CA1071236A - Extraction process - Google Patents
Extraction processInfo
- Publication number
- CA1071236A CA1071236A CA238,261A CA238261A CA1071236A CA 1071236 A CA1071236 A CA 1071236A CA 238261 A CA238261 A CA 238261A CA 1071236 A CA1071236 A CA 1071236A
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- Prior art keywords
- carbon atoms
- alkyl
- hydrogen
- compounds
- benzene
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/92—Ketonic chelates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/76—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton with the aid of ketenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/794—Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the Disclosure A process for the extraction of metals as Cu, Co, Ni, Fe, Ag, Be, Ga, Eu, In, and/or Zn from their aqueous solution con-taining the metal ions by bringing in a close contact with this agueous solution a compound of the general formula I
Description
~)71;~36 It is known how to extract metals from their aqueous solutions as they are obtained in the decomposition of minerals, with the aid of organic complex-forming compounds.
It is especially known how to use diketones, especially aromatic 1,3-diketones as complex-forming organic substances. Thus, De Kophar and Chalmers describe in "SolventE~traction of Metalsl~ (Van Nordstrand Reinhold Company London 1970), that benzoyl acetone is able to extract copper and zinc. Due to the relatively high solubility of the benzoyl acetone in water and the insufficient solubility of the metal complexes formed in hydrocarbons, for example petroleum, this compound is not suitable as metal extracting agent in the scope of a technical process.
A benzoyl acetone substituted by a tertiary butyl radical in ~-position is described by M. Bergon and J.P. Calmon (cf C.R. Acad.Sci., Ser.C
(1971) 273 (2) pages 181 - 184 and Ser. C (1970) 270 (24) pages 2.005 -
It is especially known how to use diketones, especially aromatic 1,3-diketones as complex-forming organic substances. Thus, De Kophar and Chalmers describe in "SolventE~traction of Metalsl~ (Van Nordstrand Reinhold Company London 1970), that benzoyl acetone is able to extract copper and zinc. Due to the relatively high solubility of the benzoyl acetone in water and the insufficient solubility of the metal complexes formed in hydrocarbons, for example petroleum, this compound is not suitable as metal extracting agent in the scope of a technical process.
A benzoyl acetone substituted by a tertiary butyl radical in ~-position is described by M. Bergon and J.P. Calmon (cf C.R. Acad.Sci., Ser.C
(1971) 273 (2) pages 181 - 184 and Ser. C (1970) 270 (24) pages 2.005 -
2.008). IBut a use of this compound for metal extraction has not been pro-posed. It has also appeared that the metal complex compounds of the tert.
butyl benzoyl acetone, too, do not have any solubility in hydrocarbons such as petroleum sufficient for a technical extraction process.
Now~ a process for the extraction of metals from their aqueous solutions has been found which comprises contacting an aqueous solution con-taining metal ions with a compound of the general formula I
O O
R2 ~ " " ( ) (I) ~! 2 - ~
1~71236 wherein R is an aIkyl radical having 3 to 12, preferably 6 to 12 carbon atoms, R is hydrogen or an aIkyl or alkoxy radical having 1 to 8, prefer-ably 1 to 4 carbon atoms, R3 is hydrogen or an aIkyl radical having 1 to 4 carbon atoms, preferably hydrogen, or methyl, ethyl or propyl, and Y is hy-drogen, chlorine or fluorine, to obtain an organic and an aqueous phase, separating the two phases and separating the metal from the organic phase with acid.
Preferably hydrogen and the sum of the hydrocarbon atoms of the radicals R , R and R is preferably at least 6, especially 6 to 12. If desired the compound of formula I may be dissolved in an inert organic water-insoluble solvent when contacting the aqueous solution.
The alkyl radicals R , R and R are preferably branched radicals.
Special mention is made of compounds in which Y is hydrogen, R is hydrogen or an alkyl group, at least one of the alkyl groups R , R or R is branched and the sum of the carbon atoms present in these alkyl groups is not greater than 6.
Some compounds within the general formula I are novel. Those com-pounds are novel wherein, R, R and Y have the meanings given above and R
is alkyl of 1 to 4 carbon atoms, with the proviso that if R is hydrogen the sum of the carbon atoms R and R i9 not greater than 5. Preferred novel compounds are those in which Y is hydrogen, at least one of R, R and R3 is a branched alkyl radical and R is alkyl having 1 to 3 carbon atoms, the sum of the carbon atoms present in R , R and R being not greater than 6.
Particular mention is made of compounds in which R is aIkyl or alkoxy of 1 to 3 carbon atoms.
~ 'A`~ - 3 ~
,. ' ` ~0'71Z36 The compounds of the formula I may be obtained according to known processes, for example according to J.C. Reid and M. Cal~in, J. Am. Chem.
Soc. 72 (1950) 2948 or corresponding to the preparation of benzoyl acetone (cf. Beilstein, Handbuch der organischen Chemie, volume VII, page 681 (1925) and ~ 3a -107~Z36 1st, 2nd and 3rd complementary volume) by reacting an alkyl benzene according to a Friedel Crafts acylation with acetyl chloride to obtain the corresponding alkyl acetophenone and condensing this compound in a Claisen condensation in the presence of strong bases, as for example sodium ethylate or sodium hy-dride, with ethyl acetate to obtain the acetoacetyl alkyl benzene.
The disadvantages of this process are especially the hydrolysis and the loss of the aluminum chloride in the first phase; in the second phase the necessary use of dry solvents, for example ether, and of two mols of a base as well as the necessary working up of the acetoacetyl alkyl benzene obtained as alkali salt.
The compounds of the formula I may also be prepared according to the process of Canadian Patent Application No. 205.306. According to this process aromatic 1,3-diketones are obtained by reacting acetoacetyl flouride which is optionally substituted in ~ -position by 1 to 3 halogen atoms, with solid or liquid aIkyl- or aIkoxy-aromatic compounds at temperatures of from ~0 to ~50 Cin at least 90 % hydrofluoric acid. As solid or liquid aromatic compounds there may be used above all benzene derivatives of the general formula R "R
R" ' wherein R~, R~ and R" ' represent independently from one another hydrogen, al~l, alkoxy or alkylthio radicals having 1 to 12 carbon atoms or halogen.
With regard to the use as extracting agents for metals there are preferred among the components of the formula I and among the starting ~1 _ 1071Z3~
compounds of the formula V
R2~ (V), wherein R , R , R have the meaning indicated in formula I, the compounds in which R and/or R represent hydrogen or aIkyl groups. In most cases compounds of the formula I are used wherein Y is hydrogen. In case that Y is halogen, F is preferred. It is particularly preferred that the three substituents Y are identical.
In the compounds of the formula I the position of the substituents R , R and R may vary. If R and R are hydrogen the 4-position is pre-ferred for the alkyl radical R ; furthermore there is considered above all the 2-position or mixtures of para and ortho substituted compounds.
If only of the radicals R and R is hydrogen the substituents are preferably in 2,4-position. Moreover, compounds with 3,4-substitution or mixtures of compounds with 2,4- and 3,4-substitution are considered. If none of the radicals R , R and R3 is hydrogen the compounds are preferably 2,4,6-substituted; there are also used compounds substituted in 2,4,5-position and mixtures of compounds substituted in 2,4,6- and 2,4,5-position.
As compounds of the formula I there are considered for example l_[21,4'-diisopropyl-phenyl~-butane-l,3-dione, l-[2'-methyl-4'-hexyl-phenyl~-butane-l,3-dione in mixture with 1_[2'-hexyl-4'-methyl-phenyl]-butane-1,3-dione, l-(2'-2"ethylhexoxy-4'-methylphenyl)-butanedione-l,3 ~071Z36 1-(21,5'-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-dodecyl benzene 4-acetoacetyl-n-nonyl benzene 4-acetoacetyl-n-heptyl benzene 4-acetoacetyl-hexyl benzene 1-[2'4'-dimethyl 5'-(1"-methyl-nonyl)~-phenyl-butane-1,3-dione 1-(4'-hexylphenyl)-4,4,4-trifluoro-butane-1,3-dione, 1-(4'-hexylphenyl)-4,4,4-trichloro-butane-1,3-dione.
The above-mentioned diones mostly contain small amounts of diones which are isomer in the phenyl radical, but which need not be separated for the use of the compounds of the formula I as extracting agent. It has proved that isomer mixtures as well as mixtures of different substituted acetoacetyl aromatic substances show in many cases a particularly good extracting effect.
me extracting agents of the formula I may be used for the extrac-tion of metals which form with them a stable complex compound. The con-ditions under which this happens depend above all on the pH-value of the aqueous solution which may vary between 1 and 11 depending on the metal.
Metals to be extracted according to the invention which in form of their cations form stable complexes with the compounds of the formula I
are for example: Cu, Co, Ni, Fe, Ag, 8e~ Ga, Eu, In, Zn.
The corresponding complex compounds of these metals are well soluble in the usual inert organic solvents not miscible with water used for such extraction processes, such as chloroform carbon tetrachloride, chloro-benzene, alkyl ethers such as diisopropyl ether, aliphatic hydrocarbons such as kerosin or petroleum, or aromatic compounds such as benzene, tol~ene, xylene and higher alkylated homologues, especially the compounds of the formula V.
Therefore, the extracting agents of the formula I are preferably used in the presence of the above-mentioned or analogous solvents. It is also preferable to use additives of long-chained alcohols, such as dodecanol or phenols such as isononyl phenol in the extraction.
To obtain a sufficient solubility of the metal complexes obtained in the extraction benzoyl acetones are required which are substituted by one or more long-chained or branched hydrocarbon chains. The solubility of the metal complexes increases with the number of hydrocarbons of these chains.
Since the reaction of the benzoyl acetones of the formula I with the metal component is carried out in defined stoichiometrical ratios, with copper for example in the molar ratio of 2:1, it is possible but generally not useful to use compounds of the formula I, the substituents of which contain con-siderably more than 12 carbon atoms to obtain a high metal binding capacity.
Compounds with substituents having a smaller total number of hydrocarbons than 6 may also be used for extraction in a diluent as for example petroleum or kerosin. In this case it is necessary to add suitable solubilizers such as isodecanol or nonyl phenol.
Thus, as starting products for preparing the benzoyl acetones of the formula I for the reaction with acetoacetyl fluorides of the formula III
-.
o o ,. ...................................... .
F - C - CH - C - C(Y) (III) wherein Y has the above meaning, the following comp~unds may be mentioned:
m-hexyl toluene, dodecyl benzene, tetrapropylene benzene, (i-dodecyl-benzene), i-nonyl-benzene, heptyl benzene, i-heptyl benzene, hexyl benzene in mixture with ~l-methyl-pentyll-benzene and ~l-ethyl-butyl3-benzene~ 1,3-dimethyl-4-[l~-methyl-nonyl~-benzene, m-di-isopropyl benzene, 1,3,5-triisopropyl benzene, 1,4-dimethyl-5-octylbenzene, 1,3-dimethyl-4-octyl benzene, technical aIkyl benzene mixtures with boiling points of for example 180 to 300 C, l-methyl-
butyl benzoyl acetone, too, do not have any solubility in hydrocarbons such as petroleum sufficient for a technical extraction process.
Now~ a process for the extraction of metals from their aqueous solutions has been found which comprises contacting an aqueous solution con-taining metal ions with a compound of the general formula I
O O
R2 ~ " " ( ) (I) ~! 2 - ~
1~71236 wherein R is an aIkyl radical having 3 to 12, preferably 6 to 12 carbon atoms, R is hydrogen or an aIkyl or alkoxy radical having 1 to 8, prefer-ably 1 to 4 carbon atoms, R3 is hydrogen or an aIkyl radical having 1 to 4 carbon atoms, preferably hydrogen, or methyl, ethyl or propyl, and Y is hy-drogen, chlorine or fluorine, to obtain an organic and an aqueous phase, separating the two phases and separating the metal from the organic phase with acid.
Preferably hydrogen and the sum of the hydrocarbon atoms of the radicals R , R and R is preferably at least 6, especially 6 to 12. If desired the compound of formula I may be dissolved in an inert organic water-insoluble solvent when contacting the aqueous solution.
The alkyl radicals R , R and R are preferably branched radicals.
Special mention is made of compounds in which Y is hydrogen, R is hydrogen or an alkyl group, at least one of the alkyl groups R , R or R is branched and the sum of the carbon atoms present in these alkyl groups is not greater than 6.
Some compounds within the general formula I are novel. Those com-pounds are novel wherein, R, R and Y have the meanings given above and R
is alkyl of 1 to 4 carbon atoms, with the proviso that if R is hydrogen the sum of the carbon atoms R and R i9 not greater than 5. Preferred novel compounds are those in which Y is hydrogen, at least one of R, R and R3 is a branched alkyl radical and R is alkyl having 1 to 3 carbon atoms, the sum of the carbon atoms present in R , R and R being not greater than 6.
Particular mention is made of compounds in which R is aIkyl or alkoxy of 1 to 3 carbon atoms.
~ 'A`~ - 3 ~
,. ' ` ~0'71Z36 The compounds of the formula I may be obtained according to known processes, for example according to J.C. Reid and M. Cal~in, J. Am. Chem.
Soc. 72 (1950) 2948 or corresponding to the preparation of benzoyl acetone (cf. Beilstein, Handbuch der organischen Chemie, volume VII, page 681 (1925) and ~ 3a -107~Z36 1st, 2nd and 3rd complementary volume) by reacting an alkyl benzene according to a Friedel Crafts acylation with acetyl chloride to obtain the corresponding alkyl acetophenone and condensing this compound in a Claisen condensation in the presence of strong bases, as for example sodium ethylate or sodium hy-dride, with ethyl acetate to obtain the acetoacetyl alkyl benzene.
The disadvantages of this process are especially the hydrolysis and the loss of the aluminum chloride in the first phase; in the second phase the necessary use of dry solvents, for example ether, and of two mols of a base as well as the necessary working up of the acetoacetyl alkyl benzene obtained as alkali salt.
The compounds of the formula I may also be prepared according to the process of Canadian Patent Application No. 205.306. According to this process aromatic 1,3-diketones are obtained by reacting acetoacetyl flouride which is optionally substituted in ~ -position by 1 to 3 halogen atoms, with solid or liquid aIkyl- or aIkoxy-aromatic compounds at temperatures of from ~0 to ~50 Cin at least 90 % hydrofluoric acid. As solid or liquid aromatic compounds there may be used above all benzene derivatives of the general formula R "R
R" ' wherein R~, R~ and R" ' represent independently from one another hydrogen, al~l, alkoxy or alkylthio radicals having 1 to 12 carbon atoms or halogen.
With regard to the use as extracting agents for metals there are preferred among the components of the formula I and among the starting ~1 _ 1071Z3~
compounds of the formula V
R2~ (V), wherein R , R , R have the meaning indicated in formula I, the compounds in which R and/or R represent hydrogen or aIkyl groups. In most cases compounds of the formula I are used wherein Y is hydrogen. In case that Y is halogen, F is preferred. It is particularly preferred that the three substituents Y are identical.
In the compounds of the formula I the position of the substituents R , R and R may vary. If R and R are hydrogen the 4-position is pre-ferred for the alkyl radical R ; furthermore there is considered above all the 2-position or mixtures of para and ortho substituted compounds.
If only of the radicals R and R is hydrogen the substituents are preferably in 2,4-position. Moreover, compounds with 3,4-substitution or mixtures of compounds with 2,4- and 3,4-substitution are considered. If none of the radicals R , R and R3 is hydrogen the compounds are preferably 2,4,6-substituted; there are also used compounds substituted in 2,4,5-position and mixtures of compounds substituted in 2,4,6- and 2,4,5-position.
As compounds of the formula I there are considered for example l_[21,4'-diisopropyl-phenyl~-butane-l,3-dione, l-[2'-methyl-4'-hexyl-phenyl~-butane-l,3-dione in mixture with 1_[2'-hexyl-4'-methyl-phenyl]-butane-1,3-dione, l-(2'-2"ethylhexoxy-4'-methylphenyl)-butanedione-l,3 ~071Z36 1-(21,5'-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-dodecyl benzene 4-acetoacetyl-n-nonyl benzene 4-acetoacetyl-n-heptyl benzene 4-acetoacetyl-hexyl benzene 1-[2'4'-dimethyl 5'-(1"-methyl-nonyl)~-phenyl-butane-1,3-dione 1-(4'-hexylphenyl)-4,4,4-trifluoro-butane-1,3-dione, 1-(4'-hexylphenyl)-4,4,4-trichloro-butane-1,3-dione.
The above-mentioned diones mostly contain small amounts of diones which are isomer in the phenyl radical, but which need not be separated for the use of the compounds of the formula I as extracting agent. It has proved that isomer mixtures as well as mixtures of different substituted acetoacetyl aromatic substances show in many cases a particularly good extracting effect.
me extracting agents of the formula I may be used for the extrac-tion of metals which form with them a stable complex compound. The con-ditions under which this happens depend above all on the pH-value of the aqueous solution which may vary between 1 and 11 depending on the metal.
Metals to be extracted according to the invention which in form of their cations form stable complexes with the compounds of the formula I
are for example: Cu, Co, Ni, Fe, Ag, 8e~ Ga, Eu, In, Zn.
The corresponding complex compounds of these metals are well soluble in the usual inert organic solvents not miscible with water used for such extraction processes, such as chloroform carbon tetrachloride, chloro-benzene, alkyl ethers such as diisopropyl ether, aliphatic hydrocarbons such as kerosin or petroleum, or aromatic compounds such as benzene, tol~ene, xylene and higher alkylated homologues, especially the compounds of the formula V.
Therefore, the extracting agents of the formula I are preferably used in the presence of the above-mentioned or analogous solvents. It is also preferable to use additives of long-chained alcohols, such as dodecanol or phenols such as isononyl phenol in the extraction.
To obtain a sufficient solubility of the metal complexes obtained in the extraction benzoyl acetones are required which are substituted by one or more long-chained or branched hydrocarbon chains. The solubility of the metal complexes increases with the number of hydrocarbons of these chains.
Since the reaction of the benzoyl acetones of the formula I with the metal component is carried out in defined stoichiometrical ratios, with copper for example in the molar ratio of 2:1, it is possible but generally not useful to use compounds of the formula I, the substituents of which contain con-siderably more than 12 carbon atoms to obtain a high metal binding capacity.
Compounds with substituents having a smaller total number of hydrocarbons than 6 may also be used for extraction in a diluent as for example petroleum or kerosin. In this case it is necessary to add suitable solubilizers such as isodecanol or nonyl phenol.
Thus, as starting products for preparing the benzoyl acetones of the formula I for the reaction with acetoacetyl fluorides of the formula III
-.
o o ,. ...................................... .
F - C - CH - C - C(Y) (III) wherein Y has the above meaning, the following comp~unds may be mentioned:
m-hexyl toluene, dodecyl benzene, tetrapropylene benzene, (i-dodecyl-benzene), i-nonyl-benzene, heptyl benzene, i-heptyl benzene, hexyl benzene in mixture with ~l-methyl-pentyll-benzene and ~l-ethyl-butyl3-benzene~ 1,3-dimethyl-4-[l~-methyl-nonyl~-benzene, m-di-isopropyl benzene, 1,3,5-triisopropyl benzene, 1,4-dimethyl-5-octylbenzene, 1,3-dimethyl-4-octyl benzene, technical aIkyl benzene mixtures with boiling points of for example 180 to 300 C, l-methyl-
3-hexobenzene.
It is no disadvantage but it is preferable to react isomer mixtures or technical alkyl benzene distillation fractions which, as to their composi-tion, essentially correspond to the formula II, with acetoacetyl fluoride.
Moreover, it may be advantageous in the case of substances which react only with great difficulty or not at~all with diketene, to add a second substance in about molar amounts having similar properties especially those having shorter side chains which are more reactive against diketene; by this way the reaction may be induced with the more inactive substance. Thus, for example, by reaction of a mixture of 1 mol of dodecyl benzene and 1 mol of tetralin with 2 mols of diketene in hydrogen fluoride acetoacetyl-dodecyl-benzene is obtained in an amount of 40 % which may hardly be obtained without addition of tetralin salt. The same applies to the mixture of iso-dodecyl benzene/m-di-isoprppyl benzene. The preferred ratios of such mixtures are between 2:1 and 1:2.
Other novel compounds prepared according to the process of the ~_ ~071Z36 invention are the isomer acetoacetyl tetralins a~ well as the acetoacetyl diethyl benzenes. These compounds may be obtained as a mixture for example in the preparation of acetoacetyl-dodecyl benzenes when admixing the corres-ponding aromatic compound and they may be used - as other (C6-C12~ alkylated aromatic 1,3-diketones - as addition to the abo~e novel aromatic 1,3-diketones mono-, di- or trialkylated with (C6-C12).
The starting product which has not been completely reacted in the reaction of above-mentioned aromatic compounds with acetoacetyl fluoride may either be recovered and used again or serve as co-solvent for the aro-matic 1,3-diketone w1th regard to the adjustment of concentration.
Therefore, the object of the invention are mixtures of compounds of the formula I with one another or with short-chained compounds homologous to formula I in the ratio of 50:50 to 90:10 as well as the use of such mix-tures in the extraction of metals. Such mixtures may consist for example in acetoacetyl diisopropyl benzene on one hand with acetoacetyl-diethyl ben-zene, acetoacetyl tetralin, n-hexyl-benzoyl acetone, isonoroxy-benzoyl acetone and/or triethyl-benzoyl acetone on the other.
The invention further relates to mixtures of compounds of the formula I (or the mixtures thereof, especially mixtures of isomers) with the corresponding compounds (or mixtures) of the formula II as they are obtained for example by the incomplete reaction when carrying out the process of the invention, as well as their use in the extraction of metals.
The extraction process of the invention is above all suitable for the extraction of copper components from acidic to especially ammoniac aqueous solutions and for the separation of Cu and Zn from these solutions.
_g _ - ' - ~ ' , 107~Z36 Such solutions may be obtained for example by ammonia leaching of oxidic or sulfidic ore or of scrap or metal waste in the presence of oxygen. me separation of Cu and Zn from such solution is expediently carried out at a pH range of about 2 to 11, especially 4 to 11 and preferably 8 to 11. In the reaction of the metal cation with the benzoyl acetone derivatives hydro~en ions are formed which are bound in ammonia solution by ammonia in excess and taken out of the reaction balance. If the extraction is carried out in an acidic medium it is sometimes expedient, above all for a high metal loading capacity of the organic phase, to bind the hydrogen ions formed by addition of bases as for example sodium hydroxide, calcium hydroxide, ammonia etc.
The metal extraction process is generally carried out in such a manner as to allow that the aqueous solution containing metal ions is brought into a narr~w contact or intimately mixed with the extracting agent, preferably dissolved in organic solvents not miscible with water and under the conditions of the extraction inert with regard to water, the metallic compounds and the compounds of the formula I, with 1 to 20, preferably 4 to 20 parts by weight per 1 part by weight of extracting agent. The ratio of the volume of organic to aqueous phase may vary within wide limits; it generally ranges between about 5:1 to 1:5. It is advantageous but not absolutely necessary to use for extraction an amount of solvent which is sufficient to ensure a complete dissolution of the complex compound formed, since a compound which is in excess of the complex compound being in dissolu-tion remains completely in the organic solvent as suspension, the two phases are separated again and the metals taken up are reextracted from the organic phase in known manner with aqueous mineral acid. ~hen the extracting agent/
-1~
solvent is available for another extraction. Such extracting process is carried out in known manner continuously, especially in the counter current process.
Thus the extraction process of the invention is expediently carried out in such a way that the organic and the metal-containing aqueous phase are intimately mixed in mixers or columns to adjust faster the extraction balance. The mixture is subsequently transported in settlers, where a sep-aration in two phases takes place due to the different densities. The or-ganic phase is subsequently separated. The process may be carried out dis-continuously and preferably continuously.
For further working up the metal being in the organic phase maybe removed from the organic phase by a so-called strip process. This is possible by adjusting conditions under which the complex is instable and decomposed. In most cases the addition of mineral acid is sufficient, the concentration of which is adjusted in such a way that the concentration of hydrogen ions is higher than the concentration at which the extraction takes place. Reducing media which cause a change of the valence of the metal may also be used.
The reaction for the preparation of the compounds of formula I may be carried out in a temperature range of about ~0 to +50 C, temperatures of from -30 to +20 C, preferably -20 to +20C are preferably used. With these temperatures it is possible to do without special pressure vessels.
Besides plastics such as polyethylene, polypropylene or polyvinyl chloride preferred vessel materials are metals, especially steel.
Since during the reaction no water is formed the hydrofluoric acid '' ~ '' .
, -. : .
used may be recovered to a large extent by distillation. Recovering is also possible for the portion of non-reacted aromatic compound.
The reaction pressures essentially correspond to the individual pressure of the hydrofluoric acid. mis acid shall have a minimum content of HF of about 90 % by weight; there is preferably used about 95 to 100 %, especially about 98 to loo % hydrofluoric acid, the rest is water.
Depending on the reaction temperature the reaction time is half an hour to several hours, for example at reaction temperatures below 0 C 6 to 24 hours, whereas at room temperature about 2 to 12 hours and at tempera-tures about 50 C already 30 to 120 minutes are sufficient.
The process may be carried out for example by dissolving the aro-matic substances and acetoacetyl fluoride in about molar amounts in the hydrofluoric acid, at temperatures being expediently below +20C, preferably between 0 to -30 C, and by bringing the reaction mixture, to the reaction temperature desired, expediently with stirring.
An excess of acetoacetyl fluoride is possible but hardly necessary.
For a better efficiency the aromatic compound may be used in excess (1 to S
mols). Since the aromatic compound does not show any secondary reactions a non-reacted portion of this compound may be recovered according to known methods and used again or used for metal extraction as inert solvent for the metal complex formed.
The amount of hydrofluoric acid used is 1 to 20 parts by weight per one part of aromatic compound, preferably 3 to 10 parts. The reactants are added in any order desired, especially one or two may be added continu-ously. The whole process may also be carried out in a simple way continuously, ~071Z36 by introducing all components homogeneously into a reaction vessel or reac-tion tube. Instead of acetoacetyl fluoride the analogous chloride which reacts with hydrofluoric acid to the fluoride may also be used.
A process is preferred in which the acetoacetyl fluoride is pro-duced in situ by addition of diketene to hydrofluoric acid in excess acetoa-cetyl fluoride from molar amounts of diketene and hydrogen fluoride s.G.A.
Olah and S.J. Kuhn, J. Org. Chem. 26, 225 (1961) in the presence or absence of the aromatic compound, preferably at -20 to o C and then reacted at the reaction temperature required. In this preparation of the acetoacetyl fluo-ride the excess of hydrofluoric acid is expediently chosen in such amountthat with deduction of the consumption during the formation of acetoacetyl fluoride the amounts of hydrofluoric acid mentioned above for the reaction with aromatic compounds are obtained.
It is also possible to prepare the alkyl aromatic compounds in known manner by reaction of alkanols, aIkyl chlorides or preferably alkenes with benzene or alkyl aromatic compounds in the presence of Friedel-Crafts catalysts and to react them furth~r in a "one-pot-process~' with acetoacetyl fluoride to obtain the desired aIkyl acetoacetyl aromatic compounds or with acetyl chloride to obtain the alkyl acyl aromatic compounds las preliminary product of the ester condensation). Ftr example, benzene may be reacted with 3 mols of propene in hydrogen fluoride to obtain tri-isopropyl benzene;
after subsequent addition of diketene acetoacetyl-tri-iso-propyl benzene is obtained. By varying the reaction conditions mixtures of mono-, di-, tri-or tetra-substituted aromatic compounds are obtained. As starting materials there may also be reacted technical distillation fraction haring a high - -- ~
- ' ' ' ' ' .~, '' ' ~ : ' content of alkyl benzene and boiling points of from 180 to 300 C.
The acetoacetyl halides substituted in ~-position by halogen atoms may be obtained according to known methods, for example described in Houben-Weyl "Methoden der organischen Chemie" volume 7/4, pages 203 and 251, Georg Thieme Yerlag, Stuttgart 1968. As acetoacetyl halides substituted by ~ -halo-gen there may be mentioned: ~ -trifluoroacetoacetyl fluoride and ~ -trichlor-oacetoacetyl chloride.
When the reaction is finished the hydrofluoric acid is expediently distilled off at normal pressure, the residue is washed free from acid with water and, if desired, distilled off, When the reaction is finished the hydrofluoric acid solution may also be introduced into water and the reaction products are extracted with carbon halides or aliphatic or aromatic hydro-carbons .
The following Examples illustrate the invention. Parts and per-centages are by weight unless stated otherwise.
EXAMPLE 1:
0.5 1 of anhydrous technical hydrofluoric acid were mixed dropwise, while stirring, at -10 C, with 0.5 mol of technical (96 %) diketene, and then 0.5 mol of 1,3,5-triethylene-benzene was introduced. After stirring over night at 10 - 20 C the solution was introduced while stirring into 5 1 of ice water and extracted with cyclohexane. It was washed free from acid, dried, the solvent was suction-filtered and then 240 g of colorless crystals of the 2,4,6-triethylene-benzoyl acetone were obtained (92.3 % after gas chromatography); melting point: 44 - 4S& (isopropanol).
Boiling point: 108 C/0.15 mm mercury.
1~71Z36 Yield of the theory: 90.5 %.
The following compounds were prepared in analogous manner:
No Compound _ Properties 2 4-n-hexyl-benzoyl acetone colorless crystals, m.p. 42 C
3 4-n-heptyl-benzoyl acetone colorless crystals, m.p. 35 - 37 C
It is no disadvantage but it is preferable to react isomer mixtures or technical alkyl benzene distillation fractions which, as to their composi-tion, essentially correspond to the formula II, with acetoacetyl fluoride.
Moreover, it may be advantageous in the case of substances which react only with great difficulty or not at~all with diketene, to add a second substance in about molar amounts having similar properties especially those having shorter side chains which are more reactive against diketene; by this way the reaction may be induced with the more inactive substance. Thus, for example, by reaction of a mixture of 1 mol of dodecyl benzene and 1 mol of tetralin with 2 mols of diketene in hydrogen fluoride acetoacetyl-dodecyl-benzene is obtained in an amount of 40 % which may hardly be obtained without addition of tetralin salt. The same applies to the mixture of iso-dodecyl benzene/m-di-isoprppyl benzene. The preferred ratios of such mixtures are between 2:1 and 1:2.
Other novel compounds prepared according to the process of the ~_ ~071Z36 invention are the isomer acetoacetyl tetralins a~ well as the acetoacetyl diethyl benzenes. These compounds may be obtained as a mixture for example in the preparation of acetoacetyl-dodecyl benzenes when admixing the corres-ponding aromatic compound and they may be used - as other (C6-C12~ alkylated aromatic 1,3-diketones - as addition to the abo~e novel aromatic 1,3-diketones mono-, di- or trialkylated with (C6-C12).
The starting product which has not been completely reacted in the reaction of above-mentioned aromatic compounds with acetoacetyl fluoride may either be recovered and used again or serve as co-solvent for the aro-matic 1,3-diketone w1th regard to the adjustment of concentration.
Therefore, the object of the invention are mixtures of compounds of the formula I with one another or with short-chained compounds homologous to formula I in the ratio of 50:50 to 90:10 as well as the use of such mix-tures in the extraction of metals. Such mixtures may consist for example in acetoacetyl diisopropyl benzene on one hand with acetoacetyl-diethyl ben-zene, acetoacetyl tetralin, n-hexyl-benzoyl acetone, isonoroxy-benzoyl acetone and/or triethyl-benzoyl acetone on the other.
The invention further relates to mixtures of compounds of the formula I (or the mixtures thereof, especially mixtures of isomers) with the corresponding compounds (or mixtures) of the formula II as they are obtained for example by the incomplete reaction when carrying out the process of the invention, as well as their use in the extraction of metals.
The extraction process of the invention is above all suitable for the extraction of copper components from acidic to especially ammoniac aqueous solutions and for the separation of Cu and Zn from these solutions.
_g _ - ' - ~ ' , 107~Z36 Such solutions may be obtained for example by ammonia leaching of oxidic or sulfidic ore or of scrap or metal waste in the presence of oxygen. me separation of Cu and Zn from such solution is expediently carried out at a pH range of about 2 to 11, especially 4 to 11 and preferably 8 to 11. In the reaction of the metal cation with the benzoyl acetone derivatives hydro~en ions are formed which are bound in ammonia solution by ammonia in excess and taken out of the reaction balance. If the extraction is carried out in an acidic medium it is sometimes expedient, above all for a high metal loading capacity of the organic phase, to bind the hydrogen ions formed by addition of bases as for example sodium hydroxide, calcium hydroxide, ammonia etc.
The metal extraction process is generally carried out in such a manner as to allow that the aqueous solution containing metal ions is brought into a narr~w contact or intimately mixed with the extracting agent, preferably dissolved in organic solvents not miscible with water and under the conditions of the extraction inert with regard to water, the metallic compounds and the compounds of the formula I, with 1 to 20, preferably 4 to 20 parts by weight per 1 part by weight of extracting agent. The ratio of the volume of organic to aqueous phase may vary within wide limits; it generally ranges between about 5:1 to 1:5. It is advantageous but not absolutely necessary to use for extraction an amount of solvent which is sufficient to ensure a complete dissolution of the complex compound formed, since a compound which is in excess of the complex compound being in dissolu-tion remains completely in the organic solvent as suspension, the two phases are separated again and the metals taken up are reextracted from the organic phase in known manner with aqueous mineral acid. ~hen the extracting agent/
-1~
solvent is available for another extraction. Such extracting process is carried out in known manner continuously, especially in the counter current process.
Thus the extraction process of the invention is expediently carried out in such a way that the organic and the metal-containing aqueous phase are intimately mixed in mixers or columns to adjust faster the extraction balance. The mixture is subsequently transported in settlers, where a sep-aration in two phases takes place due to the different densities. The or-ganic phase is subsequently separated. The process may be carried out dis-continuously and preferably continuously.
For further working up the metal being in the organic phase maybe removed from the organic phase by a so-called strip process. This is possible by adjusting conditions under which the complex is instable and decomposed. In most cases the addition of mineral acid is sufficient, the concentration of which is adjusted in such a way that the concentration of hydrogen ions is higher than the concentration at which the extraction takes place. Reducing media which cause a change of the valence of the metal may also be used.
The reaction for the preparation of the compounds of formula I may be carried out in a temperature range of about ~0 to +50 C, temperatures of from -30 to +20 C, preferably -20 to +20C are preferably used. With these temperatures it is possible to do without special pressure vessels.
Besides plastics such as polyethylene, polypropylene or polyvinyl chloride preferred vessel materials are metals, especially steel.
Since during the reaction no water is formed the hydrofluoric acid '' ~ '' .
, -. : .
used may be recovered to a large extent by distillation. Recovering is also possible for the portion of non-reacted aromatic compound.
The reaction pressures essentially correspond to the individual pressure of the hydrofluoric acid. mis acid shall have a minimum content of HF of about 90 % by weight; there is preferably used about 95 to 100 %, especially about 98 to loo % hydrofluoric acid, the rest is water.
Depending on the reaction temperature the reaction time is half an hour to several hours, for example at reaction temperatures below 0 C 6 to 24 hours, whereas at room temperature about 2 to 12 hours and at tempera-tures about 50 C already 30 to 120 minutes are sufficient.
The process may be carried out for example by dissolving the aro-matic substances and acetoacetyl fluoride in about molar amounts in the hydrofluoric acid, at temperatures being expediently below +20C, preferably between 0 to -30 C, and by bringing the reaction mixture, to the reaction temperature desired, expediently with stirring.
An excess of acetoacetyl fluoride is possible but hardly necessary.
For a better efficiency the aromatic compound may be used in excess (1 to S
mols). Since the aromatic compound does not show any secondary reactions a non-reacted portion of this compound may be recovered according to known methods and used again or used for metal extraction as inert solvent for the metal complex formed.
The amount of hydrofluoric acid used is 1 to 20 parts by weight per one part of aromatic compound, preferably 3 to 10 parts. The reactants are added in any order desired, especially one or two may be added continu-ously. The whole process may also be carried out in a simple way continuously, ~071Z36 by introducing all components homogeneously into a reaction vessel or reac-tion tube. Instead of acetoacetyl fluoride the analogous chloride which reacts with hydrofluoric acid to the fluoride may also be used.
A process is preferred in which the acetoacetyl fluoride is pro-duced in situ by addition of diketene to hydrofluoric acid in excess acetoa-cetyl fluoride from molar amounts of diketene and hydrogen fluoride s.G.A.
Olah and S.J. Kuhn, J. Org. Chem. 26, 225 (1961) in the presence or absence of the aromatic compound, preferably at -20 to o C and then reacted at the reaction temperature required. In this preparation of the acetoacetyl fluo-ride the excess of hydrofluoric acid is expediently chosen in such amountthat with deduction of the consumption during the formation of acetoacetyl fluoride the amounts of hydrofluoric acid mentioned above for the reaction with aromatic compounds are obtained.
It is also possible to prepare the alkyl aromatic compounds in known manner by reaction of alkanols, aIkyl chlorides or preferably alkenes with benzene or alkyl aromatic compounds in the presence of Friedel-Crafts catalysts and to react them furth~r in a "one-pot-process~' with acetoacetyl fluoride to obtain the desired aIkyl acetoacetyl aromatic compounds or with acetyl chloride to obtain the alkyl acyl aromatic compounds las preliminary product of the ester condensation). Ftr example, benzene may be reacted with 3 mols of propene in hydrogen fluoride to obtain tri-isopropyl benzene;
after subsequent addition of diketene acetoacetyl-tri-iso-propyl benzene is obtained. By varying the reaction conditions mixtures of mono-, di-, tri-or tetra-substituted aromatic compounds are obtained. As starting materials there may also be reacted technical distillation fraction haring a high - -- ~
- ' ' ' ' ' .~, '' ' ~ : ' content of alkyl benzene and boiling points of from 180 to 300 C.
The acetoacetyl halides substituted in ~-position by halogen atoms may be obtained according to known methods, for example described in Houben-Weyl "Methoden der organischen Chemie" volume 7/4, pages 203 and 251, Georg Thieme Yerlag, Stuttgart 1968. As acetoacetyl halides substituted by ~ -halo-gen there may be mentioned: ~ -trifluoroacetoacetyl fluoride and ~ -trichlor-oacetoacetyl chloride.
When the reaction is finished the hydrofluoric acid is expediently distilled off at normal pressure, the residue is washed free from acid with water and, if desired, distilled off, When the reaction is finished the hydrofluoric acid solution may also be introduced into water and the reaction products are extracted with carbon halides or aliphatic or aromatic hydro-carbons .
The following Examples illustrate the invention. Parts and per-centages are by weight unless stated otherwise.
EXAMPLE 1:
0.5 1 of anhydrous technical hydrofluoric acid were mixed dropwise, while stirring, at -10 C, with 0.5 mol of technical (96 %) diketene, and then 0.5 mol of 1,3,5-triethylene-benzene was introduced. After stirring over night at 10 - 20 C the solution was introduced while stirring into 5 1 of ice water and extracted with cyclohexane. It was washed free from acid, dried, the solvent was suction-filtered and then 240 g of colorless crystals of the 2,4,6-triethylene-benzoyl acetone were obtained (92.3 % after gas chromatography); melting point: 44 - 4S& (isopropanol).
Boiling point: 108 C/0.15 mm mercury.
1~71Z36 Yield of the theory: 90.5 %.
The following compounds were prepared in analogous manner:
No Compound _ Properties 2 4-n-hexyl-benzoyl acetone colorless crystals, m.p. 42 C
3 4-n-heptyl-benzoyl acetone colorless crystals, m.p. 35 - 37 C
4 2-methoxy-5-iso-hexyl benzoyl colorless oil, boil-acetone ing point 152 -165 C, 1.8 mm mercury 2 isomers with regard to the hexyl group in the ratio of 1:3.5 2-methoxy-5-iso-nonyl-benzoyl colorless oil, boil-acetone ing point 180 - 200C, 2 mm mercury 3 isomers with regard to the nonyl group in the ratio of 80:9:7 6 2-n-heptoxy-5-sec-butyl- colorless oil, boil-benzoyl acetone ing point 220 C/
3 mm mercury, nD2~;
1.5310 (95 % after gas chromatography) .:
.
, ` . : . ~ -. .
7 2-n-dodecyloxy-5-methyl-benzoyl pale pink crystalsacetone mp.: 54 - 57 G
8 2-n-butoxy-4-sec-butyl-benzoyl colorless crystals acetone mp.: 44 - 46 C
9 2,5-dimethyl-4-n-octyl-benzoyl colorless crystalsacetone mp.: 30 - 32 C
EXAMPLE 10:
At 5 - 15 C 0.5 1 of technical anhydrous hydrofluoric acid were added to O.S mol of benzene, 1.5 mols of propene were introduced while stirring well and stirred for two days. At -10C 1 mol of technical 96 %
diketene were added dropwise while stirring well, to the heterogenous reac-tion mixture, and poured into ice water at room temperature after stirring over njght, whereby colorless crystals were separated. After extraction with cyclohexane, washing free from acid, drying and removing the solvent 106 g of yellow crystals were obtained 88 % by weight of which consist of 2,4,6-tri-isopropyl-acetoacetyl benzene.
Melting point: 84 C after recrystallization from ethanol Yield: 65 % of the theory calculated on benzene.
EXAMPLE 11:
The operation was carried out as in Example 10 but instead of cumol benzene was reacted. A yellow oily/solid mixture with 60 % of 2,4,6-tri-isopropyl-acetoacetyl benzene and 27 % of 2,4-diisopropy~etoacetyl benzene (after gas chromatography) were obtained.
EXAMPLE 12:
1 Mol of benzene in 0.5 1 of technical anhydrous hydrofluoric acid , - : .
, was reacted with 2.5 mols of propene at 5 - 15 C and stirred for 5 hours.
At -10 C 1 mol of diketene was added dropwise and after stirring over night and working up as described in Example 1, 191 g of yellow liquid were iso-lated which consisted after gas chromatography of 32.5 % of alkyl aromatic compounds (4 % of cumol, 25 % of diisopropyl benzene~ 3,5 % of triisopropyl benzene), 4 % of acetoacetyl cumol, 37.5 % of di-isopropylacetoacetyl benzene and 20.5 % of triisopropyl acetoacetyl benzene.
EXAMPLE 13:
0.5 1 of anhydrous hydrofluoric acid were dropwise mixed at -30 C
o with 100.8 g (1.2 mols) of diketene and a mixture of 0.6 mol of tetralin and 0.6 mol of n-dodecyl benzene was introduced dropwise. After stirring for 12 hours at room temperature the solution was introduced while stirring into 3 1 of ice water. It was extracted with methylene chloride, the organic phàse was washed free from acid and the methylene chloride was distilled off. The distillation of the reaction product (according to determination of the content of the fractions by gas chromatography) have a yield of 86 %
of acetoacetyl tetralin with a boiling point of 135 C/0.5 mm mercury and 40 % of 4-acetoacetyl-dodecyl benzene with a boiling point of 160 C/0.5 mm mercury, which contained small amounts of 2-acetoacetyl-dodecyl benzene.
(Yields calculated on amounts used of tetralin or d~decyl benzene).
EXAMPLE 14:
700 g of technical diketene (8 mols) were introduced dropwise, while stirring, at -20 C, to 4 1 of technical anhydrous hydrofluoric acid and then 1408 g of technical hexyl toluene (8 mols) were introduced. After heating to +15 C the whole was stirred over night. After distilling the .
hydrogen fluoride to a sump temperature of 80 C the residue was introduced into ice water, the organic phase was separated and washed until neutral.
By distillation over a 1 m vacuum jacket column with Raschig rings 1340 g of a colorless methyl hexyl benzoyl acetone having a melting point of 135 -145 C/1.5 mm mercury were obtained which had a content of 98 %, consisting of 2 isomers in the weight ratio of about 4:3.
When using ~-trihalogeno-acetoacetyl halide the following com-pounds were prepared in analogous way:
a 1-(2,4,5-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 ~ (2,4-diisopropylphenyl)-4,4,4-trifluorobutane-1,3,-dione f. 1-(2,4-diisopropylphenyl)-4,4,4-trichlorobutane-1,3-dione (boiling point: 135 C/0.03 mm mercury) EXAMPLE ~s Into 1 1 of anhydrous technical hydrofluoric acid 175 g of technical diketene (2 mols) were added dropwise, while stirring and then mixed with a mixture of 162 g (1 mol) of m-di-isopropyl-benzene and 246 g (1 mol) of i-dodecyl benzene ("tetra-propylene benzene") and stirred over night at +15 C.
After distilling the hydrogen fluoride the whole was mixed with ice water, the organic phase was extracted with cyclohexane and washed until neutral.
After distilling the cyclohexane 434 g of a yellow-orange liquid were obtained which contained 50 ~ of 2,4-di-isopropyl-benzoyl acetone, 15 % of 4-acetoa-cetyl-i-dodecyl benzene and 25 % of i-dodecyl benzene.
EXAMP~E 16:
52 g (0.2 mol) of 4-acetyl-n-decyl benzene (boiling point 125C/
0.02 mm mercury) prepared by acylation of n-decyl benzene for example in analogy to Organikum page 306, VEB Deutscher Verlag der Wissenschaften, Berlin 1965~ were stirred in 200 ml of diisopropyl ether with 17.6 g (0.2 mol) of ethyl acetate and 19.2 g of a 52 % technical sodium hydride were introduced. After stirring for a short time a violent reaction took place which was maintained under control by cooling to 40C and maintaining this temperatu~e. Stirring was continued for one hour. The brown crystal slurry was suction-filtered and the grey crystals obtained were washed out with ether. Then the crystals were introduced into 1 1 of water and adjusted to an acidic range while stirring by addition of 2N hydrochloric acid. 25 g of light brown crystals were obtained which yielded after recrystallization from acetonitrile colorless crystals of 4-acetoacetyl-n-decyl benzene having a melting point of 45 C.
The following compounds were prepared in analogous way:
a) 4-acetoacetyl-n-nonyl benzene colorless crystals mp: 26 C
b~ 4-acetoacetyl-n-octyl benzene colorless crystals mp: 39C
and when using trihalogen-acetic acid ethyl ester and sodium methylate the following compounds were obtained:
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) 1-(4_n-hexylphenyl)-4,4,4-trifluorobutane-1,3-dione f) 1_(4-n-hexylphenyl)-4,4~4-trichlorobutane-1,3-dione -: ,` ' ' .:
:
- . ~. ~ .. -. ; . ~ . ...
.. ~ , , . . . .. -~ \
EXAMPLE 17: (extraction) 50 g of 2,4-diisopropyl-benzoyl acetone were completed to 1 liter with petroleum. 50 ml of the orgaric phase thus obtained were shaken for 10 minutes in a separatory funnel with 50 ml of an aqueous phase which contained per liter 10 g of Cu , S g of Zn , 35 g (NH4~2C03 and 34 g of NH3- After separating the two phases the content of copper and zinc in the organic phase was determined. The organic phase had taken up 4.9 g of Cu2+ and 0.01 g of Zn, corresponding to a Cu/Zn separating factor of 490.
EXAMPLE 18: (extraction) 50 ml of an organic base prepared by dissolving 15 g of i-dodecyl-benzoyl acetone in 100 ml of petroleum was often brought into contact with an aqueous phase always fresh which contained per liter 10 g of Cu, 5 g of Zn, 35 g of (NH4)2C03 and 34 g of NH3, until the organic phase was saturated with copper. The quantitative determination showed that 10.9 g of Cu and 0.03 g of 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 shaken for 10 minutes in the volume ratio of 2:1 with an aqueous solution of 25 g of Cu2+/1 and 50 g of H2S04/1. After adjusting the reaction balance the aqueous phase contained per liter 46.3 g of Cu and 0.04 g of Zn. In the organic phase 0.94 g of Cu remained per liter; that means that 91.4 % of the copper were removed by a one-phase reextraction EXAMPLE 19: lextraction) ~.85 g of CuS04 5 H20 were dissolved with 1 % aque~us ammonia and completed to 1 liter. 50 ml of this solution were shaken for 5 minutes in a 1~7~Z36 separatory funnel in a volume ratio of 1:1 with a petrol solution of 5 g of acetoacetyl hexyl toluene in 100 ml of petroleum. The content of copper was subsequently determined in the aqueous phase; the value found was 1 mg of Cu/l. This means that the copper was converted into the organic phase nearly quantitatively, EXAMPLE 20: (extraction) 40 ml of an aqueous phase which contained 10 g of copper per liter and was adjusted to a pH value of 4.9 were superimposed in a beaker with 40 ml of organic phase prepared from 10 g of diisopropyl benzoyl acetone and 100 ml of petroleu~. With a magnetical stirrer the two phases were intimately mixed in the aqueous phase (dropwise addition of sodium hydroxide solution) while maintaining constant the pH value. When the reaction was completed -which was the case when the pH value did not decrease any longer after the addition of alkali the two phases were introduced into a separatory funnel and s0parated.
The quantitative determination of the copper yielded a content of 9.7 g of copper per liter of organic phase.
If the pH value was not maintained constant during the reaction the balance pH value was at 1.8 and only 1.1 g of copper/l passed to the organic phase.
EXAMPLE 21:
At -10 C 1 mol of diketene was added dropwise to 0.5 1 of hydrogen fluoride and then 151 g of a technical distillation mixture of alkyl benzene having a boiling point of 203 - 267 C and a content of aromatic compounds of a~out 80 C were added. After stirring for 10 hours at room temperature - .
'' ' ' ~- ' ' -the mixture was poured into ice water. After extraction with cyclohexane and subsequent distillation 135 g of a yellowish liquid having a boiling point of 100 C to 150 C/0.15 mm mercury were isolated, which according to the proton nuclear resonance spectroscopy represented a mixture of acetoacety-lated alkyl benzenes having an average number of about 8 carbon atoms in the alkyl radicals.
3 mm mercury, nD2~;
1.5310 (95 % after gas chromatography) .:
.
, ` . : . ~ -. .
7 2-n-dodecyloxy-5-methyl-benzoyl pale pink crystalsacetone mp.: 54 - 57 G
8 2-n-butoxy-4-sec-butyl-benzoyl colorless crystals acetone mp.: 44 - 46 C
9 2,5-dimethyl-4-n-octyl-benzoyl colorless crystalsacetone mp.: 30 - 32 C
EXAMPLE 10:
At 5 - 15 C 0.5 1 of technical anhydrous hydrofluoric acid were added to O.S mol of benzene, 1.5 mols of propene were introduced while stirring well and stirred for two days. At -10C 1 mol of technical 96 %
diketene were added dropwise while stirring well, to the heterogenous reac-tion mixture, and poured into ice water at room temperature after stirring over njght, whereby colorless crystals were separated. After extraction with cyclohexane, washing free from acid, drying and removing the solvent 106 g of yellow crystals were obtained 88 % by weight of which consist of 2,4,6-tri-isopropyl-acetoacetyl benzene.
Melting point: 84 C after recrystallization from ethanol Yield: 65 % of the theory calculated on benzene.
EXAMPLE 11:
The operation was carried out as in Example 10 but instead of cumol benzene was reacted. A yellow oily/solid mixture with 60 % of 2,4,6-tri-isopropyl-acetoacetyl benzene and 27 % of 2,4-diisopropy~etoacetyl benzene (after gas chromatography) were obtained.
EXAMPLE 12:
1 Mol of benzene in 0.5 1 of technical anhydrous hydrofluoric acid , - : .
, was reacted with 2.5 mols of propene at 5 - 15 C and stirred for 5 hours.
At -10 C 1 mol of diketene was added dropwise and after stirring over night and working up as described in Example 1, 191 g of yellow liquid were iso-lated which consisted after gas chromatography of 32.5 % of alkyl aromatic compounds (4 % of cumol, 25 % of diisopropyl benzene~ 3,5 % of triisopropyl benzene), 4 % of acetoacetyl cumol, 37.5 % of di-isopropylacetoacetyl benzene and 20.5 % of triisopropyl acetoacetyl benzene.
EXAMPLE 13:
0.5 1 of anhydrous hydrofluoric acid were dropwise mixed at -30 C
o with 100.8 g (1.2 mols) of diketene and a mixture of 0.6 mol of tetralin and 0.6 mol of n-dodecyl benzene was introduced dropwise. After stirring for 12 hours at room temperature the solution was introduced while stirring into 3 1 of ice water. It was extracted with methylene chloride, the organic phàse was washed free from acid and the methylene chloride was distilled off. The distillation of the reaction product (according to determination of the content of the fractions by gas chromatography) have a yield of 86 %
of acetoacetyl tetralin with a boiling point of 135 C/0.5 mm mercury and 40 % of 4-acetoacetyl-dodecyl benzene with a boiling point of 160 C/0.5 mm mercury, which contained small amounts of 2-acetoacetyl-dodecyl benzene.
(Yields calculated on amounts used of tetralin or d~decyl benzene).
EXAMPLE 14:
700 g of technical diketene (8 mols) were introduced dropwise, while stirring, at -20 C, to 4 1 of technical anhydrous hydrofluoric acid and then 1408 g of technical hexyl toluene (8 mols) were introduced. After heating to +15 C the whole was stirred over night. After distilling the .
hydrogen fluoride to a sump temperature of 80 C the residue was introduced into ice water, the organic phase was separated and washed until neutral.
By distillation over a 1 m vacuum jacket column with Raschig rings 1340 g of a colorless methyl hexyl benzoyl acetone having a melting point of 135 -145 C/1.5 mm mercury were obtained which had a content of 98 %, consisting of 2 isomers in the weight ratio of about 4:3.
When using ~-trihalogeno-acetoacetyl halide the following com-pounds were prepared in analogous way:
a 1-(2,4,5-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 ~ (2,4-diisopropylphenyl)-4,4,4-trifluorobutane-1,3,-dione f. 1-(2,4-diisopropylphenyl)-4,4,4-trichlorobutane-1,3-dione (boiling point: 135 C/0.03 mm mercury) EXAMPLE ~s Into 1 1 of anhydrous technical hydrofluoric acid 175 g of technical diketene (2 mols) were added dropwise, while stirring and then mixed with a mixture of 162 g (1 mol) of m-di-isopropyl-benzene and 246 g (1 mol) of i-dodecyl benzene ("tetra-propylene benzene") and stirred over night at +15 C.
After distilling the hydrogen fluoride the whole was mixed with ice water, the organic phase was extracted with cyclohexane and washed until neutral.
After distilling the cyclohexane 434 g of a yellow-orange liquid were obtained which contained 50 ~ of 2,4-di-isopropyl-benzoyl acetone, 15 % of 4-acetoa-cetyl-i-dodecyl benzene and 25 % of i-dodecyl benzene.
EXAMP~E 16:
52 g (0.2 mol) of 4-acetyl-n-decyl benzene (boiling point 125C/
0.02 mm mercury) prepared by acylation of n-decyl benzene for example in analogy to Organikum page 306, VEB Deutscher Verlag der Wissenschaften, Berlin 1965~ were stirred in 200 ml of diisopropyl ether with 17.6 g (0.2 mol) of ethyl acetate and 19.2 g of a 52 % technical sodium hydride were introduced. After stirring for a short time a violent reaction took place which was maintained under control by cooling to 40C and maintaining this temperatu~e. Stirring was continued for one hour. The brown crystal slurry was suction-filtered and the grey crystals obtained were washed out with ether. Then the crystals were introduced into 1 1 of water and adjusted to an acidic range while stirring by addition of 2N hydrochloric acid. 25 g of light brown crystals were obtained which yielded after recrystallization from acetonitrile colorless crystals of 4-acetoacetyl-n-decyl benzene having a melting point of 45 C.
The following compounds were prepared in analogous way:
a) 4-acetoacetyl-n-nonyl benzene colorless crystals mp: 26 C
b~ 4-acetoacetyl-n-octyl benzene colorless crystals mp: 39C
and when using trihalogen-acetic acid ethyl ester and sodium methylate the following compounds were obtained:
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) 1-(4_n-hexylphenyl)-4,4,4-trifluorobutane-1,3-dione f) 1_(4-n-hexylphenyl)-4,4~4-trichlorobutane-1,3-dione -: ,` ' ' .:
:
- . ~. ~ .. -. ; . ~ . ...
.. ~ , , . . . .. -~ \
EXAMPLE 17: (extraction) 50 g of 2,4-diisopropyl-benzoyl acetone were completed to 1 liter with petroleum. 50 ml of the orgaric phase thus obtained were shaken for 10 minutes in a separatory funnel with 50 ml of an aqueous phase which contained per liter 10 g of Cu , S g of Zn , 35 g (NH4~2C03 and 34 g of NH3- After separating the two phases the content of copper and zinc in the organic phase was determined. The organic phase had taken up 4.9 g of Cu2+ and 0.01 g of Zn, corresponding to a Cu/Zn separating factor of 490.
EXAMPLE 18: (extraction) 50 ml of an organic base prepared by dissolving 15 g of i-dodecyl-benzoyl acetone in 100 ml of petroleum was often brought into contact with an aqueous phase always fresh which contained per liter 10 g of Cu, 5 g of Zn, 35 g of (NH4)2C03 and 34 g of NH3, until the organic phase was saturated with copper. The quantitative determination showed that 10.9 g of Cu and 0.03 g of 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 shaken for 10 minutes in the volume ratio of 2:1 with an aqueous solution of 25 g of Cu2+/1 and 50 g of H2S04/1. After adjusting the reaction balance the aqueous phase contained per liter 46.3 g of Cu and 0.04 g of Zn. In the organic phase 0.94 g of Cu remained per liter; that means that 91.4 % of the copper were removed by a one-phase reextraction EXAMPLE 19: lextraction) ~.85 g of CuS04 5 H20 were dissolved with 1 % aque~us ammonia and completed to 1 liter. 50 ml of this solution were shaken for 5 minutes in a 1~7~Z36 separatory funnel in a volume ratio of 1:1 with a petrol solution of 5 g of acetoacetyl hexyl toluene in 100 ml of petroleum. The content of copper was subsequently determined in the aqueous phase; the value found was 1 mg of Cu/l. This means that the copper was converted into the organic phase nearly quantitatively, EXAMPLE 20: (extraction) 40 ml of an aqueous phase which contained 10 g of copper per liter and was adjusted to a pH value of 4.9 were superimposed in a beaker with 40 ml of organic phase prepared from 10 g of diisopropyl benzoyl acetone and 100 ml of petroleu~. With a magnetical stirrer the two phases were intimately mixed in the aqueous phase (dropwise addition of sodium hydroxide solution) while maintaining constant the pH value. When the reaction was completed -which was the case when the pH value did not decrease any longer after the addition of alkali the two phases were introduced into a separatory funnel and s0parated.
The quantitative determination of the copper yielded a content of 9.7 g of copper per liter of organic phase.
If the pH value was not maintained constant during the reaction the balance pH value was at 1.8 and only 1.1 g of copper/l passed to the organic phase.
EXAMPLE 21:
At -10 C 1 mol of diketene was added dropwise to 0.5 1 of hydrogen fluoride and then 151 g of a technical distillation mixture of alkyl benzene having a boiling point of 203 - 267 C and a content of aromatic compounds of a~out 80 C were added. After stirring for 10 hours at room temperature - .
'' ' ' ~- ' ' -the mixture was poured into ice water. After extraction with cyclohexane and subsequent distillation 135 g of a yellowish liquid having a boiling point of 100 C to 150 C/0.15 mm mercury were isolated, which according to the proton nuclear resonance spectroscopy represented a mixture of acetoacety-lated alkyl benzenes having an average number of about 8 carbon atoms in the alkyl radicals.
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the extraction of metals from their aqueous solutions which comprises contacting an aqueous solution containing metal ions with a compound of the general formula I
wherein R1 is an alkyl radical having 3 to 12 carbon atoms, R2 is hydrogen or an alkyl or alkoxy radical having 1 to 8 carbon atoms, R3 is hydrogen or an alkyl radical having 1 to 4 carbon atoms and Y is hydrogen, chlorine or fluo-rine, to obtain an organic and an aqueous phase, separating the two phases and separating the metal from the organic phase with acid.
wherein R1 is an alkyl radical having 3 to 12 carbon atoms, R2 is hydrogen or an alkyl or alkoxy radical having 1 to 8 carbon atoms, R3 is hydrogen or an alkyl radical having 1 to 4 carbon atoms and Y is hydrogen, chlorine or fluo-rine, to obtain an organic and an aqueous phase, separating the two phases and separating the metal from the organic phase with acid.
2. A process according to claim 1 wherein the compound of formula I
is in solution in an inert organic water-insoluble solvent when contacting the aqueous solution.
is in solution in an inert organic water-insoluble solvent when contacting the aqueous solution.
3. A process according to claim 1 wherein the sum of the carbon atoms present in the radicals R1, R2 and R3 is at least 6.
4. A process according to claim 1 or 2 wherein when Y is hydrogen, R2 is hydrogen or an alkyl group of 1 to 3 carbon atoms and at least one of R1, R2 and R3 is branched, the sum of the carbon atoms present in R1, R2 and R3 is not greater than 6.
A process according to claim 1 or 2 wherein R1, R2 and R3 are iso-propyl or isobutyl radicals.
6. A process according to claim 1 or 2 wherein R1 and R2 are isopro-pyl or isobutyl radicals and R3 is hydrogen.
7. A process according to claim 1 or 2 wherein the aqueous solution containing metal ions is contacted with a mixture of compounds of formula I.
8, A process according to claim 1 or 2 wherein the aqueous solution containing metal ions is contacted with a mixture of a compound of formula I
and a compound of formula V
wherein R1, R2 and K nave the meanings given above.
and a compound of formula V
wherein R1, R2 and K nave the meanings given above.
9. A process according to claim 1, 2 or 3 wherein the metal being extracted is copper, cobalt, nickel, iron, silver, beryllium, gallium, euro-pium, indium or zinc.
10. Compounds of the general formula I
wherein R1 is alkyl having 3 to 12 carbon atoms, R2 is hydrogen or alkyl or alkoxy having 1 to 8 carbon atoms, R3 is alkyl having 1 to 4 carbon atoms and Y is hydrogen, chlorine or fluorine; with the proviso that if R2 is hydro-gen, the sum of the carbon atoms of the alkyl radicals R1 and R3 is not greater than 5.
wherein R1 is alkyl having 3 to 12 carbon atoms, R2 is hydrogen or alkyl or alkoxy having 1 to 8 carbon atoms, R3 is alkyl having 1 to 4 carbon atoms and Y is hydrogen, chlorine or fluorine; with the proviso that if R2 is hydro-gen, the sum of the carbon atoms of the alkyl radicals R1 and R3 is not greater than 5.
11. Compounds according to claim 10 wherein when Y is hydrogen, at least one of R1 R2 and R3 is h branched alkyl radical and R3 is alkyl having 1 to 3 carbon atoms, the sum of the carbon atoms present in R1, R2 and R3 is not greater than 6.
12. Compounds according to claim 11 wherein R2 is alkyl or alkoxy of 1 to 3 carbon atoms,
13. 1-(2',4',6'-Triisopropylphenyl)-butanedione-1,3.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742451006 DE2451006A1 (en) | 1974-10-26 | 1974-10-26 | Benzoyl acetone derivs as extractants for metals - used esp for copper extn from acid or ammoniacal solns |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1071236A true CA1071236A (en) | 1980-02-05 |
Family
ID=5929288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA238,261A Expired CA1071236A (en) | 1974-10-26 | 1975-10-24 | Extraction process |
Country Status (3)
| Country | Link |
|---|---|
| BR (1) | BR7507002A (en) |
| CA (1) | CA1071236A (en) |
| DE (1) | DE2451006A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6716999B2 (en) | 1999-12-06 | 2004-04-06 | Lonza Ag | Pyrone derivatives and method for producing same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE411231B (en) * | 1978-05-02 | 1979-12-10 | Mx Processer Reinhardt | PROCEDURE FOR RECYCLING AN AMMONIAL - CALTIC BATH |
| DE2918775A1 (en) * | 1979-05-10 | 1980-11-20 | Merck Patent Gmbh | DIKETONES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS COMPONENT LIQUID CRYSTAL IN DIELECTRICS |
| SE420737B (en) * | 1980-03-18 | 1981-10-26 | Mx Processer Reinhardt | PROCEDURE FOR EXTRACTION OF COPPER FROM AN AMMONIACAL COPPER SOLUTION AND MEANS FOR EXECUTING THE PROCEDURE |
| US4622344A (en) * | 1984-03-05 | 1986-11-11 | Bend Research, Inc. | Recovery of ammoniacal copper with novel organogels |
| US5281571A (en) * | 1990-10-18 | 1994-01-25 | Monsanto Company | Herbicidal benzoxazinone- and benzothiazinone-substituted pyrazoles |
| ATE264850T1 (en) * | 1999-12-06 | 2004-05-15 | Lonza Ag | PYRON DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF |
-
1974
- 1974-10-26 DE DE19742451006 patent/DE2451006A1/en active Pending
-
1975
- 1975-10-24 CA CA238,261A patent/CA1071236A/en not_active Expired
- 1975-10-24 BR BR7507002*A patent/BR7507002A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6716999B2 (en) | 1999-12-06 | 2004-04-06 | Lonza Ag | Pyrone derivatives and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2451006A1 (en) | 1976-04-29 |
| BR7507002A (en) | 1976-08-17 |
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