DE2451006A1 - Benzoyl acetone derivs as extractants for metals - used esp for copper extn from acid or ammoniacal solns - Google Patents

Abstract

The extn. of metals from their aq. solns. comprises contacting the aq. soln. contg. metal ions with novel cpds. of formula (I): (where R1 is 3-12C alkyl or alkenyl, R2 is H or 1-8C alkyl or alkoxy, R3 is H or 1-4C alkyl, Y is the same or different substituent chosen from H, Cl and F, the sum of C atoms in R1-r3 is at least 6) opt. dissolved in an inert, wate-insol. solvent, sepg. both phases formed and recovering the metal from the organic phase. For those metals forming a stable complex, e.g. Cu, Co, Ni, Fe, Ag, Be, Ga, Eu, In and esp. Cu from acid or ammoniacal copper solns.

Description

EXTRACTION METHODS It is known to remove metals from their aqueous solutions, as they arise in the digestion of ores, with the help of organic complexing agents Extract connections.

In particular, it is known here as complex-forming organic Substances to use diketones, especially aromatic 1,3 diketones. So describe De Kophar and Chalmers in "Solvent Extraction of LIetalls" (Van Nordstrand Reinhold Company London 1970) that benzoylacetone can extract copper and zinc. Because the relatively high solubility in water of the benzoylacetone and the insufficient solubility the resulting metal complexes in hydrocarbons, e.g. petroleum, this compound is not suitable as a metal extractant in the context of a technical process.

One through a tert. Benzoylacetone substituted in the butyl radical is by M. Bergon and J.P. Calmon (cf. C.R. Acad. Sci., Ser.C (1971) 273 (2) pages 181-184 and Ser. C (197o) 27o (24) pages 2.oo5 - 2.oo8). One Use of this compound in metal extraction is not here, however suggested. It was also found that the metal complex compounds of the tert. Butylbenzoylacetone is also not sufficient for a technical extraction process Have solubility in hydrocarbons such as petroleum.

A process has now been found for the extraction of metal components from their aqueous solutions, which is characterized in that compounds of the general formula I are used as extractants, in which h is an alkyl or alkenyl radical with 3 to 12, preferably 6 to 12 carbon atoms, R2 is hydrogen or an alkyl or alkenyl radical with 1 to 8, preferably 1 to 4 carbon atoms, R, hydrogen or an alkyl radical with 1 to 4 carbon atoms, preferably hydrogen or methyl or the same or different substituents from the group consisting of hydrogen, chlorine and fluorine, preferably hydrogen, the sum of the carbon atoms of the radicals R1, R2 and R3 being at least 6, in particular 6 to 12.

The invention also relates to new compounds of the general Formula I in which R1, R2, R3 and the meanings given above for this formula own.

The compounds of the formula I can be prepared by processes known per se for example according to J.C. Reid and M. Calvin, J.Am.

Chem. Soc. 72 (1950) 2948 or corresponding to the preparation of benzoylacetone (Compare Beilstein, Handbuch der Organic Chemistry Volume VII p. 681 (1925) as well as 1.2. and 3.

Supplementary tape) ~ obtained ~ by adding an alkylbenzene in the manner of a Friedel-Crafts acylation with acetyl chloride to give the corresponding alkylacetophenone is implemented and this in a Claisen condensation in the presence of strong bases, such as sodium ethylate or sodium hydride, with ethyl acetate to form acetoacetylalkylbenzene is condensed.

Particularly disadvantages of this process are hydrolysis and loss of the aluminum chloride in the 1st stage; in the 2nd stage the required effort of dry solvents, for example Xther, and of 2 moles of base as well as the necessary work-up of the acetoacetylalkylbenzene obtained as alkali salt.

The compounds of the formula I can also be prepared according to the method of the German patent applications P 23 37 396.8 and P 24 29 674.0. To these processes aromatic 1,3-diketones are obtained by adding acetoacetyl fluoride, which is optionally substituted in) F-position by 1 to 3 halogen atoms, with solid or liquid aromatic compounds at temperatures from -40 to + 5o0C is reacted in at least 90% hydrofluoric acid.

Solid or liquid aromatic compounds that can be used here include benzene derivatives of the general formula in which Rl, R11 and R'11 are independently hydrogen, alkyl, alkoxy or alkylthio radicals having 1-4 carbon atoms or halogen, are used. It has now been found that these are in patent applications -P 23 37 396.8 and P 24 29 674.0 proposed reaction also with benzene derivatives of the general formula II in which Rt denotes an alkyl or alkenyl radical having 6 to 12 carbon atoms and R2 and R3 have the meanings given above for formula I, can be undertaken.

With a view to being used as an extractant for metals among the compounds of the formula I - and thus also among the compounds for their preparation Starting compounds of the formula II to be used - those preferred in which R, R denote hydrogen and alkyl groups.

On the other hand, preference is given to those in which Y is hydrogen. For in the event that Y is halogen, F is preferred.

In particular, it is preferred that the three substituents Y be the same are.

In the compounds of the formula I, the position of the substituents R¹, R² and R³ vary as desired. If R² 3 and R3 are hydrogen, is for the alkyl or alkenyl radical R is preferably in the 4-position; next to it comes above all the 2-position or mixtures of para- and ortho-substituted compounds in Consideration.

If only one of the radicals R² and R³ is hydrogen, they are located the substituents are preferably in the 2,4-position.

In addition, there are primarily compounds with 1,2-substitution or Mixtures of compounds with 2,4- and 1,2-substitution into consideration. Doesn't mean nobody the radicals R¹, R2 and R3 are hydrogen, they are preferably 2,4,6-substituted Links; in addition, there are compounds substituted in the 2,4,5-position in particular and mixtures of 2,4,6- and 2,4,5-substituted compounds are contemplated.

Examples of possible compounds of the formula I are: 1- [2 ', 4'-diisopropyl-phenyl] -butane-1,3-dione, 1- [2'-methyl-4'-hexyl-phenyl] -butane-1,3-dione in a mixture with 1- [2'-hexyl-4'-methyl-phenyl] -butane-1,3-dione, 1- (2'-2 "ethylhexoxy-4'-methylphenyl) -butanedione-1,3 1- (2 ', 5'-dimethyl-4'-n-octylphenyl) -butanedione-1,3 1- (2 ', 4', 6'-triisopropylphenyl) -butanedione-1,3 1, 4-di-n-butyl-2-acetoacetyl-benzene, 4-acetoacetyl-i-dodecylbenzene, 4-acetoacetyl-n-nonylbenzene, 4-acetoacetyl-n-heptylbenzene, 4-Acetoacetyl-hexylbenzene ~ '4'-Dimethyl-5' - (1 "-methyl-nonylg -phenyl-butane-1,3-dione, 1- (4'-hexylphenyl) -4,4,4-trifluoro-butane-1,3-dione, 1- (4t-hexylphenyl) -4s4s4-trichloro-butane-ls3-dione The aforementioned diones are mostly isomeric diones with smaller amounts in the phenyl radical afflicted that for the inventive use of the compounds of formula I as extractants, however, do not have to be separated off. Rather, it has shown that both isomer mixtures and mixtures of various substituted Acetoacetyl aromatics exhibited a particularly good extraction effect in many cases.

The extractants of the formula I according to the invention can be used for extraction of those metals which form a stable complex compound with them enter. The conditions under which this happens depend primarily on the the aqueous solution, which can be between 1 and 11 depending on the metal.

As minerals to be extracted according to the invention, in the form of their Cations form stable complexes with the compounds of the formula I according to the invention, for example: Cu, Co, Ni, Fe, Ag, Be, Ga, Eu, In.

The corresponding complex compounds of these metals are in the the usual inert water-immiscible ones used for such extraction processes organic solvents such as chloroform, carbon tetrachloride, chlorobenzene, alkyl ethers such as diisopropyl ether, aliphatic hydrocarbons such as kerosene or petroleum, or aromatics such as benzene, toluene, xylene and higher alkylated homologues, in particular also readily soluble in the compounds of formula II.

The extractants of the formula I are therefore preferred in the presence the abovementioned or analogous solvents are used. Also additions of long-chain Alcohols - such as dodecanol - or phenols - such as isononylphenol - can be used in the Extraction can be applied.

To ensure sufficient solubility of the obtained during the extraction To achieve metal complexes, benzoylacetones are required by one or several longer hydrocarbon chains are substituted. The solubility of the Metal complexes increase with the carbon number of these chains. However, since the reaction of the benzoylacetones of the formula I with the metal component in defined stoichiometric ratios takes place, with copper for example in the molar ratio 2: 1, it is possible to achieve a high metal binding capacity, but in general it is impractical to use compounds of the formula I, their substituents a total of significantly more than 12 carbon atoms contain compounds with substituents, which have a total carbon number less than 6 can also be used for extraction be used in a diluent such as petroleum or kerosene. In this case, however, it is necessary to use suitable solubilizers such as Add isodecanol or nonylphenol.

As starting products for the preparation of the benzoylacetones of the formula I to be used according to the invention for the reaction with acetoacetyl fluorides of the formula III in which Y has the meaning given above, for example: m-IIexyltoluene, dodecylbenzene, tetrapropylenebenzene, (i-dodecylbenzene), i-nonylbenzene, heptylbenzene, i-heptylbenzene, hexylbenzene mixed with r-methyl- pen type -benzene and -ethylbutyl7-benzene, 1,3-dimethyl-4-L7-methyl-nony-benzene, m-diisopropylbenzene, 1,3,5-triisopropylbenzene, 1,4-dimethyl-5-octylbenzene, 1,3 -Dimethyl-4-octylbenzene, technical-grade alkylbenzene mixtures with boiling points of, for example, 180 to 300 ° C, 1-methyl-3-hexoxybenzene.

It is not disadvantageous, but often advantageous, to use mixtures of isomers subject to the reaction with acetoacetyl fluoride. It can also be beneficial in the case of substances which react only very poorly or not at all with diketene in hydrofluoric acid add a second substance in roughly molar quantities with similar properties, especially those with shorter side chains, which is more reactive towards diketene; in this way the reaction with the more inactive substance can be induced. For example, by reacting a mixture of 1 mole of dodecylbenzene and 1 mole of tetralin with 2 moles of diketene in hydrogen fluoride acetoacetyl-dodecyl-benzene 40% can be obtained, which can hardly be obtained without the addition of tetra-lin. Analog applies to the mixture of iso-dodecylbenzene / m-di-isopropylbenzene. The preferred proportions such mixtures are between 2: 1 and 1: 2.

Likewise new compounds that are obtained by the process according to the invention are the isomeric Acetoacetyltetraline and the Acetoacetyl diethylbenzenes. These can be added, for example, when the corresponding starting benzenes are mixed in the acetoacetyldodecyl representation in a mixture with incurred and - as well as others (C6-C12) -alkylated aromatic 1,3-diketones - as an addition to the above new with (total C6-C12) mono-, di- or trialkylated aromatic 1,3-diketones can be used0 Not complete when converting the above-mentioned aromatics with acetoacetyl fluoride converted starting product can either be recovered and reused or as a co-solvent for the aromatic 1,3-diketone in terms of concentration adjustment to serve.

The invention therefore also relates to mixtures of compounds of the formula I with one another or with shorter-chain compounds that are homologous to the formula I in a ratio of 50:50 to 90:10, the invention also relates to mixtures of compounds of the formula I (or mixtures thereof, in particular mixtures of isomers) with the corresponding compounds (or mixtures) of the formula II, as they are for Example due to incomplete conversion when carrying out the process according to the invention attack.

The extraction method according to the invention is suitable for extraction of copper components from acidic to, in particular, ammoniacal aqueous solutions and to separate Cu and Zn from these solutions. Such solutions can for example by ammoniacal leaching of ores of an oxidic or sulphidic nature or obtained from scrap or metal waste in the presence of oxygen will. The separation of Cu and Zn from such solutions is expediently carried out at one pH range from about 2 to 11, especially 4 to 11 and preferably 8 to 11. In the Reaction of the metal cation with the benzoylacetone derivatives results in hydrogen ions, which is bound in ammoniacal solution by excess ammonia and from the Reaction equilibrium can be taken. If the extraction is carried out in an acidic medium, so it is sometimes useful, especially in terms of a high metal loading capacity the organic phase, the resulting hydrogen ions by adding bases such as sodium hydroxide, calcium hydroxide, ammonia, etc. to bind.

The extraction process of the present invention is generally such carried out that the aqueous) metal ion-containing solution with the extractant, preferably dissolved in organic solvents which are immiscible with water and under the conditions of extraction against water, the metallic compounds and the compounds of formula I are inert, et 1 to 2o, preferred with 4 to 20 parts by weight to 1 part by weight of extractant, brought into close contact or is intimately mixed. The ratio of the volume of organic to the aqueous phase can vary within wide limits; it lies in general in the range of about 5: 1 to 1: 5. It is beneficial, but not essential, to to use an amount of solvent in the extraction which is sufficient to to ensure a complete solution of the complex compound formed, as a Compound present in excess to the complex compound in solution usually remains completely as a suspension in the organic solvent, the two phases are separated again and from the organic phase in a manner known per se Wise, the absorbed metals are re-extracted with aqueous mineral acid. Thereafter the extractant / solvent is available for a further extraction. Such an extraction process is preferred continuously in a manner known per se, in particular carried out in the countercurrent process.

The extraction process according to the invention is expediently carried out in such a way that that the organic and the metal-containing aqueous phase in mixers or columns for more rapid adjustment of the extraction equilibrium intensively mixed with one another will. The mixture is then transported to settlers or sedimentation tanks. There, due to the difference in density, the separation takes place in two phases.

The organic phase is then separated off. The procedure can be carried out both batchwise and, preferably, continuously.

The metal in the organic phase can be used for further Processing (e.g. for extraction electrolysis) from the organic phase through a so-called Stripping process are removed. this is possible by setting conditions at which the complex is unstable and disintegrates. In most cases it is sufficient to add mineral acid, the concentration of which is like this is set so that the hydrogen ion concentration is higher than that at which the extraction takes place. Also reducing media that change the value of the metal can be used.

The invention also relates to a process for the preparation of compounds of the general formula IV in which R 3 R, R 4 and Y have the meanings mentioned above, which is characterized in that benzene derivatives of the formula II are reacted with acetoacetyl fluorides of the formula III in highly concentrated, at least 90% hydrofluoric acid.

The reaction conditions correspond to those in the patent applications P 23 37 396.8 and P 24 29 674.o process described The reaction can take place in the temperature range from about -40 to + 50 ° C, temperatures from -30 to + 20 ° C are advantageous, preferably -20 to + 20 ° C used. These temperatures allow it without special Pressure vessels get along. Preferred vessel materials are in addition to plastics such as Polyethylene, polypropylene or polyvinyl chloride metals, especially steel.

Since no water is produced during the reaction, the Hydrofluoric acid can be largely recovered by distilling off. The same - the extensive recovery - applies to the proportion of unreacted aromatic compound.

The reaction pressures essentially correspond to the autogenous pressure Hydrofluoric acid. This should have a minimum HF content of about 90 percent by weight; about 95 to 100%, in particular about 98 to 100% goat hydrofluoric acid is preferred Rest water.

Depending on the reaction temperature, the reaction time is half a to for several hours, so at reaction temperatures below OOC 6 to 24 hours, while at room temperature about 2 to 12 hours and temperatures around 50C already 30 to 12o Minutes are sufficient.

The method according to the invention can, for example, be carried out in this way be that at temperatures expediently below + 2O0C, preferably from 0 to -30C, the aromatics and acetoacetyl fluoride in approximately molar proportions in hydrofluoric acid dissolves and the reaction mixture, advantageously with stirring, to the desired reaction temperature brings.

An excess of acetoacetyl fluoride is possible, but hardly necessary. For better utilization, however, the aromatic can be used in excess (1-5 mol) will. Since no side reactions occur on the aromatic compound an unconverted portion of it recovered by methods known per se and re-used or as an inert solvent for the metal complex formed can also be used for metal extraction.

The amount of hydrofluoric acid used is 1 to 20 parts by weight to 1 part aromatic compound, preferably 3 - lo parts. Of course it is Any order of addition of the reactants, in particular one can or both are added continuously. Also, the whole procedure can be made in simpler Way to be done continuously by putting all components evenly fed to a reaction vessel or reaction tube. Instead of acetoacetyl fluoride itself One can of course also use the analogous chloride, which turns with hydrofluoric acid to form fluoride implements, use.

Preferred is a method in which the acetoacetyl fluoride in situ by adding diketene to excess hydrofluoric acid (Acetoacetyl fluoride from molar amounts of diketene and hydrogen fluoride see G.A. Olah and S.J. Kuhn, J. Org. Chem. 26, 225 (1961) in the presence or absence of the aromatic, preferably in -20 to OOC generated and then implemented at the required reaction temperature will. The excess of hydrofluoric acid in this preparation of the acetoacetyl fluoride is expediently chosen so that, after deducting the consumption in its formation, the The amounts of hydrofluoric acid mentioned above for the reaction with the aromatic can be achieved.

It is also possible to use the alkyl aromatics required as starting material in a manner known per se by reacting alkanols, alkyl chlorides or - preferred - alkenes with benzene or alkyl aromatics in the presence of Friedel-Crafts catalysts and in the "one-pot process" with acetoacetyl fluoride directly to the desired alkylacetoacetyl aromatics or with acetyl chloride to form the alkyl acyl aromatics (as a preliminary product of the ester condensation) to implement. For example, benzene can be used 3 moles of propene are reacted in hydrogen fluoride to give tri-isopropylbenzene, with after subsequent addition of diketene, acetoacetyl-tri-isopropylbenzene was obtained will. By varying the reaction conditions, mixtures of mono-, di-, tri or tetrasubstituted aromatics are obtained. As starting materials you can also technical distillation cuts with high alkylbenzene content and boiling points from 180 to 3oo0C are implemented.

The acetoacetyl halides substituted by halogen atoms in the n-position are by known methods, as described, for example, in Houben-Weyl "methods of organic chemistry "Vol. 7/4, pp. 203 and 251, Georg Thieme Verlag, Stuttgart 1968, accessible. The following are mentioned as t-halogen-substituted acetoacetyl halides: t -trifluoroacetoacetyl fluoride and t-trichloroacetoacetyl chloride.

After the reaction has ended, the procedure is such that one the hydrofluoric acid is distilled off at normal pressure, and the residue is acid-free with water washes and, if necessary, distilled. The hydrofluoric acid solution can also be used after the reaction has ended entered in water and the reaction products with halogenated hydrocarbons or aliphatic or aromatic hydrocarbons are extracted.

The following examples serve to illustrate the invention. In the Unless expressly stated otherwise, examples mean the percentages Weight percent Example 1: 0.5 l of anhydrous, technical hydrofluoric acid was at -1o0C with 0.5 mol technical (96%) diketene dropwise with stirring added and then entered 0.5 m of 1,3,5-triethylenebenzene. After stirring overnight at 10 ° to 20 ° C., the mixture was stirred into 5 1 of ice water and mixed with cyclohexane extracted. It was washed acid-free, dried, and the solvent was filtered off with suction and then 240 g of colorless crystals of 2,4,6-triethylenebenzoylacetone are obtained - (92.3% according to gas chromatography) m.p. 44-450 (isopropanol) b.p. 1008C / 0.15 mm Hg Theoretical yield: 90.5% The following were shown in the same way: No. Compound properties 2) 4-n-hexyl-benzoylacetone colorless crystals, m.p. 420C 3) 4-n-heptyl-benzoylacetone colorless crystals, m.p. 35-37 ° C. 4) 2-methoxy-5-iso-hexyl colorless oil, b.p. 152-1650 ° C. benzoylacetone 1.8 mm Hg 2 isomers with respect to the hexyl group in a ratio of 1: 3.5 5) 2-methoxy-5-isononyl colorless oil, boiling point 180-200 C benzoylacetone 2 mm Hg 3 Isomers with respect to the nonyl group in the ratio 80: 9: 7 6) 2-n-heptoxy-5-sec-butyl- colorless oil, boiling point 2200C / 3 mm Hg benzoylacetone nD20; 1.5310 (95% according to G.C.) 7) 2-n-Dodecyloxy-5-methyl- pale pink crystals benzoylacetone mp. 54-57 ° C 8) 2-n-butoxy-4-sec-butyl- colorless crystals of benzoylacetone, melting point 44-460C 9) 2,5-dimethyl-4-n-octyl-colorless Crystals benzoylacetone m.p. 30-32 0C - Example 10: To 0.5 mol Benzene was added at 5-15 ° C Q, 5 liters of technical anhydrous hydrofluoric acid, under 1.5 mol propene introduced and stirred for two days. Subsequently was with thorough stirring in the heterogeneous reaction mixture at -1 0 1 mol technical 96% diketene was added dropwise and after stirring overnight at room temperature in ice water poured, whereby colorless crystals separate out. After extraction with cyclohexane, acid-free washing, drying and removal of the solvent gave 106 g of yellow Crystals are obtained which are 88% by weight from 2,4,6-tri-isopropyl-acetoacetylbenzene consist: Fp .: 840C after recrystallization from ethanol.

Yield: 65% of theory based on benzene.

Example 11: With otherwise the same procedure as in example lo Cumene implemented instead of benzene. A yellow oily / solid mixture was behaved, 60% by weight of 2,4,6-tri-isopropylacetoacetylbenzene and 27% by weight of 2,4-diisopropylacetoacetylbenzene (according to gas chromatographic determination) existed.

Example 12: 1 mol of benzene in 0.5 l techn. anhydrous hydrofluoric acid reacted with 2.5 mol propene at 5-15 ° C. and stirred for 5 hours. Afterward 1 mol of diketene was added dropwise at −10 ° C. and, after stirring overnight, as well as above Working up described in Example 1 isolates 191 g of yellow liquid which after gas chromatography to 32.5% by weight from alkyl aromatics (4% cumene, 25% diisopropylbenzene, 3.5% triisopropylbenzene) and 4% by weight from acetoacetylcumene, 37.5% by weight from di-isopropylacetoacetylbenzene and to 20.5% by weight from triisopropylacetoacetylbenzene duration.

Example 13: 0.5 liters of anhydrous hydrofluoric acid were added dropwise at -3o0C with 100.8 g (1.2 mol) of diketene and a mixture of 0.6 mol of tetralin and 0.6 mol of n-dodecylbenzene was added dropwise. After stirring at room temperature for 12 hours stirred into 3 l of ice water. It was extracted with methylene chloride, the organic Phase washed acid-free and the methylene chloride is distilled off. The distillation of the reaction product (according to gas chromatographic determination of the content of the fractions) a yield of 86% by weight of acetoacetyltetralin from bp.

135 ° C / o, 5 Torr and 40 wt .-% of 4-acetoacetyl-dodecylbenzene of bp. 16o0C / 0.5 Torr, which still contained a small amount of 2-acetoacetyldodecylbenzene.

(Yields based in each case on the amounts of tetralin used, respectively Dodecylbenzene) Example 14: 700 g of technical diketene (8 mol) were at -2o0C below Stirring added dropwise to 4 l of technical, anhydrous hydrofluoric acid and then 1408 g technical-grade hexyltoluene (8 mol) entered. After warming to + 15 ° C, over Stirred night. After distilling off the hydrogen fluoride up to a sump temperature from 80 ° C., the residue was introduced into ice water, and the organic phase was separated off and washed again. By distillation through a 1 m vacuum jacketed column with Raschig rings were 1340 g of colorless methylhexyl-benzoylacetone with a boiling point of 135-1450C / 1.5 mm Hg with a content of 98 wt .-% obtained, consisting of 2 isomers in weight ratio about 4: 3.

Analogously using & -Trihalogenacetoacetylhalogenid shown: a / 1- (2,4,6-triethylphenyl) -4,4,4-trichlorobutane-1,3-dione b / 1- (2,4,6-triethylphenyl) -4,4,4-trifluorobutane -1,3-dione c / 1- (2,5-dimethyl-4-octylphenyl) -4,4,4-trichlorobutane-1,3-dione d / 1- (2,5-dimethyl-4-octylphenyl) -4,4,4 -trifluorobutane-1,3-dione e / 1- (2,4-diisopropylphenyl) -4,4,4-trifluorobutane-1,3-dione fj 1- (2,4-diisopropylphenyl) -4,4,4-trichlorobutane-1,3-dione (Boiling point 1350 / o, o3 mm Hg) Example 14: In 1 1 anhydrous, Technical hydrofluoric acid was added with stirring at -3o0C 175 g of technical diketene (2 Mol) was added dropwise and then with a mixture of 162 g (1 mol) of m-diisopropylbenzene and 246 g (1 mole) of i-dodecylbenzene ("tetrapropylene benzene") were added and overnight stirred at + 150C.

After the hydrogen fluoride had been distilled off, ice water was added, the organic phase extracted with cyclohexane and washed neutral. After distilling off of the cyclohexane, 434 g of a yellow-orange liquid were obtained, containing 50% by weight of 2,4-di-isopropyl-benzoylacetone, 15% by weight of 4-acetoacetyl-idodecylbenzene and 25% by weight of i-dodecylbenzene.

Example 15: 52 g (0.2 mol) of 4-acetyl-n-decylbenzene (bp. 125 ° C / 0.2 mm Hg;) represented by acylation of n-decylbenzene for example analogous to (Organikum P. 306, VEB Deutscher Verlag der Wissenschaften, Berlin 1965) were in 200 ml of diisopropyl ether stirred with 17.6 g (0.2 mol) of ethyl acetate and 19.2 g of 52% technical grade sodium hydride registered. After a short time with stirring, a violent reaction took place Cooling to and at 40 ° C was kept under control. The mixture was subsequently stirred for an hour. The brown crystal pulp was suctioned off and the gray crystals obtained with it Aether washed out. The crystals were then added to 1 l of water and acidified by adding 2N hydrochloric acid with stirring.

25 g of light brown crystals were obtained, which after recrystallization colorless crystals of 4-acetoacetyl-n-decylbenzene with a melting point of 450C were obtained from acetonitrile.

The following was represented analogously: a / 4-acetoacetyl-n-nonylbenzene colorless Crystals, mp 260 b / 4-acetoacetyl-n-octylbenzene, colorless crystals, Afp. 39 as well when using ethyl trihaloacetate and sodium methylate c / 1- (4-n-Nonylphenyl) -4,4,4-trifluorobutane-1,3-dione d / 1- (4-n-Nonylphenyl) -4,4,4-trichlorobutane 1,3-dione e / l- (4-n-Hexylphenyl) -4,4,4-trifluorobutane-1,3-dione f / 1- (4-n-Hexylphenyl) -4,4,4-trichlorobutane-1,3-dione Example 16: (Extraction) 50 g of 2,4-diisopropylbenzoylacetone were mixed with petroleum filled up to one liter. 50 ml of the organic phase thus obtained were with 50 ml of an aqueous phase containing lo g Cu2 +, 5 g Zn2 +, 35 g (NlI4) 2C03 per liter, Shaken in a separatory funnel for 10 minutes. After separating the two phases the copper and zinc content in the organic phase was determined. The organic The phase had taken up 4.9 g Cu2 + usd 0.16 g Zn, corresponding to a Cu / Zn separation factor from 490.

Example 17: (Extraction) 50 ml of an organic phase, prepared by dissolving 15 g of i-dodecyl-benzoylacetone in loo ml of petroleum was so often with a repeatedly fresh aqueous phase containing lo g Cu, 5 g Zn, 35 g (NlI4) 2C03 and contained 34 g of NH3 brought into contact until the organic phase was saturated with copper was. The quantitative determination showed that 10.9 g Cu2 + and 0.03 g Zn per liter of organic Phase were bound, corresponding to a Cu / Zn ratio of 363: 1.

The organic phase saturated with copper was then in the volume ratio Shaken 2: 1 with an aqueous solution of 25 g 2 + / 1 about 50 g H2SOd / 1 for 10 minutes. After the reaction equilibrium had been established, the aqueous phase contained 1 liter 46.3 g Cu and 0.04 g Zn. In the organic phase, 0.94 g Cu remained per liter; that is, 91.4% by weight of the copper has already been recovered by one-stage re-extraction removed.

Example 18: (Extraction) 7.85 g of C: uS04 5 5 H20 were mixed with 1% brought aqueous ammonia into solution and made up to 1 liter. 50 ml of this solution were in a volume ratio of 1: 1 with a petroleum solution of 5 g of acetoacetylhexyltoluene Shaken in 100 ml of petroleum in a separating funnel for 5 minutes. In the aqueous Phase, the copper content was then determined.

A value of <1 mg Cu / l was found. That means that Copper was practically quantitatively transferred into the organic phase.

Example 19: (Extraction) 40 ml of an aqueous phase containing 10 g of copper per liter and was adjusted to a p11 value of 4.9, were in one Beaker with 40 ml organic phase, made from 10 g diisopropylbenzoylacetone and 100 ml of petroleum, overlaid. Using a magnetic stirrer, both phases were while keeping the pH value constant in the aqueous phase (dropwise addition of sodium hydroxide solution) intimately mixed. After the reaction has ended, this can be recognized by the fact that after cessation After the addition of alkali, the pH no longer fell, both phases were transferred to a separating funnel transferred and separated.

The quantitative determination of the copper showed a content of 9.7 g copper per liter organic phase.

If the pH value is not kept constant during the reaction, - so the equilibrium pH value is 1.8 and only 1.1 g copper / l go into the organic phase over.

Example 20: 1 mol of diketene became 0.5 l of hydrogen fluoride at -loOC added dropwise and then 151 g of a technical alkylbenzene distillation mixture from boiling point 203 to 2670C and about 80% aromatic content added. After ten hours Stirring at room temperature was poured into ice water. After extraction with cyclohexane and subsequent distillation, 135 g of a yellowish liquid with a boiling point were obtained loo to 15o0C / ° t ol5 mm Hg isolated, according to the detection of the proton nuclear resonance -Spectroscopy of a mixture of acetoacetylated alkylbenzenes with a mean Represents total number of about 8 carbon atoms in the alkyl radicals.

Claims (6)

Claims i) Process for the extraction of metals from their aqueous solutions, characterized in that the aqueous solutions containing metal ions with compounds of the general formula I in which R1 is an alkyl or alkenyl radical with 3 to 12 carbon atoms, R2 is hydrogen or an alkyl or alkoxy radical with 1 to 8 carbon atoms, R3 is hydrogen or an alkyl radical with 1 to 4 carbon atoms and Y is identical or different substituents from the group consisting of hydrogen and chlorine and fluorine, where the sum of the carbon atoms of the radicals R1, R2 and R is at least 6, optionally dissolved in inert organic water-insoluble solvents, brings into close contact and, after separation of the two phases, separates the metal from the organic phase with acids. 2) Method according to claim 1, characterized in that such compounds of formula 1 are used in which R and R2 propyl or butyl radicals and R3 Represent hydrogen or likewise propyl or butyl. 3) Method according to claim 2, characterized in that mixtures such compounds can be used. 4) Compounds of general formula I according to claim 1, in which R s R, R and Y have the meanings given for this formula. 5) Compounds of the general formula According to claim 4, characterized characterized in that R1 is an alkyl or alkenyl radical comprising 6 to 12 carbon atoms means. 6) 2,4-Diisopropylbenzoylacetone 7) 2,4,6-Triisopropylbenzoylacetone Process for the preparation of compounds of the general formula IV in which R4 is an alkyl or alkenyl radical having 6 to 12 carbon atoms and R, R3 and Y have the meanings given in claim 1, characterized in that substituted benzenes of the general formula II in which R4, R2 and R3 have the meanings given above, with acetoacetyl fluorides of the general formula III in which Y has the meaning given above, is reacted in at least 90% hydrofluoric acid at temperatures in the range from -40 to + 50C.