MXPA97007801A - Dinalogenated ferrocenes and processes to supreparate - Google Patents

Abstract

The present invention relates to a compound of the formula I: wherein: R1 is alkyl of 1 to 8 carbon atoms, phenyl or phenyl substituted by 1 to 3 alkyl substituents of 1 to 4 carbon atoms or alkoxy of 1 to 4 atoms of carbon, R2 and R3 are each independently of the other, hydrogen or alkyl of 1 to 12 carbon atoms, and Hal is F, Cl, Br, or I. A process for the preparation of a compound of the formula I, wherein a compound of the formula II: wherein: R1, R2 and R3 as defined above, is reacted in an organic solvent first with one equivalent of lithium alkyl and then, in the presence of an amine complexing agent for Li, with a second equivalent of lithium and then the product is reacted with a halogenating agent. The use of a compound of formula III or VI as a ligand for rhodium or iridium in the catalytic hydrogenation of carbon / carbon or carbon / heteroate double bonds

Description

FE ROCENOS DIHAL0GENAD08 AND PROCESSES FOR YOUR PREPARATION The invention relates to ferrocenes substituted in positions 1,2 and 1 ', and to processes for their preparation. Ferroceilic diphosphine ligands having a silylene group are important intermediates for ferrocellic diphosphines, and their metal complexes with transition metals, such as rhodium or iridium, bonded via the silylene group with inorganic or organic polymeric carriers. These complexes are widely used in the hydrogenation of double or triple organic bonds, especially olefinic double bonds and carbon-heteroatom double bonds. The complexes are especially suitable for enantioselective hydrogenation using chiral ferrocelic diphosphines and the corresponding prochiral unsaturated compounds. European Patents Nos. EP-A-0-496, 699 and EP-A-0-496,700 disclose dioxolane and pyrrolidine diphosphines containing silane group, and their rhodium or iridium complexes, which are fixed to an inorganic carrier such as, for example, a silicate. In this way, in the hydrogenation, a heterogeneous reaction mixture is obtained from which the inorganically bound catalyst can be easily separated when the reaction is completed. W.R. Cullen et al. Describe, in J. of Organometallic Chemistry, 333 (1987), 269-280, derivatives of ferrocene, such as, for example, N, N-dimethyl-l- (2-diphenylphosphinoferrocenyl) ethyl amine which is directly linked to an oxidized polystyrene group. In the method proposed therein, a maximum of 20 percent of the ferrocene derivative used is bonded to the polymeric carrier, and the ferrocenyl ligand is bonded to the polymer in a non-specific and non-selective manner partially by means of one or the other cyclopentadienyl ring. As a result of the direct link to the polymer backbone, the mobility of the phosphine ligand is restricted in the same way. It seems desirable to start from starting materials having known properties, and to modify these starting materials using catalytically active compounds, such that the properties are altered only very slightly, and there are no inclusions or any other alterations to the catalytically active part; depending on the hydrogenation reaction, inorganically bound or organically linked ferrocenyl diphosphine ligands may be more convenient. However, it is also possible to functionalize the silylated ferrocenyl diphosphines in such a way that they can be copolymerized, for example, by means of an olefinically unsaturated bond. These methods are described, for example, in J. Org. Chem. 1981, 46, 2960-2965. In the case of ferroceilic diphosphine ligands bonded with polymer, for example, the reaction that is going to Catalyzing can be carried out in a heterogeneous or homogeneous manner, depending on the selected polymer. The polymer can be selected in such a manner, and can also be subsequently modified in a directed manner such that the catalyst can be easily separated and reused after the reaction. The catalysts can be reused several times. By choosing the polymer, it is possible to couple the catalyst in an optimum manner with the reaction medium during the hydrogenation step, and then remove it completely afterwards, which is of particular importance in relation to the hydrogenation performed on an industrial scale. In all cases, recovery of the noble metals present is facilitated if the catalyst has to be changed after frequent recycling. It is often also possible to eliminate an additional purification of the hydrogenated product, since the catalyst can be removed in general in a quantitative manner. Ferrocellic diphosphines containing an organic radical bonded via a silylene group to a cyclopentadienyl ring can be immobilized in a simple manner, either on inorganic carriers or on polymeric organic carriers, or, after the introduction of a polymerizable group, they can also be immobilized by copolymerization. With rhodium and iridium, ferrocenic diphosphine ligands lica immobilized form complexes that can be used as highly active catalysts in the enantioselective hydrogenation of carbon-carbon, carbon-nitrogen, or carbon-oxygen double bonds. The selectivity and the total yield are surprisingly high for the immobilized systems. Iridium catalysts are especially suitable for the hydrogenation of imine, since they clearly have the highest activity and the highest catalyst productivity compared to other immobilized systems. In the same way, its selectivity is very good. The catalysts can be easily separated from the reaction solution, and can be used again. Virtually no metal and ligand losses. Accordingly, the use of these immobilized catalysts makes it possible for the hydrogenation to be carried out in an economical manner, especially on an industrial scale. The preparation of these immobilized ferrocellic diphosphines has been made possible only by the provision of correspondingly functionalized ferrocellic diphosphines. These intermediaries and their preparation, therefore, are of great importance. Ferrocenes that are substituted by two phosphine groups in a cyclopentadienyl ring are known, and their preparation and use as ligands in metal complexes for stereoselective hydrogenation are described, for example, in European Patent Number EP-A-564,406.

Until now, a process allowing, for example, stereoselectively in amine (R) - or (S) -N, N-dimethyl-1-ferrocerethylene, has not been disclosed, in a first step, the introduction of a phosphorus group as an electrophilic with high selectivity in an already substituted cyclopentadienyl ring, and in a second step, the introduction of a silylene group selectively into the other cyclopentadienyl ring. However, using that procedure, it is possible for the first time to prepare a number of valuable intermediates for ferrocellic diphosphines and their metal complexes. Dihalogenated, but otherwise unsubstituted ferrocenes having a halogen atom bonded to both cyclopentadienyl groups at positions 1 and 1 'are known, for example, from R.F. Kovar et al., Organo etal. Chem. Syn., 1 (1970/1971) 173-181. In the same way, its preparation is made available by means of lithiation and the subsequent halogenation. However, ferrocenes l, l '-dihalogenates substituted at position 2 have not been disclosed so far. According to the above, the invention relates to compounds of the formula I: (I) where: R? is alkyl of 1 to 8 carbon atoms, phenyl or phenyl substituted by 1 to 3 alkyl substituents of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; R2 and R3 are each independently of the other, hydrogen or alkyl of 1 to 12 carbon atoms; and Hal is F, Cl, Br, or I.

R? as alkyl, it is preferably linear. Preference contains from 1 to 4 carbon atoms. Examples of this alkyl are methyl, ethyl, normal propyl and isopropyl, normal butyl, isobutyl, and tertiary butyl, pentyl, hexyl, heptyl, and octyl. Preference is given to methyl and ethyl, and methyl is especially preferred. ? as phenyl substituted preferably contains 1 or 2 substituents Alkyl substituents may be, for example, methyl, ethyl, normal propyl and isopropyl, normal butyl, isobutyl, and tertiary butyl; methyl and ethyl are preferred. The alkoxy substituents may be, for example, methoxy, ethoxy, normal propoxy and isopropoxy, normal butoxy, isobutyl and tertiary butoxy; methoxy and ethoxy are preferred. In a group of compounds of the formula I, R ^. it is preferably phenyl, or phenyl substituted by one or two alkyl substituents of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms. R2 and R3 as alkyl may be linear or branched.

Examples of alkyl of 1 to 8 carbon atoms are mentioned above, and include, in addition, the different isomers of nonyl, decyl, undecyl, and dodecyl. R2 and R3 can also be linked to each other and form a cyclic alkyl group. The resulting examples are pyrrolidine and piperidine. Preferably, R2 and R3 are each independently of the other, hydrogen, methyl, or ethyl, and also especially are both hydrogen or methyl. Hal is preferably Cl, Br, or I.The compounds of formula I can be prepared according to analogous process in a manner known per se, as described, for example, by R.F. Kovar et al., Organometal. Che. Syn., 1 (1970/1971) 173-181, for the reaction of compounds diluted with halogenating agents, or by T. Hayashi et al., Bull Chem. Soc. Jpn., 53 (1980) 1138-1151 for lithiation stereoselective. The invention also relates to a process for the preparation of compounds of the formula I, wherein a compound of the formula II: where: ^ - ^ fl. Ri / R2 'and R3 are as defined above, reacted in an organic solvent first with one equivalent of alkyl lithium, and then, in the presence of an amine complexing agent for Li, with a second equivalent of alkyl lithium, and then the product is reacted with a halogenating agent. An example of an amine complexing agent for Li is N, N, N, N-tetramethylethylene diamine. Alkyl lithium should be understood in the context of this invention, preferably, as tertiary butyl lithium, secondary butyl, or normal butyl. Halogenation agents are known in the general prior art for many reactions. Some are also mentioned, for example, in Gmelin, Handbuch der Anorganischen Chemie, Eisen-Organische Verbindungen Teil A Ferrocen 7, Eighth Edition, Springer Verlag 1980, pages 128-136. Preference is given to a halogenating agent selected from the group consisting of Cl 2, hexachloroethane, 1,2-dichlorotetrafluoroethane, toluene-4-sulfonyl chloride, Br 2, 1,2-dibromotetrachloroethane, 1,2-dibromotetrafluoroethane, bromide toluene-4-sulfonyl, 2,3-dimethyl-2,3-dibromobutane, I2, 1,2-diiodotetrafluoroethane, perfluoropropyl iodide, perfluoroethyl iodide, toluene-4-sulfonyl iodide, and perfluoromethyl iodide. The compounds of the formula I act as starting materials for the preparation of compounds of the formula III, which in the same way are novel and are an object of this invention. The invention also relates to compounds of formula III: wherein: R1 t R2, R3, and Hal are as defined above; R10 and Rn are identical or different, and are alkyl 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, cycloalkyl of 5 to 12 carbon atoms substituted by alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, or substituted phenyl by 1 to 3 alkyl substituents of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, -SiR4R5R6, halogen, -S03M, -C02, -P03M, -NR7Rβ, - [* NR7R8R9] X "O fluoroalkyl of 1 to 5 carbon atoms, or the group PR10Rn is a radical of formula IV, IVa, IVb, Ó IVc: R4-R5 'and R6 are ca (independently of one another, alkyl of 1 to 12 carbon atoms or phenyl; R7 and R8 are H, alkyl of 1 to 12 carbon atoms, or phenyl, or R7 and R8 are together tetramethylene, pentamethylene, or 3-oxa-1, 5-pentylene, R9 is H or alkyl of 1 to 4 carbon atoms, M is H or an alkali metal, X "is the anion of a monobasic acid.

R 10 and R 1 as alkyl may be linear or branched, and preferably contain from 1 to 8, and especially from 1 to 4 carbon atoms. Examples of this alkyl are methyl, ethyl, normal propyl and isopropyl, normal butyl, isobutyl and tertiary butyl, pentyl, hexyl, heptyl, nonyl octyl, decyl, undecyl, and dodecyl. Methyl, ethyl, normal propyl and isopropyl, normal butyl, isobutyl and tertiary butyl are preferred. When R10 and Rl? they are identical, such as alkyl, they are especially isopropyl or tertiary butyl. RIVER AND Rn as cycloalkyl preferably contain to 8, and especially 5 or 6 ring carbon atoms. Examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl. Preference is given to cyclopentyl and cyclohexyl, and especially cyclohexyl is preferred.

The cycloalkyl may be substituted, for example, by 1 to 3 alkyl or alkoxy substituents. Examples of these substituents have been given above. Methyl and ethyl and methoxy and ethoxy are preferred. Examples of substituted cycloalkyl are methyl- and methoxy-cyclopentyl and -cydohexyl. R 10 and l as substituted preferably contain 1 or 2 substituents. When phenyl contains 2 or 3 substituents, these substituents may be identical or different. Examples of the alkyl and alkoxy substituents have been given above; Preferred alkyl and alkoxy substituents for phenyl are methyl, ethyl, and methoxy and ethoxy. When the phenyl substituent is halogen, it is preferably -F, -Cl, or -Br. When the phenyl substituent is fluoroalkyl of 1 to 5 carbon atoms, it is alkyl of 1 to 5 total or partially fluorinated carbon atoms. Examples thereof are the positional isomers of mono- to deca-fluoropentyl, mono- to octa-fluorobutyl, mono- to hexa-fluoropropyl, mono- to tetra-fluoroethyl, and mono- and di-fluoro-methyl. Of the partially fluorinated alkyl radicals, those of the formulas -CF2H and -CF2 (alkyl of 1 to 4 carbon atoms) are especially preferred. A special preference is given to perfluorinated alkyl. Examples thereof are perfluoropentyl, perfluorobutyl, perfluoropropyl, perfluoroethyl, and especially trifluoromethyl. Alkyl groups substituted by fluorine are preferably linked in the positions 3, 4, and 5. R4 / R5 and R6 can be linear or branched alkyl containing preferably from 1 to 8, and especially from 1 to 4 carbon atoms. Examples of alkyl have been given above. The preferred alkyl is methyl, ethyl, normal propyl, normal butyl, or tertiary butyl. The substituent -SiR4R5R6 is preferably trimethylsilyl. Of the acid phenyl substituents -S03M, -C02M, and -P03M, the -S03M and -C02M groups are preferred. M is preferably H, Li, Na, or K. R7 and R8 as alkyl preferably contain from 1 to 6, and especially from 1 to 4, carbon atoms. The alkyl is preferably linear. Preferred examples are methyl, ethyl, normal propyl, and normal butyl. R9 as alkyl is preferably methyl. X ~ as an anion of a monobasic acid is preferably Cl ~, Br ~, or the anion of a carboxylic acid, for example, formate, acetate, trichloroacetate, or trifluoroacetate. Preferred examples of R 10 and R as substituted phenyl are 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4-ethyl-, 2- or 4-isopropyl-, 2- or 4-butyl. tertiary-, 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-S03H-, 2- or 4-S03Na-, 2- or 4 - [+ NH3Cl "] -, 3,4,5-trimethylphen-1-yl, 2,4,6 -trimethylphen-1-yl, 4-trifluoromethyl-phenyl or 3,5-di (trifluoromethyl) phenyl R 10 and R 1 are especially preferably cyclohexyl, tertiary butyl, phenyl, 2- or 4-methylphenol -l-ilo, 2-or 4-methoxyphen-1-yl, 2- or 4- (dimethylamino) phen-1-yl, 3,5-dimethyl-4- (dimethylamino) -phen-1-yl, or , 5-dimethyl-4-methoxyphen-1-yl, but especially cyclohexyl, phenyl, 4-methylphen-1-yl, or tertiary butyl In the same way, the process for the preparation of the compounds of the formula III is novel and it is an object of this invention The process for the preparation of the compounds of the formula III is as follows: in a first step, alkyl lithium is added to a compound of the formula I in an inert organic solvent, and it is left to react , and then an organic solution of a compound of the formula V, CIPCR ^ ^) (V) is added, and further reacted, to form a compound of formula III, wherein R 10 and R have the definitions and preferred meanings given above. The substitution of the halogen atom takes place predominantly in the cyclopentadienyl ring carrying the second substituent (alkyl amine). Therefore, it is possible, using this process, to obtain asymmetric ferrocenes in good performance, which is of great significance with regarding commercial production. The process is preferably carried out by adding lithium lithium at a temperature of -90 ° C to + 20 ° C. In the second step, the compound of formula V is preferably added at a temperature of -90 ° C to + 20 ° C. The invention also relates to ferrocellic diphosphines of the formula VI, which are obtained by using compounds of the formula III as starting materials: wherein: Ri, io »n and Hal have the definitions and preferred meanings given above, and R12 and Ru are each independently of the other, alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, cycloalkyl of 5 to 12 carbon atoms substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, or phenyl mono- or poly-substituted by 1 to 3 alkyl substituents of 1 to 4 atoms carbon, alkoxy of 1 to 4 carbon atoms, -SiR4R5R6, halogen, -S03M, -C02M, -P03M, -NR7Rβ, - [* NR7RβR,] X- or fluoroalkyl of 1 to 5 carbon atoms; or the group -PR? 2Ri3 is a radical of formula IV, IVa, IVb, or IVC R4, R5, R5, R7, R8, R9, M and X "have the definitions and preferred meanings given above Examples of alkyl, cycloalkyl, substituted phenyl, phenyl and fluoroalkyl, have already been given above, and are also applied to the definitions of R.sub.12 and R.sub.13, R.sub.12 and R.sub.3 are Preferential to alkyl of 1 to 8 carbon atoms The examples of alkyl of 1 to 8 carbon atoms have already been mentioned, R12 and R13 are identical Preference and are isopropyl or tertiary butyl, R12 and R13 as cycloalkyl preferably contain from 5 to 8 carbon atoms, Another preferred group of compounds is obtained when R12 and R13 are unsubstituted phenyl, or phenyl substituted by 1 or 2 substituents. R 13 as substituted phenyl are especially preferably 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4- Ethyl-, 2- or 4-isopropyl-, 2- or 4-tertiary 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-S03H-, 2- or 4-S03Na-, 2- or 4 - [+ NH3Cl ~] -, 3,4,5-trimethylphen-1-yl, 2,4,6-trimethylphenol- ilo, 4-trifluoromethyl-phenyl or 3,5-di (trifluoromethyl) phenyl. An additional group of especially preferred compounds is obtained when R 12 and R 3 are identical and are phenyl, cyclohexyl, 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-methoxyphen-1-yl; R1 and R13 are more especially identical radicals, and are cyclohexyl or phenyl. The compounds where R? is methyl, R12 and R13 are each cyclohexyl or phenyl, and R10 and Rl? they are phenyl, cyclohexyl, or tertiary butyl, they are especially preferred. The process for the preparation of the compounds of the formula VI can be carried out in a manner analogous to the processes known in the prior art. For example, this substitution is disclosed in European Patent Number EP-A-612,758. The process for the preparation of the compounds of the formula VI comprises reacting a compound of the formula III with a compound of the formula H-P (R12R13) in acetic acid, having R12 and R13 the definitions and the preferred meanings given above. The compounds of formulas I, III, and VI can be obtained in the form of racemates, pure enantiomers, or mixtures of enantiomers. If the synthesis is carried out using enantiomerically pure compounds of the formula II as starting materials, very preferably only one of the two possible diastereomers of the compounds of the formula I is formed, and consequently, also of the compounds of the formulas III and SAW. If racemates or optically active mixtures are used as starting materials, they can be separated into the stereoisomers by known methods, with chromatographic methods being generally preferred. The optical isomers of the compounds of the formula VI are especially valuable starting materials for the preparation of immobilized hydrogenation catalysts. The isolation and purification of the compounds are carried out according to methods known per se, for example distillation, extraction, crystallization, and / or chromatographic methods. The compounds of formula VI, in a first step, can be lithiated with alkyl lithium in a known manner, as described, for example, in J. Chem. Soc. Chem. Commun., 1994, 2347-2348. In a further step, a compound of the formula VII is then added: ClSi (R14) 2- (R15) -Cl (VII), and reacted to form compounds of formula VIII: wherein the radicals R14 are each independently of the other alkyl of 1 to 12 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, benzyl or phenyl, or are together alkylene of 4 to 12 carbon atoms, and R15 is alkylene of 1 to 12 carbon atoms or phenylene. Preferably R1 is methyl and R15 is propyl R] ^ to R13 are defined above. The compounds of the formula VIII can be obtained by, in a first step, the lithiation of compounds of the formula III according to the known processes, and then in a second step, the reaction with the compounds of the formula VII to form compounds of the formula IX: the definitions and the preferred meanings of the radicals Rí to R15 have been given previously. The compounds of the formula IX can be further reacted with a compound of the formula HP (R12R13) in acetic acid, in a manner analogous to the processes known in the prior art, and thus the compounds of the invention are also obtained. the formula VIII. This substitution is disclosed by analogy in European Patent Number EP-A-612,758. The compounds of the formula IX can also be used as hydrogenation and hydrosilylation catalysts in a manner analogous to the diphosphines containing amine group described by Cullen et al. In Can. J. Chem. Volume 60, 1982, pages 1793 to 1799. In the same manner, the compounds of formula IX can be immobilized on polymers, and can be used as immobilized ligands in enantioselective catalytic reactions. The compounds of the formula VIII can be further reacted, according to known processes, with compounds of the formula X: NH 2 (alkyl of 1 to 12 carbon atoms (X), to form compounds of the formula Villa: (Villa), or the compounds of the formula VIII are first reacted with potassium italic imide, and then with hydrazine, to form compounds of the formula VlIIb: (Vlllb), and optionally, in a further step, the compounds of the formula Villa or Vlllb can be reacted with the compounds of the formula XI: Ra (R170) 2Si-R16-NCO (XI), to form compounds of the formula VIIIc: (Vlllc), wherein Ra is alkyl of 1 to 4 carbon atoms or 0R17, A is NH or N (alkyl of 1 to 12 carbon atoms), R16 is alkylene of 1 to 12 carbon atoms, and R17 is alkyl of 1 to 12 carbon atoms. The remaining radicals R? to R15 have the definitions given above, including the preferred meanings.

The steps of the reaction are analogously processes which are described, for example, in European Patent Number EP-A-612,758 and in European Patent Number EP-A-496, 699. The step of amination to form the compounds of the formula Villa is known by the expert in this field from the current reference books on organic chemistry. The compounds Villa and Vlllb can then be reacted to form a polymeric organic material having structural repeating units of the formula XII: wherein: A and R1 to R15 are as defined above, Q is a bridge group formed by a diisocyanate, and MW is the radical of a polymer-forming monomer which contains, as a functional group, linked directly or in a side chain , a hydroxy group or a primary or secondary amine group which is linked to the diphosphine by means of a bridge group Q formed by a diisocyanate. Preferred diisocyanates are 1,6-bis [isocyanato] hexane, 5-isocyanato-3- (isocyanatomethyl) -l, 1,3-trimethylcyclohexane, 1,3-bis [5-isocyanato-1,3,3- trimethyl-f-enyl] -2,4-dioxo-l, 3-diaceti-dine, 3,6-bis [9-isocyanato-nonyl] -4,5-di (1-heptenyl) cyclohexene, bis [4-isocyanate] -cyclohexyl] ethane, trans-1,4-bis [isocyanate] cyclohexane, 1,3-bis [isocyanatomethyl] -benzene, 1,3-bis [l-isocyanato-1-methyl-ethyl] benzene, 1,4-bis [2-isocyanato-ethyl] -cyclohexane, 1,3-bis [isocyanatomethyl] cyclohexane, 1,4-bis [1-isocyanato-l-methylethyl] -benzene, bis [isocyanato] isododecylbenzene, 1,4-bis [isocyanato] benzene, 2,4-bis [isocyanato-3-toluene, 2,6-bis [isocyanato] toluene, 2, 4- / 2, 6-bis [isocyanato] toluene, 2-ethyl-l, 2,3-tris [3-isocyanato-4-methyl-anilinocarbonyloxy] propane, N, N'-bis [3-isocyanate-4-] methyl-f-enyl-3-urea, 1,4-bis [3-isocyanato-4-methyl-e-nyl] -2,4-dioxo-1,3-diazetidine, 1,3,5-tris [3-isocyanate-4] -methylphenyl] 2,4,6-trioxohexahydro-1,3,5-triazine, 1,3-bis [3-isocyanato-4-methylphenyl] -2,4,5-trioxoimidazolidine, bis [2-isocyanofenyl] methane, (2-isocyanato-phenyl) - (4-isocyanato-phenyl) -methane, bis [4-isocyanato-phenyl] methane, 2,4-bis [4-isocyanatobenzyl] -l-isocyanatobenzene, [4- isocyanato-3- (4-isocyanato-benzyl) -phenyl] - [2-isocyanato-5- (4-isocyanato-benzyl) -phenyl] meta-no, tris [4-isocyanato-phenyl] methane, 1, 5- bis [ isocyanate] naphthalene, and 4,4'-bis [isocyanato] -3,3'-dimethyl-bifenyl.

Particularly preferred diisocyanates are 1,6-bis [isocyanato] hexane, 5-isocyanato-3- (isocyanatomethyl) -1, 1,3-trimethylcyclohexane, 2,4-bis [isocyanato] toluene, 2,6-bis [isocyanate] -nato] toluene, 2, 4- / 2, 6-bis [isocyanato] toluene, and bis [4-isocyanato-phenyl] methane. The polymers according to the invention may be non-crosslinked, crosslinked, or structurally crosslinked thermoplastic polymers. The polymers can be polymerized from olefinically unsaturated monomers, for example polyolefins, polyacrylates, polyisoprene, polybutadiene, polystyrene, polyphenylene, polyvinyl chloride, polyvinylidene chloride, or polyallyl compounds. They can also be polyaddition compounds, for example polyurethanes or polyethers. The polycondensed products that may be mentioned are polyesters or polyamides. Preference is given to the polymer-forming monomers selected from the group consisting of styrene, p-methylstyrene, and α-methylstyrene, at least one of which contains a hydroxy group or a primary or secondary amine group bonded as a functional group . Another preferred group of polymers is formed by monomers derived from α, β-unsaturated acids and their esters and amides, whose structural units contain a hydroxy group or a primary or secondary amine group bonded as a functional group.

A special preference is given to the monomers from the group of the acrylates and the alkyl esters of 1 to 4 carbon atoms thereof, methacrylates and the alkyl esters of 1 to 4 carbon atoms thereof, acrylamide and acrylonitrile, whose structural units contain a hydroxy group or a primary or secondary amine group linked as a functional group in the ester or amide group. Preferably, the functional or primary or secondary amine hydroxy functional monomers form from 1 to 100 molar percent, preferably from 5 to 100 molar percent, and especially from 10 to 100 molar percent of the polymer structure in the case of soluble or swellable polymers where the functional group is already present. In the case of the crosslinked polymers, which are subsequently functionalized, from 1 to 50 molar percent, especially from 1 to 20 molar percent, of hydroxy or functional primary or secondary amine functional groups, the molar percentages being based on the monomer that forms most of the polymer. The charge of the polymer with the ferrocellic diphosphines according to the invention is preferably 5 to 100 molar percent, especially 5 to 50 molar percent, based on the hydroxy group or on the available primary or secondary amine group of the polymer . Polymeric carriers can be prepared as follows: polymers having structural repeating units of at least one monomer containing a hydroxy group or a primary or secondary amine group bonded as a functional group directly in the polymer backbone or in a side chain, A) in a first step, they are reacted totally or partially, in an inert organic solvent, with a diisocyanate forming a bridge group Q, and in a second step the product is reacted with a diphosphine containing tertiary phosphine groups linked at positions 1,2 of a ring of cyclopentadienyl, one of whose tertiary phosphine groups is directly linked, and the other of which is linked by means of a group CHR1 with the cyclopentadienyl ring, and which contains a silylene group -Si (R14) 2 -R15- A- linked to the other cyclopentadienyl radical; or B) in a first step, a diphosphine containing tertiary phosphine groups linked at positions 1,2 of a cyclopentadienyl ring, one of whose tertiary phosphine groups is directly linked, and the other of which is linked to a group CHR1 with the cyclopentadienyl ring, and containing a silylene group -Si (R14) 2 -R15-A- linked to the other cyclopentadienyl ring, is reacted totally or partially, in an inert organic solvent, with a diisocyanate which forms a bridge group Q, and in a second step, the product is reacted totally or partially with a polymer having structural repeating units of at least one monomer containing a hydroxy group or a primary or secondary amine group bonded as a functional group, and C) any remaining free isocyanate groups are crosslinked with a diol of 2 to 24 carbon atoms or with a diamine of 2 to 24 carbon atoms, or are removed by their reaction with an alcohol of 2 to 12 carbon atoms or an amine of 2 to 12 carbon atoms. The diisocyanates forming a bridge group Q can be reacted with the amine or hydroxy groups of the polymer and the diphosphine at room temperature or at an elevated temperature, for example, from 30 ° C to 100 ° C, in accordance with methods known in the literature. The subsequent introduction of, for example, a hydroxy group into the highly crosslinked polystyrene, can be carried out according to the known procedures. Chloromethylation is first performed as described in J. Mol. Catal. 51 (1989), 13-27, and then a hydrolysis according to the method given by J.M. Frechet et al. In Polymer, 20 (1979) 675-680. The compounds of formula VIIId can be reacted to form ferroceilic diphosphines fixed on inorganic carriers by means of an analogous reaction procedure - as disclosed in European Patent Number EP-A-0,496,699.

The solid carrier T may be a silicate or a semi-metal oxide or a metal oxide or a glass, which is preferably present in the form of powders having average particle diameters of 10 nanometers to 2,000 microns, preferably from 10 nanometers to 1,000 microns, and especially from 10 nanometers to 500 microns. They can be compact or porous particles. The porous particles preferably have large internal surface areas, for example, from 1 to 1,200 square meters, preferably from 30 to 600 square meters. Examples of oxides and silicates are Si02, Ti02, Zr02, MgO, NiO, W03, A1203, La203, silica gels, clays, and zeolites. Preferred carriers are silica gels, aluminum oxide, titanium oxide, or glass, and mixtures thereof. An example of a glass as a carrier is "controlled pore glass", which is commercially available. Using the organophosphines or inorganically bound diphosphines, it is possible to prepare rhodium or iridium metal complexes by reacting the organic or inorganic carriers with which the diphosphines bind, with a metal compound of the formula [Me (Y) D] 2 + or Me (Y) 2+ E ", where Me is rhodium or iridium, and represents two monoolefin ligands or a diene ligand; D is -Cl, -Br, or -I, and E" is the anion of an oxyacid or a complex acid.

Preferred are metal complexes wherein Y is 1,5-hexadiene, 1,5-cyclooctadiene, or norbornadiene. In the metal complexes according to the invention, D is preferably -Cl, -br, or -I. In the preferred metal complexes, E ~ is C104", CF3S03 ~, CH3S03", HS04 ~, BF4", B (phenyl) 4 ~, PF6", SbCl6", AsF6", or SbF6". The reaction is conveniently carried out under an inert gas atmosphere, for example argon, and conveniently at temperatures of 0 ° C to 40 ° C, preferably at room temperature, in the case of soluble polymer-bound diphosphines. Conveniently a solvent or a mixture of solvents is conveniently used, for example, hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, chlorobenzene), alkanols (methanol, ethanol, glycol monomethyl ether) of ethylene), and ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether), or mixtures thereof. Preferably, the metal complexes are used for the asymmetric hydrogenation of prochiral compounds having carbon-carbon or carbon-heteroatom double bonds, especially the Ir complexes for the hydrogenation of asymmetric ketimines. These hydrogenations with soluble homogenous ferroceilic diphosphine metal complexes are disclosed, for example, in European Patent Number EP-A-612,758.

The following examples illustrate the invention.

General process procedure: All operations are carried out under an atmosphere of inert gas (argon or nitrogen).

Abbreviations used: TMEDA: diamine N, N, N, N-tetramethylethylene n-BuLi: normal butyl lithium COD: 1,5-cyclooctadiene Example Al. Preparation of the compound of the formula I Amine (R) -N, N-dimethyl-l- [(S) -l ', 2-bis (chloro) ferrocenyl] ethyl. 2.92 milliliters (4.6 millimoles) of a 1.6M n-BuLi solution are added dropwise at room temperature, with stirring, to a solution of 1 gram (3.9 millimoles) of amine (R) -N, N-dimethyl-1. -ferrocenylethyl in 8 milliliters of diethyl ether. After 1.5 hours, an additional solution consisting of 2.92 milliliters (4.6 millimoles) of an solution of BuLi 1.6M in hexane, and 0.67 milliliter (4.4 mmol) of TMEDA, and the reaction mixture is stirred for 5 hours. Then the tanned nebulous reaction mixture is cooled to -72 ° C to -78 ° C with a dry ice / isopropanol bath, and with stirring, 2.21 grams (9.4 millimoles) of hexachloroethane are slowly added in portions, so that the temperature of the mixture does not exceed -74 ° C. The mixture is stirred for an additional 1 hour with cooling, and then for an additional 2 hours without cooling. 20 milliliters of ice water are added to the resulting orange suspension, and the mixture is extracted repeatedly by stirring with 5 milliliters of ethyl acetate. The organic phases are collected, washed with water, dried over Na 2 SO 4 and concentrated in a rotary evaporator. The crude brown product is purified by chromatography (silica gel, Merck 60, eluent: acetone). 0.54 grams of compound 2 are obtained (43% yield, orange oil). Analysis: ^ -NMR (CDC13): S 1.53 (d, 3H, J = 7, C-CH3), 2.13 (s, 6H, N (CH3) 2), 3.83 (q, ÍH, J = 7, CH- Me), 4.0-4.5 (m, 7H, C5H3FeC5H4). Microanalysis, calculated for C 14 H 17 Cl 2 FeN: C, 51.57; H, 5.26; N, 4.30; Cl, 21.75. Found: C, 51.42; H, 5.28; N, 4.28; Cl, 21.48.

Example A2 Preparation of the compound of the formula 2 Amide (R) -N, N-dimethyl-l- [(S) -l ', 2-bis (bromo) ferrocenyl] ethyl. .6 milliliters (33 millimoles) of a 1.6M n-BuLi solution are added dropwise at room temperature, with stirring, to a solution of 7.71 grams (30 millimoles) of amine (R) -N, N-dimethyl-1 -ferrofenthylethyl in 50 milliliters of diethyl ether. After 1.5 hours, an additional solution consisting of 22.5 milliliters (36 millimoles) of a BuLi 1.6M solution in hexane, and 4.95 milliliters (33 millimoles) of TMEDA, is added dropwise, and the reaction mixture is stirred overnight . Then the tanned nebulous reaction mixture is cooled to -72 ° C to -78 ° C in a dry ice / isopropanol bath, and with stirring, 7.9 milliliters (66 millimoles) of 1,2- dibromotetrachloroethane, in such a way that the temperature of the mixture does not exceed -74 ° C. The mixture is stirred for an additional 1 hour with cooling, and then for an additional 2 hours without cooling. 50 milliliters of ice water are added to the resulting orange suspension, and the mixture is extracted repeatedly by stirring with 25 milliliters of ethyl acetate. The organic phases are collected, washed with water, dried over Na 2 SO 4 and concentrated in a rotary evaporator. The raw chestnut product is purified by chromatography (silica gel: Merck 60, eluent, acetone). 7.5 grams of compound 2 are obtained (yield of 60 percent, brown oil). Analysis: ^ -NRM (CDC13): d 1.53 (d, 3H, J = 7, C-CH3), 2.13 (s, 6H, N (CH3) 2), 3.78 (q, lH, J = 7, CH- Me), 4.03-4.5 (m, 7H, C5H3FeC5H4). Microanalysis calculated for C14H17NBr2Fe: C, 40.52; H, 4.13; N, 3.38; Br, 38.51; Faith, 13.46. Found: C, 40.80; H, 4.10; N, 3.30; Br, 38.18. Example A3 Preparation of the compound of the formula 3 Amine (R) -N, N-dimethyl-l- [(S) -l ', 2-bis (iodo) ferrocenyl] ethyl © (3) 2.92 milliliters (4.6 millimoles) of a 1.6M n-BuLi solution is added dropwise at room temperature, with stirring, to a solution of 1 gram (3.9 millimoles) of amine (R) -N, N-dimethyl-1-ferrocenylethyl in 8 milliliters of diethyl ether. After 1.5 hours, an additional solution consisting of 2.92 milliliters (4.6 millimoles) of a solution of BuLi 1.6M in hexane, and 0.67 milliliters (4.4 millimoles) of TMEDA, is added dropwise, and the reaction mixture is stirred for 5 hours . Then the brownish nebulous reaction mixture is cooled to -72 ° C to -78 ° C in a dry ice / isopropanol bath, and with agitation, 2.37 grams (9.3 millimoles) of iodine are added slowly in portions, in such a way that the temperature of the mixture does not exceed -74 ° C. The mixture is stirred for an additional hour with cooling, and then for an additional 2 hours without cooling. 20 milliliters of ice water are added to the resulting orange suspension, and the mixture is extracted repeatedly by stirring with 20 milliliters of ethyl acetate. The organic phases are collected, washed with water, dried over Na 2 SO 4 and concentrated in a rotary evaporator. The crude brown product is purified by chromatography (silica gel, Merck 60, eluent: acetone). 0.17 grams of compound 3 are obtained (yield of 9 percent, reddish-brown oil). Analysis: ^ -RMN (CDC13): d 1.50 (d, 3H, J = 7, C-CH3), 2.15 (s, 6H, N (CH3) 2), 3.65 (q, ÍH, J = 7, CH- Me), 4.03 (m, 7H, C5H3FeC5H4). Microanalysis calculated for C14H17Nl2Fe: C, 33.04; H, 3.37; N, 2.75; I, 49.87. Found: C, 32.89; H, 3.56; N, 2.63; I, 49.08. Example A4. Preparation of the compound of the formula 4 Amine (R) -N, N-dimethyl-l- [l- (bromo), (S) -2-diphenylphosphino) ferro-cenyl] ethyl 0.37 milliliters (0.6 millimoles) of a 1.6M BuLi solution in hexane are added dropwise, at -40 ° C to -30 ° C, with stirring, to a solution of 250 milligrams (0.6 millimoles) of the compound of Example 2 (compound 2) in 4 milliliters of diethyl ether. The mixture is then cooled to -78 ° C, and 0.133 milliliters (0.72 millimoles) of Cl-PPh2 are added slowly. Then the mixture is allowed to rise slowly to room temperature, and then it is stirred for an additional 1 hour. Then 10 milliliters of water are added to the resulting yellow suspension, and the mixture is extracted repeatedly by stirring with ethyl acetate. The organic phases are collected, washed with water, dried over Na 2 SO 4 and concentrated with a rotary evaporator. The yellowish chestnut crude product is purified by chromatography on silica gel or Alox. 159 milligrams of compound 4 are obtained (yield of 51 percent, almost solid orange chestnut). If the same reaction is performed on pentane under conditions that are otherwise the same, a yield of 61 percent is obtained. Analysis: ^ -NRM (CDC13): 5 1.25 (d, 3H, 3 = 1, C-CH3), 1.75 (s, 6H, N (CH3) 2), 4.15 (m, ÍH, J = 7, CH- Me), 3.7-4.4 (m, 7H, C5H3FeC5H4), 7.1-7.65 (m, 10H, P (C6H5) 2 .31P-NMR (CDC13): -5 -24.568.

Example A5. Preparation of the compound of the formula 5 Amin (R) -N, N-dimethyl-l- [l * - (l "-dimethylsilyl-3" -chloropropyl) - (S) -2-diphenylphosphinoferrocenyl] ethyl. 0.2 milliliters (0.32 millimoles) of a 1.6M BuLi solution in hexane are added dropwise at -40 ° C to -30 ° C, with stirring, to a solution of 136 milligrams (0.26 millimoles) of compound 4 of Example 4, in 4 milliliters of diethyl ether. The mixture is then cooled to -78 ° C, and 0.056 milliliters (0.34 millimoles) of 3-chloropropyl-dimethylchlorosilane are added slowly. Then the mixture is allowed to rise slowly to room temperature, and then it is stirred for an additional 1 hour. Then 10 milliliters of water are added to the resulting orange suspension, and the mixture is extracted repeatedly by stirring with ethyl acetate. The organic phases are collected, washed with water, dried over Na 2 SO 4 and concentrated in a rotary evaporator. The yellowish chestnut crude product is purified by chromatography (silica gel: Merck 60, eluent: ethyl acetate). 85 milligrams of compound 5 are obtained (yield of 50 percent, almost solid orange).

Analysis: XH-NMR (CDC13): d 0.05 (s, 3H, Si-CH3), 0.15 (s, 3H, Si-CH3), 0.61 (m, 2H, CH2-Si), 1.28 (d, 3H, J = 7, C-CH3), 1.5-1.9 (m, 2H, CH2 ~ CH2-C / 1.75), 1.78 (s, 6H, N (CH3) 2), 3.4 (t, 3H, CH2-C1), 3.5 -4.4 (m, 8H, C5H4FeC5H3CH), 7.1-7.65 (m, 10H, P (C6H5) 2 .31P-NMR (CDC13): 5-23306.

Example A6. Preparation of the compound of the formula 6 Phosphine (R) -1- [1 '- (bromo) - (S) -2-diphenylphosphino-ferrocenyl] ethyldi-cyclohexyl. ^ t (6) cy = cyclohexyl A mixture of 199 milligrams (0.38 millimoles) of compound 4 of Example 4, and 0.093 milliliters of dicyclohexyl phosphine in 2 milliliters of acetic acid, is stirred at 100 ° C (bath temperature) for 2.5 hours. After cooling, 10 milliliters of water are added to the orange solution, and the mixture is extracted repeatedly by stirring with toluene. The organic phases are collected, washed with water, dried over Na 2 SO 4 and concentrated in a rotary evaporator. He The crude orange product is purified by chromatography (silica gel: Merck 60, eluent: hexane / ethyl acetate 4/1). 174 milligrams of compound 6 are obtained (yield of 67 percent, almost orange solid). Analysis: 1H-NMR (CDC13): d 0.9-2 (m, 25H, P (C6H11) 2, C-CH3), 3.25 (m, ÍH, CH-CH3), 3.45-4.4 (m, 7H, C5H3FeC5H4) , 7.1-7.7 (m, 10H, P (C6H5) 2). 31P-NMR (CDC13): < S -27.2 (d, PPh2), 16.0 (d, Pcy2), JPP 35 Hz.

Example A7. Preparation of the compound of the formula 7 a) Phosphine (R) -l- [l, - (l "-dimethylsilyl-3" -chloropro-pyl) - (S) -2- (diphenylphosphino) ferrocenyl] ethyldicyclohexyl.

Cy = cyclohexyl 0.36 grams (1.8 mmol) of dicyclohexyl phosphine in 2 milliliters of acetic acid are added to 1 gram (1.73 mmol) of compound 5 of Example 5 in 4 milliliters of acetic acid, and the mixture is stirred at 95 ° C in a Oil bath for 90 minutes. After cooling, the reddish-brown solution is extracted by stirring in 10 milliliters of toluene and 30 milliliters of an aqueous solution of 5 percent NaCl. The aqueous phase is then extracted by stirring 3 times with 5 milliliters of toluene. Then the organic phases are collected, washed with 15 milliliters of water, dried with Na 2 SO 4, and concentrated in a rotary evaporator under reduced pressure. The crude product is purified by column chromatography (eluent: hexane / diethyl ether). 0.95 grams of compound 7 (chestnut powder, 75 percent yield) are obtained. Characterization: 31P-NMR (CDC13): d -26.5 (d, PPh2), 15.8 (d, Pcy2), JPP 34Hz.

^ -RN (CDC13): d 0.05 (s, 3H, Si-CH3), 0.15 (s, 3H, Si-CH3), 0.6 (m, 2H, CH2-Si), 0.9-2.0 (m, 27H, cy , CH2-CH2C1, CH-CH3), 3.41 (t, 2H, J = 7, CH2-C1), 3.1-4.5 (m, 8H, C5H4FeC5H3CH), 7.1-7.75 (m, 10H, P (C6H5) 2) . b) Phosphine (R) -1- [1 '- (1"-dimethylsilyl-3" -chloropro-phenyl) - (S) -2- (diphenylphosphino) ferrocenyl] ethyldicyclohexyl. 0.2 milliliters (0.32 millimoles) of a 1.6M butyl lithium solution in hexane are added dropwise at -40 ° C to -30 ° C, with stirring, to a solution of 167 milligrams (0.25 millimoles) of compound 6 of the Example 6 in 3 milliliters of diethyl ether. The mixture is then cooled to -78 ° C, and 0.057 milliliters (0.35 mmol) of 3-chloropropyl-dimethylchlorosilane are added slowly. Then the mixture is allowed to rise slowly to room temperature, and then it is stirred for 1 hour additional. Then 5 milliliters of water are added to the resulting orange suspension, and the mixture is extracted repeatedly by stirring with CH2C12. The organic phases are collected, washed with water, dried over Na 2 SO 4 and concentrated in a rotary evaporator. The crude orange product is purified by chromatography (silica gel: Merck 60; eluyenté: hexane / ethyl acetate 4/1). 127 milligrams of compound 7 are obtained (yield of 70 percent, almost solid orange). Characterization: 31P-NMR (CDC13): d -26.5 (d, PPh2), 15.8 (d, Pcy2), JPP 34 Hz. 1 H-NMR (CDC 13): d 0.05 (s, 3 H, Si-CH 3), 0.15 (s, 3 H, Si-CH 3), 0.6 (m, 2 H, CH 2 -Si), 0.9-2.0 (m, 27 H, cy , CH2-CH2-C1, CH-CH3), 3.41 (t, 2H, J = 7, CH2-C1), 3.1-4.5 (m, 8H, C5H4FeC5H3CH), 7.1-7.75 (m, 10H, P (C6H5) 2).

Example A8. Preparation of the compound of the formula 8: The primary amine (8) is prepared by means of Gabriel synthesis (conversion of the chloride into the italic imide, and release of the amine with hydrazine hydrate) from the compound (7) of Example 7: (8) 450 milligrams of potassium italic imide, and 120 milligrams of hexadecyltributyl phosphonium bromide (catalyst) are added to a solution of 1.4 grams (1.94 millimoles) of the compound of formula 7 of Example 7 in 3 milliliters of dimethyl formamide, and the mixture stir at 96 ° C for 1.5 hours. After cooling, the mixture is extracted by stirring in water / toluene, and the organic phase is dried with sodium sulfate and concentrated in a rotary evaporator. After purification by chromatography (eluent: hexane / ethyl acetate), 1.32 grams of an orange powder are obtained (81 percent yield). Characterization: 31P-NMR (CDC13): d -26.5 (d, PPh2), 15.8 (d, Pcy2), JPP 34Hz. - [H-NMR (CDC13): d characteristic signals 3.58 (t, 2H, J = 7, CH2-N), 7.6-7.9 (m, 4H, italic imide). 1.24 grams (1.48 millimoles) of the orange powder, and 0.3 milliliters of hydrazine hydrate in 12 milliliters of ethanol, are heated at reflux for 2 hours. After cooling, 25 milliliters of methylene chloride are added, and the suspension is filtered and washed. The solution is concentrated on a rotary evaporator under reduced pressure, and the product is purified by chromatography (eluent: MeOH with 2 percent triethyl amine). 0.98 grams of an almost solid orange oil of the compound of formula 8 (94 percent yield) are obtained.

Characterization: 31P-NMR (CDC13): -26.5 (d, PPh2), 15.7 (d, Pcy2), JPP 33Hz. 1 H-NMR (CDC13): < S characteristic signals: 2.6 (t, 2H, J = 7, CH2- N).

Example A9. Synthesis of the ligand of formula 9 immobilizable on organic carriers. 0.24 milliliters (0.9 millimoles) of l-triethoxysilyl-3-isocyanatopropane are added dropwise to a solution of 506 milligrams (0.71 millimoles) of the compound of formula 8 of Example 8 in 10 milliliters of methylene chloride, and the mixture it is stirred at room temperature overnight. The solvent is then evaporated on a rotary evaporator under reduced pressure, and the product is purified by chromatography (eluent: ethyl acetate). 530 milligrams of an orange viscous foam of the compound of formula 7c are obtained (yield of 72 percent). Characterization: 31 P-NMR (CDCl 3): d -26.5 (d, PPh 2), 15.7 (d, Pcy 2), JPP 33Hz. X H-NMR (CDCl 3): .5 1.22 (t, 3 = 1, 9 H, 0-CH 2 -CH 3), 2.95 - 3.25 (m, 4 H, CH 2 -NH-C (0) -NH-CH 2), 3.81 ( q, 3 = 1, 6H, 0-CH2).

Example A10. Preparation of the compound of the formula 10 Preparation of phosphine (R) -N, N-dimethyl-l- [l '- (bromo) - (S) -2-diphenylphosphino-ferrocenyl] ethyldiXylyl.

"FTPPh ^ Br CH'C00H ^ Bt (4) (10) 6. 75 grams (13 mmol) of the compound of the formula 4, and 3.2 grams of bis (3,5-xylyl) phosphine (13.2 mmol) in 5 milliliters of toluene are stirred in 80 milliliters of acetic acid at 100 ° C (bath temperature) for 4 hours. After cooling, the reaction mixture is concentrated to dryness in vacuo in a rotary evaporator at 40-50 ° C, and then purified by chromatography (silica gel: Merck 60, eluent: hexane / ethyl acetate 20/1) . 7.7 grams of the product are obtained (82% yield, orange powder). ^ -RN (CDC13): d 1.45 (t, 3H, C-CH3), 2.20 and 2.28 (each 1 s, 12H, Ph-CH3), 3.45-4.3 (m, 7H, C5H3FeC5H4 and ÍH, OI-CH3 ), 6.75-7.7 (m, 16H, P (C6H5) 2 and P (C6H3Me2) .31P-NMR (CDC13): <7.75 (d, Pxililo2), -26.4 (d, PPh2), JPP 22 Hz, Example All. Preparation of the compound of the formula 11 Phosphine (R) -N, N-dimethyl-l- [1 '- (bromo) - (S) -2-diphenylphosphino-ferrocenyl] ethyldiphenyl. (4) 2. 03 grams (3.9 millimoles) of the compound of the formula 4, and 0.8 milliliters of diphenyl phosphine (4.5 millimoles) are stirred in 20 milliliters of acetic acid at 100 ° C (bath temperature) for 4 hours. After cooling, 50 milliliters of water are added to the orange solution, and the mixture is extracted repeatedly by stirring with toluene. The organic phases are collected, washed with water, dried with Na 2 SO, and concentrated in a rotary evaporator. The crude orange product is purified by chromatography (silica gel: Merck 60; eluent: hexane / ethyl acetate, 30/1). 2.1 grams of the product are obtained (81% yield, orange powder). Analysis: : H-NMR (CDC13): d 1.45 (t, 3H, C-CH3), 3.5-4.3 (m, 7H, C5H3FeCsH4 and ÍH, CH-CH3), 7.1-7.8 (m, 20H, P (C6H5) 2 ). P-NMR (CDCl 3): d 7.12 (d, CH (Me) -PPh2, -27.18 (d, PPh2), JPP 25 Hz.

Example A12. Preparation of the compound of the formula 12 Phosphine (R) -1- [1 '- (1"-dimethylsilyl-3" -chloropropyl) - (S) -2- (diphenylphosphino) ferrocenyl] ethyldi-3, 5-xylyl starting at from the compound of the formula (10) of Example 10. (10) (12) 2.5 millimoles of a 1.6M BuLi solution in hexane are added dropwise from -40 ° C to -30 ° C, with stirring, to a solution of 1 gram (1.9 millimoles) of the compound of the formula (10) in 18 milliliter of diethyl ether. The mixture is then cooled to -78 ° C, and 460 milligrams (2.69 mmol) of 3-chloropropyl-dimethylchlorosilane are added slowly. Then the mixture is allowed to rise slowly to room temperature, and then it is stirred for an additional 1 hour. Then 20 milliliters of water are added, and the reaction mixture is extracted repeatedly by stirring with CH2C12. The organic phases are collected, washed with water, dried with Na2SO4, and concentrated in a rotary evaporator. The crude orange product is purified by chromatography (silica gel: Merck 60, eluent: hexane / diethyl ether 30/1). 1.1 grams of the compound of the formula (10) are obtained (yield of 75 percent, orange powder). Characterization: 31P-NMR (CDC13): 5 -26.5 (d, PPh2), 6.7 (d, Pxililo2), JPP 21Hz. 1 H-NMR (CDC 13): d 0.04 (s, 3 H, Si-CH 3), 0.14 (s, 3 H, Si-CH 3), 0.6 (, 2 H, CH 2 -Si), 1.43 (d, 3 H, CH-CH 3) , 1.5-1.7 (m, 2H, CH2-CH2-Cl), 2.20 and 2.30 (two s, each 6H, C6H3 (CH3) 2, 3.41 (t, 2H, 3 = 1, CH2-C1), 3.2 - 4.5 (m, 8H, C5H4FeC5H3CH), 6.7-7.8 (m, 16H, P (C6H5) 2 and P (C6H3Me2) 2).

Example A13. Preparation of the compound of the formula 13 The primary amine of the formula 13 is prepared by means of Gabriel synthesis (conversion of the chloride into the italic imide, and release of the amine with hydrazine hydrate): (13) 464 milligrams of potassium imide is added (2.5 millimoles), and 125 milligrams of hexadecyltributyl phosphonium bromide (catalyst) to a solution of 1.53 grams (2 millimoles) of the compound of formula 12 in 4 milliliters of dimethyl formamide, and the mixture is stirred at 100 ° C (bath temperature) for 2 hours. After cooling, the mixture is extracted by stirring in water / toluene, and the organic phase is dried with sodium sulfate and concentrated in a rotary evaporator. After purification by chromatography (silica gel: Merck 60, eluent: hexane / ethyl acetate 9/1). 1.58 grams of italic imide are obtained in the form of an orange powder (90 percent yield). Characterization: 31P-NMR (CDC13): d -25.3 (d, PPh2), 7.0 (d, PxÍÜl? 2), JPP 21 Hz. ^ -RN (CDC13): d 0.04 (s, 3H, Si-CH3), 0.1 (s, 3H, Si-CH3), 0.5 (m, 2H, CH2-Si), 1.44 (m, 3H, CH-CH3 ), 1.4 - 1.7 (m, 2H, CH2-CH2-N), 2.20 and 2.27 (two s, each 6H, C6H3 (CH3) 2), 3.58 (t, 2H, 3 = 1, CH2-N), 3.2 - 4.4 (m, 8H, C5H4FeC5H3CH), 6.7-7.8 (m, 16H, P (C6H5) 2), P (C6H3 (Me) 2), 7.6-7.9 (m, 4H, italic imide). 1. 58 grams (1.78 millimoles) of the phthalic imide obtained in the first step, and 0.5 milliliters of hydrazine hydrate in 20 milliliters of ethanol, are boiled under reflux for 2 hours. After cooling, 50 milliliters of toluene are added, and the suspension is filtered and washed with 2 x 10 milliliters of water. The solution is dried with sodium sulfate, and concentrated on a rotary evaporator under reduced pressure; the product is again converted into a suspension with 20 milliliters of diethyl ether, and filtered. After concentration in a rotary evaporator, 1.34 grams of an orange foam (99 percent yield) are obtained. Characterization: 31P-NMR (CDC13): d -25.2 (d, PPh2), 6.7 (d, Plyxyl2), JPP 22 Hz. 1 H-NMR (CDC 13): d 0.03 (s, 3 H, Si-CH 3), 0.11 (s, 3 H, Si-CH 3), 0.48 (m, 2 H, CH 2 -Si), 1.15 - 1.45 (m, 2 H, CH 2 -CH2-N), 1.45 (m, 3H, CH-CH3), 2.20 and 2.27 (two s, each 6H, C6H3 (CH3) 2), 2.58 (t, 2H, J = 7, CH2-N), 3.2 - 4.45 (m, 8H, C5H4FeC5H3CH), 6.7-7.75 (m, 16H, P (C6H5) 2), P (C6H3 (Me) 2).

Example A14. Preparation of the compound of the formula 14 Synthesis of the ligand of the formula (14) immobilizable on inorganic carriers. (14) 0.7 milliliters (2.6 millimoles) of l-triethoxysilyl-3-isocyanatopropane are added dropwise to a solution of 1.5 grams (1.99 millimoles) of the compound of the formula (13) in 10 milliliters. of methylene chloride, and the mixture is stirred overnight at room temperature. The solvent is then evaporated on a rotary evaporator under reduced pressure, and the crude product is purified by chromatography (silica gel: Merck 60; eluent: hexane / ethyl acetate), 1.47 grams of an orange viscous foam are obtained ( 74 percent). Characterization: 31P-NMR (CDC13): < S 25.2 (d, PPh2), 6.7 (d, Pxililo2), JPP 21Hz. 1H-NMR (CDC13) characteristic signals: < S 0.03 (s, 3H, Si-CH3), 0.11 (s, 3H, Si-CH3), 0.48 (m, 2H, CH2-Si-cp), 0.61 (m, 2H, CH2-YES (OEt) 3) , 1.2-1.8 (m, 4H, CH2-CH2NHCONHCH2CH2), 1.22 (t, 3 = 1, 9H, 0-CH2-CH3), 1.47 (m, 3H, CH-CH3), 2.20 and 2.28 (two s, each 6H, C6H3 (CH3) 2), 2.95 - 3.25 (m, 4H, CH2-NHCONH-CH2), 3.83 (q, 3 = 1, 6H, 0-CH2), 6.7 - 7.8 (m, 16H, P (C6H5 ) 2), P (C6H3 (Me) 2). Mass spectrum: 1001 (M + H +).

Example B. Ligands immobilized on silica gel or polystyrene Examples B1-B3. Ligands immobilized on silica gel. Immobilization: before use, the carrier is dried at 130 ° C for 3 hours under a high vacuum, and then placed under argon. Then an immobilizable ligand solution of the formula 9 of Example A9, or of the formula 14 of Example A14, is added and the mixture is stirred at 85-90 ° C for 20 hours.

After cooling and settling, the supernatant solution is removed using a syringe. The mixture is then washed six times with MeOH (7 milliliters per gram of carrier each time), and finally dried at 40-50 ° C under a high vacuum. The results are given in Table 1.

TABLE 1 The carrier used is supplied by W. R. Grace Company: Grace 332; Specific surface area = 320 square meters / gram, particle size = 35-70 microns.

Example B4. Ligands immobilized on polystyrene In a container that has a stirrer and a glass frit, 900 milligrams of polymer (aminomethylated polystyrene, crosslinked with 1 percent divinyl benzene, amine content = 0.56 millimoles / gram, supplied by Novabiochem, Ol64-0010 ), which has been dried under a high vacuum at 50 ° C, is stirred in 32 milliliters of methylene chloride until the carrier has swollen. Then 1.2 milliliters (8.3 millimoles) of 2,4-toluylene diisocyanate (TDI) are added rapidly, and the mixture is stirred for an additional 1 hour. The excess 2,4-toluylene diisocyanate is then removed by filtering the solution and washing five times with 30 milliliters of methylene chloride. The carrier which has reacted with the 2,4-toluylene diisocyanate is then stirred in 30 milliliters of methylene chloride, and a solution of 100 milligrams (0.133 mmol) of the compound of the formula (13) is added dropwise thereto. of Example A13 in 2 milliliters of methylene chloride. The mixture is stirred overnight. In order to convert the residual isocyanate groups to carbamates, 10 milliliters of ethyl alcohol containing 30 microliters of triethyl amine is added as catalyst, and the mixture is stirred overnight at 40 ° C. Then the yellowish orange carrier is filtered and washed five times using 20 milliliters of methylene chloride each time. Finally the carrier dries under a high vacuum. Analysis: content of P = 0.62 percent. This corresponds to a loading of 0.1 millimole of ligand per gram of carrier.

Example Cl. Hydrogenations General: all operations are carried out under inert gas. The 50 milliliter steel autoclave is equipped with a magnetic stirrer (1,500 revolutions per minute), and a flow switch. Before each hydrogenation, the inert gas in the autoclave is displaced by hydrogen in 4 cycles (10 bar, normal pressure). Then the desired hydrogen pressure is established in the autoclave, and hydrogenation is started by igniting the agitator. The conversion is determined by gas chromatography, and the optical yield is determined by means of high performance liquid chromatography (column: Chiracel OD), using for this purpose a sample that has been purified by evaporation chromatography (gel silica: Merck 60, eluent = hexane / ethyl acetate).

Example Cl A solution of 4.06 milligrams of [Rh- (COD) 2] BF4 in 3.3 milliliters of methanol is added to 122 milligrams of the ligand of Example Bl (Ligand 9), and the mixture is stirred slowly, the yellow solution being completely discolored. Then 554 milligrams of substrate (amine N- (2 ', 6 • -dimethylphenyl-1 * -yl) -N- (methoxyacetyl) -l-methoxycarbonyl-ethenyl) dissolved in 5 milliliters of methanol are added, and the mixture is heated at 40 ° C in an oil bath, and hydrogenated at that temperature. After 1 hour, the reaction is discontinued, and the hydrogen in the hydrogenation flask is replaced by inert gas. The catalyst is allowed to settle, and the supernatant solution is removed using a syringe. The conversion is complete, and the optical performance is 82.2 percent (R).

Example C2 A solution of 3.5 milligrams of [Ir- (C0D) C1] 2 (0.0104 millimoles of Ir) in 2 milliliters of tetrahydrofuran, all at once, is added to 250 milligrams (0.013 millimoles) of the ligand of Example B3 fixed in silica gel, and the mixture is stirred slowly, the yellow solution becoming completely discolored. The catalyst is then allowed to settle, and the supernatant of tetrahydrofuran is removed using a syringe, and the catalyst is dried under a high vacuum. 10 milligrams of tetrabutyl ammonium iodide, and finally 4.25 grams (20.8 millimoles) of imine are added to a second flask, the solution is placed under inert gas, and added to the catalyst. Then the reaction mixture is introduced under pressure into a steel autoclave of 50 milliliters, using a steel capillary against a stream of inert gas, and then hydrogenated at 25 ° C at a hydrogen pressure of 80 bar. After 2 hours, the hydrogen is depressurized, and the catalyst is filtered under argon. The conversion is complete, and the optical performance is 77.5 percent (S). Reuse: 4.25 grams (20.8 millimoles) of imine and 10 milligrams of tetrabutyl ammonium iodide are added, all at the same time, to the separated catalyst. Then the reaction mixture is introduced under pressure into a 50 milliliter steel autoclave using a steel capillary against a stream of inert gas, and then hydrogenated at 25 ° C at a hydrogen pressure of 80 bar. After 2 hours, the hydrogen is depressurized, and the catalyst is filtered under argon. The conversion is complete and the optical performance is 77.8 percent (S).

Example C3 60 milligrams (0.006 millimoles) of Xiliphos bonded with polymer of Example B4 are added, all at once, and stirred in 2 milliliters of tetrahydrofuran for 5 minutes. Then a solution of 1.7 milligrams of [Ir (COD) Cl] 2 (0.005 millimole of Ir) in 2 milliliters of tetrahydrofuran is added, and the mixture is stirred slowly, the yellow solution becoming discolored. 5 milligrams of tetrabutyl ammonium iodide and 2.1 grams (10.2 millimoles) of imine N- (2'-methyl-e'-ethylphen-l'-il) -N- are added. (1-methoxymethyl) -ethyl to a second flask, the solution is placed under an inert gas, and added to the catalyst. Then the reaction mixture is introduced under pressure in a 50 milliliter steel autoclave, using a steel capillary against a stream of inert gas, and then hydrogenated at 25 ° C at a hydrogen pressure of 80 bar. After 16 hours the hydrogenation is discontinued, the hydrogen is depressurized, and the catalyst is filtered. The conversion is 68 percent after that time, and the optical performance is 71.1 percent (S).

Claims (30)

1. NOVELTY OF THE INVENTION

   Having described the above invention, it is considered as a novelty, and therefore, the content of the following is claimed as property:

   A compound of the formula I:

   where: R? is alkyl of 1 to 8 carbon atoms, phenyl or phenyl substituted by 1 to 3 alkyl substituents of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; R2 and R3 are each independently of the other, hydrogen or alkyl of 1 to 12 carbon atoms; and Hal is F, Cl, Br, or I.
2. 2. A compound of the formula I according to claim 1, wherein R? as alkyl is linear.
3. 3. A compound of formula I in accordance with

   Claim 2, wherein R-j ^ is methyl or ethyl.
4. 4. A compound of the formula I according to claim 1, wherein R? is phenyl, or phenyl substituted by 1 or 2 alkyl substituents of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.
5. 5. A compound of the formula I according to claim 1, wherein R2 and R3 are each independently of the other, hydrogen, methyl, or ethyl.
6. 6. A compound of the formula I according to claim 1, wherein R2 and R3 are both hydrogen or methyl.
7. 7. A compound of the formula I according to claim 1, wherein Hal is Cl, Br, or I.
8. 8. A process for the preparation of a compound of the formula I according to claim 1, wherein a composed of formula II:

   wherein: R-_, R2, and R3 are as defined in the claim

   1, is reacted in an organic solvent first with an alkyl lim equivalent, and then, in the presence of an amine complexing agent for Li, with a second

   equivalent of alkyl lim, and then the product is reacted with a halogenating agent.
9. 9. A process for the preparation of a compound of the formula I according to claim 1, wherein the halogenating agent is selected from the group consisting of Cl 2, hexachloroethane, 1,2-dichlorotetrafluoroethane, toluene-4-chloride sulfonyl, Br2, 1,2-dibromotetrachloroethane, 1,2-dibromotetrafluoroethane, toluene-4-sulfonyl bromide, 2,3-dimethyl-2,3-dibromobutane, I2, 1,2-diiodotetrafluoroethane, perfluoropropyl iodide, iodide perfluoroethyl, toluene-4-sulfonyl iodide, and perfluoromethyl iodide.
10. 10. A compound of formula III:

    wherein: Rlf R, R3, and Hal are as defined in claim 1; R10 and R11 are identical or different, and are alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, cycloalkyl of 5 to 12 carbon atoms substituted by alkyl of 1 to 4 carbon atoms or alkoxy

    the 4 carbon atoms, or phenyl substituted by 1 to 3 alkyl substituents of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, -SiR4R5R6, halogen, -S03M, -C02M, -P03M, -NR7R8 , - [* NR7RßR9] X "or fluoroalkyl of 1 to 5 carbon atoms, or the group PR10Rn is a radical of formula IV, IVa, IVb, or IVc:

    4 / s / Y Rß are each independently of the others, alkyl of 1 to 12 carbon atoms or phenyl; R7 and R8 are H, alkyl of 1 to 12 carbon atoms, or phenyl, or R7 and R8 are together tetramethylene, pentamethylene, or 3-oxa-1,5-pentylene; R9 is H or alkyl of 1 to 4 carbon atoms; M is H or an alkali metal; X "is the anion of a monobasic acid
11. 11. A compound of the formula III according to claim 10, wherein R10 and RX1 as alkyl are alkyl of 1 to 8 carbon atoms
12. 12. A compound of the formula III according to the

    claim 10, wherein R 10 and R as cycloalkyl contain from 5 to 8 carbon atoms.
13. 13. A compound of the formula III according to claim 10, wherein R10 and R1: L are unsubstituted phenyl, or phenyl substituted by 1 or 2 substituents.
14. 14. A compound of the formula III according to claim 10, R10 and Rn as substituted phenyl are 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4-ethyl-, 2- or 4-isopropyl-, 2- or 4-tertiary 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-S03H-, 2- or 4-S03Na-, 2- or 4 - [+ NH3Cl "] -, 3, 4, 5- trimethylphen-1-yl, 2,4,6-trimethylphen-1-yl, 4-trifluoromethyl-phenyl or 3,5-di (trifluoromethyl) phenyl
15. 15. A compound of the formula III according to claim 10 , wherein R10 and R are cyclohexyl, tertiary butyl, phenyl, 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-methoxyphenyl-1-yl
16. 16. A process for the preparation of a compound of the formula III in accordance with Claim 10, wherein in a first step, lithium alkyl is added of a compound of the formula I according to claim 1, in a solvent

    inert organic, and allowed to react, and then an organic solution of a compound of the formula V, CIP (R10R11) (V) is added, and further reacted, with R10 and Rn as defined in claim 10.
17. 17 A process according to claim 16, wherein alkyl lithium is added at a temperature of -90 ° C to + 20 ° C.
18. 18. A process according to claim 16, wherein the compound of the formula V is added at a temperature of -90 ° C to + 20 ° C.
19. 19. A compound of formula VI:

    wherein: Ri 'R10' R? i 'v Ha ^ are as defined in claim 1, and R12 and R13 are each independently of the other, alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms carbon, phenyl, cycloalkyl of 5 to 12 carbon atoms substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, or phenyl mono- or poly-substituted by 1 to 3 alkyl substituents of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, -SiR4R5R6, halogen, -

    S03M, -C02M, -P03M, -NR7R8, - [+ NR7R8R9] X ~ or fluoroalkyl of 1 to 5 carbon atoms; or the group - i2R? 3 is a radical of formula IV, IVa, IVb, or IVc:
20. 20. A compound of formula VI according to claim 19, wherein R12 and R13 are alkyl of 1 to 8 carbon atoms.
21. 21. A compound of the formula VI according to claim 19, wherein R12 and R13 are identical, and are isopropyl or tertiary butyl.
22. 22. A compound of the formula VI according to claim 19, wherein R12 and R13 as cycloalkyl contain from 5 to 8 carbon atoms.
23. 23. A compound of the formula VI according to claim 19, wherein R12 and R13 are unsubstituted phenyl, or phenyl substituted by 1 or 2 substituents.
24. 24. A compound of formula VI according to claim 19, R12 and R13 as substituted phenyl are 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4-ethyl-, 2- or 4- isopropyl-, 2- or 4-
25. tertiary 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-S03H-, 2- or 4-S03Na-, 2- or 4 - [+ NH3Cl "] -, 3, 4, 5-trimethylphen-1-yl, 2,4,6-trimethylphen-1-yl, 4-trifluoromethyl-phenyl or 3,5-di (trifluoromethyl) useful) A compound of the formula VI according to claim 19, wherein R12 and R13 are identical and are phenyl, cyclohexyl, 2- or 4-methylphen-1-yl, 2- or 4-methoxyphen- l -yl, 2- or 4- (dimethylamino) phen-1-yl, 3,5-dimethyl-4- (dimethylamino) phen-1-yl, or 3,5-dimethyl-4-methoxyphen-1-yl.
26. 26. A compound of the formula VI according to claim 19, wherein R12 and R13 are identical radicals, and are cyclohexyl or phenyl
27. 27. A compound of the formula I according to claim 19, wherein R x is methyl and R 12 and R 13 are each cyclohexyl or phenyl, and R 10 and R are phenyl, cyclohexyl, or tertiary butyl.
28. 28. A process for the preparation of a compound of the formula VI, wherein a compound of the formula III according to claim 10, is reacted with a compound of the formula HP (R12R13) in acetic acid, where R12 and R13 as defined in claim 19.
29. 29. The use of a compound of formula III or VI as a ligand for rhodium or iridium in the catalytic hydrogenation of carbon / carbon or carbon / heteroatom double bonds.
30. 30. The use of a compound of formula VI, in the preparation of inorganically or polymerically bound ligands for rhodium or iridium, in the catalytic hydrogenation of carbon / carbon or carbon / heteroatom double bonds.

    SUMMARY OF THE INVENTION

    The invention relates to a compound of the formula I:

    where: ? is alkyl of 1 to 8 carbon atoms, phenyl or phenyl substituted by 1 to 3 alkyl substituents of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; R2 and R3 are each independently of the other, hydrogen or alkyl of 1 to 12 carbon atoms; and Hal is F, Cl, Br, or I. The compounds of the formula I have valuable intermediates for the compounds of the formula III, which are also an object of this invention:

    (lll),

    wherein: R R2 R3 and Ha ^ are or were previously defined; Rio and Ru are identical or different, and are alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, cycloalkyl of 5 to 12 carbon atoms substituted by alkyl of 1 to 4 carbon atoms or C 1-4 alkoxy, or phenyl substituted by 1 to 3 alkyl substituents of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, -SiR «R5R6, halogen, -S03M, -C02M, -P03M, -NR7R8, - [* NR7R8R9] X "or fluoroalkyl of 1 to 5 carbon atoms, or the group PR ^ R ^ is a radical of formula IV, IVa, IVb, or IVe:

    R / Rs "and R" are each independently of the others, alkyl of 1 to 12 carbon atoms or phenyl; R7 and R8 are H, alkyl of 1 to 12 carbon atoms, or phenyl, or R7 and R8 are together tetra ethylene, pentamethylene, or 3-oxa-1,5-pentylene; R9 is H or alkyl of 1 to 4 carbon atoms;

    M is H or an alkali metal; X "is the anion of a monobasic acid.

    The compounds of formula III are themselves important intermediates for ferrocenyl silylated diphosphines and their metal complexes. Ferrocellic diphosphines containing an organic radical linked by means of a silylene group with a cyclopentadienyl ring can be immobilized in a simple manner, either on inorganic carriers or polymeric organics, or, after the introduction of a polymerizable group, can be immobilize also by copolymerization. With rhodium and iridium, immobilized ferroceilic diphosphine ligands form complexes that can be used as highly active catalysts in the enantioselective hydrogenation of carbon-carbon, carbon-nitrogen, or carbon-oxygen double bonds.

    * * * * *