Monoarylation of aromatic amines

Patent metadata

Field	Value
Publication number	US-2016257650-A1
Application number	US-201415030639-A
Country	US
Kind code	A1
Filing date	Oct 17, 2014
Priority date	Oct 21, 2013
Publication date	Sep 8, 2016
Grant date	—

Abstract

The present invention relates to a selective process for performing the Hartwig-Buchwald coupling of biphenyl derivatives.

First claim

1 .- 16 . (canceled)

17 . A process for selective arylation of a primary aromatic amine of the formula A-NH 2 with an aromatic compound of the formula X—B to give a secondary aromatic amine A-NH—B, the radicals A and B independently of one another being identical or different, substituted or unsubstituted aromatic radicals and the radical X being a halogen or a trifluoromethylsulphonic acid radical, the aromatic carbon atoms in the secondary aromatic amine being bonded directly to the nitrogen atom, and at least one of the radicals, A or B, comprising a biphenyl unit, and the reaction being carried out in the presence of a base and a palladium complex, the palladium atom being complexed by at least one bis(dialkylphosphinoferrocene) ligand.

18 . The process according to claim 17 , wherein the alkyl substituents of the bis(dialkylphosphinoferrocene) ligands having two to five carbon atoms.

19 . The process according to claim 17 , wherein the alkyl substituents being selected from the group consisting of isopropyl, isobutyl, tert-butyl and combinations thereof.

20 . The process according to claim 17 , wherein both aromatic substituents, A and B, comprising a biphenyl unit, these units being identical to or different from one another.

21 . The process according to claim 17 , wherein the biphenyl unit being bonded directly to the secondary nitrogen atom of the amine.

22 . The process according to claim 17 , wherein the biphenyl unit being a bridged biphenyl unit of the formula 2 or 3

where D is oxygen, sulphur, nitrogen or carbon and is optionally substituted in the case of nitrogen singly or in the case of carbon doubly by methyl, ethyl, biphenyl, naphthyl or phenyl.

23 . The process according to claim 17 , wherein the biphenyl unit being 2-fluorene, 3-fluorene, 2-(9,9-diphenylfluorene), 2-(9,9-dimethylfluorene), 3-(9,9-diphenylfluorene), 3-(9,9-dimethylfluorene), 3-(4-phenyl)-9-phenyl-9H-carbazole, 3-(4-phenyl)-9-methyl-9H-carbazole, 3-(4-phenyl)-9-biphenyl-9H-carbazole, 2-(4-phenyl)-9-phenyl-9H-carbazole, 2-(4-phenyl)-9-methyl-9H-carbazole, 2-(4-phenyl)-9-biphenyl-9H-carbazole, 3-(4-biphenyl)-9-phenyl-9H-carbazole, 3-(4-biphenyl)-9-methyl-9H-carbazole, 3-(4-biphenyl)-9-biphenyl-9H-carbazole, 2-(4-biphenyl)-9-phenyl-9H-carbazole, 2-(4-biphenyl)-9-methyl-9H-carbazole, 2-(4-biphenyl)-9-biphenyl-9H-carbazole, 3-(9-phenyl-9H-carbazole), 3-(9-methyl-9H-carbazole), 3-(9-biphenyl-9H-carbazole), 2-(9-phenyl-9H-carbazole), 2-(9-methyl-9H-carbazole), 2-(9-biphenyl-9H-carbazole) or triphenylene.

24 . The process according to claim 17 , wherein the palladium complex being used in amounts of 0.01 mol % to 1.5 mol %, based on the total molar amount of both reactants, of the primary aromatic amine A-NH 2 and of the haloaromatic X—B.

25 . The process according to claim 17 , wherein the palladium complex being used as a solid, solution or powder mixture with a solid bis(dialkylphosphinoferrocene).

26 . The process according to claim 17 , wherein comprising the steps of:
providing the primary aromatic amine A-NH 2 , the haloaromatic X—B, a suitable solvent and optionally a bis(dialkylphosphinoferrocene) in a reaction vessel; adding a palladium complex in which the palladium atom is complexed by at least one bis(dialkylphosphinoferrocene) ligand, in the form of a solid or a solution; heating the resulting reaction mixture in the reaction vessel; isolating the reaction product, a secondary aromatic amine A-NH—B; and optionally purifying the secondary aromatic amine A-NH—B.

27 . The process according to claim 17 , wherein the compounds

being present.

28 . The process according to claim 17 , wherein the palladium atom in the palladium complex being complexed additionally by 2,4,6,8-tetramethylcyclotetrasiloxane, bis(dibenzylideneacetone) or maleimide.

29 . The process according to claim 17 , wherein the palladium atom in the palladium complex being complexed by 1,1′-bis(diisopropylphosphino)ferrocene.

30 . A chemical compound comprising 1,1′-bis(diisopropylphosphino)ferrocene-palladium(0)-maleimide [Pd(dippf)(maleimide)]; 1,1′-bis(diiso-propylphosphino)ferrocenepalladium(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane [Pd(dippf)(VTS)]; 1,1′-bis(diisopropylphosphino)ferrocenepalladium(0)-bis(dibenzylideneacetone) [Pd(dippf)(dba)]; 1,1′-bis(diisopropylphosphino)ferrocene-palladium(0)-naphthoquinone [Pd(dippf)(naphthoquinone)]; 1,1′-bis(diisopropylphosphino)ferrocenepalladium(0)-maleic anhydride [Pd(dippf)(maleic anhydride)]; 1,1′-bis(diisopropylphosphino)ferrocenepalladium(0)-diethyl maleate [Pd(dippf)(diethyl maleate)]; or 1,1′-bis(diisopropylphosphino)ferrocenepalladium(0)-norbornene [Pd(dippf)(norbornene)].

31 . A powder mixture comprising a bis(dialkylphosphinoferrocene) and a palladium complex in which the palladium atom is complexed by at least one bis(dialkylphosphinoferrocene) ligand.

32 . A catalyst for Hartwig-Buchwald coupling which comprises the compound according to claim 30 .

33 . A catalyst for Hartwig-Buchwald coupling which comprises the powder mixture according to claim 31 .

Assignees

• Umicore Ag & Co Kg

Inventors

• Goossen Lukas
• Gruenberg Matthias

Classifications

• C07C211/54

  having amino groups bound to two or three six-membered aromatic rings · CPC title

• C07C2603/18

  Fluorenes; Hydrogenated fluorenes · CPC title

• C07F15/0066

  without a metal-carbon linkage · CPC title

• C07D209/86 Primary

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system · CPC title

• C07F17/02

  of metals of Groups 8, 9 or 10 of the Periodic Table · CPC title