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

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.