DE10333519A1 - Two-stage hydroformylation process - Google Patents

Abstract

The present invention relates to a process for the preparation of hydroformylation products of olefins, wherein
a) feeding into an initial reaction zone an olefin-containing feed and carbon monoxide and hydrogen and reacting in the presence of a first catalyst system,
b) separating from the effluent from the first reaction zone a liquid stream consisting essentially of unreacted olefins and optionally saturated hydrocarbons,
c) feeds the liquid stream obtained in step b) and carbon monoxide and hydrogen into a second reaction zone and reacts in the presence of a second catalyst system.

Description

The The present invention relates to a process for the preparation of Hydroformylation products of olefins, in which in a first Reaction zone an olefin-containing feed in the presence of a first catalyst system converts the discharge from the first reaction zone one not separated stream containing olefins and this in a second reaction zone in the presence of a second catalyst system implements. The invention further relates to a process for the preparation of 2-propylheptanol comprising such hydroformylation.

The Hydroformylation or oxo synthesis is an important large-scale process Process and serve for the production of aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes may optionally be in the same Operation with hydrogen to the corresponding oxo-alcohols be hydrogenated. The reaction itself is highly exothermic and generally runs under increased Pressure and at elevated Temperatures in the presence of catalysts from. As catalysts become Co, Rh, Ir, Ru, Pd or Pt compounds or complexes used for the activity and / or selectivity may be modified with N- or P-containing ligands. at the hydroformylation reaction of olefins having more than two carbon atoms It may be due to the possible CO attachment to each of the two C atoms of a double bond to form come from mixtures of isomeric aldehydes. Additionally, it may be in use of olefins having at least four carbon atoms also to one Double bond isomerization, i. H. to a shift internal double bonds to a terminal position and vice versa.

On Reason of much larger technical Meaning of α-aldehydes will optimize the hydroformylation process to achieve preferably high sales at the same time as possible low tendency to form olefins with non-α-double bonds sought. In addition, there is a need for hydroformylation processes, which also starting from internal linear olefins in good yields to α-permanent and especially n-standing Aldehydes lead. Here, the catalyst used both the setting an equilibrium between internal and terminal double bond isomers as well as possible selectively allow the hydroformylation of the terminal olefins.

For example, for the preparation of ester plasticizers having good performance properties, there is a need for plasticizer alcohols having about 6 to 12 carbon atoms which are branched to a low degree (so-called semi-linear alcohols) and to corresponding mixtures thereof. These include in particular 2-propylheptanol and alcohol mixtures containing it. For their preparation can be, for example, C ₄ -hydrocarbon mixtures containing butenes or butenes and Bu tane, subjected to a hydroformylation and subsequent aldol condensation. When using hydroformylation catalysts with insufficient n-selectivity, then, in the hydroformylation, not only the formation of n-valeraldehyde but also undesired product aldehydes can easily occur, thereby economically disadvantageing the entire process.

It is known in the rhodium-low-pressure hydroformylation phosphorus-containing Ligands for stabilizing and / or activating the catalyst metal use. Suitable phosphorus ligands are z. B. phosphines, Phosphinites, phosphonites, phosphites, phosphoramidites, phospholes and phosphabenzenes. Currently the most widely used ligands are triarylphosphines, such as. B. triphenylphosphine and sulfonated Triphenylphosphine, as these under the reaction conditions a sufficient activity and have stability. However, a disadvantage of these ligands is that generally only very high ligand excesses satisfactory In particular, provide yields of linear aldehydes and internal Olefins are virtually unreacted.

If the hydroformylation is carried out as a one-step process, complete or almost complete conversions of the olefins used can often not be realized for technical or process-economical reasons. This is especially true for the use of olefin mixtures containing olefins of different reactivity, for example olefins with internal and olefins with terminal double bonds. It is known to use two or more reaction stages for the hydroformylation, in which the reactors are present, for example, in the form of a cascade in which the individual reactors are operated under different reaction conditions in order to achieve a higher conversion for a given reaction space than in a single reactor of the same volume. For example, describe the DE-A-100 35 120 and DE-A-100 35 370 Process for the hydroformylation of olefins in a two-stage reaction system.

The EP-A-0 188 246 describes a two-stage hydroformylation process in which the gaseous effluent from the first hydroformylation stage containing unreacted olefins, product aldehydes and by-product saturated hydrocarbons is fed without separation to the second hydroformylation stage. The catalyst compositions may differ in the first and the second hydroformylation stage.

The EP-A-0 423 769 describes a two-stage hydroformylation process, wherein the reactors used in the first and in the second stage differ in their mixing characteristics. The effluent from the first reactor system is subjected to separation to yield a stream containing the unreacted olefins which is fed to the second reactor system. In both reaction stages, the same catalyst system is used, which differs only in the amount used.

The EP-A-0 213 639 describes bridged bisphosphite compounds with a diorganophosphite functionality and a triorganophosphite functionality and their use as ligands in rhodium-catalyzed hydroformylation. It is quite generally and without support by an embodiment pointed to a possible use of these catalyst systems in a two-stage hydroformylation, in which, for example, α-olefins are reacted in a first reactor and internal olefins in a second reactor.

The EP-A-0 562 451 describes the preparation of mixtures of isomeric decyl alcohols by two-stage hydroformylation of a butene-1 and butene-2-containing olefin mixture, aldol condensation of the resulting aldehyde mixture and subsequent hydrogenation. The hydroformylation is carried out in the first stage in the presence of a homogeneous two-phase reaction system using rhodium complexes based on water-soluble phosphines and in the second stage in a homogeneous phase. How the reaction effluent of the first stage is taken and fed to the second stage is not disclosed; Embodiments are missing.

The EP-A-0 646 563 has one of the EP-A-0 562 451 comparable disclosure content, the reaction being carried out in the second stage in a homogeneous phase in the presence of cobalt compounds as catalysts.

The DE-A-195 30 698 discloses a process for working up a substantially liquid hydroformylation effluent by first depressurizing it into a flash vessel, comprising a liquid phase containing the catalyst, the high boilers and residual amounts of hydroformylation product and unreacted olefin, and a substantially hydroformylation product, unreacted olefin, saturated hydrocarbon and unreacted synthesis gas containing gas phase is formed, the liquid phase in the upper and the gas phase passes into the lower part of a column and the phases in countercurrent, withdrawn at the top of the column enriched with olefin and hydroformylation product gaseous stream and further processed and withdrawing a liquid stream at the bottom of the column and recycled back into the hydroformylation.

The WO 02/068370 describes a two-stage hydroformylation process, the first step being homogeneous, two-phase in the presence of water using water-soluble Rhodium complex catalysts is carried out and in the first Stage unreacted olefins in a second stage in the presence a homogeneous reaction system, which acts as a ligand Chelatdiphosphine comprising a xanthene scaffold. In this process In the first reaction stage, an exhaust gas flow is withdrawn, which in the Substantially unreacted olefinic compounds, carbon monoxide, Carbon dioxide, hydrogen and the hydrogenation products of the olefin and without further workup gaseous in the second reaction stage fed.

The WO 02/068371 has a disclosure content comparable to WO 02/068370, wherein the reaction in the first reaction stage in a homogeneous one-phase reaction system takes place.

The The method disclosed in the last two documents can be found due to the gas feed from the first to the second reaction stage and the associated need for using compressors industrially implement only with great effort and is therefore economically disadvantaged.

Of the The present invention is based on the object, a method for the preparation of hydroformylation products of olefins for disposal to put that simple and economical hydroformylation of olefin mixtures, the olefins contain different reactivity. The procedure in particular, the hydroformylation of technical mixtures from olefins with terminal and more inside Double bond, e.g. As 1-butene / 2-butene mixtures, to aldehyde products with high linearity enable good sales. The invention is further based on the object, a method to provide for the production of 2-propylheptanol.

• a) in eine erste Reaktionszone einen olefinhaltigen Zulauf sowie Kohlenmonoxid und Wasserstoff einspeist und in Gegenwart eines ersten Katalysatorsystems umsetzt,
• b) vom Austrag aus der ersten Reaktionszone einen im Wesentlichen aus nicht umgesetzten Olefinen und gegebenenfalls gesättigten Kohlenwasserstoffen bestehenden flüssigen Strom abtrennt,
• c) den in Schritt b) erhaltenen flüssigen Strom sowie Kohlenmonoxid und Wasserstoff in eine zweite Reaktionszone einspeist und in Gegenwart eines zweiten Katalysatorsystems umsetzt.

Accordingly, a process for the preparation of hydroformylation products of olefins has been found in which

• a) feeding into an initial reaction zone an olefin-containing feed and carbon monoxide and hydrogen and reacting in the presence of a first catalyst system,
• b) separating from the effluent from the first reaction zone a liquid stream consisting essentially of unreacted olefins and optionally saturated hydrocarbons,
• c) feeds the liquid stream obtained in step b) and carbon monoxide and hydrogen into a second reaction zone and reacts in the presence of a second catalyst system.

One Another object of the invention is a process for the preparation of 2-propylheptanol, the hydroformylation of butene by the aforesaid process, an aldol condensation of the resulting hydroformylation products and the subsequent one Hydrogenation of the condensation products includes.

The inventive method comprises as stages a first hydroformylation of olefins (e.g. B. an olefin-containing hydrocarbon feedstock) to to a partial conversion (stage a)), the separation of the reaction effluent the first hydroformylation to yield a substantially from unreacted olefins and, if present, saturated Hydrocarbons existing liquid stream (stage b)) and a subsequent one second hydroformylation of the resulting olefin-containing stream (stage c)). An essential feature of the invention is that for the first and for the second hydroformylation two different catalyst systems be used. By a suitable choice of the catalyst systems allows present method a plurality of olefinically unsaturated Compounds, in particular mixtures of olefins with different Reactivity across from a hydroformylation, with high conversions and, if desired, also with a high n-selectivity to hydroformylate.

suitable Olefin feedstocks for the inventive method are in principle all compounds which one or more ethylenic unsaturated Double bonds included. These include olefins with terminal and with inside Double bonds, straight and branched olefins, cyclic olefins as well as olefins, which under the hydroformylation conditions substantially having inert substituents. Preference is given to olefin feedstocks, the olefins having 4 to 12, more preferably having 4 to 6 carbon atoms contain. Preference is given to those used for the hydroformylation Olefins selected under linear (straight-chain) olefins and olefin mixtures, the contain at least one linear olefin. With the method according to the invention can in particular linear α-olefins, linear internal olefins and mixtures of linear α-olefins and linear internal olefins are hydroformylated.

Suitable α-olefins as substrates for the hydroformylation process according to the invention are preferably C ₄ -C ₂₀ -α-olefins, e.g. 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, allyl alcohols, etc .. Preferred are linear α-olefins and olefin mixtures containing at least one linear α-olefin.

Preferably, the unsaturated compound used for the hydroformylation is selected from among internal linear olefins and olefin mixtures containing at least one internal linear olefin. Suitable linear 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.

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, cyclo hexene, 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 also 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, monoesters 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, oleic acid methyl ester, methyl acrylate and methyl methacrylate. Suitable olefins to be hydroformylated are also unsaturated nitriles, such as 3-pentenenitrile, 4-pentenenitrile and acrylonitrile. Also suitable are vinyl ethers, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc. Suitable olefins to be hydroformylated are also alkenols, alkenediols and alkadienols, such as 2,7-octadienol-1. Suitable olefins to be hydroformylated 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, 1,9-decadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene, Butadiene homo- and copolymers and olefins having terminal and internal double bonds, such as 1,4-octadiene.

Preferably is in the hydroformylation process according to the invention a technically available standing olefin-containing hydrocarbon mixture used.

Preferred industrially available olefin mixtures result from hydrocarbon cracking in petroleum processing, for example by cracking, such as fluid catalytic cracking (FCC), thermocracking or hydrocracking followed by dehydrogenation. A suitable technical olefin mixture is the C _{4 cut} . C ₄ cuts are available, for example, by fluid catalytic cracking or steam cracking of gas oil or by steam cracking of naphtha. Depending on the composition of the C _{4 cut, a} distinction is made between the total C _{4 cut} (crude C _{4 cut} ), the so-called raffinate I obtained after the separation of 1,3-butadiene and the raffinate II obtained after the isobutene separation. Another suitable technical olefin mixture is the C _{5 cut} available from naphtha cleavage. Suitable olefin-containing hydrocarbon mixtures having 4 to 6 carbon atoms for use in step a) can furthermore be obtained by catalytic dehydrogenation of suitable industrially available paraffin mixtures. For example, it is possible to produce C ₄ -olefin mixtures from liquefied petroleum gas (LPG) and liquefied natural gas (LNG). The latter, in addition to the LPG fraction, additionally comprise relatively large amounts of relatively high molecular weight hydrocarbons (light naphtha) and are thus also suitable for the preparation of C ₅ and C ₆ olefin mixtures. The preparation of olefin-containing hydrocarbon mixtures which contain monoolefins having 4 to 6 carbon atoms from LPG or LNG streams is possible by customary methods known to the person skilled in the art, which generally comprise one or more work-up steps in addition to the dehydrogenation. These include, for example, the separation of at least part of the saturated hydrocarbons contained in the aforementioned olefin feed mixtures. For example, these may be reused to produce olefin feeds by cracking and / or dehydrogenation. However, the olefins used in the process according to the invention may also contain a proportion of saturated hydrocarbons which are inert to the hydroformylation conditions according to the invention. The proportion of these saturated components is generally at most 60 wt .-%, preferably at most 40 wt .-%, particularly preferably at most 20 wt .-%, based on the total amount of the olefin contained in the hydrocarbon feedstock and saturated hydrocarbons.

A suitable for use in the process according to the invention raffinate II, for example, has the following composition:
From 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, propene, propane, cyclopropane, propadiene, methylcyclopropane, vinylacetylene, pentenes, pentanes, etc. in the range of not more than 1 wt .-%.

The reaction system used according to the invention has two reaction zones which may each comprise one or more, identical or different reactors. In the simplest case, a reaction zone is formed by a single reactor. Both the reactors of each individual zone and the reactors forming the various stages may each have the same or different mixing characteristics. If desired, the individual reactors of the two zones can be subdivided one or more times by means of internals. Two or more reactors form a zone (stage) of the reaction system tems, so they can be interconnected with each other, z. B. parallel or in series.

suitable pressure-resistant reaction apparatus for the hydroformylation are known to the skilled person. These include the commonplace Reactors for Gas-liquid reactions, such. B. tubular reactors, stirred tank, Gas circulation reactors, bubble columns etc., which may be divided by internals, if necessary.

Carbon monoxide and hydrogen are usually used in the form of a mixture, the so-called synthesis gas. The composition of the synthesis gas used in the process according to the invention can vary within wide limits. In this case, identical or different molar ratios of CO to H ₂ can be set in the two reaction zones forming the reaction system and optionally in the reactors forming a reaction zone. The molar ratio of carbon monoxide and hydrogen is generally 1: 1000 to 1000: 1, preferably 1: 100 to 100: 1.

The Temperature in the hydroformylation reaction is in the two Reaction zones generally in a range of about 20 to 200 ° C, preferably about 50 to 190 ° C, in particular about 60 to 180 ° C. If desired, can in the second reaction zone, a higher temperature than in the first reaction zone can be adjusted, for. B. as possible complete To achieve conversion of heavier hydroformylatable olefins. includes a reaction zone more than one reactor, they may also be the same or have different temperatures. The implementation will be in the two Reaction zones preferably at a pressure in a range of about 1 to 700 bar, particularly preferably 3 to 600 bar, in particular 5 up to 50 bar. The reaction pressure can be used in the hydroformylation used Zones in dependence from the activity of the hydroformylation catalyst used can be varied. So allow the closer in the following described hydroformylation catalysts z. T. an implementation in a range of low pressures, such as in the range of about 1 to 100 bar.

The Reactor volume and / or the residence time of the first reaction zone are chosen that generally at least about 10 wt .-% of the fed Olefins, based on the Gesamtolefinehalt of the hydroformylation used olefin-containing hydrocarbon mixture reacted becomes. Preferred is the conversion based on the olefin content of the olefin-containing feed at least 20% by weight in the first reaction zone.

suitable Hydroformylation catalysts for the first and second hydroformylation stage are generally the usual, the transition metal compounds known to the person skilled in the art and complexes used both with and without cocatalysts can be. Preferably, the transition metal is a metal the VIII. subgroup of the periodic table and in particular Co, Ru, Rh, Pd, Pt, Os or Ir, specifically Rh, Co, Ir or Ru.

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.

Of the Expression "alkylene" within the meaning of the present Invention stands for straight-chain or branched alkanediyl groups having 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 includes saturated, cycloalipha groups having in general from 4 to 7, preferably 5 or 6, ring atoms in which 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from the elements oxygen, nitrogen and sulfur and which may optionally be substituted, in the case of substitution these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1 substituent selected from alkyl, aryl, COOR ^f , COO ^- M ⁺ and NE ¹ E ² , preferably alkyl, can carry. 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" in the context of the present invention comprises unsubstituted and substituted aryl groups, and is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthacenyl, particularly preferably phenyl or naphthyl, these aryl groups in the In the case of a substitution generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent 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.

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 Pyrrolgruppenein heiten 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, where in this information to the number of possible Substi tuenten the linking of the Pyrrolgruppenein units by direct chemical bonding or by the means of the aforementioned groups mediated linking is not considered as a substitution.

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 , NE ²² E ²³ and NE ²⁵ E ²⁶ 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, for example, halide ions X ^- , such as chloride and bromide. Preferred anions are sulfate and sulfonate, for example SO ₄ ^2- , tosylate, trifluoromethanesulfonate and methylsulfonate.

The Values for x stand for an integer of 1 to 240, preferably an integer of 3 to 120.

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.

Preferred complex compounds comprise at least one phosphorus atom-containing compound as ligands. Preferably, the phosphorus atom-containing compounds are selected from PF ₃ , phospholes, phosphabenzenes, mono-, di- and polydentate phosphine, phosphinite, phosphonite, phosphoramidite, phosphites and mixtures thereof.

The according to the invention for the first and second hydroformylation used catalysts can still at least one further ligand, which is preferably selected halides, amines, carboxylates, acetylacetonate, aryl or Alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers and Mixtures thereof.

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 radical used in each case. wherein M is a metal of the VIII. Subgroup, L for a phosphorus-containing compound and q, x, y, z are integers, depending on the valency and nature of the 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.

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 phosphorus atom-containing ligands, 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 sulphate, 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 BF ₃ , AlCl ₃ , ZnCl ₂ , SnCl 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.

suitable Hydroformylation catalysts for the first and second hydroformylation stage be z. In Beller et al., Journal of Molecular Catalysis A, 104 (1995), p. 17-85, which is incorporated herein by reference.

The concrete selection of the first and second catalyst system takes place in accordance with of the olefin-containing hydrocarbon feedstock. It will the first catalyst system chosen so that the first Stage targeted partial sales achieved with the desired product selectivity becomes. In a preferred embodiment is in the first hydroformylation a targeted implementation of Olefins with terminal Double bonds aimed at high n-selectivity. The second hydroformylation stage preferably completes of turnover terminal Olefins and / or for the specific implementation of olefins with internal double bonds also with high n-selectivity.

Preferably For example, the first catalyst system comprises at least one complex of one Metal of the VIII. Subgroup of the Periodic Table of the Elements with at least one organic phosphorus (III) compound as ligands.

Preferably, the organic phosphorus (III) compound is selected from compounds of the general formula PR ¹ R ² R ³ , wherein R ¹ , R ² and R ³ independently of one another are 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, COOH, carboxylate, SO ₃ H, sulfonate, NE ¹ E ² , NE ¹ E ^Z E ³⁺ X ^-, halogen, nitro, acyl or cyano may have, wherein mean e ^1, e ² and e ³ are identical or different radicals chosen from hydrogen, alkyl, cycloalkyl, or aryl, and X ^- is an anion equivalent, and where the cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals may have 1, 2, 3, 4 or 5 substituents which are selected from alkyl and the substituents previously mentioned for the alkyl radicals R ¹ , R ² and R ³ , where R ¹ and R ² together with the phosphorus atom to the s The bonded are also a 5- to 8-membered heterocycle, which is optionally additionally fi-, di- or tri-fused with cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the heterocycle and, if present, the fused groups independently depending one, two, three or four substituents which are selected from alkyl and the substituents previously mentioned for the alkyl radicals R ¹ , R ² and R ³ .

Suitable organic phosphorus (III) compounds are also chelate compounds of the general formula R ¹ R ^Z PY ¹ -PR ¹ R ² , wherein R ¹ and R ^{2 have} the meanings given above and Y ^{1 is} a divalent bridging group. The two radicals R ¹ , the two radicals R ² and the two radicals R ^{3 may} each have the same or different meanings.

worin
R^I, R^II, R^II, R^IV, R^V und R^VI unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, Hydroxy, Thiol, Polyalkylenoxid, Polyalkylenimin, Alkoxy, Halogen, COOH, Carboxylat, SO₃H, Sulfonat, NE⁷E⁸, Alkylen-NE¹E⁸, Trifluormethyl, Nitro, Alkoxycarbonyl, Acyl oder Cyano stehen, worin E⁷ und E⁸ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten,
wobei 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, und
R^d und R^e unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen.Preferably, the bridging group Y ^{1 is} selected from the groups of the formulas III.a to III.t described below, to which reference is hereby made in its entirety. In a particularly preferred embodiment, Y ^{1 is} a group of the formula III.a. In a further particularly preferred embodiment Y ^{1 is} a radical of the formula

wherein
R ^I , R ^II , R ^II , R ^IV , R ^V and R ^VI are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, COOH, carboxylate, SO ₃ H, sulfonate, NE ⁷ E ⁸ , alkylene-NE ¹ E ⁸ , trifluoromethyl, nitro, alkoxycarbonyl, acyl or cyano, in which E ⁷ and E ⁸ each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
wherein 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, and
R ^d and R ^{e are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

Especially preferred hydroformylation catalysts for use in the first Reaction zone are phosphorus-containing rhodium catalysts, as they z. B. under the hydroformylation in situ from a Rhodium source and a triarylphosphine, e.g. B. triphenylphosphine, be formed.

Also suitable for use as the first catalyst system are the catalysts disclosed in WO 00/56451 based on at least one phosphinamidite ligand. Also suitable are those of Veen et al. in Angew. Chem. Int. Ed. 1999, 38, 336 described catalysts based on chelate diphosphines with spines of the xanthene type. Also suitable are the metal complexes with adamantane ligands described in WO 01/85661 and the metal complexes based on diphosphine ligands with two bridged phosphaadamantyl radicals or phospha-oxa-adamantyl radicals described in WO 01/85662. Also suitable are those in the DE-A-100 23 471 hydroformylation catalysts described. The hydroformylation catalysts described in WO 01/58589 are preferably based on phosphorus-containing, diaryl-fused bicyclo [2.2.n] basic bodies.

worin
Y² für eine zweiwertige verbrückende Gruppe steht,
R^α, R^β, 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, NE¹⁰E¹¹, NE¹⁰E¹¹E¹²⁺X^–, Halogen, Nitro, Acyl oder Cyano aufweisen können, worin E¹⁰, E¹¹ und E¹² 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^α, R^β, 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^α, R^β, R^γ und R^δ genannten Substituenten, oder
R^α und R^β und/oder R^γ und R^δ zusammen mit dem Phosphoratom und, falls vorhanden, den Gruppen X¹, X², X⁵ und X⁶, 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, NE¹³E¹⁴, NE¹³E¹⁴E¹⁵⁺X^–, Nitro, Alkoxycarbonyl, Acyl oder Cyano stehen, worin E¹³, E¹⁴ und E¹⁵ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten und X^– für ein Anionäquivalent steht,
X¹, X², X³, X⁴, X⁵ und X⁶ unabhängig voneinander ausgewählt sind unter O, S, SiR^εR^ξ und NR^η, worin R^E, R^ξ und Rⁿ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, und d, e, f, g, h und i unabhängig voneinander für 0 oder 1 stehen.Preferably, the second catalyst system comprises at least one complex of a metal of Group VIII of the Periodic Table of the Elements with at least one phosphorochelate compound as ligands. The phosphorochelate compound is preferably selected from compounds of the general formula I.

wherein
Y ^{2 is} a divalent bridging group,
R ^α , R ^β , 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, polyalkylene oxide, polyalkyleneimine, COOH, carboxylate, SO ₃ H, sulfonate, NE ¹⁰ E ¹¹ , NE ¹⁰ E ¹¹ E ¹²⁺ X ^- , halogen, nitro, acyl or cyano in which E ¹⁰ , E ¹¹ and E ^{12 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 ^α , R ^β , R ^γ and R ^{δ may have} 1, 2, 3, 4 or 5 substituents which are selected from alkyl and those previously for the alkyl radicals R ^α , R ^β , R ^γ and R ^δ substituents, or
R ^α and R ^β and / or R ^γ and R ^δ together with the phosphorus atom and, if present, the groups X ¹ , X ² , X ⁵ and X ⁶ to which they are attached, for a 5- to 8-membered Heterocycle, which is optionally additionally fi-, di- or tri-fused with cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the heterocycle and, if present, the fused groups independently of one another can carry one, two, three or four substituents are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, COOH, carboxylate, SO ₃ H, sulfonate, NE ¹³ E ¹⁴ , NE ¹³ E ¹⁴ E ¹⁵⁺ X ^- , Nitro, alkoxycarbonyl, acyl or cyano in which E ¹³ , E ¹⁴ and E ¹⁵ each represent identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl and X ^{- represents} an anion equivalent,
X ^1, X ^2, X ^3, X ^4, X ⁵ and X ⁶ are independently selected ^ξ from O, S, SiR ^ε R and NR ^η, wherein R ^E, R ^ξ and R ⁿ are independently hydrogen, alkyl, Cycloalkyl, heterocycloalkyl, aryl or hetaryl, and d, e, f, g, h and i independently represent 0 or 1.

The bridging group Y ² preferably is selected in the formula I under the conditions described in the following groups of the formulas III.a to III.t, incorporated herein by reference in its entirety.

Especially are the phosphorochelate compounds used as the second catalyst system selected is among chelated phosphonites, chelated phosphites and chelated phosphoramidites.

Suitable for one Use as a second catalyst system are those in WO 02/22261 described catalysts containing at least one complex of a Comprising metal of VIII. Subgroup with at least one ligand, the selected is among chelated phosphonites and chelated phosphites with xanthene backbone. Suitable are furthermore the pnicogen chelate complexes described in WO 02/083695 based on pnicogen chelate compounds as ligands, which are a skeleton of the xanthene or triptycene type exhibit. Also suitable are those described in WO 03/018192 Catalysts with at least one pyrrole-phosphorus compound as Ligands. Also suitable are those in the German patent application 102 43 138.8 described catalysts. On the revelation of The above documents are fully incorporated by reference.

als Liganden, worin
R⁴, R⁵, R⁶ und R⁷ unabhängig voneinander für heteroatomhaltige Gruppen stehen, die über ein Sauerstoffatom oder ein gegebenenfalls substituiertes Stickstoffatom an das Phosphoratom gebunden sind oder R⁴ gemeinsam mit R⁵ und/oder R⁶ gemeinsam mit R⁷ eine zweibindige heteroatomhaltige Gruppe bilden, die über zwei Heteroatome, ausgewählt unter Sauerstoff und/oder gegebenenfalls substituiertem Stickstoff, an das Phosphoratom gebunden sind,
a und b unabhängig voneinander die Zahl 0 oder 1 bedeuten, und
Y³ für eine zweiwertige verbrückende Gruppe mit 2 bis 20 Brückenatomen zwischen den flankierenden Bindungen steht, wobei mindestens zwei Brückenatome Teil einer alicyclischen oder aromatischen Gruppe sind.The second catalyst system preferably comprises at least one complex of a metal of transition group VIII of the Periodic Table of the Elements with at least one phosphorochelate compound of general formula II

as ligands, in which
R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently heteroatom-containing groups which are bonded via an oxygen atom or an optionally substituted nitrogen atom to the phosphorus atom or R ⁴ together with R ⁵ and / or R ⁶ together with R ^{7 is} a divalent form heteroatom-containing group which are bonded to the phosphorus atom via two heteroatoms selected from oxygen and / or optionally substituted nitrogen,
a and b are independently 0 or 1, and
Y ^{3 is} a divalent bridging group having 2 to 20 bridging atoms between the flanking bonds, at least two bridging atoms being part of an alicyclic or aromatic group.

The individual phosphorus atoms of the phosphorochelate compounds of the formula II are each connected via two covalent bonds with the substituents R ⁴ and R ⁵ or R ⁶ and R ⁷ , where the substituents R ⁴ , R ⁵ , R ⁶ and R ⁷ in a first embodiment of heteroatom-containing groups which are bonded via an oxygen atom or an optionally substituted nitrogen atom to the phosphorus atom, wherein R ⁴ and R ⁵ or R ⁶ and R ^{7 are} not joined together. Preferably, R4, R5, R ⁶ and R ⁷ then for bound via the pyrrole nitrogen atom to the phosphorus atom Pn pyrrole. The meaning of the term pyrrole group corresponds to the definition given above.

In a further embodiment, R ⁴ together with R ⁵ and / or R ⁶ together with R ^{7 form} a divalent heteroatom-containing group which are bonded to the phosphorus atom via two heteroatoms selected from oxygen and optionally substituted nitrogen. Advantageously, then the substituent R ⁴ together with the substituent R ⁵ and / or the substituent R ⁶ together with the substituent R ^{7 can form} a bound via the pyrrole nitrogen atoms to the phosphorus atom bispyrrole group. Furthermore, advantageously, the substituent R ⁴ together with the substituent R ⁵ and / or the substituent R ⁶ together with the substituent R ^{7 form} a bridging group bonded via two oxygen atoms to the phosphorus atom.

worin
Alk eine C₁-C₄-Alkylgruppe ist und
R^o, R^p, R^q und R^r 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 ⁴ , R ⁵ , R ⁶ and R ⁷ are selected independently of one another from groups of the formulas II.a to IIk:

wherein
Alk is a C ₁ -C ₄ alkyl group and
R ^o , R ^p , R ^q and R ^r independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, acyl, halogen, trifluoromethyl, C ₁ -C ₄ -alkoxycarbonyl or carboxyl.

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, the substituent R ⁴ together with the substituent R ⁵ or the substituent R ⁶ together with the substituent R ^7, a bonded via the pyrrole nitrogen atom to the phosphorus pyrrole group containing divalent group of the formula Py-IW form,
wherein
Py is a pyrrole group,
I ^ξ for a chemical bond or O, S, SiR ^ε R, NR ^η or optionally substituted C ₁ -C ₁₀ alkylene, preferably CR ^λ R ^μ, is,
W is cycloalkyloxy or amino, aryloxy or amino, hetaryloxy or amino
and
R ^ε , R ^ξ , R ^η , R ^λ and R ^μ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
wherein the terms used herein have the meaning explained above.

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

bildet, worin
I für eine chemische Bindung oder für O, S, SiR^εR^ξ,NR^η oder gegebenenfalls substituiertes C₁-C₁₀-Alkylen, bevorzugt CR^λR^μ, steht, worin R^ε, R^ξ, R^η, R^λ und R^μ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
R³⁵, R^35', R³⁶, R³⁶, R³⁷, R^37', R³⁸ und R^38' 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'NE¹⁶E¹⁷ W'(NE¹⁶NE¹⁷NE¹⁸)⁺X^–, W'OR^f, W'SR^f, (CHR^gCH₂O)_xRf, (CH₂NE¹⁶)_xR^f, (CH₂CH₂NE¹⁶)_XR^f, Halogen, Trifluormethyl, 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, E¹⁶, E¹⁷, E¹⁸ 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 jeweils zwei benachbarte Reste R³⁵ und R³⁶ und/oder R^35' und R^36' 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.Preference is given to phosphorus chelate compounds in which the substituent R ⁴ together with the substituent R ⁵ or the substituent R ⁶ together with the substituent R ^{7 is} a bispyrrole group of the formula

forms, in which
I ^ξ for a chemical bond or O, S, SiR ^ε R, NR ^η or optionally substituted C ₁ -C ₁₀ alkylene, be preferably CR ^λ R ^μ , in which R ^ε , ^Rξ , R ^η , R ^λ and R ^μ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R ³⁵ , R ^{35 '} , R ³⁶ , R ³⁶ , R ³⁷ , R ^37' , R ³⁸ and R ^{38 '} 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 ¹⁶ E ¹⁷ W' (NE ¹⁶ NE ¹⁷ NE ¹⁸ ) ⁺ X ^- , W'OR ^f , W'SR ^f , (CHR ^g CH ₂ O) _x Rf, (CH ₂ NE ¹⁶ ) _x R ^f , CH ₂ CH ₂ NE ¹⁶ ) _X R ^f , halogen, trifluoromethyl, nitro, acyl or cyano, in which
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 ¹⁶ , E ¹⁷ , E ^{18 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,
wherein in each case two adjacent radicals R ³⁵ and R ³⁶ and / or R ^{35 '} and R ^36' together with the carbon atoms of the pyrrole ring to which they are attached may also be a fused ring system having 1, 2 or 3 further rings.

Preferably, I is a chemical bond or a C ₁ -C ₄ -alkylene group, more preferably a methylene group.

As an illustration, some advantageous "bispyrrolyl groups" are listed below:

stehen, worin
k und l 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, NE⁴E⁵, Alkylen-NE⁴E⁵, 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.Further preferred phosphorus chelate compounds of general formula II, wherein R ⁴ and R ⁵ and / or R ⁶ and R ^{7 are} each taken together with the pnicogen atom to which they are attached, for a group of general formula II.A

stand in which
k and l 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 ⁴ E ⁵ , alkylene -NE ⁴ E ⁵ , 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 is 1, 2 or 3 optionally substituted heteroatoms may be interrupted.

Depending on whether the group of the general formula II.A via an oxygen atom (a or b = 1) or a covalent bond (a or b = 0) is bound to the group Y ³ , and whether k and l is 0 or 1, stand the phosphorus lat compounds of the formula II according to the invention thus at least one phosphine, phosphinite, phosphonite and / or phosphite radical. The groups of the formula II.A are preferably bonded to the group Y ³ via an oxygen atom and k and l are 1 (phosphite groups).

The radical Q preferably represents a C ₂ -C ₆ -alkylene bridge, which is fused to aryl once or twice and / or which may have a substituent which is selected from alkyl, optionally substituted cycloalkyl and optionally substituted aryl, and / or which may be interrupted by an optionally substituted heteroatom.

The fused aryls of the radicals Q are preferably benzene or naphthalene. 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 ⁴ E ⁵ , alkylene-NE ⁴ E ⁵ , 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.

When the C ₂ -C ₆ -alkylene bridge of the radical Q is interrupted by 1, 2 or 3, optionally substituted heteroatoms, these are preferably selected from O, S or NR ^m , where R ^{m is} alkyl, cycloalkyl or aryl. Preferably, the C ₂ -C ₆ -alkylene bridge of the radical Q is interrupted by an optionally substituted heteroatom.

When the C ₂ -C ₆ -alkylene bridge of the radical Q is substituted, it preferably has 1, 2 or 3, in particular 1, substituent (s) selected from alkyl, cycloalkyl and aryl, the aryl substituent being 1, 2 or 3 of the substituents mentioned for aryl. Preferably, the alkylene bridge Q has a substituent selected from methyl, ethyl, isopropyl, phenyl, p- (C ₁ -C ₄ alkyl) phenyl, preferably p-methylphenyl, p- (C ₁ -C ₄ alkoxy) phenyl, preferably p-methoxyphenyl, p-halophenyl, preferably p-chlorophenyl and p-trifluoromethylphenyl.

The radical Q is preferably a C ₃ -C ₅ -alkylene bridge which is fused and / or substituted as described above and / or interrupted by optionally substituted heteroatoms. In particular, the radical Q is a C ₃ -C ₆ -alkylene bridge which is fused once or twice with benzene and / or naphthalene, the phenyl or naphthyl groups carrying 1, 2 or 3, in particular 1 or 2, of the abovementioned substituents can.

worin
Z¹ für O, S oder NR^m steht, wobei
R^m für Alkyl, Cycloalkyl oder Aryl steht,
oder Z¹ für eine C₁-C₃-Alkylenbrücke steht, die eine Doppelbindung und/oder wenigstens einen Substituenten, ausgewählt unter Alkyl-, Cycloalkyl- oder Arylsubstituenten, aufweisen kann, wobei die Alkyl-, Cycloalkyl- oder Arylsubstituenten ihrerseits einen, zwei oder drei der eingangs für diese Gruppen genannten Substituenten tragen können,
oder Z¹ für eine C₂-C₃-Alkylenbrücke steht, die durch O, S oder NR^m unterbrochen ist,
R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸ und R²⁹ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Alkoxy, Halogen, SO₃H, Sulfonat, NE¹⁹E²⁰, Alkylen-NE¹⁹E²⁰, Trifluormethyl, Nitro, Alkoxycarbonyl, Carboxyl oder Cyano stehen, worin E¹⁹ und E²⁰ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl oder Aryl stehen.Preferably, the radical Q (ie R ⁴ and R ⁵ or R ⁶ and R ⁷ together) together with the phosphorus atom and the oxygen atoms to which it is attached, represents a 5- to 8-membered heterocycle, wherein Q (R ⁴ and R ⁵ or R ⁶ and R ⁷ together) is a radical which is selected from the radicals of the formulas II.1 to II.5,

wherein
Z ^{1 is} O, S or NR ^m , where
R ^{m is} alkyl, cycloalkyl or aryl,
or Z ^{1 is} a C ₁ -C ₃ -alkylene bridge which may have a double bond and / or at least one substituent selected from alkyl, cycloalkyl or aryl substituents, the alkyl, cycloalkyl or aryl substituents in turn having one, two or more substituents or three of the substituents mentioned at the outset for these groups,
or Z ^{1 is} a C ₂ -C ₃ -alkylene bridge which is interrupted by O, S or NR ^m ,
R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are each independently hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, SO ₃ H, sulfonate, NE ¹⁹ E ²⁰ , alkylene-NE ¹⁹ E ²⁰ , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, wherein E ¹⁹ and E ^{20 are} independently hydrogen, alkyl, cycloalkyl or aryl.

Preferably, Q is a radical of formula II.1, wherein R ²⁰ , R ²¹ and R ^{22 are} hydrogen.

worin
R²⁰ und R²⁴ für Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, SO₃H, Sulfonat, NE⁹E¹⁰, Alkylen-NE⁹E¹⁰, vorzugsweise Wasserstoff, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy, insbesondere Methyl, Methoxy, Isopropyl oder tert.-Butyl, steht,
R²¹ und R²³ für Wasserstoff, C₁-C₄-Alkyl, bevorzugt Methyl, Isopropyl oder tert.-Butyl, C₁-C₄-Alkoxy, bevorzugt Methoxy, Fluor, Chlor oder Trifluormethyl, steht. R²¹ kann auch für SO₃H, Sulfonat, NE⁹E¹⁰ oder Alkylen-NE⁹E¹⁰ stehen.Preferably, Q is a radical of the formula II.2a

wherein
R ²⁰ and R ^{24 are} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, SO ₃ H, sulfonate, NE ⁹ E ¹⁰ , alkylene-NE ⁹ E ¹⁰ , preferably hydrogen, C ₁ -C ₄ -Alkyl or C ₁ -C ₄ -alkoxy, in particular methyl, methoxy, isopropyl or tert-butyl,
R ²¹ and R ^{23 are} hydrogen, C ₁ -C ₄ -alkyl, preferably methyl, isopropyl or tert-butyl, C ₁ -C ₄ -alkoxy, preferably methoxy, fluorine, chlorine or trifluoromethyl. R ²¹ can also stand for SO ₃ H, sulfonate, NE ⁹ E ¹⁰ or alkylene-NE ⁹ E ¹⁰ .

worin
R²⁰, R²¹, R²³ und R²⁴ die zuvor bei der Formel II.2a angegebenen Bedeutungen besitzen,
Rⁿ für Wasserstoff, C₁-C₄-Alkyl, bevorzugt Methyl oder Ethyl, Phenyl, p-(C₁-C₄-Alkoxy)phenyl, bevorzugt p-Methoxyphenyl, p-Fluorphenyl, p-Chlorphenyl oder p-(Trifluormethyl)phenyl steht.Preferably, Q is a radical of the formula II.3a

wherein
R ²⁰ , R ²¹ , R ²³ and R ^{24 have} the meanings given above for the formula II.2a,
R ^{n is} hydrogen, C ₁ -C ₄ alkyl, preferably methyl or ethyl, phenyl, p- (C ₁ -C ₄ alkoxy) phenyl, preferably p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl or p- (trifluoromethyl ) phenyl.

Preferably, Q is a radical of formula II.4, wherein R ²⁰ to R ^{29 are} hydrogen.

Q preferably represents a radical of the formula II.4 in which R ²⁰ , R ²¹ , R ²² , R ²³ , R ²³ , R ²⁵ , R ²¹ and R ^{29 are} hydrogen and the radicals R ²⁶ and R ²⁸ are each independently Alkoxycarbonyl, preferably methoxy, ethoxy, n-propyloxy or Isopropyloxycarbonyl stand. In particular, the radicals R ²⁶ and R ²⁸ are ortho to the phosphorus atom or, if present (k and / or l = 1), oxygen atom.

Q preferably represents a radical of the formula II.5 in which R ²⁰ to R ^{29 are} hydrogen and Z ^{1 is} CR ⁿ R ^{n '} , where R ⁿ and R ^n' are each, independently of one another, hydrogen, C ₁ -C ₄ - Alkyl, preferably methyl or ethyl, phenyl, p- (C ₁ -C ₄ alkoxy) phenyl, preferably p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl or p- (trifluoromethyl) phenyl.

Preferably, Q is a radical of formula II.5, wherein R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ^{29 are} hydrogen, Z ^{1 is} CR ⁿ R ^{n '} and the radicals R ²⁶ and R ²⁸ independently of one another are alkoxycarbonyl, preferably methoxy, ethoxy, n-propyloxy or isopropyloxycarbonyl. In particular, the radicals R ²⁶ and R ²⁸ are ortho to the phosphorus atom or oxygen atom.

worin
R^I, R^I', R^II, R^II', R^III, R^IV', R^IV', R^V, R^VI, 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, NE²²E²³, Alkylen-NE²²E²³, Trifluormethyl, Nitro, Alkoxycarbonyl, Carboxyl, Acyl oder Cyano stehen, worin E²² und E²³ jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten,
Z für O, S, NR¹⁵ oder SiR¹⁵R¹⁶ steht, wobei
R¹⁵ und R¹⁶ 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 NR¹⁵ oder SiR¹⁵R¹⁶ 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 geminate 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 kann,
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 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 für eine zweibindige Brückengruppe der allgemeinen Formel

steht, in der
R⁹, R^9', R¹⁰ und R^10' unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, Carboxyl, Carboxylat oder Cyano stehen,
wobei R^9' auch gemeinsam mit R^10' für den Bindungsanteil einer Doppelbindung zwischen den beiden Kohlenstoffatomen, an die R^9' und R^10' gebunden sind, stehen kann, und/oder R⁹ und R¹⁰ 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^f, COO^–M⁺, SO₃R^f, SO^– ₃M⁺, NE²⁵E²⁶, Alkylen-NE²⁵E²⁶, NE²⁵E²⁶E²⁷⁺X^–, Alkylen-NE²⁵E²⁶E²⁷⁺X^–, OR^f, SR^f, (CHR^gCH₂O)_yR^f, (CH₂N(E²⁵))_yR^f, (CH₂CH₂N(E²⁵))_yR^f, Halogen, Trifluormethyl, Nitro, Acyl oder Cyano, stehen, worin
R^f, E²⁵, E²⁶ und E²⁷ 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
y für eine ganze Zahl von 1 bis 120 steht, und
c 0 oder 1 ist.In a preferred embodiment, the bridging group Y ^{3 is} selected from groups of formulas III.a to III.t.

wherein
R ^I , R ^{I '} , R ^II , R ^II' , R ^III , R ^{IV '} , R ^IV' , R ^V , R ^VI , 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 ²² E ²³ , alkylene-NE ²² E ²³ , trifluoromethyl, nitro, Alkoxycarbonyl, carboxyl, acyl or cyano in which E ²² and E ²³ each represent identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl,
Z is O, S, NR ¹⁵ or SiR ¹⁵ R ¹⁶ , where
R ¹⁵ and R ¹⁶ 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 ¹⁵ or SiR ¹⁵ R ¹⁶ ,
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, wherein in the groups of the formulas III.g to III.m two geminate 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 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 of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl 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 of the general formula

stands in the
R ⁹ , R ^{9 '} , R ¹⁰ and R ^10' independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano,
wherein R ^{9 'may} also be taken together with R ^10' for the bond portion of a double bond between the two carbon atoms to which R ^{9 '} and R ^{10' are} bonded, and / or R ⁹ and R ¹⁰ 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 selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COOR ^f , COO ^- M ⁺ , SO ₃ R ^f , SO ^- ₃ M ⁺ , NE ²⁵ e ^{26 25} e ²⁶ alkylene-NE, NE ²⁵ e ²⁶ e ²⁷⁺ X ^-, alkylene-NE ²⁵ e ²⁶ e ²⁷⁺ X ^-, OR ^f, SR ^f, (CHR ^g CH ₂ O) _y R ^f, (CH ₂ N (E ²⁵ )) _y R ^f , (CH ₂ CH ₂ N (E ²⁵ )) _y R ^f , halogen, trifluoromethyl, nitro, acyl or cyano, in which
R ^f , E ²⁵ , E ²⁶ and E ^{27 are} each the same 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
y is an integer from 1 to 120, and
c is 0 or 1.

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

The bridging group Y ^{3 is} preferably a group of the formula III.a. In group III.a, the groups A ¹ and A ^{2 may be,} in general, independently O, S, SiR ^a R ^b , NR ^c or CR ^d R ^e , wherein the substituents R ^a , R ^b and R ^c in general independently of one another can have the meaning hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, whereas the groups R ^d and R ^e independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R ^d together with another Group R ^d or the group R ^e together with another group R ^e can form an intramolecular bridging group D.

in denen R⁹, R^9', R¹⁰ und R^10' unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, Carboxyl, Carboxylat oder Cyano stehen oder miteinander zu einer C₃-C₄-Alkylengruppe verbunden sind und R¹¹, R¹², R¹³ und R¹⁴ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, COOH, Carboxylat, Cyano, Alkoxy, SO₃H, Sulfonat, NE¹E², Alkylen-NE¹E²E³⁺X^–, Aryl oder Nitro stehen können. Vorzugsweise stehen die Gruppen R⁹, R^9', R¹⁰ und R^10' für Wasserstoff, C₁-C₁₀-Alkyl oder Carboxylat und die Gruppen R¹¹, R¹², R¹³ und R¹⁴ für Wasserstoff, C₁-C₁₀-Alkyl, Halogen, insbesondere Fluor, Chlor oder Brom, Trifluormethyl, C₁-C₄-Alkoxy, Carboxylat, Sulfonat oder C₁-C₈-Aryl. Besonders bevorzugt stehen R⁹, R^9', R¹⁰, R^10', R¹¹, R¹², R¹³ und R¹⁴ 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 R¹¹, R¹², R¹³ und/oder R¹⁴ für eine COO^–M⁺, eine SO₃ ^–M⁺ oder eine (NE¹E²E³)⁺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 ⁹ , R ^{9 '} , R ¹⁰ 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 group and 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 ^- , aryl or nitro can stand. The groups R ⁹ , R ^{9 '} , R ¹⁰ and R ^10' are preferably hydrogen, C ₁ -C ₁₀ -alkyl or carboxylate and the groups R ¹¹ , R ¹² , R ¹³ and R ^{14 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 preferably R ⁹ , R ^{9 '} , R ¹⁰ , R ^10' , R ¹¹ , R ¹² , R ¹³ and R ^{14 are} 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 ¹¹ , R ¹² , R ¹³ and / or R ¹⁴ for a COO ^- M ⁺ , a SO ₃ ^- M ⁺ or a (NE ¹ E ² E ³ ) ⁺ 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 ^d forms an intramolecular bridging group D with another group R ^d or R ^e with another group R ^e , ie the index c is 1 in this case, it necessarily follows that both A ¹ and A ² together form a bridging group, preferably a CR ^d R ^e group and the bridging group Y ^{3 of} the formula III.a in this case preferably has a triptycene-like or ethanoanthracene-like carbon skeleton.

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

Particularly preferred bridging groups Y ^{3 of} the formula III.a are thus those which are synthesized from a triptycene-like, ethanoanthracene-like or xanthene-like (A ¹ : CR ^d R ^e , A ² : O) skeleton.

In the bridge groups Y ³ of the formula III.a the substituents R ^I, R ^II, R ^III, R ^IV, R ^V and R ^VI is 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 ^II , 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 formula III.a standing in the bridging groups Y ^3, 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, COOR ^f , 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 ³ is 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 ³ is 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 ³ is 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 ³ furthermore preferably represents 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 ³ is 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 ^{3 is} 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 ³ 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 ^{3 is} 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.

Y ³ furthermore 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 ³ 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.

Y ³ furthermore preferably represents a group of the formula III.h in which R ¹ , R ^{1 '} , R ^II , R ^II' , R ^III and R ^{III 'are} hydrogen.

Y ³ furthermore preferably represents 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.

Y ³ furthermore 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 stand for hydrogen.

Y ³ furthermore 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 ³ is preferably 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 ³ is preferably a group of the formula III.m where R ¹ , R ^{1 '} , R ^II , R ^II' , R ^III , R ^{III '} , R ^IV and R ^{IV are} hydrogen.

Furthermore, Y ³ is preferably 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 stand for hydrogen.

Y ³ furthermore preferably represents 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.

Furthermore, Y ³ is preferably a group of the formula III.o in which R ¹ , R ^II , R ^III and R ^{IV are} hydrogen.

Y ³ furthermore preferably represents 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, Y ³ is preferably 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 ^II, R ^III and R ^IV are independently C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy. Particularly preferably, R ^I , R ^II , R ^III and R ^{IV are} then independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.

Furthermore, Y ³ is preferably 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 ³ is 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.

The procedural embodiment of the method according to the invention is explained in more detail below:
The effluent from the first reaction zone is subjected to a one or more stage separation operation to obtain at least one stream containing the majority of the hydroformylation product and a stream consisting essentially of unreacted olefin and optionally saturated hydrocarbon. Saturated hydrocarbons originate, for example, from the olefin-containing feed used for the hydroformylation, which may contain them as an admixture, or else to a small extent from the hydrogenation of the olefin used. Depending on the discharge and separation processes used, other streams are optionally obtained, such as synthesis gas-containing exhaust gases, high-boiling by-products of the hydroformylation and / or hydroformylation catalyst-containing streams which - optionally after work-up - are completely or partially recycled to the first reaction zone or discharged from the process ,

• i) das Hydroformylierungsprodukt, d. h. die aus dem eingesetzten Olefin oder Olefingemischen bereits in der ersten Reaktionszone erzeugten Aldehyde,
• ii) die hochsiedenden Nebenprodukte der Hydroformylierung, wie sie z. B. aus der Aldolreaktion der gebildeten Aldehyde resultieren,
• iii) den homogen gelösten ersten Hydroformylierungskatalysator,
• iv) nicht umgesetzte Olefine,
• v) leichtsiedende Komponenten, wie Alkane, und
• vi) gelöstes Synthesegas.

Preferably, a liquid discharge is removed from the first reaction zone (liquid discharge process). This liquid discharge contains as essential components:

• i) the hydroformylation product, ie the aldehydes already produced in the first reaction zone from the olefin or olefin mixtures used,
• ii) the high-boiling by-products of the hydroformylation, as described, for. B. resulting from the aldol reaction of the aldehydes formed,
• iii) the homogeneously dissolved first hydroformylation catalyst,
• iv) unreacted olefins,
• v) low-boiling components, such as alkanes, and
• vi) dissolved synthesis gas.

If an inert solvent, such as toluene or xylene, is used for the hydroformylation, this too is contained in the liquid discharge from the first reaction zone. As a rule, as a solution mean the formed in the hydroformylation (eg by aldol condensation), higher than the hydroformylation product boiling by-products used.

Preferably becomes the liquid Hydroformylation discharge from the first reaction zone for work-up subjected to a two-stage degassing. This can happen the first degassing stage to a rest and / or relaxation stage act. In the simplest version The first degassing stage as a rest zone is the liquid hydroformylation discharge transferred from the first reaction zone in a container which under the pressure of the Reaction zone is. This is a separation into a first Liquid phase and a first gas phase. To separate the first gas phase as possible without liquid components a corresponding device for removal entrained Tröpchen (Demister) be provided.

Especially preferred is the liquid Hydroformylation discharge from the first reaction zone for work-up subjected to a two-stage relaxation. The hydroformylation in the first reaction zone is preferably carried out at a pressure in Range from 5 to 50 bar. Preference is given to the liquid hydroformylation discharge from the first reaction zone in a first expansion stage a pressure relaxed, the 0.1 to 20 bar below the reactor pressure lies. In this case, a separation into a first liquid phase takes place and a first gas phase. The first liquid phase is preferred relaxed in a second expansion stage to a pressure, the lower than the pressure in the first expansion stage. there a separation into a second liquid phase and a second gas phase takes place.

The Partial relaxation in the first expansion stage can, for example in a usual Pressure separator done. The obtained first gas phase consists in Essentially from synthesis gas and possibly small proportions on unreacted olefin and / or low boiling components (saturated hydrocarbons). The first gas phase can be reused in the process according to the invention or independent thereof supplied in other methods become. It can, for example, usually after compression to the reactor pressure, returned to the reactor or, depending on the quantity, partially or completely a thermal utilization supplied become.

The in the first expansion stage deposited first liquid phase is then usually considered more fluid Electricity discharged from the flash tank and relaxed in a second expansion stage to a pressure, which is lower than the pressure of the first expansion stage. Preferably is relaxed to a pressure in the second expansion stage, which is in the range of 0 to 10 bar, preferably 0.1 to 5 bar. The pressure in the second expansion stage is generally by 2 to 20 bar, in particular by 3 to 15 bar, lower than that Pressure in the first relaxation stage.

The from the first rest / relaxation stage obtained first liquid phase is in the second expansion stage (degassing) in a second liquid phase and a second gas phase separated. The second liquid phase contains the higher as the hydroformylation product boiling by-products, the homogeneous dissolved first hydroformylation catalyst and a portion of the hydroformylation product. The second gas phase contains the unreacted olefin, saturated Hydrocarbons and also a part of the hydroformylation product.

The second expansion stage is in a preferred embodiment as a combination of the relaxation step (Flash) with a thermal Separation step performed. For example, in this thermal separation step to act around a distillation. Preference is given to distillation for the second liquid phase and second gas phase from the second expansion step in countercurrent guided and so in particularly intimate contact (stripping). second Relaxation step and thermal separation step may occur in separate devices or advantageously in a single device, z. B. a so-called "flash / strip column" done.

In the embodiment of the second expansion stage with separate thermal separation, the first liquid phase discharged from the first expansion stage can first be expanded in a flash tank. The resulting second gas phase is passed into the bottom or the lower part of a downstream distillation column. The (second) liquid phase from the flash vessel is fed to this distillation column above the feed of the gas phase. For this purpose, the (second) liquid phase can be supplied from the flash vessel to this distillation column, for example at or just below the top. For this purpose, the second liquid phase can be heated beforehand, for example in a heat exchanger. Preferably, the second liquid phase is heated to a temperature which is about 10 ° C to 120 ° C above the temperature of the liquid phase in the flash tank (in the second expansion stage). Suitable columns are the usual, known in the art distillation columns, z. B. with packing, packaging or installation are equipped for an intensive gas / liquid exchange.

at the configuration of the second expansion stage as "flash / strip column" is from the first expansion stage discharged first liquid phase in one area above the bottom and below the top of the flash / strip column fed and relaxed. The separation takes place in the second gas phase and the second liquid phase. Preferably takes place the feed within the lower half, especially within the lower third of the flash / strip column. At the bottom of the flash / strip column becomes a liquid Power removed and the column at or below the head again fed. Thus, the runaway liquid phase becomes the second gas phase led to stripping. This can be the liquid phase previously heated become. Preferably, the withdrawn from the sump liquid phase heated to a temperature which is about 10 ° C up to 120 ° C above the Temperature of the swamp is. The columns used have in the upper area, in particular within the upper third, preferably Internals for one intensive gas / liquid exchange on.

Either in embodiment of the second expansion stage with separate thermal Separation as well as the use of a flash / strip column one solved first hydroformylation catalyst and higher than the hydroformylation product boiling third by-products of the hydroformylation liquid Phase and a hydroformylation product that is unreacted Olefin and saturated hydrocarbons containing third gas phase.

The third liquid Phase may, optionally after a separation of the high boilers, to avoid their accumulation, be returned to the first reaction zone.

The in the second relaxation (strip) stage obtained third gas phase is a separation into a substantially hydroformylation product containing fraction and a substantially unreacted Subjected to fraction containing olefin and low-boiling components. This can be the third gas phase of a fractional condensation be subjected. The third gas phase can continue to be completely condensed and subsequently be subjected to thermal separation. The hydroformylation product is supplied to a further utilization, as described below. The unreacted olefin and low boiling components containing Fraction can after condensation as a liquid stream in the second Reaction zone are fed. In a special embodiment this faction will be an extra Workup to separate at least part of the contained inert components (saturated Hydrocarbons). For example, the group can a renewed fractional condensation or a complete condensation with following Be subjected to distillation.

• b1) den flüssigen Austrag aus der ersten Reaktionszone, der als wesentliche Bestandteile das Hydroformylierungsprodukt, höher als das Hydroformylierungsprodukt siedende Nebenprodukte, den homogen gelösten ersten Hydroformylierungskatalysator, nicht umgesetztes Olefin, gesättigte Kohlenwasserstoffe und nicht umgesetztes Synthesegas enthält einer Entgasung unterzieht, wobei gegebenenfalls der Druck und/oder die Temperatur gegenüber der Reaktionszone er niedrigt werden, und wobei eine erste im Wesentlichen das nicht umgesetzte Synthesegas enthaltende Gasphase und eine erste im Wesentlichen das Hydroformylierungsprodukt, höher als das Hydroformylierungsprodukt siedende Nebenprodukte, den homogen gelösten ersten Hydroformylierungskatalysator, nicht umgesetztes Olefin und gesättigte Kohlenwasserstoffe enthaltende flüssige Phase resultieren,
• b2) die erste Gasphase einer Verwertung zuführt,
• b3) die erste flüssige Phase einer Entspannung unterzieht, wobei der Druck gegenüber der ersten Entgasung soweit erniedrigt wird, das eine zweite das nicht umgesetzte Olefin, gesättigte Kohlenwasserstoffe und einen Teil des Hydroformylierungsprodukts enthaltende Gasphase und eine zweite die höher als das Hydroformylierungsprodukt siedenden Nebenprodukte, den homogen gelösten ersten Hydroformylierungskatalysator und einen Teil des Hydroformylierungsprodukts enthaltende flüssige Phase resultieren,
• b4) die zweite Gasphase in den Sumpf oder den unteren Teil einer Kolonne einspeist und die zweite flüssige Phase, gegebenenfalls nach Erwärmung, in flüssiger Form oberhalb der Einspeisung der Gasphase in diese Kolonne einspeist und der Gasphase entgegenführt,
• b5) am Sumpf der Kolonne eine im Wesentlichen den gelösten ersten Hydroformylierungskatalysator und die höher als das Hydroformylierungsprodukt siedenden Nebenprodukte der Hydroformylierung enthaltende dritte flüssige Phase abzieht und am Kopf der Kolonne eine das Hydroformylierungsprodukt, das nicht umgesetzte Olefin und gesättigte Kohlenwasserstoffe enthaltende dritte Gasphase abzieht,
• b6) die dritte flüssige Phase, gegebenenfalls nach Abtrennung wenigstens eines Teils der höher als das Hydroformylierungsprodukt siedenden Nebenprodukte in die erste Reaktionszone zurückführt, und
• b7) die dritte Gasphase einer Aufarbeitung zum Erhalt einer im Wesentlichen das Hydroformylierungsproduktenthaltenden Fraktion und einer im Wesentlichen das nicht umgesetzte Olefin und gesättigte Kohlenwasserstoffe enthaltenden Fraktion unterzieht.

In summary, step b) is preferably an embodiment according to which one

• b1) degassing the liquid effluent from the first reaction zone, which contains as essential constituents the hydroformylation product, by-products boiling higher than the hydroformylation product, the homogeneously dissolved first hydroformylation catalyst, unreacted olefin, saturated hydrocarbons and unreacted synthesis gas, where appropriate the pressure and or the temperature relative to the reaction zone is lowered, and wherein a first substantially unreacted synthesis gas containing gas phase and a first substantially the hydroformylation product, higher than the hydroformylation product boiling by-products, the homogeneously dissolved first hydroformylation, unreacted olefin and saturated hydrocarbons containing liquid phase result,
• b2) supplies the first gas phase to recovery,
• b3) subjecting the first liquid phase to a relaxation, wherein the pressure compared to the first degassing is lowered so far, the second containing the unreacted olefin, saturated hydrocarbons and a portion of the hydroformylation product gas phase and a second higher boiling than the hydroformylation by-products, the homogeneously dissolved first hydroformylation catalyst and a portion of the hydroformylation product containing liquid phase result,
• b4) feeds the second gas phase into the bottom or the lower part of a column and feeds the second liquid phase, optionally after heating, in liquid form above the feed of the gas phase into this column and leads it to the gas phase,
• b5) withdrawing at the bottom of the column a third liquid phase containing essentially the dissolved first hydroformylation catalyst and the by-products of hydroformylation boiling higher than the hydroformylation product, and at the top of the column a third gas phase containing the hydroformylation product containing unreacted olefin and saturated hydrocarbons,
• b6) the third liquid phase, optionally after separation of at least a portion of the higher than the hydroformylation product boiling by-products in the first reaction zone, and
• b7) subjecting the third gas phase to a workup to obtain a fraction containing substantially the hydroformylation product and a fraction substantially containing the unreacted olefin and saturated hydrocarbons.

• d) vom Austrag aus der zweiten Reaktionszone einen im Wesentlichen aus gesättigten Kohlenwasserstoffen und gegebenenfalls einem geringen Anteil nicht umgesetztn Olefins bestehenden Strom abtrennt,
• e) gegebenenfalls den in Schritt d) erhaltenen Strom durch Rektifikation in eine Olefin-angereicherte und eine Olefin-abgereicherte Fraktion trennt, und die Olefinangereicherte Fraktion zumindest teilweise in die erste und/oder die zweite Reaktionszone zurückführt
• f) den in Schritt d) erhaltenen oder die in Schritt e) erhaltene Olefin-abgereicherte Fraktion einer Verwertung zuführt.

The work-up of the discharge from the second reaction zone can in principle be carried out according to the processes described for the first reaction zone. For this purpose, the discharge is preferably subjected to a multistage separation operation, as described above, whereby at least one stream containing the main amount of the second hydroformylation product and optionally further streams are obtained. In a suitable embodiment, a stream consisting essentially of saturated hydrocarbons and optionally a small proportion of unreacted olefins is also separated from the discharge from the second reaction zone. The method according to the invention then preferably comprises the following steps, after which additionally

• d) separating from the effluent from the second reaction zone a stream consisting essentially of saturated hydrocarbons and optionally a small proportion of unreacted olefin,
• e) optionally separating the stream obtained in step d) by rectification into an olefin-enriched and an olefin-depleted fraction, and at least partially recycling the olefin-enriched fraction into the first and / or the second reaction zone
• f) the recovery of the obtained in step d) or the obtained in step e) olefin-depleted fraction.

The Rectification in step e) is usually carried out at low temperature and / or elevated Pressure, the exact temperature and / or pressure conditions of Factors such as the carbon number of the olefin / saturated to be separated Hydrocarbons, etc. depend. The rectification is generally carried out in a column with a sufficiently large one Number of rectification floors is provided. Columns for such Separation tasks are known and are z. B. for separation of olefins and saturated hydrocarbons used, which are contained in the cracking gas of a steam cracker. Appropriately, can an olefin-enriched at the top or top of the column Fraction and at the bottom or bottom of the column an olefin-depleted Be removed. The olefin-enriched fraction, the if desired still shares in saturated May contain hydrocarbons, e.g. as electricity in the first or second reaction zone recycled or as a feed for other chemical reactions are used. The olefin-depleted Faction is expelled from the system. You can z. B. burned or as a feedstock for chemical reactions or z. B. serve as a feed in the steam cracker.

The Utilization in step f) comprises, for example, a thermal Recycling, a use for syngas production or use as cracker feed.

The from the discharges the first and second reaction zone product streams can immediately for the further implementation, z. B. for the production of propylheptanol used become. You can if desired also a further work-up according to customary, known in the art Method, such. B. by distillation, subjected and then processed become.

An advantageous embodiment of the method according to the invention is in 1 and is explained below.

1 shows a schematic representation of the method according to the invention after the Flüssigaustragverfahren. Self-evident plant details, which are not necessary to illustrate the method according to the invention, have been omitted for reasons of clarity.

According to 1 is added to the reactor ( 1 ) an olefin-containing feed ( 10a ), which contains olefin to be hydroformylated and optionally saturated hydrocarbon, and through the pipeline ( 10b ) Syngas and through the pipeline ( 13 ) recycled hydroformylation catalyst, optionally after a Hochsiederausschleusung not shown, fed and hydroformylated there to a partial conversion. From the reactor, a liquid discharge is taken, containing as essential constituents the hydroformylation product, higher than the hydroformylation by-boiling by-products, the homogeneously dissolved first hydroformylation catalyst, unreacted olefin, saturated hydrocarbons and unreacted synthesis gas. The stream is in the pressure separator ( 2 ), wherein a phase separation into a gaseous portion, which consists essentially of synthesis gas, and a liquid portion takes place. The synthesis gas is called gaseous stream ( 11 ) and can optionally be fed again to the hydroformylation. The liquid fraction is added to the flasher ( 3 ) and into a liquid stream ( 12a ) and a gaseous stream ( 12b ) separated. The liquid stream becomes at the head and the gaseous Stream into the bottom of the strip column ( 4 ) and subjected to distillation with stripping action. At the bottom of the column ( 4 ) the first catalyst system is taken ( 13 ), which, optionally after further work-up for the separation of high-boiling by-products, are returned to the hydroformylation reactor ( 1 ). The top-removed mixture of hydroformylation product, olefin and saturated hydrocarbon ( 14 ) is condensed and in the distillation column ( 5 ). In the bottom of the distillation column ( 5 ), the hydroformylation product ( 15 ), which can then be further processed. The overhead mixture of olefin and optionally saturated hydrocarbon ( 16 ) is liquid after intermediate condensation in the second hydroformylation reactor ( 6 ) fed. In addition, the second hydroformylation reactor ( 6 ) through the pipeline ( 17 ) Syngas and through the pipeline ( 20 ) fed back second catalyst system and there hydroformylated to the desired conversion. From the reactor ( 6 ), a liquid discharge is withdrawn into the pressure separator ( 7 ) is fed. The stream is in the pressure separator ( 7 ), wherein a phase separation into a gaseous portion, which consists essentially of synthesis gas, and a liquid portion takes place. The synthesis gas is called gaseous stream ( 18 ) and can optionally be fed again to the hydroformylation. The liquid fraction is added to the flasher ( 8th ) and into a liquid stream ( 19a ) and a gaseous stream ( 19b ) separated. The liquid stream is at the top and the gaseous stream is added to the bottom of the bottom of the strip column ( 9 ) and subjected to distillation with stripping action. At the bottom of the column ( 9 ) the second catalyst system is removed ( 20 ), which, optionally after further work-up for the separation of high-boiling by-products, are returned to the hydroformylation reactor ( 6 ). The overhead mixture of hydroformylation product, saturated hydrocarbon and optionally residual amounts of olefin ( 21 ) is condensed and in the distillation column ( 10 ). In the bottom of the distillation column ( 10 ), the hydroformylation product ( 22 ), which can then be further processed. The overhead hydrocarbon ( 23 ) can be discharged or forwarded to the recovery of still contained olefin a further separation.

If desired, in the method according to 1 Flashers ( 3 ) and strip column ( 4 ) and / or flashers ( 8th ) and strip column ( 9 ) in a single apparatus, a so-called flash / strip column.

• i) Buten oder ein Buten enthaltendes C₄-Kohlenwasserstoffgemisch einer Hydroformylierung nach dem zuvor beschriebenen Verfahren unterzieht,
• ii) gegebenenfalls das Hydroformylierungsprodukt einer Auftrennung unter Erhalt einer an n-Valeraldehyd angereicherten Fraktion unterzieht,
• iii) das in Schritt i) erhaltene Hydroformylierungsprodukt oder die in Schritt ii) erhaltene an n-Valeraldehyd angereicherte Fraktion einer Aldolkondensation unterzieht,
• iv) die Produkte der Aldolkondensation mit Wasserstoff katalytisch zu Alkoholen hydriert, und
• v) 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

• i) subjecting butene or a butene-containing C ₄ -hydrocarbon mixture to a hydroformylation by the method described above,
• ii) optionally subjecting the hydroformylation product to separation to give a fraction enriched in n-valeraldehyde,
• iii) subjecting the hydroformylation product obtained in step i) or the n-valeraldehyde-enriched fraction obtained in step ii) to aldol condensation,
• iv) catalytically hydrogenating the products of aldol condensation with hydrogen to give alcohols, and
• v) optionally subjecting the hydrogenation products to a separation to give a fraction enriched in 2-propylheptanol.

Preferably in step i) a rhodium / triphenylphosphine catalyst as first hydroformylation catalyst used. Preferably in step i) as the second hydroformylation catalyst, a hydroformylation catalyst used, the at least one complex of a metal of VIII. Subgroup with at least one ligand of the general formula II includes. In terms of suitable and preferred ligands of the formula II is the previous versions Referenced.

i) 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. Preferably, the previously described C ₄ cuts, which are incorporated herein by reference.

The two-stage hydroformylation process according to the invention is advantageously suitable for the use of C ₄ cuts containing 1-butene in a mixture with 2-butene. In the first stage, a catalyst is used which is capable of hydroformylating 1-butenes with high n-selectivity. In the second stage, a catalyst is used, which is capable of isomerizing hydroformylation of 2-butene with high n-selectivity.

Regarding suitable and more preferably hydroformylation catalysts, activating agents, solvents Reaction conditions and reactors for hydroformylation in Step i) is based on the previous general remarks fully referenced to the hydroformylation.

ii) separation

To a suitable process variant will be the united in step i) product-enriched fractions obtained a further separation to obtain a n-valeraldehyde enriched fraction. The separation of the hydroformylation product into an n-valeraldehyde enriched fraction and a n-valeraldehyde depleted fraction takes place according to usual, known to those skilled in the process. Preference is given to the distillation using known separation equipment, 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.

iii) 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 alumina, can also be used (cf., for example, US Pat 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 i) or after the separation in step ii) has further C ₅ -aldehydes, such as 2-methylbutanal and optionally 2,2-dimethylpropanal or 3-methylbutanal or traces of other aldehydes, these likewise react in 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 C ₁₀ -alcohol mixtures not contrary.

iv) 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 50 to 350 bar.

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

v) 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 resulting 2-propylheptanol can by customary, known in the art Process to plasticizers further processed.

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

It the following ligands were used:

ligand I ) Triphenylphosphine

Ligand II

Of the Ligand II was prepared according to a literature procedure by Veen et al. in Angew. Chem. Int. Ed. 1999, 38, 336.

Ligand III

Of the Ligand III was prepared according to WO 01/58589.

Ligand IV

The Synthesis of ligand IV was carried out according to WO 02/083695.

Ligand V

The Synthesis of ligand V was carried out according to WO 03/018192.

Ligand VI

Synthesis of the ligand VI:

6.8 g (52 mmol) of 3-methylindole (skatole) were initially charged in 400 ml of absolute tetrahydrofuran (THF) under argon, cooled to -75 ° C. and then admixed with 40 ml (288 mmol) of triethylamine. Subsequently, 2.4 ml (28 mmol) of PCl ₃ were slowly added at -75 ° C. The reaction mixture was brought to room temperature and then stirred for 16 h at room temperature. ( ³¹ P NMR (crude) δ = 99 (s) and 100 (s)). Then, 2.88 g (10.7 mmol) of 2,2'-dihydroxy-3,3 ', 4,4', 6,6'-hexamethylbiphenol (obtained according to the DE 103 052 25.9 in 30 ml of absolute THF was added dropwise over 6 h at room temperature and the reaction mixture was stirred overnight at room temperature ( ³¹ P-NMR (crude) δ = 100 (s) chelate ligand (integral: 10) and 125 (s) monoligand (integral: 2 )). The precipitated colorless solid (triethylamine hydrochloride) was filtered off with suction through a protective gas frit, the solvent distilled off in vacuo at 40 ° C, the residue slurried twice with pentane and then dried in vacuo, leaving a sticky, slightly yellow solid remains. This solid is suspended at 50 ° C in methanol, then filtered with suction through a protective gas frit, then washed twice with pentane and then dried in vacuo. There were obtained 4.2 g (52% of theory) of product.
MS (ionization: APCI): m / z = 850
¹ H-NMR (C ₆ D ₆ , 360 MHz, 298K)
δ = 1:41 (s, _CH3, 6H), 1:54 (s, _CH3, 6H), 2.01, (s, _CH3, 6H), 2:07 (s, _CH3, 6H), 2.10 (s, _CH3, 6H ), 6.39 (s, "eiphenol-H", 2H), 7.05-7.10 (m, skat-H (H5 + H6), 8H), 7.33 (br s, skat-H (H2), 4H), 7.37- 7.41 (m, 2H), 7.59-7.61 (m, 2H), 7.78-7.81 (m, 2H): signals in the range 7.37-7.81 (Skat-H (H4 and H7)).
³¹ P NMR (C6D6, 146 MHz, 298K)
δ = 103 (s).

Hydroformylierungsbeispiele

For the hydroformylation, a raffinate II of the following composition was used as the olefin mixture:
Isobutane 1.7%, n-butane 12.4%, trans-2-butene 31.7%, cis-2-butene 16.8%, 1-butene 35.1%, isobutene 2.4

Example 1:

• 1st stage: Rh / triphenylphosphine
• 2nd stage: Rh / ligand IV

1st stage:

6.4 mg of Rh (CO) ₂ acac (acac = acetylacetonate) and 1.9 g of triphenylphosphine were weighed in separately, dissolved in 5 g of toluene, mixed and mixed at 90 ° C. with 10 bar of synthesis gas (CO: H ₂ = 1: 1) gassed (preformation). After 1 h was relaxed. Then, 15 g of raffinate II (isobutane 1.7%, n-butane 12.4%, trans-2-butene 31.7%, cis-2-butene 16.8%, 1-butene 35.1%, isobutene 2.4%) by means of a pressure lock, adjusted with synthesis gas (CO: H ₂ = 1: 1) a total pressure of 20 bar and hydroformylated at 90 ° C for 2 h (95 ppm Rh). The autoclave was subsequently cooled, carefully expanded over a cold trap and both reaction effluents (reactor and cold trap) were analyzed by gas chromatography. The 1-butene conversion was 85%, the yield of valeraldehyde 38% and the linearity (n-portion) 78.0%. [The linearity (n-fraction) is defined as the quotient of n-valeraldehyde to the sum of n-valeraldehyde and i-valeraldehyde multiplied by 100]. The composition of the liquefied gas discharge in the cold trap was: isobutane 1%, n-butane 13.7%, trans-2-butene 48.2%, cis-2-butene 28.9%, 1-butene 8.2%.

2nd stage:

5 mg Rh (CO) ₂ acac (acac = acetylacetonate) and 191 mg ligand IV were weighed separately, dissolved in 5 g toluene, mixed and gassed at 90 ° C with 10 bar synthesis gas (CO: H ₂ = 1: 2) (preforming). After 1 h was relaxed. Then, 7.3 g of 1st stage liquefied petroleum gas (so: isobutane 1%, n-butane 13.7%, trans-2-butene 48.2%, cis-2-butene 28.9%, 1-butene 8 , 2%) by means of a pressure lock, with synthesis gas (CO: H ₂ = 1: 2) set 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 subsequently hydroformylated at 90 ° C. for 4 h (122 ppm Rh). The conversion of 1-butene was 81%, the conversion of 2-butene was 65%, the yield of valeraldehyde 37% and the linearity (n-portion) 93.9%.

The proportion of n over the two stages (1st stage: Rh / PPh _3; 2nd stage: Rh / Ligand IV) was 82.5%.

Example 2:

• 1st stage: Rh / ligand II
• 2nd stage: Rh / ligand V

1st stage:

6.3 mg of Rh (CO) ₂ acac (acac = acetylacetonate) and 168 mg of ligand II were weighed in separately, dissolved in 5 g of toluene, 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 14.4 g of raffinate II were added by means of a pressure lock, adjusted to a total pressure of 20 bar with synthesis gas (CO: H ₂ = 1: 1) and hydroformylated at 90 ° C for 4 h (102 ppm Rh). The autoclave was subsequently cooled, carefully expanded over a cold trap and both reaction effluents (reactor and cold trap) were analyzed by gas chromatography. The 1-butene conversion was 79%, the yield of valeraldehyde 33% and the linearity (n-portion) 96.5%. The composition of the liquefied gas discharge in the cold trap was: isobutane 0.7%, n-butane 12.4%, trans-2-butene 46.9%, cis-2-butene 19.3%, 1-butene 10.7% ,

2nd stage:

5 mg Rh (CO) ₂ acac (acac = acetylacetonate) and 168 mg Ligand V were weighed separately, dissolved in 5 g toluene, mixed and gassed at 90 ° C with 10 bar synthesis gas (CO: H ₂ = 1: 2) (preforming). After 1 h was relaxed. Then, 6.1 g of 1st stage liquefied petroleum gas (so: isobutane 0.7%, n-butane 12.4%, trans-2-butene 46.9%, cis-2-butene 19.3%, 1- Butene 10.7%) by means of a pressure lock, with synthesis gas (CO: H ₂ = 1: 2) set 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 subsequently hydroformylated at 90 ° C. for 4 h (114 ppm Rh). The conversion of 1-butene was 83%, the conversion of 2-butene 59%, the yield of valeraldehyde 34% and the linearity (n-portion) 95.6%.

Of the n share over both stages (1st stage: Rh / ligand II, 2nd stage: Rh / ligand V) 96.2%.

Example 3:

• 1st stage: Rh / ligand II
• 2nd stage: Rh / ligand VI

1st stage:

6 mg of Rh (CO) ₂ acac and 111 mg of ligand II were weighed in separately, dissolved in 5 g of toluene, mixed and gassed at 90 ° C. with 10 bar of synthesis gas (CO: H ₂ = 1: 1) (preformation). After 1 h was relaxed. Then 14.6 g of raffinate II were added by means of a pressure lock, set with synthesis gas (CO: H ₂ = 1: 1) a total pressure of 20 bar and hydroformylated at 90 ° C for 4 h (97 ppm Rh). The autoclave was subsequently cooled, carefully expanded over a cold trap and both reaction effluents (reactor and cold trap) were analyzed by gas chromatography. The 1-butene conversion was 65%, the yield of valeraldehyde 15% and the linearity (n-portion) 98.4%. The composition of the liquefied gas discharge in the cold trap was: iso-butane 0.7%, n-butane 11.8%, trans-2-butene 46.1%, cis-2-butene 28.5%, 1-butene 13.0%.

2nd stage:

5 mg of Rh (CO) ₂ acac and 165 mg of ligand VI were weighed in separately, dissolved in 5 g of toluene, mixed and gassed at 90 ° C. with 10 bar of synthesis gas (CO: H ₂ = 1: 2) (preformation). After 1 h was relaxed. Then, 7.8 g of LPG of the 1st stage (so: iso-butane 0.7%, n-butane 11.8%, trans-2-butene 46.1%, cis-2-butene 28.5%, 1-butene 13.0%) were added by pressure lock and with synthesis gas (CO: H ₂ = 1: 2) set 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 (111 ppm Rh). The conversion of 1-butene was 84%, the conversion of 2-butene 38%, the yield of valeraldehyde 28% and the linearity (n-portion) 96.2%.

Of the n share over both stages (1st stage: Rh / ligand 1, 2nd stage: Rh / ligand XII) 97.3%.

Claims (19)

Process for the preparation of hydroformylation products of olefins, in which one a) in a first reaction zone a fed olefin-containing feed and carbon monoxide and hydrogen and in the presence of a first catalyst system, b) from the discharge from the first reaction zone one essentially unreacted olefins and optionally saturated Hydrocarbons separates existing liquid stream, c) the liquid obtained in step b) Electricity and carbon monoxide and hydrogen in a second reaction zone fed and reacted in the presence of a second catalyst system. Process according to claim 1, wherein in step b) from the first reaction zones a substantially liquid discharge takes off and undergoes a two-stage relaxation. Method according to one of claims 1 or 2, in which one in Step b) b1) the liquid Discharge from the first reaction zone, which as essential components the hydroformylation product, higher as the Hydroformyllerungsprodukt boiling by-products, the homogeneous dissolved first hydroformylation catalyst, unreacted olefin, saturated Hydrocarbons and unreacted synthesis gas contains one Subjecting degassing, where appropriate, the pressure and / or the Temperature opposite the reaction zone are lowered, and wherein a first substantially the unreacted synthesis gas containing gas phase and a first essentially the hydroformylation product, higher than the hydroformylation product boiling byproducts, the homogeneously dissolved first hydroformylation catalyst, unreacted olefin and saturated Hydrocarbons containing liquid phase result, b2) the first gas phase is sent for recycling, b3) the first liquid phase undergoes a relaxation, the pressure against the the first degassing so far the second one is not lowered reacted olefin, saturated Hydrocarbons and part of the hydroformylation product containing gas phase and a second higher than the hydroformylation product boiling by-products, the homogeneously dissolved first hydroformylation catalyst and a portion of the hydroformylation product-containing liquid phase result, b4) the second gas phase into the sump or the feeds the lower part of a column and the second liquid phase, optionally after heating, in liquid Form feeds above the feed of the gas phase in this column and the gas phase leads, b5) at the bottom of the column, a substantially the first dissolved Hydroformylation and the higher than the hydroformylation product boiling by-products of hydroformylation containing third liquid phase withdraws and at the top of the column a hydroformylation product, the unreacted olefin and saturated hydrocarbons containing withdrawing third gas phase, b6) the third liquid phase, optionally after separation of at least a portion of the higher than the hydroformylation product boiling by-products in the first reaction zone, and b7) the third gas phase of a workup to obtain a substantially the hydroformylation product-containing fraction and an im Essentially containing the unreacted olefin and saturated hydrocarbons Subject fraction. A method according to claim 3, wherein for carrying out the Steps b3) and b4) a flash / strip column is used and the first liquid phase in an area above the swamp and below the head of the Flash / stripping column is fed and relaxed, while a separation into the second Gas phase and the second liquid phase takes a liquid stream taken from the bottom of the flash / strip column and the Column at or below the head fed back and the second gas phase being led becomes. The method of claim 1, wherein additionally d) from the discharge from the second reaction zone a substantially from saturated Hydrocarbon and optionally a small proportion not separated from existing olefin existing stream, e) if necessary the stream obtained in step d) into an olefin-enriched and separates an olefin-depleted fraction and the olefin-enriched Fraction at least partially in the first and / or the second reaction zone returns, and f) the stream obtained in step d) or that obtained in step e) Olefin-depleted fraction of a reject feed. Method according to one of the preceding claims, wherein the first catalyst system at least one complex of a metal the VIII. Subgroup of the Periodic Table of the Elements with at least an organic phosphorus (III) compound as ligands. A process according to claim 6, wherein the organic phosphorus (III) compound is selected from compounds of the formula PR ¹ R ² R ³ , wherein R ¹ , R ² and R ^{3 are} independently alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the alkyl radicals 1, 2, 3, 4 or 5 substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, COOH, carboxylate, SO ₃ H, sulfonate, NE ¹ E ² , NE ¹ E ² E ³⁺ X ^- , halogen, nitro, acyl or cyano may have, wherein E ¹ , E ² and E ³ each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl, or aryl and X ^- for a Anion equivalent, and wherein the cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals may have 1, 2, 3, 4 or 5 substituents which are selected from alkyl and the substituents previously mentioned for the alkyl radicals R ¹ , R ² and R ³ wherein R ¹ and R ² together with the phosphorate om, to which they are attached, may also stand for a 5- to 8-membered 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 independently of one another may each carry one, two, three or four substituents selected from alkyl and the substituents previously mentioned for the alkyl radicals R ¹ , R ² and R ³ . The method of claim 6, wherein the first catalyst system a complex of rhodium with triphenylphosphine as ligands. A process according to claim 6, wherein the organic phosphorus (III) compound is selected from chelate compounds of the formula R ¹ R ² PY ¹ -PR ¹ R ² , wherein R ¹ and R ² are as defined in claim 7 and Y ^{1 is} a divalent one bridging group stands. The method of claim 9, wherein the bridging group Y ^{1 is} selected from groups of the formula

wherein R ^I , R ^II , R ^III , R ^IV , R ^V and R ^{VI are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, COOH, carboxylate, SO ₃ H, sulfonate, NE ⁶ E ⁷ , alkylene-NE ⁶ E ⁷ , trifluoromethyl, nitro, alkoxycarbonyl, acyl or cyano in which E ⁶ and E ⁷ each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl in which 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, and R ^d and R ^e independently of one another represent hydrogen, Alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. The method of claim 9, wherein the bridging group Y ^{1 is} a group of formula IIIa as defined in claim 16. Method according to one of the preceding claims, wherein the second catalyst system at least one complex of a metal of the VIII. Subgroup of the Periodic Table of the Elements with at least a phosphorochelate compound of general formula I.

as ligands, wherein Y ^{2 is} a bivalent bridging group, R ^α , R ^β , R ^γ and R ^δ independently of one another are alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the alkyl radicals 1, 2, 3, 4 or 5 Substituen th, selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, COOH, carboxylate, SO ₃ H, sulfonate, NE ¹⁰ E ¹¹ , NE ¹⁰ E ¹¹ E ¹²⁺ X ^- , halogen, nitro, acyl or cyano may have, wherein E ¹⁰ , E ¹¹ and E ¹² each represent 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 ^α , R ^β , R ^γ and R ^{δ may have} 1, 2, 3, 4 or 5 substituents which are selected from alkyl and those previously described for the alkyl radicals R ^α , R ^β , R ^γ and R ^δ substituent en, or R ^α and R ^β and / or R ^γ and R ^δ together with the phosphorus atom and, if present, the groups X ¹ , X ² , X ⁵ and X ⁶ to which they are attached, for a 5- to 8-membered heterocycle, which is optionally additionally fi-, di- or tri-fused with cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the heterocycle and, if present, the fused groups independently carry one, two, three or four substituents may be selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, COOH, carboxylate, SO ₃ H, sulfonate, NE ¹³ E ¹⁴ , NE ¹³ E ¹⁴ E ¹⁵⁺ X ^- , nitro, alkoxycarbonyl, acyl or cyano, wherein E ¹³ , E ¹⁴ and E ^{15 are} each identical or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl and X ^{- is} an Anionäqivalent, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ^{6 are} independently are selected from O, S, SiR ^ε R ^ξ and NR ^η , wherein R ^ε , R ^ξ and R ^{η are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, and d, e, f, g, h and i independently represent 0 or 1. Method according to one of the preceding claims, wherein the second catalyst system at least one complex of a metal of VIII. Subgroup of the Periodic Table of the Elements with at least one phosphorochelate compound of the general formula II

as ligands, wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ independently represent heteroatom-containing groups which are bonded via an oxygen atom or an optionally substituted nitrogen atom to the phosphorus atom or R ⁴ together with R ⁵ and / or R ^{6 in} common with R ^{7 form} a divalent heteroatom-containing group which are bonded to the phosphorus atom via two heteroatoms selected from oxygen and / or optionally substituted nitrogen, a and b independently of one another denote the number 0 or 1, and Y ^{3 represents} a divalent bridging group with 2 to 20 bridge atoms between the flanking bonds, with at least two bridge atoms being part of an alicyclic or aromatic group. A process according to claim 13, wherein R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently selected from groups of formulas II.a to II.k

in which Alk is a C ₁ -C ₄ -alkyl group and R ^g , R ^h , R ⁱ and R ^k 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. Process according to Claim 13, in which R ⁴ and R ⁵ and / or R ⁶ and R ^{7 are} each taken together with the phosphorus atom to which they are attached, for a group of general formula II.A

wherein k and l independently represent 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, which optionally mono-, di- or trihydric 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 ⁴ E ⁵ , alkylene-NE ⁴ E ⁵ , nitro and cyano NEN and / or Q one, two or three substituents which are selected from alkyl, alkoxy, optionally substituted cycloalkyl and optionally substituted aryl, aufwei sen and / or Q may be interrupted by 1, 2 or 3 optionally substituted heteroatoms. Method according to one of claims 13 to 15, wherein in the formula I, the bridging group Y ^{3 is} selected from groups of the 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 ²² E ²³ alkylene-NE ²² E ²³ , trifluoromethyl, nitro, Alkoxycarbonyl, carboxyl, acyl or cyano, wherein E ²² and E ^{23 are} each identical or different radicals selected from hydrogen, or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl, Z is O, S, NR ¹⁵ or SiR ¹⁵ R ^16, where R ¹⁵ and R ¹⁶ are independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or Z is a C ₁ -C ₄ alkylene bridge which is 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 by O, S or NR ¹⁵ or SiR ¹⁵ R ^{16 is} interrupted, wherein 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, also for a fused ring system with 1, 2 or 3 further rings, where in the groups of the formulas III.g to III.m two geminate 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 are each independently O, S, SiR ^a R ^b , NR ^c or CR ^d R ^e , where R ^a , R ^b and R ^{c are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl , R ^d and R ^e independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl 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 of the general formula

in which R ⁹ , R ^{9 '} , R ¹⁰ and R ^10' independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano, where R ^{9 'is} also together with R ^10' for the bond portion of a double bond between the two carbon atoms to which R ^{9 '} and R ^{10' are} bonded, and / or R ⁹ and R ¹⁰ 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 ^f , COO ^- M ⁺ , SO ₃ R ^f , SO ^- ₃ M ⁺ , NE ²⁵ E ²⁶ , alkylene-NE ²⁵ E ²⁶ , NE ²⁵ e ²⁶ e ²⁷⁺ X ^-, alkylene-NE ²⁵ e ²⁶ e ²⁷⁺ X ^- , OR ^f , SR ^f , (CHR ^g CH ₂ O) _y R ^f , (CH ₂ N (E ²⁵ )) _y R ^f , (CH ₂ CH ₂ N (E ²⁵ )) _y R ^f , halogen, trifluoromethyl, Nitro, acyl or cyano, wherein R ^f , E ²⁵ , E ²⁶ and E ^{27 are} each identical or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl, R ^{9 is} hydrogen, methyl or ethyl, M ⁺ for a cation is an anion, and y is an integer from 1 to 120, and c is 0 or 1. Method according to one of the preceding claims, in an olefin mixture is used, the olefins with internal double bonds and olefins with terminal Contains double bonds. The method of claim 17, wherein an olefin mixture is used, the 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 1 to 16 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.