WO2000068237A1 - Complexes pd et ni de biphenyl-2-yl-phosphanes et leur utilisation dans des couplages catalytiques c,c-, c,n- et c,o - Google Patents

Complexes pd et ni de biphenyl-2-yl-phosphanes et leur utilisation dans des couplages catalytiques c,c-, c,n- et c,o Download PDF

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WO2000068237A1
WO2000068237A1 PCT/EP2000/003710 EP0003710W WO0068237A1 WO 2000068237 A1 WO2000068237 A1 WO 2000068237A1 EP 0003710 W EP0003710 W EP 0003710W WO 0068237 A1 WO0068237 A1 WO 0068237A1
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alkyl
phenyl
alkynyl
mmol
alkenyl
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PCT/EP2000/003710
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German (de)
English (en)
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Steffen Haber
Andreas Meudt
Antje NÖRENBERG
Stefan Scherer
Frank VOLLMÜLLER
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Clariant Gmbh
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    • 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
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Definitions

  • C, C, C, N and C O-linked biaryls, styrenes, phenylacetylenes, anilines, phenol ethers and diaryl ethers are important intermediates in the chemical industry.
  • Previously known catalyst systems made it possible to carry out C, C, C, N and C, O couplings on iodine and bromoaromatics and on the triflates or nonaflates obtainable from corresponding phenols. Coupling reactions on unactivated chloroaromatics have hitherto not been able to be carried out or have been carried out only in low yields.
  • the invention was therefore based on the object of providing catalyst systems which are C, C-, C, N- and C, O- in a simple and inexpensive manner.
  • the catalysts according to the invention are very efficient in Suzuki, Grignard, Stille couplings and couplings of arylsilanes and arylzinc compounds and also show high reaction rates in Heck reactions of olefins and acetylenes. Non-activated chloroaromatics can also be converted into the desired products in high yields.
  • the catalysts mentioned are new and the subject of the present invention.
  • the present invention relates to complexes of palladium or nickel with biphenyl-2-ylphosphanes of the general formula (I),
  • R 1 and R 2 are the same or different and are straight-chain or branched alkyl having 1 to 8 C atoms, cycloalkyl having 4 to 8 ring C atoms, (C 2 -C 12 ) alkenyl, (C 2 -
  • Ci 2 ) -alkynyl, unsubstituted or substituted phenyl, the substituents being 1 to 3 in number and the meaning (CrC 4 ) -alkyl, (CC) -alkoxy, F or
  • R 1 and R 2 together are a 1, ⁇ -alkanediyl chain with 3 to 8 C atoms;
  • R 3 is hydrogen, CrC 12 alkyl, (C 2 -C 12 ) alkenyl, (C 2 -C 12 ) alkynyl, phenyl, naphthyl,
  • Heteroaryl Li, Na, K, MgCI, MgBr, Mgl, Mg 0 ,, ZnCI, ZnBr, Zn 0 , 5 , POPhenyl 2l
  • RCC 4 is alkyl, CF 3 , phenyl or tolyl; or R 3 is a polymeric matrix which is connected directly or via an aliphatic, aromatic or araliphatic bridge member to the phenolic oxygen atom adjacent to R 3 ; and R 4 to R 11 independently of one another are hydrogen, CrCi2-alkyl, (C- 2 -C12) -
  • Alkenyl, (C 2 -Ci 2 ) alkynyl, phenyl, OSO 2 R 'or SiR' 3 , or once two adjacent radicals R 4 to R 11 together form a unit of the formula are in which the radicals R 'independently of one another are hydrogen, -CC 12 -alkyl or phenyl.
  • the complexes according to the invention preferably correspond to the general formula (Ia)
  • L is a ligand or a combination of ligands, for example H, NO, halogen, such as Cl, cyclopentadienyl, cyclooctadiene, phosphine, phosphite, CO, CN, (CC-alkyl) CN, CC 12 -alkyl, aryl, for example phenyl, substituted phenyl , for example tolyl, alkylaryl, for example benzyl, or naphthyl, heteroaryl, such as pyridinyl, C 2 -C 8 alkenyl, in particular allyl, C ⁇ -Cs alkynyl, nitrate or acetate; and R 1 to R 11 are as defined above.
  • halogen such as Cl, cyclopentadienyl, cyclooctadiene, phosphine, phosphite
  • CO CN, (CC-alkyl) CN, CC
  • R 1 and R 2 are -CC alkyl, C 5 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, phenyl, fluorophenyl, pyridyl, tolyl, difluorophenyl, methoxyphenyl or bis (trifluoromethyl) phenyl, or R 1 and R 2 together form a 1, ⁇ -alkanediyl chain with 4 to 5 carbon atoms.
  • Preferred radicals R 3 are hydrogen, CC 4 alkyl, C 2 -C 6 alkenyl, C 2 -C 4 alkynyl, phenyl, pyridyl, triflate, mesylate, tosylate or trimethylsilyl.
  • R 3 is preferably a radical M-, M- (CrC 8 ) alkylene, M-polyoxyalkylene, such as, for example, M- [XO] a -, where X - (CH 2 ) 2 -, - (CH 2 ) 3 -, -CH (CH 3 ) -CH 2 - or -CH 2 -CH (CH 3 ) - and a is a number from 1 to 20, preferably 2 to 10, M-polyiminoalkylene, such as, for example, M- [ X-NH-] a -, where X and a are as defined above, and M is a polymeric matrix.
  • M-polyoxyalkylene such as, for example, M- [XO] a -, where X - (CH 2 ) 2 -, - (CH 2 ) 3 -, -CH (CH 3 ) -CH 2 - or -CH 2 -CH (CH 3 ) - and
  • the polymer matrix M can be, for example, a polystyrene.
  • R 4 to R 11 are hydrogen, CC 4 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, phenyl, OSO 2 CH 3 , OSO 2 C 6 H 5 or OSO 2 C 6 H 4 CH 3 , e.g.
  • R is preferably methyl or phenyl.
  • R ' is preferably hydrogen or methyl.
  • the invention also relates to a process for the preparation of the complexes defined above, characterized in that a biphenyl-2-ylphosphine of the formula (I)
  • Molar ratios of biphenyl-2-yl-phosphane to Pd or Ni compound of 0.7 to 1 to 8 to 1 are preferred, particularly preferably 0.95 to 1 to 4.0 to 1.
  • any Pd or Ni salt or any Pd or Ni complex can be used in which a complete or partial ligand exchange or ligand addition takes place with the formation of biphenyl-2-yl-phosphine-palladium or nickel complexes can.
  • the Pd or Ni compound is, for example, a compound of the formula (II)
  • L and y are as defined above, and w is a number from y to 8y.
  • PdCI 2 (cyclooctadiene) PdCl2, Pd (OAc) 2 , (H 3 CCN) 2 PdCI 2 , Na 2 PdCI 4 , H 2 PdCI 4 , Pd (NO 3 ) 2 , Pd (acetylacetonate), proved to be particularly advantageous.
  • Biphenyl-2-yl-phosphanes of the formula (I) can be prepared from oxaphosphorine chlorides of the formula (III) according to the following scheme.
  • R 1 Met and R 2 Met are organometallic compounds, where R 1 and R 2 are as defined above, and Met is a metal ion or a metal halide ion, for example Li, MgCl, MgBr, ZnCl, ZnBr, Mg 0.5 or Zn 0.5 means.
  • Oxaphosphorines are known from DE-A1-195 21 339 and can be prepared by the method described there or by the method described in DE-A1-195 21 340.
  • the present invention also relates to the use of the Pd and Ni complexes according to the invention as a catalyst for C, C, C, N and C, O couplings, in particular of aryl metallates, alkyl metallates, phenols, phenolates, alcohols, alkoxides, amines or amides with aryl halides, preferably aryl chlorides, or aryl sulfonates.
  • aryl metallates alkyl metallates
  • phenols, phenolates alcohols, alkoxides, amines or amides with aryl halides, preferably aryl chlorides, or aryl sulfonates.
  • aryl metallates in particular of aryl metallates, alkyl metallates, phenols, phenolates, alcohols, alkoxides, amines or amides with aryl halides, preferably aryl chlorides, or aryl sulfonates.
  • the Pd or Ni complex according to the invention can be used as a solid or in solution, or can be prepared in situ by adding a Pd or Ni salt and a biphenyl-2-ylphosphine of the formula ( I) adds.
  • the coupling reactions can be carried out analogously to general coupling regulations of the prior art (e.g. F. Diederich et al., "Metal-catalyzed cross coupling reactions", Wiley-VCH, Weinheim 1998).
  • Example 4 A solution of 55.7 g of chlorobenzene in 150 ml of THF is mixed with 0.1 mmol of the catalyst solution prepared in Example 2 at room temperature. After heating to reflux temperature, the slow dropwise addition of a solution of 500 mmol p-tolylmagnesium chloride is started. After completion of the addition and stirring for three hours at reflux temperature, the reaction mixture is poured onto water. After phase separation, extraction of the aqueous phase twice with toluene and removal of the organic solvents by distillation, 4-methylbiphenyl remains as a colorless solid which is recrystallized from methanol; Melting point 48 ° C, yield 77.4 g (93%).
  • Example 4 A solution of 55.7 g of chlorobenzene in 150 ml of THF is mixed with 0.1 mmol of the catalyst solution prepared in Example 2 at room temperature. After heating to reflux temperature, the slow dropwise addition of a solution of 500 mmol p-tolylmagnesium chloride is started. After completion
  • Example 11 4'-cyano-4-ethoxybiphenyl from 4-ethoxyphenylzinc bromide and 4-cyanophenyl mesylate
  • Example 14 trans-4-methoxystilbene by Heck reaction of styrene and p-chloroanisole
  • NiC-b 5 mmol NiC-b are introduced into 50 ml of toluene and '-hydroxybiphenyl treated with 10 mmol of 2- (pentamethylene-1, 5-diylphosphino) -2.
  • Example 19 (application example)
  • Example 18 The catalyst solution obtained in Example 18 is added to 30 mmol of chlorobenzene, 5 mmol of piperidine and 10 mmol of potassium carbonate in 40 ml of DMSO at room temperature. After heating to 90 ° C. for eight hours and working up with water, N-phenylpiperidine is obtained in a yield of 86%.
  • 4-fluorobiphenyl is obtained from 10 mmol of p-fluorochlorobenzene and 11 mmol of phenylmagnesium chloride (27% by weight in THF) with the catalyst prepared in Example 22 (1 mol%), after 8 hours of stirring at reflux, in a yield of 93 % receive; Melting point 73 ° C.
  • Example 24 4-methyldiphenyl ether from 4-chlorotoluene and phenol

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Abstract

Complexes Pd et Ni de biphényl-2-yl-phosphanes et leur utilisation dans des copulations catalytiques C,C, C,N et C,O. La présente invention concerne de nouveaux complexes Pd et Ni avec un biphényl-2-yl-phosphane de formule (I). Ces nouveaux complexes peuvent être utilisés en tant que catalyseurs pour des couplages C,C, C,N et C,O, par ex. pour des couplages de Suzuki, de Grignard ou de Stille, ainsi que pour des réactions de Heck.
PCT/EP2000/003710 1999-05-06 2000-04-26 Complexes pd et ni de biphenyl-2-yl-phosphanes et leur utilisation dans des couplages catalytiques c,c-, c,n- et c,o WO2000068237A1 (fr)

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DE19920847A DE19920847A1 (de) 1999-05-06 1999-05-06 Pd- und Ni-Komplexe von Biphenyl-2-yl-phosphanen und ihre Anwendung in katalytischen C,C-,N- und C,O-Kupplungen
DE19920847.6 1999-05-06

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7091373B2 (en) 2002-03-18 2006-08-15 Sumitomo Chemical Company, Limited Production method for biarylalanine
WO2007000250A1 (fr) * 2005-06-27 2007-01-04 Archimica Gmbh Procede de production d'arylamines, d'arylethers et d'arylthioethers

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