CA2828330A1 - Process for the preparation of primary amines by homogeneously catalyzed alcohol amination - Google Patents

Abstract

The invention relates to a method for producing primary amines by means of the alcohol amination of alcohols with ammonia, with water being eliminated. The method comprises the steps of: (a) a homogenously-catalysed reaction of a reaction mixture which contains at least one alcohol, ammonia, at least one non-polar solvent, and at least one catalyst containing at least one element selected from groups 8, 9 and 10 of the periodic table in the liquid phase, a product mixture (P) thus being obtained; (b) separating the phases of product mixture (P) which was obtained in step (a), if necessary after a reduction in temperature, a reduction in pressure and/or the addition of at least one polar solvent with a miscibility gap in relation to the non-polar solvent, and thus obtaining at least one polar product phase (A) and at least one non-polar phase (B) containing at least one portion of the catalyst that was introduced, with said non-polar phase (B) being separated off, (c) returning at least one portion of the non-polar phase (B) into the reaction in step (a), and (d) separating the amination product from the polar product phase (A). The non-polar solvent introduced in (a) and the catalyst introduced in step (a) are selected such that the catalyst in the non-polar phase (B) becomes enriched.

Description

PF0000071687/MKr CA 02828330 2013-08-27 As originally filed Process for the preparation of primary amines by homogeneously catalyzed alcohol amination The present invention relates to a process for the preparation of primary amines by homogeneously catalyzed alcohol amination of alcohols and alkanolamines with ammonia with the 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 of the Elements and at least one nonpolar solvent.
Primary amines are compounds which have at least one primary amino group (-NH2).
Primary diamines have two primary amino groups. Primary triamines have three primary amino groups. Primary polyamines have more than three primary amino groups.
Primary amines are valuable products with a large number of different uses, for example as solvents, stabilizers, for the synthesis of chelating agents, as starting materials for producing synthetic resins, inhibitors, interface-active substances, intermediates in the manufacture of fuel additives (US 3,275,554 A, DE 2125039 A
and DE 36 11 230 A), surfactants, drugs and crop protection agents, hardeners for epoxy resins, catalysts for polyurethanes, intermediates for producing quaternary ammonium compounds, plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile auxiliaries, dyes, vulcanization accelerators and/or emulsifiers.
Primary diamines and triamines are valuable products with a large number of different uses, for example as solvents, stabilizers, for the synthesis of chelating agents, as starting materials for producing synthetic resins, drugs, inhibitors, corrosion protectants, polyurethanes, as hardeners for epoxy resins, and interface-active substances.
Primary diamines and triamines are currently prepared by heterogeneously catalyzed alcohol amination of primary diols and triols with ammonia. WO 2008/006752 Al describes a process for the preparation of amines by reacting primary or secondary alcohols with ammonia in the presence of a heterogeneous catalyst which comprises zirconium dioxide and nickel. WO 03/051508 Al relates to a process for the amination of alcohols using specific heterogeneous Cu/Ni/Zr/Sn catalysts. EP 0 696 572 Al discloses nickel-, copper-, zirconium- and molybdenum oxide-comprising heterogeneous catalysts for the amination of alcohols with ammonia and hydrogen.
According to the documents cited above, the reactions are carried out at temperatures in the range from 150 to 210 C and ammonia pressures in the range from 30 to PF0000071687/MKr CA 02828330 2013-08-27 200 bar. However, in the case of the heterogeneously catalyzed processes described in the above documents, the often undesired monoamination products and cyclic amines such as piperazines, pyrrolidines and morpholines are formed as main products. The desired primary diamines are obtained only in extremely low yields, if at all, in the processes described above. The documents cited above describe in particular the reaction of diethylene glycol with ammonia.

o/
NH

In this process, monoaminodiethylene glycol and morpholine are obtained as main products. The desired diaminated diaminodiethylene glycol is obtained only in extremely low yields, if at all, in the amination reactions of the documents specified above.
The highest yield of diaminodiethylene glycol, at 5%, is obtained according to WO 03/051508 A1, with the formation of 22% morpholine and 36% monoamino-diethylene glycol as by-products.
During the amination of diethanolamine with ammonia, piperazine is obtained as the main product. Here too, the desired linear diamination product diethylenetriamine is only produced in traces if high diethanolamine conversions are operated.

HN NH/
1-1(3.NOH

In the case of the reaction of polyetherols to give polyetheramines, with the processes described above, undesired secondary reactions to give the dimeric secondary amine or polymeric coupling product are observed to a high degree on account of the harsh reaction conditions prevailing during the heterogeneously catalyzed amination, as is illustrated below with reference to diethylene glycol. These by-products are difficult to separate off from the desired primary diamination product.

PF0000071687/MKr CA 02828330 2013-08-27 -1(20 A further problem which is observed during the amination of polyetherols, especially in the case of polyethylene and polypropylene glycol derivatives, is the decomposition of these ethers under the reaction conditions described above since, in particular, the high temperatures and a hydrogen support pressure are required. Under these reaction conditions, gaseous decomposition products are formed which make special safety precautions necessary.
Another disadvantage in the heterogeneous catalysis of the amination of alcohols with ammonia is the high pressures required therefor.
The homogeneously catalyzed amination of alcohols has been known since the 1970s where, in most cases, ruthenium or iridium catalysts are described. Compared with heterogeneously catalyzed reactions, the homogeneously catalyzed amination proceeds at significantly lower temperatures of from 100 to 150 C. The reaction of monoalcohols with primary and secondary amines is described, for example, in the following publications: US 3,708,539; Y. Watanabe, Y. Tsuji, Y. Ohsugi, Tetrahedron Lett. 1981, 22, 2667-2670; S. Bahn, S. Imm, K. Mevius, L. Neubert, A. Tillack, J. M. J.
Williams, M. Beller, Chem. Eur. J. 2010, 001: 10.1002/chem.200903144; A.
Tillack, D.
Hollmann, D. Michalik, M. Beller, Tetrahedron Lett. 2006, 47, 8881-8885; D.
Hollmann, S. Bahn, A. Tillack, M. Beller, Angew. Chem. Int. Ed. 2007, 46, 8291-8294; A.
Tillack, D. Hollmann, K. Mevius, D. Michalik, S. Bahn, M. Beller, Eur. J. Org. Chem.
2008, 4745-4750; 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, 1766-1774; 0.
Saidi, A. J. Blacker, M. M. Farah, S. P. Marsden, J. M. J. Williams, Chem. Commun.
2010, 46, 1541-1543; EP 239943; N. Andrushko, V. Andrushko, P. Roose, K. Moonen, A.
Borner, ChemCatChem, 2010, 2, 640-643; K. I. Fujita, R. Yamaguchi, Synlett, 2005, 4, 560-571; A. Tillack, D. Hollmann, D. Michalik, M. Beller, Tet. Lett. 2006, 47, 8881-8885;
A. Del Zlotto, W. Baratta, M. Sandri, G. Verardo, P. Rigo, Eur. J. Org. Chem.
2004, 524-529; A. Fujita, Z. Li, N. Ozeki, R. Yamaguchi, Tetrahedron Lett. 2003, 44, 2690; Y. Watanabe, Y. Morisaki, T. Kondo, T. Mitsudo J. Org. Chem. 1996, 61, 4218, B. Blank, M. Madalska, R. Kempe, Adv. Synth. Catal. 2008, 350, 749-750, A.
Martinez-Asencio, D. J. Ramon, M. Yus, Tetrahedron Lett. 2010, 51, 325-327.
The greatest disadvantage of the systems described above is that with these processes only the amination of alcohols with primary and secondary amines is possible.
The PF0000071687/MKr CA 02828330 2013-08-27 reaction of alcohols with ammonia to give primary amines, which is the economically most attractive amination reaction, is not described in these works. Neither is any reference made to an efficient recycling of the precious metal catalysts.
The homogeneously catalyzed amination of alcohols with ammonia is only described in a few works. S. Imm, S. Bahn, L. Neubert, H. Neumann, M. Beller, Angew. Chem.
2010, 122, 8303-8306 and D. Pingen, C. Muller, D. Vogt, Angew. Chem. 2010, 122, 8307-8310 disclose the amination of secondary alcohols such as cyclohexanol with ammonia homogeneously catalyzed with ruthenium catalysts. However, using the systems disclosed therein, it is only possible to aminate secondary alcohols with ammonia. The amination of diols and triols is not described in these works.
WO 201 0/01 8570 and C. Gunanathan, D. Milstein, Angew. Chem. mt. Ed. 2008, 47, 8661-8664 discloses the amination of primary alcohols with ammonia to give primary monoamines with the help of ruthenium-phosphane complexes. For the amination, specific, acridine-based pincer ligands are used. The reaction is carried out at temperatures of from 110 to 180 C and NH3 pressures of up to 7.5 bar. Under these conditions, when using primary alcohols, the by-products that are formed are primarily the corresponding imines and dialkylamines. The formation of dialkylamines is especially disadvantageous during the amination of diols since, under these conditions, the cyclic amines are able to form, which likewise fall within the group of secondary amines. The amination of diols and triols with ammonia is not described.
R. Kawahara, K.I. Fujita, R. Yamaguchi, J. Am. Chem. Soc. DOI:
10.1021/ja107274w describes the amination of primary monoalcohols and triols with ammonia using an iridium catalyst which has, as ligand, Cp* (1,2,3,4,5-pentamethylcyclopentadienyl) and ammonia. However, using the catalyst system described therein, when reacting primary monoalcohols with ammonia, the undesired tertiary amines are exclusively obtained. The reaction of glycerol with ammonia leads exclusively to the undesired bicyclic quinolizidine.
EP 0 234 401 Al describes the reaction of diethylene glycol with ammonia in the presence of a ruthenium carbonyl compound. In the process described in EP 0 234 401 Al, only the monoamination product (monoethanolamine), the secondary and tertiary amines (di- and triethanolamine) and cyclic products (N-(hydroxyethyl)piperazine and N,N'-bis(hydroxyethyl)piperazine) are formed. The desired 1,2-diaminoethane is not obtained in this process.
All of the processes described above for the reaction of alcohols with ammonia have the disadvantage that the desired primary amines are not formed as the main products.
Moreover, no concepts for recycling the expensive precious metal catalysts are PF0000071687/MKr CA 02828330 2013-08-27 described, although this is required for an industrial transfer of these processes for reasons of cost.
It is an object of the present invention to provide a process for the preparation of 5 primary amines by alcohol amination of mono-, di-, tri- and polyols, and also of alkanolamines with the favorable aminating agent ammonia, in which the catalyst used can be separated off and reused. The reaction should proceed under milder conditions and produce higher selectivities with regard to the formation of primary amines than the established, heterogeneously catalytic reactions. In particular, the selectivity in the preparation of linear primary amines, and also the selectivity in the preparation of di-, tri- and polyamines should be improved.
According to the invention, this object is achieved by the following process for the preparation of primary amines by alcohol amination of alcohols with ammonia with the elimination of water, comprising the steps (a) homogeneously catalyzed reaction of a reaction mixture comprising at least one alcohol, ammonia, at least one nonpolar solvent and at least one catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table of the Elements in the liquid phase, giving a product mixture (P), (b) phase separation of the product mixture (P) obtained in step (a), optionally after lowering the temperature, lowering the pressure and/or adding at least one polar solvent which has a miscibility gap with the nonpolar solvent, to give at least one polar product phase (A) and at least one nonpolar phase (B) comprising at least some of the catalyst used and separating off the nonpolar phase (B), (c) returning at least some of the nonpolar phase (B) to the reaction in step (a) and (d) separating off the amination product from the polar product phase (A), where the nonpolar solvent used in (a) and the catalyst used in step (a) are selected such that the catalyst accumulates in the nonpolar phase (B).
Surprisingly, it has been found that with the complex catalysts used in the process according to the invention which comprise at least one element selected from group 8, 9 and 10 of the Periodic Table of the Elements, it is possible to obtain primary amines, preferably di-, tri- and polyamines, and also alkanolamines by the homogeneously catalyzed amination of alcohols with ammonia with the elimination of water.
The process according to the invention has the advantage that it produces primary mono-, di-, tri- and polyamines and also alkanolamines in considerably improved yields PF0000071687/MKr CA 02828330 2013-08-27 compared with the processes described in the prior art. Moreover, the formation of undesired by-products such as secondary and tertiary amines and also cyclic amines is reduced compared with the prior art. Through appropriate choice of the catalyst and the solvent used, after the reaction, a liquid two-phase system is obtained in which the catalyst accumulates preferentially in the nonpolar phase and the amination product accumulates preferentially in the polar phase, meaning that the catalyst can be easily separated off from the product phase with the nonpolar phase and be reutilized.
Starting materials In the process according to the invention, alcohols which have at least one OH
group, preferably in the form of the functional group of the formula (¨CH2-OH) (primary alcohol group) or (>CH-OH) (secondary alcohol group), are used as starting materials.
Preferably, the alcohols have at least one further functional group (-X), where (-X) is selected from hydroxyl groups (-OH) and primary amino groups (-NH2). In this connection, in the process according to the invention, particular preference is given to using starting materials in which (-X) is selected from the group of functional groups of the formulae (¨CH2-0H) and (>CH-OH) and (-CI-12-NH2) and (>CH-NH2). The starting materials then have at least one functional unit of the formula (¨OH), preferably of the formula (¨CH2-0H) and (>CH2-0H) and/or at least one further functional group selected from the group of functional groups of the formula (¨CH2-0H) and (>CH2-0H) and (-CH2-NH2) and (>CH2-NH2). According to the invention, very particular preference is given to using the starting materials described above which, when reacted with NH3, produce linear primary amines, and very particular preference is given to using linear diols which have at least 2 OH groups, i.e. have two primary and/or secondary alcohol groups, and also linear alkanolamines which have at least one primary or secondary alcohol group in the form of (¨CH2-0H) or (>CH-OH).
Suitable starting materials are practically all alcohols which satisfy the prerequisites specified above. The alcohols may be linear, branched or cyclic, preferably linear.
Moreover, the alcohols can carry substituents which exhibit inert behavior under the reaction conditions of the alcohol amination, for example alkoxy, alkenyloxy, alkylamino, dialkylamino and halogen (F, CI, Br, l).
Suitable starting materials which can be used in the process according to the invention are, for example, monoalcohols, diols, triols, polyols and alkanolamines which have at least one OH group, preferably in the form of the functional groups of the formula (-CH2-0H) or (>CH-OH) and at least one further functional group (-X), where (-X) is selected from hydroxyl groups and primary amino groups.

PF0000071687/MKr CA 02828330 2013-08-, Moreover, diols, triols, polyols and alkanolamines which have at least one OH
group and at least one further functional primary or secondary OH unit or NH2 unit are suitable.
5 Starting materials which can be used are all known diols which have at least one primary or secondary OH group. Examples of diols which can be used as starting materials in the process according to the invention are 1,2-ethanediol (ethylene glycol), 1,2-propanediol (1,2-propylene glycol), 1,3-propandiol (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, 2,2-dimethy1-1,3-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-dimethy1-2,5-hexanediol, hydroxypivalic acid neopentyl glycol ester, diethylene glycol, triethylene glycol, 2-butene-1,4-diol, 2-butyne-1,4-diol, poylethylene glycols, 15 polypropylene glycols, such as 1,2-polypropylene glycol and 1,3 polypropylene glycol, polytetrahydrofu ran, diethanolamine, 1,4-bis-(2-hydroxyethyl)piperazine, diisopropanolamine, N-butyldiethanolamine, 1 ,10-decanediol, 1,12-dodecanediol, 2,5-(dimethanol)-furan, 1,4-bis(hydroxymethyl)cyclohexane, C36-diol (mixture of isomers of alcohols of the empirical formula (Cs6H7402)) and N-methyldiethanolamine, isosorbide (1,4:3,6¨dianhydroglucitol), isomannitol (1,4:3,6-dianhydromannitol, diisopropanol-p-toluidine, N,N-di(2-hydroxyethyl)anilines, diisopropanolamine.
Preference is given to diols which have two functional groups of the formula (-CH2-0H).
25 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 (1,4-butylene glycol), 2-methyl-1,3-propanediol, 2,2-dimethy1-1,3-propanediol (neopentyl glycol), 1,5-pentanediol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, diethylene glycol, triethylene glycol, polyethylene glycols, polypropylene glycols, such as 1,2-polypropylene glycol and 1,3 polypropylene glycol, polytetrahydrofuran, diethanolamine, diisopropanolamine, N-butyldiethanolamine, 2,5-(dimethanol)-furan and N-methyldiethanolamine.
All known triols can be used as starting materials, preference being given to triols 35 which have at least one functional group of the formula (¨CH2-0H) or (>CH-OH), and particular preference being given to triols with at least two functional groups of the formula (¨CH2-0H) or (>CH-OH). Examples of triols which can be used as starting materials in the process according to the invention are glycerol, trimethylolpropane, triisopropanolamine and triethanolamine.
Particularly preferred triols are glycerol, trimethylolpropane and triethanolamine.

PF0000071687/MKr CA 02828330 2013-08-27 All known polyols can be used as starting materials; these preferably comprise at least one functional group of the formula (¨CH2-0H) or (>CH-OH). Examples of polyols which can be used as starting materials in the process according to the invention are polyvinylalcohol, 2,2-bis(hydroxymethyl)-1,3-propanediol (pentaerythritol), sorbitol, inositol, sugars and polymers such as, for example, glucose, mannose, fructose, ribose, deoxyribose, galactose, N-acetylglucosamine, fucose, rhamnose, sucrose, lactose, cellobiose, maltose and amylose, cellulose, starch and xanthan.
Preference is given to polyols which have at least two functional groups of the formula (-CH2-0H) or (>CH-OH).
Particularly preferred polyols are glucose and cellulose.
Starting materials which can be used are also all known alkanolamines which have at least one OH group, preferably a primary or secondary hydroxyl group and at least one primary amino group (-NH2). Within the context of the invention, the alkanolamines are included among the alcohols to be used as starting materials. Examples of alkanol-amines which can be used as starting materials in the process according to the invention are monoaminoethanol, 3-aminopropan-1-ol, 2-aminopropan-1-ol, 4-aminobutan-1-ol, 2-aminobutan-1-ol, 3-aminobutan-1-ol, 5-aminopentan-1-ol, 2-aminopentan-1-ol, 6-aminohexan-1-ol, 2-aminohexan-1-ol, 7-aminoheptan-1-ol, 2-aminoheptan-1-ol, 8-aminooctan-1-ol, 2-aminooctan-1-ol, N-(2-hydroxyethyl)aniline, 2-(2-aminoethoxy)ethanol, N-(2-hydroxyethyl)-1,3-propanediamine and aminodiethylene glycol (2-(2-aminoethoxy)ethanol).
Preference is given to alkanolamines which have at least one primary hydroxyl group (-CH2-0H) and at least one primary amino group of the formula (-CH2-NF12).
Particularly preferred alkanolamines are monoaminoethanol, 3-aminopropan-1-ol, aminopropan-1-01, 4-aminobutan-1-ol and 2-(2-aminoethoxy)ethanol.
Complex catalyst The process according to the invention uses at least one complex catalyst which comprises at least one element selected from groups 8, 9 and 10 of the Periodic Table of the Elements (nomenclature in accordance with IUPAC). The elements of group 8, 9 and 10 of the Periodic Table of the Elements 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 ruthenium and iridium.

, PF0000071687/MKr CA 02828330 2013-08-27 , The complex catalyst comprises preferably at least one donor ligand, in particular one phosphorus donor ligand. The complex catalyst particularly preferably comprises at least one element selected from ruthenium and iridium and at least one phosphorus donor ligand.
In one embodiment, the process according to the invention is carried out in the presence of at least one complex catalyst of the general formula (I):
xi i \R

L1--------%ii---------=-_12 (I) in which L1 and L2 independently of one another, are phosphine (PRaRb), amine (NRaRb), sulfide, SH, sulfoxide (S(=0)R), C5-C10-heteroaryl comprising at least one heteroatom selected from nitrogen (N), oxygen (0) and sulfur (S), arsine (AsRaRb), stibane (SbRaRb) or N-heterocyclic carbenes of the formula (II) or (III):

N¨ R3 ¨N( R4 R5 N¨R5 = =
(II) (III) .
, L3 is a monodentate two-electron donor selected from the group carbon monoxide (CO), PRaRbRc, NO, AsRaRbRc, SbRaRbRe, SRaRb, nitrite (RCN), isonitrile (RNC), nitrogen (N2), phosphorus trifluoride (PF3), carbon monosulfide (CS), pyridine, thiophene, tetrahydrothiophene and N-heterocyclic carbenes of the formula (II) or (III);
R1 and R2 are both hydrogen or, together with the carbon atoms to which they are bonded, are a phenyl ring which, together with the quinolinyl unit of the formula (I), forms an acridinyl unit;
R, Ra, Rb, Rc, R3, V< ¨4, and R5, independently of one another, are unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-Ci0-, PF0000071687/MKr CA 02828330 2013-08-27 heterocyclyl comprising at least one heteroatom selected from N, 0 and S, C5-C10-aryl or C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S, 5 where the substituents are selected from the group consisting of:
F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
Y is monoanionic ligand selected from the group H, F, Cl, Br, I, OCOR, OCOCF3, OSO2R, OSO2CF3, CN, OH, OR and N(R)2 or 10 neutral molecule selected from the group NH3, N(R)3 and R2NSO2R;
X1 is 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 X1, independently of the others, is selected from the group consisting of hydrogen, F, Cl, Br, I, OH, NH2, NO2, -NC(0)R, C(0)NR2, -0C(0)R, -C(0)0R, CN and borane derivatives which are obtainable from the catalyst of the formula (I) by reaction with NaBH4, and unsubstituted or at least monosubstituted C1-C10-alkoxy, Cl-C10-alkyl, C3-C10-cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, C5-C10-aryl and C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of:
F, CI, Br, OH, CN, NH2 and C1-C10-alkyl;
and M is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum.
Here, it is to be noted that the complex catalyst of the formula (I) for cases where Y is a neutral molecule from the group NH3, NR3, R2NSO2R, carries a positive charge.
In a preferred embodiment, the process according to 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 meaning:

PF0000071687/MKr CA 02828330 2013-08-27 L1 and L2, independently of one another, are PRaRb, NRaRb, sulfide, SH, S(=0)R, C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S;
L3 is a monodentate two-electron donor selected from the group CO, PRaRbRc, NO, RCN, RNC, N2, FF3, CS, pyridine, thiophene and tetrahydrothiophene;
R1 and R2 are both hydrogen or, together with the carbon atoms to which they are bonded, are a phenyl ring which, together with the quinolinyl unit of the formula (I), forms an acridinyl unit;
R, Ra, Rb, Rb, R3, R4, and R5, independently of one another, are unsubstituted alkyl, C3-C10-cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, C5-C10-aryl or C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S;
is monoanionic ligand selected from the group H, F, Cl, Br, OCOR, OCOCF3, OSO2R, OSO2CF3, CN, OH, OR or N(R)2;
X1 is 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 X1, independently of the others, is selected from the group consisting of hydrogen, F, Cl, Br, I, OH, NH2, NO2, -NC(0)R, C(0)NR2, -0C(0)R, -C(0)0R, CN and borane derivatives which are obtainable from the catalyst of the formula (I) by reaction with NaBH4, and unsubstituted Cl-Cio-alkoxy, C3-C10-cycloalkyl, C3-C10-heterocyclyI comprising at least one heteroatom selected from N, 0 and S, C5-C1o-aryl and C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S;
and is ruthenium or iridium.
In a further preferred embodiment, the process according to the invention is carried out in the presence of at least one homogeneously dissolved complex catalyst, where R1 and R2 are both hydrogen and the complex catalyst is a catalyst of the formula (IV):

, PF0000071687/MKr CA 02828330 2013-08-27 xi N"--L.-Y
(iv) and X1, Ll, L2, L3 and Y have the meanings given above.
In a further preferred embodiment, the process according to the invention is carried out in the presence of at least one homogeneously dissolved complex catalyst, where R1 and R2, together with the carbon atoms to which they are bonded, form a phenyl ring which, together with the quinolinyl unit of the formula (I), forms an acridinyl unit and the complex catalyst is a catalyst of the formula (V):
xi \
N

Li--------/-rr-s-'-L2 (v) and X1, Ll, L2, L3 and Y have the meanings given above.
By way of example, a number of complex catalysts (formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII)) which can be used in the process according to the invention are listed below:

, PF0000071687/MKr CA 02828330 2013-08-27 xi xi * *
N
N
R
/ oc Rb Y Rb Y
Rb Rb (VI) (VII) Ix 110 x' IN /H
R
,,, ......''W
Rb Y
Rb Rb Y
Rb (VIII) (IX) x' x' 10 N \
N
I /H
IR I /H
-..._ , R
Rp r N R
, , 0. \ / oc \
Rb Y Rb Y
Rb Rb (X) (XI) x\ l xl 10 \N
N
I /H R I /H
R -........ N7"------_________ N../
Re--......N__________-----11------______:1_,N _..."-/ OC I \ / \
y Rb Y Rb OC
Rb Rb (Xii) (Xiii) In a further preferred embodiment, the process according to the invention is carried out in the presence of at least one complex catalyst from the group of catalysts of the 5 formula (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII), where Ra and Rb independently of one another, are unsubstituted or at least mono-substituted Cl-C10-alkyl, C3-C10-cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, C5-C10-aryl or C5-C10-heteroaryl 10 comprising at least one heteroatom selected from N, 0 and S, PF0000071687/MKr where the substituents are selected from the group consisting of: F, Cl, Br, OH, ON, NH2 and C1-C10-alkyl;
= is a monoanionic ligand selected from the group H, F, Cl, Br, OCOR, 000CF3, OSO2R, OSO2CF3, ON, OH, OR, N(R)2;
= is unsubstituted or at least monosubstituted C1-C10-alkyl, 03-C10-cycloalkyl, C3-010-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, 05-C10-aryl, C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, ON, NH2 and 01-C10-alkyl;
X1 is 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 X1, independently of the others, is selected from the group consisting of hydrogen, F, CI, Br, I, OH, NH2, NO2, -NC(0)R, C(0)NR2, -OC(0)R, -C(0)OR, ON and borane derivatives which are obtainable from the catalyst of the formula (I) by reaction with NaBH4, and unsubstituted 01-010-alkoxy, 01-010--alkyl, C3-C10-cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, 05-010-aryl and 05-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S;
and = is ruthenium or iridium.
In a further preferred embodiment, the process according to the invention is carried out in the presence of at least one complex catalyst from the group of catalysts of the formula (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII), where Ra and Rb independently of one another, are methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, phenyl or mesityl;
is a monoanionic ligand selected from the group H, F, CI, Br, 000CH3, OCOCF3, OSO2CF3, CN and OH;
X1 is a substituent on an atom of the acridinyl unit or a substituent on an atom of the quinolinyl unit, PF0000071687/MKr where X' is selected from the group consisting of hydrogen, F, CI, Br, OH, NH2, NO2, -NC(0)R, C(0)NR2, -0C(0)R, -C(0)0R, ON and borane derivatives which are obtainable from the catalyst of the formula (I) by reaction with NaBH4, and unsubstituted C1-C10-alkoxy, C1-010-alkyl, C3-C10-cycloalkyl, C3-C10-heterocycly1 5 comprising at least one heteroatom selected from N, 0 and S, C5-C10-aryl and C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S;
is ruthenium or iridium.
10 In a further preferred embodiment, the process according to the invention is carried out in the presence of at least one complex catalyst from the group of catalysts of the formula (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII), where Ra and Rb, independently of one another, are methyl, ethyl, isopropyl, tert-butyl, 15 cyclohexyl, cyclopentyl, phenyl or mesityl;
is monoanionic ligand from the group F, Cl, Br, I, 0000H3, OCOCF3, OSO2CF3, ON and OH;
X' is hydrogen;
and is ruthenium or iridium.
In a particularly preferred embodiment, L3 is carbon monoxide (CO).
In a particularly preferred embodiment, the process according to the invention is carried out in the presence of a complex catalyst of the formula (XlVa):

NO

.==
==< OC I
CI
(XlVa) In a veryl particularly preferred embodiment, the process according to the invention is carried out in the presence of a complex catalyst of the formula (XIVb):

PF0000071687/MKr ./ 1101 /H
/ I
(pc ci (X1Vb) In a further particularly preferred embodiment, the process according to the invention is carried out in the presence of at least one homogeneously dissolved complex catalyst of the formula (XV) in which R1, R2, R3, Ll, L2 and L3 have the meanings described above.
H

p B.
Ff (XV) Complex catalysts of the formula (XV) are obtainable by reacting catalysts of the formula (I) with sodium borohydride (NaBH4). The reaction follows the general reaction equation:
H
40\
Na131-14 N

In a further particularly preferred embodiment, the process according to the invention is carried out in the presence of a complex catalyst of the formula (XVIa):

. PF0000071687/MKr 11, H
S., , I: I, . .. p N--.) , B
1 Fli X OC I
H
(XVIa) In a further particularly preferred embodiment, the process according to the invention is carried out in the presence of a complex catalyst of the formula (XVIb):
hi, H
µ

,...õ1-14 ti õ.......õ, N---_.. --I FB
(15 0 C I
H
(XVIb) The borane derivative of the formula (XVIa) is accessible according to the following reaction equation:
H H
#4,, IPNaB H 4 (1 equivalent) N r > )4 r 1 H 2 li loom tempet atm e 110 N----.)13-,......,pt1 I -----------P
/K Cl OC I
H

The borane derivative of the formula (XVIb) is accessible according to the following reaction equation:

PF0000071687/MKr H 1:1 NaBH 4 (1 =cpu, akin) sin 41---/Er.
H 2 11 room t,=mpclature CLp OC/
00, Within the context of the present invention, C1-C10-alkyl are understood as meaning branched, unbranched, saturated and unsaturated groups. Preference is given to alkyl groups having 1 to 6 carbon atoms (C1-C6-alkyl). More preference is given to alkyl groups having 1 to 4 carbon atoms (C1-C4-alkyl).
Examples of saturated alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl and hexyl.
Examples of unsaturated alkyl groups (alkenyl, alkynyl) are vinyl, allyl, butenyl, ethynyl and propynyl.
The C1-C10-alkyl group can be unsubstituted or substituted with one or more substituents selected from the group F, Cl, Br, hydroxy (OH), C1-C10-alkoxy, aryloxy, C6-C10-alkylaryloxy, C6-C10-heteroaryloxy comprising at least one heteroatom selected from N, 0, S, oxo, C3-Cl0-cycloalkyl, phenyl, C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0, S, C5-C10-heterocycly1 comprising at least one heteroatom selected from N, 0, S, naphthyl, amino, C1-C10-alkylamino, C5-arylamino, C5-C10-heteroarylamino comprising at least one heteroatom selected from N, 0, S, C1-C10-dialkylamino, C10-C12-diarylamino, C10-C20-alkylarylamino, C1-C10-acyl, C1-C10-acyloxy, NO2, C1-C10-carboxy, carbamoyl, carboxamide, cyano, sulfonyl, sulfonylamino, sulfinyl, sulfinylamino, thiol, C1-C10-alkylthiol, C5-C10-arylthiol or 0l-C10-alkylsulfonyl.
In the present case, 03-C10-cycloalkyl is understood as meaning saturated, unsaturated monocyclic and polycyclic groups. Examples of 03-C10-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. The cycloalkyl groups can be unsubstituted or substituted with one or more substituents, as has been defined above in relation to the group C1-C10-alkyl.
Within the context of the present invention, 06-010-aryl is understood as meaning an aromatic ring system having 5 to 10 carbon atoms. The aromatic ring system can be monocyclic or bicyclic. Examples of aryl groups are phenyl, naphthyl such as PF0000071687/MKr , 1-naphthyl or 2-naphthyl. The aryl group can be unsubstituted or substituted with one or more substituents as defined above under C1-C10-alkyl.
Within the context of the present invention, C5-C10-heteroaryl is understood as meaning a heteroaromatic system which comprises at least one heteroatom selected from the group N, 0 and S. The heteroaryl groups can be monocyclic or bicyclic. For the case that nitrogen is a ring atom, the present invention also comprises N-oxides of the nitrogen-comprising heteroaryls. Examples of heteroaryls are thienyl, benzothienyl, 1-naphthothienyl, thianthrenyl, fury!, benzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, isoindolyl, indazolyl, purinyl, isoquinolinyl, quinolinyl, acridinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, piperidinyl, carbolinyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl. The heteroaryl groups can be unsubstituted or substituted with one or more substituents which have been defined above under C1-C10-alkyl.
Within the context of the present invention, C3-C10-heterocycly1 is understood as meaning five- to ten-membered ring systems which comprise at least one heteroatom from the group N, 0 and S. The ring systems can be monocyclic or bicyclic.
Examples of suitable heterocyclic ring systems are piperidinyl, pyrrolidinyl, pyrrolinyl, pyrazolinyl, pyrazolidinyl, morpholinyl, thiomorpholinyl, pyranyl, thiopyranyl, piperazinyl, indolinyl, dihydrofuranyl, tetrahydrofuranyl, dihydrothiophenyl, tetrahydrothiophenyl, dihydropyranyl and tetrahydropyranyl.
In a further embodiment, the process according to the invention uses at least one complex catalyst which comprises at least one element selected from the groups 8, 9 and 10 of the Periodic Table of the Elements (nomenclature according to IUPAC), and also at least one phosphorus donor ligand of the general formula (XXI), \
p/R23 /
R22 1 I I\ R24 I
P, /\

i in (XXI) where PF0000071687/MKr n is 0 or 1;
R21, R22, R23, R24, R25, R26 are, independently of one another, unsubstituted or at least monosubstituted C1-C10-alkyl, C1-C4-alkyldiphenylphosphine 5 (-C1-C4-alkyl-P(pheny1)2), C3-C10-cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, C5-C14-aryl or C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, 10 OH, CN, NH2 and C1-C10-alkyl;
A is i) a bridging group selected from the group unsubstituted or at least monosubstituted N, 0, P, C1-C6-alkane, C3-C10-cycloalkane, C3-C10-15 heterocycloalkane comprising at least one heteroatom selected from N, and S, C5-C14-aromatic and C5-C6-heteroaromatic comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of:

20 C1-C4-alkyl, phenyl, F, Cl, Br, OH, OR27, NH2, NHR27 or N(R27)2, where R27 is selected from C1-C10-alkyl and C5-C10-aryl;
Or ii) a bridging group of the formula (XXII) or (XXIII):
(R28)m (R29)q (R28)õ, X13 (R29) q X 1 1 x12 (XXII) (XXIII) m, q are, independently of one another, 0, 1, 2, 3 or 4;
R28, R29 are, independently of one another, selected from the group C1-C10-alkyl, F, CI, Br, OH, OR27, NH2, NHR27 and N(R27)2, where R27 is selected from C1-C10-alkyl and C5-C10-aryl;
x11, x12 are, independently of one another, NH, 0 or S;

PF0000071687/MKr X13 is a bond, NH, NR30, 0, S or CR31R32;
R3 is unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, C5-C14-aryl or C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
R31, R32 are, independently of one another, unsubstituted or at least monosubstituted C1-C10-alkyl, C1-C10-alkoxy, C3-C10-cycloalkyl, C3-C10-cycloalkoxy,C3-C10-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, C5-C14-aryl, C5-C14-aryloxy or C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
yl, y2, s T are, independently of one another, a bond, unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, where the substituents are selected from the group consisting of: F, Cl, Br, OH, OR27, CN, NH2, NHR27, N(R27)2 and C1-C10-alkyl, where R27 is selected from C1-C10-alkyl and C5-C10-aryl.
According to the invention, A is a bridging group. For the case that A is selected from the group unsubstituted or at least monosubstituted C1-C6-alkane, C3-C10-cycloalkane, C3-C10-heterocycloalkane, C5-C14-aromatic and C5-C6-heteroaromatic and bridging groups of the formula (II) or (III), for the case (n = 0), two hydrogen atoms of the bridging group are replaced by bonds to the adjacent substituents Y1 and Y2.
For the case (n = 1), three hydrogen atoms of the bridging group are replaced by three bonds to the adjacent substituents Y1, Y2 and Y3.
For the case that A is P (phosphorus), the phosphorus forms for the case (n =
0) two bonds to the adjacent substituents Y1 and Y2 and one bond to a substituent selected PF0000071687/MKr from the group consisting of CI-al-alkyl and phenyl. For the case (n = 1), the phosphorus forms three bonds to the adjacent substituents Y1, Y2 and Y3.
For the case that A is N (nitrogen), the nitrogen for the case (n = 0) forms two bonds to the adjacent substituents Y1 and Y2 and one bond to a substituent selected from the group consisting of C1-C4-alkyl and phenyl. For the case (n = 1), the nitrogen forms three bonds to the adjacent substituents Y1, Y2 and Y3.
For the case that A is 0 (oxygen), n = 0. The oxygen forms two bonds to the adjacent substituents Y1 and Y2.
Preference is given to complex catalysts which comprise at least one element selected from ruthenium and iridium.
In a preferred embodiment, the process according to the invention is carried out in the presence of at least one complex catalyst which comprises at least one element selected from the groups 8, 9 and 10 of the Periodic Table of the Elements and also at least one phosphorus donor ligand of the general formula (XXI), where n is 0 or 1 ;
R21, R22, R23, R24, R25, R26 are, independently of one another, unsubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-Cl0-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, C5-C14-aryl or C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S;
A is i) a bridging group selected from the group unsubstituted C1-C6-alkane, C3-C10-cycloalkane, C3-C10-heterocycloalkane comprising at least one heteroatom selected from N, 0 and S, C5-C14-aromatic and C5-C6-heteroaromatic comprising at least one heteroatom selected from N, 0 and S;
Or ii) a bridging group of the formula (XXII) or (XXIII):

PF0000071687/MKr (R28)m (R29) (R286 X13 (R29)q )(11 x12 (XXII) (XXIII) m, q are, independently of one another, 0, 1, 2, 3 or 4;
R28, R29 are, independently of one another, selected from the group C1-C10-alkyl, F, Cl, Br, OH, OR27, NH2, NHR27 and N(R27)2, where R27 is selected from C1-C10-alkyl and C5-C10-aryl;
x11, x12 are, independently of one another, NH, 0 or S;
X13 is a bond, NH, NR30, 0, S or CR31R32;
R3 is unsubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-00-heterocyclyl comprising at least one heteroatom selected from N, 0 and S, C5-C14-aryl or C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S;
R31, R32 are, independently of one another, unsubstituted C1-C10-alkyl, C1-C10-alkoxy, C3-C10-cycloalkyl, C3-C10-cycloalkoxy, C3-Clo-heterocyclyl comprising at least one heteroatom selected from N, 0 and S, C5-C14-aryl, C5-C14-aryloxy or C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S;
yl, y2, r s,3 are, independently of one another, a bond, unsubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene.
In a further preferred embodiment, the process according to the invention is carried out in the presence of at least one complex catalyst which comprises at least one element selected from groups 8, 9 and 10 of the Periodic Table of the Elements and also at least one phosphorus donor ligand of the general formula (XXV), PF0000071687/MKr \
p_yl_A- y2- p/
/ \

(XXV) where R21 , R22, R23, R24 are, independently of one another, unsubstituted or at least monosubstituted Cl-C10-alkyl, Craralkyldiphenylphosphine (-C1-C4-alkyl-P(pheny1)2), C3-C10-cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, C5-C14-aryl or C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
A is i) a bridging group selected from the group unsubstituted or at least monosubstituted N, 0, P, C1-C6-alkane, C3-C10-cycloalkane, 03-010-heterocycloalkane comprising at least one heteroatom selected from N, 0 and S, C5-C14-aromatic and C5-C6-heteroaromatic comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of:
C1-C4-alkyl, phenyl, F, Cl, Br, OH, OR27, NH2, NHR27 or N(R27)2, where R27 is selected from C1-C10-alkyl and C5-C10-aryl;
Or ii) a bridging group of the formula (XXII) or (XXIII):
(R28)m (R29)_ (R286 29 x13 (R)9 \., )(11 x12 (XXII) (XXIII) PF0000071687/MKr m, q are, independently of one another, 0, 1, 2, 3 or 4;
R28, R29 are, independently of one another, selected from the group 01-C10-alkyl, F, Cl, Br, OH, OR27, NH2, NHR27 and N(R27)2, where R27 is selected from 01-010-alkyl and 05-C10-aryl;
X11, x12 are, independently of one another, NH, 0 or S, 10 X13 is a bond, NH, NR30, 0, S or CR31 R32;
R3 is unsubstituted or at least monosubstituted 01-010-alkyl, 03-010-cycloalkyl, 03-C10-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, 05-C14-aryl or C5-C10-15 heteroaryl comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, ON, NH2 and 01-010-alkyl;
R31, R32 are, independently of one another, unsubstituted or at least monosubstituted 01-C10-alkyl, 01-010-alkoxy, 03-010-cycloalkyl, 03-010-cycloalkoxy, C3-010-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, 05-C14-aryl, C5-014-aryloxy or 05-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, ON, NH2 and 01-010-alkyl;
Y1, y2 are, independently of one another, a bond, unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, where the substituents are selected from the group consisting of: F, CI, Br, OH, OR27, ON, NH2, NHR27, N(R27)2 and 01-C10-alkyl, where R27 is selected from 01-010-alkyl and 05-C10-aryl.
In a further preferred embodiment, the process according to the invention is carried out in the presence of at least one complex catalyst which comprises at least one element PF0000071687/MKr CA 02828330 2013-08-27 selected from groups 8, 9 and 10 of the Periodic Table of the Elements and also at least one phosphorus donor ligand of the general formula (XXVI), R21 \R

p_yi_A___. y2- p/
I \

I
P
/ \

(XXVI) where R21, R22, R23, R24, R25, R26 are, independently of one another, unsubstituted or at least monosubstituted C1-C10-alkyl, C1-C4-alkyldiphenylphosphine, C3-C10-cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom selected from N, 0 and S, C5-C14-aryl or C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of: F, Cl, Br, OH, ON, NH2 and C1-C10-alkyl;
A is a bridging group selected from the group unsubstituted or at least mono-substituted N, P, C1-C6-alkane, C3-C10-cycloalkane, C3-Clo-heterocycloalkane comprising at least one heteroatom selected from N, 0 and S, C5-C14-aromatic and C5-C6-heteroaromatic comprising at least one heteroatom selected from N, 0 and S, where the substituents are selected from the group consisting of:
C1-C4-alkyl, phenyl, F, CI, Br, OH, OR27, NH2, NHR27 or N(R27)2, where R27 is selected from C1-C10-alkyl and C5-C10-aryl;
Y1, y2, y3 are, independently of one another, a bond, unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, where the substituents are selected from the group consisting of: F, Cl, Br, OH, OR27, ON, NH2, NHR27, N(R27)2 and C1-C10-alkyl, where R27 is selected from C1-C10-alkyl and C5-C10-aryl.

PF0000071687/MKr CA 02828330 2013-08-27 In a further preferred embodiment, the process according to the invention is carried out in the presence of at least one complex catalyst which comprises at least one element selected from groups 8, 9 and 10 of the Periodic Table of the Elements and also at least one phosphorus donor ligand of the general formula (XXV), where R21, R22, R23, R24 are, independently of one another, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, or mesityl;
A is i) a bridging group selected from the group methane, ethane, propane, butane, cyclohexane, benzene, napthalene and anthracene;
Or ii) a bridging group of the formula (XXVII) or (XXVIII):
xi, x13 x12 (XXVII) (XXVIII) Xi', x12 are, independently of one another, NH, 0 or S;
X13 is a bond, NH, 0, S or CR31R32;
R31, R32 are, independently of one another, unsubstituted C1-C10-alkyl;
y1, y2 are, independently of one another, a bond, methylene or ethylene.
In a particularly preferred embodiment, the process according to the invention is carried out in the presence of at least one complex catalyst which comprises at least one element selected from groups 8, 9 and 10 of the Periodic Table of the Elements and also at least one phosphorus donor ligand of the general formula (XXIX) or (XXX), PF0000071687/MKr CA 02828330 2013-08-27 (R28)m (R29)q R28 29 (R29)q xõ )(12 (XXIX) (XXX) where for m, q, R21, R22, R23, R24, R28, R29, x19, x12 and X13, the definitions and preferences listed above are applicable.
In a further particularly preferred embodiment, the process according to the invention is carried out in the presence of at least one complex catalyst which comprises at least one element selected from the group ruthenium and iridium and also at least one phosphorus donor ligand selected from the group 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), bis(2-diphenylphosphinoethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos).
In a further particularly preferred embodiment, the process according to the invention is carried out in the presence of a complex catalyst which comprises ruthenium and at least one phosphorus donor ligand selected from the group 4,5-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 according to the invention is carried out in the presence of a complex catalyst which comprises iridium and also at least one phosphorus donor ligand selected from the group 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-diphenylphosphino-ethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos).
Within the context of the present invention, C1-C10-alkyl is understood as meaning branched, unbranched, saturated and unsaturated groups. Preference is given to alkyl groups having 1 to 6 carbon atoms (C1-C6-alkyl). More preference is given to alkyl groups having 1 to 4 carbon atoms (C1-C4-alkyl).
Examples of saturated alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl and hexyl.

PF0000071687/MKr CA 02828330 2013-08-27 Examples of unsaturated alkyl groups (alkenyl, alkynyl) are vinyl, allyl, butenyl, ethynyl and propynyl.
The C1-C10-alkyl group can be unsubstituted or substituted with one or more substituents selected from the group F, Cl, Br, hydroxy (OH), C1-C10-alkoxy, aryloxy, C5-C10-alkylaryloxy, C5-C10-heteroaryloxy comprising at least one heteroatom selected from N, 0, S, oxo, C3-C10-cycloalkyl, phenyl, C5-C10-heteroaryl comprising at least one heteroatom selected from N, 0, S, C5-C10-heterocycly1 comprising at least one heteroatom selected from N, 0, S, naphthyl, amino, C1-C10-alkylamino, C5-arylamino, C5-C10-heteroarylamino comprising at least one heteroatom selected from N, 0, S, C1-C10-dialkylamino, C10-C12-diarylamino, C10-C20-alkylarylamino, C1-C10-acyl, C1-C10-acyloxy, NO2, C1-C10-carboxy, carbamoyl, carboxamide, cyano, sulfonyl, sulfonylamino, sulfinyl, sulfinylamino, thiol, C1-C10-alkylthiol, C5-C10-arylthiol or C1-C10-alkylsulfonyl.
The above definition for C1-C10-alkyl applies correspondingly to C1-C30-alkyl and to C1-C6-alkane.
C3-C10-cycloalkyl is understood in the present case as meaning saturated, unsaturated monocyclic and polycyclic groups. Examples of C3-C10-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. The cycloalkyl groups can be unsubstituted or substituted with one or more substituents as has been defined above in connection with the group C1-C10-alkyl.
The definition of C3-C10-cycloalkyl specified above applies accordingly to C3-cycloalkane.
The homogeneous catalysts can be generated directly in their active form or else are only generated under the reaction conditions starting from customary precursors with the addition of the corresponding ligands. Customary precursors are, for example, [Ru(p-cymene)C12]2, [Ru(benzene)C12], [Ru(C0)2C12],, [Ru(C0)3C12]2 [Ru(COD)(allyI)], [RuCI3*H20], [Ru(acetylacetonate)3], [Ru(DMS0)4C12], [Ru(PPh3)3(C0)(H)CI], [Ru(PPh3)3(CO)C12], [Ru(PPh3)3(C0)(H)2], [Ru(PPh3)3Cl2], [Ru(cyclopenta-dienyl)(PRh3)2C1], [Ru(cyclopentadienyl)(C0)2CIL
[Ru(cyclopentadienyl)(C0)2H], [Ru(cyclopentadienyl)(C0)2]2, [Ru(pentamethylcyclopentadienyl)(C0)2C1], [Ru(penta-methylcylcopentadienyl)(C0)2H], [Ru(pentamethylcyclopentadienyl)(C0)212, [Ru(indenyl)(C0)2C1], [Ru(indenyl)(C0)21-1], [Ru(indenyl)(C0)2]2, Ruthenocene, [Ru(binap)C12], [Ru(bipyridine)2C12*2H20], [Ru(COD)C12]2, [Ru(pentamethylcyclo-pentadienyl)(COD)C1], [Ru3(C0)12], [Ru(tetraphenylhydroxycyclopentadienyl)(C0)2H], [Ru(PMe3)4(1--1)2], [Ru(PEt3)4(H)2], [Ru(PnPr3)4(H)2], [Ru(PnBu3)4(H)2], [Ru(PnOcty13)4(H)2], [IrCI3*H20], KIrCI4, K3IrC16, [Ir(COD)C1]2, Dr(cyclooctene)2C92, [I r(ethene)2C1]2, [I r(cyclopentadienyl)C12]2, [I
r(pentamethylcyclopentadienyl)C12]2, PF0000071687/MKr CA 02828330 2013-08-27 [Ir(cylopentadienyl)(C0)2], [Ir(pentamethylcyclopentadienyl)(C0)2], [Ir(PPh3)2(C0)(H)l, [Ir(PPh3)2(C0)(C1)], [I r(PPh3)3(C1)].
Alcohol amination (step (a)) The alcohol amination in step (a) takes place by homogeneously catalyzed reaction of one or more hydroxyl-group-comprising starting materials with ammonia in the presence of at least one of the complex catalysts described above.
10 During the amination reaction, according to the invention, at least one hydroxyl group (-OH) of the starting material is reacted with ammonia to give a primary amino group (-N H2), with the formation of in each case 1 mol of water of reaction per mole of reacted hydroxyl group.
15 Thus, in the case of the reaction of alkanolamines which have only one hydroxyl group, the corresponding diamines are formed. The reaction of monoaminoethanol thus leads to the corresponding 1,2-diaminoethane.
In the case of the reaction of starting materials which have a further hydroxyl group 20 (diols), reaction with ammonia leads to the corresponding primary diamines or alkanol-amines depending on the reaction conditions. The reaction of 1,2-ethylene glycol thus leads to the corresponding 1,2-diaminoethane or monoaminoethanol.
In the case of the reaction of starting materials which have two further hydroxyl groups 25 as well as one hydroxyl group (triols), two or three hydroxyl groups are reacted with ammonia to give the corresponding primary diamines or triamines. The formation of diamines or triamines can be controlled here via the amount of ammonia used and via the reaction conditions. The reaction of glycerol thus leads to the corresponding 1,3-diaminopropanol (1,3-diaminopropan-2-ol) or to 1,2,3-triaminopropane.
In the case of the reaction of starting material which, as well as the one hydroxyl group, have more than three further hydroxyl groups (polyols), two, three or more hydroxyl groups are reacted with ammonia to give the corresponding primary diamines, triamines or polyamines. The formation of the corresponding primary diamines, triamines or polyamines can be controlled here via the amount of ammonia used and via the reaction conditions.
Within the context of the present invention, homogeneously catalyzed is understood as meaning that the catalytically active part of the complex catalyst is present in at least partially dissolved form in the liquid reaction medium. In a preferred embodiment, at least 90% of the complex catalyst used in the process is present in dissolved form in , PF0000071687/MKr CA 02828330 2013-08-27 the liquid reaction medium, more preferably at least 95%, especially preferably more than 99%, most preferably the complex catalyst is present in completely dissolved form in the liquid reaction medium (100%), in each case based on the total amount in the liquid reaction medium.
The amount of metal component in the catalyst, preferably ruthenium or iridium, is generally 0.1 to 5000 ppm by weight, in each case based on the total liquid reaction mixture in the reaction space.
The reaction in step (a) takes place in the liquid phase generally at a temperature of from 20 to 250 C. Preferably, the process according to the invention is carried out at temperatures in the range from 100 C to 200 C, particularly preferably in the range from 110 to 160 C.
The reaction is generally carried out at a total pressure of from 0.1 to 20 MPa absolute, which can either be the intrinsic pressure of the solvent and of the ammonia at the reaction temperature, and also the pressure of a gas such as nitrogen, argon or hydrogen. Preferably, the process according to the invention is carried out at a total pressure up to 15 MPa absolute, particularly preferably at a total pressure of up to 10 MPa absolute.
The aminating agent (ammonia) can be used in stoichiometric, substoichiometric or superstoichiometric amounts with regard to the hydroxyl groups to be aminated.
In a preferred embodiment, ammonia is used in a 1.0- to 250-fold, preferably in a 1.5- to 100-fold, especially in a 2- to 10-fold, molar excess per mole of hydroxyl groups to be reacted in the starting material. Even higher excesses of ammonia are possible. The ammonia can be added in gaseous form, in liquid form or dissolved in one of the solvents.
According to the invention, the reaction takes place in the presence of at least one nonpolar solvent. In this connection, one nonpolar solvent or mixtures of two or more nonpolar solvents can be used.
The nonpolar solvent is generally selected from saturated hydrocarbons such as hexane, heptane, octane and cyclohexane; linear and cyclic ethers such as diethyl ether, 1,4-dioxane, tert-butyl methyl ether, tert-amylalcohol, tert-butanol, diglyme and 1,2-dimethoxyethane and aromatic hydrocarbons such as benzene, toluene, o-, m-, p-xylene and mesitylene and mixtures thereof. Preference is given to using aromatic solvents, particularly preferably toluene, o-, m-, p-xylene, mesitylene and mixtures thereof.

PF0000071687/MKr CA 02828330 2013-08-27 In this connection, nonpolar solvent and homogeneous catalyst are selected such that the catalyst accumulates in the nonpolar phase (B) obtained following the phase separation in step (b). According to the invention, accumulated is understood as meaning that the quantitative partition coefficient Pmc = [amount of dissolved catalyst in the nonpolar phase (B)]/[amount of dissolved catalyst in the polar product phase (A)] is greater than 1. Preferably, Pm, is at least 1.5, particularly preferably at least 5.
In a preferred embodiment, nonpolar solvent and homogeneous catalyst are selected such that the catalyst dissolves better in the nonpolar phase (B) obtained following the phase separation in step (b) than in the polar phase (A). The catalyst concentration is then higher in the nonpolar phase (B) than in the polar phase (A), i.e. the partition coefficient Pc, = [concentration of the dissolved catalyst in the nonpolar phase (B)]/[concentration of the dissolved catalyst in the polar product phase (A)]
is greater than 1. Preferably, Pc is at least 1.5, particularly preferably at least 5.
The choice of the homogeneous catalyst and of the nonpolar solvent is usually made by means of a simple experiment in which the partition coefficient P of the chosen catalyst is determined experimentally under the planned process conditions together with the substrate and product and also the polar solvent. In particular, the lipophilicity of the catalyst and thus its solubility in nonpolar and/or polar phases can be influenced in a targeted manner by the choice of ligands.
As a rule, the nonpolar solvent is selected such that the homogeneous catalyst preferentially dissolves therein compared to the polar solvent. According to the invention, this means that the partition coefficient Pc2 = [concentration of the catalyst in the nonpolar solvent]/[concentration of the catalyst in the polar solvent] is greater than 1, preferably at least 2 and particularly preferably at least 5. Further preferred Pc2 is at least 1.5.
For the reaction in the liquid phase, ammonia, the at least one alcohol, the at least one nonpolar solvent are usually fed into a reaction space together with the complex catalyst. The reaction can be carried out in customary devices or reactors known to the person skilled in the art for liquid-gas reactions in which the catalyst is present in homogeneously dissolved form in the liquid phase. For the process according to the invention, all reactors can in principle be used which are fundamentally suitable for gas/liquid reactions under the stated temperature and the stated pressure.
Suitable standard reactors for gas-liquid and for liquid-liquid reaction systems are discussed for example in K.D. Henkel, "Reactor Types and Their Industrial Applications", in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-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, tubular PF0000071687/MKr CA 02828330 2013-08-27 reactors or bubble column reactors. The introduction of ammonia, starting material, nonpolar solvent and complex catalyst can take place here simultaneously or separately from one another. The reaction can be carried out here discontinuously in a batch procedure or continuously, semicontinuously with or without recycling.
The average residence time in the reaction space is generally 15 minutes to 100 hours.
The product mixture (P) obtained in step (a) comprises the homogeneous catalyst, the amination product, nonpolar solvent, unreacted starting materials and any by-products formed, and also water formed during the amination. It may also be advantageous to continuously remove the water formed during the reaction from the reaction mixture.
The water of reaction can be separated off directly by distillation from the reaction mixture or as azeotrope with the addition of a suitable solvent (entrainer) and using a water separator, or can be removed by adding water-removing auxiliaries.
In step (b) of the process according to the invention, a phase separation of the product mixture (P) obtained in step (a) takes place, optionally after lowering the temperature and/or adding at least one polar solvent which has a miscibility gap with the nonpolar solvent used in step (a), to give at least one polar product phase (A) and at least one nonpolar phase (B) comprising at least some of the catalyst used, and separating off the nonpolar phase (B).
Both phases (A) and (B) are liquid phases, the catalyst being present in accumulated form in the nonpolar phase (B), and the amination product being present in accumulated form in the polar phase. With regard to the amination product, "accumulated" in the present case means that the quantitative partition coefficient of the amination product PA = [amount of amination product in the polar phase (A)]/[amount of amination product in the nonpolar phase (B)] is greater than 1, preferably at least 1.5, particularly preferably at least 5.
In a preferred embodiment, the polar solvent is selected such that the amination product dissolves better in the polar phase (A) obtained following phase separation in step (b) than in the nonpolar phase (B). The amination product concentration is then higher in the polar phase (A) than in the nonpolar phase (B), i.e. the partition coefficient of the amination product PAi = [concentration of the amination product in the polar phase (A)]/[concentration of the amination product in the nonpolar phase (B)]
is greater than 1, preferably at least 1.5, particularly preferably at least 5.
Depending on the choice of components, it is possible that the product mixtures (P) is present in single-phase liquid form after step (a). In this case, a phase separation can be achieved by cooling and/or adding one or more polar solvents.

PF0000071687/MKr CA 02828330 2013-08-27 Suitable polar solvents are, for example, water, dimethylformamide, formamide, acetonitrile, the alcohol(s)/alkanolamine(s) used as starting materials in step (a), and mixtures thereof. In addition, the product can also be used as solvent.
Preference is given to using water. The polar solvent can be added either already to the reaction mixture before or in step (a), or after the reaction in step (b) in addition to the water of reaction that is formed during the reaction.
According to the invention, the polar solvent should be matched to the nonpolar solvent and the amination product that is formed in such a way that the amination product is present in accumulated form in the polar phase (A). The selection of nonpolar and polar solvent generally takes place by simple experimentation, in which the solubility of the desired product is determined experimentally in the two phases (A) and (B) under the planned process conditions.
As a rule, the polar solvent is selected such that the amination product preferentially dissolves therein compared to the nonpolar solvent used. According to the invention, this means that the partition coefficient PA2 = [concentration of amination product in polar solvent]/[concentration of amination product in nonpolar solvent] is greater than 1, preferably at least 2 and particularly preferably at least 5. Further preferred PA2 is at least 1.5.
Within the context of the present invention, in each case it is possible to use one solvent or mixtures of 2 or more solvents. This applies to the nonpolar solvents and also the polar solvents.
The dielectric constant DC can be used as a measure for assigning a solvent to the group polar/nonpolar. Solvents with DC greater than about 15 are usually regarded as polar (e.g. acetonitrile has a DC of about 37), solvents with a lower DC are usually regarded as nonpolar, for example the DC of benzene is 2.28.
Even if the product mixture obtained in step (a) is already present in two phases, the addition of polar solvent may be advantageous if, as a result, a more favorable partition of the catalyst and of the amination product in the two phases (A) and (B) is achieved.
The same applies to the lowering of the temperature.
The phase separation of the two phases (A) and (B) in step (b) generally takes place by gravimetric phase separation. The reaction space in which the reaction according to step (a) has taken place, for example a reactor, can serve as phase separation vessel.
The separation of two liquid phases is per se a standard procedure which is known to the person skilled in the art. Standard methods and processes are described, for example, in E. Muller et al., "Liquid-Liquid Extraction" in Ullmann's Encyclopedia of PF0000071687/MKr CA 02828330 2013-08-27 Industrial Chemistry, 2005, Wiky-VCH-Verlag, 10.1002/14356007.603-06, Chapter 3, "Apparatus".
In step (c) of the process according to the invention, at least some of the phase (B) 5 separated off in step (b), is returned again to the reaction in step (a), optionally after one or more steps for the purposes of purification, such as distillation. In this connection, the entire separated-off nonpolar phase (B) can be returned, although it may also be sensible, for the purposes of removing undesired by-products and impurities, to remove some of the nonpolar phase from the process in order to avoid an 10 accumulation of undesired components in the process.
As a rule, the polar phase will also comprise at least small amounts of the catalyst. If it is necessary to further reduce the catalyst fraction in the polar phase (A), then it can be extracted with a nonpolar solvent. The extraction of the catalyst can be carried out in 15 any suitable device known to the person skilled in the art, preferably in countercurrent extraction columns, mixer settler cascades or combinations of mixer settler apparatuses with extraction columns. The nonpolar extract comprising the catalyst can then, optionally after removing excess nonpolar solvent by evaporation, be returned again to the amination reaction in step (a). Preferably, the extractant used is the 20 nonpolar solvent used in step (a). The extraction of the catalyst from the polar product phase (B) can be carried out before or after separating off the amination product in step (d). According to a preferred embodiment, the extracted catalyst is returned at least in part to the reaction.
25 In step (d) of the process according to the invention, the amination product is separated off from the polar product phase (A). Thus, in step (d), the polar solvent can be separated off from the amination product by distillation and either be returned to the process or be discarded. Unreacted starting material (alcohol), any excess ammonia present or by-products can likewise be removed from the amination product by 30 distillation. Thermal removal of the polar solvent takes place by prior art methods known to the person skilled in the art, preferably in an evaporator or in a distillation unit, comprising evaporator and column(s), which usually has a plurality of trays, arranged packing or dumped packing.
35 The addition of bases can have a positive effect on the product formation. Suitable bases which may be mentioned here are alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, alkaline earth metal alcoholates, alkali metal carbonates and alkaline earth metal carbonates, which can be used in an amount of from 0.01 to 100 molar equivalents based on the metal catalyst used.
The invention is illustrated by the examples below without limiting it thereto.

PF0000071687/MKr CA 02828330 2013-08-27 , Examples:
General procedure for the catalytic amination according to the invention of alcohols 5 with ammonia Ligand L, metal salt M or catalyst complex XlVb (for preparation see below, weighing in under inert atmosphere), solvent (sufficient for the total solvent volume to be 50 ml) and the alcohol to be reacted were introduced as initial charge under an Ar atmosphere in a 160 ml Parr autoclave (stainless steel V4A) with magnetically coupled slanted-10 blade stirrer (stirring speed: 200-500 revolutions/minute). The stated amount of ammonia was either precondensed at room temperature or directly metered in from the NH3 pressurized-gas bottle. If hydrogen was used, this was carried out by means of iterative differential pressure metering. The steel autoclave was heated electrically up to the stated temperature and heated (internal temperature measurement) for the 15 stated time with stirring (500 revolutions/minute). After cooling to room temperature, decompressing the autoclave and outgassing the ammonia at atmospheric pressure, 5 or 50 ml of water were added, whereupon two liquid phases were obtained, which were separated by means of phase separation. The reaction mixture was analyzed by means of GC (30 m RTX5 amine 0.32 mm 1.5 pm). The ruthenium content of the 20 respective liquid phase was ascertained by means of atomic absorption spectroscopy.
The results for the amination of 1,4-butanediol (Table 1), diethylene glycol (Table 2) and monoethylene glycol (Table 3) are given below:
Synthesis of the catalyst complex XlVb PCy2 ,Br / "N / \ N 1111(¨
HPCy2 [RuH0I(C0)(PPh3)3]
N 31...
Me0H Toluene = 410 ( 3`- -7`4 Fi --)"
Br ''', CO
\
PCy2 XlVb a) Synthesis of 4,5-bis(dicyclohexylphosphinomethyl)acridine A solution of 4,5-bis(bromomethypacridine1 (5.2 g, 14.2 mmol) and 30 dicyclohexylphosphine (8.18 g, 36.8 mmol) in 65 ml of anhydrous, degassed methanol was heated at 50 C under an inert argon atmosphere for 66 h. After cooling to room temperature, triethylamine (5.72 g, 56.7 mmol) was added and the mixture was stirred for 1 h. Evaporation of the solvent produced a yellow-white solid in red oil.
Extraction by means of 3 x 40 ml of MTBE and concentration of the filtrate produced a red-brown 35 oil (1H NMR: mixture of product & HPCy2). Taking up in a small amount of warm MTBE

=
PF0000071687/MKr CA 02828330 2013-08-27 followed by addition of ice-cooled methanol resulted in precipitation of a yellow, microcrystalline solid. Isolation and drying in vacuo gave air-sensitive 4,5-bis(dicyclo-hexylphosphinomethyl)acridine (2.74 g, 33%) as yellow powder. 1H NMR (360.63 MHz, toluene-d8): 6 [ppm] = 8.07 (s, 1H, H9), 7.91 (d, J = 8.3 Hz, 2H, 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, -CH2-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).
31P{1H}
NMR (145.98 MHz, toluene-d8): 6 [ppm] = 2.49 (s, -CH2-P(CY)2).
b) Synthesis of the catalyst complex XlVb 4,5-Bis(dicyclohexylphosphinomethyl)acridine (1855 mg, 3.1 mmol) and [RuHCI(C0)(PPh3)3]2 (2678 mg, 2.81 mmol) were heated at 70 C in 80 ml of degassed toluene for 2 h. 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 in vacuo gave Ru-PNP pincer complex XlVb (1603 mg, 75%) as an orange-brown powder.
1H NMR (360.63 MHz, toluene-d8): 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-PCy2), 3.54 (d, J = 12.2 Hz, 2H, -CHH-PCy2), 2.87 (bs, 2H, -P(CaH(CH2)5)2), 2.54 (bs, 2H, -P(CbH(CH2)5)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). 31P{1H} NMR (145.98 MHz, toluene-d8): 6 [ppm] = 60.89 (s, -CH2-P(CY)2).
1 J. Chiron, J.P. Galy, Synlett, 2003, 15, 2349-2350.
2 Literature procedure: 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.

PF0000071687/MKr Table 1: Reaction of 1,4-butanediol L J J
NH 3 H(:) NH2 + H2NN H2 4. N N
H
a b c No!) T Time NH3 Reac- Metal salt Metal Ligand [L] Ligand Pmc Pc Con- Selectivityc) ( C) (h) [eq.] e} tion [M] (mol%) [L] (Ru)q) (Ru)q) ver- a : b : c n pres- (mol%)4 (mol /0) sion b) I\) sure r) ico I.) [bar]
CO
UJ
UJ
1d) 155 12 6 49 [RuHCI(C0)(PPh3)3] 0.1 Triphos 0.1 1.8 74.7 59.1 0.7 6.7 0 I.) 2d) 155 12 6 66h) [RuHCI(CO)(PPh3)3] 0.1 Triphos 0.1 3.2 61.8 78.0 0.6 5.4 0 F-, UJ
I
3d) 155 12 6 45 [RuHCI(C0)(PPh3)3] 0.1 Xantphosg) 0.1 1.4 35.0 81.8 0.0 6.4 0 4d) 155 60 6 61 h) [RuHCI(C0)(PPh3)3] 0.2 Triphos 0.2 11.5 1.7 99.5 23.6 8.2 62.3 I.) 5d) 155 60 6 61h) [RuHCI(C0)(PPh3)3] 0.1 Triphos 0.1 14.0 2.0 98.5 34.2 11.4 49.6 6d) 155 12 6 81') [RuHCI(C0)(PPh3)3] 0.1 Triphos 0.1 10.0 1.4 10.5 97.3 0 0.9 7d) 180 12 6 89 [RuHCI(C0)(PPh3)3] 0.1 Triphos 0.1 12.0 1.7 9.2 97.5 0 0.8 8k) 155 12 6 90') Catalyst complex XlVb 0.1 -3.5 3.6 74,8 44.7 2.1 41.0 9c 155 12 6 41 [RuHCI(C0)(PPh3)3] 0.1 Triphos 0.1 2.1 66.3 62.1 0.5 5.8 10d) 155 12 6 41 [RuHCI(C0)(PPh3)3] 0.1 Xanthphosg) 0.1 1.6 34.3 79.6 0 4.9 11d) 155 12 6 41 _ Catalyst complex XlVb 0.1 1.1 63.0 71.8 9.3 17.3 , , PF0000071687/MKr 12d) 155 12 6 61 h) [RuHCI(C0)(PPh3)3] 0.1 Xanthphosg) 0.1 1.4 29.3 79.8 0 3.3 13d) 155 12 6 61 h) [Ru(COD)methylally12] 0.1 (Tetraphos)l) 0.1 1.3 10.9 33.2 0 0.6 14d) 155 12 6 5511) Catalyst complex XlVb 0.1 1.5 ' 25 81 4.8 13.6 15d) 180 12 6 39h) [RuHCI(C0)(PPh3)3] 0.2 Triphosf) 0.2 5.7 99.9 1.7 4.7 37.7 16d) 155 12 ' 6 35 [RuHCI(C0)(PPh3)3] 0.2 Triphosf) 0.2 1.8 75.5 60.4 0.7 20.5 17d) 155 12 6 40 Catalyst complex XlVa 0.1 1.2 56.1 79.7 3 16.3 18d) 180 2 6 53 Catalyst complex XlVb 0.2 1.1 91.5 36.4 25.8 35.4 19d) 180 12 6 70h) Catalyst complex XlVb 0.1 1.2 94.2 30.1 37.2 31.6 n 20d) 155 12 1.5 11 Catalyst complex XlVb 0.1 1.1 81.6 35.4 9 51 0 I.) 21d) 155 12 6 70n) [RuHCI(C0)(PPh3)3] 0.1 Triphosf) 0.1 3.4 19.8 95.4 0 1.5 K) u.) 22d) 155 12 6 38 [RuHCI(C0)(PPh3)3] 0.2 DPPEPP 0.2 1.0 66.6 68.1 0.1 11 u.) 23d) ) 155 12 6 41 [RuHCI(C0)(PPh3)31 0.2 DPPEPP 0.2 4.3 39.4 56.2 0 4.3 "

H
2e) 180 12 6 82n) Catalyst complex XlVb 0.1 2.3 89.9 36.2 35.4 27.7 u.) a) 50 ml of toluene; batch size: 25 mmol of 1,4-butanediol, co 1.3 b) Evaluation by means of GC (area `)/0);
C) Product selectivity determined by means of GC;
d) Ru partition coefficient was determined by reference to the measured Ru contents in 50 ml of organic solvent and 5 ml of water (addition after the end of the reaction);
e) Molar equivalents of NH3 per OH function on the substrate;
f) Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, CAS 22031-12-5;
. g) Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, CAS 161265-03-8;
' h) 5 bar H2 injected cold;
i) 20 bar H2 injected cold;
j) 30 bar H2 injected cold;
k) Ru partition coefficient was determined by reference to the measured Ru contents in 50 ml of organic solvent and 50 ml of water (addition after the end of the PF0000071687/MKr reaction), I) Tetraphos = tris[2-(diphenylphosphino)ethyllphosphine, CAS 23582-03-8, m) 5 mol% water per OH function on the substrate, n) 10 bar H2 injected cold, o) 0.2 mol% potassium tert-butanolate, p) Bis(2-diphenylphosphinoethyl)phenylphosphine, CAS: 23582-02-7 q) Pmc = mRu (upper phase)/mRu (lower phase); Pc = cRu (upper phase)/cRu (lower phase);
r) mol% based on number of OH functions on the substrate co co CO

PF0000071687/MKr Table 2: Reaction of diethylene glycol NH3 /----- \
HO,..õ.-----, -----,_,....OH -1.- HO,.....õ----. ts11-4, 4. H2N,õ....---...
----....õ.NH2 +

0 0 0 \ /
a b c No. T ( C) Time (h) Reaction Metal salt Metal Ligand N Ligand Pc (m) PC
(c) Conver- Selectivity pressure [M] (mol%) (Ru) (RU) sion a : b : c r) [bar] (mol%) I.) 1d) 155 12 59k) [RuHCI(C0)(PPh3)31 0.1 Triphosf) 0.1 2.5 16.2 87.3 0.1 2.3 I.) co u.) u.) 2d) 135 12 37 Catalyst complex XlVb 0.1 3.3 42.1 87.1 3.3 6.5 I.) 3d) 155 12 43 Catalyst complex XlVb 0.1 1.7 82.4 55.3 20.1 10.9 H
LO
I

CO
4d) 180 12 87" [RuHCI(C0)(PPh3)3] 0.2 Triphos" 0.2 15.6 2.3 24.1 93.0 1.2 5.3 1 I.) -.1 59) 155 12 67" Catalyst complex XlVb 0.1 1.9 2.0 12.2 94.1 2.1 ' 2.0 69) 155 12 82" Catalyst complex XlVb 0.1 5.9 6.1 4.2 93.3 0 2.1 79) 155 12 94n) Catalyst complex XlVb 0.1 5.4 5.7 2.2 91.9 0 0 89) 155 12 43 Catalyst complex XlVb 0.1 1.9 2.0 79.6 57.6 22.4 12.8 9d/ 155 12 42.6 [RuHCI(C0)(PPh3)3] 0.10 Xanthphost) 0.10 1.1 27.7 67.1 0.2 5.26 PF0000071687/MKr 10d) 155 15 46.4 Catalyst complex XlVb 0.10 1.1 77.5 49.1 23.7 13.08 0) 11d) 155 12 41.8 [RuHCI(C0)(PPh3)3] 0.10 Triphos" 0.10 1.0 52.4 66.2 0.9 6.60 12d) 155 12 61.2k) [RuHCI(C0)(PPh3)3] 0.10 Xanthphos" 0.10 1.2 19.0 75.0 0.1 5.85 13d) 155 12 57.1k) Catalyst complex XlVb 0.10 1.3 29.4 87.0 6.7 3.58 140) 180 12 64.7 [RuHCI(C0)(PPh3)3] 0.20 Triphos" 0.20 2.0 97.6 26.4 13.4 53.98 n 15" 155 12 7.5 Catalyst complex XlVb 0.10 1.4 85.9 18.4 7.5 41.55 op I.) 160) 155 12 58.8 [RuHCI(C0)(PPh3)3] 0.40 Triphos" 0.40 1.1 64.7 65.2 1.3 17.97 op u.) u.) 170) 180 12 61.1k) [RuHCI(C0)(PPh3)3] 0.20 Triphos" 0.20 1.7 93.0 43.7 11.6 38.76 I.) H
LO
I
180) 180 12 60.6 k) [RuHCI(C0)(PPh3)3] 0.40 Triphos" 0.40 2.4 95.3 38.0 9.8 48.00 0 op 190) 155 60 60.1 k) [RuHCI(C0)(PPh3)3] 0.20 Triphos" 0.20 6.0 86.1 52.4 6.9 35.35 I.) -A
200) 155 60 58.8 k) [RuHCI(C0)(PPh3)3] 0.10 Triphos" 0.10 3.4 85.1 52.8 8.3 31.65 210) 155 12 42.2 [RuHCI(C0)(PPh3)3] 0.20 OPPEPP1) 0.20 2.0 23.1 46.9 0.0 5.51 p) 22" 180 12 75.6" Catalyst complex XlVb 0.10 2.3 86.1 35.7 47.2 13.77 23d) 180 12 95.9" Catalyst complex XlVb 0.10 3.4 29.1 71.8 18.2 5.32 240) 180 12 79.7" [RuHCI(C0)(PPh3)3] 0.20 Triphos" 0.20 6.39 54.1 83.5 3.3 11.96 PF0000071687/MKr a) 50 ml of toluene; batch size: 25 mmol of diethylene glycol, 6 molar equivalents of NH3 per OH function on the substrate (unless stated otherwise) b) Evaluation by means of GC (area %);
c) Product selectivity determined by means of GC;
d) Ru partition coefficient was determined by reference to the measured Ru contents in 50 ml of organic solvent and 5 ml of water (addition after the end of the reaction);
e) Pmc = mRu (upper phase)/mRu (lower phase); Pc = cRu (upper phase)/cRu (lower phase);
f) Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, CAS 22031-12-5;
g) Ru partition coefficient was determined by reference to the measured Ru contents in 50 ml of organic solvent and 50 ml of water (addition after the end of the reaction), h) mol% based on number of OH functions on the substrate, i) Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, CAS 161265-03-8; 0 j) Bis(2-diphenylphosphinoethyl)phenylphosphine, CAS: 23582-02-7 co k) 5 bar H2 injected cold;
co 1)10 bar H2 injected cold;

m) 20 bar H2 injected cold;

n) 30 bar H2 injected cold;
o) 5 mol% water per OH function on the substrate, co p) 0.2 mol% potassium tert-butanolate, q) Only 1 molar equivalent of NH3 per OH function on the substrate PF0000071687/MKr Table 3: Reaction of MEG
HO NH3 HO ' ..--...õ,OH ,õ. NH2 + H2N...".õõ14H2 + HOH
"-' a b c NO. a) T ( C) Time Reaction Further Metal salt Metal Ligand Ligand Pc (m) Pc (c) Conver- Selectivity c (h) pressure conditions [NA] [Li h) (M01%)g) (Re' e) (Ru)" sionb a : b : c [bar] (mol%) n 1 180 12 36 [RuHCI(C0)(PPh3)3] 0.20 Triphos 0.20 20.4 2.6 45.2 8.8 1.5 59.9 2 155 12 42 [RuHCI(C0)(PPh3)3] 0.20 Triphos 0.20 13.3 1.7 20.8 23.2 3.6 40.4 "
co I.) 3 155 12 57 [RuHCI(C0)(PPh3)3] 0.20 Triphos 0.20 21.0 2.7 19.9 25.1 3.4 34.4 co u.) u.) 4 155 12 57 [RuHCI(C0)(PPh3)3] 0.40 Triphos 0.40 14.4 1.8 34.3 19.9 2.8 15.3 0 I.) 180 12 48 1mol% KOtBu [RuHCI(C0)(PPh3)3] 0.20 Triphos 0.20 19.4 2.5 43.8 34.0 13.0 20.6 H
La I

CO
6 155 12 42 1morY0 KOtBu [RuHCI(C0)(PPh3)3] 0.20 Triphos 0.20 9.3 1.2 20.0 50.5 11.1 6.9 1 I.) 7 180 12 47 Inject 5 bar H2 [RuHCI(C0)(PPh3)3] 0.20 Triphos 0.20 8.0 1.0 41.2 10.3 2.8 57.0 cold 8 155 12 42 Inject 5 bar H2 [RuHCI(C0)(PPh3)3] 0.20 Triphos 0.20 19.9 2.6 21.6 22.2 3.5 33.9 cold 9 180 12 51 5mol% H20 [RuHCI(C0)(PPh3)3] 0.20 Triphos 0.20 11.9 1.5 39.3 11.1 3.01 54.6 155 12 40 5mol% H20 [RuHCI(C0)(Plph3)3] 0.20 Triphos 0.20 17.7 2.3 19.6 21.7 3.1 33.5 11 155 60 57 Inject 5 bar H2 [RuHCI(C0)(PPh3)3] 0.20 Triphos 0.20 63.9 8.2 57.6 14.0 5.4 62.1 cold PF0000071687/MKr 12 155 60 57 Inject 5 bar H2 [RuHCI(C0)(PPh3)3] 0.10 Triphos 0.10 24.9 3.2 35.0 15.7 7.1 63.6 cold a) 50 ml of toluene; batch size: 25 mmol of ethylene glycol, 6 molar equivalents of NH3 per OH function on the substrate;
b) evaluation by means of GC (area %);
c) product selectivity determined by means of GC;
d) Ru partition coefficient was determined by reference to the measured Ru contents in 50 ml of organic solvent and 5 ml of water;
e) Pc (m) = mRu (upper phase)/mRu (lower phase);
f) Pc (c) = cRu (upper phase)/cRu (lower phase); =
g) mol% based on number of OH functions on the substrate;
h) Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, CAS 22031-12-5 co co I\) CO
I\)

Claims (15)

1. A process for the preparation of primary amines by alcohol amination of alcohols with ammonia with the elimination of water, comprising the steps (a) homogeneously catalyzed reaction of a reaction mixture comprising at least one alcohol, ammonia, at least one nonpolar solvent and at least one catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table of the Elements in the liquid phase, giving a product mixture (P), (b) phase separation of the product mixture (P) obtained in step (a), optionally after lowering the temperature, lowering the pressure and/or adding at least one polar solvent which has a miscibility gap with the nonpolar solvent, to give at least one polar product phase (A) and at least one nonpolar phase (B) comprising at least some of the catalyst used, and separating off the nonpolar phase (B), (c) returning at least some of the nonpolar phase (B) to the reaction in step (a) and (d) separating off the amination product from the polar product phase (A), where the nonpolar solvent used in (a) and the catalyst used in step (a) are selected such that the catalyst accumulates in the nonpolar phase (B), wherein the alcohols have at least one primary or secondary alcohol group and at least a second functional group selected from primary or secondary alcohol group and primary amino group.

2. The process according to claim 1, wherein the primary amines are alkanolamines, diamines, triamines or polyamines.

3. The process according to claim 1 or 2, wherein the alcohols have at least one primary or secondary alcohol group.

4. The process according to any one of claims 1 to 3, wherein, in step (a) and/or (b), at least one polar solvent is used which has a miscibility gap with the nonpolar solvent and in which the amination product dissolves better than in the nonpolar solvent.

5. The process according to any one of claims 1 to 4, wherein the quantitative partition coefficient P MC = [amount of dissolved catalyst in the nonpolar phase (B)]/[amount of dissolved catalyst in the polar product phase (A)] is at least 1.5.

6. The process according to any one of claims 1 to 5, wherein the quantitative partition coefficient P MA = [amount of amination product in the polar phase (A)]/[amount of amination product in the nonpolar phase (B)J is at least 1.5.

7. The process according to any one of claims 1 to 6, wherein the at least one polar solvent is selected from water, dimethylformamide, formamide, acetonitrile, the alcohol used in step (a) and mixtures thereof.

8. The process according to any one of claims 1 to 7, wherein the nonpolar solvent is selected from saturated hydrocarbons such as hexane, heptane, octane and cyclohexane; linear and cyclic ethers such as diethyl ether, 1,4-dioxane, tert-butyl methyl ether, diglyme and 1,2-dimethoxyethane and aromatic hydrocarbons such as benzene, toluene, o-, m-, p-xylene and mesitylene, and mixtures thereof.

9. The process according to any one of claims 1 to 8, wherein, prior to separating off the amination product in step (d), the catalyst present in the polar product phase (B) is extracted with the nonpolar solvent used in step (a).

10. The process according to claim 9, wherein the extracted catalyst is returned at least partially to the reaction.

11. The process according to any one of claims 1 to 10, wherein, in step (d), the amination product is separated off from the polar solvent by distillation.

12. The process according to any one of claims 1 to 11, wherein the catalyst comprises Ru and/or Ir.

13. The process according to any one of claims 1 to 12, wherein the catalyst comprises at least one phosphorus donor ligand.

14. The process according to any one of claims 1 to 13, wherein the reaction in step (a) is carried out at a temperature of from 20 to 250°C and at pressures of from 0.1 to 20 MPa absolute.

15. The process according to any one of claims 1 to 14, wherein the reaction in step (a) takes place with the addition of bases.