MXPA97001901A - Procedure for the preparation of aldehi - Google Patents

Abstract

The present invention relates to a process for the preparation of aldehydes by the reaction of olefinically unsaturated compounds having at least 3 carbon atoms, with carbon monoxide and hydrogen, in liquid phase, in the presence of water, of a catalyst system containing compounds water-soluble rhodium complexes and dissolution intermediates, characterized in that the catalyst system containing the complex rhodium compounds contain as diphosphine ligands of the general formula I: that they are substituted with one or more sulfonic acid groups, where the X's are the same or different and represent alkyl radicals of 1 to 9 carbon atoms, cycloalkyl of 6 to 10 carbon atoms, aryl of 6 to 10 carbon atoms or diary of 12 carbon atoms, substituted or unsubstituted, those R 1 are the same or different and represent hydrogen, alkyl radicals from 1 to 14 carbon atoms, alkoxy from 1 to 14 carbon atoms, cycloalkyl from 6 to 1 4 carbon atoms, aryl of 6 to 14 carbon atoms or aroxy of 6 to 14 carbon atoms, or a ring of benzene cyclic, the m are the same or different and represent an integer from 0 to 5 and the n, possibly equal or different , represent an integer from 0 to 4, and use as intermediates for dissolution, compounds of the general formula II: wherein A represents an alkyl radical of 6 to 25 carbon atoms, W-hydroxyalkyl of 6 to 25 carbon atoms, straight or branched chain, or an aryl radical of 6 to 25 carbon atoms, optionally substituted, or the radical R7-CONH-CH2-CH2-CH2-, wherein R7 signifies a straight or branched chain alkyl radical, from 5 to 11 atoms of carbon, B, C and D are the same or different and represent straight or branched chain alkyl or w-hydroxyalkyl radicals, from 1 to 4 carbon atoms, or C and D, together with N, form a heterocyclic ring of five or six members, and E- represents an inorganic or organic anion

Description

PROCEDURE FOR THE PREPARATION OF ALDEHYDES The present invention relates to a process for the preparation of aldehydes, by the hydrolynination of higher olefmas, in the presence of water-soluble rhodium complex catalysts, and of dissolution mediators. The preparation of aldehydes and alcohols by the reaction of olefms with carbon and hydrogen is known. The hydroformylation is catalysed by me of carbomols of hydpdometals, preferably those of metals of group 8 of the Periodic System. In addition to cobalt, which has technical application in large volumes as a catalyst metal, in recent times rhodium has gained notoriety. In contrast to cobalt, rhodium can carry out the reaction at low pressure; therefore, n-aldehyde preferably straight chain and also iso-aldehyde can be obtained only in very low amounts. Finally, the hydrolysis of defines to saturated hydrocarbons, through the use of rhodium catalysts, gives substantially lower results than with the use of cobalt catalysts. In the process carried out according to the art, the rhodium catalyst is used in the form of rhodium hydridocarbomols, which contains additional ligands. The ligands are present, in most cases, in an excess; so that the catalyst system consists of compound rhodium compiojo and free ligand. Specifically, it is intended as tertiary osfma or fossils. Its use allows the reaction pressure during the hydroforpulaoion to be reduced to a value lower than 30 MPa. With this process, therefore, there arises the problem of the separation of the reaction product and the recovery of the loose catalyst homogeneously in the reaction product. In general, the product of the reaction of the reaction mixture is distilled therefrom. In practice, due to the thermal sensitivity of the aldehydes and alcohols formed, this route can only proceed to the hydrotorsion of lower olefins, that is, define with up to about carbon atoms in the molecule. It has been noted that the thermal load of the distillation product also leads to considerable loss of catalyst by the decomposition of the complex rhodium compounds.The indicated deficiencies can be remedied by the use of catalytic systems that are soluble in water. They are described, for example, in DE-C-26 27 354, EP-A-0 571 819 and EP-B-0 491 240. The solubility of complex rhodium compounds is obtained by the use of sulfur-containing or carboxylated triazines, for example, diphosphines as complex components of the complex, the separation of the catalyst from the reaction product after the hydroformylation reaction is terminated. on, and facilitated by these procedure variants < . s r ^ r r the aqueous and organic phases, I say, without distillation and, with it, zm thermal, additional procedural methods. This hydroform lac on with water soluble cata lyst systems has distinguished because it has worked well for the lower ethylene, propylene and butene definitions. When rattling higher olefins, such as hexene, octene or decene, the hydrophonylation reaction decreases markedly, so that the yield of the reaction in technical proportions is no longer obtained. The reaction is reduced by the reduced solubility of the higher defines in water; so the reaction between the reactants proceeds in aqueous phase. EP-B-0 157 316 discloses the hydroformil with higher fine olefins by providing an aqueous phase and an organic phase which is immiscible or only poorly soluble therewith, in the presence of dissolution intermediates. Complex rhodium compounds containing trisulfonated tpaplfosphine are used with catalysts. As regards the dissolution intermediates, reagents are used for the cationic transfer of phases of the formula: wherein A represents an alkyl, w-idrox lalkylo radical, to the optionally substituted coyl or aplo, of 6 to 25 carbon atoms, straight chain or branched chain, or represents a radical R7 -CONH-CH2 -OH2 -CH2-, where R? epresents a straight or branched chain alkyl radical of 5 to 11 carbon atoms; B, C and D are the same or different and represent alkyl or hydroxyl radicals, from 1 to 4 carbon atoms; or C and D, together with N, form a five- or six-member hoterocytic ring and E represents chloride, bromide, iodide and, especially, sulfate, terafluoroborate, acetate, ethosulfate, benzenesulphonate, alkylbenzenesulfonate, toluensui fonate, lactate or treatment. The hydroformylation of n-hexene-1 in the presence of these dissolution intermediates, in comparison with hydroforming without the dissolution intermediate, produces an increase in reaction of about 20% to 40% on average. Similarly, the ratio of n-aldehyde to iso-aldehydes of 98: 2 (without solvent) to 95: 5 to 96: 4 worsens in the presence of the d soL-tion intermediary. However, an appropriate level of reaction 40% is too much for a technical result. By optimizing the reaction conditions in the form of a decrease in the amounts of the added dissolution intermediates, the reaction can be raised from 40% to 70-75%; but at the same time, the ratio n / i to 91: 9 is reduced. This value is completely undesirable from the economic aspect, in view of the desired yield of n-aldehyde. There is, therefore, a need for a process that allows the hydroformation of higher olefins in a multi-phase system, consisting of an aqueous catalyst solution and organic starting materials and, even, products of organic reaction, as well as gaseous reactants, with high results and, at the same time, greater selectivity for the n-aldehyde. This need described in the above is relieved by means of a process for the preparation of aldehydes by the reaction of olefinically more saturated compounds, with at least 3 carbon atoms, with carbon monoxide and hydrogen in liquid phase, in the presence of of water, of a catalyst system containing rhodium complex compounds, soluble in water, and dissolution intermediates. It is characterized in that the catalyst system containing the rhodium complexes soluble in water, contains co or diphosphine ligands of the general formula T (X) 2 P P (X) 2 / l; H2C) m (CH2) m which are substituted with one or more sulphomatic acid groups, wherein the X's are the same or different and represent alkyl radicals of 1 to 9 carbon atoms / cycloalkyl of 6 to 10 carbon atoms, anyl radicals of 6 to 10 carbon atoms or diapho of 12 carbon atoms, unsubstituted or substituted; the R1 are the same or different and mean hydrogen, alkyl radicals of 1 to 14 carbon atoms, alkoxy of 1 to 14 carbon atoms, cycloalkyl of 6 to 1 < carbon atoms, 6 to 14 carbon atoms or anloxy of 6 to 14 carbon atoms, or a cyclic benzene ring; the rn are the same or different and are an integer from 0 to 5 and the n are possibly identical or different and mean an integer from 0 to 4; and as intermediary dissolution compounds, those of the general formula II are used: wherein A represents an alkyl radical of 6 to 25 atoms of carbon or w-hydroxyl alkyl of 6 to 25 carbon atoms, straight or branched chain, or a radical radical of at least 25 carbon atoms, optionally substituted, or radical R? -CONH-CH2-CH2-CH2-, where R? means a straight or branched chain alkyl radical of from 5 to 11 carbon atoms; B, C and D are the same or different and represent straight or branched chain alkyl or w-hydroxyalkyl radicals of 1 to 4 carbon atoms; or C and D, together with N, form a five or six membered heterocyclic ring; and E ~ represents an inorganic or organic anion. The hydroformylation of defines is carried out in the presence of sulfonated di phosphines of the general formula I, as constituents of the complex complex of rod or, in the presence of the said solution intermediate of the formula II with high stability in the reaction and higher selectivity for the n-aldehydes. In general formula I, X preferably represents phenyl, tolyl or naphthyl radicals; R1 preferably means if) hydrogen or a methyl, isopropyl, isobutyl, terb? Thio, femlo or naphthyl radical, or a cyclic benzene ring; Preferably, n and n is preferably 0 or 1. E-, in formula I, represents inorganic ones, preferably a halide ion, a sulfate ion, netosulfate, sulfonate or bora + o. It is especially preferred that the following is chloride, bromide, iodide, benzene, fonate, alkyl (C7-o) benzenesulon or, especially toluensulonate, or tetrafluoro steal. E-, in the formula I, represents in addition to organic ones, preferably a carboxylate ion, lactate citrate. It is especially preferred that the on acetate be used. Complex water-soluble or complex compounds which follow Formula I give fairly good results as 5 l gand when they are 2,2'-b? S (sulfenated difen? Lfosf nornet? I) - 1, i'-dinanes of formula III in the idrogeno, ammonium, a monovalent metal or the equivalent of a polyvalent metal, preferably lithium, sodium, potassium or barium; and Ph represents the radical (e), and y are the same or different and have a value of 1 or 2, preferably 2, and x are the same or different and have a value of 0, 1 or 2, preferably 1 or 2. The preparation of the sulfonated di phosphines of formulas II and III is obtained according to the usual procedure of the state of the art, which is known from EP-B-0 491 240 and EP-A-0 571 819. The dissolution intermediates of the general formula TI represent materials that are compatible both with the aqueous phase and with the organic phase and, especially, which are soluble in water. both phases at elevated temperatures. Said materials are known and can also be designated as phase transfer, surface active or amphiphilic reagents, or as surfactants. Their value consists above all in that they change the physical properties of the bordering surfaces between both aqueous phases and, in this way, they facilitate the passage of the organic reagents in the aqueous phase of the catalyst. It is of special importance in this context that the dissolution intermediary has no negative influence on the activity of the catalytically active metals. The dissolution intermediates used, of the general formula TI, belong to the class of phase transfer reagents, wherein fi represents an alkyl radical of 6 to 25 carbon atoms, preferably 8 to 20 carbon atoms, especially from 10 to 16 carbon atoms; -hydroxyalkyl of from 6 to 25 carbon atoms, preferably from 8 to 20 carbon atoms, especially from 10 to 18 carbon atoms, alkoxy from 6 to 25 carbon atoms, preferably from 8 to 20 carbon atoms, especially 10 to 16 volumes of carbon, straight chain or branched chain, or an aryl radical of 6 to 25 carbon atoms, preferably of 6 to 18 carbon atoms, especially of 6 to 12 carbon atoms, even if replaced; or represents the radical R7 -CONH-CH2 -CH2 -CH2-, wherein R7 represents a straight or branched chain alkyl radical, of 5 to 11 carbon atoms, preferably of 4 to 10 carbon atoms, especially of 3 to 9 carbon atoms; B, C and D are the same or different and represent straight-chain or branched alkyl or w-hadroxyalkyl radicals of 1 to 4 carbon atoms, preferably 2 to 3 carbon atoms; or C and D, together with N, form a six-membered heterocyclic ring. Examples of the appropriate cations L "NABCD] + are: est eapl r me ii monio, phenyl-rhenethyl ome, tmethyl-l-emL-rtinomo, benzyl-rimethyl-1-ammonium, cetyl-prene-ammonium, myristyl prnetium-1 ammonium, dodecyl pyridine or, esteaplamidoineti 1-pyridi mo, laup lt pmethylammone, benzyl pet ilaronium, inetosuiphate of N- (3-tp? net i omopropil) -n-hepta co, dodecyl-tp - -hydroxyethyl ammonia or amide methosulfate of N- (fi-trimethylamomopropyl) -n-nonanoic acid As for E- can be used in the general formula II: chloride, bromide, iodide, sulfate, tetr fluoroborate, acetate, methosulfate, benzenesul fonate, alkylbenzenesulfonate, f oluenesulfonate, lactate, or citrate, Due to its low corrosive content, methosulfate, sulfonate, and lactate are preferred.Concentration of the dissolution intermediate in the aqueous catalyst solution ranges from 0.06 to 5 percent by weight. preference of 0.07 to 2 percent by weight and, especially, from 0.1 to 0.5% in weight, with respect to the catalyst solution. The catalyst can be pre-added to the reaction system. It can also be prepared, with equally good results, from the rhodium component or rod compound and the aqueous di-phosphine solution of the formula I, under reaction conditions, in the reaction mixture, also in the presence of olefins. In addition to metallic rhodium in a finely divided form, rhodium-containing water-soluble salts, such as rhodium chloride, rhodium sulphate, acetate acetate or soluble compounds in organic media, can also be used as a source of rhodium. such as r-hate 2-ethexanoate or insoluble compounds, such as whey oxide. The concentration of rhodium in the aqueous catalyst solution varies from 10 to 2,000 pprn by weight, preferably between 20 and 300 ppm by weight and, especially, between 40 and 100 pprn by weight, with respect to the catalyst solution. The di-phosphine is added in such an amount, that per mole of rhodium, there are from 1 to 50 moles, preferably from 5 to 15 moles, of the di phosphine. The pH of the aqueous catalyst solution should not be less than 2. In general, a pH value of 2 to 13, preferably 4 to 10, is preferred. The reaction of the olefma with hydrogen and monoxide or carbon is carried out at a temperature of 20 to 150 ° C, preferably 50 to 120 ° C and pressures of 0.1 to 20 MPa, preferably 1 to 10 MPa. The composition of the synthesis gas, that is, the ratio of carbon monoxide to hydrogen, can vary within wide limits. In general, a synthesis gas is used in which the volumetric ratio of carbon monoxide to hydrogen is 1: 1 or does not deviate much from that value. The reaction can be carried out continuously as well as discontinuously. The procedure according to the invention proceeds 1? It is manufactured by hydrophoblining olefinically unsaturated compounds of at least 3 carbon atoms. Compounds of 3 to 20 carbon atoms, which have one or two internal and / or extreme ligatures, are suitable as olefinically unsaturated compounds. Substituted or unsubstituted alkenes of from 3 to 20 carbon atoms, substituted or unsubstituted dienes, from 4 to 10 carbon atoms, cycloal uenes or dicycloalkyl substituted or unsubstituted from 5 to 12 carbon atoms are suitable. -Bono on the ring system; the esters of unsaturated carboxylic acid, of 20 carbon atoms and of an aliphatic alcohol of 18 carbon atoms; the esters of saturated carboxylic acid of 2 to 20 carbon atoms and an unsaturated alcohol of 2 to 18 carbon atoms, the alcohols or esters of 3 to 20 carbon atoms, or the aliphatic olefins of 8 at 20 carbon atoms. It can be mentioned as substituted or unsubstituted alkenes, from 3 to 20 carbon atoms, straight chain or branched alkenes, with position of double binding at the end or internal. Preferably they are straight chain olefms of 6 to 18 carbon atoms, such as n-hexene-1, n-hentene-1, n-octene-1, n-noneno-l, n-decene-1, n -undecene-1, n-dodecene-1, n-octadecene-1 and acyclic terpene. Branched alkenes such as dusobut full (2,4,4-t r? Rnet? Ipenteno-1), tppropileno, tetrapropileno and di sol are also suitable.

Preferred examples of unsubstituted dienes are 4 to 10 carbon atoms: 1, 3-butadiene, 1,5-hexadiene and 1,9-decadiene. Examples of substituted and unsubstituted cycloalkenes or dicycloalkenes are to 12 carbon atoms in the ring system: cyclohexene, cyclooctene, cyclooctadiene, dicyclopentadiene and the cyclic terpenes, such as limonene, pomeno, camphor and bisabolene. An example of the arylaliphatic definitions of 8 to 20 carbon atoms is the est-ene. Examples of the esters are an unsaturated carboxylic acid of 3 to 20 atoms < For the carbon and an aliphatic alcohol of 1 to 18 carbon atoms, the ester of acrylic acid and the methacrylic acid ester of 1 to 18 carbon atoms in the alcohol component are mentioned. The esters of a carboxylic acid which is more saturated with 2 to 20 carbon atoms and an unsaturated alcohol of 2 to 18 carbon atoms include the vtmlac and allyl esters of 2 to 20 carbon atoms in the carboxylic acid component. Mention is made of more saturated alcohols and ethers, for example, allyl alcohols and vinyl ether. In the following examples for the characterization of the efficiency of the catalyst systems, in addition to the proportion of n-aldehyde to iso-aldehyde, the concept of activity is used ", defined as: mol of aldehyde g -at orno of Rh. Mm and the concept or "product ivity" of fi ned co o: g of A l dehi do c? n3 of catalyst solution h The formation of alcohol and hydrocarbon is minimal.

EXAMPLES 1-3 (Comparative, complex ligand: trisodium-tri (m-sulfophenyl) phosphine (TPPTS), addition of the dissolution intermediate) a) Catalyst pre-processing In a one-liter autoclave, 450 g (149 ml) of an aqueous solution of TPPTS with a content of 16.4% by weight of salt, as well as 300 ppm of Rh for acetate, is introduced with a dip tube. of Rh. Additionally, 75.3 g of tetradecyltrirnet-ilamomo-TPPTS solution (5.1%) is added, corresponding to 3.86 g of 100% salt, corresponding to < .1e to 0.86% of the complete TPPFS solution. The synthesis gas is put under pressure (ratio in volume of CO / H2 1: 1), up to a pressure of 2.5 MPa. The reaction solution is then treated for three hours, under stirring, at 125 ° C, with synthesis gas, so as to form the active catalyst. After cooling to approximately 30 ° C, agitation is maintained and after a standing time of 15 minutes, the excess solution is removed by means of the immersion tube and analyzed. The remaining solution remains in the autoclave. b) Hydro-hydration The solution prepared according to a) is pumped, with stirring, to 105 g of n-hexene-1. At a constant pressure of 2.5 MPa, the mixture is heated to 125 ° C and maintained at that temperature for three hours. Then it is cooled to 30 ° C and allowed to stand. The organic phase passed through the immersion tube is separated; it is recovered (see table 1) and subjected to gas chromatography. Step b) is repeated twice in total, the same yield being obtained substantially. The values given in table 1 for activity and for productivity refer to the amounts of aqueous phase and organic phase provided in the autoclave. The amount of hexene used is adjusted to the capacity of the autoclave.

TABLE 1 Example n-hexene added fg) 104 103 98 100.5 Reaction (% by gas chromatography) 75 72 74 i '3 Proportion n / a 91/9 91/9 91/9 91/9 Organic phase (g) 123.3 122.1 118 11 .4 Aqueous phase in the reactor (g) 417 411 392 402.3 Activity (mol of al of C7 * mol of Rh-lrnin- 1) 3.62 3.49 3.44 3.50 Productivi ad (g of al of C7 * cm3 of solution cat a i i a do ra - 1 h- 1) 0.079 0.076 0.075 0.076 EXAMPLES 4-6 (Comparative, complex ligand: 2,2 '-bisdlifemlfosfi noinet i l) -1, 1'-sulphonated bmaphthyl (BINAS) without the addition of an intermediate "He dissolution". a) Pre-formation «Jel catalyst In a 0.2 L autoclave with immersion tube, 109 ml (110 g) of an aqueous solution of BINAS was added, as well as 50 pprn of Rh as Rh acetate. Synthesis gas is introduced (volumetric ratio of CO / H2 1: 1) until reaching a pressure of 2.5 MPa. The reaction solution is then treated for 3 hours under stirring at 122 ° C with the synthesis gas, the active catalyst being formed. After cooling to approximately 30 ° C, the stirring is stopped and after a rest period of 15 minutes the excess solution is withdrawn through the immersion tube and analyzed. The remaining solution remains in the autoclave, b) Hydroalloy In the solution prepared according to a), 34.3 g of n-hexene-1 are pumped under agitation. At a constant pressure of 2.5 MPa, the mixture is heated to 122 ° C and left at that temperature for three hours. Post is then cooled to 30 ° C and allowed to settle. The organic phase supernatant is removed by means of the immersion tube; it is recovered and analyzed by gas chromatography. Step b) is repeated twice in all, with the "μie results being substantially equal. The values given in Table 2 for activity and productivity refer to the amounts of aqueous phase and organic phase introduced into the autoclave. The quantity "Hex-hexene" used is adjusted to the capacity of the autoclave.

TABLE 2 Example 4 5 6 n-hexene added (g) 34.3 34.3 34..3 34.3 Reaction (% by gas chromatography) 33 36 39 36 Proportion n / i 97.3 / 2.7 99.1 / 0.9 99.1 / 0.9 98.5 / 1.5 Organic phase (g) 32.0 38.4 36.9 35.8 Aqueous phase in the reactor '(g) 68.5 68.5 68.5 68.5 Activity (mol of al of C7 * mol of Rh-lrnin-1) 15.2 20.1 21.3 18.9 Productivity (g of al of 07 * crn3 <: the solution ca t to 11 za do ra - i h-) 0.049 0.065 0.069 0.061 EXAMPLES 7-9 (Complex ligand: BINAS, addition of a dissolution intermediate) a) Catalyst pre-formation In a 0.2 L autoclave with a dip tube, 112 g of an aqueous solution is added as well as 50 pprn of Rh as Rh acetate. In addition, 1 g of tetradecyl-ethyl acetate solution (27.2%) corresponding to 0.272 g of 100% salt was added. That corresponds to 0.241% of the total BINAS solution. Synthetic gas (proportion in volume of CO / H2 1: 1) is added to pressure until a pressure of 2.5 MPa is reached. Next, the reaction solution was treated at 122 ° C for a few hours or with stirring, with the synthesis gas, the active catalyst being formed. After cooling to approximately 30 ° C, the stirring is stopped and after a standing time of 15 minutes, the excess solution is removed by pressure, by means of the immersion tube, and analyzed. The remaining solution remains in the autoclave. b) The droformilation Pour into the solution prepared according to a), under stirring, 36.7 g of n-hexene-1. At a constant pressure of 25 bar (2.5 x 103 Pa), the mixture is heated to 122 ° C and maintained for three hours at that temperature. It is then cooled to 30 ° C and allowed to settle. The organic phase supernatant is removed under pressure by means of the immersion tube; it is recovered and analyzed by gas chromatography. Step b) is repeated twice in which the same result is obtained substantially. The values given in table 3 for activity and productivity are related to the amounts of aqueous phase and organic phase produced in the autoclave. The total amount of hexene is adjusted to the capacity of the autoclave.

TABLE 3 Examples 7 to 9 indicate that the BINAS compound as a complex complex, clearly elevates the reaction, the activity and the product, by the addition of the dissolution intermediate; and at the same time, the selectivity also increases with respect to when the dissolution intermediate is not added.

EXAMPLES 10-12 The procedure is carried out analogously to examples 7-9; but the preform of the catalyst is obtained at 110 ° C and the time of the hydroformylation reaction is doubled from 3 to 6 hours. The results of the hydroformation are shown in table 4.

TABLE 4 For example, 10 11 12 n-hexene added (g) 35 35 35 35 Reaction (% by gas chromatography) 85.7 84.5 82.3 84.2 Proporeion n / a 99/1 99/1 98/2 99/1 Organic phase (g) 38.2 43.0 41.1 40.8 Aqueous phase in the reactor- (g) 69.0 69.0 68.0 68.7 Activity (mol to a 1 of C7 * -rnol of Rh-lrnin * 1) 22.81 24.71 16.17 21.23 Productivity (g of al of 07 * crn3 of catalytic solution ora-lh-1) 0.076 0.082 0.054 0.071 Examples 10-12 indicate that by using a solvent, in the presence of BINES as the complex ligand, and by varying the reaction conditions, especially by lengthening the hydroformylation time, the reaction can clearly produce also excellent proportions of n / i.

Claims (11)

NOVELTY OF THE INVENTION CLAIMS

1. - Process for the preparation of aldehydes by the reaction of olefinically unsaturated compounds having at least 3 carbon atoms, with carbon dioxide and hydrogen, in the liquid phase, in the presence of water, of a catalyst system containing complex rhodium compounds soluble in water and dissolution intermediates, Characterized in that the catalyst system containing the complex compounds of rod or contain di phosphodies ligands of the general formula I: which are substituted with one or more sulfonic acid groups; in «Where the X's are the same or different and represent radicals Alkyl of 1 to 9 carbon atoms, cycloalkyl of 6 to 10 carbon atoms, 6 to 10 carbon atoms or diapho of 12 carbon atoms, substituted or unsubstituted; Rl are the same or different and mean hydrogen, alkyl radicals of 1 to 14 atoms, carbon, alkoxy, and 1 to 14 atoms. : > carbon, chloroalkyl, or "6 to 14 carbon atoms, 6 to 14 carbon atoms or aroxy of 6 to 14 carbon atoms, or a cyclic benzene ring; the rn are the same or different and represent an integer from 0 to 5 and the n, eventual and equal or different, represent an integer from 0 to 4; and that they use as dissolution mediators, composed of 1 to f or rrn or 1 to ge ne i-a 1: wherein A represents an alkyl radical of 6 to 25 carbon atoms, -hydroxyalkane of 6 to 25 carbon atoms, straight or branched chain, or an aryl radical of 6 to 25 carbon atoms, optionally substituted, or the radical R7-C0NH-CH2 ~ CH2-CH2-, wherein R7 signifies a straight or branched chain alkyl radical, of 5 to 11 carbon atoms; B, C and D are the same or different and represent straight or branched chain alkyl or hydroxyhalkyl radicals, of 1 to 4 carbon atoms; or C and D, together with N, form a five or six membered heterocyclic ring; and E- represents an organic or inorganic ammon.

2. Method according to claim 1, further characterized in that in the general formula I, the X are the same or different and represent the radicals faith, tolyl or naphthyl; and R means hydrogen, a methyl, isopropyl, isobutyl, tertbutyl, femyl or naphyl radical; is 1 and n 0 or 1.

3. Process according to claim 1 or 2, further characterized in that in general formula II, A represents an alkyl radical of 8 to 20 atoms of carbon, straight or branched chain, especially from 10 to 16 carbon atoms, wh? drox alkyl from 8 to 20 carbon atoms, especially from 10 to 18 carbon atoms, straight or branched chain, or an aryl radical from 6 to 18 carbon atoms, especially from 6 to 12 carbon atoms, possibly substituted; or represents the radical R7 -CONH-CH2 -CH2-CH2-, wherein R7 is a straight or branched chain alkyl radical, of 4 to 10 carbon atoms, especially of 3 to 9 carbon atoms; B, C and D are the same or different and mean straight chain or branched alkyl or hydroxyalkyl radicals of 2 to 3 carbon atoms; or C and D, together with N, form a six-membered heterocyclic ring.

4. Method according to one or more of claims 1 to 3, further characterized in that E ~ in the formula [represents a halogenide, sulfate, methosulfate, sulfonate or borate ion.

5. Process according to claim 4, further characterized in that E- in the formula I represents chloride, bromide, iodide, benzosulonate, C7-alkyl or benzenesulfonate, especially toluensul-fonate or tetra-luoboborate.

6. Process according to one or more of the claims 1 to 3, further characterized because E ~ in the formula T represents a carboxylate ion, preferably acetate, a lactate ion or a citrate ion.

7. Method according to one or more of claims 1 and 3 to 6, further characterized in that ligands of the rhodium complex compounds soluble in water 2, 2 '-b? S (ifemlfosf ino- etii) are used. i, l'-bmaft? sulfonated formula III: wherein Ar represents m-Cßl-SO3M, and M represents hydrogen, ammonium, a monovalent metal or the equivalent of a polyvalent metal, preferably represents lithium, sodium, potassium or barium; and Ph represents the radical femlo; the y are the same or different and have a value of 1 or 2, preferably 2; and the x's are the same or different and have a value of 0, 1 or 2, preferably 1 or 2.

8. Method of conformance with one or more of claims 1 to 7, further characterized in that the concentration "Jel intermediate" The solution in the aqueous catalyst solution is 0.05 to 5% by weight, preferably 0.07 to 2% by weight and, specifically, from 0.1 to 0.5% by weight, based on the catalyst solution. .

9. - Method according to one or more of claims 1 to 8, further characterized in that the concentration of rhodium in the aqueous catalyst solution is between 2 000 ppm by weight, preferably between 20 and 300 ppm by weight. weight and, specifically, between 40 and 100 pprn by weight, with respect to the catalyst solution; and 5 uses from 1 to 50 moles, preferably from 5 to 15 moles of di phosphine per nol of rhodium.

10. Method according to one or more of claims 1 to 9, further characterized in that the reaction is carried out at temperatures of 20 to 150 ° C, preferably 50 to 120 ° C, and pressures of 0.1 to 20 MPa , preferably from 1 to 10 MPa.

11. Process according to one or more of claims 1 to 10, further characterized in that substituted or unsubstituted alkene compounds of 3 to 20 carbon atoms, substituted or unsubstituted dienes of 4 to 10 are used as unsaturated olefinically unsaturated compounds. Carbon atoms, substituted or unsubstituted cycloalkenes or substituted or unsubstituted dicycloalkenes, "5 to 12 carbon atoms in the ring system; esters of an unsaturated carboxylic acid, of 3 to 20 carbon atoms and an aliphatic alcohol of 1 to 18 carbon atoms; esters of a saturated carboxylic acid of 2 20 carbon atoms and a saturated alcohol of 2 to 18 carbon atoms, unsaturated alcohols or ether saturated with about 3 to 20 carbon atoms, or araliphatic olefins of 8 to 20 carbon atoms ,,