DE102005061642A1 - New phosphorous chelate compounds are useful as catalysts for asymmetrical synthesis (preferably as chiral components for the production of pharmaceuticals, plant protecting agents, cosmetics or flavor materials) - Google Patents

Abstract

Phosphorous chelate compounds (I) are new. Phosphorous chelate compounds (I) of formula (R1>-P(R2>)-(X)a-Y1>-(O)b-P-((O)c-Rgamma )-(O)d-Rdelta ) are new. either R1>, R2>5-7 membered heterocyclic groups that are bonded over N atom to P atom; or PR1>R2>5-7 membered heterocycle additionally contains optionally substituted N atom and a further under oxygen and optionally substituted N atoms that are bonded directly to P atom; either Rgamma , Rdelta : akyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl (all substituted with 1-5 of cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, thiol, polyalkylenoxide, polyalkylenimine, COOH, carboxylate, SO3H, sulfonate, NE1>E2>, NE1>E2>E3>X-, halo, NO2, acyl or CN); or PRgamma Rdelta , ORgamma Rdelta : 5-8 membered heterocycle optionally annealed with 1-3 of cycloalkyl, heterocycloalkyl, aryl or hetaryl, where the heterocycle and optionally the annealed groups are substituted with 1-4 of alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkyleneoxide, polyalkylenimine, alkoxy, halo, COOH, carboxylate, SO3H, sulfonate, NE4>E5>, NE4>E5>E6>+>X->, NO2, alkoxycarbonyl, acyl or CN; E4>, E5>, E6>H, alkyl, cycloalkyl or aryl; X : O, S, SiReRf or NRg; Re, Rf, Rg : H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; X->anion; Y1>bivalent carbon containing bridge atoms; and a-d : 0-1 (where at least one of b, c or d is 1). Independent claims are also included for: (1) catalyst comprising at least one complex with a transition metal, as ligands of (I); (2) preparation of chiral compounds comprising reacting prochiral compounds containing at least ethylenic unsaturated double bond, with a substrate in the presence of a chiral catalyst; (3) a method for hydroformylation of compounds containing at least ethylenic unsaturated double bond comprising reacting with carbon monoxide and hydrogen in the presence of hydroformylating catalyst; (4) preparation of 2-propylheptanol comprising subjecting butene or butene containing C4-hydrocarbon mixture of hydroformylation to obtain n-valeraldehyde containing hydroformylating products, optionally isolating hydroformylating products under n-valeraldehyde enriched groups, subjecting the obtained hydroformylating products and n-valeraldehyde enriched groups to aldol condensation, hydrogenating the products of aldol condensation, catalytically with hydrogen to alcohols and optionally subjecting the hydrogenation products to isolate 2-propylheptanol enriched groups; and (5) a method of hydroformylation of alpha -olefine and olefine with inner double bonds containing a composition, comprising reacting with carbon monoxide and hydrogen in the presence of hydroformylating catalyst in two-stage reaction system (where the first step comprises feeding an inlet containing olefin, carbon monoxide and hydrogen and converting partly catalytically; feeding and converting the discharge from the above step; and feeding the discharge from the second step with a stream obtained from non-reacted olefine and saturated hydrocarbons).

Description

The The present invention relates to phosphorus chelate compounds, catalysts, containing such a compound as ligands and synthesis methods, in which such a catalyst is used.

homogeneous Catalysts based on transition metal complexes have found widespread use in the field of chemical synthesis. This is especially true for the hydroformylation or oxo synthesis that has been going on since their discovery by Otto Roelen in 1938 to the prime example of application homogeneous catalysis using organometallic catalysts on an industrial scale has developed. In addition to the classic method of industrial organic chemistry also increasingly has homogeneous catalyzed asymmetric Syntheses that provide access to chiral building blocks for the production of pharmaceuticals, pesticides, cosmetics and flavorings serve, dissemination found. There is thus a constant need on new homogeneous catalysts in general and specifically for asymmetric synthesis processes, in high optical purity and in high chemical yield to the desired isomer to lead.

A important class of reactions is the addition to carbon-carbon and at carbon-heteroatom multiple bonds. Here is the Addition to the two adjacent atoms of a C = X double bond (X = C, heteroatom) also referred to as 1,2-addition. Additionally, addition reactions can occur be characterized by the nature of the attached groups, where with hydro addition, the addition of a hydrogen atom and with Carbo-addition the attachment of a carbonaceous fragment referred to as. Thus, a 1-hydro-2-carbo-addition denotes a Addition of hydrogen and a carbon atom-containing group. Important representatives of this reaction are z. The hydroformylation, Hydrocyanation and carbonylation. Another very significant Addition to carbon-carbon and carbon-heteroatom multiple bonds is the hydrogenation. There is a need for asymmetric catalysts Addition reactions to prochiral ethylenically unsaturated compounds with good catalytic activity and high stereoselectivity.

While today asymmetric hydroformylation serves as an important method for the synthesis of chiral aldehydes and alcohols and thus as access to chiral building blocks for the production of pharmaceuticals, etc., several million tons of aldehydes and alcohols are produced worldwide on the basis of non-stereoselective homogeneously catalyzed hydroformylation processes. As catalysts, mainly cobalt or Rhodiumcarbonylverbindungen be used to influence the activity and / or selectivity with other ligands, eg. B. triphenylphosphine, may be modified. For the preparation of C ₃ -C ₅ aldehydes from linear olefins with terminal double bond ("α-olefins"), the use of modified rhodium carbonyl compounds is now the preferred method, whereas for the production of longer-chain aldehydes and / or alcohols still cobalt carbonyl catalyzed Hydroformylation, despite the fact that it has the disadvantage that it has to be worked at higher pressures, because of the different behavior of the catalyst metals Depending on the location of the CO addition to the double bond, linear aldehydes (n-aldehydes) or branched aldehydes (iso-aldehydes) may form in the hydroformylation of terminal olefins If high n-portion of the aldehydes in the reaction product is desired. While the rhodium triphenylphosphine catalyst system leads to high n-selectivities in the formation of short-chain aldehydes, this is not the case for the hydroformylation of longer-chain olefins. Thus, the rhodium catalyst under the conditions of the hydroformylation reaction causes a significant isomerization of terminal double bonds to internal double bonds and also has the disadvantage of a lack of hydroformylation activity with respect to these internal double bonds. The hydroformylation of longer chain olefins is of great economic importance in the production of plasticizer alcohols and surfactant alcohols. There is thus a great need for new ligands for catalysts which are suitable for the hydroformylation of mixtures of internal and terminal olefins (for example 1-butene and 2-butene in raffinate II) and which have a high activity and a high activity even in the low-pressure range achieve n selectivity.

Suitable rhodium catalyst systems suitable for isomerizing hydroformylation are described in US Pat US 3,527,809 Rhodium complexes with organophosphite ligands and in the US 4,668,651 Rhodium complexes with organochelate phosphite ligands described.

The WO 00/56451 describes hydroformylation catalysts based on Phosphinamiditliganden, wherein the phosphorus atom together with an oxygen atom to which it is attached, for a 5- to 8-membered one Heterocycle stands.

The WO 02/083695 describes pnicogen chelate compounds in which each of the pnicogen atoms has at least one pyrrole group over the pyrrolic nitrogen atom is bound. These pnicogen chelate compounds are suitable as ligands for Hydroformylation.

The WO 03/018192 describes u. a. Pyrrolphosphorverbindungen in which at least one substituted and / or fused ring system integrated pyrrole group over their pyrrolic nitrogen is covalently linked to the phosphorus atom, when used as ligands in hydroformylation catalysts by a very good stability distinguished.

The DE-A-103 42 760 describes pnicogen compounds which have two pnicogen atoms have pyrrole groups on both Pnicogenatome a pyrrolic nitrogen atom and both pnicogen atoms via a Methylene group to a bridging Group are tied. These pnicogen compounds are suitable as Ligands for Hydroformylation.

chiral Catalysts are not described in the aforementioned documents.

It It is known that the use of chelating ligands, the two for coordination enabled Groups have advantageous on the achieved stereoselectivity in asymmetric Hydroformylation reactions. For example, describe M.M. Lambers-Verstappen and J. de Vries in Adv. Synth. Catal. 2003 345, No. 4, p. 478-482, the rhodium-catalyzed hydroformylation of unsaturated Nitriles, with a satisfactory only with asymmetric BINAPHOS ligands asymmetric hydroformylation was possible.

The EP-A-0 503 884 describes an optically active in the 2-position substituted 2'-diphenylphosphine-1,1'-binaphthyl compound, Catalysts based on transition metal complexes, which have such a compound as ligands and a method for enantioselective silylation using such a catalyst.

The EP-A-0 614 870 describes a process for preparing optically active aldehydes by hydroformylation of prochiral 1-olefins in Presence of a rhodium complex as a hydroformylation catalyst, the has an asymmetric phosphorus-containing ligand with a 1,1'-binaphthylene backbone. EP-A-0 614 901, EP-A-0 614 902, EP-A-0 614 903, EP-A-0 684 249 and DE-A-198 53 748 describe unsymmetrical phosphorus atom-containing Ligands of comparable structure.

The WO 93/03839 (EP-B-0 600 020) describes an optically active metal-ligand complex catalyst, comprising an optically active pnicogen compound as ligand and Process for asymmetric synthesis in the presence of such Catalyst.

The unreleased German patent application P 103 55 066.6 relates to a method for asymmetric synthesis in the presence of a chiral catalyst, comprising at least one complex of a metal of the VIII. Subgroup with over for dimerization noncovalent bonds enabled Ligands, such catalysts and their use.

The unreleased German Patent Application P 10 2004 052040.2 describes chiral phosphorochelate compounds, in which a phosphine group and a phosphoramidite group to a bridging group are bound. Catalysts based on these ligands are suitable for asymmetrical Syntheses, in particular asymmetric hydroformylation.

Of the The present invention is based on the object, new ligands for homogeneous catalysts for disposal to deliver. These should preferably be longer-chain for the hydroformylation, terminated or internal olefins or technical mixtures of olefins with terminal and internal double bond, e.g. As 1-butene / 2-butene mixtures, too Aldehyde products with high linearity with good sales and possible low pressure. Preferably, these ligands should continue to for the preparation of high stereoselectivity and high chiral compounds Reactivity suitable.

gefunden, worin
R^α und R^β unabhängig voneinander für 5- bis 7-gliedrige heterocyclische Gruppen stehen, die über ein Ringstickstoffatom an das Phosphoratom gebunden sind oder R^α und R^β gemeinsam mit dem Phosphoratom, an das sie gebunden sind, für einen 5- bis 7-gliedrigen Heterocyclus stehen, der zusätzlich ein gegebenenfalls substituiertes Stickstoffatom und ein weiteres unter Sauerstoff und gegebenenfalls substituiertem Stickstoff ausgewähltes Heteroatom aufweist, die beide direkt an das Phosphoratom gebunden sind,
R^γ und R^δ unabhängig voneinander für Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, wobei die Alkylreste 1, 2, 3, 4 oder 5 Substituenten, ausgewählt unter Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, Alkoxy, Cycloalkoxy, Heterocycloalkoxy, Aryloxy, Hetaryloxy, Hydroxy, Thiol, Polyalkylenoxid, Polyalkylenimin, COOH, Carboxylat, SO₃H, Sulfonat, NE¹E², NE¹E²E³X^–, Halogen, Nitro, Acyl oder Cyano aufweisen können, worin E¹, E² und E³ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl, oder Aryl bedeuten und X^– für ein Anionäquivalent steht,
und wobei die Cycloalkyl-, Heterocycloalkyl-, Aryl- und Hetarylreste R^γ und R^δ 1, 2, 3, 4 oder 5 Substituenten aufweisen können, die ausgewählt sind unter Alkyl und den zuvor für die Alkylreste R^γ und R^δ genannten Substituenten, oder
R^γ und R^δ zusammen mit dem Phosphoratom und, falls vorhanden, den Sauerstoffatomen, an die sie gebunden sind, für einen 5- bis 8-gliedrigen Heterocyclus stehen, der gegebenenfalls zusätzlich ein-, zwei- oder dreifach mit Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl anelliert ist, wobei der Heterocyclus und, falls vorhanden, die anellierten Gruppen unabhängig voneinander je einen, zwei, drei oder vier Substituenten tragen können, die ausgewählt sind unter Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, Hydroxy, Thiol, Polyalkylenoxid, Polyalkylenimin, Alkoxy, Halogen, COOH, Carboxylat, SO₃H, Sulfonat, NE⁴E⁵, NE⁴E⁵E⁶⁺X^–, Nitro, Alkoxycarbonyl, Acyl oder Cyano stehen, worin E⁴, E⁵ und E⁶ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten und X^– für ein Anionäquivalent steht,
X für O, S, SiR^εR^ξ oder NR^η steht, worin R^ε, R^ξ und R^η unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
Y für eine zweiwertige verbrückende kohlenstoffatomhaltige Brücke steht, und
a, b, c und d unabhängig voneinander die Zahl 0 oder 1 bedeuten, wobei wenigstens eine der Variablen b, c oder d für 1 steht.Accordingly, phosphorus chelate compounds of general formula I

found in which
R ^α and R ^β independently represent 5- to 7-membered heterocyclic groups which are bonded via a ring nitrogen atom to the phosphorus atom or R ^α and R ^β together with the phosphorus atom to which they are bonded, for a 5- to 7 a heterocyclic compound which additionally has an optionally substituted nitrogen atom and another heteroatom selected from oxygen and optionally substituted nitrogen, both of which are bonded directly to the phosphorus atom,
R ^γ and R ^δ independently of one another are alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, where the alkyl radicals have 1, 2, 3, 4 or 5 substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy , Hetaryloxy, hydroxy, thiol, polyalkyleneoxide, polyalkylenimine, COOH, carboxylate, SO ₃ H, sulphonate, NE ¹ E ² , NE ¹ E ² E ³ X ^- , halogen, nitro, acyl or cyano, wherein E ¹ , E ² and E ^{3 are} each the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl and X ^{- is} an anion equivalent,
and where the cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals R ^γ and R ^{δ may have} 1, 2, 3, 4 or 5 substituents which are selected from alkyl and the substituents previously mentioned for the alkyl radicals R ^γ and R ^δ , or
R ^γ and R ^δ together with the phosphorus atom and, if present, the oxygen atoms to which they are attached, represent a 5- to 8-membered heterocycle, which may additionally be mono-, di- or trisubstituted by cycloalkyl, heterocycloalkyl, aryl or hetaryl fused, wherein the heterocycle and, if present, the fused groups independently of one another each carry one, two, three or four substituents which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, Polyalkyleneimine, alkoxy, halo, COOH, carboxylate, SO ₃ H, sulfonate, NE ⁴ E ⁵ , NE ⁴ E ⁵ E ^{6 +} X ^- , nitro, alkoxycarbonyl, acyl or cyano wherein E ⁴ , E ⁵ and E ^{6 are} each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl and X ^{- represents} an anion equivalent,
X ^ξ is O, S, SiR ^ε R or NR ^η, where R ^ε, R ^ξ and ^η R is independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
Y represents a divalent bridging carbon atom-containing bridge, and
a, b, c and d independently represent the number 0 or 1, wherein at least one of the variables b, c or d is 1.

"Chiral connections" are part of the present invention compounds with at least one center of chirality (i.e., at least one asymmetric atom, especially at least an asymmetric C atom or P atom), with chirality axis, chirality or screw thread.

Of the Term "chiral Catalyst "is within the scope of the present invention. He includes both catalysts having at least one chiral ligand, as well as catalysts with intrinsically achiral ligands based on the arrangement of ligands due to noncovalent interactions and / or the arrangement of ligands in complex-bound form center-chirality, axial chirality, planate chirality or helicity exhibit.

"Achiral connections" are connections, that are not chiral.

Under a "prochiral Connection "will a compound with at least one prochiral center understood. "Asymmetric synthesis" refers to a Reaction in which a compound with at least one prochiral Center a connection with at least one chiral center, a chirality axis, chirality or screw coil is generated, wherein the stereoisomeric products arise in unequal amounts.

"Stereoisomers" are compounds same constitution but different atomic arrangement in the three-dimensional Room.

"Enantiomers" are stereoisomers that behave as image to mirror image to each other. The one at a asymmetric excess enantiomeric excess (ee) is given by the formula: ee [%] = (R-S) / (R + S) × 100. R and S are the descriptors of the CIP system for the two enantiomers and represent the absolute configuration at the asymmetric atom. The enantiomerically pure compound (ee = 100%) is also called "homochiral compound".

The inventive method leads to Products related to of a particular stereoisomer are enriched. The achieved "enantiomeric excess" (ee) is in the Usually at least 20%, preferably at least 50%.

"Diastereomers" are stereoisomers, which are not enantiomeric to each other.

In the following, the term "alkyl" includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched C ₁ -C ₂₀ -alkyl, preferably C ₁ -C ₁₂ -alkyl, particularly preferably C ₁ -C ₈ -alkyl and very particularly preferably C ₁ -C ₄ -alkyl groups. Examples of alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2 Dimethyl propyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl , 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1 Ethyl 2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n -octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl.

The term "alkyl" also includes substituted alkyl groups, which are generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent selected from the groups cycloalkyl, aryl, hetaryl, halogen, NE ¹ E ² , NE ¹ E ² E ³⁺ , COOH, carboxylate, -SO ₃ H and sulfonate. A preferred fluorinated alkyl group is trifluoromethyl.

Of the Expression "alkylene" within the meaning of the present Invention stands for straight-chain or branched alkanediyl groups with, preferably 1 to 4 carbon atoms.

The term "cycloalkyl" in the context of the present invention comprises unsubstituted as well as substituted cycloalkyl groups, preferably C ₅ -C ₇ -cycloalkyl groups, such as cyclopentyl, cyclohexyl or cycloheptyl, which in the case of a substitution, in general 1, 2, 3, 4 or 5 , preferably 1, 2 or 3 and particularly preferably 1 substituent selected from the groups alkyl, alkoxy and halogen, can carry.

The term "heterocycloalkyl" in the context of the present invention comprises saturated, cycloaliphatic groups having generally 4 to 7, preferably 5 or 6, ring atoms in which 1, 2, 3 or 4 of the ring carbon atoms are represented by heteroatoms, preferably selected from the elements oxygen, nitrogen and sulfur, are replaced and may be optionally substituted. In the case of a substitution, these heterocycloaliphatic groups preferably have 1, 2 or 3, more preferably 1 or 2, in particular 1 substituent. These are preferably selected from alkyl, cycloalkyl, aryl, COOR (R = H, alkyl, cycloalkyl, aryl), COO ^- M ⁺ and NE ¹ E ² , preferably alkyl. Exemplary of such heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl, dioxanyl.

The term "aryl" for the purposes of the present invention comprises both unsubstituted and substituted aryl groups, and is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthacenyl, particularly preferably phenyl or naphthyl. In the case of a substitution, these aryl groups may generally carry 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent. These are preferably selected from the groups alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, -SO ₃ H, sulfonate, NE ¹ E ² , alkylene-NE ¹ E ² , nitro, cyano or halogen. A preferred fluorinated aryl radical is pentafluorophenyl.

The term "hetaryl" for the purposes of the present invention comprises unsubstituted or substituted heterocycloaromatic groups, preferably the groups pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, and the subgroup of the "pyrrole group", these heterocycloaromatic groups in the case of a substitution in the Generally 1, 2 or 3 substituents selected from the groups alkyl, alkoxy, carboxyl, carboxylate, -SO ₃ H, sulfonate, NE ¹ E ² , alkylene-NE ¹ E ² , trifluoromethyl or halogen, can carry.

The term "pyrrole group" in the context of the present invention is a series of unsubstituted or substituted heterocycloaromatic groups which are structurally derived from the pyrrole skeleton and contain a pyrrole nitrogen atom in the heterocycle which can be covalently linked to other atoms, for example a pnicogen atom. The term "pyrrole group" thus includes the unsubstituted or substituted groups pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1,2,3-triazolyl, 1,3,4-triazolyl and carbazolyl, which in the case of a substitution in the In general 1, 2 or 3, preferably 1 or 2, more preferably 1 substituent selected from the groups alkyl, alkoxy, acyl, carboxyl, carboxylate, -SO ₃ H, sulfonate, NE ¹ E ² , alkylene-NE ¹ E ² , Trifluoromethyl or halogen, can carry. A preferred substituted indolyl group is the 3-methylindolyl group.

als Beispiel für eine Bispyrrolgruppe, die zwei direkt verknüpfte Pyrrolgruppen, in diesem Falle Indolyl, enthält, oder die Bispyrroldiylmethan-Gruppe der Formel

als Beispiel für eine Bispyrrolgruppe, die zwei über eine Methylengruppe verknüpfte Pyrrolgruppen, in diesem Falle Pyrrolyl, enthält. Wie die Pyrrolgruppen können auch die Bispyrrolgruppen unsubstituiert oder substituiert sein und im Falle einer Substitution pro Pyrrolgruppeneinheit im Allgemeinen 1, 2 oder 3, vorzugsweise 1 oder 2, insbesondere 1 Substituenten, ausgewählt aus Alkyl, Alkoxy, Carboxyl, Carboxylat, -SO₃H, Sulfonat, NE¹E², Alkylen-NE¹E², Trifluormethyl oder Halogen, tragen, wobei bei diesen Angaben zur Anzahl möglicher Substituenten die Verknüpfung der Pyrrolgruppeneinheiten durch direkte chemische Bindung oder durch die mittels der vorstehend genannten Gruppen vermittelte Verknüpfung nicht als Substitution betrachtet wird.Accordingly, the term "bispyrrole group" for the purposes of the present invention includes divalent groups of the formula Py-I-Py, the two linked by direct chemical bonding or alkylene, oxa, thio, imino, silyl or alkylimino groups, connected pyrrole groups such as the bisindolediyl group of the formula

as an example of a bispyrrole group containing two directly linked pyrrole groups, in this case indolyl, or the bispyrrolidinylmethane group of the formula

as an example of a bispyrrole group containing two pyrrole groups linked via a methylene group, in this case pyrrolyl. Like the pyrrole groups, the bispyrrole groups may also be unsubstituted or substituted and in the case of a substitution per pyrrole group unit generally 1, 2 or 3, preferably 1 or 2, in particular 1 substituent selected from alkyl, alkoxy, carboxyl, carboxylate, -SO ₃ H, Sulfonate, NE ¹ E ² , alkylene-NE ¹ E ² , trifluoromethyl or halogen carry, said in this information on the number of possible substituents, the linkage of the pyrrole group units by direct chemical bonding or by the means of the above groups mediated linking is not considered as a substitution becomes.

Carboxylate and sulfonate in the context of this invention preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function. These include z. As the esters with C ₁ -C ₄ alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol. These include the primary amides and their N-alkyl and N, N-dialkyl derivatives.

The above explanations to the terms "alkyl", "cycloalkyl", "aryl", "heterocycloalkyl" and "hetaryl" apply mutatis mutandis for the Terms "alkoxy", "cycloalkoxy", "aryloxy", "heterocycloalkoxy" and "hetaryloxy".

Of the Expression "Acyl" is in the sense of present invention for Alkanoyl or aroyl groups of generally 2 to 11, preferably 2 to 8 carbon atoms, for example for the acetyl, propanoyl, Butanoyl, pentanoyl, hexanoyl, heptanoyl, 2-ethylhexanoyl, 2-propylheptanoyl, benzoyl or naphthoyl group.

The groups NE ¹ E ² , NE ⁴ E ⁵ , NE ⁷ E ⁸ , NE ¹⁰ E ¹¹ , NE ¹³ E ¹⁴ , NE ¹⁶ E ¹⁷ , NE ¹⁹ E ²⁰ and NE ²² E ²³ are preferably N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylamino, N, N-di-n-butylamino, N, N-di-t.-butylamino, N, N-dicyclohexylamino or N, N-diphenylamino ,

halogen stands for Fluorine, chlorine, bromine and iodine, preferred for fluorine, chlorine and bromine.

M ⁺ stands for a cation equivalent, ie for a monovalent cation or the fraction of a polyvalent cation corresponding to a positive single charge. The cation M ⁺ serves only as a counterion to the neutralization of negatively charged substituent groups, such as the COO or the sulfonate group and can in principle be chosen arbitrarily. Preferably therefore alkali metal, in particular Na ⁺ , K ⁺ -, Li ⁺ ions or onium ions, such as ammonium, mono-, di-, tri-, tetraalkylammonium, phosphonium, tetraalkylphosphonium or tetraarylphosphonium ions are used.

The same applies to the anion equivalent X ^- , which serves only as a counterion of positively charged substituent groups, such as the ammonium groups, and can be chosen arbitrarily among monovalent anions and the shares of a polyvalent anion corresponding to a negative single charge. Suitable anions are z. B. halide ions X ^- , such as chloride and bromide. Preferred anions are sulfate and sulfonate, e.g. B. SO ₄ ^2- , tosylate, trifluoromethanesulfonate and methylsulfonate.

The Values for x and y stand for an integer of 1 to 240, preferably an integer of 3 to 120th

condensed Ring systems can linked by annulation (fused) aromatic, hydroaromatic and cyclic compounds be. Condensed ring systems consist of two, three or more as three rings. Depending on the type of link, a distinction is made in fused ring systems, between ortho-annulation, d. H. Each ring has one edge, or two, with each neighboring ring Atoms in common, and a peri-annulation in which a carbon atom heard more than two rings. Preferred among the fused ring systems are orthocondensed Ring systems.

worin
R^α, R^β, R^γ, R^δ und Y die zuvor angegebenen Bedeutungen besitzen.Preference is given to phosphite-phosphoramidite chelate ligands of the general formula I.1

wherein
R ^α , R ^β , R ^γ , R ^δ and Y have the meanings given above.

In a preferred embodiment, in the phosphorochelate compounds of the general formula I and especially of the formula I.1, the substituents R ^α and R ^{β are} heteroatom-containing groups which are bonded via an optionally substituted nitrogen atom to the phosphorus atom, where R ^α and R ^{β are} not mutually exclusive are connected.

Preferably, R ^α and R ^β then represent pyrrole groups bonded via the pyrrole nitrogen atom to the phosphorus atom. The meaning of the term "pyrrole group" corresponds to the definition given at the outset.

worin
Alk eine C₁-C₄-Alkylgruppe ist und
R^a, R^b, R^c und R^d unabhängig voneinander für Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Acyl, Halogen, Trifluormethyl, C₁-C₄-Alkoxycarbonyl oder Carboxyl stehen.Preference is given to phosphorus chelate compounds in which the radicals R ^α and R ^{β are} independently selected from among groups of the formulas II.a to II.k.

wherein
Alk is a C ₁ -C ₄ alkyl group and
R ^a , R ^b , R ^c and R ^d independently of one another represent hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, acyl, halogen, trifluoromethyl, C ₁ -C ₄ -alkoxycarbonyl or carboxyl.

Preferred alkyl radicals R ^a to R ^d are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and trifluoromethyl.

Particularly preferably, at least one of the radicals R ^α and R ^{β is} an unsubstituted or substituted indolyl group, which is in particular selected from groups II.e to II.i.

Particularly preferably, both radicals R ^α and R ^{β are} such an unsubstituted or substituted indolyl group.

As an illustration, some advantageous pyrrole groups are listed below:

Especially advantageous is the 3-methylindolyl (skatolyl) of the formula II.f1. Hydroformylation catalysts based on ligands, the one or more 3-methylindolyl group (s) attached to the phosphorus atom have, are characterized by a particularly high stability and thus especially long catalyst life.

In a further advantageous embodiment of the present invention, R ^α and R ^β, together with the phosphorus atom to which they are attached, represent a 5- to 7-membered heterocycle having two ring heteroatoms bonded to the phosphorus atom, at least one of them being this ring heteroatom is an optionally substituted nitrogen atom. Preferably, the second ring heteroatom attached to the phosphorus atom is also an optionally substituted nitrogen atom. The substituent R ^α together with the substituent R ^β then particularly preferably forms a bispyrrole group bonded via the pyrrole nitrogen atoms to the phosphorus atom. The meaning of the term "bispyrrole group" corresponds to the definition given at the outset.

Preferably, R ^α and R ^β together represent a 5- to 8-membered heterocycle which is optionally fused additionally in one, two, three or four times with cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the heterocycle and, if present, the fused groups independently of one another may each bear one, two, three or four substituents which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, COOH, carboxylate, SO ₃ H , Sulfonate, NE ⁴ E ⁵ , NE ⁴ E ⁵ E ⁶ X ^- , nitro, alkoxycarbonyl, acyl and cyano, wherein E ⁴ , E ⁵ and E ⁶ each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl and X ^{- represents} an anion equivalent.

Preferably, the substituent R ^α together with the substituent R ^{β is} a divalent group of the formula ## STR4 ## containing pyrrole group bonded via the pyrrole nitrogen atom to the phosphorus atom Py-IW form,
wherein
Py is a pyrrole group,
I is a chemical bond or is O, S, SiR ^θ R ⁱ , NR ^κ or optionally substituted C ₁ -C ₁₀ alkylene, preferably CR ^λ R ^μ , wherein R ^θ , R ⁱ , R ^κ , R ^λ and R ^μ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
W is cycloalkyloxy or amino, aryloxy or amino, hetaryloxy or amino
and
R ^θ, R ^i, R ^{κ, λ} R and R ^μ are independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
wherein the terms used herein have the meaning explained above.

Suitable divalent groups of the formula Py-IW are z. B.

stehen, worin
I für eine chemische Bindung oder für O, S, SiR^ϑRⁱ, NR^κ oder gegebenenfalls substituiertes C₁-C₁₀-Alkylen, bevorzugt CR^λR^μ, steht, worin R^ϑ, Rⁱ, R^κ, R^λ und R^μ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
R⁹ und R¹⁰ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Hetaryl, Mesylat, Tosylat oder Trifluormethansulfonat stehen,
R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹ und R³⁰ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, W'COOR^f, W'COO^–M⁺, W'(SO₃)R^f, W'(SO₃)^–M⁺, W'PO₃(R^f)(R^g), W'(PO₃)^2–(M⁺)₂, W'NE⁷E⁸, W'(NE⁷E⁸E⁹)⁺X^–, W'OR^f, W'SR^f, (CHR^gCH₂O)_xR^f, (CH₂NE⁷)_xR^f, (CH₂CH₂NE⁷)_xR^f, Halogen, Nitro, Acyl oder Cyano stehen,
worin
W' für eine Einfachbindung, ein Heteroatom, eine Heteroatom-haltige Gruppe oder eine zweiwertige verbrückende Gruppe mit 1 bis 20 Brückenatomen steht,
R^f, E⁷, E⁸, E⁹ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl oder Aryl bedeuten,
R^g für Wasserstoff, Methyl oder Ethyl steht,
M⁺ für ein Kationäquivalent steht,
X^– für ein Anionäquivalent steht und
x für eine ganze Zahl von 1 bis 240 steht,
wobei in den Verbindungen der Formeln II.1 und II.2 jeweils zwei benachbarte Reste R¹ und R² und/oder R⁷ und R⁸ und in den Verbindungen der Formeln II.3, II.4 und II.5 jeweils zwei benachbarte Reste R¹¹ bis R³⁰ zusammen mit den Kohlenstoffatomen des Rings, an die sie gebunden sind, auch für ein kondensiertes Ringsystem mit 1, 2 oder 3 weiteren Ringen stehen können.Preference is given to phosphorus chelate compounds in which R ^α and R ^β, together with the phosphorus atom to which they are bonded, represent a group of the formulas II.1 to II.5

stand in which
I is a chemical bond or is O, S, SiR ^θ R ⁱ , NR ^κ or optionally substituted C ₁ -C ₁₀ alkylene, preferably CR ^λ R ^μ , wherein R ^θ , R ⁱ , R ^κ , R ^λ and R ^μ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R ⁹ and R ¹⁰ independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, hetaryl, mesylate, tosylate or trifluoromethanesulfonate,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, W ' COOR ^f , W'COO ^- M ⁺ , W '(SO ₃ ) R ^f , W' (SO ₃ ) ^- M ⁺ , W'PO ₃ (R ^f ) (R ^g ), W '(PO ₃ ) ^2- (M ⁺ ) ₂ , W'NE ⁷ E ⁸ , W '(NE ⁷ E ⁸ E ⁹ ) ⁺ X ^- , W'OR ^f , W'SR ^f , (CHR ^g CH ₂ O) _x R ^f , (CH ₂ NE ⁷ ) _x R ^f , (CH ₂ CH ₂ NE ⁷ ) _x R ^f , halogen, nitro, acyl or cyano,
wherein
W 'represents a single bond, a heteroatom, a heteroatom-containing group or a divalent bridging group having 1 to 20 bridging atoms,
R ^f , E ⁷ , E ⁸ , E ^{9 are} each identical or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
R ^{g is} hydrogen, methyl or ethyl,
M ^{+ is} a cation equivalent,
X ^{- stands} for an anion equivalent and
x is an integer from 1 to 240,
in each case two adjacent radicals R ¹ and R ² and / or R ⁷ and R ⁸ in the compounds of the formulas II.1 and II.2, and two adjacent radicals in the compounds of the formulas II.3, II.4 and II.5 Radicals R ¹¹ to R ³⁰ together with the carbon atoms of the ring to which they are attached may also stand for a fused ring system having 1, 2 or 3 further rings.

• a) R^λ, R^μ = H
• b) R^λ = H, R^μ = C₆H₅
• c) (R^λ + R^μ) = C₄H₈

Preferably, in the compounds of the general formula I and the specific embodiment I.1, the radicals R ^α and R ^β, together with the phosphorus atom to which they are bonded, stand for one of the following groups of the formula II.1

• a) R ^λ , R ^μ = H
• b) R ^λ = H, R ^μ = C ₆ H ₅
• c) (R ^λ + R ^μ ) = C ₄ H ₈

Preferably, in the groups of the formula II.3, the radicals R ⁹ and R ^{10 are} independently selected from hydrogen, C ₁ -C ₄ -alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl , C ₅ -C ₆ -cycloalkyl, in particular cyclohexyl and aryl, in particular phenyl.

Preferably, in the groups of the formula II.3, the radicals R ¹¹ , R ¹² , R ¹³ and R ^{14 are} hydrogen.

Preferably, in the groups of the formula II.4, the radicals R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^{20 are} hydrogen.

Further preferred are groups of the formula II.4, wherein R ¹⁵ and R ¹⁶ and / or R ¹⁹ and R ²⁰ together with the carbon atoms of the pyrrole ring to which they are attached, for a fused ring system with 1, 2 or 3 further rings stand. The further rings are preferably fused aromatic rings. The fused aromatic rings are preferably benzene or naphthalene. Anellated benzene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2 substituents, which are preferably selected from alkyl, alkoxy, halogen, SO ₃ H, sulfonate, NE ⁷ E ⁸ , alkylene-NE ⁷ E ⁸ , trifluoromethyl , Nitro, carboxyl, alkoxycarbonyl, acyl and cyano. Anellated naphthalenes are preferably unsubstituted or have in the non-fused ring and / or in the fused ring in each case 1, 2 or 3, in particular 1 or 2 of the substituents previously mentioned in the fused benzene rings. In the substituents of the fused aryls, alkyl is preferably C ₁ -C ₄ -alkyl and in particular methyl, isopropyl and tert-butyl. Alkoxy is preferably C ₁ -C ₄ -alkoxy and in particular methoxy. Alkoxycarbonyl is preferably C ₁ -C ₄ -alkoxycarbonyl. Halogen is especially fluorine and chlorine.

In the groups of the formula II.5, the radicals R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are preferably hydrogen.

Preference is furthermore given to groups of the formula II.5 in which (R ²³ and R ²⁴ ) or (R ²⁴ and R ²⁵ ) and / or (R ²⁶ and R ²⁷ ) or (R ²⁷ and R ²⁸ ) together with the carbon atoms of the Benzene ring to which they are attached, stand for a fused ring system with 1, 2 or 3 further rings. The further rings are preferably fused aromatic rings. The fused aromatic rings are preferably benzene or naphthalene. If desired, these may be substituted as described above for groups II.4.

As an illustration, some advantageous groups II.3 to II.5 are listed below:

stehen, worin
c und d unabhängig voneinander für 0 oder 1 stehen,
Q zusammen mit dem Phosphoratom und den Sauerstoffatomen, an die es gebunden ist, für einen 5- bis 8-gliedrigen Heterocyclus steht, der gegebenenfalls ein-, zwei- oder dreifach mit Cycloalkyl, Heterocycloalkyl, Aryl und/oder Hetaryl anelliert ist, wobei die anellierten Gruppen unabhängig voneinander je einen, zwei, drei oder vier Substituenten, ausgewählt unter Alkyl, Alkoxy, Cycloalkyl, Aryl, Halogen, Hydroxy, Thiol, Polyalkylenoxid, Polyalkylenimin, COOH, Carboxylat, SO₃H, Sulfonat, NE¹⁰E¹¹, Alkylen-NE¹⁰E¹¹, Nitro und Cyano tragen können und/oder Q einen, zwei oder drei Substituenten, die ausgewählt sind unter Alkyl, Alkoxy, gegebenenfalls substituiertem Cycloalkyl und gegebenenfalls substituiertem Aryl, aufweisen kann und/oder Q durch 1, 2 oder 3 gegebenenfalls substituierte Heteroatome unterbrochen sein kann.Preference is given to compounds of the general formula I and especially of the formula I.1 embedded image where R ^γ and R ^{δ are taken} together with the phosphorus atom and, if present, the oxygen atoms to which they are bonded, for a group of the general formula II.A

stand in which
c and d are independently 0 or 1,
Q together with the phosphorus atom and the oxygen atoms to which it is attached represent a 5- to 8-membered heterocycle, which is optionally fused once, twice or three times with cycloalkyl, heterocycloalkyl, aryl and / or hetaryl, wherein the fused groups independently of one another each one, two, three or four substituents selected from alkyl, alkoxy, cycloalkyl, aryl, halogen, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, COOH, carboxylate, SO ₃ H, sulfonate, NE ¹⁰ E ¹¹ , alkylene -NE ¹⁰ E ¹¹ , nitro and cyano and / or Q may have one, two or three substituents selected from alkyl, alkoxy, optionally substituted cycloalkyl and optionally substituted aryl, and / or Q may be 1, 2 or 3 optionally substituted heteroatoms may be interrupted.

The Group of general formula II.A can be replaced by an oxygen atom (b = 1) or a covalent bond (b = 0) to the bridging group Y be bound. With the proviso at least one of the variables b, c or d is 1, the phosphorochelate compounds according to the invention of the formula I (or I.1) thus at least one phosphinite, phosphonite and / or phosphite test. Preferably, b, c and d are all for one Value of 1 (phosphite groups).

The bridging Groups Y in formulas I and I.1 and the bridging group Q in the formula II.A are preferably independently of one another bivalent bridging Groups with 2 to 7 bridge atoms between the flanking bonds, with at least two bridge atoms Part of a polycyclic compound.

worin
R^I, R^I', R^II, R^II', R^III, R^III', R^IV, R^IV', R^V, R^VI, R^VII, R^VIII, R^IX, R^X, R^XI, und R^XII unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, Hydroxy, Thiol, Polyalkylenoxid, Polyalkylenimin, Alkoxy, Halogen, SO₃H, Sulfonat, NE¹³E¹⁴, Alkylen-NE¹³E¹⁴, Trifluormethyl, Nitro, Alkoxycarbonyl, Carboxyl, Acyl oder Cyano stehen, worin E¹³ und E¹⁴ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten,
Z für O, S, NR^χ oder SiR^ψR^ω steht, wobei
R^χ, R^ψ und R^ω unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
oder Z für eine C₁-C₄-Alkylenbrücke steht, die eine Doppelbindung und/oder einen Alkyl-, Cycloalkyl-, Heterocycloalkyl-, Aryl- oder Hetaryl-Substituenten aufweisen kann,
oder Z für eine C₂-C₄-Alkylenbrücke steht, die durch O, S oder NR^χ oder SiR^ψR^ω unterbrochen ist,
wobei in den Gruppen der Formel III.a zwei benachbarte Reste R^I bis R^VI gemeinsam mit den Kohlenstoffatomen des Benzolkerns, an die sie gebunden sind, auch für ein kondensiertes Ringsystem mit 1, 2 oder 3 weiteren Ringen stehen können,
wobei in den Gruppen der Formeln III.g bis III.m zwei geminale Reste R^I, R^I', R^II, R^II'; R^III, R^III' und/oder R^IV, R^IV'' auch für Oxo oder ein Ketal davon stehen können,
A¹ und A² unabhängig voneinander für O, S, SiR^oR^π, NR^ρ oder CR^σR^τ stehen, wobei
R^o, R^π und R^ρ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
R^σ und R^τ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen oder die Gruppe R^σ gemeinsam mit einer weiteren Gruppe R^σ oder die Gruppe R^τ gemeinsam mit einer weiteren Gruppe R^τ eine intramolekulare Brückengruppe D bilden,
D für eine zweibindige Brückengruppe der allgemeinen Formel

steht, in der
R³⁰, R^30', R³¹ und R^31' unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, Carboxyl, Carboxylat oder Cyano stehen,
wobei R^30' auch gemeinsam mit R^31' für den Bindungsanteil einer Doppelbindung zwischen den beiden Kohlenstoffatomen, an die R^30' und R^31' gebunden sind, stehen kann, und/oder R³⁰ und R³¹ gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, auch für einen 4- bis 8-gliedrigen Carbo- oder Heterocyclus stehen können, der gegebenenfalls zusätzlich ein-, zwei- oder dreifach mit Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl anelliert ist, wobei der Heterocyclus und, falls vorhanden, die anellierten Gruppen unabhängig voneinander je einen, zwei, drei oder vier Substituenten tragen können, die ausgewählt sind unter Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, COOR^h, COO^–M⁺, SO₃R^h, SO^– ₃M⁺, NE¹⁶E¹⁷, Alkylen-NE¹⁶E¹⁷, NE¹⁶E¹⁷E¹⁸⁺X^–, Alkylen-NE¹⁶E¹⁷E¹⁸⁺X^–, OR^h, SR^h, (CHRⁱCH₂O)_yR^h, (CH₂N(E¹⁶))_yR^h, (CH₂CH₂N(E¹⁶))_yR^h, Halogen, Trifluormethyl, Nitro, Acyl oder Cyano, stehen, worin
R^h, E¹⁶, E¹⁷ und E¹⁸ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl oder Aryl bedeuten,
Rⁱ für Wasserstoff, Methyl oder Ethyl steht,
M⁺ für ein Kation steht,
für ein Anion steht, und
y für eine ganze Zahl von 1 bis 120 steht, und
e 0 oder 1 ist.Preferably, the bridging groups Y and Q are independently selected from groups of formulas III.a to III.t.

wherein
R ^I , R ^{I '} , R ^II , R ^II' , R ^III , R ^{III '} , R ^IV , R ^IV' , R ^V , R ^VI , R ^VII , R ^VIII , R ^IX , R ^X , R ^XI , and R ^XII independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, SO ₃ H, sulfonate, NE ¹³ E ¹⁴ , alkylene-NE ¹³ E ¹⁴ , trifluoromethyl, nitro Alkoxycarbonyl, carboxyl, acyl or cyano in which E ¹³ and E ¹⁴ each represent identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl,
Z is O, S, NR ^χ or SiR ^ψ R ^ω , where
R ^χ , R ^ψ and R ^ω independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
or Z is a C ₁ -C ₄ -alkylene bridge which may have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent,
or Z is a C ₂ -C ₄ -alkylene bridge which is interrupted by O, S or NR ^χ or SiR ^ψ R ^ω ,
where in the groups of the formula III.a two adjacent radicals R ^I to R ^VI, together with the carbon atoms of the benzene nucleus to which they are attached, may also stand for a fused ring system having 1, 2 or 3 further rings,
where in the groups of formulas III.g to III.m two geminal radicals R ^I , R ^{I '} , R ^II , R ^II' ; R ^III , R ^{III '} and / or R ^IV , R ^{IV "may} also be oxo or a ketal thereof,
A ¹ and A ^{2 are} independently O, S, SiR ^o R ^π , NR ^ρ or CR ^σ R ^τ , where
R ^o , R ^π and R ^ρ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R ^σ and R ^τ independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R ^σ together with another group R ^σ or the group R ^τ together with another group R ^{τ form} an intramolecular bridging group D,
D is a divalent bridging group of the general formula

stands in the
R ³⁰ , R ^{30 '} , R ³¹ and R ^31' independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano,
wherein R ^{30 'may} also be taken together with R ^31' for the bond portion of a double bond between the two carbon atoms to which R ^{30 '} and R ^{31' are} bonded, and / or R ³⁰ and R ³¹ together with the carbon atoms to which they are bonded, may also be a 4- to 8-membered carbocycle or heterocycle, which is optionally additionally fi-, di- or tri-fused with cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the heterocycle and, if present, the each of which may independently bear one, two, three or four substituents which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COOR ^h , COO ^- M ⁺ , SO ₃ R ^h , SO ^- ₃ M ⁺ , NE ¹⁶ e ^{17 16} e ¹⁷ alkylene-NE, NE ¹⁶ e ¹⁷ e ^{18 +} X ^-, alkylene-NE ¹⁶ e ¹⁷ e ^{18 +} X ^-, OR ^h, SR ^h, (CHR ⁱ CH ₂ O) _y R ^h, (CH ₂ N (E ¹⁶ )) _y R ^h , (CH ₂ CH ₂ N (E ¹⁶ )) _y R ^h , halogen, trifluoromethyl, nitro, acyl or cyano, in which
R ^h , E ¹⁶ , E ¹⁷ and E ^{18 are} each the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
R ^{i is} hydrogen, methyl or ethyl,
M ^{+ stands} for a cation,
stands for an anion, and
y is an integer from 1 to 120, and
e is 0 or 1.

For the case that e = 0, the groups A ¹ and A ^{2 are} not connected to each other by a single bond.

The bridging groups Y and / or Q are preferably a group of the formula III.a. In group III.a, the groups A ¹ and A ^{2 can be,} in general, independently of one another O, S, SiR ^o R ^π , NR ^ρ or CR ^σ R ^τ , wherein the substituents R ^o , R ^π and R ^ρ in general independently of one another can have the meaning hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, whereas the groups R ^σ and R ^τ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R ^σ together with a group R ^σ or the group R ^τ together with another group R ^τ can form an intramolecular bridging group D.

in denen R³⁰, R^30', R³¹ und R^31' unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, Carboxyl, Carboxylat oder Cyano stehen oder miteinander zu einer C₃-C₄-Alkylengruppe verbunden sind und R³², R³³, R³⁴ und R³⁵ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, COOH, Carboxylat, Cyano, Alkoxy, SO₃H, Sulfonat, NE¹⁹E²⁰, Alkylen-NE¹⁹E²⁰E²¹⁺X^–, Aryl oder Nitro stehen können. Vorzugsweise stehen die Gruppen R³⁰, R^30', R³¹ und R^31' für Wasserstoff, C₁-C₁₀-Alkyl oder Carboxylat und die Gruppen R³², R³³, R³⁴ und R³⁵ für Wasserstoff, C₁-C₁₀-Alkyl, Halogen, insbesondere Fluor, Chlor oder Brom, Trifluormethyl, C₁-C₄-Alkoxy, Carboxylat, Sulfonat oder C₁-C₈-Aryl. Besonders bevorzugt stehen R³⁰, R^30', R³¹, R^31', R³², R³³, R³⁴ und R³⁵ für Wasserstoff. Für den Einsatz in einem wässrigen Reaktionsmedium sind solche Pnicogenchelatverbindungen bevorzugt, in denen 1, 2 oder 3, vorzugsweise 1 oder 2, insbesondere 1 der Gruppen R³², R³³, R³⁴ und/oder R³⁵ für eine COO^–M⁺, eine SO₃ ^–M⁺ oder eine (NE¹⁹E²⁰E²¹)⁺X^–-Gruppe stehen, wobei M⁺ und X^– die vorstehend genannte Bedeutung haben.D is preferably a divalent bridging group selected from the groups

in which R ³⁰ , R ^{30 '} , R ³¹ and R ^31' independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano, or are joined together to form a C ₃ -C ₄ -alkylene group and R ³² , R ³³ , R ³⁴ and R ³⁵ independently represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, SO ₃ H, sulfonate, NE ¹⁹ E ²⁰ , alkylene NE ¹⁹ E ²⁰ E ²¹⁺ X ^- , aryl or nitro can stand. The groups R ³⁰ , R ^{30 '} , R ³¹ and R ^31' are preferably hydrogen, C ₁ -C ₁₀ -alkyl or carboxylate and the groups R ³² , R ³³ , R ³⁴ and R ^{35 are} hydrogen, C ₁ -C ₁₀ alkyl, halogen, in particular fluorine, chlorine or bromine, trifluoromethyl, C ₁ -C ₄ alkoxy, carboxylate, sulfonate or C ₁ -C ₈ aryl. Particularly preferred stand R ³⁰ , R ^{30 '} , R ³¹ , R ^31' , R ³² , R ³³ , R ³⁴ and R ^{35 is} hydrogen. For use in an aqueous reaction medium, those pnicogen chelate compounds are preferred in which 1, 2 or 3, preferably 1 or 2, in particular 1 of the groups R ³² , R ³³ , R ³⁴ and / or R ³⁵ for a COO ^- M ⁺ , a SO ₃ ^- M ⁺ or a (NE ¹⁹ E ²⁰ E ²¹ ) ⁺ X ^- group, where M ⁺ and X ^{- have} the abovementioned meaning.

und die 1,2-Phenylengruppe

Particularly preferred bridging groups D are the ethylene group

and the 1,2-phenylene group

If R ^σ with another group R ^σ or R ^τ with another group R ^{τ forms} an intramolecular bridging group D, ie the index e is 1 in this case, it necessarily follows that both A ¹ and A ² together form a bridging group, preferably a CR ^σ R ^τ group and the bridging group Y or Q of formula III.a in this case preferably has a triptycene-like or Ethanoanthracenartiges carbon skeleton.

Preferred bridging groups Y and / or Q of the formula III.a are, apart from those having a triptycene-like carbon skeleton, those in which the subscript e is 0 and the groups A ¹ and A ^{2 are} selected from the groups O, S and CR ^σ R ^τ , in particular O, S, the methylene group (R ^σ = R ^τ = H), the dimethylmethylene group (R ^σ = R ^τ = CH ₃ ), the diethylene group (R ^σ = R ^τ = C ₂ H ₅ ), the di -n-propyl-methylene group (R ^σ = R ^τ = n-propyl) or the di-n-butylmethylene group (R ^σ = R ^τ = n-butyl). In particular, those bridging groups Y and Q are preferred in which A ¹ is different from A ² , wherein A ^{1 is} preferably a CR ^σ R ^τ group and A ^{2 is} preferably an O or S group, particularly preferably an oxo group O is.

Particularly preferred bridging groups Y and Q of the formula III.a are thus those which are composed of a triptycene-type, ethanoanthracene-type or xanthene-type (A ¹ : CR ^σ R ^τ , A ² : O) skeleton.

In the bridging groups Y and / or Q of the formula III.a, the substituents R ^I , R ^II , R ^III , R ^IV , R ^V and R ^{VI are} preferably selected from hydrogen, alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl and hetaryl. According to a first preferred embodiment, R ^I , R ^II , R ^III , R ^IV , R ^V and R ^{VI are} hydrogen. According to a further preferred embodiment, R ^I and R ^VI independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. Preferably, R ^I and R ^{VI are} selected from methyl, ethyl, isopropyl, tert-butyl and methoxy. In these compounds, R ^II , R ^III , R ^IV and R ^V are preferably hydrogen. According to a further preferred embodiment, R ^II and R ^V independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. Preferably R ^II and R ^{V are} selected from methyl, ethyl, isopropyl and tert-butyl. In these compounds, R ¹ , R ^III , R ^IV and R ^VI are preferably hydrogen.

If the bridging groups Y and / or of the formula III.a two adjacent radicals selected from among R ^I, R ^II, R ^III, R ^IV, R ^V and R ^VI is a fused-ring system, it is preferably benzene or naphthalene rings. Anellierte benzene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2 substituents which are selected from alkyl, alkoxy, halogen, SO ₃ H, sulfonate, NE ¹ E ² , alkylene-NE ¹ E ² , trifluoromethyl, Nitro, COOH, carboxylate, alkoxycarbonyl, acyl and cyano. Anellated naphthalene rings are preferably unsubstituted or have in the non-fused ring and / or in the fused ring in total 1, 2 or 3, in particular 1 or 2 of the substituents previously mentioned in the fused benzene rings.

Y and / or Q are preferably a group of the formula III.b in which R ^IV and R ^V, independently of one another, are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. Preferably, R ^IV and R ^{V are} selected from methyl, ethyl, isopropyl, tert -butyl and methoxy. In these compounds, R ¹ , R ^II , R ^III , R ^VI , R ^VII and R ^VIII are preferably hydrogen.

Furthermore, Y and / or Q are preferably a group of the formula III.b in which R ^I and R ^VIII independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. Particularly preferably, R ^I and R ^{VIII are} tert-butyl. Particularly preferred in these compounds R ^II , R ^III , R ^IV , R ^V , R ^VI , R ^{VII are} hydrogen. Furthermore, R ^III and R ^VI in these compounds are preferably each independently C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. With particular preference R ^III and R ^{VI are} independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.

Furthermore, Y and / or Q are preferably a group of the formula III.b in which R ^II and R ^{VII are} hydrogen. Preferably ₁ -C ₄ alkyl or C are independently C ₁ -C ₄ alkoxy in these compounds, R ^I, R ^III, R ^IV, R ^V, R ^VI and R ^VIII. Particularly preferably, R ^I , R ^III , R ^IV , R ^V , R ^VI and R ^{VIII are} independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.

Y and / or Q are furthermore preferably a group of the formula III.c in which Z is a C ₁ -C ₄ -alkylene group, in particular methylene. In these compounds, R ^IV and R ^V are each, independently of one another, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. More preferably, R ^IV and R ^{V are} independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy. The radicals R ^I , R ^II , R ^III , R ^VI , R ^VII and R ^VIII are preferably hydrogen.

Furthermore, Y and / or Q are preferably a group of the formula III.c in which Z is a C ₁ -C ₄ -alkylene bridge which has at least one alkyl, cycloalkyl or aryl radical. Z particularly preferably represents a methylene bridge which has two C ₁ -C ₄ -alkyl radicals, in particular two methyl radicals. In these compounds, the radicals R ¹ and R ^VIII are preferably, independently of one another, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. More preferably, R ^I and R ^{VIII are} independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.

Y and / or Q are furthermore preferably a group of the formula III.d, in which R ^I and R ^XII independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. In particular, R ^I and R ^{XII are} independently selected from methyl, ethyl, isopropyl, tert-butyl, methoxy and alkoxycarbonyl, preferably methoxycarbonyl. Particularly preferred in these compounds are the radicals R ^II to R ^{XI is} hydrogen.

Furthermore, Y and / or Q preferably represents a group of the formula III.e, in which R ^I and R ^XII independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. In particular, R ^I and R ^{XII are} independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy. Particularly preferred in these compounds are the radicals R ^II to R ^{XI is} hydrogen.

Y and / or Q are furthermore preferably a group of the formula III.f in which Z is a C ₁ -C ₄ -alkylene group which has at least one alkyl, cycloalkyl or aryl substituent. Z particularly preferably represents a methylene group which has two C ₁ -C ₄ -alkyl radicals, especially two methyl radicals. Particularly preferably, in these compounds, the radicals R ^I and R ^VIII independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. In particular, R ^I and R ^{VIII are} independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy. The radicals R ^II , R ^III , R ^IV , R ^V , R ^VI and R ^VII are preferably hydrogen.

Furthermore, Y and / or Q preferably represents a group of the formula III.g, in which R ¹ , R ^{1 '} , R ^II , R ^II' , R ^III and R ^{III '} , are hydrogen.

Furthermore, Y and / or Q preferably represents a group of the formula III.g, in which R ^II and R ^{II '} together represent an oxo group or a ketal thereof and the other radicals are hydrogen.

Furthermore, Y and / or Q preferably represents a group of the formula III.h in which R ^I , R ^{I '} , R ^II , R ^II' , R ^III and R ^{III 'are} hydrogen.

Furthermore, Y and / or Q are preferably a group of the formula III.h in which R ^II and R ^{II '} together represent an oxo group or a ketal thereof and the other radicals are hydrogen.

In addition, Y and / or Q preferably represents a group of the formula III.i in which R ^I , R ^{I '} , R ^II , R ^II' , R ^III , R ^{III '} , R ^IV and R ^{IV' are} hydrogen.

Furthermore, Y and / or Q preferably represents a group of the formula III.k, in which R ¹ , R ^{1 '} , R ^II , R ^II' , R ^III , R ^{III '} , R ^IV and R ^{IV' are} hydrogen.

Furthermore, Y and / or Q preferably represents a group of the formula III.1 in which R ¹ , R ^{1 '} , R ^II , R ^II' , R ^III , R ^{III '} , R ^IV and R ^{IV' are} hydrogen.

Furthermore, Y and / or Q preferably represents a group of the formula III.m, in which R ^{1 '} , R ^1' , R ^II , R ^{II '} , R ^III , R ^III' , R ^IV and R ^{IV 'are} hydrogen ,

Furthermore, preferably Y and / or Q is a group of the formula III.n, where R ^I , R ^{I '} , R ^II , R ^II' , R ^III , R ^{III '} , R ^IV and R ^{IV' are} hydrogen.

Furthermore, Y and / or Q are preferably a group of the formula III.n in which one of the radicals R ¹ to R ^{IV is} C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. At least one of the radicals R ¹ to R ^IV is then particularly preferably methyl, ethyl, isopropyl, tert-butyl or methoxy.

In addition, Y and / or Q preferably represents a group of the formula III.o in which R ¹ , R ^II , R ^III and R ^{IV are} hydrogen.

Furthermore, Y and / or Q are preferably a group of the formula III.o in which one of the radicals R ¹ , R ^II , R ^III or R ^{IV is} C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy , One of the radicals R ¹ to R ^{IV is} particularly preferably then methyl, ethyl, tert-butyl or methoxy.

Furthermore, preferably Y and / or Q is a group of the formula III.p in which R ^I and R ^VI independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. More preferably, R ^I and R ^{VI are} independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy. Particularly preferred in these compounds R ^II , R ^III , R ^IV and R ^{V are} hydrogen. Furthermore, preferably, in the compounds III.p R ^I, R ^III, R ^IV and R ^VI are each independently C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy. Particularly preferably, R ^I , R ^III , R ^IV and R ^{VI are} then independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.

Furthermore, preferably Y and / or Q is a group of the formula III.q, in which R ^I and R ^VI independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. More preferably, R ^I and R ^{VI are} independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy. Particularly preferred in these compounds R ^II , R ^III , R ^IV and R ^{V are} hydrogen. Furthermore, R ^III and R ^IV in these compounds are preferably independently of one another C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. R ^III and R ^{IV are} then more preferably independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.

Furthermore, Y and / or Q are preferably a group of the formula III.r, III.s or III.t, in which Z is CH ₂ , C ₂ H ₂ or C ₂ H ₄ .

In The compounds of formulas III.r, III.s and III.t are equally for the illustrated Bindings to the bridged Groups endo and exo position possible.

In a special embodiment these are the phosphorochelate compounds according to the invention of the general formula I or I.1 to chiral compounds. Then it is the bridging Group Y and / or, if present, the bridging group Q in the formula II.A is a chiral group which preferably has at least one chiral center, a chirality axis or level of chirality having.

worin
R^I, R^I', R^II, R^II', R^III, R^III', R^IV, R^IV', R^V, R^VI, R^VII, R^VIII, R^IX, R^X, R^XI, und R^XII unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, Hydroxy, Thiol, Polyalkylenoxid, Polyalkylenimin, Alkoxy, Halogen, SO₃H, Sulfonat, NE¹³E¹⁴, Alkylen-NE¹³E¹⁴, Trifluormethyl, Nitro, Alkoxycarbonyl, Carboxyl, Acyl oder Cyano stehen, worin E¹³ und E¹⁴ jeweils gleiche
oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten.Preferably, the chiral bridging groups Y and / or Q are selected from groups of formulas III.b and III.d.

wherein
R ^I , R ^{I '} , R ^II , R ^II' , R ^III , R ^{III '} , R ^IV , R ^IV' , R ^V , R ^VI , R ^VII , R ^VIII , R ^IX , R ^X , R ^XI , and R ^XII independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, SO ₃ H, sulfonate, NE ¹³ E ¹⁴ , alkylene-NE ¹³ E ¹⁴ , trifluoromethyl, nitro , Alkoxycarbonyl, carboxyl, acyl or cyano wherein E ¹³ and E ^{14 are} each the same
or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl.

Furthermore, Y and / or Q are preferably a chiral group of the formula III.b in which R ^IV and R ^V independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. Preferably, R ^IV and R ^{V are} selected from methyl, ethyl, isopropyl, tert -butyl and methoxy. In these compounds, R ¹ , R ^II , R ^III , R ^VI , R ^VII and R ^VIII are preferably hydrogen.

Furthermore, Y and / or Q preferably represent a chiral group of the formula III.b in which R ^I and R ^VIII independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. Particularly preferably, R ^I and R ^{VIII are} tert-butyl. Particularly preferred in these compounds R ^II , R ^III , R ^IV , R ^V , R ^VI , R ^{VII are} hydrogen. Furthermore, R ^III and R ^VI in these compounds are preferably each independently C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. With particular preference R ^III and R ^{VI are} independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.

Furthermore, Y and / or Q preferably represent a chiral group of the formula III.b in which R ^II and R ^{VII are} hydrogen. Preferably ₁ -C ₄ alkyl or C are independently C ₁ -C ₄ alkoxy in these compounds, R ^I, R ^III, R ^IV, R ^V, R ^VI and R ^VIII. Particularly preferably, R ^I , R ^III , R ^IV , R ^V , R ^VI and R ^{VIII are} independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.

Y and / or Q are furthermore preferably a chiral group of the formula III.d, in which R ¹ to R ^{XII are} hydrogen.

Y and / or Q are furthermore preferably a chiral group of the formula III.d, in which R ¹ and R ^XII independently of one another are C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. In particular, R ^I and R ^{XII are} independently selected from methyl, ethyl, isopropyl, tert-butyl, methoxy and alkoxycarbonyl, preferably methoxycarbonyl. Particularly preferred in these compounds are the radicals R ^II to R ^{XI is} hydrogen.

For the purpose of illustration only, some exemplary compounds of the formula I are listed below:

The preparation of phosphorochelate compounds of the general formula I according to the invention can expediently proceed from compounds of the general formula IV L ¹ - (X) _a - Y - (O) _b - L ² (IV) wherein
L ¹ and L ² independently of one another are a leaving group and X, Y, a and b have the meanings given above. In the case where a is 0, L ^{1 is} and in the case where b is 0, L ^{2 is} preferably halogen, in particular F, Cl or Br, or alkali metal, in particular Li, Na or K. Für For example, when L is 1 and X is O, L ¹ is H, C (= O) CF ₃ , SO ₂ CH ₃ , SO ₂ -olyl or SO ₂ CF ₃ . The same applies to L ² if b stands for 1. Other suitable leaving groups for various bridging groups Y are the usual, known in the art.

For attaching the groups PR ^α R ^β and / or P ((O) _c -R ^γ ) ((O) _d -R ^δ ), the compounds of the general formula IV can be prepared, for example, with a halogen compound of the formula HalPR ^α R ^β or HalP ( (O) _c -R ^γ) ((O) _d -R ^δ) are reacted in the presence of a base. Hal is preferably Cl or Br. Suitable bases are, for example, aliphatic amines, such as diethylamine, dipropylamine, trimethylamine, triethylamine and tripropylamine.

Compounds HalPR ^α R ^β can be prepared, for example, in analogy to the method of Petersen et al., J. Am. Chem. Soc. 117, 7696 (1995) by reacting the pyrrole compound concerned, z. Pyrrole, indole, benzo triazole, carbazole, 2,2'-dipyrrolmethane, 2,2'-bisindole - with the appropriate Phosportrihalogenid, z. As phosphorus trichloride, in the presence of a tertiary amine, for. For example, triethylamine, wherein the stoichiometry of this reaction is observed. In analogy to this procedure, for. B. from the relevant Hydroxyarylpyrrol compounds by reaction with the phosphorus trihalide in the presence of a tertiary amine, the corresponding starting compounds HalPR ^α R ^β are obtained.

^Β for attachment of the groups PR ^α R and / or P ((O) _c -R ^γ) ((O) _d -R ^δ in the compounds of formula IV may also be the compounds of formula IV first with a phosphorus trihalide, preferably PCl ₃ , to give a compound of formula IV.1 results: (Hal) ₂ P- (X) _a -Y- (O) _b -P (Hal) ₂ (IV.1) Hal = Cl, Br

The compounds of formula IV.1 can then be reacted with compounds HR ^α , HR ^β (ie heterocyclic compounds which have a protonated ring nitrogen atom), HOR ^γ and HOR ^δ .

The previously described processes for the preparation of compounds of general formula I can Naturally be combined with each other, with the choice of the synthesis method and sequence of reaction steps in the field of expert Can s lies.

worin R^α, R^β, Y und Q die zuvor angegebenen Bedeutungen besitzen, sind in den folgenden Schemata wiedergegeben:

Various possible synthetic routes for the preparation of a compound of the formula I.1a

wherein R ^α , R ^β , Y and Q have the meanings given above, are shown in the following schemes:

Some particularly preferred diols for preparing bridging groups Y and / or Q are listed below by way of example:

worin R^I, R^II, R^III, R^IV, R^V, R^VI, A¹, A², D, L¹ und L² die zuvor angegebenen Bedeutungen besitzen und worin a, b und e für 0 stehen gemäß den von van Leuwen et al., Organometallics 14, 3081 (1995) angegebenen Methoden.The aforementioned diols or their analogs with other leaving groups are commercially available or can be prepared by conventional methods. Thus, for example, the preparation of starting compounds of general formula IV.a succeeds

wherein R ^I , R ^II , R ^III , R ^IV , R ^V , R ^VI , A ¹ , A ² , D, L ¹ and L ^{2 have} the meanings given above and wherein a, b and e are 0 according to those of van Leuwen et al., Organometallics 14, 3081 (1995).

The starting compounds of general formula IV.a with a, b = 1, e = 0, and L = H, z. B. from the corresponding 1,8-dibromo compounds of the general formula IV.a (a, b = 0, L ¹ , L ² = Br) z. By metalation with alkali metal organyls, such as n-butyllithium, tert-butyllithium or the like, followed by reaction with a borane, preferably BH ₃ and oxidation of the resulting diborane compound with a peroxide, preferably hydrogen peroxide in the presence of aqueous alkali metal hydroxide, preferably lithium, Sodium or potassium hydroxide.

The Preparation of other starting compounds IV.a with triptycene-like Carbon skeleton can in a known manner from the corresponding Anthrachinonderivaten on the corresponding anthracene precursors (preparation see, for example: J. Org. Chem. 45, 1807 (1980); J. Org. Chem. 38, 1167 (1973); Bull Chem. Soc. Jm. 44, 1649 (1971); J. Am. Chem. Soc. 34, 3089 (1969); J. Org. Chem. 39, 770 (1974); Chem. Ber. 124, 333 (1991); J. Org. Chem. 51, 921 (1986)) by their Diels-Alder reaction with the corresponding olefins, Acetylenes or arynes take place. Information on the implementation of this Diels-Alder reactions can be found in Chem. Ber. 119, 1016 (1986) and J.C.S. Chem. Comm. 961 (1999).

One for the preparation of the phosphorochelate compounds according to the invention suitable method using an auxiliary base which is capable of Salts with low melting point (ionic liquids) is in the WO 03/062251, which is incorporated herein by reference becomes.

One Another object of the invention is a catalyst which at least a complex with a transition metal comprising as ligands at least one compound of the general Formula I, as defined above contains. When using chiral Ligands then result in inventive chiral catalysts.

The catalysts according to the invention and used according to the invention have at least one of the compounds described above as ligands. In addition to the ligands described above, you can still at least one other ligand, which is preferably selected from halides, amines, carboxylates, acetylacetonate, aryl or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers, PF ₃ , phospholes, phosphabenzenes and mono-, bi- and polydentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite ligands.

Prefers it is the transition metal a metal of the I, VI, VII or VIII subgroup of the periodic table of the elements. More preferably, the transition metal is selected from among VIII subgroup metals (i.e., Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt). In particular, the transition metal is iridium, Ruthenium, rhodium, palladium or platinum.

Another object of the invention is a process for the preparation of chiral compounds by reacting a prochiral compound containing at least one ethylenically unsaturated double bond, with a substrate in the presence of a chiral catalyst, as described above. It is only necessary that at least one of the ligands used or the catalytically active species is chiral as a whole. In general, certain transition metal complexes are formed as catalytically active species under the reaction conditions of the individual processes for producing chiral compounds. For example, catalytically active species of the general formula H _x M _y (CO) _z L _{q are} formed under hydroformylation conditions from the particular catalysts or catalyst precursors used, where M is a Transition metal, L for a Phosphorchelatverbindung and q, x, y, z are integers, depending on the valence and type of metal and the ligand L, the ligand. Preferably z and q are independently of one another at least a value of 1, such. B. 1, 2 or 3. The sum of z and q is preferably from 1 to 5. In this case, the complexes may, if desired, additionally have at least one of the further ligands described above.

The Catalytically active species is preferably as a homogeneous single-phase solution in a suitable solvent in front. This solution can additionally contain free ligands.

Prefers it is in the process of the invention for the preparation chiral compounds to a hydrogenation, hydroformylation, hydrocyanation, Carbonylation, hydroacylation (intramolecular and intermolecular), Hydroamidation, hydroesterification, hydrosilylation, hydroboration, Aminolysis (hydroamination), alcoholysis (hydroxy-alkoxy-addition), Isomerization, transfer hydrogenation, metathesis, cyclopropanation, Aldol condensation, allylic alkylation or a [4 + 2] cycloaddition (Diets-Alder reaction).

Especially The process according to the invention is preferably for the production chiral compounds to a 1,2-addition, in particular a hydrogenation or a 1-hydro-2-carbo-addition. In the context of this invention means 1,2-addition that adds to the two neighboring atoms a C = X double bond (X = C, heteroatom) takes place. 1-hydro-2-carbo-addition referred to an addition reaction in which after the reaction to an atom of Double bond hydrogen and to the other a carbon atom-containing Group is bound. Double bond isomerizations during the Addition are allowed. In the context of this invention is intended with 1-Hydro-2-Carbo-Addition in unsymmetrical substrates not too a preferred addition of the carbon fragment to the C2 atom be designated because the selectivity with respect to the orientation of the Addition usually of the agent to be added and the used Catalyst dependent is. "1-Hydro-2-Carbo" is synonymous in this sense with "1-carbo-2-hydro-".

The Reaction conditions of the process according to the invention for the preparation Chiral compounds, except for the used chiral Catalyst, usually those of the corresponding non-asymmetric Method. Suitable reactors and reaction conditions may be the Professional thus the relevant Refer to literature for each procedure and adjust routinely. Suitable reaction temperatures are generally within a range from -100 up to 500 ° C, preferably in a range of -80 to 250 ° C. suitable reaction pressures are generally in a range from 0.0001 to 600 bar, preferably from 0.5 to 300 bar. The methods can generally be continuous, be carried out semicontinuously or discontinuously. Suitable reactors for the continuous implementation are known in the art and z. In Ullmann's Encyclopaedia of the technical chemistry, Bd. 1, 3. Aufl., 1951, S. 743 ff. described. Suitable pressure-resistant reactors are also known to the person skilled in the art and are z. In Ullmann's Enzyklopadie der technischen Chemie, Vol. 1, 3rd edition, 1951, p. 769 ff.

The processes according to the invention can be carried out in a suitable solvent which is inert under the respective reaction conditions. In general, suitable solvents are z. As aromatics, such as toluene and xylenes, hydrocarbons or mixtures of hydrocarbons. Also suitable are halogenated, in particular chlorinated hydrocarbons, such as dichloromethane, chloroform or 1,2-dichloroethane. Other solvents are esters of aliphatic carboxylic acids with alkanols, for example Essigester or Texanol ^®, ethers such as tert-butyl methyl ether, dioxane 1, 4 and tetrahydrofuran, and dimethylformamide. If the ligands are sufficiently hydrophilized, it is also possible to use alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones, such as acetone and methyl ethyl ketone, etc. Further, as a solvent and so-called "ionic liquids" can be used. These are liquid salts, for example N, N'-dialkylimidazolium salts such as N-butyl-N'-methylimidazolium salts, tetraalkylammonium salts such as tetra-n-butylammonium salts, N-alkylpyridinium salts such as n-butylpyridinium salts, tetraalkylphosphonium salts such as trishexyl ( tetradecyl) phosphonium salts, e.g. As the tetrafluoroborates, acetates, tetrachloroaluminates, hexafluorophosphates, chlorides and tosylates. As a solvent, it is also possible to use an educt, product or by-product of the particular reaction.

Suitable prochiral ethylenically unsaturated compounds for the process according to the invention are in principle all prochiral compounds which contain one or more ethylenically unsaturated carbon-carbon or carbon-heteroatom double bonds. These include generally prochiral olefins (hydroformylation, intermolecular hydroacylation, hydrocyanation, hydrosilylation, carbonylation, hydroamidation, hydroesterification, aminolysis, alcoholysis, cyclopropanation, hydroboration, Diels-Alder reaction, metathesis), unsubstituted and substituted aldehydes (intramolecular hydroacylie tion, aldol condensation, allylic alkylation), ketones (hydrogenation, hydrosilylation, aldol condensation, transfer hydrogenation, allylic alkylation) and imines (hydrogenation, hydrosilylation, transfer hydrogenation, Mannich reaction).

worin R^A und R^B und/oder R^C und R^D für Reste unterschiedlicher Definition stehen. Es versteht sich von selbst, dass zur erfindungsgemäßen Herstellung chiraler Verbindungen auch die mit der prochiralen ethylenisch ungesättigten Verbindung umgesetzten Substrate sowie unter Umständen auch die Stereoselektivität bezüglich der Anlagerung eines bestimmten Substituenten an ein bestimmtes C-Atom der C-C-Doppelbindung so gewählt werden, das zumindest ein chirales Kohlenstoffatom resultiert.Suitable prochiral ethylenically unsaturated olefins are generally compounds of the formula

wherein R ^A and R ^B and / or R ^C and R ^{D are} radicals of different definitions. It goes without saying that for the production of chiral compounds according to the invention, the substrates reacted with the prochiral ethylenically unsaturated compound and possibly also the stereoselectivity with respect to the addition of a particular substituent to a particular carbon atom of the CC double bond are chosen to be at least equal a chiral carbon atom results.

R ^A , R ^B , R ^C and R ^D are preferably selected, independently of one another, from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, thiol, polyalkylene oxide, Polyalkyleneimine, COOH, carboxylate, SO ₃ H, sulphonate, NE ¹⁶ E ¹⁷ , NE ¹⁶ E ¹⁷ E ¹⁸ X ^- , halo, nitro, acyl, acyloxy or cyano, where E ¹⁶ , E ¹⁷ and E ^{18 are} each the same or different radicals , selected from among hydrogen, alkyl, cycloalkyl, or aryl and X ^{- represents} an anion equivalent,
wherein the alkyl radicals 1, 2, 3, 4, 5 or more substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, COOH, carboxylate, SO ₃ H, sulfonate, NE ¹⁹ E ²⁰ , NE ¹⁹ E ²⁰ E ²¹ X ^- , halogen, nitro, acyl, acyloxy or cyano, wherein E ¹⁹ , E ²⁰ and E ^{21 are} each identical or different radicals selected from hydrogen, alkyl , Cycloalkyl, or aryl and X ^{- represents} an anion equivalent,
and wherein the cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals R ^A , R ^B , R ^C and R ^{D may} each have 1, 2, 3, 4, 5 or more substituents selected from alkyl and those previously described for the Alkyl radicals R ^A , R ^B , R ^C and R ^D substituents, or
two or more of R ^A , R ^B , R ^C and R ^D together with the ^C - ^C double bond to which they are attached represent a mono- or poly-cyclic compound.

suitable prochiral olefins are olefins having at least 4 carbon atoms and terminal or inside Double bonds that are straight-chain, branched or cyclic Structure are.

Suitable α-olefins are z. 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-octadecene, etc.

Suitable linear (straight-chain) internal olefins are preferably C ₄ -C ₂₀ -olefins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4-octene etc.

Suitable branched, internal olefins are preferably C ₄ -C ₂₀ -olefins, such as 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal mixtures of heptene, branched, internal Octene mixtures, branched, internal nonene mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures, etc.

Suitable olefins to be hydroformylated are furthermore C ₅ -C ₈ -cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as. B. their C ₁ -C ₂₀ alkyl derivatives having 1 to 5 alkyl substituents.

Suitable are also heteroatom-substituted olefins, z. Vinyl ethers, Vinyl esters, etc.

Suitable olefins to be hydroformylated are also vinylaromatics, such as styrene, α-methylstyrene, 4-isobutylstyrene, etc., 2-vinyl-6-methoxynaphthalene, (3-ethenylphenyl) phenyl ketone, (4-ethenylphenyl) -2-thienyl ketone, 4-ethenylbenzene 2-fluorobiphenyl, 4- (1,3-dihydro-1-oxo-2H-isoindol-2-yl) styrene, 2-ethenyl-5-benzoylthiophene, (3-ethenylphenyl) phenyl ether, propenylbenzene, 2-propenylphenol, isobutyl 4-propenylbenzene, phenylvinyl ethers and cyclic enamides, e.g. For example, 2,3-dihydro-1,4-oxazines, such as 2,3-dihydro-4-tert-butoxycarbonyl-1,4-oxazine. Suitable olefins to be hydroformylated are furthermore .alpha.,. Beta.-ethylenically unsaturated mono- and / or dicar Bonsäuren, esters, half esters and amides, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, 3-pentenoic acid methyl ester, 4-pentenoic acid methyl ester, methyl oleate, methyl acrylate, methyl methacrylate, unsaturated nitriles, such as 3-pentenenitrile, 4-pentenenitrile, acrylonitrile, Vinyl ethers, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., vinyl chloride, allyl chloride, C ₃ -C ₂₀ -alkenols, -alkene diols and -alkadienols, such as allyl alcohol, hex-1-en-4-ol, oct-1-ene-4 ol, 2,7-octadienol-1. Suitable substrates are also di- or polyenes with isolated or conjugated double bonds. These include z. 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene and butadiene homo- and copolymers.

Further as synthesis building blocks important prochiral ethylenically unsaturated compounds are z. B. p-isobutylstyrene, 2-vinyl-6-methoxynaphthalene, (3-ethenylphenyl) phenylketone, (4-ethenylphenyl) -2-thienyl ketone, 4-ethenyl-2-fluorobiphenyl, 4- (1,3-dihydro-1-oxo-2H-isoindol-2-yl) styrene. 2-ethenyl-5-benzoylthiophene, (3-ethenylphenyl) phenyl ether, propenylbenzene, 2-propenylphenol, isobutyl-4-propenylbenzene, Phenyl vinyl ethers and cyclic enamides, e.g. For example, 2,3-dihydro-1,4-oxazines, such as 2,3-dihydro-4-tert-butoxycarbonyl-1,4-oxazine.

The Olefins mentioned above can used singly or in the form of mixtures.

According to a preferred embodiment, the inventive and inventively used chiral catalysts are prepared in situ in the reactor used for the reaction. If desired, however, the catalysts according to the invention can also be prepared separately and isolated by customary processes. For in situ preparation of the catalysts of the invention can be z. B. at least one ligand used in the invention, a compound or complex of a transition metal, optionally at least one further additional ligand and optionally an activating agent in an inert solvent under the conditions of the reaction (eg., Under hydroformylation, Hydrocyanierungsbedingungen, etc.) , Suitable activating agents are, for. B. Bronsted acids, Lewis acids, such as. B. BF ₃ , AlCl ₃ , ZnCl ₂ , and Lewis bases.

When Catalyst precursors are quite generally suitable transition metals, transition metal compounds and transition metal complexes.

Suitable rhodium compounds or complexes are, for. Rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II) or rhodium ( III) carboxylate, rhodium (II) - and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, Trisammoniumhexachlororhodat (III), etc. Furthermore, rhodium complexes, such as Rh ₄ (CO ) ₁₂ , rhodiumbiscarbonylacetylacetonate, acetylacetonatobisethylenrhodium (I), etc.

Also suitable are ruthenium salts or compounds. Suitable ruthenium salts are, for example, ruthenium (III) chloride, ruthenium (IV), ruthenium (VI) or ruthenium (VIII) oxide, alkali metal salts of ruthenium oxygen acids such as K ₂ RuO ₄ or KRuO ₄ or complex compounds, such as. Ru (Cl) (PPh ₃ ) ₃ , (Ru (p-cymene) Cl) ₂ , (Ru (benzene) Cl) ₂ , (COD) Ru (methallyl) ₂ , Ru (acac) ₃ . The metal carbonyls of ruthenium such as dodecacarbonyltriruthenium or octadecacarbonylhexaruthenium, or mixed forms can, in which CO has been partly replaced by ligands of the formula PR _3, such as Ru (CO) ₃ (PPh _{3) 2,} used in the inventive method.

suitable Iron compounds are for. As iron (III) acetate and iron (III) nitrate and the carbonyl complexes of iron.

suitable Nickel compounds are nickel fluoride and nickel sulfate. A to Preparation of a nickel catalyst is suitable nickel complex z. Bis (1,5-cyclooctadiene) nickel (0).

Suitable are furthermore carbonyl complexes of iridium and osmium, osmium halides, Osmium octoate, palladium hydrides and halides, platinic acid, iridium sulfate, Etc.

The mentioned and other suitable transition metal compounds and complexes are known in principle and sufficient in the literature described or you can made by the skilled artisan analogous to the already known compounds become.

In general, the metal concentration in the reaction medium is in a range of about 1 to 10,000 ppm. The molar ratio of monopnicogen ligand to transition metal is generally in a range of about 0.5: 1 to 1000: 1, preferably 1: 1 to 500: 1.

Suitable is also the use of supported Catalysts. The catalysts described above can do this suitably, for. B. by connection via suitable as anchor groups functional groups, adsorption, grafting, etc. to a suitable Carrier, z. Example of glass, silica gel, resins, polymers, etc., immobilized become. They are then also suitable for use as solid phase catalysts.

To a first preferred embodiment If the process according to the invention is a hydrogenation (1,2-H, H-addition). This is achieved by implementing a prochiral A compound which has at least one ethylenically unsaturated double bond contains with hydrogen in the presence of a chiral catalyst, as before described, to corresponding chiral compounds with a single bond. Prochiral olefins lead to chiral carbonaceous Compounds of prochiral ketones to chiral alcohols and from prochiral imines to chiral amines.

A Another important 1-Hydro-2-Carbo-Addition is the reaction with Hydrogen cyanide, hereinafter called hydrocyanation.

Also the catalysts used for hydrocyanation include complexes a metal of VIII. Subgroup, in particular cobalt, nickel, Ruthenium, rhodium, palladium, platinum, preferably nickel, palladium and platinum, and most preferably nickel. The production the metal complexes can be done as previously described. The same applies to the in situ preparation of the hydrocyanation catalysts according to the invention. Methods for hydrocyanation are described in J. March, Advanced Organic Chemistry, 4th ed., Pp. 811-812, which is incorporated herein by reference becomes.

To a further preferred embodiment it is in the 1-hydro-2-carbo-addition to a reaction with Carbon monoxide and at least one compound with a nucleophilic Group, hereinafter referred to as carbonylation.

Also the carbonylation catalysts include complexes of a metal of the VIII subgroup, preferably nickel, cobalt, iron, ruthenium, Rhodium and palladium, especially palladium. The production of Metal complexes can be done as previously described. same for for the in situ preparation of the carbonylation catalysts according to the invention.

Preferably are the compounds having a nucleophilic group selected from Water, alcohols, thiols, carboxylic esters, primary and secondary Amines.

A preferred carbonylation reaction is the conversion of olefins with carbon monoxide and water to carboxylic acids (Hydrocarboxylation).

The carbonylation can be carried out in the presence of activating agents. Suitable activating agents are, for. B. Bronsted acids, Lewis acids, such as. B. BF ₃ , AlCl ₃ , ZnCl ₂ , and Lewis bases.

A Another important 1,2-addition is hydroacylation. How to get there in asymmetric intramolecular hydroacylation Reaction of an unsaturated Aldehydes to optically active cyclic ketones. In the asymmetric Intermolecular hydroacylation is achieved by reaction of a prochiral olefin with an acyl halide in the presence of a chiral Catalyst, as described above, to chiral ketones. suitable Hydroacylation procedures are described in J. March, Advanced Organic Chemistry, 4th ed., P. 811, incorporated herein by reference becomes.

A Another important 1,2-addition is hydroamidation. How to get there by reacting a prochiral compound which at least an ethylenically unsaturated Contains double bond, with carbon monoxide and ammonia, a primary or a secondary amine in the presence of a chiral catalyst as previously described to chiral amides.

A Another important 1,2-addition is hydroesterification. How to get there by reacting a prochiral compound which at least an ethylenically unsaturated Contains double bond, with carbon monoxide and an alcohol in the presence of a chiral Catalyst, as previously described, to chiral esters.

Another important 1,2-addition is hydroboration. Thus, by reacting a prochiral compound containing at least one ethylenically unsaturated double bond with borane or ei a borane source in the presence of a chiral catalyst, as described above, to chiral trialkylboranes, which can be oxidized to primary alcohols (eg with NaOH / H ₂ O ₂ ) or to carboxylic acids. Suitable hydroboration processes are described in J. March, Advanced Organic Chemistry, 4th Ed., Pp. 783-789, which is incorporated herein by reference.

Another important 1,2-addition is hydrosilylation. Thus, by reacting a prochiral compound containing at least one ethylenically unsaturated double bond with a silane in the presence of a chiral catalyst as described above, chiral silyl functionalized compounds are obtained. Prochiral olefins result in chiral silyl-functionalized alkanes. Prochiral ketones result in chiral silyl ethers or alcohols. In the hydrosilylation catalysts, the transition metal is preferably selected from Pt, Pd, Rh, Ru and Ir. It may be advantageous to use combinations or mixtures of one of the aforementioned catalysts with other catalysts. Examples of suitable additional catalysts include platinum in finely divided form ("platinum black"), platinum chloride and platinum complexes such as hexachloroplatinic acid or divinyldisiloxane-platinum complexes, e.g. B. Tetramethyldivinyldisiloxan-platinum complexes. Suitable rhodium catalysts are, for example, (RhCl (P (C ₆ H ₅ ) ₃ ) ₃ ) and RhCl ₃ . Ge are also suitable RuCl ₃ and IrCl ₃ . Suitable catalysts are also Lewis acids such as AlCl ₃ or TiCl ₄ and peroxides.

suitable Silanes are z. Halogenated silanes such as trichlorosilane, methyldichlorosilane, Dimethylchlorosilane and trimethylsiloxydichlorosilane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1,3,3 ', 5,5', 7,7'-heptamethyl-1,1'-dimethoxytetrasiloxane and acyloxysilanes.

The Reaction temperature in the silylation is preferably in one Range from 0 to 140 ° C, more preferably 40 to 120 ° C. The reaction usually becomes carried out under normal pressure, but can also be elevated at To press, such as B. in the range of about 1.5 to 20 bar, or reduced To press, such as B. 200 to 600 mbar done.

The Reaction can be without solvent or in the presence of a suitable solvent. When solvent for example, toluene, diethyl ether, tetrahydrofuran, Dichloromethane and chloroform.

A Another important 1,2-addition is aminolysis (hydroamination). Thus one arrives by conversion of a prochiralen connection, which contains at least one ethylenically unsaturated double bond, with ammonia, a primary or a secondary one Amine in the presence of a chiral catalyst, as previously described, to chiral primary, secondary or tertiary Amines. Suitable methods of hydroamination are described in J. March, Advanced Organic Chemistry, 4th ed., Pp. 768-770, whereupon is referred to here.

A Another important 1,2-addition is the alcoholysis (hydro-alkoxy addition). Thus one arrives by conversion of a prochiralen connection, which contains at least one ethylenically unsaturated double bond, with Alcohols in the presence of a chiral catalyst as previously described to chiral ethers. Suitable methods for alcoholysis are described in J. March, Advanced Organic Chemistry, 4th ed., Pp. 763-764, which is referred to here.

A Another important reaction is isomerization. This is how you get from a prochiral compound containing at least one ethylenic unsaturated Contains double bond, in the presence of a chiral catalyst as previously described to chiral connections.

A Another important reaction is cyclopropanation. How to get there one of a prochiral compound containing at least one ethylenic unsaturated Contains double bond, with a diazo compound in the presence of a chiral catalyst, as described above, to chiral cyclopropanes.

A Another important reaction is metathesis. How to get from a prochiral compound containing at least one ethylenically unsaturated double bond contains with another olefin in the presence of a chiral catalyst, as described above, to chiral hydrocarbons.

A Another important reaction is the aldol condensation. How to get there by reacting a prochiral ketone or aldehyde with a Silyl enol ethers in the presence of a chiral catalyst as described above to chiral aldols.

A Another important reaction is allylic alkylation. How to get there by reacting a prochiral ketone or aldehyde with a allylic alkylating agent in the presence of a chiral catalyst, as described above, to chiral hydrocarbons.

A Another important reaction is the [4 + 2] cycloaddition. How to get there by reacting a diene with a dienophile, at least of which a compound is prochiral, in the presence of a chiral catalyst, as previously described, to chiral cyclohexene compounds.

To a further preferred embodiment if the process according to the invention is a reaction with carbon monoxide and hydrogen, hereinafter referred to as hydroformylation referred to as.

The asymmetric hydroformylation may be in the presence of one of the previously solvents mentioned above.

The molar ratio of phosphorochelate compound to metal of VIII. Subgroup lies generally in the range of about 1: 1 to 1000: 1, preferably 2: 1 to 500: 1.

Prefers is a process which is characterized in that the hydroformylation catalyst in is prepared, wherein at least one inventively usable Ligands, a compound or a complex of a transition metal and optionally an activating agent in an inert solvent under the hydroformylation conditions to the reaction.

at the transition metal it is preferably a metal of the VIII. Subgroup of the Periodic Table of the Elements, particularly preferably cobalt, Ruthenium, iridium, rhodium and palladium. In particular, rhodium used.

The Composition of the method used in the process according to the invention Synthesis gas from carbon monoxide and hydrogen can in wide ranges vary. The molar ratio of carbon monoxide and hydrogen is usually about 5:95 to 70:30, preferably about 40:60 to 60:40. Particularly preferred a molar ratio of carbon monoxide and hydrogen in the range of about 1: 1.

The Temperature in the hydroformylation reaction is generally in a range of about 20 to 180 ° C, preferably about 50 to 150 ° C. In general the pressure is in a range of about 1 to 700 bar, preferably 1 to 600 bar, in particular 1 to 300 bar. The reaction pressure can dependent on from the activity the hydroformylation catalyst according to the invention used be varied. In general, the catalysts of the invention allow Based on phosphorus compounds a reaction in one Range of low pressures, such as in the range of 1 to 100 bar.

The used according to the invention and the hydroformylation catalysts of the invention can be settled according to usual, the method known to those skilled in the discharge of the hydroformylation reaction disconnect and can generally again for the hydroformylation can be used.

The asymmetric hydroformylation by the process according to the invention is characterized by a high stereoselectivity. Advantageously show the inventive and the invention used Catalysts also generally have a high regioselectivity. Farther the catalysts generally have high stability on the hydroformylation conditions, so with you in the Usually longer Catalyst life can be achieved than with the state of the Technically known catalysts based on conventional chelating ligands. advantageously, show the inventive and used according to the invention Catalysts continue to have high activity, so usually the corresponding aldehydes, or alcohols obtained in good yields become.

The inventive method allows the production of optically active products with high enantioselectivity and, if necessary, regioselectivity, e.g. B. in the hydroformylation. Enantiomeric excesses (ee) of at least 50%, preferably at least 60% and in particular at least 70% can be achieved become.

The Isolation of the products obtained succeeds according to customary, known in the art Method. These include for example, solvent extraction, Crystallization, distillation, evaporation z. In a wiper blade or falling film evaporator, etc.

The according to the inventive method Obtained optically active compounds can one or more consecutive reaction (s) be subjected. Such methods are known to the person skilled in the art. To counting for example, the esterification of alcohols, the oxidation of Alcohols to aldehydes, N-alkylation of amides, addition of aldehydes on amides, nitrile reduction, acylation of ketones with esters, acylation of amines, etc. For example, by asymmetric Hydroformylation obtained optically active aldehydes an oxidation to carboxylic acids, Reduction to alcohols, aldol condensation to α, β-unsaturated compounds, reductive Amination to amines, amination to imines, etc., be subjected.

A preferred derivatization involves the oxidation of one after the asymmetric according to the invention Hydroformylierungsverfahren prepared aldehyde to the corresponding optically active carboxylic acid. So can a variety of pharmaceutically important compounds, such as S-ibuprofen, S-naproxen, S-ketoprofen, S-suprofen, S-fluorobiprofen, S-indoprofen, S-tiaprofenic etc. are produced.

The phosphorochelate compounds according to the invention of general formula I and especially of formula I.1 are suitable not only for asymmetric hydroformylations, but more generally in particularly advantageous Way for use in hydroformylation processes. Another item The invention therefore provides a process for the hydroformylation of Compounds containing at least one ethylenically unsaturated double bond contained by reaction with carbon monoxide and hydrogen in Presence of a catalyst comprising at least one complex a metal of the VIII. Subgroup of the Periodic Table of the Elements with at least one phosphorochelate compound of the general formula I, as previously defined, as ligands.

The catalysts used for non-asymmetric hydroformylation have at least one of the previously described compounds of general formula I and especially of formula I.1 as ligands. In addition to the ligands described above, the hydroformylation catalysts may contain at least one further ligand, preferably selected from halides, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, Aromatics and heteroaromatics, ethers, PF ₃ , phospholes, phosphabenzenes and mono-, bi- and polydentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite ligands.

Prefers if the metal of the VIII. subgroup is cobalt, Ruthenium, rhodium, palladium, platinum, osmium or iridium, especially preferably cobalt, rhodium, ruthenium and iridium and in particular around rhodium.

In general, catalytically active species of the general formula H _x M _y (CO) _z L _{q are} formed under hydroformylation conditions from the particular catalysts or catalyst precursors used, where M is a metal of subgroup VIII, L is a phosphorus-containing compound of the formula I and q , x, y, z are integers depending on the valence and type of metal and the ligand L's binding. Preferably z and q are independently of one another at least a value of 1, such. B. 1, 2 or 3. The sum of z and q is preferably from 1 to 5. In this case, the complexes may, if desired, additionally have at least one of the further ligands described above.

To a preferred embodiment For example, the hydroformylation catalysts are used in situ for the hydroformylation reaction used reactor prepared. If desired, the catalysts of the invention but also prepared separately and isolated by conventional methods become. For in situ preparation of the catalysts of the invention can you z. B. at least one ligand used in the invention, a Compound or a complex of a metal of VIII. Subgroup, optionally at least one additional additional ligand and optionally an activator in an inert solvent under the hydroformylation conditions implement.

suitable Rhodium compounds or complexes are e.g. Rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, Potassium rhodium sulfate, Rhodium (II) or rhodium (III) carboxylate, rhodium (II) and rhodium (III) acetate, Rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III) etc. Furthermore, rhodium complexes, such as Rhodiumbiscarbonylacetylacetonat, Acetylacetonato-bis-ethyl rhodium (I), etc. Preferably, rhodium bis-carbonyl acetylacetonate or rhodium acetate used.

Also suitable are ruthenium salts or compounds. Suitable ruthenium salts are, for example, ruthenium (III) chloride, ruthenium (IV), ruthenium (VI) or ruthenium (VIII) oxide, alkali metal salts of Ruthenium oxygen acids such as K ₂ RuO ₄ or KRuO ₄ or complex compounds, such as. B. RuHCl (CO) (PPh ₃ ) ₃ . The metal carbonyls of ruthenium such as dodecacarbonyltriruthenium or octadecacarbonylhexaruthenium, or mixed forms can, in which CO has been partly replaced by ligands of the formula PR _3, such as Ru (CO) ₃ (PPh _{3) 2,} used in the inventive method.

suitable Cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, Cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, Cobalt carboxylates, such as cobalt acetate, cobalt ethylhexanoate, cobalt naphthanoate, and the cobalt-caproate complex. Again, you can the carbonyl complexes of cobalt such as dicobaltoctacarbonyl, tetracobalt dodecacarbonyl and Hexacobalthexadecacarbonyl be used.

The mentioned and other suitable compounds of cobalt, rhodium, Ruthenium and iridium are known in principle and in the literature adequately described or they can be analogous to the expert the already known compounds are produced.

Suitable activating agents are, for. B. Bronsted acids, Lewis acids, such as. B. BF ₃ , AlCl ₃ , ZnCl ₂ , and Lewis bases.

The solvents used are preferably the aldehydes which are formed in the hydroformylation of the respective olefins, and their higher-boiling secondary reaction products, for. B. the products of aldol condensation. Also suitable solvents are aromatics, such as toluene and xylenes, hydrocarbons or mixtures of hydrocarbons, also for diluting the above-mentioned aldehydes and the secondary products of the aldehydes. Further solvents are esters of aliphatic carboxylic acids with alkanols, for example ethyl acetate or Texanol ^™ , ethers, such as tert-butyl methyl ether and tetrahydrofuran.

Furthermore, it is also possible to carry out the reactions in water or aqueous solvent systems which contain, in addition to water, a water-miscible solvent, for example a ketone, such as acetone and methyl ethyl ketone, or another solvent. For this purpose, one uses ligands containing polar groups, for example ionic groups such as SO ₃ ^- M ⁺ , CO ₂ ^- M ⁺ with M ⁺ = Na ⁺ , K ⁺ or NH ₄ ⁺ or as N (CH ₃ ) ₄ ⁺ are modified. The reactions then take place in the sense of a two-phase catalysis, the catalyst being in the aqueous phase and starting materials and products forming the organic phase. Also, the implementation in the "Ionic Liquids" can be configured as two-phase catalysis.

The molar ratio from Phosphorchelatligand to metal of the VIII. Subgroup is located in Generally in a range of about 1: 1 to 1000: 1, preferably 2: 1 to 500: 1.

When Substrates for the non-asymmetric hydroformylation are in principle all Compounds which contain one or more ethylenically unsaturated double bonds contain. These include z. For example, olefins such as α-olefins, internal straight-chain and internal branched olefins. Preference is given to α-olefins, such as Ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, etc. used.

Suitable branched, internal olefins are preferably C ₄ -C ₂₀ -olefins, such as 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal mixtures of heptene, branched, internal Octene mixtures, branched, internal nonene mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures, etc.

Suitable olefins to be hydroformylated are furthermore C ₅ -C ₈ -cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as. B. their C ₁ -C ₂₀ alkyl derivatives having 1 to 5 alkyl substituents. Suitable olefins to be hydroformylated are furthermore vinylaromatics, such as styrene, α-methylstyrene, 4-isobutylstyrene etc. Suitable olefins to be hydroformylated are also α, β-ethylenically unsaturated mono- and / or dicarboxylic acids, their esters, half-esters and amides, such as acrylic acid, methacrylic acid , Maleic acid, fumaric acid, crotonic acid, itaconic acid, methyl 3-pentenoate, methyl 4-pentenoate, methyl oleate, methyl acrylate, methyl methacrylate, unsaturated nitriles such as 3-pentenenitrile, 4-pentenenitrile, acrylonitrile, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., C ₁ -C ₂₀ alkenols, alkenediols and alkadienols, such as 2,7-octadienol-1. Suitable substrates are also di- or polyenes with isolated or conjugated double bonds. These include z. 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene and butadiene homo- and copolymers.

In a suitable embodiment, the unsaturated compound used for the hydroformylation is selected from internal linear olefins and olefin mixtures containing at least one internal linear olefin. Suitable linear (straight-chain) internal olefins are preferably C ₄ -C ₂₀ -olefins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4-octene, etc., and mixtures thereof.

worin
Z für eine verbrückende Gruppe mit 1 bis 20 Brückenatomen zwischen den flankierenden Bindungen steht und
Fu für eine funktionelle Gruppe steht, und
n für eine ganze Zahl von 1 bis 4 steht.The novel catalysts used according to the invention are also advantageously suitable for the hydroformylation of functionalized olefins, in particular functionalized 1-olefins. The olefins to be hydroformylated are preferably selected from compounds of the general formula III

wherein
Z stands for a bridging group with 1 to 20 bridge atoms between the flanking bonds and
Fu stands for a functional group, and
n is an integer from 1 to 4.

The divalent bridging group Z preferably represents a C ₁ -C ₂₀ -alkylene bridge which, depending on the number of bridging atoms, may have one, two, three or four double bonds and / or one, two, three or four substituents. wherein the cycloalkyl, aryl and hetaryl substituents in turn can carry additional one, two or three substituents selected from alkyl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano, and / or 1 to 10 non-adjacent bridging atoms of C C ₁ -C ₂₀ -alkylene bridge Z may be replaced by a heteroatom or a heteroatom-containing group and / or the alkylene bridge Z may be fused once or twice with aryl and / or hetaryl, the fused aryl and hetaryl groups each one, two or three substituents selected from alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, acyl, halogen, trifluoromethyl, nitro, cyano, carboxyl, alkoxycarbonyl or NE ²² E ²³ (E ²² and E ²³ = hydrogen, alkyl, cycloalkyl, acyl or aryl) can carry.

Preferably, the functional group Fu is selected from -OH, -SH, -Cl, -Br, -COOR ³⁶ , -OC (= O) R ³⁷ , -OC (= O) -OR ³⁶ , -OC (=) - NR ³⁷ R ³⁸ , -NR ³⁸ -C (= O) -R ³⁷ , -NR ³⁸ -C (= O) -OR ³⁶ , -NR ³⁷ -C (= O) -NR ³⁸ R ³⁹
wherein
R ^{36 is} alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R ³⁷ , R ³⁸ and R ³⁹ are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

• – thermisches Cracken (Steamcracken),
• – katalytisches Dehydrieren und
• – chemisches Dehydrieren durch Chlorieren und Dehydrochlorieren.

Preferably, an industrially available olefin mixture is used in the hydroformylation process according to the invention, which contains in particular at least one internal linear olefin. These include z. As obtained by targeted ethene oligomerization in the presence of alkylaluminum Ziegler olefins. These are essentially unbranched olefins with terminal double bond and even number of carbon atoms. These include further obtained by ethene oligomerization in the presence of various catalyst systems olefins, eg. B. obtained in the presence of alkylaluminum chloride / titanium tetrachloride catalysts, predominantly linear α-olefins and obtained in the presence of nickel-phosphine complex catalysts according to the Shell Higher Olefin Process (SHOP) α-olefins. Suitable technically accessible olefin mixtures continue to be used in the paraffin-dehydrogenation of corresponding petroleum fractions, eg. As the so-called petroleum or diesel oil fractions obtained. For the conversion of paraffins, mainly of n-paraffins into olefins, essentially three methods are used:

• - thermal cracking (steam cracking),
• - catalytic dehydrogenation and
• - chemical dehydrogenation by chlorination and dehydrochlorination.

there does that thermal cracking predominantly to α-olefins, while the other variants give olefin mixtures, which in general also larger shares on olefins with internal Have double bond. Suitable olefin mixtures are still the olefins obtained in metathesis or telomerization reactions. These include z. The olefins from the Phillips triolefin process, a modified SHOP process from ethylene oligomerization, Double bond isomerization and subsequent metathesis (ethenolysis).

Suitable technical olefin mixtures which can be used in the hydroformylation process according to the invention are furthermore selected from dibutene, tributene, tetrabutene, diprophenene, tripropene, tetra propenes, mixtures of butene isomers, in particular as raffinate II, Dimerbutenen, Dihexenen, dimers and oligomers from the Dimersol ^® process of IFP, Octolprozess ^® from Hüls, Polygasprozess etc.

Prefers is a process which is characterized in that the hydroformylation catalyst in is prepared, wherein at least one inventively usable Ligands, a compound or a complex of a metal of VIII. Subgroup and optionally an activating agent in an inert solvent under the hydroformylation conditions to the reaction.

The Hydroformylation reaction can be continuous, semi-continuous or discontinuously.

suitable Reactors for the continuous reaction is known and will be known to the person skilled in the art z. In Ullmann's Encyclopaedia of the technical chemistry, Bd. 1, 3. Aufl., 1951, S. 743 ff. described.

suitable Pressure-resistant reactors are also known to the person skilled in the art and are z. In Ullmann's Encyclopaedia of technical chemistry, Vol. 1, 3rd edition, 1951, p. 769 et seq. In general, for the inventive method used an autoclave, if desired with a stirring device and an internal lining may be provided.

The Composition of the method used in the process according to the invention Synthesis gas from carbon monoxide and hydrogen can in wide ranges vary. The molar ratio of carbon monoxide and hydrogen is usually about 5:95 to 70:30, preferably about 40:60 to 60:40. Particularly preferred a molar ratio of carbon monoxide and hydrogen in the range of about 1: 1.

The Temperature in the hydroformylation reaction is generally in a range of about 20 to 180 ° C, preferably about 50 to 150 ° C. In general the pressure is in a range of about 1 to 700 bar, preferably 1 to 600 bar, in particular 1 to 300 bar. The reaction pressure can dependent on from the activity the hydroformylation catalyst according to the invention used be varied. In general, the catalysts of the invention allow Based on phosphorus compounds a reaction in one Range of low pressures, such as in the range of 1 to 100 bar.

The phosphorochelate compounds according to the invention and catalysts based thereon are particularly suitable for the hydroformylation of α-olefins and olefinic olefins containing internal olefins in a stepwise hydroformylation in reaction zones cascaded with respect to pressure and CO / H ₂ ratio. A particularly advantageous process is the process described in PCT / EP04 / 11530 for the continuous preparation of aldehydes having 5 to 21 carbon atoms by isomerizing hydroformylation in homogeneous phase of α-olefins and olefins with internal double bond-containing olefin compositions having 4 to 20 carbon atoms by means of synthesis gas in the presence of a complexed with an oxygen and / or nitrogen atoms organophosphorus ligands, homogeneous rhodium catalyst and free ligand, at elevated temperature and pressure in a multi-stage reaction system of at least two reaction zones, which is characterized in that the olefin composition in a group of one or more first reaction zones at a total pressure of 10 to 40 bar with synthesis gas of a CO / H ₂ molar ratio of 4: 1 to 1: 2 to a conversion of α-olefins of 40 to 95% and the Hydroformylierungsaustrag from this group of one or more first reaction zones in a group of one or more subsequent reaction zones at a total pressure of 5 to 30 bar with synthesis gas of a CO / H ₂ molar ratio of 1: 4 to 1: 1000, wherein the total pressure in the one or more subsequent reaction zones are each lower by at least 1 to (G1-Gf) bar than in the respective preceding reaction zone, where G1 is the total pressure in the preceding reaction zone and Gf is the total pressure in the reaction zone following the one or more first reaction zones provided that the difference G1-Gf is greater than 1 bar, and wherein the CO partial pressure in the one or more subsequent reaction zones is lower than in the respective preceding reaction zone. The disclosure of PCT / EP04 / 11530 is hereby incorporated by reference.

The used according to the invention and the hydroformylation catalysts of the invention can be settled according to usual, the method known to those skilled in the discharge of the hydroformylation reaction disconnect and can generally again for the hydroformylation can be used.

The catalysts described above can also be suitably, for. B. by attachment via suitable as anchor groups functional groups, adsorption, grafting, etc. to a suitable carrier, eg. Example of glass, silica gel, resins, polymers, etc., be immobilized. They are also suitable for egg NEN use as solid phase catalysts.

The hydroformylation of catalysts based on the ligands described above is surprising usually higher as the isomerization activity in terms of the formation of internal double bonds.

she are thus suitable for the hydroformylation of α-olefins, Olefins with internal Double bonds and olefin mixtures containing α-olefins and olefins with internal Double bonds included.

• a) Buten oder ein Buten enthaltendes C₄-Kohlenwasserstoffgemisch in Gegenwart eines Katalysators, wie zuvor definiert, mit Kohlenmonoxid und Wasserstoff unter Erhalt eines n-Valeraldehyd enthaltenden Hydroformylierungsprodukts hydroformyliert,
• b) gegebenenfalls das Hydroformylierungsprodukt einer Auftrennung unter Erhalt einer an n-Valeraldehyd angereicherten Fraktion unterzieht,
• c) das in Schritt a) erhaltene Hydroformylierungsprodukt oder die in Schritt b) erhaltene an n-Valeraldehyd angereicherte Fraktion einer Aldolkondensation unter zieht,
• d) die Produkte der Aldolkondensation mit Wasserstoff katalytisch zu Alkoholen hydriert, und
• e) gegebenenfalls die Hydrierprodukte einer Auftrennung unter Erhalt einer an 2-Propylheptanol angereicherten Fraktion unterzieht.

Another object of the invention is a process for the preparation of 2-propylheptanol, in which

• a) hydroformylating butene or a butene-containing C ₄ -hydrocarbon mixture in the presence of a catalyst as defined above with carbon monoxide and hydrogen to obtain a n-valeraldehyde-containing hydroformylation product,
• b) optionally subjecting the hydroformylation product to a separation to give a fraction enriched in n-valeraldehyde,
• c) pulling the hydroformylation product obtained in step a) or the fraction of aldol condensation enriched in n-valeraldehyde obtained in step b),
• d) hydrogenating the products of the aldol condensation with hydrogen catalytically to alcohols, and
• e) optionally subjecting the hydrogenation products to a separation to give a fraction enriched in 2-propylheptanol.

a) hydroformylation

Suitable starting materials for the hydroformylation are both essentially pure 1-butene and mixtures of 1-butene with 2-butene and industrially available C ₄ -hydrocarbon streams which contain 1-butene and / or 2-butene. C ₄ cuts which are available in large quantities from FCC units and steam crackers are preferably suitable. These consist essentially of a mixture of the isomeric butenes and butane.

Suitable feedstock C ₄ hydrocarbon streams contain z. B. 50 to 99, preferably 60 to 90 mol% of butenes and 1 to 50, preferably 10 to 40 mol% of butanes. Preferably, the butene fraction comprises 40 to 60 mole% of 1-butene, 20 to 30 mole% of 2-butene and less than 5 mole%, more preferably less than 3 mole% of isobutene (based on the butene fraction). As a particularly preferred feedstock, the so-called raffinate II is used, which is an isobutene-depleted C _{4 cut} from an FCC plant or a steam cracker.

hydroformylation based on the invention used Phosphor chelate compounds as ligands advantageously have a high n-selectivity, also when using 2-butene and 2-butene-containing hydrocarbon mixtures as a feedstock. Thus, you can in the method according to the invention Even such feedstocks are used economically, as the aspired n-valeraldehyde results in good yields.

b) separation

To a suitable variant of the method is in step a) after Separation of the catalyst system obtained product-enriched Fraction of a further separation to obtain an n-valeraldehyde enriched Subjected to fraction. The separation of the hydroformylation product in a n-valeraldehyde enriched fraction and an n-valeraldehyde Depleted fraction is carried out according to customary, known in the art Method. Preferably, the distillation is using known Separation apparatus, such as distillation columns, z. B. tray columns, if desired with bells, sieve plates, sieve trays, Valves etc. equipped could be, Evaporators, such as thin-film evaporators, Falling film evaporator, wiper blade evaporator etc.

c) Aldol condensation

Two molecules of C ₅ aldehyde can be condensed to form α, β-unsaturated C ₁₀ aldehydes. The aldol condensation is carried out in a known manner z. B. by the action of an aqueous base, such as sodium hydroxide or potassium hydroxide. Alternatively, a heterogeneous basic catalyst, such as magnesium and / or Alu minium oxide, are used (see, for example, EP-A 792 862). This results in the condensation of two molecules of n-valeraldehyde 2-propyl-2-heptenal. If the hydroformylation product obtained in step a) or after the separation in step b) has further C ₅ -aldehydes, such as 2-methylbutanal, 3-methylbutanal and optionally 2,2-dimethylpropanal, these likewise undergo an aldol condensation, in which case the condensation products of all possible aldehyde combinations result, for example, 2-propyl-4-methyl-2-hexenal. A proportion of these condensation products, eg. B. of up to 30 wt .-%, is an advantageous further processing to softener alcohols suitable 2-propylheptanol-containing C ₁₀ -alcohol mixtures not contrary.

d) hydrogenation

The products of the aldol condensation can be catalytically hydrogenated with hydrogen to form C ₁₀ -alcohols, in particular 2-propylheptanol.

For the hydrogenation of the C ₁₀ -aldehydes to the C ₁₀ -alcohols, the catalysts of the hydroformylation are generally also suitable at relatively high temperature; in general, however, more selective hydrogenation catalysts are preferred, which are used in a separate hydrogenation step. Suitable hydrogenation catalysts are generally transition metals, such as. B. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc., or mixtures thereof, to increase the activity and stability on carriers such. As activated carbon, alumina, diatomaceous earth, etc. can be applied. To increase the catalytic activity Fe, Co and preferably Ni, also in the form of the Raney catalysts, can be used as metal sponge with a very large surface area. The hydrogenation of the C ₁₀ aldehydes takes place as a function of the activity of the catalyst, preferably at elevated temperatures and elevated pressure. Preferably, the hydrogenation temperature is about 80 to 250 ° C, preferably the pressure is about 30 to 300 bar.

The crude hydrogenation product may be prepared by conventional methods, e.g. B. by distillation, are worked up to the C ₁₀ alcohols.

e) separation

If desired, can the hydrogenation of a further separation to obtain a on 2-propylheptanol enriched fraction and one on 2-propylheptanol be subjected to depleted fraction. This separation can according to usual, known in the art methods such. B. by distillation.

The Inventors have also found that in the continuous Preparation of aldehydes by isomerizing hydroformylation of α-olefins and olefins having internal double bond-containing olefin compositions the required reactor volumes compared to those known from the prior art Procedures can be lowered. This advantage results independently from the catalyst system used for the hydroformylation. The Hydroformylation takes place in a two-stage reaction system, wherein the discharge from the second reaction stage is still unreacted Separated stream containing olefins and again in the second reaction stage is fed.

• – in die erste Reaktionsstufe einen olefinhaltigen Zulauf, Kohlenmonoxid und Wasserstoff einspeist und teilweise katalytisch umsetzt,
• – den Austrag aus der ersten Reaktionsstufe in die zweite Reaktionsstufe einspeist und weiter umsetzt,
• – vom Austrag aus der zweiten Reaktionsstufe einen im Wesentlichen aus nicht umgesetzten Olefinen und gesättigten Kohlenwasserstoffen bestehenden Strom abtrennt und zumindest teilweise in die zweite Reaktionsstufe einspeist.

Another object of the invention is therefore a process for the hydroformylation of an α-olefins and olefins containing internal double bonds composition by reaction with carbon monoxide and hydrogen in the presence of a hydroformylation in a two-stage reaction system in which

• - In the first reaction stage, an olefin-containing feed, carbon monoxide and hydrogen feeds and partially catalytically,
• - feeds the discharge from the first reaction stage into the second reaction stage and further converts,
• - Separates a current consisting essentially of unreacted olefins and saturated hydrocarbons from the effluent from the second reaction stage and feeds at least partially into the second reaction stage.

The reaction system used according to the invention has two reaction stages, each of which may comprise one or more, identical or different reactors. Both the reactors of each individual stage and the reactors forming the various stages of the reactor cascade according to the invention may each have the same or different mixing characteristics. If desired, the individual reactors of the two stages can be subdivided one or more times by means of internals. If two or more reactors form a single stage of the reaction system, these may be interchangeable be nicely interconnected, z. B. parallel or in series. Suitable reactor circuits of each stage are, for. In Dialer, Leo, monograph from Winnacker, Kuchler, Chemical Technology, Volume 7, 3rd edition 1975, Chapter 4 described. In the simplest case, a reaction stage is formed from a single reactor. In principle, all types of reactor suitable for hydroformylation reactions can be used as reactors in the process according to the invention, for example stirred reactors, bubble column reactors as described, for example, in US Pat. As described in US-A-4,778,929, circulating reactors such as. B. Subject of
EP-A-1 114 017 are tubular reactors, wherein the individual reactors of a series may have different mixing characteristics, such as e.g. For example, described in EP-A-423 769, further compartmented reactors can be used, as described for. Are the subject of EP-A-1 231 198 or US-A-5 728 893.

includes a reaction stage several reactors, can in this reaction stage same or different reactor types are used, as well can from reaction stage to reaction stage identical or different reactor types be used. Preferably, the same in the two reaction stages Reactor types used, for. B. circulation reactors or stirred tank.

The reaction conditions, such. As the residence time, the temperature, the total synthesis gas pressure, the CO and H ₂ partial pressure, etc. may be the same or different in the individual stages and reactors of the cascade.

Preferably become the reaction conditions in the first reaction stage so selected that the conversion of the α-olefin is larger as the turnover of the olefin with internal double bonds. Preferably be at least 30 wt .-% in the first reaction stage, especially preferably at least 40% by weight and in particular at least 70% by weight the α-olefins contained in the olefin-containing feed to the corresponding reacted n-aldehydes. Preferably, the n-portion of the α-olefins formed aldehydes at least 92 wt .-%, in particular at least 96% by weight. The reaction of the α-olefins preferably takes place without it to a greater extent to an isomerization of terminal double bonds to internal double bonds comes. The extent of this isomerization is preferably at most 50 Wt .-%, more preferably at most 30 wt .-% and in particular at most 10% by weight. Preferably, the reaction conditions in the second Reaction stage chosen so in that essentially those contained in the olefin-containing feed Olefins are reacted with internal double bonds. This takes place at least partially an isomerizing hydroformylation. Consequently be according to the inventive method Aldehydes with a higher n / iso ratio obtained, than the proportion of α-olefins in the olefin-containing feed corresponds. It is generally additionally the space-time yield higher as with conventional Procedure without the return of unreacted olefins in the second reaction stage.

The Reaction temperature in the two reaction stages is generally 50 to 200 ° C, preferably 50 to 150 ° C and more preferably 70 to 130 ° C. The invention described above and the closer in the following described hydroformylation allow advantageously an implementation in the area of low overall syngas pressures, such as approximately in the range of 1 to 100 bar. A suitable total pressure is in the range of about 5 to 70 bar, more preferably 10 to 40 bar and in particular 10 to 30 bar, especially 10 to 25 bar.

The recycling according to the invention of unreacted olefins obtained from the discharge of the second reaction stage into the second reaction stage is particularly advantageously suitable as an embodiment of the process described in PCT / EP04 / 11530 for the continuous preparation of aldehydes. The first reaction stage has a total synthesis gas pressure in the range from 10 to 40 bar and a CO / H ₂ molar ratio in the range from 4: 1 to 1: 2. In this procedure, predominantly α-olefins are reacted in the first reaction stage. Preferably, the conversion of the α-olefins in the first reaction stage in this embodiment is in a range of 40 to 95%. The total synthesis gas pressure in the second reaction stage in this procedure is in a range of 5 to 13 bar with a CO / H ₂ molar ratio in the range of 1: 4 to 1: 1000. In this case, for the individual reaction zones forming the two reaction stages, the total pressure in each subsequent reaction zone is lower by at least 1 to (G1-GF) bar than in the respective preceding reaction zone, G1 for the total pressure in the preceding reaction zone and GF for the total pressure in the one or more first reaction zones each subsequent reaction zone. This is true with the proviso that the difference G1 - GF is greater than 1 bar and wherein the CO partial pressure in the one or more subsequent reaction zones is in each case lower than in the respective preceding reaction zone. This process thus forms two reaction stages, in which α-olefins are reacted in particular in the first reaction stage and in the second reaction stage essentially olefins having internal double bonds are reacted. Regarding appro In order to obtain preferred reaction parameters of this process, reference is made to PCT / EP04 / 11530 in its entirety.

Of the Hydroformylation output from a reaction stage may be before entry relaxed in the subsequent reaction stage, the aldehydes formed separated and the unreacted olefins for hydroformylation be supplied to the subsequent reaction stage. Preferably according to the invention no Such workup of the hydroformylation from a Reaction stage made prior to its entry into the next reaction stage. The hydroformylation discharge is preferably from a reaction stage relaxed directly into the subsequent reaction stage. This advantageous Embodiment of the method according to the invention becomes especially in the embodiment according to PCT / EP04 / 11530 thereby possible, that the total pressure in the subsequent reaction stage is lower is as in the preceding reaction stage.

The two-stage process according to the invention is suitable for the hydroformylation of olefin compositions of preferably aliphatic C ₄ to C ₂₀ olefins which contain internal and terminal double bonds and may be straight-chain or branched. Examples of such olefin compositions are 1-butene / 2-butene mixtures as described, for. B. incurred industrially as raffinate II. Raffinate II is the C ₄ -olefin fraction obtained after separation of butadienes and acetylenes and subsequent separation of isobutene from the C _{4 cut} of steam crackers, which generally has the following composition:
0.5 to 5% by weight of isobutane
5 to 20% by weight of n-butane
From 20 to 40% by weight of trans-2-butene
10 to 20% by weight of cis-2-butene
From 25 to 55% by weight of 1-butene
0.5 to 5 wt .-% isobutene
and trace gases such as 1,3-butadiene, propadiene, propene, cyclopropane, methylcyclopropane and vinylacetylene.

Other suitable olefin compositions are e.g. B. pentene mixtures, such they z. B. in the acid-catalyzed Codimerization of ethene and propene are formed, mixtures of hexene from the acid or nickel-catalyzed (Dimersol method) provincimerization or from metathesis processes, such as In EP-A-1 069 101 and EP-A-1 134 271, Heptengemische, z. B. from the acid or Nickel-catalyzed codimerization of propene and butene, octene mixtures from the dimerization of butenes, for example according to US-A-5 849 972, nonen mixtures z. From the acid catalyzed propentrimerization, decene mixtures, z. B. from the acid-catalyzed Dimerization of pentenes, undecen mixtures z. B. from the codimerization of pentenes and hexenes, dodecene mixtures, e.g. B. from the acid-catalyzed Tetramerization of propene, the trimerization of butene mixtures, z. B. according to US-A-5 849,972 and / or dimerization of hexene mixtures e.g. B. according to WO 00/53546, Hexadecengemische, z. B. from the tetramerization of butene mixtures, z. B. according to US-A-5 849,972, octadecene mixtures e.g. B. from the dimerization of nonionic mixtures and / or mixtures of eicosene from the dimerization of decene or the tetramerization of pentene mixtures. It does not need any further explanation, that of course also compositions of olefins of different carbon number in the process according to the invention can be used. Such olefin compositions with different carbon number can z. By metathesis of butenes, as in EP-A-1 134 271 and EP-A-1 069 101 described, or about the SHOP process or the Fischer-Tropsch process. A Compilation of various suitable methods of preparation of compositions of higher Olefins can be found, for. B. in Weissermel, Arpe: Industrial Organic Chemie, pages 82-99, 5th edition, Wiley-VCH, Weinheim 1998. The according to the invention from these Olefin compositions available Aldehydes serve for. B. as a starting material for the production of plasticizer and surfactant alcohols derived therefrom either directly e.g. B. by hydrogenation of the aldehyde to the alcohol or over The stages of aldolization and hydrogenation can be obtained as z. B. 2-Propylheptanol, by the aldolization of valeraldehyde (obtained by the hydroformylation of raffinate II) followed by hydrogenation of the aldolization product 2-propylheptenal can be produced.

By way of example only, and not by way of limitation, representative of individual olefinic compounds which may be present in such olefin compositions are listed below:
Butenes such as 1-butene, 2-butene and isobutene, pentene such as 1-pentene, 2-pentene, 2-methyl-1-butene and 2-methyl-2-butene, hexenes such as 1-hexene, 2-hexene , 3-hexene, 2-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene and 3-methyl-1-pentene, heptene, such as 1-heptene, 2-heptene, 3 Heptene and the various isomers of methyl hexene, octenes, such as 1-octene, 2-octene, 3-octene, 4-octene and branched octenes with inside permanent or terminal double bond, nonenes, such as 1-nonene, 2-nonene, 3-nonene, 4-nonene and branched nonenes with internal or terminal double bond, decenes, such as 1-decene, 2-decene, 3-decene, 4 -Decene, 5-decene and branched decene with internal or terminal double bond, undecenes, such as 1-undecene, 2-undecene, 3-undecene, 4-undecene, 5-undecene and branched undecenes with internal or terminal double bond, dodecenes, such as 1-dodecene, 2-dodecene, 3-dodecene, 4-dodecene, 5-dodecene, 6-dodecene and branched dodecenes with internal or terminal double bond. Likewise, tetradecenes, pentadecenes, hexadecenes, heptadecenes, octadecenes, nonadecenes and eicosenes.

The in the process according to the invention usable olefin compositions may also contain diolefins, for example, α-ω-diolefins, such as 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene or 1,9-decadiene, as well as diolefins with both internal and external terminal Double bonds, such as 1,3-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,3-nonadiene, 1,4-nonadiene, 1,5-nonadiene, 1,6-nonadiene, 1,7-nonadiene, 1,3-decadiene, 1,4-decadiene, 1,5-decadiene, 1,6-decadiene, 1,7-decadiene, 1,8-decadiene.

The two-stage according to the invention Hydroformylation process is preferably carried out homogeneously in the reaction medium dissolved Rhodium catalysts performed, which are complexed with a phosphorus ligand containing the ability has under the reaction conditions according to the invention Isomerizing to hydroformylate olefins with internal double bonds and only a relatively low tendency to isomerization of terminal to internal double bonds under the reaction conditions according to the invention Has. Conveniently, the ligand is re of rhodium in excess used, generally with a ligand / Rh molar ratio of From 2 to 300, preferably from 2 to 20 and more preferably from 2 to 10.

The rhodium concentration in the liquid reaction mixture is generally from 10 to 500 ppm by weight, preferably from 30 to 350 ppm by weight, and more preferably from 50 to 300 ppm by weight. As rhodium source z. As rhodium salts such as rhodium acetate, rhodium chloride or rhodium nitrate, rhodium complexes such as rhodium acetylacetonate and / or rhodium carbonyl compounds such as Rh (CO) ₂ acac, Rh ₄ (CO) ₁₂ or Rh ₆ (CO) ₁₆ are used (acac: acetylacetonate). The type of rhodium source used is generally not critical to the outcome of the process of the invention.

to Hydroformylation becomes the rhodium compound serving as a rhodium source generally dissolved or suspended in the reaction mixture, as well the ligand to be used. The hydroformylation-active rhodium complex catalyst then forms in situ in the hydroformylation reactor, under the Conditions of hydroformylation reaction, d. H. under the influence from carbon monoxide and hydrogen to those containing the phosphorus Ligand complexed rhodium compound. It goes without saying that too preformed Rhodium catalyst complexes are added to the reaction mixture can.

The two-stage according to the invention Process is preferably carried out in homogeneous phase, i. H. the olefin to be hydroformylated, which is homogeneous in the reaction mixture dissolved Rhodiumhydroformylierungskatalysator, free ligand and the formed aldehyde are in a liquid phase, d. H. the inventive method does not relate to hydroformylation in two juxtaposed liquid Phases.

The hydroformylation process according to the invention can advantageously be carried out in the presence of solvents. The solvents used are preferably those aldehydes which are formed in the hydroformylation of the respective olefins, and their higher-boiling secondary reaction products, for. B. the products of aldol condensation. Also suitable solvents are aromatics, such as toluene and xylenes, hydrocarbons or mixtures of hydrocarbons, which can also serve to dilute the above-mentioned aldehydes and the secondary products of the aldehydes. Other solvents are esters of aliphatic carboxylic acids with alkanols, for example Essigester or Texanol ^®, ethers such as tert-butyl methyl ether and tetrahydrofuran. If the ligands are sufficiently hydrophilized, it is also possible to use alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones, such as acetone and methyl ethyl ketone, etc. Further, as a solvent and so-called "ionic liquids" can be used. These are liquid salts, for example N, N'-di-alkylimidazolium salts such as N-butyl-N'-methylimidazolium salts, tetraalkylammonium salts such as tetra-n-butylammonium salts, N-alkylpyridinium salts such as n-butylpyridinium salts, tetraalkylphosphonium salts such as Trishexyl (tetradecyl) phosphonium salts, e.g. As the tetrafluoroborates, acetates, tetrachloroaluminates, hexafluorophosphates, chlorides and To sylate.

In the second reaction stage is suitably, based on the olefin fed into this stage, a partial conversion per pass instead of. The turnover is generally 10 to 90% based on the fed into the second stage Olefin.

Of the Discharge from the second reaction stage is generally one subjected to single or multi-stage separation operation, wherein at least a stream containing the majority of the hydroformylation product, a substantially unreacted olefin and saturated Hydrocarbon existing stream and a hydroformylation catalyst containing stream. Depending on the discharge procedure optionally further streams obtained, such as synthesis gas-containing exhaust gases and high-boiling by-products the hydroformylation, the - optionally after work up - completely or partially recycled to the first and / or the second reaction stage or be removed from the process.

Conveniently, receives consisting essentially of unreacted olefin and saturated hydrocarbon existing current, however, by the fact that one of the discharge from the second Reaction step first separates a crude hydroformylation product, which contains unreacted olefin and saturated hydrocarbon dissolved, and then subjecting the crude hydroformylation product to a separation step, where a current is generated, consisting essentially of unreacted olefin and saturated Hydrocarbon exists. For separation, the crude hydroformylation product relaxed, heated and / or treated with a stripping gas, such as synthesis gas or nitrogen become. Conveniently, you lead the separation in a column, wherein the crude hydroformylation product is fed in the column center, at the bottom of the column freed from the unreacted olefin and saturated hydrocarbon Hydroformylation product is removed, the further workup supplied becomes, and at the column head a liquid one or gaseous Electricity is withdrawn, consisting essentially of unreacted olefin and saturated Hydrocarbon exists.

The Separation of the crude hydroformylation product from the discharge the second reaction stage is carried out in such a way that the exceptions are in excess Synthesis gas used for the hydroformylation, liquid discharge is expanded from the reaction zone, wherein as a result of the reduction in pressure the discharge into a liquid phase, which consists essentially of high-boiling by-products, the homogeneous dissolved Hydroformylation catalyst and small amounts of hydroformylation product, consists of unreacted olefin and saturated hydrocarbon, and a gaseous phase consisting essentially of hydroformylation product, unreacted olefin and saturated Hydrocarbon and unreacted synthesis gas consists, separated becomes. The liquid phase can be used as a recycle stream be directed back to the first reaction stage. At least Partial condensation of the gaseous phase becomes the crude hydroformylation product receive.

The enclosed 1 schematically shows a suitable for carrying out the two-stage process of the invention suitable for the preparation of hydroformylation products of 1-butene and 2-butene. Self-evident plant details, which are not required for the understanding of the present invention, have been omitted. Over the lines ( 1a ) and ( 1b ) are added to the reactor ( 1 ) an olefin-containing feed containing 1-butene and 2-butene, and synthesis gas fed through the pipeline ( 3a ) is supplied to a liquid stream consisting essentially of high-boiling by-products and the homogeneously dissolved hydroformylation catalyst. From the hydroformylation catalyst ( 1 ) is continuously a liquid stream ( 1c ) and into the hydroformylation reactor ( 2 ) relaxed the subsequent reaction stage. From this subsequent reactor ( 2 ) is transmitted via line ( 2a ) continuously withdrawn a liquid hydroformylation mixture and into a flash vessel ( 3 ) relaxed. In this case, a separation into a substantially higher-boiling by-products of the hydroformylation and the homogeneously dissolved hydroformylation catalyst existing liquid stream is carried out via pipeline ( 3a ) is returned to the first reactor and a gaseous stream ( 3b ), the distillation column ( 4 ). The liquid fraction from the distillation column ( 4b ), which consists essentially of the oxo product, is sent for further recovery. The top of the distillation column ( 4 ) obtained from unreacted olefins and saturated hydrocarbon ( 4a ) is fed with partial discharge again the second reaction stage.

As double bond isomerization-active catalysts for the two-stage process according to the invention, the previously described inventive phosphorus chelate compounds of general formula I and especially of general formula I.1 can be used. Other isomerizing hydroformylation catalysts are described below. The substituents used in each case have and variables not the meanings listed above in the phosphorochelate compounds according to the invention, but those mentioned in the respective formula.

in der
Q eine Brückengruppe der Formel

ist,
worin
A¹ und A² unabhängig voneinander für O, S, SiR^aR^b, NR^c oder CR^dR^e stehen, wobei
R^a, R^b und R^c unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
R^d und R^e unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen oder gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, eine Cycloalkylidengruppe mit 4 bis 12 Kohlenstoffatomen bilden oder die Gruppe R^d gemeinsam mit einer weiteren Gruppe R^d oder die Gruppe R^e gemeinsam mit einer weiteren Gruppe R^e eine intramolekulare Brückengruppe D bilden,
D eine zweibindige Brückengruppe, ausgewählt aus den Gruppen

ist, in denen
R⁹ und R¹⁰ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, Carboxyl, Carboxylat oder Cyano stehen oder miteinander zu einer C₃- bis C₄-Alkylenbrücke verbunden sind,
R¹¹, R¹², R¹³ und R¹⁴ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, COOH, Carboxylat, Cyano, Alkoxy, SO₃H, Sulfonat, NE¹E², Alkylen-NE¹E²E³⁺X^–, Acyl oder Nitro stehen,
c 0 oder 1 ist,
Y eine chemische Bindung darstellt,
R⁵, R⁶, R⁷ und R⁸ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, COOR^f, COO^–M⁺, SO₃R^f, SO^– ₃M⁺, NE¹E², NE¹E²E³⁺X^–, Alkylen-NE¹E²E³⁺X^–, OR^f, SR^f, (CHR^gCH₂O)_xR^f, (CH₂N(E¹))_xR^f, (CH₂CH₂N(E¹))_xR^f, Halogen, Trifluormethyl, Nitro, Acyl oder Cyano stehen,
worin
R^f, E¹, E² und E³ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl oder Aryl bedeuten,
R^g für Wasserstoff, Methyl oder Ethyl steht,
M⁺ für ein Kation steht,
X^– für ein Anion steht, und
x für eine ganze Zahl von 1 bis 120 steht,
oder
R⁵ und/oder R⁷ zusammen mit zwei benachbarten Kohlenstoffatomen des Benzolkerns, an den sie gebunden sind, für ein kondensiertes Ringsystem, mit 1, 2 oder 3 weiteren Ringen stehen,
a und b unabhängig voneinander die Zahl 0 oder 1 bedeuten
P für Phosphor
und
R¹, R², R³, R⁴ unabhängig voneinander für Hetaryl, Hetaryloxy, Alkyl, Alkoxy, Aryl, Aryloxy, Cycloalkyl, Cycloalkoxy, Heterocycloalkyl, Heterocycloalkoxy oder eine NE¹E²-Gruppe stehen, mit der Maßgabe, dass R¹ und R³ über das Stickstoffatom an das Phosphor P gebundene Pyrrolgruppen sind oder worin R¹ gemeinsam mit R² und/oder R³ gemeinsam mit R⁴ eine mindestens eine über das pyrrolische Stickstoffatom an das Phosphoratom P gebundene Pyrrolgruppe enthaltende zweibindige Gruppe E der Formel Py-I-W bilden, worin
Py eine Pyrrolgruppe ist,
I für eine chemische Bindung oder für O, S, SiR^aR^b, NR^c oder CR^hRⁱ steht,
W für Cycloalkyl, Cycloalkoxy, Aryl, Aryloxy, Hetaryl oder Hetaryloxy steht,
und
R^h und Rⁱ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
oder eine über die Stickstoffatome an das Phosphoratom P gebundene Bispyrrolgruppe der Formel Py-I-Py bilden.Suitable as isomerizing hydroformylation catalysts in the process according to the invention are, for example, rhodium complexes with phosphoramidite ligands of the general formula V,

in the
Q is a bridging group of the formula

is
wherein
A ¹ and A ² are each independently O, S, SiR ^a R ^b , NR ^c or CR ^d R ^e , wherein
R ^a , R ^b and R ^c independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R ^d and R ^e independently represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or together with the carbon atom to which they are attached form a cycloalkylidene group having 4 to 12 carbon atoms or the group R ^d together with another group R ^d or the group R ^e together with another group R ^{e form} an intramolecular bridging group D,
D is a divalent bridging group selected from the groups

is where
R ⁹ and R ¹⁰ independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano, or are joined together to form a C ₃ -C ₄ -alkylene bridge,
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, SO ₃ H, sulfonate, NE ¹ E ² , alkylene NE ¹ E ² e ³⁺ X ^- stand, acyl or nitro
c is 0 or 1,
Y represents a chemical bond,
R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COOR ^f , COO ^- M ⁺ , SO ₃ R ^f , SO ^- ₃ M ⁺ , NE ¹ E ² , NE ¹ e ² e ³⁺ x ^-, alkylene-NE ¹ e ² e ³⁺ x ^-, OR ^f, SR ^f, (CHR ^g CH ₂ O) _x R ^f, (CH ₂ N (e ¹⁾⁾ _x R ^f , (CH ₂ CH ₂ N (E ¹ )) _x R ^f , halogen, trifluoromethyl, nitro, acyl or cyano,
wherein
R ^f , E ¹ , E ² and E ³ each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
R ^{g is} hydrogen, methyl or ethyl,
M ^{+ stands} for a cation,
X ^{- stands} for an anion, and
x is an integer from 1 to 120,
or
R ⁵ and / or R ⁷ together with two adjacent carbon atoms of the benzene nucleus to which they are attached represent a fused ring system having 1, 2 or 3 further rings,
a and b independently of one another denote the number 0 or 1
P for phosphorus
and
R ¹ , R ² , R ³ , R ⁴ independently of one another are hetaryl, hetaryloxy, alkyl, alkoxy, aryl, aryloxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy or a NE ¹ E ² group, with the proviso that R ¹ and R ³ are pyrrole groups bonded via the nitrogen atom to the phosphorus P, or R ¹ together with R ² and / or R ³ together with R ⁴ contain a divalent group E of the formula ## STR5 ## containing at least one pyrrole group bound via the pyrrole nitrogen atom to the phosphorus atom P. Py-IW form, in which
Py is a pyrrole group,
I is a chemical bond or is O, S, SiR ^a R ^b , NR ^c or CR ^h R ⁱ ,
W represents cycloalkyl, cycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy,
and
R ^h and R ⁱ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
or a bispyrrole group of the formula bonded via the nitrogen atoms to the phosphorus atom P Py-I-Py form.

worin
R¹⁵, R¹⁶, R¹⁷ und R¹⁸ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, W'COOR^k, W'COO^–M⁺, W'(SO₃)R^k, W'(SO₃)^–M⁺, W'PO₃(R^k)(R^I), W'(PO₃)₂ ^–(M⁺)₂, W'NE⁴E⁵, W'(NE⁴E⁵E⁶)⁺X^–, W'OR^k, W'SR^k, (CHR^ICH₂O)_yR^k, (CH₂NE⁴)_yR^k, (CH₂CH₂NE⁴)_yR^k, Halogen, Trifluormethyl, Nitro, Acyl oder Cyano stehen,
worin
W' für eine Einfachbindung, ein Heteroatom oder eine zweiwertige verbrückende Gruppe mit 1 bis 20 Brückenatomen steht,
R^k, E⁴, E⁵, E⁶ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl oder Aryl bedeuten,
R^I für Wasserstoff, Methyl oder Ethyl steht,
M⁺ für ein Kationäquivalent steht,
X^– für ein Anionäquivalent steht und
y für eine ganze Zahl von 1 bis 240 steht,
wobei jeweils zwei benachbarte Reste R¹⁵, R¹⁶, R¹⁷ und R¹⁸ zusammen mit den Kohlenstoffatomen des Pyrrolrings, an die sie gebunden sind, auch für ein kondensiertes Ringsystem mit 1, 2 oder 3 weiteren Ringen stehen können,
mit der Maßgabe, dass wenigstens einer der Reste R¹⁵, R¹⁶, R¹⁷ oder R¹⁸ nicht für Wasserstoff steht, und dass R¹⁹ und R²⁰ nicht mit einander verknüpft sind,
R¹⁹ und R²⁰ unabhängig voneinander für Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
a und b unabhängig voneinander die Zahl 0 oder 1 bedeuten
P für ein Phosphoratom steht,
Q eine Brückengruppe der Formel

ist,
worin
A¹ und A² unabhängig voneinander für O, S, SiR^aR^b, NR^c oder CR^dR^e stehen, wobei
R^a, R^b und R^c unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
R^d und R^e unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen oder gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, eine Cycloalkylidengruppe mit 4 bis 12 Kohlenstoffatomen bilden oder die Gruppe R^d gemeinsam mit einer weiteren Gruppe R^d oder die Gruppe R^e gemeinsam mit einer weiteren Gruppe R^e eine intramolekulare Brückengruppe D bilden,
D eine zweibindige Brückengruppe, ausgewählt aus den Gruppen

ist, in denen
R⁹ und R¹⁰ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, Carboxyl, Carboxylat oder Cyano stehen oder miteinander zu einer C₃- bis C₄-Alkylenbrücke verbunden sind,
R¹¹, R¹², R¹³ und R¹⁴ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, COOH, Carboxylat, Cyano, Alkoxy, SO₃H, Sulfonat, NE¹E², Alkylen-NE¹E²E³⁺X^–, Acyl oder Nitro stehen,
c 0 oder 1 ist,
R⁵, R⁶, R⁷ und R⁸ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, COOR^f, COO^–M⁺, SO₃R^f, SO^– ₃M⁺, NE¹E², NE¹E²E³⁺X^–, Alkylen-NE¹E²E³⁺X^–, OR^f, SR^f, (CHR^gCH₂O)_xR^f, (CH₂N(E¹))_xR^f, (CH₂CH₂N(E¹))_xR^f, Halogen, Trifluormethyl, Nitro, Acyl oder Cyano stehen,
worin
R^f, E¹, E² und E³ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl oder Aryl bedeuten,
R^g für Wasserstoff, Methyl oder Ethyl steht,
M⁺ für ein Kation steht,
X^– für ein Anion steht, und
x für eine ganze Zahl von 1 bis 120 steht,
oder
R⁵ und/oder R⁷ zusammen mit zwei benachbarten Kohlenstoffatomen des Benzolkerns, an den sie gebunden sind, für ein kondensiertes Ringsystem, mit 1, 2 oder 3 weiteren Ringen stehen.Preferred phosphoramidite ligands are those of the formula Va

wherein
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, W'COOR ^k , W'COO ^- M ⁺ , W '(SO ₃ ) R ^k , W' ( SO ₃ ) ^- M ⁺ , W'PO ₃ (R ^k ) (R ^I ), W '(PO ₃ ) ₂ ^- (M ⁺ ) ₂ , W'NE ⁴ E ⁵ , W' (NE ⁴ E ⁵ E ⁶ ) ⁺ X ^- , W'OR ^k , W'SR ^k , (CHR ¹ CH ₂ O) _y R ^k , (CH ₂ NE ⁴ ) _y R ^k , (CH ₂ CH ₂ NE ⁴ ) _y R ^k , halogen, Trifluoromethyl, nitro, acyl or cyano,
wherein
W 'represents a single bond, a heteroatom or a divalent bridging group having 1 to 20 bridging atoms,
R ^k , E ⁴ , E ⁵ , E ⁶ each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
R ^{I is} hydrogen, methyl or ethyl,
M ^{+ is} a cation equivalent,
X ^{- stands} for an anion equivalent and
y is an integer from 1 to 240,
wherein in each case two adjacent radicals R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ together with the carbon atoms of the pyrrole ring to which they are attached may also stand for a fused ring system having 1, 2 or 3 further rings,
with the proviso that at least one of R ¹⁵ , R ¹⁶ , R ¹⁷ or R ^{18 is} not hydrogen, and that R ¹⁹ and R ^{20 are} not linked to each other,
R ¹⁹ and R ²⁰ independently of one another are cycloalkyl, heterocycloalkyl, aryl or hetaryl,
a and b independently of one another denote the number 0 or 1
P is a phosphorus atom,
Q is a bridging group of the formula

is
wherein
A ¹ and A ² are each independently O, S, SiR ^a R ^b , NR ^c or CR ^d R ^e , wherein
R ^a , R ^b and R ^c independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R ^d and R ^e independently represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or together with the carbon atom to which they are attached form a cycloalkylidene group having 4 to 12 carbon atoms or the group R ^d together with another group R ^d or the group R ^e together with another group R ^{e form} an intramolecular bridging group D,
D is a divalent bridging group selected from the groups

is where
R ⁹ and R ¹⁰ independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano, or are joined together to form a C ₃ -C ₄ -alkylene bridge,
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, SO ₃ H, sulfonate, NE ¹ E ² , alkylene NE ¹ E ² e ³⁺ X ^- stand, acyl or nitro
c is 0 or 1,
R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COOR ^f , COO ^- M ⁺ , SO ₃ R ^f , SO ^- ₃ M ⁺ , NE ¹ E ² , NE ¹ e ² e ³⁺ x ^-, alkylene-NE ¹ e ² e ³⁺ x ^-, OR ^f, SR ^f, (CHR ^g CH ₂ O) _x R ^f, (CH ₂ N (e ¹⁾⁾ _x R ^f , (CH ₂ CH ₂ N (E ¹ )) _x R ^f , halogen, trifluoromethyl, nitro, acyl or cyano,
wherein
R ^f , E ¹ , E ² and E ³ each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
R ^{g is} hydrogen, methyl or ethyl,
M ^{+ stands} for a cation,
X ^{- stands} for an anion, and
x is an integer from 1 to 120,
or
R ⁵ and / or R ⁷ together with two adjacent carbon atoms of the benzene nucleus to which they are attached represent a fused ring system having 1, 2 or 3 further rings.

Et:

Ethyl

Me:

Methyl

Such ligands are the subject of WO 02/083695, to which reference is hereby fully made and where also the preparation of these ligands is described. Preferred ligands from this class are e.g. For example, the following compounds are provided, this listing being for illustration only and not of a limiting character to the applicable ligands.

et:

ethyl

me:

methyl

suitable Phosphoramidite ligands for the isomerizing hydroformylation with rhodium complex catalysts are also the phosphoramidite ligands according to WO 98/19985 and WO 99/52632, with 2,2'-dihydroxy-1,1'-biphenylene or 2,2'-dihydroxy-1,1'-binaphtylen bridge groups, the to the phosphorus atom over the Linked nitrogen atom Heteroaryl groups, such as pyrrolyl or indolyl groups, carry, for example, the Ligands.

The 1,1'-biphenylene or 1,1'-binaphthylene bridge groups of these ligands can still be replaced by a methylene (CH ₂ -), a 1,1-ethylidene (CH ₃ -CH <) via the 1,1-position. or a 1,1-propylidene group (CH ₃ -CH ₂ -HC <) may be bridged.

Suitable phosphinite ligands for the isomerizing hydroformylation with rhodium complex catalysts include the ligands described in WO 98/19985, for example

Also suitable as ligands for the isomerizing hydroformylation with rhodium complex catalysts are phosphite and phosphonite ligands, as described, for example, in WO 01/58589. By way of example only the following ligands are mentioned:

Well suitable as ligands for the isomerizing hydroformylation with rhodium complex catalysts are also phosphine ligands with the xanthenyl-bis-phosphoxanthenyl skeleton, as for example in WO 02/068371 and EP-A-982 314. Only for By way of illustration, some of these ligands are exemplary listed.

in denen G eine substituierte oder unsubstituierte zweiwertige organische Brückengruppe mit 2 bis 40 Kohlenstoffatomen ist, M für eine zweiwertige Brückengruppe steht, ausgewählt aus -C(R^w)₂-, -O-, -S-, NR^v, Si(R^t)₂- und -CO-, worin die Gruppen R^w gleich oder verschieden sind und für Wasserstoff, eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen, eine Phenyl-, Tolyl- und Anisyl-Gruppen stehen, die Gruppen R^v Wasserstoff oder eine substituierte oder unsubstituierte Kohlenwasserstoffgruppe mit 1 bis 12 Kohlenstoffatomen ist, die Gruppen R^t gleich oder verschieden sind und für Wasserstoff oder die Methylgruppe stehen, m die Zahl 0 oder 1 bedeutet, die Gruppen Ar gleich oder verschieden sind und für eine unsubstituierte oder substituierte Arylgruppe stehen, der Index k einen Wert von 0 oder 1 hat, die Gruppen R^x gleich oder verschieden sind und für unsubstituierte oder substituierte einwertige Alkyl- oder Arylgruppen stehen und R^Y ein zweiwertiger organischer Rest ist, ausgewählt aus unsubstituierten oder substituierten Alkylen-, Arylen-, Arylen-alkylen-arylen und Bis-arylen-Gruppen. Lediglich zur Veranschaulichung jedoch ohne beschränkenden Charakter seien beispielhaft die folgenden im erfindungsgemäßen Verfahren verwendbaren Chelatphosphitliganden genannt:

Suitable chelate phosphite ligands for the isomerizing hydroformylation with rhodium complex catalysts of these ligands are, for. B. those of the general formula VI, VII and VIII

wherein G is a substituted or unsubstituted divalent organic bridging group of 2 to 40 carbon atoms, M is a divalent linking group selected from -C (R ^w ) ₂ -, -O-, -S-, NR ^v , Si (R ^t ) ₂ - and -CO-, wherein the groups R ^{w are the} same or different and are hydrogen, an alkyl group having 1 to 12 carbon atoms, a phenyl, tolyl and anisyl groups, the groups R ^{v is} hydrogen or a substituted or is unsubstituted hydrocarbon group having 1 to 12 carbon atoms, the groups R ^{t are the} same or different and are hydrogen or the methyl group, m is 0 or 1, the groups Ar are the same or different and are an unsubstituted or substituted aryl group, the Index k has a value of 0 or 1, the groups R ^{x are} identical or different and are unsubstituted or substituted monovalent alkyl or aryl groups and R ^{Y is} a bivalent organic radical, selected from unsubstituted or substituted alkylene, arylene, arylene-alkylene-arylene and bis-arylene groups. By way of illustration but not of limitation, the following are examples of the following chelating phosphite ligands useful in the process of the present invention:

Such and other bisphosphite chelating ligands are the subject of EP-A-213 369 and US-A-4,769,498 and their preparation is described there.

Instead of the abovementioned bisphosphite chelate ligands Ver in the invention also monodentate monophosphite ligands of the general formula IX P (OR ^S ) (OR ^T ) (OR ^U ) IX to complex the rhodium hydroformylation catalyst and to use it as a free ligand. The suitability of such ligands and their complexes with rhodium as catalysts for the isomerizing hydroformylation is known. In the monophosphite ligand of the general formula IX the radicals R ^S, R ^T and R ^U are, independently of one another represent identical or different organic groups which generally have from 1 to 30, preferably 5 to 30 carbon atoms, for example, substituted or unsubstituted alkyl, aryl , Arylalkyl, cycloalkyl and / or heteroaryl groups. Because of their increased hydrolysis and degradation abilities, in particular sterically hindered monophosphite ligands are preferred, as described, for example, in EP-A-155,508. For the purpose of illustration only the following monophosphite ligand structures may be mentioned by way of example:

Bu^t:

tertiär Butyl

Ph:

Phenyl

Known ligands for isomerizing hydroformylation with rhodium complex catalysts are Also, such bidentate ligands, which carry in the ligand molecule next to a phosphite group or a phosphinite or phosphine group. Such ligands are described inter alia in WO 99/50214. For the sake of explanation, some such ligands are listed below by way of example only:

Bu ^t :

tertiary butyl

Ph:

phenyl

The ligand types described above may be in the form of their complexes with rhodium and / or as free ligands in the process according to the invention are used, are preferred in the process according to the invention for isomerizing hydroformylation rhodium complex catalysts with phosphoramidite ligands with xanthene backbone, as they are the subject of WO 02/083695 used.

The two-stage process according to the invention can be used in the hydroformylation of olefin compositions which contain both α-olefins and olefins with internal double bonds, The corresponding aldehydes are obtained with a higher n / i ratio than corresponds to the proportion of α-olefins in the olefin composition and with significantly lower reaction volumes than is possible with conventional methods.

The The invention will be apparent from the following non-limiting Examples closer explained.

Example 1: Synthesis of ligand A

a) (1,1'-binaphthalene-2,2'-dioxy) chlorophosphine

14.3 g of binol were placed under argon and treated with 103 g of PCl ₃ . The reaction mixture was refluxed for 16 h. Then, excess PCl ₃ was distilled off in vacuo; the residue was taken up in 50 ml of toluene and the reaction mixture was monitored by ³¹ P-NMR (δ = 179; δ (lit., CDCl ₃ ) = 174). The solvent was removed in vacuo, the residue taken up in 25 ml of toluene and the solvent again removed in vacuo to remove residual amounts of PCl. ₃ This process was repeated again. An orange oil was obtained, which was taken up for subsequent reaction in 50 ml of toluene. The total volume of the solution was 66 ml. 50% of this solution was used in step c) (Nozaki, N. Sakai, T. Nanno, T. Higashijima, S. Mano, T. Horiuchi, H. Takaya J. Chem. Soc., 1997, 119, 4413-4423).

b) Skat ₂ PCl

13.1 g (100 mmol) of skatole were dissolved in 50 ml of abs. Submitted toluene at -70 ° C. There were added 6.9 g (50 mmol) of PCl ₃ and 21.2 g (210 mmol) of triethylamine. The reaction mixture was brought to room temperature with stirring within 16 h. Then was refluxed for 48 h. About 50 ml of toluene were added for dilution. Subsequently, the NEt ₃ · HCl was separated by means of protective gas frit. The mother liquor contained Skat ₂ PCl and the total volume was 104 ml. In the next step, only 50% of this Skat ₂ PCl solution was used.

c) ligand synthesis

9 g (25 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy-biphenyl-2,2'-diol were dissolved in 3 g of triethylamine and 75 ml of abs. Submitted toluene at -30 ° C. To the reaction mixture was added dropwise within 0.5 h 50% (= 33 ml) of the (1,1'-binaphthalene-2,2'-dioxy) chlorophosphine solution from a) at -30 ° C. The reaction mixture was brought to room temperature and stirred for 16 h at room temperature. ³¹ P-NMR control (δ = 139.0 (main signal) and 139.5, smaller signals 145.7 and 146.2). The mixture was added with 3 g of triethylamine at room temperature. Subsequently, 50% (= 52 ml) of the Skat ₂ PCl solution from b) was likewise added dropwise at room temperature and the mixture was stirred at room temperature for 16 h. The NEt ₃ · HCl was filtered off and the mother liquor was separated in vacuo. The oily residue was taken up in 50 ml of CH ₃ CN, where a colorless solid was obtained. This was filtered off and stirred in 100 ml of CH ₃ CN at 50 ° C, filtered off with suction and then washed 10 times with 100 ml of CH ₃ CN at room temperature. The mixture was then washed three times with 25 ml of toluene at room temperature. The residual colorless solid was dried in vacuo.
Yield: 7.5 g (31% of theory based on 3,3'-di-tert-butyl-5,5'-dimethoxy-biphenyl-2,2'-diol)
³¹ P-NMR (CDCl _3, 146 MHz, 298K)
δ = 102.4 (s), 139.5 (s). No other signals indicating pure chelated phosphite or chelated phosphoramidite by-product.

Example 2: Hydroformylation of 1-butene

5.1 mg of Rh (CO) ₂ acac (acac = acetylacetonate) and 193 mg of ligand A were weighed in separately, dissolved in 5 g of diphenyl ether, mixed and mixed at 90 ° C. with 10 bar of synthesis gas (CO: H ₂ = 1: 1 ) fumigated (preformation). After 1 h was relaxed. Then 10.3 g of 1-butene were added by means of a pressure lock, a total pressure of 17 bar was set with synthesis gas (CO: H ₂ = 1: 1) and hydroformylated at 90 ° C. for 2 h (99 ppm Rh; ligand: Rh = 10: 1). After the specified reaction time, the autoclave was cooled, gently expanded over a cold trap and both reaction effluents (reactor and cold trap) were analyzed by gas chromatography. The conversion was 99%, the yield of valeraldehyde 77% and the linearity (n-portion) 95.9%. The yield of 2-butene (isomerization product) was 22%. [The linearity (n-fraction) is defined as the quotient of n-valeraldehyde to the sum of n-valeraldehyde and i-valeraldehyde multiplied by 100].

Example 3: Hydroformylation of trans-2-butene

5.1 mg of Rh (CO) ₂ acac (acac = acetylacetonate) and 193 mg of ligand A were weighed in separately, dissolved in 5 g of diphenyl ether, mixed and mixed at 90 ° C. with 10 bar of synthesis gas (CO: H ₂ = 1: 2 ) fumigated (preformation). After 1 h was relaxed. Then 11.2 g of trans-2-butene were added by means of a pressure lock and set with synthesis gas (CO: H ₂ = 1: 2), a total pressure of 17 bar. The gas feed was then switched to synthesis gas (CO: H ₂ = 1: 1) to ensure a constant ratio of CO: H ₂ of 1: 2 in the reactor. The mixture was then hydroformylated at 90 ° C. for 4 h (95 ppm Rh, ligand: Rh = 10: 1). The conversion was 35%, the yield of valeraldehyde 32% and the linearity (n-portion) 90.6%.

Example 4: Hydroformylation of styrene

In the glovebox (N ₂ ), 5.1 mg (0.02 mmol) of Rh (CO) ₂ acac (acac = acetylacetonate) and 94 mg (0.10 mmol) of ligand A were dissolved in 5 g of toluene each time. The combined solutions were transferred by syringe to a CO / H ₂ purged steel autoclave with a gassing stirrer. It was adjusted by means of synthesis gas (CO: H ₂ = 1: 1) at room temperature, a pressure of 80 bar and then gassed for 1 h at 50 ° C (preformed). Subsequently, 10.0 g of styrene were pressed in by means of a pressure lock, the desired reaction pressure of 80 bar was set with synthesis gas and the reaction mixture was kept at 50 ° C. for 24 h at constant pressure. It was then cooled to room temperature and carefully released. The conversion was 85%, the yield of phenylpropionaldehyde 84% and the ratio of 2-phenylpropionaldehyde: 3-phenylpropionaldehyde = 68:32.

Example 5: Synthesis of ligand B

2 g (14.6 mmol) of PCl ₃ were dissolved in 100 ml of abs. THF submitted at room temperature. A solution consisting of 3.83 g (29.2 mmol) of 3-methylindole (skatole) and 4 g (40 mmol) of NEt ₃ in 50 ml of abs. THF added dropwise within 0.5 h. The mixture was then stirred at room temperature for 2 h and then heated under reflux for 16 h. After cooling to room temperature, the NEt ₃ · HCl was separated off by means of a protective gas frit and the resulting mother liquor was admixed with 1.5 g (15 mmol) of NEt ₃ . This Skat ₂ PCl solution was converted within 1.5 h at -40 to -20 ° C to a solution of 5.23 g (14.6 mmol) of 3,3'-di-tert-butyl-5,5 '-dimethoxy-biphenyl-2,2'-diol in 150 ml THF added dropwise. After complete addition, the mixture was stirred for 6 h between -40 and 0 ° C, warmed to room temperature over 2 h and then stirred for 12 h at room temperature. The precipitated NEt ₃ · HCl was separated by means of protective gas frit. To the resulting mother liquor, a solution of 2 g (14.6 mmol) of PCl ₃ in 50 ml of THF was added at -30 ° C within 15 minutes. The mixture was then stirred at -30 to -20 ° C for 2 h, brought to room temperature over 6 h and then stirred for 12 h at room temperature. The resulting suspension was cooled to -20 ° C and at -20 to -10 ° C within 15 minutes, a solution of 5.23 g (14.6 mmol) of 3,3'-di-tert-butyl-5, 5'-dimethoxy-biphenyl-2,2'-diol and 3 g (14.6 mmol) NEt ₃ in 60 ml THF was added dropwise. After completion of the addition, the reaction mixture was brought to room temperature over 4 h, then stirred for 10 h at room temperature and heated under reflux for a further 3.5 h. The NEt ₃ · HCl was separated by means of protective gas frit, the mother liquor was concentrated to dryness, the residue in 100 ml of acetonitrile with stirring to 50 ° C heated. Upon cooling to room temperature, a solid precipitated, which was washed twice with 70 ml each, then twice with 30 ml of acetonitrile. The resulting solid was dried in vacuo.

fine cleaning of ligand B

To ensure purity, the product was purified by preparative HPLC.
Waters Delta Prep Facility; Phenomenex LUNA phenyl-hexyl column 30 · 250 mm 5 μm, UV detector: 250 nm

The separation column was slow with the needed Flow and the initial composition of the gradient commissioned. The 5 ml sample loop was washed twice with 10 ml each of THF and acetonitrile rinsed.

Subsequently was the separation column Balanced within 10 minutes and then the to be separated mixture [665 mg of solid dissolved in 3 ml of THF] injected.

After this the injection was done, the separation was done by means of UV detector (250 nm) and the desired Collected fraction under argon in a flask (retention time range: 23.0-27.0 minutes).

The resulting solution was concentrated at 50 ° C in vacuo to dryness and the residue dried overnight in vacuo. Yield: 400 mg
¹ H-NMR (CDCl _3, 360 MHz, 298K)
δ = 0.76 (s, t Bu, 9H), 1.06 (s, t Bu, 9H), 1.13 (s, t Bu, 9H), 1.45 (s, t Bu, 9H), 2.08 ( s, Skat CH ₃ , 3H), 2.14 (s, Skat CH ₃ , 3H), 3.32 (s, OCH ₃ , 3H), 3.67 (s, OCH ₃ , 3H), 3, 69 (s, OCH ₃ , 3H), 3.74 (s, OCH ₃ , 3H), 6.29 ("m", Ar-H, 1H), 6.44 (d, J = 3.2 Hz, Ar-H, 1H), 6.53 (d, J = 3.0Hz, Ar-H, 1H), 6.56 (d, J = 3.0Hz, Ar-H, 1H), 6.67 (d, J = 3.1Hz, Ar-H, 1H), 6.78 (d, J = 3.0Hz, Ar-H, 1H), 6.81 (s, Ar-H, 1H), 6.87 (i.e. , J = 3.0 Hz, Ar-H, 1H), 6.91-7.02 (m, Ar-H, 6H), 7.15 ("d", J = 8 Hz, Ar-H, 1H ), 7.24 ("d", J = 7.7 Hz, Ar-H, 1H), 7.30 ("d", J = 7.5 Hz, Ar-H, 1H), 7.34 ( "d", J = 7.4 Hz, Ar-H, 1H): Σ aromatic-H = 18H.
³¹ P-NMR (CDCl _3, 146 MHz, 298K)
δ = 97.7 (s, integer = 5), 98.8 (s, integral = 100), 141.2 (s, integral = 100 (def.)), 142.0 (s, integer = 5). No other signals indicating pure chelate phosphite or chelated phosphoramidite by-product!

Example 6: Hydroformylation of styrene with ligand B

In the glovebox (N ₂ ), 5.1 mg (0.02 mmol) of Rh (CO) ₂ acac (acac = acetylacetonate) and 100 mg (0.10 mmol) of ligand B were dissolved in 5 g of toluene each time. The combined solutions were transferred by syringe to a CO / H ₂ purged steel autoclave with a gassing stirrer. It was adjusted by means of synthesis gas (CO: H ₂ = 1: 1) at room temperature, a pressure of 10 bar and then gassed for 1 h at 50 ° C (preformed). Subsequently, 10.0 g of styrene were pressed in by means of a pressure lock, the desired reaction pressure of 10 bar was set with synthesis gas and the reaction mixture was kept at 50 ° C. for 24 h at constant pressure. It was then cooled to room temperature and carefully released. The conversion was 53%, the yield of phenylpropionaldehyde 53% and the ratio of 2-phenylpropionaldehyde: 3-phenylpropionaldehyde = 57:43.

Example 7: Synthesis of spine 2,2'-dihydroxy-3,3 ', 7,7'-tetramethyl-1,1-binaphthol

a) 3,7-dimethyl-2-naphthol

• (L. F. Fieser, A. M. Seligman, J. Am. Chem. Soc. 1934, 56, 2690-2696, J. E. Gready, K. Hata, S. Sternhell, C. W. Tansey, Aust. J. Chem. 1990, 43, 593-600)

The synthesis of precursor 3,7, dimethyl-2-naphthol was carried out according to the literature references below.

• (LF Fieser, AM Seligman, J. Am. Chem. Soc. 1934, 56, 2690-2696, JE Gready, K. Hata, S. Sternhell, CW Tansey, Aust. J. Chem. 1990, 43, 593-600 )

b) 2,2'-dihydroxy-3,3 ', 7'-tetramethyl-1,1-binaphthol

• MS (Ionisation: EI): m/z = 342
• MS berechnet für (C₂₄H₂₂O₂): m/z = 342
• ¹H-NMR (CD₂Cl₂, 500 MHz, 298K)
• δ = 2,26 (s, CH₃, 6H), 2,48 (s, CH₃, 6H), 5,13 (s, OH, 2H), 6,82 (s, Ar-H, 2H), 7,18 (dd, J = 8,33 Hz, J = 1,1 Hz, Ar-H, 2H), 7,73 (d, J = 8,33 Hz, Ar-H, 2H). 7,78 (s, Ar-H, 2H).
• ¹³C{¹H}-NMR (CD₂Cl₂, 125 MHz, 298K)
• δ = 15,9 (CH₃, [CH, CH₃]), 20,7 (CH₃, [CH, CH₃]), 109,5 (Ar-C, [quartäres-C]), 122,0 (Ar-C, [CH, CH₃]), 125,2 (Ar-C, [quartäres-C]), 125,3 (Ar-C, [CH, CH₃]), 126,7 (Ar-C, [CH, CH₃]), 127,0 (Ar-C, [quartäres-C]), 129,6 (Ar-C, [CH, CH₃]), 131,7 (Ar-C, [quartäres-C]), 135,4 (Ar-C, [quartäres-C]), 151,5 (Ar-C_OH, [quartäres-C]).
• Elementaranalyse für C₂₄H₂₂O₂: berechnet C 84,18 H 6,48 gefunden C 84,5 H 6,5.

In a suitable flask for Kugelrohrdestille 15 g of aluminum oxide (type 506C) were introduced and treated with stirring with a solution of 3.94 g (14.6 mmol) of FeCl ₃ · 6H ₂ O in 40 ml of acetone. Subsequently, volatiles of this suspension were removed in the Kugelrohr stills under vacuum (rotating the flask) at 40 ° C. 2.5 g (14.5 mmol) of 3,7-dimethyl-2-naphthol were dissolved in 100 ml of CH ₂ Cl ₂ in an ultrasound bath and added portionwise with stirring to the FeCl ₃ / alumina. Then volatiles were removed in the Kugelrohr still under vacuum (rotating the flask) at room temperature. It was then heated for 1 h at 90 ° C in the air in the Kugelrohrdestille (turning the flask). After cooling, the reaction mixture was suspended three times with vigorous stirring in a mixture of 10 ml H ₃ PO ₄ (85%) and 30 ml of MeOH and the mother liquor was separated by filtration. Then the solid was suspended three times in 40 ml of CH ₂ Cl ₂ and the mother liquor was separated by filtration. Finally, the filter cake was washed with 100 ml of CH ₂ Cl ₂ on a frit. The combined filtrate phases were separated in a separating funnel and then the organic phase was washed with water (50 ml and three times 25 ml). After drying over MgSO ₄ and removal of the volatile constituents, 2.2 g of a brown solid were obtained, which, according to gas chromatography, the 2,2'-dihydroxy-3,3 ', 7,7'-tetramethyl-1,1-binaphthol in approx Contains 90% purity. The secondary component could be separated by column chromatography on silica gel 60M with CH ₂ Cl ₂ : hexane = 1: 2. The isolated yield after the column chromatography was 1.44 g (58% of theory). Characterization 2,2'-dihydroxy-3,3 ', 7,7'-tetramethyl-1,1-binaphthol:

• MS (ionization: EI): m / z = 342
• MS calcd for (C ₂₄ H ₂₂ O _2): m / z = 342
• ¹ H NMR (CD ₂ Cl ₂ , 500 MHz, 298K)
• δ = 2.26 (s, CH ₃ , 6H), 2.48 (s, CH ₃ , 6H), 5.13 (s, OH, 2H), 6.82 (s, Ar-H, 2H), 7.18 (dd, J = 8.33 Hz, J = 1.1 Hz, Ar-H, 2H), 7.73 (d, J = 8.33 Hz, Ar-H, 2H). 7.78 (s, Ar-H, 2H).
• ¹³ C { ¹ H} NMR (CD ₂ Cl ₂ , 125 MHz, 298K)
• δ = 15.9 (CH ₃ , [CH, CH ₃ ]), 20.7 (CH ₃ , [CH, CH ₃ ]), 109.5 (Ar-C, [quaternary C]), 122.0 (Ar-C, [CH, CH ₃ ]), 125.2 (Ar-C, [quaternary C]), 125.3 (Ar-C, [CH, CH ₃ ]), 126.7 (Ar-C, [CH, CH ₃ ]). C, [CH, CH ₃ ]), 127.0 (Ar-C, [quaternary C]), 129.6 (Ar-C, [CH, CH ₃ ]), 131.7 (Ar-C, [ quaternary C]), 135.4 (Ar-C, [quaternary C]), 151.5 (Ar-C _OH , [quaternary C]).
• Elemental analysis for C ₂₄ H ₂₂ O ₂ : Calculated C 84.18 H 6.48 found C 84.5 H 6.5.

Claims (19)

Phosphor chelate compounds of general formula I.

wherein R ^α and R ^β independently represent 5- to 7-membered heterocyclic groups which are bonded via a ring nitrogen atom to the phosphorus atom or R ^α and R ^β together with the phosphorus atom to which they are attached, for a 5- to 7-membered heterocycle, which additionally has an optionally substituted nitrogen atom and another selected from oxygen and optionally substituted nitrogen heteroatom, both of which are bonded directly to the phosphorus atom, R ^γ and R ^δ independently of one another for alkyl, cycloalkyl, heterocycloalkyl, aryl or Hetaryl, where the alkyl radicals 1, 2, 3, 4 or 5 substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, COOH, carboxylate, SO ₃ H, sulfonate, NE ¹ E ² , NE ¹ E ² E ³ X ^- , halogen, nitro, acyl or cyano, wherein E ¹ , E ² and E ^{3 are} each the same or different radicals selected from hydrogen, alkyl, cycloalkyl, or aryl and X ^{- is} an anion equivalent, and wherein the cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals R ^γ and R ^δ 1, 2, 3 , 4 or 5 substituents which are selected from alkyl and the substituents previously mentioned for the alkyl radicals R ^γ and R ^δ , or R ^γ and R ^δ together with the phosphorus atom and, if present, the oxygen atoms to which they are attached , represent a 5- to 8-membered heterocycle which is optionally additionally fi-,, or trisubstituted with cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the heterocycle and, if present, the fused groups independently of one another each , three or four substituents which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, COOH, Ca rboxylate, SO ₃ H, sulfonate, NE ⁴ E ⁵ , NE ⁴ E ⁵ E ^{6 +} X ^- , nitro, alkoxycarbonyl, acyl or cyano, where E ⁴ , E ⁵ and E ^{6 are} each the same or different radicals selected from hydrogen , alkyl, cycloalkyl and aryl, and X ^- is an anion equivalent, ^ξ X is O, S, SiR ^ε R or NR ^η, where R ^ε, R ^ξ and R ^η independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, Aryl or hetaryl, Y is a divalent bridging carbon atom-containing bridge, and a, b, c and d independently represent the number 0 or 1, wherein at least one of the variables b, c or d is 1. Compounds according to claim 1 of general formula I.1

wherein R ^α , R ^β , R ^γ , R ^δ and Y have the meanings given in claim 1. Compounds according to one of claims 1 or 2, wherein R ^α and R ^{β are} independently selected from groups of the formulas II.a to II.k

wherein Alk is a C ₁ -C ₄ alkyl group and R ^a , R ^b , R ^c and R ^{d are} independently hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acyl, halogen, C ₁ C ₄ alkoxycarbonyl or carboxyl. Compounds according to one of claims 1 or 2, in which R ^α and R ^β together with the phosphorus atom to which they are bonded represent a group of the formulas II.1 to II.5

are wherein I ^κ for a chemical bond or O, S, SiR ^θ R ^i, NR, or optionally substituted C ₁ -C ₁₀ alkylene, preferably CR ^{λ μ} R, where R ^θ, R ^i, R ^κ, R ^λ and R ^μ independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, R ⁹ and R ¹⁰ independently of one another are hydrogen, alkyl, cycloalkyl, aryl, hetaryl, mesylate, tosylate or trifluoromethanesulfonate, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ and R ^{30 are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, W'COOR ^f , W 'COO ^- M ^+, W' (SO ₃₎ R ^f, W '(SO ₃₎ ^- M ^+, W'PO ₃ (R ^f) (R ^g), W' (PO ₃₎ ^{2- (M +)} ₂ , W'NE ⁷ E ⁸ , W '(NE ⁷ E ⁸ E ⁹ ) ⁺ X ^- , W'OR ^f , W'SR ^f , (CHR ^g CH ₂ O) _x R ^f , (CH ₂ NE ⁷ ) _x R ^f , (CH ₂ CH ₂ NE ⁷ ) _x R ^f , halogen, nitro, acyl or cya where W 'is a single bond, a heteroatom, a heteroatom-containing group or a divalent bridging group having 1 to 20 bridging atoms, R ^f , E ⁷ , E ⁸ , E ^{9 are} each the same or different radicals selected from hydrogen , Alkyl, cycloalkyl or aryl, R ^{g is} hydrogen, methyl or ethyl, M ^{+ is} a cation equivalent, X ^{- is} an anion equivalent and x is an integer from 1 to 240, wherein in the compounds of formulas II.1 and II.2 each two adjacent radicals R ¹ and R ² and / or R ⁷ and R ⁸ and in the compounds of formulas II.3, II.4 and II.5 each two adjacent radicals R ¹¹ to R ³⁰ together with the carbon atoms of the ring to the they are also bonded to a fused ring system with 1, 2 or 3 other rings. Compounds according to any one of the preceding claims, wherein R ^γ and R ^{δ are taken} together with the phosphorus atom and, if present, the oxygen atoms to which they are attached, for a group of general formula II.A

wherein c and d are independently 0 or 1, Q together with the phosphorus atom and the oxygen atoms to which it is attached, represents a 5- to 8-membered heterocycle, optionally with one, two or three times with Cycloalkenyl, heterocycloalkyl, aryl and / or hetaryl, where the fused groups are each independently one, two, three or four substituents selected from alkyl, alkoxy, cycloalkyl, aryl, halogen, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, COOH, Carboxylate, SO ₃ H, sulfonate, NE ¹⁰ E ¹¹ , alkylene-NE ¹⁰ E ¹¹ , nitro and cyano and / or Q may have one, two or three substituents selected from alkyl, alkoxy, optionally substituted cycloalkyl and optionally substituted Aryl, and / or Q may be interrupted by 1, 2 or 3 optionally substituted heteroatoms. Compounds according to any one of the preceding claims, wherein the bridging groups Y and Q are independently selected from groups of formulas III.a to III.t.

in which R ^I , R ^{I '} , R ^II , R ^II' , R ^III , R ^{III '} , R ^IV , R ^IV' , R ^V , R ^VI , R ^VII , R ^VIII , R ^IX , R ^X , R ^XI , and R ^XII independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, SO ₃ H, sulphonate, NE ¹³ E ¹⁴ , alkylene-NE ¹³ E ¹⁴ , trifluoromethyl, Nitro, alkoxycarbonyl, carboxyl, acyl or cyano, wherein E ¹³ and E ^{14 are} each identical or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl, Z is O, S, NR ^χ or SiR ^ψ R ^ω , where R ^χ , R ^ψ and R ^{ω are} independently of one another hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or Z is a C ₁ -C ₄ -alkylene bridge which has a double bond and / or an alkyl, cycloalkyl, Heterocycloalkyl, aryl or hetaryl substituents may have, or Z is a C ₂ -C ₄ -alkylene, which is interrupted by O, S or NR ^χ or SiR ^ψ R ^ω in which in the groups of formula III.a two adjacent radicals R ^I to R ^VI, together with the carbon atoms of the benzene nucleus to which they are attached, can also be a fused ring system having 1, 2 or 3 further rings, wherein in the Groups of formulas III.g to III.m two geminal radicals R ^I , R ^{I '} ; R ^II , R ^{II '} ; R ^III , R ^{III '} and / or R ^IV , R ^{IV "may} also stand for oxo or a ketal thereof, A ¹ and A ² independently of one another represent O, S, SiR ^or R ^π , NR ^ρ or CR ^σ R ^τ wherein R ^o , R ^π and R ^{ρ are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, R ^σ and R ^{τ are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R ^σ together with another group R ^σ or the group R ^τ together with another group R ^{τ form} an intramolecular bridging group D, D for a divalent bridging group of the general formula

in which R ³⁰ , R ^{30 '} , R ³¹ and R ^31' independently of one another are hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano, where R ^{30 'is} also together with R ^31' for the bond portion of a double bond between the two carbon atoms to which R ^{30 '} and R ^{31' are} bonded, and / or R ³⁰ and R ³¹ together with the carbon atoms to which they are attached, also for a 4- to 8 -membered carbocyclic or heterocycle which may optionally additionally be mono-, di- or tri-fused with cycloalkyl, heterocycloalkyl, aryl or hetaryl, where the heterocycle and, if present, the fused groups are each independently one, two, three or may carry four substituents which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COOR ^h , COO ^- M ⁺ , SO ₃ R ^h , SO ^- ₃ M ⁺ , NE ¹⁶ E ¹⁷ , alkylene-NE ¹⁶ E ¹⁷ , NE ¹⁶ e ¹⁷ e ^{18 +} X ^-, alkylene-NE ¹⁶ e ¹⁷ e ¹⁸⁺ X ^- , OR ^h , SR ^h , (CHR ⁱ CH ₂ O) _y R ^h , (CH ₂ N (E ¹⁶ )) _y R ^h , (CH ₂ CH ₂ N (E ¹⁶ )) _y R ^h , halogen, Trifluoromethyl, nitro, acyl or cyano, wherein R ^h , E ¹⁶ , E ¹⁷ and E ^{18 are} each the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl, R ^{i is} hydrogen, methyl or ethyl, M ^{+ is} a cation, is an anion, and y is an integer from 1 to 120, and e is 0 or 1. Method according to one of the preceding claims, wherein the group Y and / or, if present, the group Q for a chiral one Group stands. Catalyst comprising at least one complex with a transition metal, as ligands at least one compound of formula I, as in one of the claims 1 to 7 defines. Process for the preparation of chiral compounds by Reaction of a prochiral compound containing at least one ethylenic unsaturated Contains double bond, with a substrate in the presence of a chiral catalyst, such as defined in claim 8. The method of claim 9, wherein the prochiral Connection selected is among olefins, aldehydes, ketones and imines. Method according to one of claims 9 or 10, wherein it is to a hydrogenation, hydroformylation, hydrocyanation, carbonylation, Hydroacylation, hydroamidation, hydroesterification, hydrosilylation, Hydroboration, aminolysis, alcoholysis, isomerization, metathesis, Cyclopropanation, aldol condensation, allylic alkylation or [4 + 2] cycloaddition. Method according to one of claims 9 to 11, wherein it is is a 1,2-addition, preferably a 1-hydro-2-carbo addition. Method according to one of claims 9 to 11, wherein it is is a hydrogenation. Method according to one of claims 9 to 12, in which it is is a hydroformylation. Process for the hydroformylation of compounds, which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of a A hydroformylation catalyst as defined in claim 8. The method of claim 15, wherein an olefin mixture is used, the olefins having internal double bonds and Olefin with terminal Contains double bonds. The method of claim 16, wherein an olefin mixture is used which contains 1-butene and 2-butene. A process for the preparation of 2-propylheptanol which comprises subjecting i) butene or a butene-containing C ₄ -hydrocarbon mixture to a hydroformylation as defined in any one of claims 15 to 17 to obtain a n-valeraldehyde-containing hydroformylation product, ii) optionally the hydroformylation product iii) subjecting the hydroformylation product obtained in step i) or the fraction enriched in n-valeraldehyde obtained in step ii) to aldol condensation, iv) catalytically hydrogenating the products of aldol condensation with hydrogen to give alcohols hydrogenated, and v) optionally subjecting the hydrogenation products to separation to give a fraction enriched in 2-propylheptanol. Process for the hydroformylation of an α-olefin and olefins having internal double bond-containing composition by reaction with carbon monoxide and hydrogen in the presence of a Hydroformylation catalyst in a two-stage reaction system, in which one - in the first reaction stage an olefin-containing feed, carbon monoxide and hydrogen feeds and partially catalytically converts, - the discharge fed from the first reaction stage in the second reaction stage and further implements, - from Discharge from the second reaction stage one essentially unreacted olefins and saturated hydrocarbons existing electricity is separated and at least partially in the second Feed reaction step.