadurch gekennzeichnet, daß als Lösungsmittel Kohlenwasserstoffe, insbesondere aromatische Kohlenwasserstoffe, bevorzugt Toluol oder Xylole eingesetzt werden.12. The method according to one or more of claims 5 to 1 1, characterized in that hydrocarbons, in particular aromatic hydrocarbons, preferably toluene or xylenes are used as solvents.
13. Verfahren zur Herstellung von Verbindungen nach Anspruch 1 , dadurch gekennzeichnet, daß man ein Palladaphosphacyclobutan der Formel (I) mit einem Anion einer anorganischen oder organischen Säure zu einem schwererlöslichen Palladaphosphacyclobutan umsetzt.
13. A process for the preparation of compounds according to claim 1, characterized in that a palladaphosphacyclobutane of the formula (I) is reacted with an anion of an inorganic or organic acid to give a less soluble palladaphosphacyclobutane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19647584A DE19647584A1 (en) | 1996-11-18 | 1996-11-18 | New palladaphosphacyclobutanes and a process for their preparation |
| DE19647584 | 1996-11-18 | ||
| PCT/EP1997/006327 WO1998022485A1 (en) | 1996-11-18 | 1997-11-13 | New dipalladaphosphacyclobutanes and a process for preparing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0938490A1 true EP0938490A1 (en) | 1999-09-01 |
Family
ID=7811958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97950184A Withdrawn EP0938490A1 (en) | 1996-11-18 | 1997-11-13 | New dipalladaphosphacyclobutanes and a process for preparing the same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6084114A (en) |
| EP (1) | EP0938490A1 (en) |
| JP (1) | JP2001510458A (en) |
| DE (1) | DE19647584A1 (en) |
| WO (1) | WO1998022485A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19932571A1 (en) * | 1999-07-13 | 2001-01-18 | Clariant Gmbh | Process for the preparation of biarylene using palladophosphacyclobutane catalysis |
| DE19942961A1 (en) | 1999-09-09 | 2001-03-15 | Clariant Gmbh | Process for the preparation of aromatic amines with catalysis by palladaphosphacyclobutanes |
| US7115762B2 (en) * | 2004-07-02 | 2006-10-03 | Academia Sinica | Polystyrene-supported palladacycle catalysts |
| US7449601B2 (en) * | 2004-12-16 | 2008-11-11 | E. I. Du Pont De Nemours And Company | Catalysts useful for catalyzing the coupling of arylhalides with arylboronic acids |
| JP5575702B2 (en) * | 2011-05-20 | 2014-08-20 | 株式会社クラレ | Catalyst composition for polymerization of vinyl monomers and use of the monomer for polymerization of vinyl monomers using the composition |
| CN103418438B (en) | 2013-08-22 | 2015-08-19 | 上海化工研究院 | A kind of azepine Cabbeen class palladium catalyst and its preparation method and application |
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| DE4421753C1 (en) * | 1994-06-22 | 1995-12-14 | Hoechst Ag | Palladacycles and a process for their preparation |
| US5831107A (en) * | 1994-06-22 | 1998-11-03 | Aventis Research & Technology Deutschland | Palladacycles and a process for their preparation |
-
1996
- 1996-11-18 DE DE19647584A patent/DE19647584A1/en not_active Withdrawn
-
1997
- 1997-11-13 US US09/308,259 patent/US6084114A/en not_active Expired - Fee Related
- 1997-11-13 WO PCT/EP1997/006327 patent/WO1998022485A1/en not_active Application Discontinuation
- 1997-11-13 EP EP97950184A patent/EP0938490A1/en not_active Withdrawn
- 1997-11-13 JP JP52317598A patent/JP2001510458A/en active Pending
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| Title |
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| See references of WO9822485A1 * |
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| Publication number | Publication date |
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| JP2001510458A (en) | 2001-07-31 |
| US6084114A (en) | 2000-07-04 |
| WO1998022485A1 (en) | 1998-05-28 |
| DE19647584A1 (en) | 1998-05-20 |
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