DE2617306A1 - HYDROFORMYLATION CATALYST - Google Patents

Description

According to USA patent application serial no. 569,738 (filed on April 21, 1975) can be useful hydroformylation catalysts be prepared by entering the hydroformylation reaction zone a mixture of (a) a disubstituted ferrocene and (b) a compound of a metal of the VIII. group of the periodic table, e.g. with the following general formulas

M-QR.

where M is a metal of Group VIII of the Periodic Table, preferably Rhodium, Q a phosphorus, arsenic or antimony atom,

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ORIGINAL INSPECTED

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preferably a phosphorus atom, and R a phenyl group or a lower alkyl radical, preferably a phenyl group, "mean
introduces.

That from the aforementioned combination (or from corresponding ones, also described in the mentioned US patent application Compositions) resulting catalytic complex represents - in general terms - a complex cyclic Represents a structure containing 1 mole of the aforesaid substituted ferrocene and 1 mole of the aforesaid compound of a metal the VIII. group of the periodic table includes.

It has now been found, however, that although the manner described above by reacting 1 mole of the ferrocene derivative with 1 mole of the compound of a metal of VIII. Group (e.g. rhodium) produced catalyst as a hydroformylation catalyst works with complexes of this general type for best results can be achieved when the molar ratio of the ferrocene derivative to the compound of the metal of Group VIII is 1.5: 1 instead of 1 ι 1. This has led to the realization that the optimal catalyst among those mentioned is of ferrocene differs derived complexes from those previously considered. It represents a more complicated molecule as further discussed below, although the methods for its preparation and use in hydroformylation reactions are very similar to those in the case of the complexes produced from equimolar proportions.

According to the present invention, an olefin (e.g. an alice) is hydroformylated to an aldehyde product with a predominant proportion of normal aldehyde isomer, without using an excess of any ligand, by using a complex as the hydroformylation catalyst (hereinafter referred to as " Complex A ¹¹ referred to) with the following general formula

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in which M is a metal of group VIII of the periodic table, preferably rhodium, Q is a phosphorus, arsenic or antimony atom, preferably a phosphorus atom, and R is a piienyl group or an alkyl radical, preferably a phenyl group,
begins.

One can optionally use any rhodium-donating substance with an appropriately substituted perrocene (e.g. and in particular triphenylphosphine-substituted perrocenes) according to the methods described below to the desired catalytic Implement complex.

The catalytic complex can either be in situ or ex situ be generated.

The object of the invention is therefore to provide an improved catalyst suitable for hydroformylation reactions and to provide improved methods for the hydroformylation of olefins. The following detailed Description allows this task to be specified more precisely.

The description of the invention is divided into the following sections:

1) the improved catalytic complexes of the invention;

2) methods of making the improved complexes; and

3) hydroformylation processes carried out using the improved complexes.

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The improved catalytic complexes

As mentioned, are of the improved catalytic complexes A prefers those in which M is a rhodium atom, Q is a phosphorus atom and R are a phenyl group. Suitable complexes can also be made using other metals of Group VIII, i.e. from Iron, cobalt, nickel, rhodenium, palladium, osmium, iridium or platinum are generated; however, these complexes possess less activity. As mentioned, the complex can be generated in situ in the hydroformylation reaction zone; however, it can optionally also be prepared ex situ and then together with the suitable hydroformylation reaction components Introduce into the reaction zone.

Complex A was prepared and used in the manner described below, but was not isolated in pure form. Its structure can be derived from the following facts:

Two complexes whose catalytic action in hydroformylation reaction systems previously discovered by the present inventors have actually been isolated. The structure of these two complexes has been elucidated. The first complex (hereinafter referred to as "Complex 1") has following structure:

Cl

The complex 1 is either in situ or prior to its introduction into the hydroformylation reaction zone with a hydride donor Substance or a hydride former (such as hydrogen) and. a base (such as sodium hydroxide) to remove the chlorine

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atoms implemented; the product obtained (the hydride derivative) then acts as a catalyst for the hydroformylation reaction.

In addition, it was previously determined that another complex exists which also acts as a hydroformylation catalyst is effective, but does not require an alkali pretreatment before use. This hereinafter referred to as "Complex 2" Catalyst has the following structure:

The two complexes 1 and 2 have been identified and their suitability for catalytic purposes has been demonstrated. Regarding of both types of compounds, especially those representatives were specifically identified in which M is a rhodium atom, Q represents a phosphorus atom and R represents a phenyl group.

However, tests carried out with the aforementioned complexes have shown that their catalytic effectiveness (in particular in the case of compounds in which M is a rhodium atom, Q is a phosphorus atom and R is a phenyl group) changes very significantly if you add such a measured amount of a diphenylphosphino-disubstituted to the reaction system Ferrocens introduces to the complex an additional 0.5 moles of the ferrocene derivative per equivalent of that in the original Complex 1 or complex 2 (whichever complex is currently being used) should be added. In the case of the Complex 1, this change was observed when the hydroformylation reaction zone containing the hydrido form of the complex an additional 0.5 mol of bis (diphenylphosphino) ferrocene were added. In the case of complex 2 were

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achieved the same results. In this connection, it should be noted that complex 1 and complex 2 are closely related are related, the latter by reacting the former with 1 mole of triphenylphosphine in the presence of a hydride former (as from sodium borohydride).

Upon further investigation of the phenomena occurring when introducing additional ferrocene into the molecule of complex 1 or complex 2, it was found that an addition of a further 0.5 mol of the substituted ferrocene in the hydroformylation of an alkene under typical hydroformylation reaction conditions in the presence of a Mixtures of hydrogen and carbon monoxide result in a marked increase in the degree of conversion of the alkene to the corresponding aldehyde containing an additional carbon atom. In a typical hydroformylation of 1-hexene in particular, the degree of conversion to heptanal was about 82% when the molar ratio of ferrocene derivative / rhodium atoms in the reaction zone was 1.5: 1, whereas with a molar ratio of 1: 1, only a degree of conversion of 52 % was achieved. With an average ferrocene / rhodium molar ratio (1.25 1), the degree of conversion to heptanal changed only slightly (to about 53 °). An increase in the molar ratio to more than 1.5: 1 also resulted in practically nothing further effect; the percentage conversion to heptanal was only about 0.5 point higher at a molar ratio of 3: 1 than at a molar ratio of 1.5: 1. Furthermore, a corresponding marked improvement in the ratio of normal aldehyde / branched aldehydes in the reaction product was found; this ratio was about 2.2: 1 with a ferrocene / rhodium molar ratio of 1: 1, whereas it was significantly higher (about 5.2: 1) with a ferrocene / rhodium molar ratio of 1.5: 1. As in the case of the degree of conversion to heptanal, the proportion of normal aldehyde / branched-chain aldehydes increased only slightly or

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not at all (after the initial increase to 5.2: 1) if the perrocene / rhodium molar ratio is above 1.5: (i.e. up to 3: 1). The isomerization of the 1-hexene used to the undesired 2-hexene was in Use of the ferrocene / rhodium molar ratio of 1.5 ί 1 Compared to the conditions at a molar ratio of 1: 1, it is also severely inhibited. Besides that the aforementioned changes from a technical point of view brought about by the addition of a further 0.5 mol of substituted ferrocene are extremely advantageous, suggests the sharp and pronounced which can be attributed to the additive mentioned Increase together with the fact that further additions of the ferrocene derivative are harmless, but ineffective clearly indicate that a new complex has formed. This is in contrast to some, for example earlier methods where more or less unsuccessful attempts were made by simply increasing the concentration of one Ligands in an equilibrium-type reaction to gain advantages (this being a more gradual effect rather than the sudden "step effect" characteristic of the system according to the invention is achieved). From the above facts goes show that 2 moles of complex 1 or complex 2 (depending on the individual case) with 1 mole of the substituted ferrocene to have reacted to a new complex, in the case of complex 1 of course a chloride acceptor (such as sodium hydroxide) is required. It can also be seen that the molecule of the substituted ferrocene which forms a "bridge" is linked to the complex 1 or 2 at the rhodium atom rather than at any other point, since the cleavage of the Chlorine atom from complex 1 resulting hydrido compound am Rhodium atom is coordinatively unsaturated, which makes it necessary for further complex formation (e.g. with the substituted Ferrocene) is made in a suitable place. Similarly, in the case of complex 2, it is evident that the originally triphenylphosphine group bonded to the rhodium atom the substituted ferrocene is replaced, since the one with the Phe-

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Nylphosphino substituents linked, electron-rich ferrocene derivative this gives it a higher basicity than the simple triphenylphosphine group originally present in complex 2 j thus becomes the triphenylphosphine group from the complex is displaced, and complex A, which has a bridge element, is formed:

It is believed that the foregoing explains the structure of complex A correctly. Independent however, the truth of these conclusions extends the invention to the specific ones described below Process for the preparation of the new catalytic complex regardless of its exact structure.

Generally speaking, regardless of its precise structure, the improved catalyst of the present invention can than the hydridocarbonyl of a Group VIII metal (preferably Rhodium) in complex combination with a perrocene derivative of the following general formula

in which Q is P, As or Sb (preferably P) and R is a phenyl group or a lower alkyl radical (preferably a phenyl

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group) is present. It is stated that the individual radicals R need not be identical. For the production of the preferred catalyst complex A, 1.5 molecules of the perrocene derivative must each be bound to a rhodium atom in a complex will. Molar ratios of less than 1.5: 1 result in catalytic complexes also falling under the invention, however, the ratio of 1.5: 1 leading to complex A is preferred. Molar ratios higher than 1.5: 1 are are not disadvantageous and prove to be in practice in hydroformylation reaction systems even as useful because a sufficient amount of the perrocene derivative is provided that that Requirement of a molar ratio of 1.5 ϊ 1 is met.

A process for the preparation of the improved catalysts below is to be regarded rhodium, which is the preferred metal of the VIII. Group as a typical representative of this group. Similarly, phosphorus, which is also preferred by the elements P, As and Sb, is a typical representative of these elements; that is, the phosphines are also to be regarded as representative of the arsines and stibines. Finally, the phenyl group is to be regarded as a typical representative of the “phenyl group and lower-alkyl radicals” substituents. The term "lower alkyl" as used herein refers to alkyl groups of up to about 12 carbon atoms, although there is in fact no limit to the size of the alkyl groups. Rather, these can generally be used in the production of the catalysts according to the invention, provided they are present as substituents in alkylphosphines or can be made such substituents.

In general terms, the most preferred catalysts according to the invention are prepared by reacting 1 mol of a suitable rhodium-donating substance ("Rhodium source ^11" ) with carbon monoxide (if the rhodium-donating substance is not already a carbonyl) and 1.5 mol of a 1.1 * - Bis- (dialkyl- or diarylphosphino) -ferrocene is produced; 1,1'-bis- (diphenylphosphino) -ferrocene, which is used in

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the following explanation is used as an example. The product of this broadly described reaction is the complex A. Specific methods are explained below; however, some generalized statements apply regardless of the individual steps used for the reaction as a whole. In more specific ways the following applies:

The process effort required to convert the rhodium into the desired complex A depends on the nature of the original rhodium-yielding substance. The rhodium in complex A is, for example, in the Rh valent state. If the rhodium is now in its original form as a common salt with rhodium as a cation, it can be in the Rh ⁺ valence state and must therefore be reduced in some stage of the complex formation process. The reduction is normally carried out by means of carbon monoxide (which is present from the outset in the hydroformylation reaction zone in which the catalyst is to be used) or by means of phosphine ligands (for example triphenylphosphine). Substances that supply rhodium, which are in the Rh ⁺ valence state from the start, do not require a special reduction stage. With respect to the reduction of rhodium, it has also been found that rhodium compounds having a halogen atom (e.g., chlorine atom) in the molecule require a halide acceptor upon reduction to remove the hydrohalic acid formed upon reduction from the system and to form the rhodium hydride complex. For this purpose, either hydrogen (which is already present in the hydroformylation reaction zone in which the catalyst is to be used) or an equivalent hydrogen-yielding substance, such as a hydride (for example sodium borohydride), is used. Although a simultaneous reaction of a primary rhodium-producing substance with carbon monoxide and the disubstituted ferrocene can take place to form the desired complex A, the rhodium is preferably carried out in a first stage.

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remote substance (e.g. a rhodium salt of a mineral acid or carboxylic acid) into a carbonyl derivative and sets this then with the disubstituted ferrocene to form complex A. Of course, the carbonylation stage is omitted, if the primary rhodium-supplying substance is already the carbonyl or a carbonyl-containing compound, such as a chlorocarbonyl.

Examples of suitable rhodium-supplying substances which do not already contain a carbonyl portion in the molecule are the simple salts, such as the halides (especially rhodium trichloride trihydrate), Rhodium sulfate, rhodium nitrate and rhodium carboxylates, e.g. the rhodium salts of simple carboxylic acids and dicarboxylic acids. Examples of substances that provide rhodium, which already contain carbonyl groups in the molecule Rhg (CO) -jg and dimeric rhodium carbonyl chloride. That called "rhodium on carbon "commercially available material, which is a mixture of rhodium oxides of a rather complex nature on one Is a carbon carrier is also suitable.

Some specific methods of making complex A are as follows:

a) If the rhodium is initially in a non-carbonyl form, The first step is to convert the rhodium into a carbonyl derivative by reacting it with carbon monoxide. The carbonylation can be carried out by any conventional method which has features outside of those of the invention Frame lie, take place; typical suitable methods are described, for example, in "Inorganic Synthesis", Volume 8 (1966), page 211. The carbonylation can be ex situ or in situ in the hydroformylation reaction zone be performed. The rhodium carbonyl derivative formed is then disubstituted with the Ferrocene derivative implemented, with one atom of the rhodium content in the rhodium carbonyl derivative with one molecule of the ferrocene derivative to complex 1 (its structure above is listed) reacts; by adding an additional 0.5 mol of the ferrocene derivative per mol of the complete

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read 1, this is then converted into the desired complex A. It is found that the entire ferrocene derivative can be added all at once instead of being added in the form of two partial amounts, with complex 1 being formed in the first stage, which is then converted into complex A in a second stage. If the rhodium ^{is present as Hh +} , it must, as mentioned, be reduced ^{to Rh + in order to produce the desired complex A.} The reduction can take place in the course of the reaction of the primary rhodium-supplying substance with the disubstituted ferrocene or after the addition of the disubstituted ferrocene, for example by simply adding the mixture of the rhodium carbonyl derivative and the disubstituted ferrocene within the hydroformylation reaction zone during the hydroformylation the Hg / CO mixture used. If the moiety of the molecule containing the rhodium has a halogen atom, a halide acceptor (eg a base) must be used to remove the hydrohalic acid formed in the hydrogenation. The removal or binding of halogen can take place simultaneously with the hydrogenation. The desired overall result can be achieved, for example, by using an alkali borohydride simultaneously as a hydrogenation agent and as a halide acceptor or removal agent.

b) If the rhodium is present as a carbonyl derivative from the outset, the latter can be used directly with the disubstituted ferrocene (with proportions of 1.5 moles of disubstituted ferrocene per gram atom of the rhodium contained in the rhodium carbonyl derivative) are implemented, the complex A thus being converted directly into a single stage is generated. All the complex formation reactions mentioned naturally take place in the liquid Phase takes place. If the rhodium carbonyl derivative is the particular dimeric substance suitable for the relevant purpose If rhodium carbonyl chloride is involved, the reaction between it and the disubstituted ferrocene takes place in the presence a chloride acceptor (for example sodium hydroxide, which is particularly suitable) and a hydride former

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(e.g. from hydrogen or a borohydride). Rhodium carbonyl itself can be used in the same way in which Case the chloride acceptor is not required.

c) A third alternative method is based on direct implementation of 1 mol of hydridocarbonyltris (triphenylphosphine) rhodium (I) with 1.5 mol of 1,1 * -bis (diphenylphosphino) ferrocene for Complex A, where neither a reducing agent nor a chloride acceptor is required.

d) Finally, the complex 1 with 1 mole of triphenylphosphine in the presence of a chloride acceptor and a suitable hydride former, such as hydrogen, sodium borohydride (a combined Hydride former / chloride acceptor), hydrazine (also a combined hydride former / chloride acceptor) or one any other known hydride former can be converted to complex 2, as described above. The complex 2 is then reacted with 0.5 mol of 1,1 * -bis (diphenylphosphino) ferrocene transferred to complex A.

The reactions on which the aforementioned optional processes are based all take place in the liquid phase and in the presence suitable inert solvent instead. If above triphenylphosphine or its analogues arsenic or antimony compounds are mentioned, the statements in question also relate to those compounds in which the organic fraction of lower alkyl or cycloalkyl radicals instead of phenyl groups. Furthermore, instead of triphenylphosphine, which is a preferred compound represents other triorganophosphorus compounds, such as triaryl phosphites, Trialkyl phosphites or tricycloalkyl phosphites set. Triphenylphosphine and are particularly suitable Triphenylphosph.ite (especially the former).

Regarding the influence of the reaction parameters on the

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Complex formation reactions explained above, it is found that there must be sufficient pressure to maintain a liquid phase. If the complexes are to be prepared in the hydroformylation reactor itself, in which the respective complex is to function as a catalyst, the hydroformylation reaction zone itself must always be kept at a pressure which is sufficient for this purpose. Also, the conventional hydroformylation reaction systems are always angewandxen elevated temperatures (for example temperatures in the range of about 25 to 15O ⁰ C) in each case for complex formation reactions suitable, regardless of which of the complex formation reactions described above, use is made. With regard to the type of liquid phase in which the complex formation reactions are to take place, the inert hydroformylation solvents mentioned below in the section "Hydroformylation reaction" are suitable. Occasionally it may happen that the complexes formed as intermediates or the rhodium-supplying substances from which the former are derived are actually not in solution in the inert hydroformylation solvent. In such cases, however, the complex formation reactions proceed satisfactorily if the intermediate products are simply kept in suspension by agitation or stirring. For example, "rhodium on carbon" is used in the course of the formation of the desired complexes in the form of a suspension. Complex 2 is also insoluble in numerous hydroformylation solvents, but can, as a suspended solid, be reacted with the disubstituted ferrocene to form complex A.

Some special recommendations follow, which are used in the preparation of complex A and its precursors (intermediates) Relate to the reaction parameters to be observed. In any event, however, it is appropriate to be in the hydroformylation reaction zone to maintain the conditions of elevated temperature and pressure.

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In the methods described under (a) ", the carbonylation of a non-carbonyl-containing primary rhodium-yielding substance which yields a carbonyl derivative as an intermediate product normally requires a reaction temperature of at least about 25 ° C. and a carbon monoxide partial pressure of at least about 1 atmosphere Suitable inert solvent for the primary rhodium-supplying substance, eg ethanol, methanol, benzene, toluene, xylene or diphenyl ether. However, a reaction liquid can also be used in which the rhodium-supplying substance is simply suspended instead of dissolved. The subsequent conversion of the carbonyl intermediate to complex 1 and its subsequent conversion into complex A are generally carried out at a temperature of about 25 ° C. or above (up to the temperature range of about 100 to 150 ° C. in which the hydroformylation reaction itself takes place) Similarly, at a temperature of about 6O ⁰ C or above. The halogen elimination reaction and the associated formation of the rhodium hydride complex are generally carried out at about 100 ^° C. if a base and hydrogen are used, and at about 75 ° C. if sodium borohydride is used.

The reaction of the disubstituted ferrocene with the carbonyl intermediate, complex 1 or complex 2 proceeds rapidly even at room temperature.

The above-described reaction of complex 1 with triphenylphosphine in the presence of a chloride acceptor and a hydride former for complex 2 is advantageously carried out at a temperature of about 75 ° C. or above.

The following examples illustrate methods for preparing the catalyst designated "Complex A".

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example 1

1.35 mmol of dimeric rhodium carbonyl chloride are prepared according to the method described in "Inorganic Syntheses", Volume 8 (1966), page 211 and then in 50 ml of benzene with 2.71 mmol of 1,1'-bis ( diphenylphosphino) ferrocene mixed. When the evolution of gas in the reaction mixture has ceased, the remaining solution is evaporated to dryness and the yellow, solid residue is poured into 200 ml of boiling ethanol. After the volume has decreased to 170 ml by evaporation during the boiling process, the hot solution is filtered and the piltrate is discarded. The beige-yellow solid PiIterrückstand is vacuum dried to obtain a solid product from Pp. 183-189 ⁰ G (f yield 90 °) receives. This end product is the above-described complex 1 in which M is a rhodium atom, Q is a phosphorus atom and R is a phenyl group.

The complex 1 obtained in the above manner can be easily converted into the (also described above) Complex 2 can be converted into the presence of a compound of the formula QR ^, (where Q is a phosphorus, arsenic or antimony atom and R is a phenyl group or a lower alkyl radical) with sodium borohydride to react.

The example below illustrates the conversion of complex 1 to complex 2.

Example 2

0.5 g of the complex 1 obtained according to Example 1 are in a flask with 0.2 g of triphenylphosphine (molar ratio 1: 1) mixed in 20 ml of refluxing ethanol. The mixture, which is boiling under reflux, is then slowly added with. 0.2 g of sodium borohydride in 20 ml of ethanol, resulting in a suspension of a red-brown pesticide. The plague is filtered off hot and then vacuum-dried. Included

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124 Ms obtained in 85,5prozentiger yield a product of Pp. 129 ⁰ C. This product is the complex 2.

Example 3

The complex A is conveniently prepared from the complex 1 prepared as described simply by adding a certain amount of the complex 1 together with 1,1 · bis (diphenylphosphino) ferrocene (0.5 mol per mol of Complex 1) is introduced into a suitable conventional hydroformylation solvent (eg toluene). A suitable chloride acceptor (preferably NaOH in aqueous solution) is also stirred into the mixture. At least 1 mole of sodium hydroxide is used per mole of complex 1. If the reaction components required for hydroformylation (ie an alkene and a hydrogen / carbon monoxide mixture with an H ₂ / CO ratio of about 1: 1) are then used under hydroformylation reaction conditions added mixed (for example, at about 8O ⁰ C and a pressure sufficient to maintain a liquid phase gauge), is converted to the complex 1 in situ in the complex a. This produces sodium chloride as a by-product, which is not harmful, but can be removed from the system as required. Furthermore, the hydrogen and carbon monoxide function not only as hydroformylation reaction components but also as reagents completing the conversion of complex 1 to complex A.

It is also found that the complex 1, when in the manner described above with the sodium hydroxide and the synthesis gas without the additional portion of the diphenylphosphinoferrocene is implemented, itself an active hydroformylation catalyst represents. If, however, the complex 1 in the manner mentioned with the additional 0.5 mol Diphosphinoferrocene converts, it is converted into the much more effective complex A. The transformation of the complex to complex A can be at any point in the course

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a hydroformylation process, in which the Complex 1 was initially fed into the reaction zone as a catalyst. A reaction system in which the complex 1 as Acting as a catalyst, it can easily be converted into a system with complex A as a catalyst at any time by adding another 0.5 mol of the 1,1 * -bis (diphenylphosphino) ferrocene adds 1 per mole of the complex originally fed to the system. Accordingly, he can also Complex 2 described above is converted to Complex A at any time in a hydroformylation reaction system by simply adding another 0.5 mole of bis (diphenylphosphino) ferrocene per mole of rhodium in the same way. In the latter case, in the resulting condensation per mole of the complex originally present 2 1 mole Triphenylphosphine released. The free triphenylphosphine can remain in the system with no adverse effect even though it does not take part in the hydroformylation reaction.

Hydroformylation reaction

The hydroformylation of an olefin (e.g. an alkene) according to the method according to the invention is generally thereby made that the olefin to be hydroformylated is placed in a customary reaction vessel or a customary reaction zone, a Hp / CO gas mixture and either the complex A itself or its precursor (as described) feeds. The expression "Precursor" means either Complex 1 or Complex or the starting components used for their formation, e.g. a rhodium-supplying substance of the type described above Type and a disubstituted ferrocene, such as 1,1'-bis (diphenylphosphino) ferrocene, as well as an acceptor substance (such as sodium hydroxide) in those cases where rhodium is added as chloride or other salt. A reaction solvent is also used as in conventional ones Hydroformylation is usedj toluene is a typical

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Numerous other solvents can also be used, for example benzene, xylene, diphenyl ethers, alkanes, aldehydes or esters. The choice of the particular solvent is outside the scope of the invention, which is specifically improved Catalysts for the reaction system in question and less on other modifications of the system itself. In the reaction system, the catalytic complex catalyzes the hydroformylation of the olefin with the hydrogen and the carbon monoxide to a mixture of aldehydes which have one more carbon than the olefin used. Serves as starting material expediently a terminally unsaturated olefin, the terminal carbon atom usually forming the preferred connection point for the carbonyl group introduced in the hydroformylation. The type of catalyst used has an influence on whether a normal aldehyde is formed or not ( ie whether the terminal carbon atom or the second carbon atom in the chain forms the point of attack for the hydrocarbonylation). The improved catalyst of the present invention provides excellent results in this regard, that is, it results in a high proportion of an aldehyde product in which the terminal carbon atom is hydroformylated .

According to the process according to the invention, a wide variety of olefins (in particular olefins with up to about 25 carbon atoms) hydroformylated to their aldehyde derivatives, which have at least one carbon atom more than the starting olefin exhibit. Di- or triethylenically unsaturated olefins are of course able to form derivatives after complete hydroformylation, which up to an additional Have carbon atom per ethylenically unsaturated double bond in the starting compound. Olefinic compounds with substituents, for example ethylenically unsaturated Alcohols, aldehydes, ketones, esters, carboxylic acids, acetals, ketals, nitriles or amines can also be hydroformylated

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will. Generally speaking, can olefinic compounds, which are free of other substituting atoms than oxygen and nitrogen atoms (especially such compounds, which have no other substituting atoms except oxygen atoms), easily hydroformylate. Some special Substituted classes accessible by the hydroformylation process Olefins are: unsaturated aldehydes such as acrolein or crotonaldehyde, alkenarboxylic acids such as acrylic acid, and unsaturated Acetals, such as acrolein acetal. Examples of more common starting materials are simple alkenes, such as ethylene, Propylene or the butenes, alkadienes such as butadiene or 1,5-hexadiene, and their aryl, alkaryl and aralkyl derivatives. at Hydroformylation is normally carried out on aryl-substituted olefins not on the benzene ring, but rather in the ethylenically unsaturated part of the molecule.

The process conditions used in accordance with the invention depend on the type of end product desired. In general however, correspond to the process parameters according to the invention the usual conditions in conventional hydroformylation methods. For reasons of expediency, these process parameters are generally explained below; it will however found that these conditions are not critical to the achievement of improved results according to the invention and are per se outside of the invention.

The hydroformylation is generally carried out at total reaction pressure of hydrogen and carbon monoxide from one Atmosphere (or below) to a pressure of about 70.3 kgf / cm (about 1000 psig) (or above). For economic reasons, however, in general

positive pressures significantly higher than about 28.1 kp / cm (about 400 psig) not applied.

The reaction is generally at temperatures of about

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50 to about 200 ° C carried out. Usually temperatures are employed in the range of about 75 "to about 15O ⁰ C.

The ratio of the partial pressure of hydrogen to the partial pressure of carbon monoxide in the reaction vessel can be about 10: 1 to 1:10, but is usually in the range of about 3: 1 up to about 1: 3 and is preferably at least about 1: 1.

If necessary, the reaction mixture can also contain other substances contain, for example, an organic solvent (as described), which as a reaction medium for the olefin and the oil-soluble catalytic complex is used. However, additional organic solvents are not required because the Olefin reactant also acts as a solvent.

The following examples illustrate hydroformylation reactions carried out with the aid of the abovementioned catalysts.

Example 4

Table I shows the results of some laboratory tests in which 1-hexene in the presence of toluene as the reaction solvent Is hydroformylated and initially the catalyst Complex 1 is used, with additional 1,1'-bis (diphenylphosphino) ferroene is added in the specified, to convert the complex 1 into the complex A sufficient amounts. As can be seen, tests are also carried out in which more diphenylphosphinoferrocene is added than for Formation of complex A is needed. In all cases there will be enough sodium hydroxide in the reactor feed for disposal of the chloride content originally present in complex 1. The reactor charge consists of 60 ml each Toluene, 20 ml 1-hexene and (initially) 0.2 mmol complex 1. As mentioned, additional proportions of the diphenylphosphinoferrocene are added in some experiments (see. Table I). at

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In each experiment, the toluene, the initial charge of the catalyst present in the form of complex 1, the additional ligand (as indicated) and the sodium hydroxide are placed in a pressure autoclave, which is then closed and rinsed several times with a mixture of equal parts of hydrogen and carbon monoxide. The autoclave is then brought to an overpressure of about 1.3 atmospheres and then heated to the specified reaction temperature. The 1-hexene starting material is initially in a pressure reservoir and is heated there to the aforementioned reaction temperature before being fed into the autoclave. When both the autoclave and the hexene storage tank are at the desired reaction temperature, the 1-hexene is quickly pressed into the autoclave, using part of the H ₂ / CO (1: 1) fed in from a synthesis gas high-pressure storage tank as the pressure medium. Synthesis gas is applied. The said synthesis gas is then pressurized into the autoclave up to the desired reaction pressure. Reaching this pressure is regarded as the start of the experiment, ie the point in time at which the reactor has reached the desired pressure at the desired temperature is regarded as "point in time O". The course of the reaction is then followed on the basis of the speed of the pressure drop in the synthesis gas storage container (which always has a higher pressure than the autoclave, whereby the latter can be kept at the desired pressure level).

When the reaction speed has dropped to an extremely low value, which is due to a very slow pressure drop is displayed in the synthesis gas storage tank, the autoclave is cooled and emptied. The reaction mixture is analyzed by chromatographic methods. The results shown in Table I clearly show that the catalytic effect increases sharply when the ratio of the total diphenylphosphinoferrocene (including that initially in complex 1

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809845 / 10Λ8

c-5499/5499 A 21

contained proportion) to the rhodium atoms is 1.5: 1, and that a further increase in this ratio is superfluous.

The trial numbers given in Table I correspond to those in the original records. The rhodium concentration corresponds to the concentration of rhodium introduced as complex 1 into the reaction system. The concentration of 1,1 · bis (diphenylphosphino) ferrocene represents the total concentration of this component and includes both that originally as part of the molecule of complex 1 introduced portion as well as the additional diphenylphosphinoferrocene self-fed portion. The n-aldehyde / isoaldehyde ratio is the ratio of the heptanal content to the Proportion of branched-chain isomers in the reaction product. The yields shown are percentages of the 1-hexene consumed, which is identified in the reaction product in the form of the end product named in each case will.

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09845/1043

C-5499/5499-A 22959-
14th 22959-
15th 22959-
19th T a b e lie I 22959-
12th 22959-
16 22959-
17th Experiment no. 2.5 2.5 2.5 22959-
18th 22959-
34 2.5 2.5 2.5 Rhodium concentrations
tration, mmol 2.5 2.5 3.12 2.5 2.5 5.0 5.0 7.5 Pc (P $ ₂ ) "-Con
centering *,
mmol 1.0: 1 1.0: 1 1.25: 1 3.75 3.75 2.0: 1 2.0: 3.0: 1 Pc (Pf ₂ ) ₂ / Rh-
Relationship 110 110 110 1.50: 1 1.50: 1 110 110 110 Temp., ⁰ C 110 110

Overpressure 10.55 + 0.07 10.55 + 0.07 10.55 + 0.07 10.55 + 0.07 10.55 + 0.07 10.55 + 0.07 10.55 + 0.07 10.55 + 0.07 (1: 1 H ₂ / CO), --------

a> kp / c _m 2 (psig) (150 + 1) (150 + 1) (150 + 1) (150 + 1) (150 + 1) (150 + 1) (150 + 1) (150 + 1)

5! n-aldehyde / iso-

a> aldehyde ver 2.22: 1 2.12: 1 2.76: 1 5.12: 1 5.21: 1 5.16: 1 5.25: 1 5.19: 1

j> - ratio

• ^, conversion

99.9

54.2

25.6 19.2 1.0

* Fc (P $ ₂ ) ₂ = 1.1 * -bis (diphenylphosphino) ferrocene

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104 degree, %
Yield, $ 99.9 OO Heptanal 53.8 2-methyl
hexanal 24.2 2 witches 21.0 Hexane 1.0

2.76: 1 5.12: 1 5.21: 1 98.6 98.6 96.8 57.5 82.5 82.9 20.8 16.1 15.9 20.8 0.5 0.5 0.9 0.9 0.7

16: 1 5.25: 1 95.3 98.8 82.6 83.0 16.0 15.8 0.6 0.5 0.8 0.7

99 » ¹ i «A ro
CD 82 , 6 17306 15th
0 , 9
, 6 0 , 9

c-5499/5499 A J ^

Example 5

A further series of experiments is carried out analogously to Example 4, but the reaction pressure is used to investigate the Influence of this parameter is varied. It can be seen that the diphenylphosphinoferrocene / rhodium ratio is "slight is higher than the quantitative ratio required for complete conversion of complex 1 into complex A. This Excess is applied to ensure that the conversion of complex 1 to complex A is really complete in all cases. This rules out that any uncertainties as to the nature of the catalyst complex falsify the test results.

The values shown in Table II show that optimum results at a reaction pressure (excess pressure) of about 3.51 kgf / cm (about 50 psig) can be achieved.

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609845/1048

c-5499/5499 A 22959- 22959- 22959- T a b e 1 le II 22959- 22959- 22959- 47 50 46 22959- 22959- 16 41 42 • Experiment no. 43 12th 'Rhodium Concentrations 2.5 2.5 2.5 2.5 2.5 2.5 tration, mmol 2.5 2.5 Pc (P $ ₉ ) «Conc 5.0 - 5.0 '5.0 5.0 5.0 5.0 tration * mmol 5.0 5.0 Fc (PgU / Rh- 2.0: 1 2.0: 1 2.0: 1 2.0: 1 2.0: 1 2.0: 1 relationship 110 110 110 2.0: 1 2.0: 1 110 110 110 Temperature, ⁰ C , 25 + 0.14 2.81 + 0.07 3.51 + 0.07 110 110 10.55 + 0.07 14.20 + 0.14 21.09 + 0.14 Overpressure 2 7.10 + 0.07 10.55 + 0.07 (1: 1 H ₂ / CO), (32 + 2) (40 + 1) (50 + 1) (150 + 1) (202 + 2) (300 + 2) O kp / cm2 (psig) (101 + 1) (150 + 1) CD
OO n-aldehyde / .C- Isoaldehyde 5.03: 1 5.47: 1 6.19: 1 5.25: 1 4.79: 1 4.70: 1 cn relationship 5.59: 1 5.16: 1 χ Transformation 99.8 99.6 99.8 98.8 96.1 96.2 ^c CD grad, ok 99.8 95.3 CO Yield, io 65.3 80.9 84.3 83.0 81.5 81.7 Heptanal 83.8 82.6 2-methyl 13.0 14.8 13.7 15.8 17.0 17.4 hexanal 20.3 2.6 0.7 15.0 16.0 0.5 0.5 0.5 2 witches 1.4 1.7 1.3 0.6 0.6 0.7 1.0 0.4 Hexane 0.6 0.8

* Fc (P $ p) o ⁼ ^ »1'-bis (diphenylphosphino) ferrocene

- 26 -

cn

co CD

c-5499/5499 A
Beistdel 6

Two experiments are carried out analogously to Examples 4 ″ and 5, but using complex 2 as the rhodium-supplying substance. In the first experiment (cf. Table III), complex 2 acts as the only catalyst , 0: 1. In the second experiment, ^{enough additional 1,1 f} -bis (diphenylphosphino) ferrocene is incorporated into the reaction medium that the ratio of the diphenylphosphino to the rhodium atoms is 2.0: In this example, there is no chloride acceptor ( It can be seen that in the second experiment, in which more diphenylphosphinoferrocene is used than is necessary to convert complex 2 into complex A, a greatly improved result is achieved (see table III).

Tabel

III

Experiment no. 20708-9 22959-39 Rhodium concentrations tration, mmol 1.67 2.5 Pc (P ^ ₂ ) p-concentration tration *, mmol 1.67 5.0 P c (Pf ₂ ) ₂ / Rh ratio s 1.0s1 2.0: 1 Temperature, ⁰ C 110 110 Overpressure (1: 1 H ₂ / CO), 7.03 + 0.14 10.55 + 0.07 kp / cm ^ (psig) (100 + 2) (150 + 1) n-Ald ehyd / lso aidehyd- Relationship 2.46: 1 5.01: 1 Degree of conversion, $ 94.9 99.7 Yield, $ Heptanal 51.9 82.1 2-methylhexanal 21.1 16.4 2 witches 27.0 0.4 Hexane traces 1.1

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"S 0 9 8 4 S / 1 0 4 8

c-5499/5499 A *

Example 7

Two experiments are carried out analogously to Example 6, with
However, hydridocarbonyltris (triphenylphosphine) rhodium (I) is used as the rhodium-yielding substance. As in example 1
is the diphenylphosphinoferrocene / rhodium ratio
one attempt 1.0: 1, while on a second attempt a
sufficient additional amount of 1,1V bis (diphenylphosphino) ferrocene is added to convert the hydridocarbonyltris (triphenylphosphine) rhodium (I) catalyst to complex A. The values summarized in Table IV show that the
Results essentially correspond to those of Example 6,
in which the complex 2 represented the substance supplying rhodium. As in Example 6, a greatly improved result is achieved if enough diphenylphosphinoferrocene to convert the catalyst into complex A is incorporated into the catalyst system.

Table IV

Experiment no. 0 22959-9 22959-40 Rhodium concentrations tration, mmol 2.5 2.5 Fc (P§ ₂ ) p-concentration tration, mmol 2.5 5.0 Fc (Pf ₂ ) ₂ / Rh ratio 1.0: 1 2.0: 1 Temperature, ⁰ C 110 110 Overpressure (1: 1 H _p / CO), 70.3 + 0.14 10.55 + 0.07 kp / cm (psig) (100 + 2) (150 +1) n-Ald ehyd / lso aidehyd- relationship 1.84: 1 5.05: 1 Degree of conversion, $ 99.9 98.7 Yield, $ Heptanal 54.2 82.3 2-methylhexanal 19.1 16.3 2 witches 25.8 0.5 Hexane 0.9 0.9 - 28 - 09S45 / 1048

c-5499/5499 A Oq

Example 8

A recommended method for the preparation of complex A is explained below, in which the rhodium is supplied Substance a simple salt (in this case rhodium trinitrate) is used and in which one follows the tendency of the simple salt for deposition of rhodium metal on contact with that within the hydroformylation reaction zone prevailing reducing atmosphere counteracts by using a polyalkylene glycol coupling solvent, as described in DT-OS 2 552 351, begins. The use of the coupling solvent is generally recommended when a simple rhodium salt is used as the substance supplying rhodium.

In a stirred autoclave, as an initial charge, 0.2 mmol of rhodium trinitrate in the form of an aqueous solution which contains 12.9% by weight of Rh and to which 4.11 g of diethylene glycol was admixed as a coupling solvent, together with 60 ml of toluene and 0.2618 g (1 mmol) triphenylphosphine fed. The autoclave is flushed several times with synthesis gas consisting of hydrogen and carbon monoxide (molar ratio 1: 1), then ^{heated to 110 °} C. and then stirred overnight at this temperature under a synthesis gas pressure (excess pressure) of 8.79 kp / cm (125 psig) . The rhodium is converted into a hydridocarbonyl complex with triphenylphosphine with the following formula

HRh (CO) _x (Pf ₃ ) _y

in which χ + y has the value 4.

After the formation of this complex, the autoclave is cooled to room temperature and ventilated. Its contents are mixed with a solution of 0.35 mmol of 1.1 ^f -bis (diphenylphosphino) ferrocene in 5 ml of toluene. The autoclave is then closed again and heated again to 110.degree

- 29 609845/1048

c-5499/5499 A

and charged with 20 ml of 1-hexene. Then "you act on the Autoclave with the aforementioned synthesis gas mixture (1: 1) "to 7.73 kgf / cm (110 psig) and holds him 335 minutes with stirring at this pressure.

After the 335-minute reaction period, the autoclave is cooled, ventilated and its contents are chemically analyzed. It turns out that 93.8 i <> the used 1-hexene were implemented. 30 <fo of the converted amount is accounted for by heptanal, while the ratio of heptanal / branched isomer is 5.07: 1.

When charging the autoclave, the triphenylphosphine is fed before the disubstituted perrocene to ensure that the former and not the latter is oxidized by the trivalent rhodium. As is well known, rhodium (IIl) can with Using triphenylphosphine to be reduced to rhodium (l). It is also found that no alkaline acceptor is required when using rhodium nitrate.

Example 9

A stirred autoclave is filled with 55 ml of toluene, 0.2 mmol of rhodium trichloride trihydrate and charged 1.2 ml of 0.5 η sodium hydroxide solution. The mixture is then 1 hour at 110.degree and an overpressure of equal parts hydrogen

2 and carbon monoxide synthesis gas at 10.55 kp / cm (150 psig). Then one feeds into the autoclave Solution of 0.35 mmol of 1,1'-bis (diphenylphosphino) ferrocene in 5 ml of toluene.

The autoclave is then charged with 20 ml of 1-hexene and then 140 minutes at 110 C and an excess pressure of the Syngas (1: 1 Hp / CO) maintained at 7.03 kgf / cm (100 psig).

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£ 09845/1048

e-5499/5499 A

The autoclave is then cooled to room temperature and ventilated. The chemical analysis of its contents shows that the 1-hexene was converted to 99.4 i ° . 79.1 ° i of the converted amount accounted for by n-heptaldehyde, 15.5 $, 2-methylhexanal.

Example 10

A stirred autoclave is charged as in the preceding examples with 60 ml of toluene, 0.35 mmol of 1.1 ^f -Bis- (diphenylpho sphino) -ferro c en and 0.5538 g of "rhodium on carbon ¹¹ , which is 3.72 wt .- ^ Contains Rh on powdered activated carbon.

The autoclave is then closed, several times with one made up of equal parts of hydrogen and carbon monoxide Syngas purged, pressurized to 75 psig (5.27 kgf / cm) and heated to 110C. Thereafter the pressure is increased to 7.03 kgf / cm (100 psig).

The autoclave contents (100 psig) then react with constant stirring for 60 minutes at 110 ⁰ C and a pressure of 7.03 kgf / cm left.

The autoclave is then cooled to room temperature, ventilated and its contents analyzed. The degree of conversion (conversion) of 1-hexene is 93.9 #. 78.6 # of the converted Amount allotted to heptanal, 15.4% to 2-methylhexanal.

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809845/1048

Claims (24)

Patent claims ( 1. j complex of the following general formula in which M is a metal from group VIII of the periodic table, Q is a phosphorus, arsenic or antimony atom and R is a phenyl group or a lower alkyl radical "mean. 2. Complex according to claim 1, characterized in that M is a rhodium atom. 3. Complex according to claim 2, characterized in that Q is a phosphorus atom. 4. Complex according to claim 3, characterized in that R is a phenyl group. 5. A process for the preparation of a complex suitable for catalyzing olefin hydroformylation reactions, characterized in that 0.5 mol of a disubstituted ferrocene of the general formula below - 32 - 6Ö384S / 1CU8 c-5499/5499 A in which Q is a phosphorus, arsenic or antimony atom and R denote a phenyl group or a lower alkyl radical, with 1 mole of an intermediate complex of the general formula below in which M represents a metal of group VIII of the periodic table and Q and R are each as indicated above Have meaning converts, the reaction in the liquid phase and in the presence of the chloride content of the intermediate complex at least equivalent amount of a chloride acceptor and a hydride former is carried out. 6. The method according to claim 5, characterized in that M is a rhodium atom and hydrogen as the hydride former serves. 7. The method according to claim 6, characterized in that Q is a phosphorus atom. 8. The method according to claim 7, characterized in that R is a phenyl group. 9. A process for the preparation of a complex suitable for catalyzing olefin hydroformylation reactions, - 33 - c-5499/5499 A characterized in that 0.5 mol of a disubstituted Ferrocens of the general formula below in which Q is a phosphorus, arsenic or antimony atom and R
denote a phenyl group or a lower alkyl radical, in the liquid phase with 1 mole of an intermediate complex of the general formula below in which M represents a metal of group VIII of the periodic table and Q and R each have the meaning given above,
brings to implementation. 10. Procedure according to. Claim. 9 »characterized in that M is a rhodium atom. 11. The method according to claim 10, characterized in that Q is a phosphorus atom. 12. The method according to claim 11, characterized in that R is a phenyl group. - 34 - c-5499/5499 A & 13. Process for the preparation of a component as a component of hydroformylation catalysts suitable complex of the formula below Cl in which M is a rhodium atom, Q is a phosphorus atom and R is a phenyl group ", characterized in that 0.5 mol / Rh (CO) pCl7p ^ ^{n of} the liquid phase is reacted with 1 mol of 1,1 * -bis (diphenylphosphino) ferrocene. 14. Process for the preparation of a hydroformylation catalyst and as a component of other hydroformylation catalysts suitable complex of the formula below in which M is a rhodium atom, Q is a phosphorus atom and R is a phenyl group, characterized in that 1 mole of triphenylphosphine in the liquid phase in the presence of a hydride former and a chloride removing cation with 1 mole of a complex the formula below R R Cl TS Fe 609845/1048 c-5499/5499 A 3G in which M is a rhodium atom, Q is a phosphorus atom and R is a phenyl group,
brings to implementation. 15. The method according to claim 14, characterized in that one a borohydride with an alkaline reacting cation, which functions both as a hydride-forming agent and as a chloride-removing agent Cations met, fed into the reaction zone. 16. Process for the preparation of a complex suitable for catalyzing hydroformylation reactions, thereby characterized in that one has 1.5 moles of a compound of the general formula below in which Q is a phosphorus atom and R is a phenyl group or a lower alkyl radical, in the liquid phase with 1 mol of hydride carbonyltris (triphenylpho sphin) rhodium (I) converts 17. The method according to claim 16, characterized in that R is a phenyl group. 18. Process for the preparation of a complex suitable for catalyzing hydroformylation reactions, thereby characterized in that a rhodium-yielding substance is converted into a corresponding substance by reaction with carbon monoxide Rhodium carbonyl derivative transferred and this in the liquid phase with a disubstituted Ferro cen the general formula below - 36 - 609845/1048 c-5499/5499 A in the Q a phosphorus, arsenic or antimonate atom and R denote a phenyl group or a lower alkyl radical, with a proportion of at least 1.5 moles of the disubstituted Ferrocene per gram atom of that in the rhodium carbonyl derivative contained rhodium converts, the reaction in the presence of a to convert the carbonyl derivative Hydrogen required in a corresponding hydride derivative and in the presence of one for neutralization in the reaction of the hydrogen-yielding substance with the carbonyl derivative, if this has a halide content contains, released hydrohalic acid required Halide acceptor is carried out. 19. The method according to claim 18, characterized in that Q is a phosphorus atom. 20. The method according to claim 19, characterized in that R is a phenyl group. 21. Process for the hydroformylation of an olefin with hydrogen and carbon monoxide in a liquid phase reaction zone to form an aldehyde derivative of the olefin, thereby characterized in that the hydroformylation with rhodium hydridocarbonyl, that with a ferrocene derivative the general formula below - 37 609845/1048 c-5499/5499 A in which Q is a phosphorus, arsenic or antimony atom and R
a phenyl group or a lower alkyl radical, is present in a complex combination, catalysed. 22. The method according to claim 21, characterized in that Q is a phosphorus atom. 23 «Method according to claim 22, characterized in that E is a phenyl group. 24. The method according to claim 21, characterized in that at least about 1.5 mol of des in the reaction zone
Ferrocene derivative per gram atom of rhodium maintains. 609845/1048