Method for the production of amines by reductive amination of carbonyl compounds under transfer-hydrogenation conditions

• US 20040267051A1
• Filed: 08/18/2004
• Published: 12/30/2004
• Est. Priority Date: 08/09/2001
• Status: Active Grant

• Current Assignee: Evonik Degussa GmbH
• Original Assignee: Evonik Degussa GmbH
• Inventors: Boerner, Amin, Kaxyrov, Renat, Dingerdissen, Uwe, Tararov, Vitali, Riermeier, Thomas
• Granted Patent: US 7,230,134 B2
• Time in Patent Office: Days
• US Class Current: 564/398
• CPC Class Codes: C07C 209/28 by reduction with other reducing agents
• CPC Class Codes: C07C 211/03 Monoamines
• CPC Class Codes: C07C 211/27 having amino groups linked to the six-membered aromatic ring by saturated carbon chains
• CPC Class Codes: C07C 211/29 the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
• CPC Class Codes: C07C 211/35 containing only non-condensed rings
• CPC Class Codes: C07C 211/42 with six-membered aromatic rings being part of the condensed ring systems
• CPC Class Codes: C07C 213/02 by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
• CPC Class Codes: C07C 215/50 with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
• CPC Class Codes: C07C 217/58 with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
• CPC Class Codes: C07C 231/02 from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
• CPC Class Codes: C07C 231/08 from amides by reaction at nitrogen atoms of carboxamide groups
• CPC Class Codes: C07C 237/22 having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated peptides C07K
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 2602/08 the other ring being five-membered, e.g. indane
• CPC Class Codes: C07D 213/38 having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom

Abstract

The invention relates to the production of amines by the reaction of aldehydes or ketones with ammonia or primary or secondary amines in the presence of a hydrogen-donor and the presence of homogeneous metal catalysts of the eighth sub-group under mild conditions.

Claims

1. A process for the production of amines by reductive hydride transfer amination, comprising reacting at least one ketone or at least one aldehyde with ammonia, at least one primary amine or at least one secondary amine in the presence of a hydrogen donor as reducing agent and a catalyst, wherein said catalyst is a transition metal complex containing at least one metal selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt.

2. A process according to claim 1, wherein the metal in the transition metal complex catalyst is Rh or Ru.

3. A process according to claim 1, wherein the transition metal complex catalyst contains at least one ligand selected from the group consisting of mono- or bidentate nitrogen donor ligands, phosphorus donor ligands, cyclopentadienyl ligands, arene ligands, olefin ligands, alkyne ligands, heterocycloalkyl ligands, heteroaryl ligands, hydride ligands, alkyl ligands, carbonyl ligands and a mixture of these ligands.

4. A process according to claim 1, wherein the transition metal complex catalyst contains at least one mono- or bidentate ligand of formula (VI) or (VII),

L¹—

R¹² 

 

(VI) L¹—

Q—

L² 

 

(VII)

wherein

L¹ and L², independently of one another, denote a coordinating group of the formulae (VIII) (XII) (VIII), (IX), (X), (XI) or (XII);

wherein

R⁵ to R⁹, independently of one another, are selected from the group consisting of hydrogen, (C₁-C₂₄)-alkyl, (C₂-C₂₄)-alkenyl, (C₂-C₂₄)-alkynyl, (C₅-C₁₀)-aryl, CF₃, CO-alkyl-(C₁-C₈), CO-aryl-(C₅-C₁₀), CN, COOH, COOM, COO-alkyl-(C₁-C₈), COO-aryl-(C₅-C₁₀), C(═

N-alkyl-(C₁-C₈))O-alkyl-(C₁-C₈), C(═

N-aryl-(C₅-C₁₀))(O-alkyl-(C₁-C₈)), C(═

N-alkyl-(C₁-C₈))(O-aryl-(C₅-C₁₀)), C(═

N-aryl-(C₅-C₁₀))(O-aryl-(C₅-C₁₀)), CONH₂, CONH-alkyl-(C₁-C₈), CON(alkyl-(C₁-C₈))₂, CONH-aryl-(C₅-C₁₀), CON(aryl-(C₅-C₁₀))₂, PO(aryl-(C₅-C₁₀))₂, PO(alkyl-(C₁-C₄))₂, POH(alkyl-(C₁-C₆)), POH(aryl-(C₅-C₁₀)), PO(alkyl-(C₁-C₄))(O-alkyl-(C₁-C₆)), PO(alkyl-(C₁-C₆))(O-aryl-(C₅-C₁₀)), PO(aryl-(C₅-C₁₀))(O-alkyl-(C₁-C₆)), PO₃H₂, PO₃M₂, PO(O-alkyl-(C₁-C₆))₂, PO(O-aryl-(C₅-C₁₀))₂, PO(O-alkyl-(C₁-C₆))(O-aryl-(C₅-C₁₀)), SO₃H, SO₃M, SO₃-alkyl-(C₁-C₄), SO₃-aryl-(C₅-C₁₀), SO₂-alkyl-(C₁-C₆), SO₂-aryl-(C₅-C₁₀), SO-alkyl-(C₁-C₈), SO-aryl-(C₅-C₁₀), S-alkyl-(C₁-C₈), S-aryl-(C₅-C₁₀), SH, Si(alkyl-(C₁-C₈))₃, Si(C₁-C₁₀-alkyl/C₅-C₁₀-aryl)₃, NO₂, F, Cl, Br, I, O-alkyl-(C₁-C₈), O-aryl-(C₅-C₁₀), OH, NH₂, NH(alkyl-(C₁-C₈)), N(alkyl-(C₁-C₈))₂, NH(aryl-(C₅-C₁₀)), NHCO-alkyl-(C₁-C₄), NHCO-aryl-(C₅-C₁₀), NHCOO-alkyl-(C₁-C₄), NHCOO-aryl-(C₅-C₁₀), OCO-alkyl-(C₁-C₈), OCO-aryl-(C₅-C₁₀), OPO(aryl-(C₅-C₁₀))₂, OPO(alkyl-(C₁-C₄))₂, OPOH(alkyl-(C₁-C₆)), OPO₃H₂, OPO₃M₂, OPO-alkyl-(C₁-C₄)(O-alkyl-(C₁-C₆)), OPO(O-alkyl-(C₁-C₆))₂, OPO(O-aryl-(C₅-C₁₀))₂, OSO₃H, OSO₃M, OSO₂—

CF₃, OSO₃-alkyl-(C₁-C₄), OSO₃-aryl-(C₅-C₁₀), OSO₂-alkyl-(C₁-C₆), and OSO₂-aryl-(C₅-C₁₀), wherein M represents a cation selected from the group consisting of Li⁺, Na⁺, K⁺, Mg⁺, Ca⁺, NH₄⁺, N(C₁-C₁₀-alkyl)₄⁺, and N(C₁-C₁₀-alkyl/C₅-C₁₀-aryl)₄⁺,

and wherein the residues

R¹⁰ to R¹², independently of one another, represent a hydrogen, (C₁-C₂₄)-alkyl, (C₂-C₂₄)-alkenyl, (C₂-C₂₄)-alkynyl, C₅-C₈ cycloalkenyl, (C₅-C₁₄)-aryl, O-alkyl-(C₁-C₈), O-aryl-(C₅-C

     14), O-alkenyl-(C₂-C₂₄), O-alkynyl-(C₂-C₂₄), O-cycloalkenyl-(C₅-C₈), O-aryl-(C₅-C₁₄), F, NH₂, NH(alkyl-(C₁-C₈)), NH-alkenyl-(C₂-C₂₄), NH-alkynyl-(C₂-C₂₄), NH-cycloalkenyl-(C₅-Cg), NH-aryl-(C₅-C₁₄), N(alkyl-(C₁-C₈))₂, N(alkenyl-(C₂-C₂₄))₂, N(alkynyl-(C₂-C₂₄))₂, N(cycloalkenyl-(C₅-C₈))₂, N(alkyl-(C₁-C₈))(aryl-(C₅-C₁₀)), N(aryl-(C₅-C₁₀))₂, NHCO-alkyl-(C₁-C₄), NHCO-alkenyl-(C₂-C₂₄), NHCO-alkynyl-(C₂-C₂₄), NHCO-cycloalkenyl-(C₅-C₈), NHCO-aryl-(C₅-C₁₄), OCO-alkyl-(C₁-C₄), OCO-alkenyl-(C₂-C₂₄), OCO-cycloalkenyl-(C₅-C₈), OCO-aryl-(C₅-C₁₄), or SO₂-alkyl-(C₁-C₆), SO₂-aryl-(C₅-C₁₀) residue and

wherein all the above-mentioned substituents are optionally mono- or polysubstituted, and wherein two adjacent residues together optionally form saturated or unsaturated carbocyclic or heterocyclic groups having 3 to 15 atoms, with one to four nitrogen, phosphorus, silicon, sulfur or oxygen atoms, and wherein

Q represents a bridge linking the unit L¹ with the unit L², of formula (XIII);

X¹—

Z—

X² 

 

(XIII)

wherein

X¹ and X², independently of one another, represent a direct bond or a group —

O—

, —

S—

, or —

NR¹³—

, wherein R¹³ is one of the residues defined for R¹⁰—

R¹² and

Z is a direct bond or a group of 1-16 carbon atoms linked by single or multiple bonds, wherein one to four carbon atoms are optionally replaced by heteroatoms, and wherein Z is optionally mono- or polysubstituted as stated for R⁵—

R⁹ or optionally has a keto (═

O), thioketo (═

S) or imide substituent (═

NR¹⁴), wherein R¹⁴ is one of the residues defined for R10-R12 and

wherein two of the units L¹ with R¹² and L¹ or L² with Q are optionally linked together so that a saturated or unsaturated carbocyclic skeleton having 3 to 15 atoms or a saturated or unsaturated heterocyclic skeleton containing one to four nitrogen, phosphorus, silicon, sulfur or oxygen atoms is formed.

5. A process according to claim 4, wherein Q in formula (VII) represents an aliphatic, olefinic or acetylenic bridge consisting of one to fourteen carbon atoms, wherein one to four carbon atoms are optionally replaced with nitrogen or silicon atoms or one to two carbon atoms can be are optionally replaced with oxygen or sulfur atoms and wherein the individual binding links of the group, independently of one another, optionally carry substituents as defined for R³ and R⁴ or a keto (═

O), thioketo (═

S) or imide substituent (═

NR¹⁴) wherein R¹⁴ is one of the residues defined for R¹⁰-R¹² and wherein two of the units L¹, L² and Q are optionally linked together so that a saturated or unsaturated carbocyclic skeleton having 5 to 9 atoms or a saturated or unsaturated, heterocyclic skeleton containing one to four nitrogen, phosphorus, silicon, sulfur or oxygen atoms is formed.

6. A process according to claim 1, wherein the transition metal complex catalyst contains at least one mono-, bi-, tri- or tetradentate linear, branched or polycyclic, alkyne, olefin, conjugated or non-conjugated di- tri- or tetraene with two to twelve carbon atoms, wherein one to four carbon atoms are optionally replaced with nitrogen or silicon atoms or one to two carbon atoms are optionally replaced with oxygen or sulfur atoms and wherein the individual members of the group, independently of one another, optionally have substituents as defined for R⁵-R⁹ or a keto (═

O), thioketo (═

S) or imide substituent (═

NR¹⁴), wherein R¹⁴ can be is one of the residues defined for R¹⁰-R¹².

7. A process according to claim 1, wherein the transition metal complex catalysts used can catalyst has at least one mono- or bidentate polycyclic, particularly mono and saturated or unsaturated heterocyclic ligand having 3 to 15 atoms, with one to four oxygen, sulfur or nitrogen atoms, or a (C₃-C₁₃) heteroaromatic with one to four oxygen, sulfur, nitrogen or one to two phosphorus atoms, wherein the individual binding links, independently of one another, optionally carry substituents as defined for R⁵-R⁹ or a keto (═

O), thioketo (═

S) or imide substituent (═

NR¹⁴), wherein R¹⁴ is one of the residues defined for R10-R¹².

8. A process according to claim 1, wherein the transition metal complex catalyst contains a ligand selected from the group consisting of DAIPEN, BINAP, Dnaelnd, dppb, dcypb, (R,R)-DIPAMP;

(R)-Norphos;

(R,R)-CHIRAPHOS;

(R,R)-DEGUPHOS;

(R)-CyGanterPhos;

(R,R)-Me-DUPHOS;

(R,R)-Et-DUPHOS;

(R,R)-Me-BPE;

(R,R)-Et-BPE;

(R)-bis(MePheP)benzene;

(R)-PROPHOS;

(R,R)-SKEWPHOS;

(S)-Phos4;

(R,S)-Cy-Fc-etdpp;

(R,S)-Cy-Fc-etdCyP;

(R,S)-Ph-Fc-etdtBuP;

(R,S)-JOSIPHOS;

(R)-carboxybutyl-BINAP;

(R)-BINAP;

(R)-Tol-BfNAP ((R)-2,2′

-bis(di-p-tolylphosphino)-1,1′

-binaphthyl);

(R)-MeO-BIPHEP;

(R)-p-Tol-MeO-BIPHEP;

(S,S)-1,2-(BDPPmethyl)-cyclohexane;

(S,S)-DIOP;

(S)-MOD-DIOP;

(R)-MeAAPHOS;

(S,S)-BPPM-H;

(S,S)-BPPM;

(R,R)-phenyl-CAPP;

(R)-NAPHOS;

Ph-P-Glup;

Ph-P-Glup-OH;

(phenyl 2,3-bis(O-diphenylphosphino)-p-D-glucopyranoside);

DPOE;

(R,R)-bdpch;

(R,R)-CYLOPP-2-Me;

(R,R)-CYCLOPP-4-CF3;

(R,R)-CYCLOPP-3,5-Cl;

(R,R)-CYCLOPP-3,5-CF3;

(R,R)-CYCLOPP-3,5-F;

CARBOPHOS-3,5-Me2Ph;

GLUCOPHOS-Ph-3,5-Me;

R-POP-Bz;

(R,S)-Phos3;

(S)-CyCy-OxoPRONOP;

(S)-Cy,Cy-PRONOP;

(S)-CyCyisoALANOP;

(R)-PROPRAPHOS;

PROPRAHOS analogue (R)-Cyp-PPP;

(R)-PN-Ph;

(S)-PN-iPr;

(S)-PN-iPr-Me;

(S)-PN-tBu;

(R)-QUINAP; and

(R,R)-(S,S)-EtTRAP is used.

9. A process according to claim 1, wherein the transition metal complex catalyst is produced from at least one transition metal salt or a transition metal pre-complex containing at least one metal from the eighth subgroup and at least one ligand of the formulae (VI) or (VII):

L¹—

R¹² 

 

(VI) L¹—

Q—

L² 

 

(VII)

wherein

L¹ and L², independently of one another, denote a coordinating group of formulae (VIII), (IX), (X). (XI) or (XII);

wherein

R⁵ to R⁹ independently of one another, are selected from the group consisting of hydrogen, (C₁-C₄)-alkyl, (C₂-C₂₄)-alkenyl, (C₂-C₄)-alkynyl, (C₅-C₁₀)-aryl, CF₃, CO-alkyl-(C₁-C₁₀), CO-aryl-(C₅-C₁₀), CN, COOH, COOM, COO-alkyl-(C₁-C₈), COO-aryl-(C₅-C₁₀), C(═

N-alkyl-(C₁-C₈))O-alkyl-(C C8), C(═

N-aryl-(C₅-C₁₀))(O-alkyl-(C₁-C₈)), C(═

N-alkyl-(C₁-C₈))(O-aryl-(C₅-C₁₀)) C(═

N-aryl-(C₅-C₁₀))(O-aryl-(C₅-C o)), CONH_, CONH-alkyl-(C₁-C₈) CON(alkyl-(C₁-C₈))₂, CONH-aryl-(C₅-C₁₀), CON(aryl-(C₅-C₁₀))₂, PO(aryl-(C₅-C₁₀)₂, PO(alkyl-(C₁-C₄))₂, POH(alkyl-(C₁-C₆)), POH(aryl-(C₅-C₁₀)), PO(alkyl-(C₁-C₄))(O-alkyl-(C₁-C₆))L PO(alkyl-(C₁-C₆))(O-aryl-(C₅-C₁₀)), PO(aryl-(C₅-C₁₀))(O-alkyl-(C₁-C₆)), PO₃H₂, PO₃M₂, PO(O-alkyl-(C₁-C₆))₂ PO(O-aryl-(C₅-C₁₀)₂ PO(O-alkyl-(C₁-C₆))(O-aryl-(C₅-C₁₀)), SO₃H, SO_M, SO₃-alkyl-(C₁-C₄) SO₃-aryl-(C₅-C₁₀), SO₂-alkyl-(C₁-C₆), SO₂-aryl-C₅-C₁₀), SO-alkyl-(C₁-C₈), SO-aryl-(C₅-C₁₀), S-alkyl-(C₁-C₈), S-aryl-(C₅-C₁₀), SH, Si(alkyl-(C₁-C₈))₃, Si(C₁-C₁₀-alkyl/C₅-C₁₀-aryl)₃, NO₂, F, Cl, Br, I, O-alkyl-(C₁-C₈), O-aryl-(C₅-C₁₀), OH, NH₂, NH(alkyl-(C₁-C₈)), N(alkyl-(C₁-C₈))₂, NH(aryl-(C₅-C₁₀)), NHCO-alkyl-(C₁-C₄), NHCO-aryl-((C₅-C₁₀), NHCOO-alkyl-(C₁-C₄), NHCOO-aryl-(C₅-C₁₀), OCO-alkyl-(C₁-C₈), OCO-aryl-(C₅-C₁₀), OPO(aryl-(C₅-C₁₀))₂, OPO(alkyl-(C₁-C₄)₂ OPOH(alkyl-C₁-C₆)) OPO₃H₂, OPO₃M₂, OPO-alkyl-(C₁-C₄)(O-alkyl-(C₁-C₆))OPO(O-alkyl-(C₁-C₆)) OPO(O-aryl-(C₅-C₁₀)₂, OSO₃H, OSO₃M, OSO₂—

CF₃, OSO₃-alkyl-(C₁-C₄), OSO₃-aryl-(C₅-C₁₀), OSO₂-alkyl-(C₁-C₆), and OSO₂-aryl-(C₅-C₁₀), wherein M represents a cation selected from the group consisting of Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, NH₄⁺, N(C₁-C₁₀-alkyl)₄⁺, and N(C_1-1-alkyl/C₅-C₁₀-aryl)₄⁺, and wherein the residues

R¹⁰ to R¹² independently of one another, represent a hydrogen(C₁-C₂₄)-alkyl, (C₂-C₄)-alkenyl, (C₁-C₄)-alkynyl, C₅-C₈ cycloalkenyl (C₅-C₁₄)-aryl, O-alkyl-(C₁-C₈), O-aryl-(C₅-₁₄) O-alkenyl-(C₂-C₂₄), O-alkynyl-(C₂C₂₄), O-cycloalkenyl-(C₅-C₈), O-aryl-(C₅-C₁₄), F, NH₂, NH(alkyl-(C₁-C₈)), NH-alkenyl-(C—

C<sub>—

-4</sub> NH-alkynyl-(C₂-C₂₄), NH-cycloalkenyl-(C₅-C₈), NH-aryl-(C₅-C₁₄), N(alkyl-(C₁-C₈))₂, N(alkenyl-(C₂-C₂₄))₂, N(alkynyl-(C₂-C₂₄), N(cycloalkenyl-(C₅-C₈)), N(alkyl-(C₁-C₈))(aryl-(C₅-C₁₀)), N(aryl-(C₅-C₁₀))₂, NHCO-alkyl-(C₁-C₄) NHCO-alkenyl-(C₂-C₂₄), NHCO-alkynyl-(C₁-C₄). NHCO-cycloalkenyl-(C<sub>—

—</sub>

_), NHCO-aryl-(C₅-C₁₄), OCO-alkyl-(C₁-C₄), OCO-alkenyl-(C₁-C₄) OCO-cycloalkenyl-(C₅-C₈), OCO-aryl-(C₅-C₁₄), or SO₂-alkyl-(C₁-C₆), SO₂-aryl-(C₅-C₁₀ residue and

wherein all the above-mentioned substituents are optionally mono- or polysubstituted, and wherein two adjacent residues together optionally form saturated or unsaturated carbocyclic or heterocyclic groups having 3 to 15 atoms, with one to four nitrogen, phosphorus, silicon, sulfur or oxygen atoms, and wherein

Q represents a bridge linking the unit L¹ with the unit L², of the formula (XIII);

X¹—

Z—

X² 

 

(XIII)

wherein

X¹ and X², independently of one another, represent a direct bond or a group —

O—

, —

S—

, or —

NR¹³—

, wherein R¹³ is one of the residues defined for R¹⁰—

R¹² and

Z is a direct bond or a group of 1-16 carbon atoms linked by single or multiple bonds, wherein one to four carbon atoms is optionally replaced by heteroatoms, and wherein Z is optionally mono- or polysubstituted as stated for R⁵—

R⁹ or optionally has a keto (═

O), thioketo (═

S) or imide substituent (═

NR¹⁴), wherein R¹⁴ is one of the residues defined for R¹-R² and

wherein two of the units L¹ with R¹² and L¹ or L² with Q is optionally linked together so that a saturated or unsaturated carbocyclic skeleton having 3 to 15 atoms or a saturated or unsaturated heterocyclic skeleton containing one to four nitrogen, phosphorus, silicon, sulfur or oxygen atoms is formed.

10. A process according to claim 1, wherein the hydrogen donor is selected from the group consisting of primary and secondary alcohols, hydroaromatic and heterocyclic compounds, terpenes, N-benzylaniline, hydrazine, trialkylsilanes, trialkyltin hydrides, carboxylic acids and phosphinous acids and their esters, amides and ammonium salts and mixtures thereof.

11. A process according to claim 1, wherein the hydrogen donor is a carboxylic acids acid or a primary and or secondary alcohols alcohol containing 1 to 20 carbon atoms.

12. A process according to claim 1, wherein the hydrogen donor is selected from the group consisting of isopropanol, ammonium formate, triethylammonium formate and formic acid-triethylamine mixture.

13. A process according to claim 1, comprising reacting at least one carbonyl compound of formula (I)

14. A process according to claim 13, wherein the alkyl, alkenyl, alkynyl, aryl, heterocycloalkyl and heteroaryl groups, comprise at least substituent selected from the group consisting of hydrogen, (C₁-C₂₀)-alkyl, (C₂-C₂₀)-alkenyl, (C₁-C₁₀)-haloalkyl, (C₃-C₈)-cycloalkyl, (C₅-C₈)-cycloalkenyl, (C₂-C₉)-heterocycloalkyl, (C₁-C₉)-heterocycloalkenyl, (C₅-C₁₄)-aryl, (C₂-C₁₃)-heteroaryl, wherein the number of heteroatoms selected from the group N, O, S, is optionally one to four, fluorine, chlorine, bromine, iodine, OH, NO₂, CF₃, O-alkyl-(C₁-C₈), O-aryl-(C₅-C₁₀), OCO-alkyl-(C₁-C₈), OCO-aryl-(C₅-C₁₀), NH₂, NH(alkyl-(C₁-C₈)), NH(aryl-(C₅-C₁₀)), N(alkyl-(C₁-C₈))₂, N(aryl-(C₅-C₁₀))₂, NHCO-alkyl-(C₁-C₈), NHCO-aryl-(C₅-C₁₀), CH(O-alkene-(C₂-C₆)—

O), C(O-alkene-(C₂-C₆)—

O)-alkyl-(C₁-C₈), C(O-alkene-(C₂-C₆)—

O)-aryl-(C₅-C₁₀), CH(O-alkyl-(C₁-C₈))₂, C(O-alkyl-(C₁-C₈))₂-alkyl-(C₁-C₈), C(O-alkyl-(C₁-C₈))₂-aryl-(C₅-C₁₀), CHO, CO-alkyl-(C₁-C₈), CO-aryl-(C₅-C₁₀), CN, COOH, COOM, COO-alkyl-(C₁-C₈), C(═

N-alkyl-(C₁-C₈))O-alkyl-(C₁-C₈), C(═

N-aryl-(C₅-C₁₀))O-alkyl-(C₁-C₈), C(═

N-alkyl-(C₁-C₈))O-aryl-(C₅-C₁₀), C(═

N-aryl-(C₅-C₁₀))O-aryl-(C₅-C₁₀), CONH₂, CO-alkyl-(C₁-C₈), NHCOH, NHCOO-alkyl-(C₁-C₄), CO-aryl-(C₅-C₁₀), COO-aryl-(C₅-Cia), CHCH—

COO-alkyl-(C₁-C₈), CN, COOH, COOM, CHCHCO₂H, P(aryl-(C₅-C₁₀))₂, P(alkyl-(C₁-C₈))₂, PO(aryl-(C₅-C₁₀))₂, PO(alkyl-(C₁-C₄))₂, PO₃H₂, PO(alkyl-(C₁-C₄))(O-alkyl-(C₁-C₆)), PO(O-alkyl-(C₁-C₆))₂, OPO(aryl)₂—

(C₅-C₁₀), OPO(alkyl)₂—

(C₁-C₄), OPOH(alkyl-(C₁-C₆)), OPO₃H₂, OPO₃M₂, OPO(alkyl-(C₁-C₄))(O-alkyl-(C₁-C₆)), OPO(aryl-(C₅-C₁₀))(O-alkyl-(C₁-C₆)), OPO(O-alkyl-(C₁-C₆))₂, OPO(O-aryl-(C₅-C₁₀))₂, SO₃H, SO₃M, SO₂—

O-alkyl-(C₁-C₄), SO₂—

O-aryl-(C₅-C₁₀), SO₂-alkyl-(C₁-C₆), SO₂-aryl-(C₅-C₁₀), SO-alkyl-(C₁-C₆)), SO-aryl-(C₅-C₁₀), OSO₃H, OSO₃M, OSO₂—

O-alkyl-(C₁-C₄), OSO₂-alkyl-(C₁-C₆) or Si(alkyl-(C₁-C₈))₃, and Si(C₁-C₈-alkyl/C₅-C₁₀-aryl)₃, wherein M represents a cation selected from the group consisting of Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, NH₄⁺, N(C₁-C₁₀-alkyl)₄⁺, and N(H/C₁-C₁₀ alkyl/C₆-C₁₀-aryl)₄⁺.

15. A process according to claim 13, wherein the substituents of the aryl groups are π

-bonded metal complexes of the formulae (IV) or (V),

16. A process according to claim 1, wherein the transition metal complex catalyst is used in a quantity of between 0.001 and 10 mole %, based on the carbonyl compound.

17. A process according to claim 4, wherein the transition metal complex catalyst has a ratio between metal precursor and ligand of formula (VI) or (VII) of 1:

0.01 to 1;

50.

18. A process according to claim 1, wherein the reaction is performed at temperatures of between −

78°

C. and 150°

C.

20. Use of transition metal complex catalysts according to claim 16 containing at least one ligand according to claim 3.

19. Use of transition metal complex catalysts containing at least one metal from the group Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt for the production of amines by reductive hydride transfer amination.