Process for preparing di-, tri- and polyamines by homogeneously catalyzed alcohol amination

A process for preparing a primary amine comprising a functional group of formula (—CH2—NH2) and a further primary amino group by alcohol amination, the process comprising reacting a starting material having a functional group of formula (—CH2—OH) and a further functional group (—X), with ammonia with elimination of water,

• wherein
• (—X) is selected from the group consisting of a hydroxyl group and a primary amino group, and
• the reacting is homogeneously catalyzed in the presence of a complex catalyst comprising an element selected from groups 8, 9 and 10 of the Periodic Table and also a donor ligand,
• wherein the complex catalyst has formula I:
• wherein
• L1 and L2 are each independently selected from the group consisting of PRaRb, NRaRb, sulfide, SH, S(═O)R, C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S, AsRaRb, SbRaRb and an N-heterocyclic carbene of formula II or III:
• L3 is a monodentate two-electron donor selected from the group consisting of CO, PRaRbRc, NO+, AsRaRbRc, SbRaRbRc, SRaRb, RCN, RNC, N2, PF3, CS, pyridine, thiophene, tetrahydrothiophene and an N-heterocyclic carbene of formula II or III;
• R1 and R2 are both hydrogen or together with carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl unit of formula I forms an acridinyl unit;
• R, Ra, Rb, Rc, R3, R4 and R5 are each independently 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-C10-aryl or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,
• wherein substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
• Y is a monoanionic ligand selected from the group consisting of H, F, Cl, Br, I, OCOR, OCOCF3, OSO2R, OSO2CF3, CN, OH, OR and N(R)2, or an uncharged molecule selected from the group consisting of NH3, N(R)3 and R2NSO2R;
• X1 represents one, two, three, four, five, six or seven substituents on an atom of the acridinyl unit or one, two, three, four or five substituents on an atom of the quinolinyl unit,
• where plural X1 are selected independently from the group consisting of hydrogen, F, Cl, Br, I, OH, NH2, NO2, —NC(O)R, C(O)NR2, —OC(O)R, —C(O)OR, CN, and a borane derivative that can be obtained from the catalyst of formula I by reaction with NaBH4, and unsubstituted or at least monosubstituted C1-C10-alkoxy, C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-heterocyclyl comprising a heteroatom selected from N, O and S, C5-C10-aryl and C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,
• wherein substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
• and
• M is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum.