MXPA97003388A - Substitute diffosphines and procedure for suproducc - Google Patents

Abstract

The present invention relates to compounds of the general formula I: wherein R1 represents a residue of carboxylate (-COO-), sulfonate (-SO3-), phosphonate (-PO32-) or 2-aminoethanebisphosphonate [NH-CH2-CH ( PO32-) 2], R2 symbolizes a straight-chain alkylene residue with 1-8 carbon atoms, an alkylene residue containing oxygen with 2-6 carbon atoms, a cycloalkylene residue with 3 to 10 carbon atoms or a residue of the formulas II, III, IV or V, R3 and R4 are the same or different and symbolize residues of C4-C26 alkyl, substituted or unsubstituted C6-C10 aryl, or C6-C10 cycloalkyl, or a benzyl residue, and R3 can also mean hydrogen

Description

pTFOSFTN S SUBSTITUTED AND PROCEDURE PQRQ ITS PROTOIOOTON MFMORTQ tF i Q TNVFM? TOIM and they use the phosphmas in the procedures, industp lrnonte applied more diverse. Of particular importance is its use as ligands for metal complex catalysts, which contain, as a central atom, preferably a metal of group VIII of the periodic system of the elements, as well as, if necessary, in addition to the lenses of f-osphine. suitable groups for complex training. The technique of technical olefmas carried out on a large scale is increasingly carried out in the presence of catalyst systems based on complex compounds of rhodium, which contain phosphatic or tertiary phosphites. Position < Since these ligands are generally in abundance, the catalytic sis-rema consists of complex compound and additional pure ligand. By virtue of the solubility of these catalyst systems in organic media, droforrnilac on is carried out in a homogeneous phase. For the separation of the reaction products and the recovery of the catalysts homogeneously dissolved in the reaction product, the reaction product of the reaction mixture is generally distilled. This is possible, however, because of the thermal sensitivity of the aldehydes formed, only in the hydroformylation of lower olefins has + a with about 8 carbon atoms in the molecule. In the hydroformylation of long-chain olefins or olefinic compounds with functional groups, products with high boiling point are formed, which by distillation can no longer be satisfactorily separated from the catalyst: the thermal load of the distillation product leads through the f-orrnation of dense oil to large losses in value product, as well as through the disintegration of complex compounds to losses in catalyst. This definitely reduces the economic attractiveness of the procedure. From EP-O-0 374 fild, it is known that, with the use of selective semi-permeable polylamide separating membranes, the metal-organic complex compounds, which contain phosphorus III compounds as ligands, can be separated or recovered in their entirety. the organic solvents, that is without the disintegration of the catalytically active metallic compound. A pressure difference (pressure filtration) as well as a difference in concentration (dialysis) can serve as a driving force for this separation process. The process is particularly suitable for the separation of complex compounds netalico-organics and / or metal carbonyls with phosphorus compounds II or ligands of organic solutions, in which they were applicable as homogeneous catalysts. As complex compounds of rhodium are treated, in EP-FI-0 374 615, 313 V those compounds containing co or ligands alkyl or aplaronium salts of sulfonated or carbonylated t-phosyl phosphines of the general formula wherein X means a sulfonate residue (-S03 ~) or a carboxylate residue (-C00-), X, Xs and Xa are 0 or 1, R and Ra in each case mean C residuos-Cα alkyl residues. ^, residues of the C6-C12 rile or C6-C12 cycloalkyl residues equal or different and R may also represent additionally hydrogen. Such complex rhodium compounds with alkyl- or arylammonium salts of the 1-sulfonated or carboxylated phosphines as a ligand are used for the hydrophobicization of olefinically unsaturated compounds in the homogeneous phase, but require for their stabilization a remarkable abundance of free, non-complex ligands. This remarkable abundance of ligands leads to a high concentration of salts in the hydroforming mixture, which can adversely affect the reaction of the fine olefin with carbon nonoxide and hydrogen, since it counteracts the solubility of the components of the reaction in the reaction mixture and further promotes the formation of foam. Also in a membrane filtration, which can be carried out after the hydroformylation for the separation of the catalyst system from the reaction product, the remarkable abundance of ligands, ie the high concentration of salts, is negative; one decreases the flow efficiency of membrane filtration, which can be compensated only by the use of much larger membrane surfaces, while the other decreases the maximum degree of high concentration of the substance retained. This leads to a recirculation of the retained substances containing catalyst in the hydroformylation reaction to a reduction in the volume of the reactor available to the remaining reactants, an effect which, like the large membrane surfaces, entails high process costs and decreases the economic attractiveness of the procedure. Also in the case of the renewal by distillation of the hydroformylation mixture, the high concentrations of salts are unfavorable, since they lead to a high proportion of thick oil containing salts. There was therefore the problem of making available new co-organophosphorus phospho compounds that could be used as ligands in catalyst systems based on complex rhodium compounds in the hydroformylation of olefinically unsaturated compounds in homogeneous phase, thereby leading to values high activity and selectivity and make possible a simple separation of the catalyst system of the hydroformylation product. solves this problem by compounds of the general formula I. where R 1 represents a carboxylate residue (C00-), sulfonate (c, 0a-), phosphonate or 2-arnmoethan? s phosphonate [NH-CHa-C PO: -, - ^], Ra symbolizes a straight-chain alkylene residue with 1-8 carbon atoms, an alkylene residue containing oxygen with 2-6 carbon atoms, a residue of cycloalkylene with 10 carbon atoms or a residue of formulas II, ITT, IV. or V III (CH bc (CH2- c : v a, b, c, d, e, f, g, h, k and 1 are the same or different and 0 or 1, among which at least one of the parameters a, b, c, d, e, f, g, ho 1 must be equal to, x is the same or different and 0, or 1, Ra and RA are the same or different and can symbolize C4-C2I1 alkyl residues Cs-Cio or cycloalkyl C, s, -C 0 substituted or unsubstituted or a residue of benzyl and R3 can mean - also hydrogen. The compounds of the general formula I are present as carboxylates, sulfonates or phosphonates of ammonium with univalent diphosphine anion or polyvalently charged as contigs. They are not soluble in water or they are only at a very low scale. In organic solvents, however, they have a convenient and even very convenient solubility and are therefore suitable for application in the organic phase. In the general formula I, R denotes a carboxylate, sulfonate, phosphonate or 2-ammoethaneb residue? phosphonates, preferably a sulfonate residue. Rz symbolizes a straight-chain alkylene residue with 1-8, preferably 1-5 and in particular 1-3 car-bono atoms. Rs can also represent an oxygen-containing residue with 2-5, preferably with 2-4 carbon atoms and in particular with 4 carbon atoms according to the formula (CH ") S.-0- (CH 2)? Ra also symbolizes a dikloalkylene residue with 3-10, preferably 5-10 carbon atoms or a residue of the formulas II, III, IV or V, preferably of the formula II. In the general formulas I, TI, III, IV and V are a, b, c, d, e, f, g, h, k and 1 equal or different and 0 ol, among which at least one of the parameters a , b, c, d, e, f, g, li, J, ko 1 must be equal to 1. In the compounds of the formula, in which R52 represents a residue of formula II, it is the sum of a, b, c, d, e and f, which gives the number of the residues R, preferably 1-3; if R52 is a residue of formula III, then the sum of a, b, c, d, g and h preferably represents a number 1-2. If Ra has the meaning of a straight-chain alkylene residue with 1-8 carbon atoms, of a residue containing oxygen with 2-5 carbon atoms or of a cycloalkylene residue of 3-10 carbon atoms, then the sum of a, b, c and d preferably a number of 2-4. In formulas IV and V, x is preferably l and both residues are together in orthoprosium. In general formula I, Ra and R * are the same or different and symbolize the alkyl residues C ^ -Ci = e ,, preferably CXbi-CzSj aplo C6-C10; preferably femlo residues, cycloalkyl C < α-C3.0 preferably cyclohexyl, substituted or unsubstituted, or a benzyl residue. R3 can also mean hydrogen. Os therefore, the cations [H-NRaRAR * l "'in general formula I are derived from secondary or tertiary amines NRaR * R, which together contain 8-78, preferably 12-72, particularly preferably from 21 a (50 and in particular from 36 to 54 carbon atoms in the substituents Ra and R *.) Preferably the ammonium cations are derived from ü? -2-et? Lhex? Lam? Na, Trj-n-octi la ina, Trusoocti lamina, Triisonom lamina, Tri-Isodecyllanine, Diesteplarnma, Methyl i disteaplamine, Tp-cetiima ao Tpecosilarní.A As special di-phosphine anions rnon-te appropriate in the general formula I must be mentioned di phosphine , as B? s- (s? sulfona ofen? lfosf? no) rnetano l, 2 - II is (di sul fonato feni 1 fos f Lno) ethane 1, -Bis (di sulfonatofeml fosfino) propane 1, -B? s (disulphonated phenyl phosphino) 1, 5 -Bis (di sulphonate or phenylphophine) penicillin Bis- (diphenylphosphonophilic acid) bis (phosphinoethyl ether). The invention is a proto-enzyme for the production of the compounds of the general formula 1, where R is a sulfonate, characterized in that the secondary phosphate oxide of the VT formula is converted. in the presence of a base with a halide of the formula VTT XR ^ -X VTT where Rs has the meanings mentioned in the formula T and X symbolizes a halide residue, preferably chlorine or bromine, optionally in the presence of a solvent from -20 to 100 ° C to a diphosphine oxide of the formula VTTI This di-olefin oxide of the formula VIII is reduced, if appropriate in the presence of a solvent with a silica of the formula HSiClmR sn, where rn is equal to 2 or 3, n equal to 0 or 1, m + ni gual to 3. and Rs being in place of a methylene phenyl residue, at 80-60 ° C to a disphosphine formula IX and this formula is dissolved in formula IX from 0 to 50 ° C with oleum, the sulphonation mixture is diluted with water and the ami is added to NRaR * R not soluble in water, from which the ammonium catalyst CH-NR3R R 3 * in formula I, dissolved in an organic solvent not soluble in water. The reaction of the phosphorus oxide of the formula VI with the dihalide X-R ^ -X is carried out in the ratio l: (2-3). preferably 1: 2.5. In this reaction, we work in the presence of a base, to bind with hydrogen halide, HCl or HBr, which is free in this reaction. As the base, a MeH compound may be used, wherein He symbolizes Li, Na or K, or a LiR compound, wherein R 'symbolizes an alkyl residue with 1 to 4 carbon atoms or a residue of fem. The mixtures of the bases mentioned above are also applicable. The diphosphine oxide of the formula VIII is then reduced, if appropriate, in the presence of a solvent with a solvent of the formula HSiClmR8 *, where rn and n have the above meanings, in particular a silane of the formula HSiCl ^ R3 , wherein Rs symbolizes a methyl residue or a phenyl residue, at a temperature of 100 to 150 ° C. This reduction can also be carried out at higher and lower temperatures, but a temperature scale of 100 to 150 ° C has proved adequate and sufficient in a multitude of cases. The reduction of the diphosphine oxide of the formula VIII is carried out preferably in the presence of a solvent. Usually an organic solvent is used for this, which acts under the conditions of reduction as inert, for example acetonitop, toluene or xylene. After the reduction of the diphosphine oxide of the formula VTII, the di-phosphine of the formula IX is obtained. For the introduction of sulphonic acid groups into the femlo residues and the di-phosphine di-naphthyl residues of the formula IX, if any present in the R3"residue, the diphosphme is treated with abundant sulfur trioxide in the form of oleum as sulphonation media Determinants for the achievable degree of sulfonation are in particular the concentrations of S03 in oil, the reaction temperature and the reaction time The mentioned parameters mutually influence each other. from 10 to 55% by weight, but also from sulfur trioxide In particular, the oil containing 25% by weight of sulfur trioxide has proven effective.The sulphonation medium must be applied in abundance, With respect to the di-phosphine, it is suitably used for each mole of di-phosphine of 80, preferably 15 to 30 moles of SO 3, Oleu with free SOO in high concentration, ie in a proportion of about 40 to 65% by weight and more, is used in the diphosphmas of formula IX, in which R2 represents a straight-chain alkylene residue with 1-8 carbon atoms, an alkylene residue containing oxygen with 2-6 carbon atoms or a cycloalkylene residue with 3-10 carbon atoms. Then products are obtained, which contain 2-4 and optionally more sulfonate groups. Free concentrations of S0a are used in oil (sulfuric acid vaporant), which are lower than approximately 40% by weight, in diphosphines of the formula IX, in which Rs represents a residue of the formulas II, Til, IV and V, and with lower sulfonated products with 1-3 groups of sulfonates. The reaction temperature rises from 0 to 50 ° C, preferably from 10 to 40 ° C. In principle, higher temperatures may also be applied, but they promote the oxidation of diphosphines to phosphine oxides substantially stronger than sulfonation, so that the product of sulphonated di-phosphines decreases overall. Therefore, it is not recommended to compensate the low concentrations of free S0a by raising the reaction temperature. However, it is good to influence the degree of sulfonation of diphosphine by the reaction time. Longer reaction times lead to more highly sulphonated compounds than shorter ones. Suitably sulfonation is governed by the requirement of estepic space of the resulting ligand. In simply formed compounds of the formula I, when R2 represents for example a straight chain alkylene residue with 1-8 carbon atoms, a higher degree of sulfonation of 2-4 is achieved. In compounds of the formula T spherically with more requirements, for example with a residue Rs of the formula III, only a lower degree of phonation of 1-2 is achieved. In general, the transformation in the mentioned temperature scales requires from 1 to 80 h, preferably from 6 to 72 h and in particular 10-60 h. This time frame is particularly valid with the use of oleurn, which contains approximately 40% by weight and more than sulfur trioxide. The more lowly concentrated oleum also leads only to partially sulfonated compounds with long reaction times, and in addition the increasing formation of oxidation products can not be completely avoided. The degree of sulphonation is suitably handled with respect to the reaction time. As a solvent for the starting compound to be sulphonated, the concentrated sulfuric acid has proved effective. This solution can be added in part to the oleum or mixed in part with the oil. It is advisable to stir the reaction mixture thoroughly, to cool well and to collect the reagents slowly and in small portions, so that the heat of the reaction can be dissipated without difficulty. Thus, it is achieved that the sulfonation is not carried out without control, but that sulfonate groups are introduced successively into the phenyl residues and, if appropriate, the bmaphthyl residues. In addition, an oxidation of the phosphorus compound is effectively prevented. After the addition of all the sulfonation or di-phosphine medium, the subsequent reaction can be carried out at room temperature, that is approximately 20 to 25 ° C and essentially without external coating. It is nevertheless suitable to stir the mixture also in this stage, in order to distribute uniformly and to be able to dissipate without delay, if necessary the heat-of the reaction still present. Following the sulfonation, the reaction solution is hydrolysed. With this step of the procedure, attention must be paid in that a temperature of approximately 30 ° C is not exceeded.; it is advantageous to adhere to temperatures in the range of 15 to 25 ° C. It is therefore advisable to supply the reaction mixture on ice to carry out the hydrolysis with ice or ice water and to provide intense external cooling. At the same time it is advisable to add as much water as is necessary for the dilution of the sulfuric acid present at 0.5-50% by weight, preferably 25-35% by weight. To the diluted solution, which contains essentially the sulphonation mixture of the diols ina and the sulfuric acid, the dissolved amine is supplied in an organic solvent soluble in water, from which the ammonium cation CH-RS is derived. 'R ^ R *] * in the general formula T. The amine solution contains 0.5-35% by weight, preferably 10-30% by weight and in particular 15-15% by weight of amine. 0.5-1.5 rnoles, preferably 0.8-1.2 moles of amine are used per equivalent of sulphonic acid residue. The use of abundant amine ensures that only small product losses occur. It is indeed possible an even higher abundance of amines, but it does not lead to further improvement of the product. As amines, the aforementioned secondary and tertiary amines are used. As the solvent for the amine, hydrocarbons or mixtures of aliphatic or aromatic hydrocarbons are used, for example toluene or fractions of kerosene-like hydrocarbons, as well as C alco-C20 alcohols or CT-Czo ethers. Because of the incorporation of two trivalent phosphorus atoms into the molecule, the compounds of the general formula I can be used, outstandingly as chelating ligands. In particular, they are excellently applicable as a component of the catalyst systems, for example for the hydroformylation of olefinically unsaturated compounds. This is the subject of a German patent application with reference number 196 19 527.6, filed on the same day as the present patent application.

EXAMPLES Production of the distearylammonium salt of 1.3-Bi R (i-m-sulfonatofenil os ino) Dropano (Ligand 1) It is sulfonated, 3-B? S (d? Phen? Lfosf? No)? With no oleu and the reaction mixture obtained is hydrolyzed by the addition of cold water. The phosphorus concentration III of the hydrolysis mixture amounts to 42 rnmoles / kg. 460.6 g of the hydroformylation mixture are placed in a shake flask. Then a solution of 96.6 g of disteaplarnin is added to 386 g of toluene and stirred for 60 minutes at 50 ° C. After finishing stirring, the phase of water containing sulfuric acid is separated. By the addition of 5% aqueous sodium hydroxide solution, a pH value of 2.6 is set at 45 ° C. It is subsequently reacted for 20 nm. For the best phase separation, 129 g of toluene are then added. After 30 rnin, 662.9 g of an organic phase containing ammonium salt of ligand 1 are obtained. A transition from phosphorus Til to the organic phase of 78% is calculated, with respect to what was introduced.

Claims (3)

NQVEDflP BE Lfl INVENTION CLAIMS Compounds of the general formula T wherein R represents a carboxylate residue (-C00-), sulfonate (-S03-), phosphonate (-POa2-) or 2-ammoethanob? sphospho-nato CNH-CH.2-CH (P03:? -) ü; ], R2 symbolizes a straight-chain alkylene residue with 1-8 carbon atoms, an alkylene residue containing oxygen with 2-6 atoms of carbon, a residue of carbon with a total of 3 10 carbon atoms or a residue of formulas II, III, IV or V III a, b, c, d, e, f, g, h, k and 1 are the same or different and 0 or 1, and must be at least one of the parameters a, b, c, d, e, f, g, h and 1 equals l, x is equal or different and 0 or 1, Ra and R are the same or different and symbolize residues of alkyl-C-Cae, aplo-Ctó-C or substituted or unsubstituted, or cycloalkyl -C ^ -C-LO or a benzyl residue, and R3 can also mean hydrogen. 2. Compounds according to claim 1, characterized in that R symbolizes a sulfo residue. 3. Compounds according to claim 2, further characterized by the fact that R2 symbolizes a straight-chain alkyl ene residue with 1-5 and in particular 1-3 carbon atoms, a residue of alkylen with 2-4 carbon atoms, an alkylene residue containing oxygen with 2-4 carbon atoms and in particular with 4 carbon atoms according to the formula (CHa) aO (CHa) i., a residue of cycloalkyl with 6-10 carbon atoms or a residue of formula II. 4. Compounds according to one or more of claims 1 to 3, further characterized by the suarn of a, I), c, d, e and f in the compounds of the formula I, in which R2 represents a solution of the IT formula , amounts to 1-3. 5. Compounds according to one or more of claims 1 to 3, characterized in addition to the sum of a, b, c, d, and h in the compounds of the formula I, in which R2 represents a residue of the formula Til, amounts to

1-2. 6. Compounds according to one or more of claims 1 to 3, further characterized in that the sum of a, b, c, dyk, or of a, b, c, d and 1 in the compounds of the formula I, wherein R2 represents a residue of formulas IV and V, amounts to 1-3. 7. Compounds according to one or more of claims 1 to 3, further characterized in that the sum of a, b, c and d in the compounds of the formula T, in which R2 has the meaning of a chain alkylene residue straight with 1-8 carbon atoms, an alkylene residue containing oxygen with

2-6 carbon atoms or a residue of cycloalkylene with

3-10 carbon atoms, amounts to 2-4. 8. Compounds according to one or more of claims 1-7, further characterized in that the ammonium cations H-NR3R "-RA]" f- in the general formula I are derived from secondary and tertiary amines NRaR * R * , R3 and R * being the same or different and symbolizing the residues of alkyl-Cxβ-Ca-s », substituted or unsubstituted or unsubstituted cyclohexyl and Ra can also mean hydrogen 9. Compounds according to claim 8, further characterized the ammonium cations CH-N-R3R R *] f together contain 8-78, preferably 12-72, particularly preferably 21-60 and in particular 36-54 carbon atoms in the residues R3 and R. 10. Compounds according to claim 8, further characterized in that the ammonium cations CH-NRaR * R *] "*" are derived from d? -2-et? I hexylamin, tp-n-octyl-arnine, tp isoocti lamina, tnisononilamma, triisodecilarnma, disteteaplamine, metiidiestearilarnina, tricetilamma or tn-eicosilamina. 11. Process for the production of the compounds according to claim 1, where R is an oulfonate residue, further characterized in that the secondary phosphide oxide of the formula VI in presence of a base with a dihalogenide of the formula of formula VII R2 VII in which R2 has the meanings mentioned in claim 1 and X symbolizes a halogen residue, preferably chlorine or bromine, optionally in the presence of a solvent of -20 to 100 ° C, is converted to a diphosphide oxide of The formula VIII this diphosphine oxide of the formula VIII, if appropriate in the presence of a solvent with ukn silane of the formula HS? ClmRsr where rn is equal to 2 or 3, where n is equal to 0 or 1, m + n being equal to 3 and symbolizing Ra a methyl or phenyl residue, at 8Q-160 ° C is reduced to a diphosphine of the formula IX and this di-phosphine of formula IX is sulfonated from 0 to 50 ° C with oleum, the sulphonation mixture is diluted with water and the water-soluble amine NR2R RA dissolved in an organic solvent insoluble in water is added, of which the ammonium cation [H-NR ^^ 'R *] -'- is derived in the formula I. 12.- Procedure in accordance with the rei indication 11, also characterized in that the diphosphine of the diphosphine is carried out. formula TX at 0-50 ° C, preferably 10-40 ° C, for 1-80 h, preferably 6-72 h and in particular 10-60 h, for the suffonation oleum is used, which contains 10-65% by weight , preferably 25% by weight of sulfur trioxide, and for each diphosphine level of the formula IX uses from 5 to 80, preferably from 15 to 30 moles of sulfur trioxide. 13. Process according to claim 11 and 12, further characterized in that, with the addition of the insoluble NR3R R amine in water dissolved in an organic solvent soluble in water, it is used for each equivalent of sulfuric acid residues 0.5-1.5 moles, preferably 0.8-1.2 moles of amine NRaR * R * and as solvent for the amine, toluene, kerosene-like hydrocarbon moieties, alcohol and C-C ^ or ethers are employed CT ~ C; 2Q -