Process for the preparation of primary amines by homogeneously catalyzed alcohol amination

摘要

Process for the preparation of primary amines which have at least one functional group of the formula (—CH2—NH2) by alcohol amination of starting materials which have at least one functional group of the formula (—CH2—OH), with ammonia, with the elimination of water, where the alcohol amination is carried out under homogeneous catalysis in the presence of at least one complex catalyst which comprises at least one element selected from groups 8 and 9 of the Periodic Table of the Elements, and also at least one phosphorus donor ligand of the general formula (I).

主权项

1. A process for producing a primary amine comprising a functional group having a formula of —CH2—NH2, the process comprising:
aminating a starting material comprising a functional group having a formula of —CH2—OH with ammonia, thereby eliminating water, to obtain the primary amine, wherein the aminating is homogeneously catalyzed in the presence of a complex catalyst comprising at least one element selected from groups 8 and 9 of the Periodic Table of the Elements, and a phosphorus donor ligand of formula (I);wherein:
n is 0 or 1; R1, R2, R3, R4, R5, R6 are each independently an unsubstituted or at least monosubstituted C1-C10-alkyl, C1-C4-alkyldiphenylphosphine (—C1-C4-alkyl-P(phenyl)2), C3-C10-cycloalkyl, C3-C10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aryl, or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and a C1-C10-alkyl; A is i) a bridging group selected from the group consisting of an unsubstituted or at least monosubstituted N, O, P, C1-C6-alkane, C3-C10-cycloalkane, C3-C10-heterocycloalkane comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aromatic, and C5-C6-heteroaromatic comprising at least one heteroatom selected from the group consisting of N, O and S, wherein the substituents are selected from the group consisting of a C1-C4-alkyl, phenyl, F, Cl, Br, OH, OR7, NH2, NHR7, and N(R7)2, wherein R7 is a C1-C10-alkyl or a C5-C10-aryl, or
ii) a bridging group of formula (II) or (III): wherein
m, q are each independently 0, 1, 2, 3, or 4,R8, R9 are each independently selected from the group consisting of a C1-C10-alkyl, F, Cl, Br, OH, OR7, NH2, NHR7, and N(R7)2, wherein R7 is a C1-C10-alkyl or a C5-C10-aryl,X1, X2 are each independently NH, O, or S,X3 is a bond, NH, NR10, O, S, or CR11R12,R10 is a an unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aryl, or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and a C1-C10-alkyl,R11, R12 are each independently an unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-cycloalkoxy, C3-C10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aryl, C5-C14-aryloxy, or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C1-C10-alkyl; and Y1, Y2, Y3 are each independently a bond, or an unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene, or hexamethylene, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, OR7, CN, NH2, NHR7, N(R7)2, and a C1-C10-alkyl, and wherein R7 is a C1-C10-alkyl or a C5-C10-aryl.