AU2012224719A1 - Method for producing alkanol amines obtained by homogeneously catalyzed alcohol amination - Google Patents

Method for producing alkanol amines obtained by homogeneously catalyzed alcohol amination Download PDF

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AU2012224719A1
AU2012224719A1 AU2012224719A AU2012224719A AU2012224719A1 AU 2012224719 A1 AU2012224719 A1 AU 2012224719A1 AU 2012224719 A AU2012224719 A AU 2012224719A AU 2012224719 A AU2012224719 A AU 2012224719A AU 2012224719 A1 AU2012224719 A1 AU 2012224719A1
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alkyl
formula
catalyst
substituents
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AU2012224719A
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Marion Kristina BRINKS
Boris Buschhaus
Johann-Peter Melder
Martin Merger
Rocco Paciello
Thomas Schaub
Mathias SCHELWIES
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Furan Compounds (AREA)

Abstract

The invention relates to a method for producing alkanol amines which comprise a primary amino group (-NH

Description

1 Process for preparing alkanolamines by homogeneously catalyzed alcohol amination The present invention relates to a process for preparing alkanolamines by homogeneously catalyzed alcohol amination of diols by means of ammonia with 5 elimination of water in the presence of a complex catalyst which comprises at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand. Alkanolamines are compounds which have a primary amino group (-NH 2 ) and a 10 hydroxyl group (-OH). Alkanolamines are valuable products having many different uses, for example solvents, stabilizers, for the synthesis of chelating agents, as starting materials for the production of synthetic resins, drugs, inhibitors, corrosion inhibitors, polyurethanes, as hardeners 15 for epoxy resins, as surface-active substances and for gas scrubbing. The amination of diols by means of secondary amines using homogeneous iridium and ruthenium catalysts to form amino alcohols and linear diamines having tertiary amino groups has been described, for example, in EP 239 934; J. A. Marsella, J. Org. Chem. 20 1987, 52, 467-468; US 4,855,425; K.-T. Huh, Bull. Kor. Chem. Soc. 1990, 11, 45-49; N. Andrushko, V. Andrushko, P. Roose, K. Moonen, A. B6rner, ChemCatChem, 2010, 2, 640-643 and S. Bahn, A. Tillack, S. Imm, K. Mevius, D. Michalik, D. Hollmann, L. Neubert, M. Beller, ChemSusChem 2009, 2, 551-557. In these studies, the amination is carried out at 100-180*C. 25 J. A. Marsella, J. Organomet. Chem. 1991, 407, 97-105 and B. Blank, S. Michlik, R. Kempe, Adv. Synth. Catal. 2009, 351, 2903-2911; G. Jenner, G. Bitsi, J. MoL Cat, 1988, 45, 165-168; Y. Z. Youn, D. Y. Lee, B. W. Woo, J. G. Shim, S. A. Chae, S. C. Shim, J. Mol. Cat, 1993, 79, 39-45; K. 1. Fujita, R. Yamaguchi, Synlett, 2005, 4, 30 560-571; K.I. Fujii, R. Yamaguchi, Org. Lett. 2004, 20, 3525-3528; K. I. Fujita, K. Yamamoto, R. Yamaguchi, Org. Lett. 2002, 16, 2691-2694; A. Nova, D. Balcells, N. D. Schley, G. E. Dobereiner, R. H. Crabtree, 0. Eisenstein, Organometallics DOI: 10.1021/om101015u; and M. H. S. A. Hamid, C. L. Allen, G. W. Lamb, A. C. Maxwell, H. C. Maytum, A. J. A. Watson, J. M. J. Williams, J. Am. Chem. Soc. 2009, 131, 35 1766-1774 and 0. Saidi, A. J. Blacker, G. W. Lamb, S. P. Marsden, J. E. Taylor, J. M. J. Williams, Org. Proc. Res. Dev. 2010, 14, 1046-1049 describe the amination of diols by means of primary amines using homogeneously dissolved ruthenium- and iridium based transition metal catalysts. However, the cyclic compounds and not the desired alkanolamines are formed here. The economically attractive amination of diols by 40 means of ammonia to form alkanolamines has not been described for these systems. EK11-1973PC 2 EP 0 234 401 Al describes the reaction of ethylene glycol with ammonia in the presence of a ruthenium carbonyl compound. In the process described in EP 0 234 401 Al, the monoamination product (monoethanolamine) is formed among 5 other things. In addition, large amounts of the secondary and tertiary amines (diethanolamine and triethanolamine) and cyclic products (N-(hydroxyethyl)piperazine and N,N'-bis(hydroxyethyl)piperazine) are formed as by-products. All the above-described processes for the reaction of diols have the disadvantage that 10 undesired secondary, tertiary and cyclic amines are formed to a major extent in addition to the desired alkanolamines. It is an object of the present invention to provide a process for preparing alkanolamines by alcohol amination of diols by means of ammonia with elimination of water. 15 The object is achieved by a process for preparing alkanolamines which have a primary amino group (-NH 2 ) and a hydroxyl group (-OH) by alcohol amination of diols having two hydroxyl groups (-OH) by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one 20 complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand. It has surprisingly been found that alkanolamines can be obtained by the homogeneously catalyzed amination of diols by means of ammonia with elimination of 25 water using the complex catalysts which are used in the process of the invention and comprise at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand. The process of the invention has the advantage that it gives alkanolamines in considerably improved yields compared to the processes described in the prior art. In addition, the formation of undesired by-products 30 such as secondary and tertiary amines and also cyclic amines is largely avoided. Starting materials In the process of the invention, starting materials having two hydroxyl groups are used. 35 Suitable starting materials are virtually all diols which meet the abovementioned prerequisites. The diols can be straight-chain, branched or cyclic. The alcohols can also bear substituents which are inert under the reaction conditions of the alcohol amination, for example alkoxy, alkenyloxy, alkylamino, dialkylamino and halogens 40 (F, CI, Br, I). EK11-1973PC 3 Suitable starting materials which can be used in the process of the invention are, for example, diols which have a functional group of the formula (-CH 2 -OH) and a further hydroxyl group (-OH). 5 In addition, diols having two functional groups of the formula (-CHrOH) are suitable. As starting materials, it is possible to use all known diols. Preference is given to diols which have at least one functional group of the formula (-CH 2 -OH). Greater preference 10 is given to diols which have two functional groups of the formula (-CH 2 -OH). Examples of diols which can be used as starting materials in the process of the invention are 1,2-ethanediol (ethylene glycol), 1,2-propanediol (1,2-propylene glycol), 1,3-propanediol (1,3-propylene glycol), 1,4-butanediol (1,4-butylene glycol), 1,2-butanediol (1,2-butylene glycol), 2,3-butanediol, 2-methyl-1,3-propanediol, 15 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,5-pentanediol, 1,2-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,7-heptanediol, 1,2-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-nonanediol, 2,4-dimethyl-2,5-hexanediol, the neopentyl glycol ester of hydroxypivalic acid, diethylene glycol, triethylene glycol, 2-butene-1,4-diol, 2-butyne-1,4-diol, polyethylene glycols, polypropylene glycols such 20 as 1,2-polypropylene glycol and 1,3-polypropylene glycol, polytetrahydrofuran, diethanolamine, 1,4-bis(2-hydroxyethyl)piperazine, diisopropanolamine, N-butyldiethanolamine, N-methyldiethanolamine, 1,10-decanediol, 1,12-dodecanediol, 2,5-(dimethanol)-furan and C36-diol (mixture of isomers of alcohols having the empirical formula C3 6
H
74 0 2 ). 25 Another name for 2,5-(dimethanol)-furan is 2,5-bis(hydroxymethyl)-furan. Further suitable starting materials are diols of the general formulae (XXXI), (XXXII) and (XXXIII): 30 H HOHO' OH HO OH (XXXI) (XXXII) (XXXIII) where n1 is 2-30; 35 n2 is 1-30 and n3 is 1-30. EKII-1973PC 4 Preference is given to diols having two functional groups of the formula (-CH2-OH). Particularly preferred diols are 1,2-ethanediol (ethylene glycol), 1,2-propanediol (1,2-propylene glycol), 1,3-propanediol (1,3-propylene glycol), 1,4-butanediol 5 (1,4-butylene glycol), 1,2-butanediol (1,2-butylene glycol), 2,3-butanediol, 2-methyl-1,3 propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), diethylene glycol, triethylene glycol, polyethylene glycols, polypropylene glycols such as 1,2-polypropylene glycol and 1,3-polypropylene glycol, polytetrahydrofuran, 2,5 (dimethanol)-furan and diethanolamine. 10 Complex catalyst In the process of the invention, at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table (IUPAC nomenclature) 15 and also at least one donor ligand is used. The elements of groups 8, 9 and 10 of the Periodic Table comprise iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum. Preference is given to complex catalysts which comprise at least one element selected from among ruthenium and iridium. 20 In one embodiment, the process of the invention is carried out homogeneously catalyzed in the presence of at least one complex catalyst of the general formula (1): x1 X Ri R 2 N H L L2 Y where 25 L' and L are each, independently of one another, phosphine (PR"Rb) amine (NRaRb), sulfide, SH, sulfoxide (S(=O)R), C 5
-C
1 o-heteroaryl comprising at least one heteroatom selected from among nitrogen (N), oxygen (0) and sulfur (S), arsine (AsRaRb), stibane (SbRaRb) and N-heterocyclic carbenes of the formula (11) or (Ill): EK11-1973PC 5 R R4 R R4 -- N N-R -N N-R' (il) (III La 3is a monodentate two-electron donor selected from the group consisting of carbon monoxide (CO), PRRbR', NO', AsRRbRC, 5 SbRaRbRC, SRaRb, nitrile (RCN), isonitrile (RNC), nitrogen (N 2 ), phosphorus trifluoride (PF 3 ), carbon monosulfide (CS), pyridine, thiophene, tetrahydrothiophene and N-heterocyclic carbenes of the formula (II) or (Ill); 10 R 1 and R 2 are both hydrogen or together with the carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl unit of the formula I forms an acrid inyl unit; R, R", Rb, RC, R 3 , R 4 and R 5 are each, independently of one another, 15 unsubstituted or at least monosubstituted C1-C 10 -alkyl, C3-CO1 cycloalkyl, C 3
-C
1 o-heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5 -Clo-aryl or C-C 10 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S, 20 where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1 -Oo-alkyl; Y is a monoanionic ligand selected from the group consisting of H, F, 25 C, Br, 1, OCOR, OCOCF 3 , OSO 2 R, OS02CF 3 , CN, OH, OR and
N(R)
2 or an uncharged molecule selected from the group consisting of NH 3 , N(R) 3 and R 2
NSO
2 R; X' represents one, two, three, four, five, six or seven substituents on 30 one or more atoms of the acridinyl unit or one, two, three, four or five substituents on one or more atoms of the quinolinyl unit, where the radicals X 1 are selected independently from the group consisting of hydrogen, F, Cl, Br, 1, OH, NH 2 , NO 2 , -NC(O)R, 35 C(O)NR 2 , -OC(O)R, -C(O)OR, CN and borane derivatives which EK11-1973PC 6 can be obtained from the catalyst of the formula I by reaction with NaBH 4 and unsubstituted or at least monosubstituted CC10 alkoxy, Ol-Co-alkyl, C3-CO 0 -cycloalkyl, C3-Cl 0 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and 5 S, C 5
-C
1 o-aryl and C-C 1 o-heteroaryl comprising at least one heteroatom selected from among N, 0 and S, where the substitutents are selected from the group consisting of: F, CI, Br, OH, CN, NH 2 and C 1 -0o-alkyl; 10 and M is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum. 15 It should be pointed out here that the complex catalyst of the formula (1) bears a positive charge when Y is an uncharged molecule selected from the group consisting of
NH
3 , NR 3 , R 2
NSO
2 R and M is selected from the group consisting of ruthenium, nickel, palladium and iron. 20 In a preferred embodiment, the process of the invention is carried out in the presence of at least one homogeneously dissolved complex catalyst of the formula (I), where the substituents have the following meanings: 25 L' and L 2 , are each, independently of one another, PRBRb, NRaRb, sulfide, SH, S(=O)R, C 5
-C
10 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S; L3 is a monodentate two-electron donor selected from the group consisting 30 of CO, PRaRbR, NO', RCN, RNC, N 2 , PF 3 , CS, pyridine, thiophene and tetrahydrothiophene;
R
1 and R 2 are both hydrogen or together with the carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl unit of the 35 formula (1) forms an acridinyl unit; R, Ra, Rb, RC, R 3 , R 4 and R 5 are each, independently of one another, unsubstituted
C
1 -0 1 o-alkyl, C3-Cro-cycloalkyl, C 3 -C1 0 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5 -Clo-aryl or C5-C10 EK11-1973PC 7 heteroaryl comprising at least one heteroatom selected from among N, O and S; Y is a monoanionic ligand selected from the group consisting of H, F, Cl, 5 Br, OCOR, OCOCF 3 , OSO 2 R, OSO 2
CF
3 , CN, OH, OR and N(R) 2 ;
X
1 represents one, two, three, four, five, six or seven substituents on one or more atoms of the acridinyl unit or one, two, three, four or five substituents on one or more atoms of the quinolinyl unit, 10 where X' is selected independently from the group consisting of hydrogen, F, Cl, Br, I, OH, NH 2 , NO 2 , -NC(O)R, C(O)NR 2 , -OC(O)R, -C(O)OR, CN and borane derivatives which can be obtained from the catalyst of the formula (1) by reaction with NaBH 4 and unsubstituted 15 C1-C 10 -alkoxy, C-C 10 -alkyl, C3-Cl 0 -cycloalkyl, C3-Cl 0 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C5-Co-alyl and C 5
-C
10 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S; 20 and M is ruthenium or iridium. In a further preferred embodiment, the process of the invention is carried out in the 25 presence of at least one homogeneously dissolved complex catalyst where R' and R 2 are both hydrogen and the complex catalyst is a catalyst of the formula (IV): X1 N H L fM L3? Y (IV) and X 1 , L 1 , L2, L 3 and Y are as defined above. 30 In a further preferred embodiment, the process of the invention is carried out in the presence of at least one homogeneously dissolved complex catalyst where R' and R 2 together with the carbon atoms to which they are bound form a phenyl ring which EK11-1973PC 8 together with the quinolinyl unit of the formula (I) forms an acridinyl unit and the complex catalyst is a catalyst of the formula (V): X N H / L1 L2 5 and X 1 , L, L 2 L3 and Y are as defined above. Some complex catalysts (formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII)) which can be used in the process of the invention are shown by way of example below: EK11-1973PC 9 x1 x' N N H IH RRa Ra M R 2 Ra -M R y Rb Rb Rb Vi) (vi) XX1 IX X H N Ra NM_ H OC Ra Na Rb P\(N RbY Rb b ociR R Y R OCb (Vill) (IX) X1 X1 N H Ra/ H R a SN a M Rj/H N R~ p :J/Hf -m R OC \Rb R C Rb (X) (XI) X1 X1 N 'H HRa H Ra I/HxR Ra.1 N Ra N M N Rb 0C \Rb Rb OC Rb (XII) (XIII) EK11-1973PC 10 In a further preferred embodiment, the process of the invention is carried out in the presence of at least one complex catalyst selected from the group of catalysts of the formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII), where 5 R' and Rb are each, independently of one another, unsubstituted or at least monosubstituted C1-C1o-alkyl, C3-C1 0 -cycloalkyl, C3-ClG-heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C5-C10-aryl or Cs-C1o heteroaryl comprising at least one heteroatom selected from among N, 0 and S, 10 where the substituents are selected from the group consisting of: F, CI, Br, OH, CN, NH 2 and C 1
-C
10 -alkyl; Y is a monoanionic ligand selected from the group consisting of H, F, Cl, Br, 15 OCOR, OCOCF 3 , OSO 2 R, OSO 2
CF
3 , CN, OH, OR, N(R) 2 ; R is unsubstituted or at least monosubstituted C 1
-C
10 -alkyl, C 3
-C
1 o-cycloalkyl,
C
3
-C
1 o-heterocyclyl comprising at least one heteroatom selected from among N, O and S, Co-Clo-aryl, C 5
-C
10 -heteroaryl comprising at least one heteroatom 20 selected from among N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1
-CO
10 -alkyl; 25 X' represents one, two or three substituents on one or more atoms of the acridinyl unit or one or two substituents on one or more atoms of the quinolinyl unit, where the radicals X 1 are selected independently from the group consisting of hydrogen, F, Cl, Br, I, OH, NH 2 , NO 2 , -NC(O)R, C(O)NR 2 , -OC(O)R, -C(O)OR, 30 CN and borane derivatives which can be obtained from the catalyst of the formula I by reaction with NaBH 4 and unsubstituted C 1
-C
10 -alkoxy, C 1
-C
1 0 -alkyl,
C
3
-C
10 -cycloalkyl, C 3
-C
1 o-heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C5-C1o-aryl and Cs-C 1 0 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S; 35 and M is ruthenium or iridium. EK11-1973PC 11 In a further preferred embodiment, the process of the invention is carried out in the presence of at least one complex catalyst selected from the group consisting of catalysts of the formulae (VI), (VII), (VIll), (X), (X), (XI), (XII) and (XIII), where 5 Ra and Rb are each, independently of one another, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, phenyl or mesityl; Y is a monoanionic igand selected from the group consisting of H, F, Cl, Br,
OCOCH
3 , OCOCF 3 , OSO 2
CF
3 , CN and OH; 10
X
1 is a substituent on an atom of the acridinyl unit or a substituent on an atom of the quinolinyl unit, where X 1 is selected from the group consisting of hydrogen, F, Cl, Br, OH, NH 2 , 15 NO 2 , -NC(O)R, C(O)NR 2 , -OC(O)R, -C(O)OR, CN and borane derivatives which can be obtained from the catalyst of the formula (1) by reaction with NaBH 4 and unsubstituted C1-C1 0 -alkoxy, C1-C1 0 -alkyl, C3-C1 0 -cycloalkyl, C 3
-C
10 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C5-C1O aryl and C 5
-C
1 o-heteroaryl comprising at least one heteroatom selected from 20 among N, O and S; M is ruthenium or iridium. In a further preferred embodiment, the process of the invention is carried out in the 25 presence of at least one complex catalyst from the group consisting of the catalysts of the formulae (VI), (VII), (VIll), (IX), (X), (XI), (XII) and (XIII), where R" and Rb are each, independently of one another, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, phenyl or mesityl; 30 Y is a monoanionic ligand selected from the group consisting of H, F, Cl, Br, I,
OCOCH
3 , OCOCF3, OSO 2
CF
3 , CN and OH;
X
1 is hydrogen; 35 and M is ruthenium or iridium. 40 In a particularly preferred embodiment, L3 is carbon monoxide (CO). EK11-1973PC 12 In a particularly preferred embodiment, the process of the invention is carried out in the presence of a complex catalyst of the formula (XIVa): N Y H Ru OCI 5 (XIva) In a very particularly preferred embodiment, the process of the invention is carried out in the presence of a complex catalyst of the formula (XIVb): N H 0 _P /1 P' kC 1 l (XIVb) 10 In a further particularly preferred embodiment, the process of the invention is carried out in the presence of at least one homogeneously dissolved complex catalyst of the formula (XV) in which R 1 , R 2 , R', L', L 2 and L 3 are as defined above. 15 H H R2 Y ' HI H R2 H (Xv) EK11-1973PC 13 Complex catalysts of the formula (XV) can be obtained by reacting catalysts of the formula (1) with sodium borohydride (NaBH 4 ). The reaction proceeds according to the general reaction equation: H H x R1 X% R - ~ R 2 NaBH 4 H H N 2N H I I HH 5 L H In a further particularly preferred embodiment, the process of the invention is carried out in the presence of a complex catalyst of the formula (XVI): H H H N BL P Ru~ z oc 10 (XVI) The borane derivative of the formula XVI can be obtained according to the following reaction equation: H H N NaI3H 4 (IEquiv H I H 21h Room temperature HH 02 PP 15 eo In a further embodiment, the process of the invention is carried out using at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of EK11-1973PC 14 the Periodic Table (IUPAC nomenclature) and also at least one phosphorus donor ligand of the general formula (XXI), R 21 R23 P-Y1-A-Y2_p/ R22 ' I 'R24 Y3 P R25 R26 n (XXI) 5 where n is0or1;
R,
21
R
22 , R 23 , R 24 , R 25 , R 26 are each, independently of one another, 10 unsubstituted or at least monosubstituted C 1
-C
1 o-alkyl, C 1
-C
4 alkyldiphenylphosphine (-C-C 4 -alkyl-P(phenyl) 2 ), C 3
-C
10 -cycloalkyl, C 3
-C
10 heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5 -C1 4 -aryl or C 5
-C
10 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S, 15 where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C-C 1 o-alkyl; A is 20 i) a bridging group selected from the group consisting of unsubstituted or at least monosubstituted N, 0, P, C-C 6 -alkane, C 3
-C
10 -cycloalkane,
C
3
-C
1 o-heterocycloalkane comprising at least one heteroatom selected from among N, 0 and S, C 5
-C
1 4 -aromatic and C 5 -C-heteroaromatic comprising at least one heteroatom selected from among N, 0 and S, 25 where the substituents are selected from the group consisting of:
C-C
4 -alkyl, phenyl, F, Cl, Br, OH, OR 2 7 , NH 2 , NHR 27 and N(R 27
)
2 , where R 27 is selected from among C-C 1 o-alkyl and C5-Cro-aryl; 30 EK11-1973PC 15 or ii) a bridging group of the formula (XXII) or (XXIII):
(R
2 8 )R X13 (R 29 )q X1 X12 5xxi) (XXIII) m, q are each, independently of one another, 0, 1, 2, 3 or 4;
R
2 8 , R 29 are selected independently from the group consisting of C1rC1o 10 alkyl, F, Cl, Br, OH, OR 27 , NH 2 , NHR 7 and N(R 27
)
2 , where R 27 is selected from among C 1 -o-alkyl and C 5
-C
10 -aryl;
X
1 l, X 12 are each, independently of one another, NH, 0 or S; 15 X1 is a bond, NH, NR 3 0 , 0, S or CRR 31
R
32
R
30 is unsubstituted or at least monosubstituted C-C 1 o-alkyl, C3-C10-cycloalkyl, C 3 -C1 0 -heterocyclyl comprising at least one 20 heteroatom selected from among N, 0 and S, C 5
-C
14 -aryl or
C
5
-C
1 o-heteroaryl comprising at least one heteroatom selected from among N, 0 and S, where the substituents are selected from the group consisting 25 of: F, Cl, Br, OH, CN, NH 2 and C-C 1 o-alkyl;
R,
31
R
3 2 are each, independently of one another, unsubstituted or at least monosubstituted C-C 1 o-alkyl, C-C 10 -alkoxy, C3-Cio cycloalkyl, C 3
-C
1 o-cycloalkoxy, C 3
-C
10 -heterocyclyl comprising at 30 least one heteroatom selected from among N, 0 and S, C5-C 4 aryl, C 5
-C
14 -aryloxy or C 5
-C
1 o-heteroaryl comprising at least one heteroatom selected from among N, 0 and S, where the substituents are selected from the group consisting 35 of: F, Cl, Br, OH, CN, NH 2 and C-C 1 o-alkyl; EK11-1973PC 16
Y
1 , Y 2 , Y 3 are each, independently of one another, a bond, unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, 5 where the substituents are selected from the group consisting of: F, Cl, Br, OH, OR 27 , CN, NH 2 , NHR 27 , N(R 27
)
2 and C-C 1 o-alkyl, where R 27 is selected from among C-C 1 o-alkyl and Cs-C1o-aryl. 10 According to the invention, A is a bridging group. When A is selected from the group consisting of unsubstituted or at least monosubstituted 0 1
-C
6 -alkane, C3-C10 cycloalkane, C 3 -C1 0 -heterocycloalkane, C5-C1 4 -aromatic and C 5 -C-heteroaromatic and bridging groups of the formula (II) or (Ill), two hydrogen atoms of the bridging group are 15 replaced by bonds to the adjacent substituents Y and Y 2 when n = 0. When n = 1, three hydrogen atoms of the bridging group are replaced by three bonds to the adjacent substituents Y', Y 2 and Y 3 . When A is P (phosphorus), the phosphorus forms two bonds to the adjacent 20 substituents Yi and Y2 and one bond to a substituent selected from the group consisting of C-C 4 -alkyl and phenyl when n = 0. When n = 1, the phosphorus forms three bonds to the adjacent substituents Y', Y 2 and Y. When A is N (nitrogen), the nitrogen forms two bonds to the adjacent substituents Y' 25 and Y2 and one bond to a substituent selected from the group consisting of C-C 4 -alkyl and phenyl when n = 0. When n = 1, the nitrogen forms three bonds to the adjacent substituents Y', Y 2 and Y3. When A is 0 (oxygen), n = 0. The oxygen forms two bonds to the adjacent substituents 30 Y and Y2 Preference is given to complex catalysts which comprise at least one element selected from among ruthenium and iridium. 35 In a preferred embodiment, the process of the invention is carried out in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand of the general formula (XXI), where 40 n is 0 or 1; EK11-1973PC 17
R
21 , R 22 , R 23 , R 24 , R 25 , R 26 are each, independently of one another, unsubstituted C-C 1 0 -alkyl, C 3
-C
10 -cycloalkyl, C3-C1 0 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C5-C14-aryl or C 5
-C
1 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S; A is 0 i) a bridging group selected from the group consisting of unsubstituted 0 1 -Cr-alkane, C 3
-C
10 -cycloalkane, C 3
-C
10 -heterocycloalkane comprising at least one heteroatom selected from among N, 0 and S, C 5
-C
1 4 -aromatic and C 5 -C-heteroaromatic comprising at least one heteroatom selected from among N, O and S; or ii) a bridging group of the formula (XXII) or (XXIII): (R28)m
(R
29 )q (R 28 )m 13 R29) 20(XXII1) (XXlII) m, q are each, independently of one another, 0, 1, 2, 3 or 4; R28, R2 are selected independently from the group consisting of Ci-Cia 25 alkyl, F, Cl, Br, OH, OR 27 , NH 2 , NHR and N(R2) 2 , where R 27 is selected from among Cl-C 1 o-alkyl and C 5
-C
10 -aryl;
X'
1 , X 12 are each, independently of one another, NH, 0 or S; X13 is a bond, NH, NR 30 , 0, S or CR"R32 R3 is unsubstituted C 1
-C
1 -alkyl, C 3
-C
1 0 -cycloalkyl, C3-C 0 heterocyclyl comprising at least one heteroatom selected from EK11-1973PC 18 among N, 0 and S, C 5
-C
14 -aryl or C 5 -Cw 1 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S;
R
3 1 , R 32 are each, independently of one another, unsubstituted CrC110 5 alkyl, C-C 10 -alkoxy, C 3
-C
10 -cycloalkyl, C 3
-C
10 -cycloalkoxy,
C
3
-C
10 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5
-C
14 -aryl, C-C14-aryloxy or Cs-C10 heteroaryl comprising at least one heteroatom selected from among N, 0 and S; 10
Y
1 , Y2 Y3 are each, independently of one another, a bond, unsubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene. 15 In a further preferred embodiment, the process of the invention is carried out in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand of the general formula (XXV), R 21 R23 P-Y'-A- y2p R 22 R24 20 (XXV) where
R,
2 1
R
2 2 , R 23 , R 24 are each, independently of one another, unsubstituted or at 25 least monosubstituted 0 1
-C
10 -alkyl, Cr 1
C
4 -alkyldiphenylphosphine (-Cr1C4 alkyl-P(phenyl) 2 ), C 3 -C1 0 -cycloalkyl, C 3 -C1 0 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5
-C
14 -aryl or C 5 -C1O heteroaryl comprising at least one heteroatom selected from among N, O and S, 30 where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1 o-0-alkyl; A is 35 EK11-1973PC 19 i) a bridging group selected from the group consisting of unsubstituted or at least monosubstituted N, 0, P, C-Cr-alkane, C 3
-C
10 -cycloalkane,
C
3
-C
10 -heterocycloalkane comprising at least one heteroatom selected from among N, 0 and S, C 5
-C
14 -aromatic and C 5 -C-heteroaromatic comprising 5 at least one heteroatom selected from among N, 0 and S, where the substituents are selected from the group consisting of:
C-C
4 -alkyl, phenyl, F, Cl, Br, OH, OR 2 1, NH 2 , NHR 27 or N(R27)2, 10 where R 27 is selected from among C-Clo-alkyl and C 5
-C
1 o-aryl; or ii) a bridging group of the formula (XXII) or (XXIII): 15
(R
2 8 )m R \ X1 ( 29 ) (XXII) (XXIII) m, q are each, independently of one another, 0, 1, 2, 3 or 4; 20 R 28 , R 2 9 are selected independently from the group consisting of C-Clo alkyl, F, Cl, Br, OH, OR 27 , NH 2 , NHR 27 and N(R 27
)
2 , where R 27 is selected from among C-C 1 o-alkyl and C 5
-C
1 o-aryl; 25 X", x 2 are each, independently of one another, NH, 0 or S, x1 3 is a bond, NH, NR 30 , 0, S or CR 31
R
32 ; R3 is unsubstituted or at least monosubstituted C-C 1 o-alkyl, 30 C 3
-C
10 -cycloalkyl, C 3
-C
10 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5
-C
4 -aryl or
C
5
-C
1 o-heteroaryl comprising at least one heteroatom selected from among N, 0 and S, EK11-1973PC 20 where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1
-C
1 o-alkyl;
R,
31
R
32 are each, independently of one another, unsubstituted or at 5 least monosubstituted C-C 10 -alkyl, C-C 10 -alkoxy, C3-C10 cycloalkyl, C 3
-C
10 -cycloalkoxy, C 3
-C
1 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5 -C aryl, C 5
-C
14 -aryloxy or C-C 10 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S, 10 where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1
-C
1 0 -alkyl;
Y
1 , Y 2 are each, independently of one another, a bond, unsubstituted or at 15 least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, where the substituents are selected from the group consisting of: F, Cl, Br, OH, OR 2 7 , CN, NH 2 , NHR 27 , N(R 27
)
2 and C-C 1 o-alkyl, 20 where R 27 is selected from among C-C 10 -alkyl and C 5
-C
1 o-aryl. In a further preferred embodiment, the process of the invention is carried out in the presence of at least one complex catalyst comprising at least one element selected 25 from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand of the general formula (XXVI), R21 R23 \P-Yi-A-Y2-P/ R22 I\R24 y3 / I R R (XXVI) where 30
R
21 , R 22 , R 23 , R, 24
R
25 , R 2 6 are each, independently of one another, unsubstituted or at least monosubstituted C-C 1 o-alkyl, Cr-C4 alkyldiphenylphosphine, C 3 -C1 0 -cycloalkyl, C 3
-C
1 o-heterocyclyl comprising EK11-1973PC 21 at least one heteroatom selected from among N, 0 and S, C 5
-C
14 -aryl or Cr-C1o-heteroaryl comprising at least one heteroatom selected from among N, O and S, 5 where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1
-C
10 -alkyl; A is a bridging group selected from the group consisting of unsubstituted or at least monosubstituted N, P, C-Cr-alkane, C 3
-C
10 -cycloalkane, C3-Cia 10 heterocycloalkane comprising at least one heteroatom selected from among N, 0 and S, C 5 -C1 4 -aromatic and C-Ce-heteroaromatic comprising at least one heteroatom selected from among N, 0 and S, where the substituents are selected from the group consisting of: 15 C 1
-C
4 -alkyl, phenyl, F, Cl, Br, OH, OR 2 7 , NH 2 , NHR 27 and N(R 2 7
)
2 , where R 27 is selected from among C-C 1 o-alkyl and C 5
-C
1 o-aryl; Y', Y 2 , Y 3 are each, independently of one another, a bond, unsubstituted or at 20 least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, where the substituents are selected from the group consisting of: F, Cl, Br, OH, OR 27 , CN, NH 2 , NHR 27 , N(R 27
)
2 and C-C 1 o-alkyl, 25 where R 2 7 is selected from among C 1 -0o-alkyl and Cr-Co-aryl. In a further preferred embodiment, the process of the invention is carried out in the presence of at least one complex catalyst comprising at least one element selected 30 from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand of the general formula (XXV), where
R
2 1 , R 22 , R 23 , R 24 are each, independently of one another, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, or mesityl; 35 A is i) a bridging group selected from the group consisting of methane, ethane, propane, butane, cyclohexane, benzene, naphthalene and 40 anthracene; EK11-1973PC 22 or ii) a bridging group of the formula (XXVII) or (XXVIII): 5 X13 (XXVII) (XXVIII)
X
11 , X 12 are each, independently of one another, NH, 0 or S; 10 X1 is a bond, NH, 0, S or CR 31
R
32 1
R
31 , R 32 are each, independently of one another, unsubstituted C-C 1
O
alkyl; 15 Y', Y 2 are each, independently of one another, a bond, methylene or ethylene. In a particularly preferred embodiment, the process of the invention is carried out in the presence of at least one complex catalyst comprising at least one element selected 20 from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand of the general formula (XXIX) or (XXX), (R()m
R
29 )q (R 28 )m X 29) X11 X
R
21 R22 R 23 R24 R 21
R
22 R23 R24 (XXIX) (XXX) 25 where the abovementioned definitions and preferences apply to m, q, R 2 , R 2 , R 23 , R 24
R,
2 8
R
29 , X1 9 , X 12 and X 13 . EKI1-1973PC 23 In a further particularly preferred embodiment, the process of the invention is carried out in the presence of at least one complex catalyst comprising at least one element selected from the group consisting of ruthenium and iridium and also at least one phosphorus donor ligand selected from the group consisting of 5 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), 2,3-bis(dicyclohexylphosphino)ethane (dcpe), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), 1,1,1 tris(diethylphosphinomethyl)ethane (rhodaphos), bis(2 diphenylphosphinoethyl)phenylphosphine and 1,1,1 -tris(diphenylphosphinomethyl) 10 ethane (triphos). In a further particularly preferred embodiment, the process of the invention is carried out in the presence of a complex catalyst comprising ruthenium and also at least one phosphorus donor ligand selected from the group consisting of 4,5 15 bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-diphenylphosphino ethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos). In a further particularly preferred embodiment, the process of the invention is carried out in the presence of a complex catalyst comprising iridium and also at least one 20 phosphorus donor ligand selected from the group consisting of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-diphenylphosphino ethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos). For the purposes of the present invention, the term C 1
-C
10 -alkyl refers to branched, 25 unbranched, saturated and unsaturated groups. Preference is given to alkyl groups having from 1 to 6 carbon atoms (C-C 6 -alkyl). Greater preference is given to alkyl groups having from 1 to 4 carbon atoms (C-C 4 -alkyl). Examples of saturated alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, 30 isobutyl, sec-butyl, tert-butyl, amyl and hexyl. Examples of unsaturated alkyl groups (alkenyl, alkynyl) are vinyl, allyl, butenyl, ethynyl and propynyl. 35 The C-C 1 o-alkyl group can be unsubstituted or substituted by one or more substituents selected from the group consisting of F, CI, Br, hydroxy (OH), C 1
-C
10 -alkoxy, C 5
-C
10 aryloxy, C 5 -Co-alkylaryloxy, C 5
-C
10 -heteroaryloxy comprising at least one heteroatom selected from among N, 0, S, oxo, C 3
-C
10 -cycloalkyl, phenyl, C 5
-C
1 o-heteroaryl comprising at least one heteroatom selected from among N, 0, S, C 5
-C
1 o-heterocyclyl 40 comprising at least one heteroatom selected from among N, 0, S, naphthyl, amino, EK11-1973PC 24
C
1 -0 1 o-alkylamino, C 5
-C
1 o-arylamino, C 5 -C1 0 -heteroarylamino comprising at least one heteroatom selected from among N, 0, S, C 1
-C
1 o-dialkylamino, CIO-C, 2 -diarylamino,
C
10
-C
20 -alkylarylamino, C-C 10 -acyl, C-C 10 -acyloxy, NO 2 , C-Cio-carboxy, carbamoyl, carboxamide, cyano, sulfonyl, sulfonylamino, sulfinyl, sulfinylamino, thiol, C-Cj 5 alkylthiol, C 5
-C
1 o-arylthiol and C-C 1 o-alkylsulfonyl. The above definition of C-C 1 o-alkyl applies analogously to C-C 3 o-alkyl and to CrC6 alkane. For the present purposes, the term C 3
-C
10 -cycloalkyl refers to saturated, unsaturated 10 monocyclic and polycyclic groups. Examples of C 3 -C1o-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. The cycloalkyl groups can be unsubstituted or substituted by one or more substituents as have been defined above for the C 1
-C
1 o-alkyl group. 15 The abovementioned definition of C 3
-C
1 o-cycloalkyl applies analogously to C3-C1a cycloalkane. Alcohol amination 20 The homogeneous catalysts can be produced either directly in their active form or only under the reaction conditions from customary precursors with addition of the appropriate ligands. Customary precursors are, for example, [Ru(p-cymene)C1 2
]
2 , [Ru(benzene)Cl 2 ]n, [Ru(CO) 2 Cl 2 ]n, [Ru(CO) 3
C
2
]
2 [Ru(COD)(allyl)], [RuCI3*H 2 0], [Ru(acetylacetonate) 3 ], [Ru(DMSO) 4 Cl 2 ], [Ru(PPh 3
)
3 (CO)(H)Cl], [Ru(PPh 3 )3(CO)Cl 2 ], 25 [Ru(PPh 3 )3(CO)(H) 2 ], [Ru(PPh 3
)
3
C
2 ], [Ru(cyclopentadienyl)(PPh) 2 Cl], [Ru(cyclopentadienyl)(CO)2Cl], [Ru(cyclopentadienyl)(CO) 2 H], [Ru(cyclopentadienyl)(CO) 2
]
2 , [Ru(pentamethylcyclopentadienyl)(CO) 2 CI), [Ru(penta methylcylcopentadienyl)(CO) 2 H], [Ru (penta methylcyclo pentad ienyl)(CO) 2
]
2 , [Ru(indenyl)(CO) 2 C], [Ru(indenyl)(CO) 2 H], [Ru(indenyl)(CO) 2
]
2 , ruthenocene, 30 [Ru(binap)C 2 ], [Ru(bipyridine) 2 Cl 2 *2H 2 0], [Ru(COD)C 2
]
2 , [Ru(pentamethylcyclo pentadienyl)(COD)CI], [Ru 3 (CO)12], [Ru(tetraphenylhydroxycyclopentadienyl)(CO) 2 H], [Ru(PMe 3 )4(H) 2 ], [Ru(PEt 3 )4(H) 2 ], [Ru(PnPr 3
)
4
(H)
2 ], [Ru(PnBu 3 )4(H) 2 ], [Ru(PnOctyl 3
)
4
(H)
2 ], [IrCl 3
*H
2 0], KirCl 4 , K 3 lrCl 6 , [lr(COD)C] 2 , [Ir(cyclooctene) 2
C]
2 , [lr(ethene) 2
CI]
2 , [lr(cyclopentadienyl)C 2
]
2 , [ir(pentamethylcyclopentadienyl)Cl2] 2 , 35 [lr(cylopentadienyl)(CO) 2 ], [lr(pentamethylcyclopentadienyl)(CO) 2 , [lr(PPhs) 2 (CO)(H)], [lr(PPh 3
)
2 (CO)(CI)], [Ir(PPh 3
)
3 (CI)]. For the purposes of the present invention, homogeneously catalyzed means that the catalytically active part of the complex catalyst is at least partly present in solution in 40 the liquid reaction medium. In a preferred embodiment, at least 90% of the complex EK11-1973PC 25 catalyst used in the process is present in solution in the liquid reaction medium, more preferably at least 95%, particularly preferably more than 99%; the complex catalyst is most preferably entirely present in solution in the liquid reaction medium (100%), in each case based on the total amount in the liquid reaction medium. 5 The amount of the metal component of the catalyst, preferably ruthenium or iridium, is generally from 0.1 to 5000 ppm by weight, in each case based on the total liquid reaction medium. 10 The reaction occurs in the liquid phase, generally at a temperature of from 20 to 250*C. The process of the invention is preferably carried out at temperatures in the range from 100*C to 2000C, particularly preferably in the range from 110 to 160C. The reaction can generally be carried out at a total pressure of from 0.1 to 20 MPa 15 absolute, which can be either the autogenous pressure of the solvent at the reaction temperature or the pressure of a gas such as nitrogen, argon or hydrogen. The process of the invention is preferably carried out at a total pressure in the range from 0.2 to 15 MPa absolute, particularly preferably at a total pressure in the range from 1 to 15 MPa absolute. 20 The average reaction time is generally from 15 minutes to 100 hours. The aminating agent (ammonia) can be used in stoichiometric, substoichiometric or superstoichiometric amounts based on the hydroxyl groups to be aminated. 25 In a preferred embodiment, ammonia is used in a from 1- to 250-fold, preferably a from 1- to 100-fold, in particular in a from 1.5- to 10-fold, molar excess per mole of hydroxyl groups to be reacted in the starting material. Higher excesses of ammonia are also possible. The ammonia can be introduced in gaseous form, liquid form or as a solution 30 in the solvent or starting material. The process of the invention can be carried out either in a solvent or without solvent. Suitable solvents are polar and nonpolar solvents which can be used in pure form or in mixtures. For example, it is possible to use only one nonpolar or one polar solvent in 35 the process of the invention. It is also possible to use mixtures of two or more polar solvents or mixtures of two or more nonpolar solvents or mixtures of one or more polar solvents with one or more nonpolar solvents. The product can also be used as solvent, either in pure form or in mixtures with polar or nonpolar solvents. EK11-1973PC 26 Suitable nonpolar solvents are, for example, saturated and unsaturated hydrocarbons such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and mesitylene and linear and cyclic ethers such as THF, diethyl ether, 1,4-dioxane, MTBE (tert-butyl methyl ether), diglyme and 1,2-dimethoxyethane. Preference is given to 5 using toluene, xylene or mesitylene. Suitable polar solvents are, for example, water, dimethylformamide, formamide, tert amylalcohol and acetonitrile. Preference is given to using water. The water can either be added before the reaction, be formed as water of reaction during the reaction or be 10 added after the reaction in addition to the water of reaction. A further preferred solvent is tert-amylalcohol. To carry out the reaction in the liquid phase, ammonia, the diol optionally together with one or more solvents, together with the complex catalyst are introduced into a reactor. 15 The introduction of ammonia, diol, optionally solvent and complex catalyst can be carried out simultaneously or separately. The reaction can be carried out continuously, in the semibatch mode, in the batch mode, admixed in product as solvent or without admixing in a single pass. 20 It is in principle possible to use all reactors which are basically suitable for gas/liquid reactions at the given temperature and the given pressure for the process of the invention. Suitable standard reactors for gas/liquid reaction systems and for liquid/liquid reaction systems are, for example, indicated in K.D. Henkel, "Reactor Types and Their Industrial Applications", in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley 25 VCH Verlag GmbH & Co. KGaA, DOI: 10.1002/14356007.b04_087, chapter 3.3 "Reactors for gas-liquid reactions". Examples which may be mentioned are stirred tank reactors, tube reactors or bubble column reactors. In the amination reaction, a hydroxyl group, preferably a primary hydroxyl group 30 (-CH 2 -OH), of the starting material is reacted with ammonia to form a primary amino group (-NH 2 ), with in each case one mole of water of reaction being formed per mole of reacted hydroxyl group. The reaction of 1,2-ethylene glycol leads, for example, to the corresponding 35 2-aminoethanol. The reaction output formed in the reaction generally comprises the corresponding alkanolamines, the one or more solvents if used, the complex catalyst, possibly unreacted starting materials and ammonia and also the water of reaction formed. 40 EK11-1973PC 27 Any excess ammonia present, any solvent present, the complex catalyst and the water of reaction are removed from the reaction output. The amination product obtained can be worked up further. The excess ammonia, the complex catalyst, any solvent or solvents and any unreacted starting materials can be recirculated to the amination 5 reaction. If the amination reaction is carried out without solvent, the homogeneous complex catalyst is dissolved in the product after the reaction. This can remain in the product or be separated off therefrom by a suitable method. Possibilities for separating off the 10 catalyst are, for example, scrubbing with a solvent which is not miscible with the product and in which the catalyst dissolves better than in the product as a result of a suitable choice of the ligands. The catalyst concentration in the product is optionally reduced by multistage extraction. As extractant, preference is given to using a solvent which is also suitable for the target reaction, e.g. toluene, benzene, xylenes, alkanes 15 such as hexanes, heptanes and octanes and acyclic or cyclic ethers such as diethyl ether and tetrahydrofuran, which can after concentration by evaporation be reused together with the extracted catalyst for the reaction. It is also possible to remove the catalyst by means of a suitable absorbent. The catalyst can also be separated off by adding water to the product phase if the reaction is carried out in a solvent which is 20 immiscible with water. If the catalyst in this case dissolves preferentially in the solvent, it can be separated off with the solvent from the aqueous product phase and optionally be reused. This can be brought about by selection of suitable ligands. The resulting aqueous diamines, triamines or polyamines can be used directly as technical-grade amine solutions. It is also possible to separate the amination product from the catalyst 25 by distillation. If the reaction is carried out in a solvent, the latter can be miscible with the amination product and be separated off by distillation after the reaction. It is also possible to use solvents which have a miscibility gap with the amination products or the starting 30 materials. Suitable solvents for this purpose are, for example, toluene, benzene, xylenes, alkanes such as hexanes, heptanes and octanes and acyclic or cyclic ethers such as diethyl ether, tetrahydrofuran and dioxane. As a result of suitable choice of the phosphine ligands, the catalyst preferentially dissolves in the solvent phase. The phosphine ligands can also be selected so that the catalyst dissolves in the amination 35 product. In this case, the amination product can be separated from the catalyst by distillation. The solvent can also be miscible with the starting materials and the product under the reaction conditions and only form a second liquid phase comprising the major part of 40 the catalyst after cooling. As solvents which display this property, mention may be EK11-1973PC 28 made by way of example of toluene, benzene, xylenes, alkanes such as hexanes, heptanes and octanes. The catalyst can then be separated off together with the solvent and be reused. The product phase can also be admixed with water in this variant. The proportion of the catalyst comprised in the product can subsequently be separated off 5 by means of suitable absorbents such as polyacrylic acid and salts thereof, sulfonated polystyrenes and salts thereof, activated carbons, montmorillonites, bentonites and zeolites or else be left in the product. The amination reaction can also be carried out in a two-phase system. In the case of 10 the two-phase reaction, suitable nonpolar solvents are, in particular, toluene, benzene, xylenes, alkanes such as hexanes, heptanes and octanes in combination with lipophilic phosphine ligands on the transition metal catalyst, as a result of which the transition metal catalyst accumulates in the nonpolar phase. In this embodiment, in which the product and the water of reaction and any unreacted starting materials form a second 15 phase enriched with these compounds the major part of the catalyst can be separated off from the product phase by simple phase separation and be reused. If volatile by-products or unreacted starting materials or the water formed in the reaction or added after the reaction to aid the extraction are undesirable, they can be 20 separated off from the product without problems by distillation. It can also be advantageous for the water formed in the reaction to be removed continuously from the reaction mixture. The water of reaction can be separated off from the reaction mixture directly by distillation or as azeotrope with addition of a suitable 25 solvent (entrainer) and using a water separator or be removed by addition of water withdrawing auxiliaries. The addition of bases can have a positive effect on product formation. Suitable bases which may be mentioned here are alkali metal hydroxides, alkaline earth metal 30 hydroxides, alkaline metal alkoxides, alkaline earth metal alkoxides, alkali metal carbonates and alkaline earth metal carbonates, which can be used in amounts of from 0.01 to 100 molar equivalents based on the metal catalyst used. The present invention further provides for the use of a complex catalyst comprising at 35 least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand for the homogeneously catalyzed preparation of alkanolamines which have a primary amino group (-NH 2 ) and a hydroxyl group (-OH) by alcohol amination of diols having two hydroxyl groups (-OH) by means of ammonia. EK11-1973PC 29 In a preferred embodiment, the present invention provides for the use of a homogeneously dissolved complex catalyst of the general formula (I): X NR2 H L1 L2 Y (I) 5 where
L
1 and L 2 are each, independently of one another, PRaR, NRaRb, sulfide, SH, S(=O)R, C 5
-C
10 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S, AsRaRb, SbRaRb and N 10 heterocyclic carbenes of the formula (II) or (111): R3 R4 R3 R4 -N N-R 5 N N-R (11) ("I'; L 3 is a monodentate two-electron donor selected from the group consisting of CO, PRR bR, NO', AsRaRbRe, SbRRbRC, SRaR', 15 RCN, RNC, N 2 , PF 3 , CS, pyridine, thiophene, tetrahydrothiophene and N-heterocyclic carbenes of the formula (II) or (Ill); R' and R 2 are both hydrogen or together with the carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl unit 20 of the formula (1) forms an acridinyl unit; R, Ra, R', R", R 3 , R 4 , and R 5 are each, independently of one another, unsubstituted or at least monosubstituted C 1
-C
10 -alkyl, C3-C10 cycloalkyl, C 3
-C
10 -heterocyclyl comprising at least one heteroatom 25 selected from among N, 0 and S, C 5
-C
10 -aryl or C 5
-C
10 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S, EK11-1973PC 30 where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1
-C
10 -alkyl; Y is a monoanionic ligand selected from the group consisting of H, F, 5 CI, Br, I, OCOR, OCOCF 3 , OSO 2 R, OSO 2
CF
3 , CN, OH, OR and
N(R)
2 or an uncharged molecule selected from the group consisting of NH 3 , N(R) 3 and R 2
NSO
2 R; X' represents one, two, three, four, five, six or seven substituents on 10 one or more atoms of the acridinyl unit or one, two, three, four or five substituents on one or more atoms of the quinolinyl unit, where the radicals X 1 are selected independently from the group consisting of hydrogen, F, Cl, Br, 1, OH, NH 2 , NO 2 , -NC(O)R, 15 C(O)NR 2 , -OC(O)R, -C(O)OR, CN and borane derivatives which can be obtained from the catalyst of the formula I by reaction with NaBH 4 and unsubstituted or at least monosubstituted C1-C10 alkoxy, C 1
-C
10 -alkyl, C-C1o-cycloalkyl, C 3
-C
10 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and 20 S, C 5
-C
10 -aryl and Cr-C1o-heteroaryl comprising at least one heteroatom selected from among N, 0 and S, where the substituents are selected from the group consisting of: F, CI, Br, OH, CN, NH 2 and C 1
-C
10 -alkyl; 25 and M is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum, 30 for the homogeneously catalyzed preparation of alkanolamines which have a primary amino group (-NH 2 ) and a hydroxyl group (-OH) by alcohol amination of diols having two hydroxy groups (-OH) by means of ammonia, where the definitions and preferences described above for the process of the invention apply to the catalyst of 35 the general formula (I). In a further preferred embodiment, the present invention relates to the use of a homogeneously dissolved complex catalyst of the general formula (XV): EK11-1973PC 31 H H H H where L' and L 2 are each, independently of one another, PRRb, NRaRb, sulfide, 5 SH, S(=0)R, C 5 -C1 0 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S, AsRaR, SbR"R' or N-heterocyclic carbenes of the formula (II) or (111): R R4 R R4 _N N-R -N N-RS 10 LS 3is a monodentate two-electron donor selected from the group consisting of CO, PRaRbR0, NO+, AsRaRRC, SbR"RRc, SRaR, RCN, RNC, N 2 , PF 3 , CS, pyridine, thiophene, tetrahydrothiophene and N-heterocyclic carbenes of the formula (II) or (Ill); 15
R
1 and R 2 are both hydrogen or together with the carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl unit of the formula (1) forms an acridinyl unit; 20 R, R", Rb, RC, R 3 , R 4 and R 5 are each, independently of one another, unsubstituted or at least monosubstituted C 1 -0 1 o-alkyl, C 3
-C
10 cycloalkyl, C 3
-C
10 -heterocyclyl comprising at least one heteroatom selected from among N, C and S, C 5
-C
1 o-aryl or C 5
-C
10 -heteroaryl comprising at least one heteroatom selected from among N, C and 25 S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C-C 1 o-alkyl; EK11-1973PC 32 Y is a monoanionic ligand selected from the group consisting of H, F, CI, Br, , OCOR, OCOCF 3 , OSO 2 R, OSO 2
CF
3 , CN, OH, OR and
N(R)
2 or uncharged molecules selected from the group consisting 5 of NH 3 , N(R) 3 and R 2
NSO
2 R; X' represents one, two, three, four, five, six or seven substituents on one or more atoms of the acridinyl unit or one, two, three, four or five substituents on one or more atoms of the quinolinyl unit, 10 where the radicals X 1 are selected independently from the group consisting of hydrogen, F, Cl, Br, I, OH, NH 2 , NO 2 , -NC(O)R,
C(O)NR
2 , -OC(O)R, -C(O)OR, CN and borane derivatives which can be obtained from the catalyst of the formula I by reaction with 15 NaBH 4 and unsubstituted or at least monosubstituted C1-C10 alkoxy, C-C 1 o-alkyl, C3-Cl 0 -cycloalkyl, C3-C1o-heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5
-C
10 -aryl and Cs-C 10 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S, 20 where the substituents are selected from the group consisting of: F, CI, Br, OH, CN, NH 2 and C 1
-C
10 -alkyl; and 25 M is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum, for the homogeneously catalyzed preparation of alkanolamines which have a primary 30 amino group (-NH 2 ) and a hydroxyl group (-OH) by alcohol amination of diols having two hydroxyl groups (-OH) by means of ammonia, where the definitions and preferences described above for the process of the invention apply to the catalyst of the general formula (XV). 35 The present invention further provides for the use of a complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand of the general formula (XXI), EK11-1973PC 33 P-Y-A--Y2_P R22 r - i R24 R25 R26 n (XXI) where n isOor; 5
R,
21
R,
22
R
23 , R 24 , R 2 5 , R 2 6 are each, independently of one another, unsubstituted or at least monosubstituted C-C 1 o-alkyl, C1-C4 alkyldiphenylphosphine (-C-C 4 -alkyl-P(phenyl) 2 ), C 3
-C
1 o-cycloalkyl, C3-C10 heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5
-C
14 -aryl or C-C1 0 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C-Clo-alkyl; A is i) a bridging group selected from the group consisting of unsubstituted or at least monosubstituted N, 0, P, C-C 6 -alkane, C 3
-C
10 -cycloalkane, 20 C 3 -Clo-heterocycloalkane comprising at least one heteroatom selected from among N, 0 and S, C 5
-C
14 -aromatic and C 5 -C-heteroaromatic comprising at least one heteroatom selected from among N, 0 and S, where the substituents are selected from the group consisting of: 25 C-C 4 -alkyl, phenyl, F, Cl, Br, OH, OR 27 , NH 2 , NHR 2 1 or N(R1)2, where R 27 is selected from among C-Clo-alkyl and C 5
-C
10 -aryl; or 30 ii) a bridging group of the formula (XXII) and (XXIII): EK11-1973PC 34 (R21)m
(R
29 )q (R 28 ) X13 (R29) x-- x 12 (XXII) (XXIII) 5 m, q are each, independently of one another, 0, 1, 2, 3 or 4;
R
28 , R 29 are selected independently from the group consisting of C-Clo alkyl, F, Cl, Br, OH, OR 2 7 , NH 2 , NHR 27 and N(R 27
)
2 , de where R 27 is selected from among C 1 -0o-alkyl and C 5
-C
10 -aryl;
X
1 ", X1 2 are each, independently of one another, NH, 0 or S; X1 is a bond, NH, NR 30 , 0, S or CR 1
R
32
R
30 is unsubstituted or at least monosubstituted C-C 1 o-alkyl,
C
3
-C
10 -cycloalkyl, 03-Cl-heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5
-C
14 -aryl or
C
5
-C
10 -heteroaryl comprising at least one heteroatom selected 20 from among N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1
-C
1 o-alkyl; 5 R, 31
R
32 are each, independently of one another, unsubstituted or at least monosubstituted C 1
-C
1 o-alkyl, C-C 1 -alkoxy, C-C1o cycloalkyl, C 3 -C1 0 -cycloalkoxy, 3-Cl 0 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, Cs-C14 aryl, C 5
-C
14 -aryloxy or C 5
-C
1 0 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and Ci-Co-alkyl; EK11-1973PC 35 Y', Y 2 , Y 3 are each, independently of one another, a bond, unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, 5 where the substituents are selected from the group consisting of: F, Cl, Br, OH, OR 27 , CN, NH 2 , NHR 27 , N(R 27
)
2 and C 1
-C
1 o-alkyl, where R 27 is selected from among C-C 1 o-alkyl and C 5 -C1 0 -aryl, 10 for the homogeneously catalyzed preparation of alkanolamines which have a primary amino group and a hydroxyl group by alcohol amination of diols having two hydroxyl groups (-OH) by means of ammonia. The definitions and preferences described for the process of the invention apply to the 15 use of the complex catalyst of the formula (XXI) for the homogeneously catalyzed preparation of alkanolamines which have a primary amino group (-NH 2 ) and a hydroxyl group (-OH) by alcohol amination of diols having two hydroxyl groups (-OH) by means of ammonia. 20 The invention is illustrated by the following examples without being restricted thereto. Example General method for the catalytic amination of alcohols by means of ammonia according 25 to the invention Ligand L, metal salt M or catalyst complex XIVb (for preparation, see below, weighed out under an inert atmosphere), solvent and the alcohol to be reacted were placed under an Ar atmosphere in a 160 ml Parr autoclave (stainless steel V4A) having a 30 magnetically coupled inclined blade stirrer (stirring speed: 200-500 revolutions/minute). The indicated amount of ammonia was introduced at room temperature either in precondensed form or directly from the pressurized NH 3 gas bottle. If hydrogen was used, this was effected by iterative differential pressure metering. The steel autoclave was electrically heated to the temperature indicated and heated for the time indicated 35 while stirring (500 revolutions/minute) (internal temperature measurement). After cooling to room temperature, venting the autoclave and outgassing the ammonia at atmospheric pressure, the reaction mixture was analyzed by GC (30m RTX5 amine 0.32 mm 1.5 pm). The results for the amination of 1,4-butanediol (tables 1 a, 1b and 2), diethylene glycol (tables 3a, 3b and 4), monoethylene glycol (table 5) and EK1-1973PC 36 diethanolamine (table 6), 1,5-pentanediol, 1,9-nonanediol, 1,6-hexanediol and 1,10 decanediol (table 7) and 2,5-(dimethanol)-furan (table 8) are given below. Synthesis of the catalyst complex XIVb Br PCy 2 / HPCy 2 [RuHCI(CO)(PPh 3
)
3 ] \- N N - N CQ CI J MeOH Toluene Br PCy 2 CO 5 XIVb a) Synthesis of 4,5-bis(dicyclohexylphosphinomethyl)acridine A solution of 4,5-bis(bromomethyl)acridine (5.2 g, 14.2 mmol) and 10 dicyclohexylphosphine (8.18 g, 36.8 mmol) in 65 ml of anhydrous, degassed methanol was heated at 500C under an inert argon atmosphere for 66 hours. After cooling to room temperature, triethylamine (5.72 g, 56.7 mmol) was added and the mixture was stirred for 1 hour. Evaporation of the solvent gave a whitish yellow solid in a red oil. Extraction by means of 3 x 40 ml of MTBE and concentration of the filtrate gave a 15 reddish brown oil ( 1 H NMR: mixture of product & HPCy 2 ). Taking up in a little warm MTBE followed by addition of ice-cooled methanol resulted in precipitation of a yellow, microcrystalline solid. Oscillation and drying under reduced pressure gave air sensitive 4,5-bis(dicyclohexylphosphinomethyl)acridine (2.74 g, 33%) as a yellow powder. 'H NMR (360.63 MHz, d8-toluene): 6 [ppm] = 8.07 (s, 1H, H9), 7.91 (d, J = 8.3 Hz, 2H, 20 Ar-H), 7.42 (d, J = 8.3 Hz, 2H, Ar-H), 7.21 (dd, J = 8.3 Hz, J = 7.2 Hz, 2H, Ar-H), 3.89 (bs, 4H, -CH 2 -P), 1.96-1.85 (m, 8H, Cy-H), 1.77-1.54 (m, 20H, Cy-H), 1.26-1.07 (m, 16H, Cy--H). 3 1P{ 1 H} NMR (145.98 MHz, d8-toluene): 6 [ppm] = 2.49 (s, -CH 2 -P(Cy) 2 ). b) Synthesis of the catalyst complex XIVb 25 4,5-bis(dicyclohexylphosphinomethyl)acridine (1855 mg, 3.1 mmol) and [RuHCI(CO)(PPh) 3
]
2 (2678 mg, 2.81 mmol) were heated at 70*C in 80 ml of degassed toluene for 2 hours. The resulting dark brown solution was evaporated to dryness, the residue was slurried in 3 x 20 ml of hexane and isolated by filtration. Drying under 30 reduced pressure gave Ru-PNP Pincer complex XIVb (1603 mg, 75%) as an orange brown powder. 1 H NMR (360.63 MHz, d8-toluene): 6 [ppm] = 8.06 (s, 1H, H9), 7.43 (d, J = 7.6 Hz, 2H, Ar-H), 7.33 (d, J = 6.5 Hz, 2H, Ar-H), 7.06-7.02 (m, 2H, Ar-H), 5.02 (d, J = 11.9 Hz, 2H, -CHH-PCy 2 ), 3.54 (d, J = 12.2 Hz, 2H, -CHH-PCy 2 ), 2.87 (bs, 2H, EK11-1973PC 37 -P(CaH(CH 2
)
5
)
2 ), 2.54 (bs, 2H, -P(CbH(CH 2 )s) 2 ), 2.18 (bs, 2H, Cy-H), 1.88-1.85 (m, 8H, Cy-H), 1.65 (bs, 6H, Cy-H), 1.42-1.35 (m, 14H, Cy-H), 1.17-0.82 (m, 12H, Cy-H), -16.29 (t, J = 19.1 Hz, 1H, Ru-H). "P{ 1 H} NMR (145.98 MHz, d8-toluene): J [ppm] = 60.89 (s, -CH 2 -P(Cy) 2 ). 5 [1] J. Chiron, J.P. Galy, Synlett, 2003, 15, 2349-2350. [2] Literature instructions: Inorganic Syntheses 1974, 15, 48. See also: T. Joseph, S. S. Deshpande, S. B. Halligudi, A. Vinu, S. Ernst, M. Hartmann, J. Mol Cat. (A) 2003, 206, 13-21. 10 Ligand name CAS IUPAC Triphos 22031-12-5 1,1,1-tris(diphenylphosphinomethyl)ethane Xantphos 161265-03-8 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene Rhodaphos 22031-14-7 1,1,1-tris(diethylposphinomethyl)ethane DPPEPP 23582-02-7 bis(2-diphenylphosphinoethyl)phenylphosphine Tetraphos 23582-03-8 tris[2-(diphenylphosphino)ethyl]phosphine dppb 7688-25-7 1,4-Bis(diethylphospino)butane EKII-1973PC U ( D Q o . .(0 C) 0 0 UL 6 C6 co n o 030 U CD CD wl 0 0 0 =g a +U a - o (a z_ -0 -L C L.- 0 Cj CN~' 0 666 6 66 C -T o' -- - - n U U) 0 03 U) z) CL 60 2Ow 0 00 > O w ( : z r~o (0- c C 0 t co On r (0 CU2- CE, - o.. C '0 2 . C 0 -- o a o 0 / (.
--- o 0 000 > CL - a. O 45 -D o c fnL0 0 c .- . a.on a a >~ co U)0 U* (D 0 . - C- L . -LU c 00 o .2 C-4 t = - Cu C I 0 - uO CL -oo o ca e n OE c b a = C0 0 Z-. to - E r EI C C O . .* E cc DCZ d/) 1C o C0 _ L - -) X N x Fu uo . 0 N o) o N N No o 0 E o2M d Eo N o o N C Cc c co z' ro D -5o + O O z -a .2 .0 E -N o _ o ''D + o o o o c 2:1it + - * -'>, a o o 6 LO LO L L E O .o W T o - - - -r 'T- -r -- - - w o
-
CUI - c2 c U)e o n) E 00 N 60 0 z a oc oc Mco m o D C* C) U C r- ) .0 z LO LOU Lo to n 'n m LO a .20 o t D 0C C 0 JUKU > C Z D 0 0 E- Z D aN) a C0) a)0 U) a. n =U o 6 O Cfl ) C'6 0 U U) C .. co a) C') r C EL - D . . - - - - " > -( c c. C Nro d) E o .2 C og o i o N C') >% O I -- X -- W U) Co" Z 0 CL S c 0 > m C a) .C a) + ZE 666660 E0 c = E n cn oa w 03Y S 0 0 0 _0 D. D_ 0._ >'.. N C O a. _ + i3 I, CCz +m m) rn - C -/-- - - - - .- - -- o w 0k SE 0 4)WA E N = o f E C o --- - -- 2 a) E- C a) a) (D ) <' c r-OaOC C U) c-------- o a) ) 6) (D ) a to m O~L o oo -o o oo o) o o o i- - |- - 1- *0 o E r- e to e O o o .2 r, D Ca 4-.... -, *to. c9 a 0 + U) ' -,c * 0 N 4N Cc E2E c;o o 0 - -c 0g +~ -, I . 0 zO o> 2E o >0 za z *. <z 0) -- 45v > CO -o - FN N o z r - C -Lco -- c ii0 c E 4-O O ,_ C /E /N CCJ - 0 - - 32 ..- s o co|- tNo oco 1d z2 - %JC Z r CD -0 0 C o 0q ( 0 V) Li
LO
LO r 7l L(? O " Ci CL C6 o LO C) - .a co 'K <o N C% N r - N 00C 0 a ) co L cc) (6 cc ,j r: cc Co LA 06 " O ilOsLA(0c 0 -> 0 2 ) r Nmw &C0mt r z - 0. EE + (3 U2*C V O O C ( N( C L N C z 0 CO O - - - - - - - -a 4 + c 5 EC CO tC4L 00 C L L + 16. . d 4 N E LL 1 1u L IN - O l I00ILO1 .2 (n CL Ce)Ce) M M t o m e , .Z (eo (D (D T M L (C) c C . c c c c c cN- c c c c -- a 0 o - r 1- r- | r- (- (- r '- - r- 1- c . o -2: 0 -) a). z - ro r- r r r- r r r r r r c C C ~ ~ ( I-- OW 0))0(1 CL C)S )0)WnSO a)r -~6 tN CO ItLO ( co Z -N COn:V)(0ON-C0)r F- - . . . . . . . . . . .
Nt - N C a C v R 0-I XM CL 0 o a 0c 0> on >u 0 -o .0 0C-, u , EE o C In '0
EN
C( cca CU W> U) > a 0 o o o a CL CL -0 : oILI CL~ en -0 cp 0 U) U) (p U) M> .0~~~ (Dor ujj )1%) rC*M DCDOC1-JO o CDLr~CCD a > C
I.
E Ev Lo Q o L.,N0" co :3 0 U%(2 l)( C> z 0 m LO 0 It Nt c C)o Z) + rx E 0 o 0 O0 zo E E. CD CO -I-D CD C: z z o o' Eo U) 0 Un 0)0 / LLO ) rn 0 6 o c -: 0 0 a) ( ) a D ( C a) E _0VOL. Ao IF F-IF-C n M 0 0~ E~C. Eo oS - C3 o. F- 0 O- M O DM LiO C)CVVUr T )C0D C) C - o C o Co Co co Co Co t C 0 0 0 W W Lo M M - E o o 5' oo66i :c vicr 0nn e o- - c :2 >x o o O e ( 0 OD o o0Nr C) -q - r. t 0 0 N 0 U' T M Vo "; M C" T IT L O N N1 E E z z 1 a ~o C * 0 0> a)C E x > cao + c r- o L U O w T N VD oU C 'U m Lo LO to C> M m (2 z + E gn E N . L3 W 3: C'4 + r. N 0) 0 M o zz -On }E E E a~ > .2 z co lq E LO It t I CL~ E q Nr ;r t- o n z Oc Z=c E zo m __ --- - - - - . - .- . - ) - D - - D - c-o .o (q (D mC 0( ( :3 .- E 19 C4 CI 04 cq CN cq 10 a)o ocz -a - o) o oro I",C CO -a O ". OooiO E | z r N COO to 0 oE I~~~~~ Z N ot fl 0 C )r (D C 0.U Z= -MM2 M M 4 aL 0000 F'- 0 NT C1 RT 0 4 '~ o Cl~~~~~ O I cqC C- )
--
- -- -) m 0 2 vi cdcv 6u L6 cd'; i -3 >1m 0 CD 0 C) . 0 0aO) 02e to 6u co 66t a o ca, --.. ac U) E '~ '~ '~ 1 000 0 000 0 0 0 o ooo666666 0 oL CD .-. W 2 .a c . CL a .2 " o -F- c a- a ' o o. 1, o1oHoOo H Ho t e 0) - 0 c 0 C -C - -------.. S- -' -n '- n '-r N c 3 o M m c c M ccc .0 = r- f _C r_ = . m CL C C C C I c C) Q C) C C) d)C) 0 > 0a a0. 0 .. O o o o o o -+ - - - - w -d D Caa I o -E Nu _u z m z > 0 x W ro 0 I oD o ) 0 o o t , a, -5 ,a - - O 5 5e s e . Oz < r E0 E M EE c EE 0LA 0 aC J J54 N r N rL z LO D U) U) ,) LA l LO LA -- o L LO L ' LA LA L 0 Oo e - Sw = c )c c DCe c 4) C_ r_ Cu Cu u S+' m m w w w w CD > 2.s xx x x a cc C 0 < ( a a a, CL a vL 0 m- c aU rre rL e rr o - E 0 .0 r 0 0 H~~ r' eLV L -( ) -- - - - - - - oI o e O o * EO C'J ED = 04 o) e d o> a > * r N 0 () 0 "t 0 a)a o
M
a o -'I 0 00 (Da aj-0 a oo E S- o_ .c 0 0 ) (0 U - .2 O ) 0 .> ii 0 u. .o M -r > a W 0U 075 Fo~t N .c r= -- -E co~ .c o m ca o <a r_ - 9 ' ~ .0 .- co E 0- 0 cz o .N 0 D (L) . IE -- 0 ---- 0 E U co N LC 2 o c c0 .r. 0- -0 c -) - - - - o - o Lo

Claims (11)

  1. 2. The process according to claim 1, wherein the complex catalyst is a catalyst of the formula (1): Xi X ~R1 R2 N I L' L2 L3 15 (I where L' and L 2 are each, independently of one another, PR"Rb, NR"Rb, sulfide, SH, S(=O)R, C 5 -C 1 o-heteroaryl comprising at least one heteroatom 20 selected from among N, 0 and S, AsRaRb, SbR"R' and N heterocyclic carbenes of the formula (II) or (III): RR 3 4R4 _N N-R 5 -N N-R (li) (iII 25 L is a monodentate two-electron donor selected from the group consisting of CO, PRRbR', NO*, AsRaRRC, SbRaRRC, SRRb, RCN, RNC, N 2 , PF 3 , CS, pyridine, thiophene, tetrahydrothiophene and N-heterocyclic carbenes of the formula (II) or (Ill); EK11-1973PC 50 R' and R 2 are both hydrogen or together with the carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl unit of the formula (1) forms an acridinyl unit; 5 R, Ra, Rb, Rc, R 3 , R 4 and R 5 are each, independently of one another, unsubstituted or at least monosubstituted C-C, 0 -alkyl, C3-C10 cycloalkyl, C 3 -C 1 o-heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5 -Co-aryl or C 5 -C 1 o-heteroaryl comprising at least one heteroatom selected from among N, 0 and 10 S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C-C 1 o-alkyl; 15 Y is a monoanionic ligand selected from the group consisting of H, F, Cl, Br, I, OCOR, OCOCF 3 , OSO 2 R, OSO 2 CF 3 , CN, OH, OR and N(R) 2 or an uncharged molecule selected from the group consisting of NH 3 , N(R) 3 and R 2 NSO 2 R; 20 X1 represents one, two, three, four, five, six or seven substituents on one or more atoms of the acridinyl unit or one, two, three, four or five substituents on one or more atoms of the quinolinyl unit, where the radicals X 1 are selected independently from the group 25 consisting of hydrogen, F, Cl, Br, I, OH, NH 2 , NO 2 , -NC(O)R, C(O)NR 2 , -OC(O)R, -C(O)OR, CN and borane derivatives which can be obtained from the catalyst of the formula (I) by reaction with NaBH 4 and unsubstituted or at least monosubstituted CrC-10 alkoxy, C-C 1 o-alkyl, C3-C 10 -cycloalkyl, C 3 -C 10 -heterocyclyl 30 comprising at least one heteroatom selected from among N, 0 and S, C 5 -C 10 -aryl and C 5 -C 10 -heteroaryl comprising at least one heteroatom selected from among N, 0 and S, where the substitutents are selected from the group consisting of: 35 F, Cl, Br, OH, CN, NH 2 and C 1 -Oo-alkyl; and M is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, 40 iridium or platinum. EK11-1973PC 51
  2. 3. The process according to claim 1 or 2, wherein R 1 and R 2 are both hydrogen and the complex catalyst is a catalyst of the formula (IV): xi N H L3 5 (IV) and X 1 , L 1 , L 2 L 3 and Y are as defined in claim 2.
  3. 4. The process according to claim 1 or 2, wherein R and R 2 together with the carbon atoms to which they are bound form a phenyl ring which together with the 10 quinolinyl units of the formula (I) forms an acridinyl unit and the complex catalyst is a catalyst of the formula (V): X1 N H L M L (v) 15 and X 1 , L 1 , L 2 , L 3 and Y are as defined in claim 2.
  4. 5. The process according to claim 1 or 2, wherein the complex catalyst is selected from the group of catalysts of the formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII): EK11-1973PC 52 x1 x N Ntt N /H H RRa Ra R a MRa Y Rb (VI) (VII) x x XKX1 N /H N Rb MRN / R McN (XII) (IX) x1 x N N Ra/HRa H Ra N f RaN M Rb CR Rb OC RD (Xil) (XI) NN H H Rbcc(XI)a 'I/ Ra Y Rb (XI) and X R1, Rb and Yare as defined in claim 2. EK1 1-1 973PC 53
  5. 6. The process according to claim 1 or 2, wherein the complex catalyst is a catalyst of the formula (XIVa): 5 P P Cl (XIV)
  6. 7. The process according to claim 1 or 2, wherein the complex catalyst is a catalyst of the formula (XIVb): 10 N Pj/P c (XIVb)
  7. 8. The process according to claim 1, wherein the complex catalyst is a catalyst of the formula (XV): 15 H H X1 R' H H N H L L2 H (XV) where EK11-1973PC 54 L' and L 2 are each, independently of one another, PRRb, NR8Rb, sulfide, SH, S(=O)R, C 5 -Clo-heteroaryl comprising at least one heteroatom selected from among N, 0 and S, AsRRb, SbRaR or 5 N-heterocyclic carbenes of the formula (11) or (111): R R4 R RP -N N-R 5 -N N-R (11) (il1) L3 is a monodentate two-electron donor selected from the group 10 consisting of CO, PRR RC, NO*, AsR"R Rc, SbRR'R, SRBRb, RCN, RNC, N 2 , PF 3 , CS, pyridine, thiophene, tetrahydrothiophene and N-heterocyclic carbenes of the formula (II) or (111); R 1 and R 2 are both hydrogen or together with the carbon atoms to which they 15 are bound form a phenyl ring which together with the quinolinyl unit of the formula (1) forms an acridinyl unit; R, R 2 , Rb, RC, R 3 , R 4 and R5 are each, independently of one another, unsubstituted or at least monosubstituted C-Clo-alkyl, C 3 -C 10 20 cycloalkyl, C 3 -C 10 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5 -C 10 -aryl or C 5 -Clo-heteroaryl comprising at least one heteroatom selected from among N, 0 and S, 25 where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C-C 1 o-alkyl; Y is a monoanionic ligand selected from the group consisting of H, F, Cl, Br, I, OCOR, OCOCF 3 , OSO 2 R, OSO 2 CF 3 , CN, OH, OR and 30 N(R) 2 or uncharged molecules selected from the group consisting of NH 3 , N(R) 3 and R 2 NSO 2 R; X' represents one, two, three, four, five, six or seven substituents on one or more atoms of the acridinyl unit or one, two, three, four or 35 five substituents on one or more atoms of the quinolinyl unit, EK11-1973PC 55 where the radicals X' are selected independently from the group consisting of hydrogen, F, Cl, Br, I, OH, NH 2 , NO 2 , -NC(O)R, C(O)NR 2 , -OC(O)R, -C(O)OR, CN and borane derivatives which 5 can be obtained from the catalyst of the formula (1) by reaction with NaBH 4 and unsubstituted or at least monosubstituted -Ca alkoxy, C-C 1 o-alkyl, C-C1o-cycloalkyl, C 3 -Clo-heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5 -C 1 o-aryl and C 5 -C 10 -heteroaryl comprising at least one 10 heteroatom selected from among N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C-C 1 0 -alkyl; 15 and M is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum. 20 9. The process according to either claim 1 or 8, wherein the complex catalyst is a catalyst of the formula (XVI): H H XX N QCH (xvi H (XVI) 25 10. The process according to any of claims 1 to 5, wherein Y in the complex catalyst is selected from among F, CI and Br.
  8. 11. The process according to any of claims 1 to 10, wherein L 3 in the complex catalyst is CO. 30
  9. 12. The process according to claim 1, wherein the alcohol amination is carried out in the presence of at least one complex catalyst comprising at least one element EK11-1973PC 56 selected from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand of the general formula (XXI), R 21 R23 P--Y'-A-Y2p R22 R24 Y3 R25 R 26 n (XXI) 5 where n is0or1, 10 R, 21 R 22 , R 23 , R 24 , R 25 , R 2 6 are each, independently of one another, unsubstituted or at least monosubstituted C-C 1 o-alkyl, Cj-C4 alkyldiphenylphosphine (-C 1 -C 4 -alkyl-P(phenyl) 2 ), C 3 -C1 0 -cycloalkyl, C3-C1 heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5 -C 14 -aryl or C 5 -C 10 -heteroaryl comprising at least one heteroatom 15 selected from among N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1 -0 1 o-alkyl; 20 A is i) a bridging group selected from the group consisting of unsubstituted or at least monosubstituted N, 0, P, C-C 6 -alkane, C 3 -C 10 -cycloalkane, C3rCo-heterocycloalkane comprising at least one heteroatom selected from among N, 0 and S, C 5 -C 14 -aromatic and C 5 -C 6 -heteroaromatic comprising 25 at least one heteroatom selected from among N, 0 and S, where the substituents are selected from the group consisting of: C-C 4 -alkyl, phenyl, F, Cl, Br, OH, OR 27 , NH 2 , NHR 27 and N(R 27 ) 2 , 30 where R 27 is selected from among C-Clo-alkyl and Cs-Clo-aryl; EK11-1973PC 57 or ii) a bridging group of the formula (XXII) or (XXIII): 5 (R 2 ),,\ (R 2 )q (R2) x13 (R 2 ), x11 X 12 (XXII) (XXIII) m, q are each, independently of one another, 0, 1, 2, 3 or 4, 10 R 28 , R 29 are selected independently from the group consisting of CIC1o alkyl, F, Cl, Br, OH, OR 2 7 , NH 2 , NHR 27 and N(R 27 ) 2 , where R 27 is selected from among C-C 1 o-alkyl and C 5 -C 10 -aryl; 15 X' 1 , x 2 are each, independently of one another, NH, 0 or S, x 3 is a bond, NH, NR 30 , 0, S or CR 3 R 32 ; R30 is unsubstituted or at least monosubstituted C-C 1 o-alkyl, 20 C 3 -C 10 -cycloalkyl, C 3 -C 10 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C 5 -C 14 -aryl or C 5 -C 1 o-heteroaryl comprising at least one heteroatom selected from among N, 0 and S, 25 where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1 -C 1 o-alkyl; R, 31 R 32 are each, independently of one another, unsubstituted or at least monosubstituted C-C 1 o-alkyl, C-C 10 -alkoxy, C3-C10 30 cycloalkyl, C3-C1o-cycloalkoxy, C 3 -C 10 -heterocyclyl comprising at least one heteroatom selected from among N, 0 and S, C5 C 1 4 -aryl, C 5 -C 14 -aryloxy or C 5 -C 1 o-heteroaryl comprising at least one heteroatom selected from among N, 0 and S, EK11-1973PC 58 where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C-C 1 o-alkyl; Y', Y 2 , Y 3 are each, independently of one another, a bond, unsubstituted or at 5 least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, where the substituents are selected from the group consisting of: F, Cl, Br, OH, OR 27 , CN, NH 2 , NHR 27 , N(R 27 ) 2 and C 1 -C, 0 -alkyl, 10 where R 27 is selected from among C 1 -0o-alkyl and C 5 -C 1 o-aryl.
  10. 13. The process according to any of claims I to 11, wherein the diol has two functional groups of the formula (-CH 2 -OH). 15
  11. 14. The process according to any of claims 1 to 13, wherein the preparation of the alcoholamines is carried out at a temperature of from 110 to 160*C and a pressure of from 1 to 15 MPa. 20 15. The use of a complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one phosphorus donor ligand for the homogeneously catalyzed preparation of alkanolamines which have a primary amino group (-NH 2 ) and a hydroxyl group (-OH) by alcohol amination of diols having two hydroxyl groups (-OH) by means of ammonia. EK11-1973PC
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CN109678732B (en) * 2019-02-14 2022-04-08 中国科学院兰州化学物理研究所 Method for continuously producing 5-amino-1-pentanol
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