HRP960295A2 - Process for the hydrogenation of imines in the presence of immobilized iridium-diphosphine catalysts - Google Patents

Description

The proposed invention relates to the process of hydrogenation of imines with hydrogen at elevated pressure, in the presence of iridium diphosphine catalysts immobilized on a support material, and halides. The reaction mixture must necessarily contain some inorganic or organic acid.

The processes of catalytic hydrogenation of tmin with iridium catalysts have been known for a relatively long time from earlier articles. For example, US-A-4 994 615 describes a procedure for the asymmetric hydrogenation of prochiral N-arylketimine, in which an Iridium catalyst with chiral diphosphine ligands is used.

These homogeneous catalytic processes have proven to be valuable, but in the case of larger processing quantities or especially at the industrial level, it becomes on the contrary obvious that catalysts are often prone to deactivation to a lesser or greater degree, depending on the used catalyst precursor, substrate and diphosphine ligand. Especially at elevated temperatures - for example >, necessary to achieve a short reaction time - it is often no longer possible to achieve complete conversion. The catalyst efficiency is therefore not completely satisfactory from the point of view of adequate profitability for the industrial use of the hydrogenation process.

Furthermore, catalysts in these homogeneous processes cannot be renewed, or are renewed only by expensive methods, which is always associated with unwanted losses.

In addition to homogeneous catalysts, heterogeneous catalysts have also been proposed for enantioselective hydrogenation of multiple bonds.

For example, EP-A-0 496 699 and EP-A-0 496 700 propose dioxolane- and pyrrolidemibsphines containing silane groups, and their iridium complexes, fixed on an inorganic support material, for example silicate. A heterogeneous reaction solution was obtained in this way during hydrogenation, and the catalyst fixed on the inorganic support can be easily separated from the solution at the end of the reaction.

There is a need for reusable catalysts that can be easily separated, and whose activity and, above all, selectivity are mostly retained during reuse, especially in the case of various industrial hydrogenation processes.

Despite the advantages in the simplicity of separation and reprocessing of catalysts fixed on a support material, often the activity, productivity and selectivity of such immobilized systems are not entirely satisfactory.

Now, surprisingly, it has been found that the catalytic activity can be significantly increased if the reaction mixture additionally contains an acid, in addition to halides.

Furthermore, it was unexpectedly found that at the same time, in this way, catalyst deactivation can be significantly reduced or completely eliminated, and a significant increase in catalyst productivity can be achieved. In addition, it was surprisingly found that under the selected conditions the enantioselectivity is high, and high optical yields can be achieved, for example up to about 80%, even at relatively high reaction temperatures.

Catalysts can be easily separated and reused, without significant loss of activity, which makes their use in various industrial processes particularly advantageous and economical.

The invention relates to the process of hydrogenation of imines with hydrogen under elevated pressure in the presence of iridium catalysts with or without inert solvents, wherein the reaction mixture contains iridium catalysts immobilized on a support material, ammonium chloride, bromide or iodide or metal chloride, bromide or iodide soluble in the reaction mixture , and additionally some acid.

Imines are especially those containing at least one group >C=N-, If the groups are unsymmetrically substituted and therefore compounds with a prochiral ketimine group are formed, mixtures of optical isomers or pure optical isomers can be formed by the process according to the invention, if an enantioselective or diastereoselective iridium catalyst is used . Imines may contain further chlorine C-atoms. The free bonds in the above formulas can be saturated with H or organic radicals having 1 to 22 C-atoms or organic heteroradicals having 1 to 20 C-atoms and at least one heteroatom from the group consisting of O, S, N and P. The N-atom of the group >C=N- can also be saturated with NH2 Either a primary amino group with 1 to 22 C-atoms or a secondary amino group with 2 to 40 C-atoms. Organic radicals can be substituted, for example, with F, Cl, Br, C1-C12-alkyl esters or amides, or phenyl esters or benzylic esters from the group -CO2H, -SO3H or -PO3H2. Aldlmine and ketalmine groups are particularly reactive, and selective hydrogenation of the groups is possible

>C=N- or >C=N-N-

in the presence of an additional unsaturated group

>C=O< or >C=O-

procedures according to the invention.

Under aldimilnsklm and ketimitne groups are also meant hydrazotic groups

>C=N-N-.

The process according to the invention is particularly suitable for the hydrogenation of aldimines, ketimines and hydrazones, resulting in the corresponding amines and hydrazines. Ketimines are primarily N-substituted. It is advantageous to use chiral iridium catalysts and hydrogenate enantiomerically pure, chiral or prochiral ketimines. For the preparation of optical isomers, the optical yields (enantiomeric excess, ee) are, for example, more than 30%, preferably more than 50%, and yields greater than about 80% can be achieved.

Imines are primarily those of formula I

[image]

which are hydrogenated into amines of formula II

[image]

in which R3 is preferably a substituent, and in which R3 is straight-chain or branched C1-C12-alkyl, cycloalkyl with 3 to 8 ring C-atoms; heterocycloalkyl linked through a C-atom and having 3 to 8 ring atoms and 1 to 2 heteroatoms from the group consisting of O, S and NR 6 ; C7-C16-aralkyl linked via an alkyl-C or C1-C12-alkyl substituted by cycloalkyl or heterocycloalkyl or said heteroaryl; or wherein R 3 denotes C 6 -C 12 -aryl or C 4 -C 11 -heteroaryl which is attached via a ring atom and has 1 or 2 ring heteroatoms; where R 3 is unsubstituted or substituted with -CN, -NO 2 , F, Cl, C 1 -C 12 -alkyl, C 1 -C 12 -alkoxy, C 1 -C 12 -alkylthio, C 1 -C 6 -haloalkyl, -OH, C 6 -C 12 -aryl or -aryloxy or -arylthio, C7-C16-aralkyl or -aralkoxy or -aralkylthio, by a secondary amino group with 2 to 24 atoms, -CONR4R5 or -COOR4, and where the aryl radicals and aryl groups are in aralkyl, aralkyl and aralkylthio on their part unsubstituted or substituted with -CN, -NO2. F, Cl, C1-C4-alkyl, -alkoxy, -alkylthio, -OH, -CONR4R6 or -COOR4; R4 and R5 independently of each other are H, C1-C4-alkyl, phenyl or benzyl, or R4 and R5 together denote tetra- or pentamethylene or 3-oxapentylene; R 6 is independently defined as R 4 ;

R1 and R2 independently of each other are a hydrogen atom, C1-C12-alkyl or cycloalkyl with 3 to 8 ring C-atoms which are unsubstituted or substituted by -OH, C1-C12- alkoxy, phenoxy, benzyloxy, a secondary amino group with 2 to 24 atoms, -CONR4R5 or -COOR4; C6-C12-aryl or C7-C16-aralkyl which are unsubstituted or substituted as R3, or -CONR4R6 or -COOR4, wherein R4 and R5 have the meanings given above; or R3 is defined as above, a

R1 and R2 together denote an alkylene with 2 to 5 C-atoms which is interrupted or not interrupted by 1 to 2 -O-, -S- or -NR6- and/or unsubstituted or substituted by =O or as above for alkyl R1 and R2 and/or is bonded with benzene, pyridine, ptrymidine, furan, thiophene or pyrrole; or R 2 is as defined above and R 1 and R 3 together are alkylene having 2 to 5 C-atoms, OR are alkylene having 2 to 5 C-atoms and is terminated by 1 or 2 -O-, -S- or -NR6-, and/or is unsubstituted or substituted with -O or as above substituted with =O or as above for alkyl R1 and R2 and/or is bonded with benzene, pyridine, pyrimidine, furan, thiophene or pyrrole.

The radicals R1, R2 and R3 may contain one or more chiral centers.

R1, R2 and R3 can be substituted in any position by identical or different radicals, for example with 1 to 5, preferably 1 to 3 substituents.

Suitable substituents for R1, as well as for R2 and R3 are: C1-C12-, preferably C1-C6-, and in particular C1-C4-alk11, -alkoxy or -alkylthio, for example methyl, ethyl, propyl, n-, i- and t-butyl, isomers of pentyl, hexyl, octyl nonyl, decyl, undecyl and dodecyl, and corresponding alkoxy and alkylthio radicals;

C1-C6-, preferably C1-C4-haloalkyl with preferably F and C1 as halogens, for example trifluoro or trichloromethyl, difluoro-chloromethyl, fluorodichloromethyl, 1,1-difluoroethyl-1-yl, 1,1-dichloroethyl-1-yl, 1,1,1-trichloro- or -trifluoroethyl-2-yl, pentachloroethyl, pantafluoro-ethyl, 1,1,1-trifluoro-2,2-dichloroethyl, n-perfluoropropyl, i-perfluoropropyl, n-perfluorobutyl, fluoro- or chloromethyl, difluoro- or dichloro-methyl, 1-fluoro-or -chloroethyl-2-yl or -eth-1-yl, 1-, 2- or 3-fluoro- or -chloroprop-1-yl or -prop- 2-yl or -prop-3-yl, 1-fluoro or -chlorobut-1-yl, -but-2-yl, -but-3-yl or -but-4-yl, 2,3-dichloroprop-1 -yl, 1-chloro-2-fluoro-prop-3-yl, 2,3-dichlorobut-1-yl;

C6-C12-aryl, -aryloxy or -arylthio, in which the aryl is preferably naphthyl and, especially phenyl, or C7-C16-aralkyl, -araloxy and -aralkylthio, in which the aryl radical is preferably naphthyl, and especially phenyl, and alkylene the radical is straight-chain or branched and contains 1 to 10, preferably 1 to especially 1 to 3 C-atoms, for example benzyl, naphthylmethyl, 1-or 2-phenyleth-1-yl or -eth-2-yl, or 1-, 2 - or 3-phenylprop-1-yl, -prop-2-yl or -prop-3-yl, and benzyl is particularly preferred;

Radicals containing the above-mentioned aryl groups can, on the contrary, be mono- or polysubstituted, for example with C1-C4-alkyl, -alkoxy or -alkylthio, halogemm, -OH, -CONR4R5 or -COOR5, in which

R4 and R5 have the meanings mentioned earlier;

examples are methyl, ethyl, n- and i-propyl, butyl, the corresponding alkoxy- and alkylthio radicals, F, Cl, Br, dimethyl-, methylethyl- or diethylcarbamoyl and methoxy-, ethoxy-, phenoxy- and benzyloxycarbonyl;

halogen, especially F and Cl;

a secondary amino group having 2 to 24, preferably. 2 to especially 2 to 6 C-atoms, where the secondary amino group preferably contains 2 alkyl groups, for example dimethyl-, methylethyl-, diethyl-, methylpropyl-, -methyl-n-butyl-, di-n-propyl-, di- n-butyl and di-n-hexylamino;

-CONR4R5 in which

R4 and R5 independently of each other denote C1-C12-, preferably C1-C6-, and especially C1-C4-alkyl, or R4 and R5 together form tetra- or pentamethylene or 3-oxapentlene, where alkyl can be straight-chain or branched, for example dimethyl -, methylethyl-, diethyl-, methyl-n-propyl-, ethyl-n-propyl, dl-n-propyl-, methyl-n-butyl-, n-propyl-n-butyl- and di-n-butylcarbamoyl;

-COOR4 in which it is

R4 C1-C12-, preferably C1-C6-alkyl which can be straight-chain or branched, for example methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, and isomers of pentyl, hexyl, heptyl, octyl , nonila, decila, undecila and dodecila.

R1, R2 and R3 may contain, in particular, functional groups, for example keto groups, -CN, -NO2, carbon double bonds, N-O-, aromatic halogen groups and amide groups.

Heteroaryl R1 and R2 is preferably a 5- or 6-membered ring with 1 to 2 identical or different heteroatoms, especially O, S or N, which preferably contains 4 to 5 C-atoms and can be joined with benzene. Examples of heteroaromatics from which R1 can be derived are furan, pyrrole, thiophene, pyridine, pyrimidine, indole and quinoline.

Alkyl R1 and R2 substituted with heteroaryl are preferably derived from a 5- or 6-membered ring having 1 or 2 identical or different heteroatoms, especially O, S or N, which preferably contains 4 or 5 C-atoms and can be joined with benzene. Examples of heteroaromatics are furan, pyrrole, thiophene, pyridine, pyrimidine, indole and quinoline.

Heterocycloalkyl R1 and R2 or alkyl R1 and R2 substituted with heterocycloalkyl preferably contains 4 to 6 ring atoms and 1 or 2 identical or different heteroatoms from the group containing O, S and NR6. It can be combined with benzene. It can be derived, for example, from pyrrolidine, tetrahydrofuran, tetrahydrothiophene, indane, pyrazolidine, oxazolidine, piperidine, piperazine or morpholine.

Alkyl R1, R2 and R3 are preferably unsubstituted or substituted C1-C6-, especially C1-C4-alkyl, which can be straight-chain or branched. Examples are methyl, ethyl, i- and n-propyl, i-, n- and t-butyl, and pentyl, hexyl, hetyl, octyl, nonyl, decyl, undecyl and dodecyl isomers.

Unsubstituted or substituted cycloalkyl R 1 , R 2 and R 3 preferably contain 3 to 6, especially 5 or 6 ring carbon atoms. Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Aryl R1, R2 and R3 are preferably unsubstituted or substituted naphthyl and especially phenyl. Aralkyl R1, R2 and R3 are preferably unsubstituted or substituted phenylalkyl having 1 to 10, preferably 1 to especially 1 to 4 C-atoms in alkylene, where alkylene can be straight-chain or branched. Examples are in particular benzyl, as well as 1-phenyleth-1-yl, 2-phenyleth-1-yl, 1-phenylprop-1-yl, 1-phenylprop-2-yl, 1-phenylprop-3-yl, 2-phenylprop -1-yl, 2-phenylprop-2-yl and 1-phenylbut-4-yl.

In -CONR4R5 and -COOR4, R3, R4 and R5 are preferably C1-C6-, especially C1-C4-alkyl, or R4 and R5 together are tetramethylene, pentamethylene or 3-oxapentylene. Examples of alkyl are listed earlier.

Alkylene R1 and R2 together or R1 and R3 together are preferably terminated by -O-, -S- or -NR6-, preferably -O-. R1: and R2 together or R1: and R3 together preferably form, with the C-atom or with the -N=C group to which they are attached, a 5- or 6-membered ring. Preferred substituents are listed earlier. The linked alkylene R1 and R2 together or R1 and R3 together are preferably alkylene linked with benzene or with pyridine. Examples of alkylene are: ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene and 1,6-hexylene. Examples of interrupted alkylenes or alkylenes substituted with =O are 2-oxa-1,3-propylene, 2-oxa-1,4-butylene, 2-oxa or 3-oxa-1,5-pentylene, 3-thia-1, 5-pentylene, 2-thia-1,4-butylene, 2-thia-1,3-propylene, 2-methylamino-1,3-propylene, 2-ethylamino-1,4-butylene, 2- or 3-methylamino - 1,5-pentylene, 1-oxo-2-oxa-1,3-propylene, 1-oxo-2-oxa-1,4-butylene, 2-oxo-3-oxa-1,4-butylene and l -oxa-2-oxo-1,5-pentylene. Examples of fused alkylenes are:

[image]

Examples of fused and interrupted alkylenes that are unsubstituted or substituted with =O are:

[image]

R 4 and R 5 independently of each other are preferably H, C 1 -C 4 alkyl, phenyl or benzyl. R6 is preferably H or C1-C4-alkyl.

Another group that is preferred is that of prochloric acid, in which in formula I, R1, R2 and R3 differ from each other and are not hydrogen.

In the group that is especially at an advantage, in formula I,

R3 is 2,6-di-C1-C4-alkylphen-1-yl and especially 2,6-dimethylphen-1-yl or 2-methyl-6-ethylen-1-yl,

R1 is C1-C4-alkyl, especially ethyl or methyl, and

R 2 is C 1 -C 4 -alkyl, C 1 -C 4 -alkoxyethyl, and especially methoxymethyl.

Apart from these, imini formula

[image]

are of particular importance, as well as the names of the formulas

[image]

Imines of formula I are known or can be prepared by known methods from aldehydes or ketones and primary amines.

Iridium catalysts are preferably homogeneous or inhomogeneous catalysts, which are soluble, which swell, or are mostly insoluble in the reaction medium. The term catalyst also includes the catalyst precursor, which is converted to active catalytic species at the start of hydrogenation. Catalysts preferably correspond to formulas III, IIIa, IIIb, IIIc and IIId,

[image]

in which

X denotes olefinic ligands or one diene ligand, Y is a ditertiary diphosphine, (a) phosphine groups of which are attached to different C-atoms of a carbon chain with 2 to 4 C-atoms, or (b) phosphine groups of which are attached either directly or through bridging groups -CRaRb- in the ortho positions of the cyclopentadienyl ring or on at least one cyclopentadienyl ring of ferrocenyl, or (c) one phosphine group of which is attached to a carbon chain with 2 to 3 C-atoms and the other phosphine group of which is attached to an oxygen atom or a nitrogen atom terminally attached to that carbon chain, or (d) phosphine groups of which are attached to two oxygen atoms or nitrogen atoms terminally attached to the C2-carbon chain, and in cases (a), (b), (c) and (d), together with the Ir atom forms a 5-, 6- or 7-membered ring,

the radicals Z independently mean Cl, Br or I,

An is the anion of the oxygen atom, a

M+ is an alkali metal cation or a quaternary ammonium ion,

and R a and R b are independently H, C 1 -C 8 -alkyl, C 1 -C 4 -fluoroalkyl, phenyl or benzyl, or phenyl or benzyl substituted with 1 to 3 C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy. Rb is preferably H. Ra is preferably C1-C4-alkyl and especially methyl.

Diphosphine Y preferably contains at least one chiral C-atom, and diphosphine is preferably an optically pure stereoisomer (enantiomer or diastereomer), or a diastereomer pair, since optical induction is achieved during asymmetric hydrogenation with catalysts containing these ligands.

The olefinic ligands X can be branched or preferably straight-chain C2-C12-alkylenes, especially C2-C6-alkyenes. Some examples are dodecylene, decylene, octylene, 1-, 2- or 3-hexene. 1-, 2- and 3-pentene, 1- or 2-butene, propene and ethene. The diene ligands X can be open-chain or cyclic dienes with 4 to 12, preferably 5 to 8 C-atoms, wherein the diene groups are preferably separated by one or two saturated C-atoms. Some examples are butadiene, pentadiene, hexadiene, heptadiene, octadiene, decadiene, dodecadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, and bridged cyclodienes such as norbornadiene and bicyclo-[2.2.2]octadiene. Hexadiene, cyclooctadiene and norbornadiene are preferred.

An overview of catalysts fixed on inorganic supports, their preparation and their field of application was presented, for example, by M. Capka in Collect. Czech. Chem. Commun., 55 (1990) 2803-2839 and U. Nagel et al. in J. Chem. Soc, Chem. Commun., (1986) 1098-1099.

Preferably, the diphosphine Y is bound via a silyl group to an inorganic support material T which is selected from the group consisting of silicates, semi-metallic or metal oxides, glasses or mixtures thereof.

The solid carrier material T is preferably a powder whose average particle diameter is 10 nm to 2000 µm, preferably 10 nm to 1000 µm, and especially 10 nm to 500 µm.

The carrier can consist of either compact or porous particles. Porous particles preferably have large internal surfaces (determined by the BET method), for example 1 to , preferably 30 to . Examples of oxides and silicates are SiO2, TiO2 ZrO2, MgO, NiO, WO3, Al2O3, La2O3, silica gels, clays and zeolites. Carrier materials that are advantageous are silica gels, aluminum oxide, titanium oxide or glass, and their mixtures. An example of glass as a carrier material is "controlled pore glass", which is commercially available.

The group of diphosphines fixed on an inorganic support material, which is preferred, consists of ferrocenyl diphosphines of the formula Iva

[image]

where

R 7 denotes C 1 -C 8 -alkyl, phenyl, or phenyl substituted with 1 to 3 C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy;

R8 and R9 mutually independently represent C1-C12-alkyl or C6-C12-cycloalkyl, phenyl, C5-C12-cycloalkyl which is substituted with C1-C4-alkyl or C1-C4-alkoxy, or phenyl which is mono- or polysubstituted with one to three C1-C4-alkyl, C1-C4-alkoxy, -SiR10R11R12, halogen, -SO3Me, -CO2Me, -PO3Me, -NR13R14, -[+NR13R14R15]X or C1-C5-fluoroalkyl; or

The group -PR8R9 is a radical of formula V, Va, Vb or Vc

[image]

and

R10, R11 and R12 independently of each other denote C1-C12-alkyl or phenyl;

R13 and R14 are H, C1-C12-alkyl or phenyl or

R 13 and R 14 together are tetramethylene, pentarnethylene or 3-oxa-1,5-pentylene;

R 15 is H or C 1 -C 4 -alkyl;

R16 and R17 are identical or different and denote C1-C12-alkyl, C5-C12-cycloalkyl, phenyl, C5-C12-cycloalkyl which is substituted with C1-C4-alkyl, C1-C4-alkoxy, or phenyl which is substituted with one to three C1-C4-alkyl, C1-C4-alkoxy, -SiR10R11R12 > halogen, -SO3Me, -CO2Me, -PO3Me, -NR13R14, -[+NR13R14R15]X or C1-C5-fluoroalkyl; or

Group –PR16R17 is a radkal of formula V, Va, Vb or Vc

[image]

Radicals R18 are identical or different radicals and independently mean C1-C12-alkyl, C3-C7-cycloalkyl, benzyl or phenyl, or together C5-C12-alkylene and

R19 is C1-C12-alkylene or phenylene,

Me is H or an alkali metal,

X is the anion of a monobasic acid,

A is NH or N(C1-C12-alkyl),

R20 is C1-C4-alkyl or O-C1-C12-alkyl,

R21 is C1-C12-alkyl,

T is the inorganic carrier material defined earlier, te

if n is 0, r is 1, 2 or 3,

if n is 1, r is 1 or 2,

and if n equals 2, r is 1.

Another preferred group of diphosphines attached to an inorganic support material is compounds of the structures shown by formulas IVb or IVc

[image]

in which the groups (R22)2P(CH2)mi are in the o- or m-position relative to each other, and

radicals R22 are identical or different radicals,

m and n are independently 0 or 1,

radicals R22 independently of each other denote C1-C12-alkyl, C5-C12-cycloalkyl, phenyl, C5-C12-cycloalkyl which is substituted by C1-C4-alkyl or C1-C4-alkoxy or phenyl which is substituted by one to three C1- C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl,

or two radicals in the group (R22)2P together are o,o-diphenylene,

-R23-U-is a bond or -(CxH2x-0)y-,

or U is -O-, a

R23 is C1-C6-alkylene,

x is an integer from 2 to

y is a number from 2 to 6,

R24 is C2-C18-alkylene, phenylene or benzylene,

R25 is hydrogen, straight-chain or branched C1-C12-alkyl, phenyl or benzyl,

r is 0, 1 or

R21 and T are as defined in claim 21.

Examples of halogen, unsubstituted or substituted alkyl, alkylene, cycloalkyl, alkoxy or fluoroalkyl have already been mentioned earlier, and can be used as examples for the radicals R 7 to R 22 .

Compounds of formulas IVa, IVb and IVc are idealized in terms of bond positions on a solid support material and represent the most probable number of bonds that occur on a solid support material. In particular, the following cases may normally occur during distribution

[image]

(IV d), in which r is a number from 0 to 2,

[image]

(IV e), in which r is the number 0 or 1,

[image]

R 21 and T have the meaning set forth above, including whichever is preferred, and R 21 is preferably C 1 -C 4 -alkyl.

Compounds of formulas IVb and IVc are known, and their preparation is described in EP-A-0 496 699, EP-A-0 496 700 and in Heterogeneous Catalysis and Fine Chemicals HL Stud. Surf. ScL and Cat, 78 (1993) 107-114.

Diphosphinyl of formula IVa can react in a reaction procedure analogous to that described in EP-A-0 496 699, by reacting compounds of formula VIIIa

[image]

in which the radicals are mentioned earlier, with a solid inorganic support material, wherein the reaction is conveniently carried out under an inert gas, for example argon, and at a temperature of 40 to . First of all, the solid material is initially introduced into the reaction vessel, a solution of the compound of formula VIIIa is added, and the mixture is stirred at an elevated temperature, for example 50 to . Suitable solvents are listed earlier, and toluene and xylene are particularly preferred. For Isolation, the product can either be decanted, centrifuged or filtered. The residue can be cleaned by washing with alkanol and then dried under high vacuum.

Compounds of formula VIIIa can be prepared by a process in which in the first step a) compounds of formula VIIIb

[image]

they take up lithium in a reaction with butyllithium in a known manner in some inert organic solvent in the presence of some amine complex reagent for lithium, and the reaction product then reacts with a mixture of compounds of formula VIIIc

C1PR16R17 (VIIIc)

and VIIId

ClSi(R28)2-(R19)-Cl (VIIId) whereby compounds of formula VIIIe are formed

[image]

in the second step b) compounds of formula VIIIe react in an organic solvent with compounds of formula VIIIf

HPR8R9 (VIIIf) whereby compounds of formula VIIIg are formed

[image]

c) compounds of formula VIIIg react with compounds of formula VIIIh

NH2(C1-C12-alkyl) (VIIIh)

thereby forming compounds of formula VIIIk

[image]

or compounds of formula VIIIg are first reacted with potassium phthalimide, and then with hydrazine, resulting in compounds of formula VIIIm

[image]

and finally, in a further step,

d) compounds of formula VIIIk or VIIIm react with compounds of formula VIIIn

R20(R21O)2Si-(C1-C12-alkyl)-NCO (VIIIn)

thereby forming compounds of formula VIIIa

[image]

where

the radicals R7, R8, R9, R16, R18, R19, R20, R21 and A have the previously stated meaning.

An example of an amine complex reagent for lithium is N,N,N,N-tetra-methyleneethylenediamine.

Compounds of formulas VIIb, VIIIc, VIIId, VIIIf, VIIIh and VIIIn are known and in some cases commercially available. In addition, they can be prepared by procedures described in the literature.

The procedures for their preparation have not been described so far, especially reaction step a). Reaction steps b), c) and d) are processes analogous to those described, for example, in EP-A-612 758 for b) and in EP-A-496 699 for d). Step c) is known to experts from standard organic chemistry textbooks.

The mixture of compounds of formulas VIIIc and VIIId is preferably present in reaction step a) in a molar ratio of 1:10 to 10:1, especially 1:1 to 10:1.

Reaction step a) is preferably carried out at a temperature of up to +, and the mixture of compounds VIIIc and VIIId is preferably added at a temperature of up to , especially at a temperature of up to .

The compound of formula VIIId in reaction step a) is in particular 1-(dimethylchlorosilyl)-3-chloropropane.

Reaction step b) is described for example in EP-A-612 758. The reaction temperature in step b) can be, for example, 20 to , preferably 40 to . Suitable solvents are polar protic and aprotic solvents, which can be used separately or as a mixture of two or more solvents. Some examples of solvents are alkanols, such as methanol and ethanol, and carboxylic acids, such as formic acid and acetic acid.

Compounds of formulas VIIIa, VIIIg, VIIIk and VIIIm were obtained as racemates, pure enantiomers or mixtures of enantiomers. Racemates and mixtures of enantiomers can be separated into stereoisomers using known methods, whereby chromatographic methods are generally preferred.

Compounds are isolated and purified by methods known per se, for example by distillation, extraction, crystallization and/or chromatographic methods.

In a preferred process, hydrazine is used as hydrazine hydrate in reaction step c).

Organic polymer support materials can also be used without problems in the present process. Here, the method of binding the diphosphine component to the polymer can be achieved in different ways. A review of polymer-bound diphosphines and their metal complexes is presented, for example, by J.K. Stille in Reactive Polymers, 10 (1989) 165-174 and Seike et al. in J. Mol. Catal, 56 (1989) 315-328.

Thus, for example, polymer carrier materials were discovered in which the diphosphine component is on the copolymer unit, which is copolymerized together with other monomers, and the diphosphine or its metal complex is attached directly to the polymer chain.

K. Achiwa describes in J, Chem. Japan. Soc, Chemistry Letters, (1978) 905-908 polystyrene copolymers, the benzene radicals of which contain pyrrolide-diphosphine-N-carbonyl groups which form complexes with rhodium.

Another possibility involves the preparation of functionalized polymers in a first step, either by copolymerization or subsequent functionalization of previously created polymers, and incorporation of a diphosphine ligand at the functionalized site in a second step.

Examples of this procedure were described, among others, by Stille et al. in J. Amer. Chem. Soc. 100 (1978) 268-272 and Kagan et al. in J. Amer. Chem. Soc. 95 (1973) 8295-8299.

Another possibility is to start with polymers of known properties, and modify them with catalytically active compounds so that the polymer properties change only slightly and no inclusions or other changes can occur on the catalytically active part of the compound.

The catalyst can be optimally adapted to the reaction medium during the hydrogenation step by choosing a polymer, and then completely separated, which is especially important for large-scale industrial hydrogenation. The cleaning of the hydrated final products is thus much easier.

Diphosphine Y is preferably attached to partially cross-linked swelling or highly cross-linked or straight-chain carrier materials that are soluble in organic solvents.

A preferred group of diphosphines attached to organic polymers is obtained when diphosphine Y is attached to the support material in the form of a copolymer.

The copolymer is primarily formed from monomers with olefinic C=C bonds, of which at least one monomer contains a diphosphine radical.

Another group of polymer-bound diphosphine ligands, which is also advantageous, is obtained by binding a diphosphine with a functional group to a polymer functional group, either directly or by means of a bridging group.

The functional groups in the diphosphine and in the polymer are preferably selected independently from the group consisting of -OH, -NH2, -NH(C1-C12-alkyl), -NCO, -COOH, -COO(C1-C12-alkyl), - CO-halogen and glycidyl groups.

The bridging group preferably contains 2 to 30 carbon atoms, which are directly bonded to each other or interrupted by a heteroatom, and a functional group that can react with the polymer and diphosphine functional group present at both ends.

The functional groups at both ends of the bridging group are preferably identical, and are selected from the group consisting of -OH, -NH2, -NH(C1-C12-alkyl), -NCO, -COOH, -COO(C1-C12-alkyl ), -CO-halogen and glycidyl groups.

Particularly advantageous is the group of polymer-bound diphosphines obtained starting from polymer base structures containing a hydroxyl or primary or secondary amine functional group, some or all of whose functional groups are attached to a diisocyanate that provides distance from the polymer chain, and form a urethane or urea bridge, whose is a second isocyanate group attached to a diphosphine Y that also contains a hydroxyl or primary or secondary amine group.

Diphosphine Y is preferably an aliphatic, cycloaliphatic, heterocycloaliphatic, aromatic or heteroaromatic 1,2-, 1,3-, 1,4- or 1,5-tertiary diphosphine Y.

Ligand mobility and accessibility can be tailored by choosing the nature and length of the diisocyanate. Diphosphines bound in this way are valuable catalysts for hydrogenations, especially for enantio-selective hydrogenations.

The term tertiary phosphine group refers to a phosphorus atom bonded to three carbon atoms, as defined in H. Beyer, Lehrbuch der Organischen Chemie (Textbook of organic chemistry), S. Hirzel Verlag Leipzig, 1968, p. 138.

The polymers can be polymers of olefinic unsaturated monomers, for example polyolefin, polyacrylates, polyisoprene, polybutadiene, polystyrene, polyphenylene, polyvinyl chloride, polyvinylidene chloride or polyallyl compounds. These can be polyaddition compounds, for example polyurethanes or polyethers. Polycondensed products are polyesters or polyamides.

If the polymers are essentially non-crosslinked (thermoplastics), they can be polymers soluble in organic solvents. Partially cross-linked polymers are usually only swellable in organic solvents, and highly cross-linked polymers can be insoluble and conveniently porous materials.

Cross-linked polymers (thermosetting resins) can be phenol-aldehyde resins, for example in the form of commercially available Bakelite®, urea- or melamine-formaldehyde resins, cross-linked polyurethanes or cross-linked epoxy resins.

Di- or triamines are particularly suitable cross-linking components for epoxy resins.

Cross-linked polymers based on triglycidyl isocyanurate are also possible.

Also suitable are, for example, unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and vinyl compounds as crosslinking agents.

Crosslinkable acrylic resins are also possible, which are derived from substituted esters of acrylic acid, for example from epoxy acrylate, urethane acrylate or polyester acrylate.

The second group consists of alkyd resins, polyester resins and acrylate resins, which are cross-linked with melamine resins, urea resins, polyisocyanates or epoxy resins.

Preferred cross-linked systems are those of olefinically unsaturated monomers. Examples are polyacrylates, polyolefins or polystyrenes. The network component is also olefinically unsaturated. An example is polystyrene cross-linked with divinylbenzene.

Polymers for use according to the invention are known per se, are in some cases commercially available, or can be prepared by known polymerization processes or by subsequent polymer modification.

Examples of straight chain polymers soluble in organic solvents are listed below.

The monomers forming the polymer are preferably selected from the group consisting of styrene, p-methylstyrene and α-methylstyrene, at least one of which contains a hydroxyl group or a primary or secondary amine group linked as a functional group.

Other comonomers may be present which form a copolymer with styrene derivatives, for example styrene, p-methylstyrene or α-methylstyrene, butadiene, maleic anhydride, acrylates or methacrylates and ethylene, propylene or butylene.

Then there are: copolymer, for example styrene/butadiene, styrene/acrylonitrile, styrene/acrylic methacrylate, styrene/butadiene/alkylacrylate and methacrylate, styrene/maleic anhydride or styrene/acrylonitrile/methylacrylate; mixtures of styrene copolymers and other polymers, for example polyacrylate, diene polymer or some ethylene/propylene/diene terpolymer; block copolymers of styrene, for example styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene-butylene/styrene or styrene/ethylene-propylene/styrene.

Polymers are also graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on copolymers of polybutadiene/styrene, or polybutadiene/acrylonitrile, or styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide to polybutadiene, styrene and alkyl acrylates or alkyl methacrylates to semi-butadiene, styrene and acrylonitrile to ethylene/propylene/diene terpolymers, styrene and acrylonitrile to polyalkyl acrylates or polyalkylmethacrylates and styrene and acrylonitrile to acrylate/butadiene copolymer.

Diene or acyl comonomers. derivatives, for example butadiene, acrylonitrile, alkyl methacrylate, butadiene/alkyl acrylate and methacrylate, maleic anhydride and acrylonitrile/methyl acrylate which form random or block copolymers are preferred.

Another preferred group of polymers is formed from monomers derived from α,β-unsaturated acids or their esters or amides, whose structural elements contain a hydroxyl group or a primary or secondary amine group that is connected as a functional group.

Monomers from the group consisting of acrylates and their C1-C4-alkyl esters, methacrylates and their C1-C4-alkyl esters, acrylamide and acrylonitrile, the structural elements of which contain a hydroxyl group or a primary or secondary amine group which are connected as functional groups, in particular, they are at an advantage.

It is also possible to have further comonomers which form copolymers, which are derived from olefinically unsaturated monomers and which form random polymers or block polymers. Suitable comonomers are acrylates and their C1-C4-alkyl esters, methacrylates and their C1-C4-alkyl esters, acrylamide and acrylonitrile, as well as butadiene, vinyl chloride or vinyl fluoride.

Another group of polymers that are advantageous are formed by monomers containing vinyl alcohol as a homopolymer or vinyl alcohol as a copolymer with vinyl acetate, stearate, benzoate or maleate, vinyl butyral, allyl phthalate or allyl melamine.

Polymers are preferably also formed from phenol and C1-C4-aldehydes, especially from phenol and formaldehyde. The polymers are known as phenol-formaldehyde resins, more specifically novolacs, and are commercially available.

Another group of preferred polymers is derived from bisglycidyl ethers and diols. These are hydroxyl-functional polyethers that are prepared, for example, from bisglycidyl ether and bisphenol A. Polyepoxides can be formed from diepoxide comonomers with primarily 6 to especially 8 to 30 C-atoms, and diols as comonomers, with 2 to 200, especially 2 to 50 C- atoms. A preferred group lz derived from them is created from monomers that form a polymer of cyclic C3-C6-ethers or C2-C6-alkylene glycols with bisglycidyl ethers. Bisglycidyl ethers can be aromatic, aliphatic or cycloaliphatic.

Other preferred polymers with hydroxyl groups as functional groups are polysalirides.

Particularly advantageous are partial cellulose acetates, propionates or butyrates, partial cellulose ethers, starch, chitin and chitosan.

Other polymers are derived from polymers with reducing groups, for example nitrile groups, ketone groups, carboxylic acid esters and carboxylic acid amides.

Polymers insoluble in the reaction medium, but functionalized with a hydroxyl or amine group on the surface, using a chemical or physical process, can also be used. For example, partially unsaturated polymers can be provided with hydroxyl groups on the surface, by oxidation, for example, with hydrogen peroxide. Another option is plasma treatment in, for example, an oxygen atmosphere, or a nitrogen or ammonium atmosphere. Polymers are preferably in powder form. Among these carrier materials, polystyrene is particularly advantageous, which is subsequently functionalized with hydroxyl, amino or hydroxymethyl groups according to known methods.

Another group of compounds which is particularly advantageous is that which has structural repeating units of formula VI

[image]

where

A, R 7 , R 8 , R 9 , R 16 , R 17 , R 18 and R 19 have the meanings given above; Q is bridged by a diisocyanate group; PM is a polymer-forming monomer radical containing, directly or on a side chain, a hydroxyl group or a primary or secondary amine group attached as a functional group, which is linked to a diphosphine by a bridging group Q formed from diisocyanates.

Compounds which are also preferred are those in which the diphosphine with a hydroxyl or primary or secondary amine functional group is a compound of formula VIIa or VIIb

[image]

in which

B represents -NR27- or -O-;

R27 is hydrogen or straight-chain or branched C1-C6-alkyl, a

R22, R23, R25, m and n have the meaning given earlier.

Diphosphines of formula 100, 101, 102, 103, 104, 105, 106, 107, 108, 111, 109 are also very suitable for the process.

[image]

The diisocyanate forming the bridging group Q is preferably selected from the group consisting of

1,6-bis[isocyanato]hexane,

5-isocyanato-3-isocyanomethyl-1,1,3-trimethylcyclohexane,

1,3-bis[5-isocyanato-1,3,3-trimethylphenyl]-2,4-dioxo-1,3-diazetidine,

3,6-bis[9-isocyanatononyl]-4,5-di-(1-heptenyl)cyclohexene,

bis[4-isocyanatocyclohexyl]methane,

trans-1,4-bis[isocyanato]cyclohexane,

1,3-bis[isocyanatomethyl]benzene,

1,3-bis[1-isocyanato-1-methylethyl]benzene,

1,4-bis[2-isocyanatoethyl]cyclohexane,

1,3-bis[isocyanatomethyl]cyclohexane,

1,4-bis[1-isocyanato-1-methylethyl]benzene,

bis[isocyanato]isododecylbenzene,

1,4-bis[isocyanato]benzene,

2,4-bis[isocyanato]toluene,

2,6-bis[isocyanato]toluene,

2,4-/2,6-bis[isocyanato]toluene,

2-ethyl-1,2,3-tris[3-isocyanato4-methanilinocarbonyloxy]propane,N,N-bis[3-isocyanato-4-methylphenyl]urea,

1,4-bis[3-isocyanato-4-methylphenyl]-2,4-dioxo-1,3-diazetidine,

1,3,5-tris[3-isocyanato-4-methylphenyl]-2,4,6-trioxohexahydro-1,3,5-triazine,

1,3-bis[3-isocyanato-4-methylphenyl]-2,4,5-trioxoimidazolidine,

bis[2-isocyanatophenyl]methane,

(2-isocyanatophenyl)-(4-isocyanatophenyl)methane,

bis[4-isooxy anatophenyl]methane,

2,4-bis[4-isocyanatobenzyl]-1-isocyanatobenzene,

[4-isocyanato-3-(4-isocyanatobenzyl)phenyl]-[2-isocyanato-5-(4-isocyanatobenzyl)phenyl]methane,

tris[4-isocyanatophenyl]methane,

1,5-bis[isocyanato]naphthalene and

4,4,-bis[isocyanato]-3,3'-dimethylbiphenyl

A monomer containing a hydroxyl or primary or secondary araine functional group preferably participates in the construction of the polymer in an amount of 5 to 100 mol percent, especially preferably 10 to 100 mol percent.

The polymer is preferably loaded with between 5 and 100 mol % of tertiary diphosphine groups, based on available hydroxyl or primary or secondary amine groups.

The monomers forming the polymer are selected from the group consisting of styrene, p-methylstyrene and α-methylstyrene, at least one of which contains a hydroxyl or primary or secondary amine group which is linked as a functional group,

Other comonomers of diene or acrylic derivatives, for example butadiene, acrylonitrile, alkyl methacrylate, butadiene/alkyl acrylate and methacrylate, maleic anhydride and acrylonitrile/methyl acrylate, which form random or block polymers, are also preferably present.

Monomers that form the polymer, and are particularly advantageous, are selected from the group consisting of α,β-unsalted acids and their esters and amides, at least one of which contains a hydroxyl or primary or secondary amine group that is connected as a functional group.

The monomers forming the polymer are particularly preferably selected from the group consisting of acrylates and their C1-C4-alkyl esters, methacrylates and their C1-C4-alkyl esters, acrylamide and acrylonitrile, at least one of which contains a hydroxyl or primary or secondary amine group which is connected as a functional group.

Other preferred polymers are present if the polymer is made from monomers containing vinyl alcohol as a homopolymer or vinyl alcohol as a copolymer with vinyl acetate, stearate, benzoate or maleate, vinyl butyral, allyl phthalate or allyl melamine.

Phenol and C1-C4-aldehyde are also preferred as monomers that form the polymer.

Other preferred polymers are polyepoxides and are made of cyclic C3-C6-ethers or C2-C6-alkylene glycols and bisglycidyl ethers.

Polysaccharides are also particularly suitable.

If the polymers are highly cross-linked, highly cross-linked macroporous polystyrenes or polyacrylates are particularly advantageous.

The particle size of cross-linked polymers is preferably 10 µm to 2000 µm.

The specific surface area of porous highly cross-linked polymers is preferably 5 to .

Diphosphines attached to the polymer can be copolymerized, for example by the process described above and mentioned earlier.

If the diphosphines are attached via a bridging group Q to a polymer that is soluble, swellable or insoluble in organic solvents, they can be prepared by a process in which polymers with a repeating structural unit of at least one monomer MM, containing, directly or in a side chain, a hydroxyl group or a primary or secondary amine group attached as a functional group.

A) in the first step they react completely or partially with a diisocyanate that forms a bridging group Q in some inert organic solvent, and in the second step the product reacts completely or partially with an aliphatic, cycloaliphatic, heterocycloaliphatic, aromatic or heteroaromatic ditertiary diphosphine, whose phosphine groups are attached to the carbon chain in mutually relative positions 1,2-, 1,3-, 1,4- or 1,5-, and which contain a hydroxyl group or a primary or secondary amine group; or

B) in the first step, some aliphatic, cycloaliphatic, heterocycloaliphatic, aromatic or heteroaromatic ditertiary diphosphine, whose phosphine groups are attached to the carbon chain in relative positions 1,2-, 1,3-, 1,4- or 1,5 -, and which contain a hydroxyl group or a primary or secondary amine group reacts completely or partially with a diisocyanate that forms a bridging group Q in some inert organic solvent, and in the second step the product reacts completely or partially with a polymer with a repeating structural unit of at least one monomer containing a hydroxyl group or a primary or secondary amine group attached as a functional group; and

C) if appropriate, further free isocyanate groups are crosslinked with C2-C24-diol or C2-C24-diamine or reacted with C2-C12-alcohol or C2-C12-amine.

The properties of the polymer can subsequently be modified further in a controlled manner in this way.

The above definitions apply to Q, 1,2-, 1,3-, 1,4- or 1,5-diphosphonic bridging groups and polymers formed from monomers.

When cross-linked polymers are prepared, preferably 0.01 to 10 mole percent of the total isocyanate groups present are cross-linked.

The process is primarily carried out in a polar or non-polar aprotic solvent, and halogenated hydrocarbon, ester, ketone, acid amide, ether, dimethylsulfoxide, aromatic compound or alkane are particularly suitable solvents.

The reaction of the hydroxyl group or the primary or secondary amine group is carried out by known procedures, preferably in the temperature range from to .

The subsequent introduction of, for example, a hydroxyl group into highly cross-linked polystyrene can be carried out by known procedures. Chloromethylation is first carried out as described in Mol. Catal. 51 (1989) 13- hydrolysis is then carried out by the method described by J. M. Frechet et al. in Polymer, 20 (1979) 675-680.

Subsequent modification can also be carried out in bulk, for example by plasma processes. Chemical processes in solution or in emulsion are also possible.

When necessary, insoluble polymers are pre-milled by known procedures and adjusted to the desired particle size.

In compounds of formula IVa, R7 is preferably methyl or ethyl.

Substituted phenyl R8, R9, R16 and R17 in compounds of formula IVa are preferably 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4-ethyl-, 2- or 4-i-propyl-, 2- or 4-t-butyl-, 2-methoxy-, 3-methoxy-, 4-methoxy-, 2- or 4-ethoxy-, 4-trimethylsilyl-, 2- or 4-fluoro-, 2,4-difluoro- , 2- or 4-chloro-, 2,4-dichloro-, 2,4-dimethyl-, 3,5-dimethyl-, 2-methoxy-4-methyl-, 3,5-dimethyl-4-methoxy-, 3,5-dimethyl-4-(dimethylamino)-, 2- or 4-amino-, 2- or 4-methylamino-, 2- or 4-(dimethylamino)-, 2- or 4-SO3H-, 2- or 4-SO3Na-, 2- or 4-[+NH3Cl], 3,4,5-trimethylphen-1-yl, 2,4,6-trimethylphen-1-yl, 4-trifluoromethylphenyl or 3,5-di(trifluoromethyl )- phenyl.

In a preferred group, R 8 and R 9 in the compounds of formula IVa are identical radicals and denote cyclohexyl or phenyl.

The second group is preferably formed if R16 and R17 in the compounds of formula IVa are identical and denote cyclohexyl, phenyl, t-butyl, 2- or 4-methylphen-1-yl, 2- or 4-methoxyphen-1-yl, 2- or 4-(dimethylamino)phen-1-yl, 3,5-dimethyl-4-(dimemamino)phen-1-yl, or 3,5-dimethyl-4-methoxyphen-1-yl.

In the compounds of formulas IVb and IVc, the radicals R22 are preferably identical or different and denote 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4-ethyl-, 2- or 4-i-propyl-, 2- or 4-t-butyl-, 2-methoxy-, 3-methoxy-, 4-methoxy-, 2- or 4-ethoxy-, 4-trimethylsylyl-, 2- or 4-fluoro-, 2,4-difluoro- , 2- or 4-chloro-, 2,4-dichloro-, 2,4-dimethyl-, 3,5-dimethyl-, 2-methoxy-4-methyl-, 3,5-dimethyl-4-methoxy-, 3,5-dimethyl-4-(dimethylamino)-, 2- or 4-amino-, 2- or 4-methylamino-, 2- or 4-(dimethylamino)- 2- or 4-SO3H-, 2- or 4 -SO3Na-, 2- or 4-[+NH3Cl]-, 3,4,5-trimethylphen-1-yl, 2,4,6-trimethylphen-1-yl, 4-trifluoromethylphenyl or 3,5-di(trifluoromethyl ).

In the compounds of formulas IVb and IVc, the radical R22 is especially advantageously phenyl, cyclohexyl, t-butyl, 2- or 4-methylphen-1-yl, 2- or 4-methoxyphen-1-yl, 2- or 4-(dimethylamino) phen-1-yl, 3,5-dimethyl-4-(dimethylamino)phen-1-yl, or 3,5-dimethyl-4-methoxy-phen-1-yl, 4-trifluoromethylphenyl or 3,5-di( trifluoromethyl).

In the compounds of formula IVb and IVc, R22 is particularly preferably phenyl and m+n in formula IVb is 0, 1 or 2.

Iridium catalysts shown in formulas III, IIIa, IIIb, IIIe and IIId are preferred.

An in formula IIIa can be derived from inorganic or organic oxygen acids. Examples of such acids are H2SO4, HC1O4, HC1O3, HBrO4 H1O4, HNO3, H3PO3, H3PO4, CF3SO3H, C6H6SO3H, CH3COOH, CF3COOH and CCl3COOH. Complex acids from which An can be derived are, for example, halogen complex acids of the elements B, P, As, Sb and Bi. Preferred examples of An in formula IIIa are ClO4 , CF3SO3 , BF4 , B(phenyl)4 , PF6 , SbCl6 , AsF6 and SbF6 .

M+ in formula IIIb as alkali metal cations can be, for example, Li, Na, K, Rb or Cs cations. M+ as quaternary ammonium can be quaternary ammonium containing a total of 4 to 40, preferably 4 to 24 C-atoms. M+ can have the formula phenylN+(C1-C6-alkyl)3, benzylN+(C1-C6-alkyl)3 or (C1-C6-alkyl)4N+ M+ in formula IIIb is preferably LI+ Na+ or K+ or (C1-C6-alkyl) 4N+.

Z in formula III is preferably Br or Cl, and especially Cl. Z in formula IIIb is preferably Br or I, and Z in formulas IIIc and IIId is preferably I.

The preparation of catalysts is known per se and is described, for example, in US-A-4 994 615, US-A-5 011 995, US-A-5 112 999 and EP-A-0 564 406. Catalysts of formula III can be prepared for example by reacting the diiridium complex of the formula [IrXZ]2 with diphosphine Y. Iridium catalysts can be added to the reaction mixture as isolated compounds. However, it proved convenient to prepare the catalysts in situ before the reaction, with or without solvent, and if appropriate to add some of the total amount of acid and some ammonium halide or alkali metal halide.

The molar ratio of the imine to the iridium catalyst can be, for example, 5,000,000 to 10, preferably 2,000,000 to 20, especially 1,000,000 to 500,000 to 100.

The process is primarily carried out at a temperature of -20 to , especially 0 to , and especially preferably 10 to , and primarily under a hydrogen pressure of 2x105 to 150x105 Pa (2 to 150 bar), especially 106 to 107 Pa (10 to 100 bar) .

The chlorides, bromides and iodides used are preferably applied in concentrations of 0.01 to 500 mmol/l, especially 0.01 to 50 mmol/l, based on the volume of the reaction mixture.

The process according to the invention includes the additional use of ammonium or metal chloride, bromide or iodide. Chlorides, bromides and iodides are preferably used in amounts from 0.01 to 200, especially 0.05 to 100 equivalents, and especially preferably 0.5 to 50 equivalents, based on the iridium catalyst. Iodides are preferred. Ammonium is preferably tetraalkylammonium with 1 to 6 C-atoms in the alkyl group, and sodium, lithium or potassium are preferred as metals. Tetrabutylammonium iodide and sodium iodide are particularly advantageous.

Practically all metal chlorides, bromides and iodides, i.e. those of the main and subgroups of the periodic table of elements can be used in the process according to the invention, if they are soluble in the reaction mixture and oxidation reactions with other reactants can be excluded.

The reaction can be carried out without or with the presence of a solvent. Suitable solvents, which can be used alone or as a mixture of solvents, are: aliphatic and aromatic hydrocarbons, for example pentane, hexane, cyclohexane, methylcyclohexane, benzene, toluene and xylene; ethers, such as diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons, such as methylene chloride, chloroform, 1,1,2,2-tetrachloroethane and chlorobenzene; esters and lactones, such as ethyl acetate, butyrolactone and valerolactone; acid amides and lactams, such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; ketones, such as acetone, dibutyl ketone, methyl isobutyl ketone and methoxyacetone; and alcohols, such as methanol, ethanol, propanol or butanol.

The process according to the invention further includes the use of an acid. Such acids can be inorganic, or preferably organic acids. The acid is preferably used in at least the same molar amount as the iridium catalyst (the same catalytic amount), and it can also be used in excess. The excess may even involve the use of acid as a solvent. Preferably, 0.001 to 50, especially 0.005 to 50% by mass of acid, based on the amine, is used. In some cases, it may be convenient to use anhydrous acid.

Some examples of inorganic acids are H2SO4, highly concentrated sulfuric acid (oleum), H3PO4, orthophosphoric acid, HF, HCl, HBr, HI, HClO4, HBF4, HPF6, HAsF6, HSbCl3, HSbF6, and HB(phenyl)4. H2SO4 is particularly advantageous.

If hydrogen iodide is used as the acid, the addition of a further halide can be omitted. Then there is no need to add ammonium chloride, bromide or iodide, or metal chloride, bromide or iodide, which are soluble in the reaction mixture.

The molar ratio of the dark to hydrogen iodide is preferably 500,000 to especially 10,000 to 1,000. Hydrogen iodide can be added here in gaseous form or as an aqueous solution or in the form of any solution. In some cases, it is convenient to work in anhydrous conditions.

Examples of organic acids are aliphatic or aromatic non-halogenated or halogenated (fluorinated or chlorinated) carboxylic acids, sulfonic acids and phosphoric (V) acids (e.g. phosphonic acids and phosphonic acids) with preferably 1 to 20, especially 1 to especially preferably 1 to 6 C-atoms. Examples are formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, phenylacetic acid, cyclohexane carboxylic acid, chloro- or fluoroacetic acid, dichloro- or difluoroacetic acid, trichloro- or trifluoroacetic acid, chlorobenzoic acid, methanesulfonic acid, ethanesulfonic acid , benzenesulfonic acid, p-toluenesulfonic acid, chlorobenzenesulfonic acid, trifluoromethanesulfonic acid, methylphosphonic acid and phenylphosphonic acid. Acetic acid, propionic acid, trifluoroacetic acid, methanesulfonic acid and chloroacetic acid are preferred.

The solid inorganic or organic support material can also be pre-treated with acid, so that the acid is released again to a sufficient degree during hydration. Porous inorganic or organic support materials that bind the acid, for example adsorptively, and release it again under hydration conditions, are particularly suitable for such pre-treatment.

It is also possible to use solid acid. Solid acids can mean, for example: zeolites, such as zeolite A, ZSM-5, ZSM-, X, Y, mordenite or TiSi, and wide-pore zeolites, such as MCM-41, AIPO, SAPO or VAPO; phyllosilicates, such as montmorillonite, hectorite, vermiculite or kaolinite; metal oxide systems in gel form, such as SiO2, Al2O3, TiO2, ZrO or their combination; acid resins of ion exchangers, for example Amberlvst® or Nafion®.

In particular, the process according to the invention can be carried out by first preparing the catalyst, for example by dissolving (IrdienCl)2 in a solvent or in an acid or both, then adding diphosphine and then alkali metal halide or ammonium halide, and. by mixing the mixture. (IridenCl)2 can also be used as a solid. The imine solution is added to this catalyst solution (or vice versa), and hydrogen is introduced into the autoclave, while the appropriately used inert gas is removed. It is convenient to ensure a short standing time of the catalyst solution and to carry out the hydrogenation of the imine as directly as possible after the preparation of the catalyst solution. The reaction mixture is heated, if appropriate, and hydrated. After completion of the reaction, the mixture is cooled, if appropriate, and the autoclave is turned off. The reaction mixture is expelled from the autoclave using nitrogen, and the hydrated organic compound can be isolated and purified in a manner known per se, for example by precipitation, extraction or distillation.

You can also follow a procedure in which a solution of (IrdienCl)2, for example, is first prepared in tetrahydrofuran, this solution is added to the diphosphine ligand, and the mixture is mixed well, the solvent is then decanted and the product created is dried in a vacuum. For the purpose of hydration, an imine, acid and halide are added to this product, and as a rule, a solvent is additionally used.

After hydration, the catalyst can usually be separated by filtration and reused several times.

In the case of hydrogenation of aldimines and ketimines, they can also be prepared in situ before or during hydrogenation. In the overall implementation, a procedure is followed in which some amine and some aldehyde or ketone are mixed, the mixture is added to the catalyst solution, and the aldimine or ketimine formed in situ is hydrogenated. However, it is possible to introduce the amine, ketone or aldehyde into the reaction vessel together with the catalyst, and add the ketone or aldehyde or amine immediately in full or gradually in measured portions.

Hydration can be carried out continuously or discontinuously, i.e. in batches, in different types of reactors. The advantages are those reactors that enable comparatively favorable thorough mixing and good heat removal, for example a circular reactor. This reactor proved to be particularly suitable for the use of small amounts of catalyst.

The molar ratio of imine to iridium catalyst is preferably from 500,000 to 100.

The reaction temperature is preferably -20 to , and the hydrogen pressure is preferably 2x105 Pa to 150x106 Pa.

Aldimine or ketimine formed in situ before or during hydrogenation is preferentially hydrogenated.

The process according to the invention gives the corresponding amines with high chemical conversions in short reaction times, achieving surprisingly excellent optical yields (ee) of 70% or more, even at higher temperatures than above and even with high molar ratios of imine to catalyst .

Hydrated organic compounds that can be prepared according to the invention, for example amines, are biologically active substances or intermediates for the preparation of such substances, especially in the field of pharmaceutical preparations and agrochemicals. For example, they are derivatives of o,o-dialkylarylketamines, preferably those that have alkyl and/or aryl groups that act as fungicides, especially as herbicides. Derivatives can be amine salts, acid amides, for example chloroacetic acid, tertiary amines and ammonium salts (cf. e.g. EP-A-0 077 755 and EP-A-0 115 470).

In this connection, the optically active amines of formulas IIa and IIb are of particular importance

[image]

prepared from imines of formulas Ia and Ib by the process according to the invention, which can be converted into important herbicides of the chloroacetanilide type using chloroacetic acid, by conventional methods.

The following examples outline the invention in more detail.

Conditions of the general synthesis procedure

Unless otherwise stated, all reactions are carried out under inert gas and in solvents without gas content (degassed solvents). For column chromatography, silica gel 60, Merck, is used in all cases.

Abbreviations used in the description of the experiment:

TMEDA: N,N,N;N-tetramethylethylenediamine

BPPFA: N,N-dimethyl-1-[1,2-bis(diphenylphosphine)ferrocenyl]ethylamine

DMF: N,N-dimethylformamide

COD: 1,5-cyclooctadiene

Synthesis of intermediate products

Used inorganic carriers:

Silica gel, Grace 332, from W.R. Grace, specific surface area = 320 m2/g, particle size = 35-70 micrometers. Controlled pore glass, Grace 500A, by W.R. Grace, specific surface area = 80 m2/g, pore diameter - 50 nm.

And the synthesis of intermediates

Example A1 Synthesis of (R)-N,N-dimethyl-1-[1'(1"-dimethylsilyl-3"-chloropropyl)-(S)-2-diphenylphosphinoferrocenyl]ethylamine (2)

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32.5 ml of a 1.6 molar solution of butyllithium in hexane (52 mmol) was added dropwise to a solution of (40 mmol) (R)-N,N dimethyl-1-fercenylethylamine in 50 ml of diethyl ether at room temperature, with stirring. The mixture is stirred for 1 hour, and then a solution containing 35.6 ml of a 1.6 molar solution of butyllithium in hexane (57 mmol) and 7.5 ml of TMEDA (50 mmol) is added drop by drop, and the red-brown reaction solution is stirred for another 5 hours. After that, a mixture solution of 7.4 ml of chlorodiphenylphosphine (40 mmol) and 22.9 ml of 3-chloropropyl-dimethylchlorosilane (140 mmol) was added drop by drop. The reaction mixture is then stirred overnight at room temperature.

Processing:

10 ml of saturated NaHCO3 solution and then 100 ml of water are slowly added to the reaction mixture at , and extracted three times with 50 ml of ethyl acetate each. The organic phase is extracted with 50 ml of water, dried with Na2SO4 and concentrated in vacuo (10- Hg). The excess hydrolyzed chlorosilane is separated by distillation (bath temperature up to ) from the solid product under high vacuum (about Hg). A mixture of (R)-(S) isomers of the compound of formula 2 and a little BPPFA is obtained by ordinary column chromatography (mobile phase = hexane/acetic acid). BPPFA can be removed by crystallization from a 1:1 methanol/ethanol mixture. 95% purity is obtained by this method (yield 55%, red-brown viscous oil).

Characterization:

31P NMR (CDCl3): δ -23.71

1H NMR (CDCl3): δ 0.05 (s, 3H, Si-CH3), 0.15 (s, 3H, Si-CH3), 0.6 (m, 2H, CH2-Si), 1.28 (d, J 7 Hz, CH- CH3), 1.5-1.9 (m, 2H, CH2-CH2-Cl), 1.78 (s, 6H, N(CH3)2), 3.4 (t, 2H, J 7 Hz, CH2-Cl), 3.5-4, 4 (m, 8H, C5H4FeC5H3CH), 7.1-7.7 (m, 10H, P(C6H5)2).

The compound of formula 2, (S)-(R) configuration, was prepared in the same manner starting from (S)-N,N-dimethyl-1-ferrocenylethylamine.

Example A2; synthesis with the compound of formula 3a;

All of the following syntheses were carried out starting from the compound of formula 2 in the (R)-(S) configuration and afforded the corresponding (R)-(S) ligands.

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Example. A2a: Synthesis of (R)-1-[1'-(1''-dimethylsilyl-3''-chloropropyl-(S)-2-diphenylphosphino-ferrocenyl]ethyldi-3,5-xyl-1-ylphosphine 3a

(4.6 mmol) of bis(3(5-xylyl)phosphine in 5 ml of acetic acid was added to (4.6 mmol) of the compound prepared in Example A1 in 10 ml of acetic acid, and the mixture was stirred in an oil bath for 90 minutes. After cooling , the red-brown solution is extracted into 30 ml of toluene and 100 ml of 5% aqueous NaCl solution. The aqueous phase is then extracted 3 times with 15 ml of toluene. The organic phases are then collected, washed with 50 ml of water, dried with Na2SO4 and concentrated under reduced under pressure. The solid product is purified by column chromatography (mobile phase hexane/diethyl ether). 3a is obtained (orange powder, yield 52%). Characterization:

31P NMR (CDCl3): δ -25.46 (d, PPh2), 6.65 (d, Pxyl2), JPP 21 Hz.

Example A3; Synthesis of primary amines of formula 5a

Primary amines can be prepared via the Gabriel synthesis (conversion of chloride into phthalimide and release of amine using hydrazine hydrate):

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Example A3a

492 mg of potassium phthalimide and 130 mg of hexadecyltributylphosphonium bromide (catalyst) were added to a solution (2.1 mmol) of the compound of formula 3a from Example A2a in 2 ml of DMF, and the mixture was stirred at 2.5 h. After cooling, it is extracted into water/toluene and the organic phase is dried with sodium sulfate and concentrated. After purification by chromatography (mobile phase: hexane/ethyl acetate), an orange powder is obtained (yield 96%).

Characterization:

31P NMR (CDCl3): δ -25.33 (d, PPh2), 6.97 (d, Pxyl2), JPP 22 Hz.

1H NMR (CDCl3): δ characteristic signals 3.6 (t, 2H, J=7, CH2N), 7.6-7.9 (m, 4H, phthalimide).

(2.04 mmol) of orange powder and 0.4 ml of hydrazine hydrate in 20 ml of ethanol is heated under reflux for 4 hours. After cooling, 50 ml of methylene chloride is added, the suspension is filtered, and the residue is washed. The solution is concentrated under reduced pressure, the product is resuspended in 50 ml of methylene chloride and the suspension is filtered. After evaporation of the filtrate on a rotavapor, an orange powder of the compound of formula Va is obtained (yield 97%).

Characterization:

31P NMR (CDCl3): δ -25.38 (d, PPh2), 6.6 (d, Pxyl2), JPP 22 Hz.

1H NMR (CDCl3): δ characteristic signals 2.58 (t, 2H, J=7, CH2-N).

Example A4: Preparation of secondary amine of formula 6a

[image]

400 mg (0.518 mmol) of the compound of formula 3a from example A2a is heated under reflux in the presence of 12 mg of tetrabutylammonium iodide in 5 ml of N-butylamine for 20 hours. The butylamine is then removed by distillation under reduced pressure, and the mixture is extracted with water/ethyl acetate. The organic phase is dried with Na2SO4 and concentrated, and the solid product is purified by chromatography (mobile phase: ethyl acetate with 2% triethylarnine). An orange viscous oil of the compound of formula 6a is obtained (88% yield).

Characterization:

31P NMR (CDCl3): δ -25.1 (d, PPh2), 6.8 (d, Pxyl2), JPP 21 Hz.

1H NMR (CDCl3): δ characteristic signals 0.9 (t, 3H, J=7, CH2-CH3), 2.45-2.6 (m, 4H, J=7, two CH2-N).

Example A5; Synthesis of ligands of formulas 7a and 8a immobilized on inorganic supports

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Example A5a

0.65 ml (2.46 mmol) of 1-tertethoxysyl-3-isocyanatopropane is added dropwise to a solution of (1.97 mmol) of the compound of formula 5a from example A3a in 20 ml of methylene chloride, and the mixture is stirred overnight at room temperature. The solvent is then removed under reduced pressure, and the solid product is purified by chromatography (mobile phase: hexane/ethyl acetate). Orange viscous foams of formula 7a are obtained (74% yield).

Characterization:

31P NMR (CDCl3): δ -25.2 (d, PPh2), 6.7 (d, Pxyl2), JPP 21 Hz.

1H NMR (CDCl3): δ 1.22 (t, 9H, J=7, O-CH2-CH3), 3.81 (q, J=7,6H, O-CH2).

Example A5d

0.1 ml (0.37 mmol) of 1-triethoxysilyl-3-isocyanatopropane is added drop by drop to a solution of 251 mg (0.31 mmol) of the compound of formula 6a from example A4 in 4 ml of methylene chloride, and the mixture is stirred at room temperature for 2.5 hours. The solvent is then removed under reduced pressure, and the solid product is purified by chromatography (mobile phase: hexane/ethyl acetate). 230 mg of orange viscous oil of formula 8a is obtained (70% yield).

Characterization:

31P NMR (CDCl3): δ -25.3 (d, PPh2), 6.7 (d, Pxyl2), JPP 21 Hz.

1H NMR (CDCl3): δ characteristic signals 0.9 (t, 3H, J=7, CH2-CH3), 1.22 (t, 9H, J=7, 0-CH2-CH3).

Example B: Ligands immobilized on silica gel or on glass with controlled pores

Immobilization: In each case, before use, the carrier material was dried for 3 hours under high vacuum, and then stored under argon. A solution of the immobilizing ligand from Example A5 in toluene is then added and the mixture is stirred at 85- for 20 hours. After the mixture has cooled and settled, the supernatant solution is withdrawn with a syringe. The mixture is then washed 6 times with MeOH (in each case 7 ml per g of carrier) and finally dried at 40- under high vacuum. The result is shown in table 1.

The preparation of ligand C, serial number 207 in Table 1, was carried out as described in EP-A-0 496 699.

Example C: Polymer bound ligands

Example C1 Immobilization of the ligand of formula 5a from example A3a on functionalized polystyrene

930 mg of polymer (aminomethylated polystyrene, cross-linked with 1% divinylbenzene, amine content = 0.56 mmol/g; supplier: Novabiochem) dried under high vacuum is mixed in 35 ml of methylene chloride in a vessel equipped with a stirrer and provided with a frit, until the bearing the material does not swell. Then 1.2 ml (8.3 mmol) of 2,4-tolylene diisocyanate (TDI) was quickly added and the mixture was stirred for a further 1 hour. Excess TDI was then removed by filtering the solution and washing 5 times with 30 ml of methylene chloride. The TDI-reacted carrier is then mixed into 30 ml of methylene chloride, and a solution of 94 mg (0.125 mmol) of the compound of formula 5a from Example A3a in 2 ml of methylene chloride is added dropwise. The mixture is stirred overnight. To convert the remaining isocyanate groups into carbamate groups, 10 ml of ethyl alcohol is added with 30 microliters of triethylamine as a catalyst, and the mixture is stirred for 8 hours. The yellow-orange carrier is then filtered off and washed 5 times with 20 ml of methylene chloride each. Finally, it is dried under high vacuum.

Analysis: P content = 0.59 %. This corresponds to a layer of 0.095 mmol of ligand per g of support.

Characterization of immobilized ligands.

Table 1

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D Examples of hydration

[image]

General:

All manipulations are carried out under inert gas. The 50 ml steel autoclave is equipped with a magnetic stirrer (1500 rpm) and a flow switch. The inert gas in the autoclave is replaced by hydrogen in 4 cycles each time (10 bar, normal pressure) before hydration. The desired water pressure is then established in the autoclave and hydration begins by turning on the mixer. Conversion is always determined by gas chromatography, optical recovery by HPLC (column: Chiracel OD), and the sample is purified by thin layer chromatography (silica gel, Merck 60, mobile phase = hexane/ethyl acetate).

Example D1

A solution of 0.64 mg of [Ir(COD)Cl]2 (0.0019 mmol of Ir) in 1 ml of THF was added all at once to 53 mg of ligand 201 in the (R),(S) configuration (Si-Xyliphos 1), and the mixture was stirred slowly. until the yellow solution becomes colorless. The catalyst is then allowed to settle, the THF supernatant is withdrawn with a syringe, and the catalyst is dried under high vacuum. In the second flask, 10 mg of tetrabutylammonium iodide, 0.5 ml of acetic acid and finally (94.6 mmol) N-(2'-methyl-6',-ethylphen-1-yl)-N-(1-methoxymethyl)-ethylimine, solution is allowed to stand under inert gas and added to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 17 hours, the hydrogen is turned off and the catalyst is filtered off. The conversion is 100 %, and the optical efficiency is 78.1 % (S).

Example D2

A solution of 1.65 mg of [Ir(COD)Cl]2 (0.0049 mmol of Ir) in 2 ml of THF was added all at once to 128 mg of ligand 202 in the (R),(S) configuration (Si-Xyliphos 2), and the mixture was stirred slowly. until the yellow solution becomes colorless. The catalyst is then allowed to settle, the THF supernatant is withdrawn with a syringe, and the catalyst is dried under high vacuum. 10 mg of tetrabutylammonium iodide, 2 ml of acetic acid and finally (94 mmol) N-(2'-methyl-6'-ethylphen-1'-yl)-N-(1-methoxymethyl)ethylimine solution are placed in the second flask. stand under an inert gas and add to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 2.5 hours, the hydrogen is switched off and the catalyst is filtered. The conversion is 100% and the optical efficiency is 77% (S). Analysis of the iridium content in the filtered product solution shows that more than 97% of the used catalyst was recovered.

Example D3

A solution of 0.27 mg of [Ir(COD)Cl]2 (0.00082 mmol of Ir) in 1 ml of THF was added all at once to 40 mg of ligand 202 in the (R),(S) configuration (Si-Xyliphos 2), and the mixture was stirred slowly. until the yellow solution becomes colorless. The catalyst is then allowed to settle, the THF supernatant is withdrawn with a syringe, and the catalyst is dried under high vacuum. In the second flask, 10 mg of tetrabutylammonium iodide, 2 ml of acetic acid and finally (94.6 mmol) N-(2'-mem-6'-ethylphen-1,-yl)-N-(1-methoxymethyl)-ethylimine, solution is allowed to stand under an inert gas and added to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 17 hours, the hydrogen is turned off and the catalyst is filtered off. The conversion is 100 %, and the optical efficiency is 78.2 % (S).

Example D4

A solution of 0.64 mg of [Ir(COD)Cl]2 (0.0019 ppm Ir) in 2 ml of THF was added all at once to 143 mg of ligand 203 in the (R),(S) configuration (Si-Xyliphos 3), and the mixture was stirred slowly. until the yellow solution becomes colorless. The catalyst is then allowed to settle, the THF supernatant is withdrawn with a syringe, and the catalyst is dried under high vacuum. In the second flask, 10 mg of tetrabutylammonium iodide, 2 ml of acetic acid and finally (94.6 mmol) N-(2,-methu-6'-ethylphen-1'-yl)-N-(1-methoxylmethyl)-ethylimine, solution is allowed to stand under an inert gas and added to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 28 hours, the hydrogen is turned off and the catalyst is filtered off. The conversion is 97%, and the optical efficiency is 76.9% (S).

Example D5

A solution of 1.65 mg of [Ir(COD)Cl]2 (0.0049 mmol of Ir) in 2 ml of THF was added all at once to 206 mg of ligand 204 in the (R),(S) configuration (Si-Xyliphos 4), and the mixture was stirred slowly. until the yellow solution becomes colorless. The catalyst is then allowed to settle, the THF supernatant is withdrawn with a syringe, and the catalyst is dried under high vacuum. In the second flask, 10 mg of tetrabutylammonium iodide, 2 ml of acetic acid and finally (94.6 mmol) N-(2,-methyl-6'-ethylphen-1'-yl)-N-(1-methoxymethyl)-ethylimine, solution is allowed to stand under inert gas and added to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 16 hours, the hydrogen is turned off and the catalyst is filtered off. The conversion is 100 %, and the optical efficiency is 78.9 % (S).

Example D6

A solution of 1.65 mg of [Ir(COD)Cl]2 (0.0094 mmol of Ir) in 5 ml of THF was added all at once to 900 mg of ligand 205 in the (R),(S) configuration (CPG-Xyliphos), and the mixture was stirred slowly while the yellow solution does not discolor. The catalyst is then allowed to settle, the THF supernatant is withdrawn with a syringe, and the catalyst is dried under high vacuum. In the second flask, 10 mg of tetrabutylammonium iodide, 2 ml of acetic acid and finally (96 mmol) N-(2'-methyl-6'-ethylphen-1'-yl)-N-(1-methoxymethyl)-ethylimine, solution is allowed to stand under inert gas and added to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 17 hours, the hydrogen is turned off and the catalyst is filtered off. The conversion is 100 %, and the optical efficiency is 78.0 % (S).

Example D7

A solution of 1.65 mg of [Ir(COD)Cl]2 (0.0049 mmol of Ir) in 5 ml of THF was added all at once to 60 mg of ligand 206 in the (R),(S) configuration (PS-Xyliphos), and the mixture was stirred slowly while the yellow solution does not discolor. In the second flask, 10 mg of tetrabutylammonium iodide, 2 ml of acetic acid and finally (95 mmol) N-(2'-methyl-6'-ethylphen-1'-yl)-N-(1-methoxymethyl)-ethylimine, solution is allowed to stand under inert gas and added to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 16 hours, the hydrogen is turned off and the catalyst is filtered off. The conversion is 99.8 %, and the optical efficiency is 76.6 % (S). Analysis of the iridium content in the solution of the filtered product shows that more than 95% of the catalyst has been recovered.

Example D8

A solution of 0.64 mg of [Ir(COD)Cl]2 (0.0019 mmol of Ir) in 8 ml of THF was added all at once to 25 mg of ligand 206 in the (R),(S) configuration (PS-Xyliphos 1), and the mixture was stirred slowly while the yellow solution does not discolor. In the second flask, 10 mg of tetrabutylammonium iodide, 2 ml of acetic acid and finally (95 mmol) N-(2'-methyl-6'-ethylphen-1'-yl)-N-(1-methoxymethyl)-ethylimine, solution is allowed to stand under an inert gas and added to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 41 hours, the hydrogen is turned off and the catalyst is filtered off. The conversion is 95 %, and the optical efficiency is 77.8 % (S).

Example D9

A solution of 1.65 mg of [Ir(COD)Cl]2 (0.0049 mmol of Ir) in 2 ml of THF was added all at once to 130 mg of ligand 202 in the (R),(S) configuration (Si-Xyliphos 2), and the mixture was stirred slowly. until the yellow solution becomes colorless. The catalyst is then allowed to settle, the THF supernatant is withdrawn with a syringe, and the catalyst is dried under high vacuum. In the second flask, 24 mg of tetrabutylammonium iodide, 0.1 ml of trifluoroacetic acid and finally (49 mmol) N-(2'-methyl-6'-ethylphen-1'-yl)-N-(1-methoxymethyl)-ethylimine, solution is allowed to stand under inert gas and added to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 100 minutes, there is no more hydrogen consumption. After 3 hours, the hydrogen is turned off and the catalyst is filtered off. The conversion is 100 %, and the optical efficiency is 78.1 % (S).

Example D10

A solution of 1.65 mg of [Ir(COD)Cl]2 (0.0049 mmol of Ir) in 4 ml of THF was added all at once to 60 mg of ligand 206 in the (R),(S) configuration (PS-Xyliphos), and the mixture was stirred slowly while the yellow solution does not discolor. In the second flask, 4.8 mg of tetrabutylammonium iodide, 0.03 ml of trifluoroacetic acid and finally (12 mmol) N-(2'-methyl-6'-ethylphen-1'-yl)-N-(1-methoxymethyl)-ethylimine, solution is allowed to stand under an inert gas and added to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 50 minutes, there is no more hydrogen consumption. After 3.5 hours, the hydrogen is switched off and the catalyst is filtered off. The conversion is complete, and the optical efficiency is 77.6 % (S).

Example D11

A solution of 3.3 mg of [Ir(COD)Cl]2 (0.0097 mmol of Ir) in 2 ml of THF was added all at once to 128 mg of ligand 207 in the (R),(S) configuration (Si-PPM), and the mixture was stirred slowly while the yellow solution does not discolor. The catalyst is then allowed to settle, the THF supernatant is withdrawn with a syringe, and the catalyst is dried under high vacuum. In the second flask, 10 mg of tetrabutylammonium iodide, 0.05 ml of trifluoroacetic acid and finally (20 mmol) N-(2'-methyl-6'-ethylphen-1'-yl)-N-(1-methoxymethyl)-ethylimine, solution is allowed to stand under an inert gas and added to the catalyst. The reaction mixture is then introduced using a steel capillary with countercurrent inert gas into a 50 ml steel autoclave, and hydrogenation is carried out under a hydrogen pressure of 80 bar at . After 3 hours, the hydrogen is turned off and the catalyst is filtered off. The conversion is 99.5 %, and the optical efficiency is 47.4 % (R).

Claims (71)

1. The imine hydrogenation process, indicated by the fact that it is carried out with hydrogen under elevated pressure in the presence of an iridium catalyst, and with or without an inert solvent, while the reaction mixture contains an iridium catalyst immobilized on a support material, ammonium chloride, bromide or iodide, or metal chloride, bromide or iodide which is soluble in the reaction mixture, and in addition some acid. 2. The method according to claim 1, characterized in that the imine contains at least one group >C=N-. 3. The method according to claim 1, characterized in that the imine contains at least one of the groups >C=N- or >C=N-N- and also unsaturated groups >C=C< or >C=O. 4. The process according to claim 3, characterized in that the free bonds are saturated with H or organic radicals with 1 to 22 C-atoms or organic heteroradicals with 1 to 20 C-atoms and at least one heteroatom from the group consisting of O, S , N and P; or the N-atom from the group >C=N- is saturated with NH2 or a primary amino group with 1 to 22 C-atoms or a secondary amino group with 2 to 40 C-atoms. 5. Process according to claim 1, characterized in that the aldimine, ketimine or hydrazone is hydrogenated. 6. The process according to claim 5, characterized in that the imine has formula I [image] and is hydrogenated into the amine of formula II [image] in which it is R3 straight-chain or branched C1-C12-alkyl, cycloalkyl with 3 to 8 ring C-atoms; heterocycloalkyl bonded through a C-atom and having 3 to 8 ring atoms and 1 to 2 heteroatoms from the group consisting of O, S and NR 6 ; C7-C16-aralkyl linked via an alkyl-C or C1-C12-alkyl substituted by cycloalkyl or heterocycloalkyl or said heteroaryl; or wherein R 3 denotes C 6 -C 12 -aryl or C 4 -C 11 -heteroaryl which is attached via a ring atom and has 1 or 2 ring heteroatoms; where R 3 is unsubstituted or substituted with -CN, -NO 2 , F, Cl, C 1 -C 12 -alkyl, C 1 -C 12 -alkyl, C 1 -C 12 -alkylthio, C 1 -C 6 -haloalkyl, -OH, C 6 -C 12 -aryl or -aryloxy or -arylthio, C7-C16-aralkyl or -aralkoxy or -aralkylthio, a secondary amino group with 2 to 24 atoms, -CONR4R5 or -COOR4, and where the aryl radicals and aryl groups are in aralkyl, aralkoxy and aralkylthio in turn unsubstituted or substituted with -CN, -NO2, F, Cl, C1-C4-alkyl, -alkoxy, -alkylthio, -OH, -CONR4R5 or -COOR4; R4 and R5 are independently H, C1-C4-alkyl, phenyl or benzyl, or R4 and R5 together denote tetra- or pentamethylene or 3-oxapentylene; R6 is independently defined as R4 R1 and R2 independently of each other are a hydrogen atom, C1-C12-alkyl or cycloalkyl with 3 to 8 ring C-atoms which are unsubstituted or substituted with -OH, C1-C12- alkoxy, phenoxy, benzyloxy, a secondary amino group with 2 to 24 atoms, -CONR4R5 or -COOR4; C6-C12-aryl or C7-C16-aralkyl which are unsubstituted or substituted as R3, or -CONR4R5 or -COOR4, in which R 4 and R 5 have the meanings given above; or is R3 defined as above, a R 1 and R 2 together denote alkylene with 2 to 5 C-atoms which is interrupted or uninterrupted by 1 to 2 -O-. -S- or -NR6- and/or unsubstituted or substituted with =O or as above for alkyl R1 and R2 and/or is bonded with benzene, pyridine, pyrimidine, furan, thiophene or pyrrole; or R2 is as defined above and R1 and R3 together are alkylene having 2 to 5 C-atoms, or are alkylene having 2 to 5 C-atoms and is terminated by 1 or 2 -O-, -S- or - NR6-, and/or is unsubstituted or substituted with =O or as above substituted with =O or as above for alkyl R1 and R2 and/or is bonded with benzene, pyridine, pyrimidine, furan, thiophene or pyrrole. 7. The method according to claim 5, characterized in that the heteroaryl R1 and R2 is a 5- or 6-membered ring with 1 or 2 identical or different heteroatoms. 8. The method according to claim 5, characterized in that alkyl R1 and R2 substituted with heteroaryl are derived from a 5- or 6-membered ring with 1 or 2 identical or different heteroatoms. 9. The method according to claim 5, characterized in that heterocycloalkyl R1 and R2 or alkyl R1 and R2 substituted by heterocycloalkyl contain 4 to 6 ring atoms and 1 or 2 identical or different heteroatoms from the group consisting of O, S and NR6 in wherein R6 is H, C1-C12-alkyl, phenyl or benzyl. 10. The method according to claim 5, characterized in that alkyl R1, R2 and R3 denote unsubstituted or substituted C1-C6-alkyl. 11. The method according to claim 5, characterized in that unsubstituted or substituted cycloalkyl R1, R2 or R3 contain 3 to 6 ring carbon atoms. 12. The method according to claim 5, characterized in that aryl R1, R2 and R3 denote unsubstituted or substituted naphthyl or phenyl, and aralkyl R1, R2 and R3 unsubstituted or substituted phenylalkyl with 1 to 10 atoms in alkylene. 13. The method according to claim 5, characterized in that R1 and R2 together or R1 and R3 together with a C-atom or with a -N=C group to which they can be attached, form a 5- or 6-membered ring. 14. The method according to claim 5, indicated by the fact that in formula I R3 denotes 2,6-di-C1-C4-alkylphen-1-yl, R1 is C1-C4-alkyl, C1-C4-alkoxymethyl or C1-C4- Alkoxyethyl. 15. The method according to claim 14, characterized in that R3 denotes 2,6-dimethylphen-1-yl or 2-methyl-6-ethylphen-1-yl, R1 is ethyl or methyl and R2 is methoxymethyl. 16. Process according to claim 6, characterized in that the imine has formulas Ia, Ib or Ic [image] 17. The process according to claim 1, characterized in that the catalysts preferably correspond to formulas III, IIIa, IIIb, IIIc and IIId, [image] in which X denotes olefinic ligands or one diene ligand, Y is a diphosphine that has tertiary, phosphine groups and is attached to an inorganic or polymeric organic support material, (a) the phosphine groups of which are attached to different C-atoms of the carbon chain with 2 to 4 C-atoms, or (b) the phosphine shell of which are attached either directly or via a bridging group -CRaRb- in the ortho positions of the cyclopentadienyl ring or to at least one cyclopentadienyl ring of ferrocenyl, or (c) one phosphine group of which is attached to a carbon chain with 2 to 3 C-atoms and another phosphine group which is attached to an oxygen atom or a nitrogen atom terminally attached to that carbon chain, or (d) phosphine groups which are attached to two oxygen atoms or nitrogen atoms terminally attached to the C2-carbon chain, and in cases (a), (b) ), (c) and (d), together with the Ir atom forms a 5-, 6- or 7-membered ring, the radicals Z independently mean Cl, Br or I, An is an anion of oxygen acid or complex acid, a M+ is an alkali metal cation or quaternary ammonium ion, a Ra and Rb are independently H. C1-C3-alkyl, C1-C4-fluoroalkyl, phenyl or benzyl, or phenyl or benzyl substituted with 1 to 3 C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy. 18. The method according to claim 17, characterized in that, for the purpose of enantioselective hydrogenation, diphosphine Y contains at least one chiral group. 19. The method according to claim 17, characterized in that the olefinic ligand X is a branched or straight-chain C2-C12-alkylene, and the diene ligand X is an open-chain or cyclic diene with 4 to 12 carbon atoms. 20. The method according to claim 17, characterized in that the diphosphine Y is bound via a silyl group to an inorganic support material T which is selected from the group containing silicates, semi-metals or metals, oxides, glasses or their mixtures. 21. The method according to claim 20, characterized in that diphosphine Y has the structure of formula Iva [image] where R 7 denotes C 1 -C 8 -alkyl, phenyl, or phenyl substituted with 1 to 3 C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; R8 and R9 mutually independently represent C1-C12-alkyl or C5-C12-cycloalkyl, phenyl, C5-C12-cycloalkyl which is substituted with C1-C4-alkyl or C1-C4-alkoxy, or phenyl which is mono- or polysubstituted with one to three C1-C4-alkyl, C1-C4-alkoxy, -SiR10R11R12, halogen, -SO3Me, -CO2Me, -PO3Me, -NR13R14, -[+NR13R14R15]X or C1-C5-fluoroalkyl; or the group -PR8R9 is a radical of formula V, Va, Vb or Vc [image] and R10, R11 and R12 independently of each other denote C1-C12-alkyl or phenyl; R13 and R14 are H, C1-C12-alkyl or phenyl or R13 and R14 together are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene; R 15 is H or C 1 -C 4 -alkyl; R16 and R17 are identical or different and denote C1-C12-alkyl, C5-C12-cycloalkyl, phenyl, C5-C12-cycloalkyl which is substituted with C1-C4-alkyl, C1-C4-alkoxy, or phenyl which is substituted with one to three C1-C4-alkyl, C1-C4-alkoxy, -SiR10R11R12, halogen, -SO3Me, -CO2Me, -PO3Me, -NR13R14, -[+NR13R14R15]X or C1-C5-fluoroalkyl; or the group -PR16R17 is a radical of formula V, Va, Vb or Vc [image] Radicals R18 are identical or different radicals and mutually independently mean C1-C12-alkylene, C3-C7-cycloalkyl, benzyl or phenyl, or together C5-C12-alkylene and R19 is branched or unbranched C1-C12-alkylene, phenylene, or alkylene-phenylene, Me is H or an alkali metal, X is the anion of a monobasic acid, A is NH or N(C1-C12-alkyl), R20 is C1-C4-alkyl or O-C1-C12-alkyl, R21 is C1-C12-alkyl, T is the inorganic carrier material defined in claim 20, and if n is 0, r is 1, 2 or 3, if n equals 1, r is 1 or if n equals 2, r is 1. 22. The method according to claim 20, characterized in that diphosphine Y has the structure of formulas IVb or IVc [image] [image] in which the groups (R22)2P(CH2)mi n are in the o- or m-position relative to each other, and the radicals R22 are identical or different radicals, min independently of each other are 0 or 1, radicals R22 independently of each other denote C1-C12-alkyl, C5-C12-cycloalkyl, phenyl, C5-C12-cycloalkyl which is substituted by C1-C4-alkyl or C1-C4-alkoxy or phenyl which is substituted by one to three C1- C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl, or two radicals in the group (R22)2P together are o,o-dtphenylene, -R23-U- is a bond or -(CxH2x-O)y, or U is -O-, a R23 is C1-C6-alkylene, x is an integer from 2 to y is a number from 2 to 6, R24 is C2-C18-alkylene, phenylene or benzylene, R25 is hydrogen, straight-chain or branched C1-C12-alkyl, phenyl or benzyl, r is 0, 1 or R21 and T are as defined in claim 21. 23. The method according to claim 17, characterized in that the diphosphine Y is bound to a straight-chain polymer support material that is soluble, partially cross-linked and swellable, or highly cross-linked and insoluble in organic solvents. 24. The method according to claim 23, characterized in that diphosphine Y is bound to the carrier material as a copolymer. 25. The method according to claim 24, characterized in that the copolymer is formed from monomers with olefinic C=C bonds, at least one of which monomers is a diphosphine radical. 26. The method according to claim 23, characterized in that the diphosphine is bound by a functional group either directly, or via a bridging group, to the functional group of the polymer. 27. The method according to claim 26, characterized in that the functional groups in the diphosphine and in the polymer are selected independently of each other from the group consisting of -OH, -NH2, -NH(C1-C12-alkyl), -NCO, -COOH, - COO(C1-C12-alkyl), -CO-halogen, halide or glycidyl groups. 28. The method according to claim 26, characterized in that the bridging group preferably contains 2 to 30 carbon atoms, which are directly bonded to each other or interrupted by a heteroatom, and a functional group that can react with functional groups of polymers and diphosphine is present at both ends. 29. The method according to claim 28, characterized in that the functional groups at both ends of the bridging group are identical, and are selected from the group consisting of -OH, -NH2, -NH(C1-C12-alkyl), -NCO, - COOH, -COO(C1-C12-alkyl), -CO-halogen and glycidyl groups. 30. The method according to claim 23, indicated by the fact that the diphosphine group Y is attached via a bridging group, formed by a diisocyanate, to a polymer that has repeating structural elements, from at least one monomer that contains, directly or on the side chain, a hydroxyl group or a primary or secondary amine group as a functional group, and is attached at the other end of the bridging group Q to the hydroxyl group or the primary or secondary amine group of diphosphine Y. 31. The method according to claim 30, characterized in that repeating structural elements of formula VI are present [image] where A, R7, R8, R9, R16, R17, R18 and R19 have the meaning specified in claim 21; Q is a bridging group formed by a diisocyanate; PM is a polymer-forming monomer radical containing, directly or on a side chain, a hydroxyl group or a primary or secondary amine group attached as a functional group, which is linked to a diphosphine by a bridging group Q formed from diisocyanates. 32. The method according to claim 30, characterized in that the diphosphine with a hydroxyl or primary or secondary amine functional group is a compound of formula VIIa or VII. b [image] in which B represents -NR27- or -O-; R27 is hydrogen or straight or branched C1-C6-alkyl, a R22, R23, R25, m and n have the meaning given in claim 22. 33. The method according to claim 30, characterized in that diphosphines containing hydroxyl or primary or secondary amine functional groups are compounds of formulas 100, 101, 102, 103, 104, 105, 106, 107, 108 or 109: [image] [image] 34. The method according to claim 30, characterized in that the diisocyanate forming the bridging group Q is preferably selected from the group consisting of: 1,6-bis[isocyanato]hexane, 5-isocyanato-3-isocyanomethyl-1,1,3-trimethylcyclohexane, 1,3-bis[5-isocyanato-1,3,3-trimethylphenyl]-2,4-dioxo-1,3-diazetidine, 3,6-bis[9-isocyanatononyl]-4,5-di-(1-heptenyl)cyclohexene, bis[4-isocyanatocyclohexyl]methane, trans-1,4-bis[isocyanato]cyclohexane, 1,3-bis[isocyanatomethyl]benzene, 1,3-bis[1-isocyanato-1-methylethyl]benzene, 1,4-bis[2-isocyanatoethyl]cyclohexane, 1,3-bis[isocyanatomethyl]cyclohexane, 1,4-bis[1-isocyanato-1-methylethyl]benzene, bis[isocyanato]isododecylbenzene, 1,4-bis[isocyanato]benzene, 2,4-bis[isocyanato]toluene, 2,6-bis[isocyanato]toluene, 2,4-/2,6-bis[isocyanato]toluene, 2-ethyl-1,2,3-tris[3-isocyanato4-methylanilinocarbonyloxy]propane, N,N'-bis[3-isocyanato-4-methylphenyl]urea, 1,4-bis[3-isocyanato-4-methylphenyl]-2,4-dioxo-1,3-diazetidine, 1,3,5-tris[3-isocyanato-4-methylphenyl]-2,4,6-trioxohexahydro-1,3,5-triazine, 1,3-bis[3-isocyanato-4-methylphenyl]-2,4,5-trioxoimidazolidine, bis[2-isocyanatophenyl]methane, (2-isocyanatophenyl)-(4-isocyanatophenyl)methane, bis[4-isocyanatophenyl]methane, 2,4-bis[4-isocyanatobenzyl]-1-isocyanatobenzene, [4-isocyanato-3-(4-isocyanatobenzyl)phenyl]-[2-isocyanato-5-(4-isocyanatobenzyl)phenyl]methane, tris[4-isocyanatophenyl]methane, 1,5-bis[isocyanato]naphthalene and 4,4'-bis[isocyanato]-3,3'-dimethylbiphenyl. 35. The method according to claim 30, characterized in that the monomer containing a hydroxyl or primary or secondary amine functional group participates in the construction of the polymer in an amount of 5 to 100 mole percent. 36. The method according to claim 30, characterized in that the monomer containing a hydroxyl or primary or secondary amine functional group participates in the construction of the polymer in an amount of 10 to 100 mole percent. 37. The method according to claim 30, characterized in that the polymer is loaded with between 5 and 100 mol % of tertiary diphosphine groups, based on available hydroxyl or primary or secondary amine groups. 38. The method according to claim 30, characterized in that the monomers that form the polymer are selected from the group consisting of. styrene, p-methylstyrene and α-methylstyrene, at least one of which contains a hydroxyl or primary or secondary amine group attached as a functional group. 39. The method according to claim 30, characterized in that other comonomers are dienes or acrylic derivatives, for example butadiene, acrylonitrile, alkyl methacrylate, butadiene/alkyl acrylate and methacrylate, maleic anhydride and acrylonitrile/methyl acrylate, which form random or block polymers. 40. The method according to claim 30, characterized in that the monomers forming the polymer are selected from the group consisting of α,β-unsaturated acids and their esters and amides, at least one of which contains a hydroxyl or primary or secondary amine group that is connected as a functional group. 41. The method according to claim 40, characterized in that the monomers forming the polymer are selected from the group consisting of acrylates and their C1-C4-alkyl esters, methacrylates and their C1-C4-alkyl esters, acrylamide and acrylonitrile, at least one of which contains a hydroxyl or primary or secondary amine group which is linked as a functional group. 42. The method according to claim 30, characterized in that the polymer is made of monomers containing vinyl alcohol as a homopolymer or vinyl alcohol as a copolymer with vinyl acetate, stearate, benzoate or maleate, vinyl butyral, allyl phthalate or allyl melamine. 43. The method according to claim 30, characterized in that phenol and C1-C4-aldehyde are monomers that form the polymer. 44. The method according to claim 30, characterized in that the monomers forming the polymer form polyepoxides of cyclic C3-C6-ethers or C2-C6-alkylene glycols and bisglycidyl ethers. 45. The method according to claim 30, characterized in that the polymer is a polysaccharide. 46. The method according to claim 23, characterized in that the polymers are highly cross-linked macroporous polystyrenes or polyacrylates. 47. The method according to claim 23, characterized in that the particle size is 10 µm to 2000 µm. 48. The method according to claim 23, characterized in that the specific surface area of porous highly cross-linked polymers is preferably 5 to . 49. The method according to claim 21, characterized in that R7 in the compounds of formula IVa denotes methyl or ethyl. 50. The method according to claim 21, characterized in that substituted phenyl R8, R9, R16 and R17 in compounds of formula IVa denotes 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4-ethyl-, 2- or 4-i-propyl-, 2- or 4-t-butyl-, 2-methoxy-, 3-methoxy-, 4-methoxy-, 2- or 4-ethoxy-, 4-trimethylsilyl-, 2- or 4 -fluoro-, 2,4-difluoro-, 2- or 4-chloro-, 2,4-dichloro-, 2,4-dimethyl-, 3,5-dimethyl-, 2-methoxy-4-methyl-, 3 ,5-dimethyl-4-methoxy-, 3,5-dimethyl-4-(dimethylamino)-, 2- or 4-amino-, 2- or 4-methylamino-, 2- or 4-(dimethylamino)-, 2 - or 4-SO3H-, 2- or 4-SO3Na-, 2- or 4-[+NH3Cl], 3,4,5-trimethylphen-1-yl, 2,4,6-trimethylphen-1-yl, 4 -trifluoromethylphenyl or 3,5-di(trifluoromethyl)-phenyl. 51. The method according to claim 21, characterized in that R8 and R9 in the compounds of formula IVa are identical radicals and denote cyclohexyl or phenyl. 52. The method according to claim 21, characterized in that R16 and R17 in the compounds of formula IVa are identical and denote cyclohexyl, phenyl, t-butyl, 2- or 4-methylene-1-yl, 2- or 4-methoxyphen-1- yl, 2- or 4-(dimethylamino)phen-1-yl, 3,5-dimethyl-4-(dimethylamino)phen-1-yl, or 3,5-dimethyl-4-methoxy-phen-1-yl. 53. The method according to claim 22, characterized in that in the compounds of formula IVb and FVc the radicals R22 are identical or different and denote 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4-ethyl-, 2- or 4-i-propyl, 2- or 4-t-butyl-, 2-methoxy-, 3-methoxy-, 4-methoxy-, 2- or 4-ethoxy, 4-trimethylsityl-, 2- or 4-fluoro -, 2,4-difluoro- 2- or 4-chloro-, 2,4-dichloro-, 2,4-dimethyl-, 3,5-dimethyl-, 2-methoxy-4-methyl-, 3,5- dimethyl-4-methoxy-, 3,5-dimethyl-4-(dimethylamino)-, 2- or 4-amino-, 2- or 4-methylamino-, 2- or 4-(dimethylamino)-, 2- or 4 -SO3H-, 2- or 4-SO3Na-, 2- or 4-[+NH3Cl], 3,4,5-trimethylphen-1-yl, 2,4,6-trimethylphen-1-yl, 4-trifluoromethylphenyl or 3,5-di(tylfluoromethyl). 54. The method according to claim 22, characterized in that in the compounds of formula IVb and IVc the R22 radicals are identical and denote phenyl, cyclohexyl, t-butyl, 2- or 4-methylphen-1-yl, 2- or 4-methoxyphen-1 -yl, 2-or 4-(dimethylamino)phen-1-yl, 3,5-dunethyl-4-(dimethylamino)phen-1-yl, or 3,5-dimethyl-4-methoxy-phen-1-yl , 4-trifluoromethylphenyl or 3,5-di(trifluoromethyl). 55. The method according to claim 22, characterized in that in the compounds of formula IVb and IVc, R22 is phenyl and m+n in formula IVb is 0, 1 or 2. 56. The method according to claim 1, characterized in that ammonium chloride, bromide or iodide or metal chlorides, bromides or iodides, which are soluble in the reaction mixture, are used in amounts from 0.01 to 200 equivalents, based on the iridium catalyst. 57. Procedure according to watering 1, indicated that. chlorides, bromides or iodides of alkali metals are used as metal chlorides, bromides or iodides. 58. The method according to claim 1, characterized in that the ammonium chloride, bromide or iodide is tetraalkylammonium chloride, bromide or iodide with 1 to 6 C-atoms in the alkyl groups, and the alkali metal chloride, bromide or iodide is sodium, lithium or potassium chloride , bromide or iodide. 59. The method according to claim 1, characterized in that the acid is an inorganic or organic acid. 60. The method according to claim 1, characterized in that the acid is used in amounts of 0.001 to 50, especially 0.005 to 50% by mass of acid, based on the imine. 61. The method according to claim 59, characterized in that the organic acid is an aliphatic or aromatic carboxylic acid, sulfonic acid or phosphoric (V) acid. 62. The method according to claim 59, characterized in that the organic acid is acetic acid, propionic acid, trifluoroacetic acid, chloroacetic acid or methanesulfonic acid, and the inorganic acid is H2SO4. 63. The method according to claim 59, characterized in that the acid is hydrogen iodide. 64. The process according to claim 63, characterized in that the process is carried out without the addition of ammonium chloride, bromide or iodide or metal chlorides, bromides or iodides that are soluble in the reaction mixture. 65. The method according to claim 63, characterized in that a solid acid is used. 66. The method according to claim 65, characterized in that acidic zeolite, phyllosilicate or metal oxide in the form of a gel or acid ion exchanger resin is used as a solid acid. 67. The method according to claim 1, characterized in that the molar ratio of imitium to iridium catalyst is 500,000 to 100. 68. The method according to claim 1, characterized in that the reaction temperature is -20 to . 69. The method according to claim 1, characterized in that the hydrogen pressure is 2x105 Pascals to 150x105 Pascals. 70. The process according to claim 1, characterized in that the hydrogenation is carried out in a circular reactor. 71. The process according to claim 1, characterized in that the aldimine or ketimine formed in situ before or during the hydrogenation is hydrogenated.