Patent DE-10133782-A1 (DE)
Title: Production of amines, useful for the production of pharmaceuticals, agrochemicals, foodstuffs, dyes or cosmetics comprises hydrogenation of hemiaminal ethers, hemiaminals and aminals
IPC: B01J31/24
Filed: 2001-07-16
Abstract: A process for the production of amines comprises hydrogenation of hemiaminal ethers, hemiaminals and aminals in the presence of hydrogen and a catalyst system comprising at least a metal atom comprising Rh, Ru, Ir, Pd, Pt, Co or Ni and one or more mono or bidentate achiral or chiral ligands.  Production of amines of formula (II) comprises hydrogenation of hemiaminal ethers, hemiaminals and aminals of formula (I) in the presence of hydrogen and a catalyst system comprising at least a metal atom comprising Rh, Ru, Ir, Pd, Pt, Co or Ni and one or more mono- or bidentate achiral or chiral ligands of formula (R<8>Y<1>)(R<7>Y<1>)P<1>X<1>ZX<2>P<2>(Y<2>R<9>)(Y<2>R<1>0) (III) or (R<7>Y<1>)(R<8>Y<1>)(R<9>Y<1>)P (4).  Y = N or O; R<1>-R<6> = H, 1-24C alkyl, 2-24C alkenyl, alkynyl, 6-10C aryl, CF3, CN, COOH, COOM, CHO, SO3H, COO-(1-8C)-alkyl, CONH2, CONH-(1-8C alkyl), CON-(1-8C alkyl)2, CO-(1-8C alkyl), CO-phenyl, COO-phenyl, COO-(6-10C aryl), CO-(6-10C aryl), P(6-10C aryl)2, PO(o-1-6C alkyl)2, SO3-1-4C alkyl, SO2-1-6C alkyl, SO-1-6C alkyl or Si(1-8C alkyl)3; R3,R4=o-(1-8C alkyl), OCO-(1-8C alkyl), o-(6-10C aryl), F, OYH, NH2, NH-(1-8C alkyl), N(1-8C alkyl)2, NHCO-(1-4C alkyl), NH(6-10C aryl), NHCOO-(1-4C alkyl) whereby alkyl is an optionally branched aliphatic or (hetero)cyclic group having 1-4 heteroatoms comprising N, O, S and optionally substituted by H, o-(1-8C alkyl), OCO-(1-8C alkyl), O-phenyl, phenyl, 6-10C aryl, F, Cl, Br, I, OH, NO2, CF3, CN, COOH, COOM, CHO, SO3H, NH2, NH-(1-8C alkyl), CONH2, CO-(1-8C alkyl), NHCOH, NHCOO-(1-4C alkyl), CO-phenyl, COO-phenyl, COO-(6-10C aryl), CO-(6-10C aryl), CHCHCO2-(1-8C alkyl), P(6-10C aryl)2, CHCHCO2H, P-(1-8C alkyl)2, PO-(6-10C aryl)2, PO(1-4C alkyl)2, PO3H2, PO(1-4C alkyl)(O-1-6C alkyl), PO(O-1-6Calkyl)2, SO3-(1-4C alkyl), SO2-(1-6C alkyl), SO(1-6C alkyl) or Si(1-8C alkyl); R<7>-R<10> = H, 1-24C alkyl, 2-20C alkenyl, 3-8C cycloalkyl, 5-8C cycloalkenyl, 6-14C aryl, phenyl, naphthyl, fluorenyl or 2-13 heteroaryl having 1-4 heteroatoms comprising N, O, S and optionally substituted by H, 1-20C alkyl, 2-20C alkenyl, 1-10C haloalkyl, 3-8C cycloalkyl, 5-8C cycloalkyl, 2-9C heterocycloalkyl, 1-9C heterocycloalkenyl, 6-14C aryl, phenyl, 2-13C heteroaryl having 1-4 N, O or S atoms, 1-10 C alkoxy, OCO-(1-8C alkyl), O-(5-10C aryl), O-phenyl, 1-9C trihalomethylalkyl, F, Cl, Br, I, nitro, OH, trifluoromethylsulfonato, oxo, thio, thiolato, amino, di(1-8C)alkylamino or 2-8C alkenylamino or mono, di, tri-6-8C arylamino, or N(1-8C alkyl) (6-8C aryl), NH-CO-(1-8C alkyl), NHCO-(6-8C aryl), cyano, 1-8C acyloxy, carboxyl, or COOR<1>2; R<12> = monovalent cation, NH4<+>, N(1-10C alkyl)4<+>, N(1-10C alkyl/6-10C aryl)4<+> or 1-18C alkyl, 6C aryl, tri(1-6C alkyl)silyl whereby two of the substituents may be bridged and R<7> and R<8> and/or R<9> and R<1>0 are linked by a covalent bond to form a 4-8C cyclic compound; X<1>,X<2> = a direct phosphorous-carbon bond, O, S or -NR; R = R<7>-R<1>0; Z = 1-6C linking group containing single or multiple bonds whereby Z is part of an aliphatic, cycloaliphatic, olefinic, cycloolefinic system having 1-4C atoms replaced by N, O or S, or part of a metallocene or (hetero)aromatic ring system optionally substituted by substituents noted for R<7>-R<1>0 or 1-10C alkoxy, OCO-(1-8C alkyl), O-(5-10C aryl), O-phenyl, 1-9C trihalomethylalkyl, trifluoromethyl, trichloromethyl, F, Cl, Br, I, NO3, OH, trifluoromethylsulfonato, oxo, thio, thiolato, amino, NH(1-8C alkyl), NH-(5-6C aryl), N-(1-8C alkyl)2, N(5-6C aryl)2, N-(1-8C alkyl)3<+>, N(5-6C aryl)2(5-6C aryl)<+>, 1-6C acyloxy, COOH, COOR<1>2, SO3H, SO3R<1>2, PO3H2, PO3HR<1>2, PO3R<1>22.