EP0938490A1 - Nouveaux palladaphosphacyclobutanes et leur procede de preparation - Google Patents

Nouveaux palladaphosphacyclobutanes et leur procede de preparation

Info

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Withdrawn
Application number
EP97950184A
Other languages
German (de)
English (en)
Inventor
Holger Geissler
Peter Gross
Bianca Guckes
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Aventis Research and Technologies GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Aventis Research and Technologies GmbH and Co KG filed Critical Aventis Research and Technologies GmbH and Co KG
Publication of EP0938490A1 publication Critical patent/EP0938490A1/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • 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

L'invention concerne des palladaphosphacyclobutanes de formule (I), dans laquelle R<1>, R<2> désignent indépendamment hydrogène, alkyle (C1-C4), cycloalkyle (C3-C12), alkoxy (C1-C4), fluor, N(alkyle)2-(C1-C4), CO2-alkyle-(C1-C4), OCO-alkyle-(C1-C4), ou aryle; R<3>, R<4>, R<5>, R<6> désignent indépendamment alkyle (C1-C8), cycloalkyle (C3-C12) ou aryle; ou dans laquelle R<1> et R<2>, R<1> ou R<2> et R<3> ou R<4>, R<3> et R<4>, R<3> ou R<4> et R<5> ou R<6>, ou R<5> et R<6> forment ensemble un anneau aliphatique; ou dans laquelle R<5> et R<6>, R<3> ou R<4> et R<5> ou R<6> forment ensemble un anneau aromatique; et Y désigne un anion d'un acide inorganique ou organique, à l'exception des composés di- mu -chloro-bis[2-[bis(1,1-diméthyléthyl)phosphino]-2-méthylpropyl-C,P]dipalladium (II), di- mu -bromo-bis[2-[bis(1,1-diméthyléthyl)phosphino]-2-méthylpropyl-C,P]dipalladium (II), di- mu -trifluoroacetato-bis[2-[bis(1,1-diméthyléthyl)phosphino]-2-méthylpropyl-C,P]dipalladium (II), di- mu -chloro-bis[2-[(1,1-diméthyléthyl)phénylphosphino]-2-méthylpropyl-C,P]dipalladium (II), mu -chloro- mu -methoxy-bis[2-[bis(1,1-diméthyléthyl)phosphino]-2-méthylpropyl-C,P]dipalladium (II).
EP97950184A 1996-11-18 1997-11-13 Nouveaux palladaphosphacyclobutanes et leur procede de preparation Withdrawn EP0938490A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19647584 1996-11-18
DE19647584A DE19647584A1 (de) 1996-11-18 1996-11-18 Neue Palladaphosphacyclobutane sowie ein Verfahren zu ihrer Herstellung
PCT/EP1997/006327 WO1998022485A1 (fr) 1996-11-18 1997-11-13 Nouveaux palladaphosphacyclobutanes et leur procede de preparation

Publications (1)

Publication Number Publication Date
EP0938490A1 true EP0938490A1 (fr) 1999-09-01

Family

ID=7811958

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97950184A Withdrawn EP0938490A1 (fr) 1996-11-18 1997-11-13 Nouveaux palladaphosphacyclobutanes et leur procede de preparation

Country Status (5)

Country Link
US (1) US6084114A (fr)
EP (1) EP0938490A1 (fr)
JP (1) JP2001510458A (fr)
DE (1) DE19647584A1 (fr)
WO (1) WO1998022485A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19932571A1 (de) 1999-07-13 2001-01-18 Clariant Gmbh Verfahren zur Herstellung von Biarylen unter Palladophosphacyclobutan-Katalyse
DE19942961A1 (de) 1999-09-09 2001-03-15 Clariant Gmbh Verfahren zur Herstellung von aromatischen Aminen unter Katalyse von Palladaphosphacyclobutanen
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 (ja) * 2011-05-20 2014-08-20 株式会社クラレ ビニル系モノマー重合用触媒組成物および該組成物を用いたビニル系モノマーの重合への使用
CN103418438B (zh) 2013-08-22 2015-08-19 上海化工研究院 一种氮杂卡宾类钯催化剂及其制备方法和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4421753C1 (de) * 1994-06-22 1995-12-14 Hoechst Ag Palladacyclen sowie ein Verfahren zu ihrer Herstellung
US5831107A (en) * 1994-06-22 1998-11-03 Aventis Research & Technology Deutschland Palladacycles and a process for their preparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9822485A1 *

Also Published As

Publication number Publication date
JP2001510458A (ja) 2001-07-31
DE19647584A1 (de) 1998-05-20
US6084114A (en) 2000-07-04
WO1998022485A1 (fr) 1998-05-28

Similar Documents

Publication Publication Date Title
EP0794957B1 (fr) Procede de production de phosphines de metallocenyle optiquement actives
EP1507783B1 (fr) Hydroxydiphosphines et leur utilisation en catalyse
GB2055839A (en) Ferrocene compounds suitable as ligands for rhodium based catalysts
EP0583433B1 (fr) Ligands diphosphiniques
EP0582692A1 (fr) Ligands diphosphiniques
DE2035582A1 (de) Organometallverbindungen und Verfahren zu ihrer Herstellung
DE69412309T2 (de) Phosphinverbindung und diese als Ligand enthaltender Übergangsmetall-Phosphinkomplex
DE2805488A1 (de) Verfahren zur herstellung einer 2-arylpropionsaeure
DE69727460T2 (de) Eine verbindung, die in einer katalytischen zusammensetzung verwendbar ist
EP0946573A1 (fr) Catalyseurs constitues de composes de metaux de transition et de ligands de 4,5-diphosphinoacridine
EP0938490A1 (fr) Nouveaux palladaphosphacyclobutanes et leur procede de preparation
EP0795559B1 (fr) Diphényl phosphanes substitués et procédé pour leur préparation
EP0491240B1 (fr) Procédé de préparation de diphosphanes sulphonés solubles dans l&#39;eau
DE69403697T2 (de) Phosphinverbindungen und Übergangsmetall-Phosphin-Komplexverbindungen, die diese als Liganden enthalten
EP1436305A1 (fr) Nouveaux ligands chiraux et leurs complexes de metaux de transition ainsi que leur utilisation catalytique
DE60206262T2 (de) Neues verfahren zur herstellung von metall-carben-komplexen
EP1174435B1 (fr) Procédé de préparation des complexes de platine et des alkénylsiloxanes, en particulier de platine et le divinyltétraméthylsiloxane
EP0688779B1 (fr) Palladocycles et procédé de leur préparation
EP1019422B1 (fr) Sels de cobalticinium substitues par phosphane, leur preparation et leur utilisation comme constituant de catalyseur
Ganesan et al. Reductive carbonylation route to Co (0) and Co (I) carbonyl complexes containing bridging, chelating and cleaved diphosphazanes. Structures of [Co (CO){P (OR) 2 (NHMe)} 2 {P (O)(OR) 2}{P (H)(OR′) 2}](R= CH2CF3, R′= CH2CH3),[Co2 (CO) 2 {μ-MeN {P (OR) 2} 2} 3](R= CH2CF3), and [Co (CO){η2-MeN {P (OR) 2} 2} 2][CoCl3 (OC4H8)](R= Ph)
EP0778281B1 (fr) Procédé de préparation de composés renfermant des hétéroatomes et contenant un pont méthylène et nouveaux bis (diorganylphosphino) méthanes
WO2007079963A1 (fr) Procede de fabrication et utilisation de nouveaux catalyseurs organometalliques contenant des carbenes carbocycliques en tant que ligands de stabilisation et de commande
DE69913003T2 (de) 1,2-bis(methyl(1,1,3,3-tetramethylbutyl)-phosphino)ethan, verfahren zur herstellung davon, übergangsmetall-komplexe, die dieses als liganden enthalten und ihre verwendung
DE19836722A1 (de) Wasserlösliche Übergangsmetallcluster
CH640500A5 (en) Magnesium halide complexes of 2-arylpropionic acids, and their preparation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990618

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT NL

17Q First examination report despatched

Effective date: 20010418

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: DEGUSSA AG

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20020530