WO2003016322A1

WO2003016322A1 - Novel bisphosphite compounds and the metal complexes thereof

Info

Publication number: WO2003016322A1
Application number: PCT/EP2002/009053
Authority: WO
Inventors: Cornelia Borgmann; Detlef Selent; Armin BÖRNER; Dieter Hess; Klaus-Diether Wiese
Original assignee: Oxeno Olefinchemie Gmbh
Priority date: 2001-08-16
Filing date: 2002-08-13
Publication date: 2003-02-27
Also published as: DE10140072A1

Abstract

Disclosed are novel biophosphites of formula (I) and the metal complexes thereof, the production and use of said biphosphites as ligands in catalytic reactions, especially in methods for hydroformylation of olefins.

Description

NEW BISPHOSPHITE COMPOUNDS AND THEIR METAL COMPLEXES

The present invention relates to bispnosphites and their metal complexes, the preparation and the use of the bisphosphites as ligands in catalytic reactions.

The reaction between olefin compounds, carbon monoxide and hydrogen in the presence of a catalyst to form a carbon atom-rich aldehydes is known as hydroformylation (oxidation). Compounds of the transition metals of the 8th to 10th group of the Periodic Table of the Elements, in particular compounds of rhodium and cobalt, are frequently used as catalysts in these reactions. Hydroformylation with rhodium compounds generally offers the advantage of higher selectivity compared to catalysis with cobalt compounds and is therefore usually more economical. In the hydroformylation catalyzed by rhodium, complexes are usually used which consist of rhodium and preferably trivalent phosphorus compounds as ligands. Known ligands are, for example, compounds from the classes of the phosphines, phosphites and phosphonites. An overview of hydroformylation of olefins can be found in B. CORNILS, W. A. HERRMANN, "Applied Homogeneous Catalysis with Organometallic Compounds", Vol. 1 & 2, VCH, Weinheim, New York, 1996.

Every catalyst system (cobalt or rhodium) has its specific advantages. Depending on the starting material and target product, different catalyst systems are used. When working with rhodium and triphenylphosphine, α-olefins can be hydroformylated at lower pressures. Triphenylphosphine is generally used in excess as the phosphorus-containing ligand, a high ligand / rhodium ratio being necessary in order to increase the selectivity of the reaction to the commercially desired n-aldehyde product.

US-A-4,694,109 and US-A-4,879,416 relate to bisphosphine ligands and their use in the hydroformylation of olefins at low synthesis gas pressures. Particularly in the hydroformylation of propene, high activities and high n / i selectivities are achieved with ligands of this type.

WO-A-95/30680 describes bidentate phosphine ligands and their use in catalysis, including in hydroformylation reactions. Ferrocene-bridged bisphosphines are disclosed, for example, in US-A-4, 169,861, US-A-4,201,714 and US-A-4,193,943 as ligands for hydroformylations.

The disadvantage of bidentate phosphine ligands is the relatively complex production. It is therefore often not profitable to use such systems in technical processes.

Rhodium-monophosphite complexes are suitable catalysts for the hydroformylation of branched olefins with internal double bonds, but the selectivity for terminally hydroformylated compounds is low.

EP-A-0 155 508 discloses the use of bisarylene-substituted monophosphites in the rhodium-catalyzed hydroformylation of sterically hindered olefins, e.g. B. isobutene known. Rhodium-bisphosphite complexes catalyze the hydroformylation of linear olefins with terminal and internal double bonds, predominantly terminal hydroformylated products being formed, whereas branched olefins with internal double bonds are only converted to a small extent. When coordinated to a transition metal center, these phosphites give rise to catalysts of increased activity, but the service life of these catalyst systems is unsatisfactory, inter alia because of the sensitivity to hydrolysis of the phosphite ligands. Substantial improvements could be achieved by using substituted bisaryldiols as starting materials for the phosphite ligands, as described in EP-A-0214622 or EP-A-0472071.

According to the literature, the rhodium complexes of these ligands are extremely active hydroformylation catalysts for α-olefins. US-A-4,668,651, US-A-4,748,261 and US-A-4,885,401 describe polyphosphite ligands with which α-olefins, but also 2-butene, can be reacted with high selectivity to give the terminally hydroformylated products. In US-A-5,312,996 bidentate ligands of this type are also used for the hydroformylation of butadiene.

Although the phosphites mentioned are good complex ligands for rhodium hydroformylation catalysts, it is desirable to develop novel, easily prepared phosphites to further improve their effectiveness, for example in hydroformylation. It has surprisingly been found that new bisphosphites of the general structural formula I,

where R ¹ and R ^{u are} each independently selected from monovalent substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, and mixed aliphatic-heterocyclic hydrocarbon radicals having 1 to 50 carbon atoms, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently selected from monovalent substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radicals with 1 to 50 carbon atoms, H, F, Cl, Br, I, -CF ₃ , -CH ₂ (CF ₂ ) _j CF ₃ with j = 0-9, -OR ⁹ , -COR ⁹ , -CO ₂ R ⁹ , -CO ₂ M, -SR ⁹ , -SO ₂ R ⁹ , -SOR ⁹ , -SO ₃ R ⁹ , -SO ₃ M, -SO ₂ NR ⁹ R ¹⁰ , -NR ⁹ R ¹⁰ , -N = CR ⁹ R ¹⁰ , where R ⁹ and R ¹⁰ independently of one another from H, monovalent substituted or unsubstituted aliphatic and aromatic hydrocarbon radicals having 1 to 25 carbon atoms are selected and M is an alkali metal, formally half an alkaline earth metal, ammonium or phosphonium ion, or neighboring radicals R ¹ to R ⁶ together form a condensed substituted or unsubstituted iate aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system; W is the divalent radical -CR ⁷ R ⁸ - and R ⁷ and R ^{8 are defined} as R ⁹ and R ¹⁰ ; k = 0 or 1, m = 0 or 1 and n = 0 or 1, are suitable complex ligands. The invention also relates to complexes of the bisphosphite ligands with a metal of the 4th, 5th, 6th, 7th, 8th, 9th or 10th group of the Periodic Table of the Elements and their preparation.

Furthermore, the present invention is directed to the use of the bisphosphites or the bisphosphite metal complexes in catalysis, preferably in homogeneous catalysis, in particular in the hydroformylation of olefins.

Further aspects of the invention are a process for the hydroformylation of olefins and a process for the preparation of the bisphosphite ligands.

In a preferred bisphosphite according to formula I, R ¹ and R ^{11 are} each independently selected from aromatics or heteroaromatics which are unsubstituted or with at least one radical selected from aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radicals with 1 to 25 carbon atoms, F, Cl, Br, I, -CF ₃ , -CH ₂ (CF ₂ ) jCF ₃ with j = 0 - 9, -OR ⁹ , -COR ⁹ , - CO ₂ R ⁹ , -CO ₂ M, -SR ⁹ , -SO ₂ R ⁹ , -SOR ⁹ , -SO ₃ R ⁹ , -SO ₃ M, -SO ₂ NR ⁹ R ¹⁰ , -NR ⁹ R ¹⁰ , or -N = CR ⁹ R ¹⁰ , where R ⁹ , R ¹⁰ and M are as previously defined.

In a likewise preferred embodiment, R ¹ and R ^{11 are} each independently selected from aromatics or heteroaromatics which have fused aromatic, heteroaromatic and / or aliphatic rings which are unsubstituted or with at least one radical selected from aliphatic, alicyclic, aromatic, mixed aliphatic - alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radicals with 1 to 25 carbon atoms, F, Cl, Br, I, -CF ₃ , -CH ₂ (CF ₂ ) jCF ₃ with j = 0 - 9, - OR ⁹ , -COR ⁹ , -CO ₂ R ⁹ , -CO ₂ M, -SR ⁹ , -SO ₂ R ⁹ , -SOR ⁹ , -SO ₃ R ⁹ , -SO ₃ M, -SO ₂ NR ⁹ R ¹⁰ , -NR ⁹ R ¹⁰ , or -N = CR ⁹ R ¹⁰ , where R ⁹ , R ¹⁰ and M are as previously defined.

It is further preferred if radicals R ¹ to R ⁶ together form a condensed aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system which is unsubstituted or with at least one radical selected from aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radicals with 1 to 50 carbon atoms, F, Cl, Br, I, -CF ₃ , -CH ₂ (CF ₂ ) _j CF ₃ with j = 0-9, -OR ⁹ , -COR ⁹ , -CO ₂ R ⁹ , -CO ₂ M, -SR ⁹ , -SO ₂ R ⁹ , -SOR ⁹ , -SO ₃ R ⁹ , -SO ₃ M, -SO ₂ NR ⁹ R ¹⁰ , -NR ⁹ R ¹⁰ , or -N = CR ⁹ R ¹⁰ , where R ⁹ , R ¹⁰ and M are as previously defined.

Representative bisphosphite ligands according to formula I are:

The bisphosphites according to the invention can be prepared by a sequence of reactions of phosphorus halides with alcohols, carboxylic acids and / or α-hydroxyarylcarboxylic acids, in which halogen atoms on phosphorus are exchanged for oxygen groups. The basic procedure is exemplified by a route to compounds according to general formula I:

In a first step, a bis (α-hydroxyaryl) dicarboxylic acid (1) with a with a phosphorus trihalide PX ₃ , such as PC1 ₃ , PBr ₃ and PJ ₃ , preferably phosphorus trichloride PC1 ₃ , in the presence of a base, preferably in equivalents or is used in catalytic amounts to a bis (halodioxaphosphorinone) (2).

(1) (2)

In a second reaction step, the desired bisphosphite according to the formula is converted from the bis (halodioxaphosphorinone) (2) by reaction with an alcohol HO-R ¹ or a carboxylic acid HOOC-R ¹ in the presence of a base, which is preferably used in equivalent or catalytic amounts (I) obtained in which R ¹ = R ¹¹ . In the case of reaction with an alcohol, m and k in the bisphosphite of the formula (I) are 0; in the case of reaction with a carboxylic acid, m and k are 1.

R ¹ to R ⁶ , W, R ¹ and n have the meanings given above.

Depending on the desired end product, the second reaction step can also be carried out in a different way. The bis (halodioxaphosphorinone) (2) is first treated with one equivalent of HO-R in the presence of a base, which is preferably used in equivalent or catalytic amounts, and then with one equivalent of HO-R ¹¹ in counter were a base, which is preferably used in equivalent or catalytic amounts, reacted to a bisphosphite according to formula (I) with R ¹ ≠ R ¹¹ and m, k = O. or first with an equivalent of HOOC-R ¹ in the presence of a Base, which is preferably used in equivalent or catalytic amounts, and then with an equivalent of HOOC-R ¹¹ in the presence of a base, which is preferably used in equivalent or catalytic amounts, to form a bisphosphite according to formula (I) with R ¹ ≠ R to obtain ^u and m, k = 1, where R ¹ to R ⁶ , W, n, R ¹ and R ^{11 have} the meanings given above.

Yet another product is obtained if the second reaction step is carried out as follows. The bis (chlorodioxaphosphorinone) (2) is first treated with one equivalent of HO-R ¹ or HOOC-R ¹ in the presence of a base, which is preferably used in equivalent or catalytic amounts, and then with one equivalent of HOOC-R ¹¹ or HO- R ¹¹ is reacted in the presence of a base, which is preferably used in equivalent or catalytic amounts, in order to obtain a bisphosphite of the formula (I) with R ¹ ≠ R ^u and m = 0 or 1 and k = 0 or 1, where R ¹ to R ⁶ , W, n, R ¹ and R ^{11 have} the meanings given above.

Since the alcohols or carboxylic acids used and their secondary products are often solid, the reactions are generally carried out in solvents. Non-protic solvents which do not react with the alcohols or carboxylic acids or with the phosphorus compounds are used as solvents. Suitable solvents are, for example, tetrahydrofuran, ethers such as diethyl ether or MTBE (methyl tertiary butyl ether) or aromatic hydrocarbons such as toluene.

The reaction of phosphorus halogens with alcohols produces hydrogen halide, which is bound by added bases. For example, tertiary amines such as triethylamine, pyridine or N-methylpyrrolidinone are used for this. In some cases, it is also sensible to convert the alcohols to metal alcoholates before the reaction, for example by reaction with sodium hydride or butyllithium.

The bisphosphites are suitable ligands for complexing metals of the 4th, 5th, 6th, 7th, 8th, 9th or 10th group of the Periodic Table of the Elements. The complexes can be one or contain several bisphosphite ligands and optionally further ligands and are suitable as catalysts, preferably in homogeneous catalysis. Examples of suitable metals are rhodium, cobalt, iridium, nickel, palladium, platinum, iron, ruthenium, osmium, chromium, molybdenum and tungsten. In particular with metals of the 8th, 9th and 10th group, the resulting complexes can be used as catalysts for hydroformylation, carbonylation, hydrogenation and hydrocyanation reactions; rhodium, cobalt, nickel, platinum and ruthenium are particularly preferred. For example, high catalytic activities result in hydroformylation reactions, particularly when rhodium is used as the catalyst metal. The catalyst metals are used in the form of salts or complexes, in the case of rhodium, for example, rhodium carbonyls, rhodium nitrate, rhodium chloride, Rh (CO) ₂ (acac) (acac = acetylacetonate), rhodium acetate, rhodium octanoate or rhodium nonanoate.

The active catalyst species for homogeneous catalysis is formed from the bisphosphite ligands according to the invention and the catalyst metal under reaction conditions, for example in the case of hydroformylation upon contact with synthesis gas, a carbonylhydride phosphite complex. The bisphosphites and optionally other ligands can be added to the reaction mixture in free form together with the catalyst metal (as a salt or complex) in order to generate the active catalyst species in situ. It is also possible to use a bisphosphite metal complex which contains the above-mentioned. Bisphosphite ligands and the catalyst metal contains to be used as a precursor for the actual catalytically active complex. These bisphosphite metal complexes are prepared by reacting the corresponding catalyst metal of the 4th to 10th group in elemental form or in the form of a chemical compound with the bisphosphite ligand.

Phosphorus-containing ligands, preferably phosphines, bisphosphites, phosphonites or phosphinites, can be used as additional ligands present in the reaction mixture.

Examples of such ligands are:

Phosphines: triphenylphosphine, tris (p-tolyl) phosphine, tris (m-tolyl) phosphine, tris (o-tolyl) phosphine, tris (p-methoxyphenyl) phosphine, tris (p-dimethylaminophenyl) phosphine, tricyclohexylphosphine, tricyclopentylphosphine, triethyl tri (l-naphthyl) phosphine, Tribenzylphosphine, tri-n-butylphosphine, tri-t-butylphosphine.

Phosphites: trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, tri-i-propyl phosphite, tri-n-butyl phosphite, tri-i-butyl phosphite, tri-t-butyl phosphite, tris (2-ethylhexyl) phosphite, triphenyl phosphite, tris (2, 4-di-t-butylρhenyl) ρhosρhit, tris (2-t-butyl-4-methoxyphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (p-cresyl) phosphite. In addition, sterically hindered phosphite ligands, as described, inter alia, in EP-A-155 508, US-A-4,668,651, US-A-4,748,261, US-A-4,769,498, US-A-4,774,361, US-A-4,835,299, US Pat. A-4,885,401, US-A-5,059,710, US-A-5, 113,022, US-A-5,179,055, US-A-5,260,491, US-A-5,264,616, US-A-5,288,918, US-A-5,360,938, EP- A-472071, EP-A-518241 and WO-A-97/20795, suitable ligands.

Phosphonites: methyldiethoxyphosphine, phenyldimethoxyphosphine, phenyldiphenoxyphosphine, 2-phenoxy-2H-dibenz [c, e] [l, 2] oxaphosphorine and its derivatives, in which the hydrogen atoms are completely or partially replaced by alkyl and / or aryl radicals or halogen atoms and ligands , which are described in WO-A-98/43935, JP-A-09-268152 and DE-A-198 10794 and in German patent applications DE-A-199 54721 and DE-A-199 54 510.

Common phosphinite ligands are described, inter alia, in US Pat. No. 5,710,344, WO-A-95/06627, US Pat. No. 5,360,938 or JP-A-07-082281. Examples of these are diphenyl (phenoxy) phosphine and its derivatives in which the hydrogen atoms are replaced in whole or in part by alkyl and / or aryl radicals or halogen atoms, diphenyl (methoxy) phosphine and diphenyl (ethoxy) phosphine.

The bisphosphites or bisphosphite metal complexes according to the invention can be used in processes for the hydroformylation of olefins, preferably having 2 to 25 carbon atoms, to give the corresponding aldehydes. Bisphosphite complexes with metals from the 8th, 9th or 10th group are preferably used here, particularly preferably bisphosphite complexes with metals from the 9th group as catalyst precursors.

In general, 1 to 500 mol, preferably 1 to 200 mol, more preferably 2 to 50 mol of the bisphosphite according to the invention are used per mol of metal from the 8th subgroup. Fresh bisphosphite ligand can be added at any point in the reaction to keep the concentration of free ligand constant. The concentration of the metal in the reaction mixture is in the range from 1 ppm to 1000 ppm, preferably in the range from 5 ppm to 300 ppm, based on the total weight of the reaction mixture.

The hydroformylation reactions carried out with the bisphosphites according to the invention or the corresponding metal complexes were carried out according to known regulations, such as, for. B. in J. FALBE, "New Syntheses with Carbon Monoxide", Springer Verlag, Berlin, Heidelberg, New York, page 95 ff, (1980). In the presence of the catalyst, the olefin compound (s) is (are) reacted with a mixture of CO and H ₂ (synthesis gas) to give the aldehydes which are richer by one carbon atom.

The reaction temperatures for a hydroformylation process using the bisphosphites or bisphosphite metal complexes according to the invention as catalyst are preferably between 40 ° C. and 180 ° C. and more preferably between 75 ° C. and 140 ° C. The pressures at which the hydroformylation takes place are preferably 1 to 300 bar synthesis gas and more preferably 10 to 64 bar. The molar ratio between hydrogen and carbon monoxide (H ₂ / CO) in the synthesis gas is preferably 10/1 to 1/10 and more preferably 1/1 to 2/1.

The catalyst or ligand is homogeneously dissolved in the hydroformylation mixture consisting of starting materials (olefins and synthesis gas) and products (aldehydes, alcohols, high boilers formed in the process). Optionally, a solvent can also be used.

Because of their high molecular weight, the bisphosphites according to the invention have low volatility. They can therefore be easily separated from the more volatile reaction products. They are sufficiently soluble in common organic solvents.

The starting materials for the hydroformylation are olefins or mixtures of olefins having 2 to 25 carbon atoms with a terminal or internal C = C double bond. They can be straight-chain, branched or of a cyclic structure and also have several olefinically unsaturated groups. Examples are propene; 1-butene, cis-2-butene, trans-2-butene, isobutene, butadiene, mixtures of the C -olefins; C ₅ olefins such as 1-pentene, 2-pentene, 2-methylbutene-1, 2-methylbutene-2, 3-methylbutene-1; C ₆ olefins such as 1-hexene, 2-hexene, 3-hexene, the C ₆ -olefin mixture obtained in the dimerization of propene (dipropen); C ₇ olefins such as 1-heptene, further n-heptenes, 2-methyl-1-hexene, 3-methyl-1-hexene; C ₈ olefins such as 1-octene, further n Octenes, 2-methylheptenes, 3-methylheptenes, 5-methylheptenes-2, 6-methylheptenes-2, 2-ethylhexene-1, the isomeric C ₈ -olefin mixture (dibutene) obtained in the dimerization of butenes; C ₉ -olefins such as 1-nonen, further n-nonenes, 2-methyloctenes, 3-methyloctenes, the C -olefin mixture obtained during the trimerization of propene (tripropen); C ₁₀ olefins such as n-decenes, 2-ethyl-1-octene; C ₁₂ olefins such as n-dodecenes, the C ₁₂ olefin mixture (tetrapropene or tributes) obtained in the tetramerization of propene or the trimerization of butenes, C ₁ olefins such as n-tetradecenes, C ₁₆ olefins such as n-hexadecenes C ₁₆ olefin mixture (tetrabutene) resulting from the tetramerization of butenes and olefin mixtures produced by cooligomerization of olefins with different C numbers (preferably 2 to 4), if appropriate after separation by distillation into fractions with the same or similar C number. It is also possible to use olefins or olefin mixtures which are produced by Fischer-Tropsch synthesis, and also olefins which are obtained by oligomerization of ethene or which are accessible via methathesis reactions or telomerization reaction.

Preferred starting materials are generally α-olefins such as propene, 1-butene, 2-butene, 1-hexene, 1-octene, and dimers and trimers of butene (dibutene, di-n-butene, di-isobutene, tributes).

The hydroformylation can be carried out continuously or batchwise. Examples of technical designs are stirred tanks, bubble columns, jet nozzle reactors, tubular reactors, or loop reactors, which can be cascaded and / or provided with internals.

The reaction can be carried out continuously or in several stages. The separation of the resulting aldehyde compounds and the catalyst can be carried out by a conventional method such as fractionation. Technically, this can be done, for example, by distillation, a falling film evaporator or a thin film evaporator. This is especially true when the catalyst is dissolved in a high-boiling solvent and separated from the lower-boiling products. The separated catalyst solution can be used for further hydroformylations. When using lower olefins (e.g. propene, butene, pentene) it is also possible to discharge the products from the reactor via the gas phase.

The following examples are intended to illustrate the present invention without the in the Restrict the scope of protection defined in patent claims.

Standard Schlenk technology was used under protective gas. The solvents were dried with suitable drying agents before use.

1. Synthesis of the bisphosphite compound K:

1st stage: reaction of embonic acid with phosphorus trichloride

10.3 g embonic acid (26.0 mmol) are dissolved in 75 ml propylene carbonate and 10.4 g triethylamine (102.0 mmol). 7.2 g of phosphorus trichloride (52.0 ml) in 30 ml of propylene carbonate are added dropwise to this solution with stirring. The yellow suspension is heated to 80 ° C. for 2.5 h, cooled to room temperature and filtered through a frit. The orange-red filtrate is used in stage 2 without working up.

2nd stage: Synthesis of the bisphosphite compound K 10.2 g of triethylamine (100.0 mmol) in 12 ml of THF are added to a solution of 10.4 g of 2,4-di-tert-butylphenol (50.0 mmol) in 75 ml of propylene carbonate. The resulting solution is added dropwise to the 1st stage filtrate at 0 ° C. After warming to room temperature, the mixture is heated at 80 ° C. for 2 h and filtered after cooling to 40 ° C. The filtrate is stored at -20 ° C for 14 h. The resulting precipitate is filtered off.

Yield: 5.5 g (6.5 mmol) corresponding to 25% of theory. ³¹ P NMR (toluene-D8): δ 133.2 ppm. Hydroformylation of 1-octene using the bisphosphite compounds K The hydroformylation experiments were carried out in a 100 ml Parr autoclave equipped with pressure maintenance, gas flow measurement, paddle stirrer and HPLC pump. 2.55 g of a solution of 0.357% by mass of Rh-nonanoate in toluene and 4.50 g of a solution of 2.204% by mass of the bisphosphite compound K in toluene were introduced into the autoclave under an argon atmosphere. The amount of toluene was made up to 30 g. The rhodium-ligand mixture was then stirred (1000 rpm) with synthesis gas (CO / H2 1: 1) to a pressure of 5 to 10 bar (target pressure 20 bar) or 10 to 15 bar (target pressure 40 bar) brought and heated to 100 ° C or 120 ° C. After the desired reaction temperature had been reached, 1-octene was added via an HPLC pump and the pressure was adjusted to the target pressure of 20 or 40 bar. Samples were taken at fixed intervals during the test period. The reaction was carried out at constant pressure (pressure regulator from Bronkhorst (NL)) for 5 h. After the trial period, the autoclave was cooled to room temperature, decompressed and flushed with argon. 0.2 ml of the autoclave solution was mixed with 0.8 ml of n-pentane and analyzed by gas chromatography.

Test Parameters:

1st experiment: rhodium concentration = 40 ppm, ratio

Rh: ligand: 1-octene = 1: 5: 11800; T - 100 ° C, p = 20 bar, synthesis gas (CO / H ₂ = 1: 1), t = 5 h, solvent: toluene

2nd experiment: hodium concentration = 40 ppm, ratio

Rh: ligand: 1 octene = 1: 5: 11800; T = 120 ° C, ρ = 40 bar, synthesis gas (CO / H ₂ 1: 1), t = 5 h, solvent: toluene

Table: Hydroformylation of 1-octene

The yield is the total yield of C ₉ aldehydes. With n selectivity is the ratio of terminally to internally hydroformylated C ₉ aldehydes.

The olefin hydrogenation does not play an important role, so only 0.3% octane was found in the second experiment at 40 bar.

Claims

Claims:

1. bisphosphite according to formula I.

where R ¹ and R ^{11 are} each independently selected from monovalent substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, and mixed aliphatic-heterocyclic hydrocarbon radicals having 1 to 50 carbon atoms,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently selected from monovalent substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic heterocyclic hydrocarbon radicals with 1 to 50 carbon atoms, H, F, Cl, Br, I, -CF ₃ , -CH ₂ (CF ₂ ) _j CF ₃ with j = 0 - 9, -OR ⁹ , -COR ⁹ ,

-CO ₂ R ^y , -CO ₂ M, -SR ^y , -SO ₂ R ^y , -SOR ^y , -SO ₃ R ^y , -SO ₃ M, -SO ₂ NR 9 ^y rR> 1 ^ι 0 ^υ , - NR> 9 ^y rR> 1 ^ι 0 ^υ , -N = CR ⁹ R ¹⁰ , where R ⁹ and R ^{10 are} independently selected from H, monovalent substituted or unsubstituted aliphatic and aromatic hydrocarbon radicals having 1 to 25 carbon atoms and M is an alkali metal , formally half an alkaline earth metal, ammonium or phosphonium ion, or neighboring radicals R ¹ to R ⁶ together form a fused substituted or unsubstituted aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system; W is the divalent radical -CR ⁷ R ⁸ - and R ⁷ and R ^{8 are defined} as R ⁹ and R ¹⁰ ; k = 0 or 1, m = 0 or 1 and n = 0 or 1.

2. Bisphosphite according to claim 1, wherein R ¹ and R ^{u are} each independently selected from aromatics or heteroaromatics which are unsubstituted or with at least one radical selected from aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic -aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radicals with 1 to 25 carbon atoms, F, Cl, Br, I, -CF ₃ , -CH ₂ (CF ₂ ) _j CF ₃ with j = 0 - 9, -OR ⁹ , - COR ⁹ , -CO ₂ R ⁹ , -CO ₂ M, -SR ⁹ , -SO ₂ R ⁹ , -SOR ⁹ , -SO ₃ R ⁹ , -SO ₃ M, -SO ₂ NR ⁹ R ¹⁰ , -NR ⁹ R ¹⁰ , or -N = CR ⁹ R ¹⁰ , are substituted, wherein R ⁹ , R ¹⁰ and M are as defined in claim 1.

3. bisphosphite according to claim 1, wherein R ¹ and R ^{11 are} each independently selected from aromatics or heteroaromatics which have fused aromatic, heteroaromatic and / or aliphatic rings which are unsubstituted or with at least one radical selected from aliphatic, alicyclic, aromatic , heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radicals with 1 to 25 carbon atoms, F, Cl, Br, I, -CF ₃ , -CH ₂ (CF ₂ ) jCF ₃ with j = 0-9, -OR ⁹ , -COR ⁹ , -CO ₂ R ⁹ , -CO ₂ M, -SR ⁹ , -SO ₂ R ⁹ , -SOR ⁹ , -SO ₃ R ⁹ , -SO ₃ M, -SO ₂ NR ⁹ R ¹⁰ , -NR ⁹ R ¹⁰ , or -N = CR ⁹ R ^{10 are} substituted, wherein R ⁹ , R ¹⁰ and M are as defined in claim 1.

4. bisphosphite according to any one of claims 1 to 3, wherein adjacent radicals R ¹ to R ⁶ together form a condensed aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system which is unsubstituted or with at least one radical , selected from aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radicals with 1 to 50 carbon atoms, F, Cl, Br, I, -CF ₃ , -CH ₂ ( CF ₂ ) _j CF ₃ with j = 0-9, -OR ⁹ , -COR ⁹ , -CO ₂ R ⁹ , -CO ₂ M, -SR ⁹ , -SO ₂ R ⁹ , -SOR ⁹ , -SO ₃ R ⁹ , -SO ₃ M, -SO ₂ NR ⁹ R ¹⁰ , -NR ⁹ R ¹⁰ , or -N = CR ⁹ R ¹⁰ , where R ⁹ , R ¹⁰ and M are as defined in claim 1.

5. bisphosphite metal complex containing a metal of the 4th, 5th, 6th, 7th, 8th, 9th or 10th group of the Periodic Table of the Elements and one or more bisphosphites according to one of Claims 1 to 4.

6. bisphosphite metal complex according to claim 5, wherein the metal is rhodium, platinum, palladium, cobalt or ruthenium.

7. Use of a bisphosphite according to one of claims 1 to 4 or a bisphosphite metal complex according to claim 5 or 6 in catalysis.

8. Use of a bisphosphite according to one of claims 1 to 4 or a bisphosphite metal complex according to claim 5 or 6 in homogeneous catalysis.

9. Use of a bisphosphite according to one of claims 1 to 4 or a bisphosphite metal complex according to claim 5 or 6 in a process for the hydroformylation of olefins.

10. Use according to claim 9, wherein further phosphorus-containing ligands are present.

11. A process for the hydroformylation of olefins, comprising the reaction of a monoolefin or monoolefin mixture with a mixture of carbon monoxide and hydrogen in the presence of a bisphosphite according to one of claims 1 to 4 or a bisphosphite metal complex according to claim 5 or 6.

12. A method for producing a bisphosphite according to any one of claims 1 to 4, comprising

(a) reaction of a bis (α-hydroxyaryl) dicarboxylic acid according to formula (1)

with PC1 ₃ , PBr ₃ or PI ₃ in the presence of a base to form a bis (halodioxaphosphorinone) according to formula (2), wherein Hai = Cl, Br or I, and

(b) reaction of the bis (halodioxaphosphorinone) (2) in the presence of a base with (i) an alcohol HO-R ¹ to give a bisphosphite according to formula (I) with R ¹ = R ^u and m, k = 0 or

(ii) a carboxylic acid HOOC-R ¹ to obtain a bisphosphite according to formula (I) with R ¹ = R ¹¹ and m, k = 1, wherein R ¹ to R ⁶ , W, n and R ¹ as in claim 1 are defined.

13. A method for producing a bisphosphite according to any one of claims 1 to 4, comprising (a) producing a bis (halodioxaphosphorinone) according to step (a) from claim 12 and (b) reaction of bis (halodioxaphosphorinone) (2) with

(i) first an equivalent of HO-R ¹ in the presence of a base and then with an equivalent of HO-R ¹¹ in the presence of a base to form a bisphosphite according to formula (I) with R ¹ ≠ R ^u and m, k = 0, or

(ii) first an equivalent of HOOC-R ¹ in the presence of a base and then with an equivalent of HOOC-R ¹¹ in the presence of a base to give a bisphosphite according to formula (I) with R ¹ ≠ R ¹¹ and m, k = 1 to obtain, wherein R ¹ to R ⁶ and R ¹ and R ^{11 are} as defined in claim 1.

14. A method for producing a bisphosphite according to any one of claims 1 to 4, comprising

(a) Preparation of a bis (halodioxaphosphorinone) according to step (a) from claim 12 and

(b) reaction of the bis (halodioxaphosphorinone) (2) with first one equivalent of HO-R ¹ or HOOC-R ¹ in the presence of a base and then with one equivalent of HOOC-R ¹¹ or HO-R ¹¹ in the presence of a base, to obtain a bisphosphite of the formula (I) with R ¹ ≠ R ¹¹ and m, k = 0 or 1, where R ¹ to R ⁶ and R ¹ and R ^{11 are} as defined in claim 1.

15. A method for producing a bisphosphite metal complex according to claim 5 or 6, comprising the reaction of a metal of the 4th, 5th, 6th, 7th, 8th, 9th or 10th group of the periodic table in elemental form or in the form of a chemical A compound with a bisphosphite according to any one of claims 1 to 4.