WO1984001946A1 - New chelate forming bisquinoline compounds and processes for recovering metals - Google Patents

New chelate forming bisquinoline compounds and processes for recovering metals Download PDF

Info

Publication number
WO1984001946A1
WO1984001946A1 PCT/SE1983/000386 SE8300386W WO8401946A1 WO 1984001946 A1 WO1984001946 A1 WO 1984001946A1 SE 8300386 W SE8300386 W SE 8300386W WO 8401946 A1 WO8401946 A1 WO 8401946A1
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
group
mixture
bis
quinolinyloxy
Prior art date
Application number
PCT/SE1983/000386
Other languages
French (fr)
Inventor
Sverker Hoegberg
Bjoern Elman
Hay Liem
Khorshed Madan
Christina Moberg
Mamoun Muhammed
Birger Sjoeberg
Michael Weber
Original Assignee
Sverker Hoegberg
Bjoern Elman
Hay Liem
Khorshed Madan
Christina Moberg
Mamoun Muhammed
Birger Sjoeberg
Michael Weber
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sverker Hoegberg, Bjoern Elman, Hay Liem, Khorshed Madan, Christina Moberg, Mamoun Muhammed, Birger Sjoeberg, Michael Weber filed Critical Sverker Hoegberg
Publication of WO1984001946A1 publication Critical patent/WO1984001946A1/en

Links

Classifications

    • 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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • 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
    • C22B3/36—Heterocyclic compounds
    • C22B3/362—Heterocyclic compounds of a single type
    • C22B3/364—Quinoline
    • 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

Definitions

  • the present invention relates to new organic bisquinoline compounds with chelate forming abilities.
  • the new compounds are intended for use as key chemicals, e.g. reagents or specialty chemicals, in different technical processes.
  • An important feature of the new compounds is that they exhibit improved selectivity effects when binding to metal ions or ionic compounds such as solid or dissolved metal salts, minerals, and metal surfaces, when compared with previously known compounds.
  • the improved selectivity applies especially to ions and ionic compounds of certain heavy metals, such as copper and zinc, over ions and ionic compounds of other metals and non-metals, such as ferrous and ferric ions.
  • the compounds described in the present invention also exhibit selectivity for copper and zinc over cadmium, nickel, cobalt, chromium, manganese, alkali and alkaline earth metals.
  • one object of the present invention is to provide new chelate forming agents for selectively separating heavy metal ions or ionic compounds from a mixture of metal ions or ionic compounds.
  • Another feature is to provide a process for selectively separating heavy metal ions and ionic compounds from a mixture of metal ions and ionic compounds.
  • this invention relates to processes for extracting metal ions from aqueous solutions, e.g. from aqueous solutions obtained on recovering metals from ores and from natural, industrial or urban effluents.
  • the processes involve treatment of the aqueous solution with a water immiscible organic solution of the extracting agent or reagent of the invention and subsequent separation of the aqueous phase from the organic phase containing the complexed metal ions.
  • the new chelate forming agents are bisquinaldic acids which may be represented by the general formula I:
  • R is a lipophilizing hydrocarbon group which may be aliphatic or aromatic, straight or branched, saturated or unsaturated.
  • the chelate forming agent should preferably have at least one or two lipophilizing groups R and R should be an alkyl or alkenyl group with 3-24 carbon atoms, optimally 6-18.
  • Suitable R groups are decyl, 3-(5,5,7,7-tetramethyt-loctenyl) and 1-(5,5,7,7-tetramethyl-2-octenyl) groups.
  • the total number of carbon atoms in all R groups should not exceed 40.
  • primary structure elements special, so called primary, structure elements, the function of which is to direct and limit the coordination geometry of the metal complex by sterical influence.
  • secondary structure elements which are decided by and adapted for the technical processes for which the compounds are intended.
  • the secondary structure elements modify the physical properties of the compounds such as solubility, hydrophobicity etc., properties determining the distribution of the compounds between different phases in multiple phase systems such as oil/ water, solid phase/liquid phase.
  • the secondary elements are designed and positioned so that they do not interfere with the function of the primary structure elements and with the bonding ability of the compounds.
  • An essential feature of the structure of the compounds of the invention is the primary structure element, the flexible molecular chain joining the two quinoline nuclei in the 8-positions.
  • This chain should be an ⁇ , ⁇ -bisoxy or -bisthio group with at least two carbon atoms.
  • the substituents in the 3-, 4-, 5- and 6-positions of the quinoline nuclei are not critical and are chosen to give sufficient lipophilicity to the reagent.
  • the selectivity of the tetradentate bisquinaldic acids is related to their ability to disfavour the extraction of certain hexacoordinating metal ions such as Fe 3+ and Fe 2+ ions, while simultaneously enhancing the extraction of certain tetracoordinating metal ions such as Cu 2+ and Zn 2+ ions.
  • This discriminating effect may be rationalized by the fact that in a one-to-one complex between a hexacoordinating metal ion and a tetradentate organic reagent, only four out of six ligand sites, which are occupied by hydrophilic inorganic ligands in the original aquo-complex, are replaced by the lipophilizing organic reagent. Such a mixed and consequently only partially lipophilized metal ion complex is then less likely to be extracted into an organic phase relative to the fully lipophilized one-to-one complex resulting from the complexation by the same tetradentate reagent with a tetracoordinating metal ion.
  • the tetradentate bisquinaldic acid derivatives of the present invention may be obtained by hydrolysis of the corresponding dinitriles, which are prepared by alkylation of 8hydroxyquinaldonitriles with the appropriate ditosylates or dihalides.
  • the 8-hydroxyquinaldonitriles are synthesized from 8-hydroxyquinolines, which can be synthezised by literature methods or are commercially available.
  • the 8-hydroxyquinolines are oxidized to the N-oxides, which are transformed into 8-hydroxy-l-methoxy-quinolinium methyl sulfates using dimethyl sulfate. Reaction with sodium cyanide gives 8-hydroxy-2-cyanoquinolines.
  • An alternative route for the preparation of the reagents involve alkylation of 2-nitrophenols or 2-aminothiophenols with an ⁇ , ⁇ -dihalide and, after reduction of the former to the corresponding bis-aniline compound, reaction with diethyl oxalacetic acid sodium salt or dimethyl acetylene dicarboxylate, followed by 0-alkylation with an appropriate alkyl halide and hydrolysis of the ester groups.
  • the new quinaldic acids are excellent reagents for the solvent extraction of metal ions that can form a complex compound soluble in an organic solvent, in particular copper(II) and zinc (II) .
  • Any organic solvent or mixture of solvents may be used which is immiscible with water and chemically stable. Nonflammability and low toxicicy are desirable properties.
  • Modifiers such as long chain aliphatic alcohols, which improve solubility, phase separation and general extraction performance may be added, suitably in amounts from 0.4 to 20% by weight of the organic solvent. Emulsification may be reduced by the addition of surface active agents such as ethylene oxide/alkyl phenyl condensates. Solubility and extraction performance may be further enhanced by using mixtures of quinaldic acids with different lipophilizing substituents R 3 -R 6 and A.
  • the process of the invention may be applied to aqueous leach solutions of minerals, scrap metal or other metai-containing by-products or residues obtained by treatment thereof with acids such as sulfuric, sulfurous, hydrochloric or nitric acids.
  • the extraction may be performed in any pH range in which the metal hydroxides are not precipitated.
  • the pH may be chosen in such a way that only the desired metal ion is extracted; a convenient pH range is 1-5.
  • the process is in general particularly suitable for the recovery of metals from solutions containing at least 5 g per litre.
  • the liquid-liquid contacting mixture should be mixed intimately to obtain maximum mass transfer. It should also be given a sufficiently long setting or quiescent period to allow the phases to separate. These conditions may be fulfilled by using mixer-settlers, differential contactors or centrifugal separators.
  • the organic phase is stripped with a strong aqueous acid.
  • the organic phase may then be conditioned in a wash step to remove complexed acid prior to the next loading step.
  • the extraction process is essentially a steady-state process and should be run as a continous, rather than batch, operation. If a series of mixer-settlers are used they should always be run with countercurrent flows for maximum efficiency.
  • the metal ion selectivities expressed by the present class of chelating compounds can be advantageously used in other separation processes such as liquid or solid supported membrane technique and ore flotation.
  • the specific compounds used in these other separation methods are derived from parent structures possessing the same primary structural elements as described above, but with different secondary elements specifically adopted for the actual process.
  • the dinitrile was hydrolyzed to the dicarboxylic acid by potassium hydroxide (KOH) in aq. ethanol at 70oC until the evolution of ammonia had ceased (40 h).
  • KOH potassium hydroxide
  • the reaction mixture was poured into water, neutralized with 2M HCl, and the product, 1,3-bis(2-carboxy-8-quinolinyloxy) propane m.p. 181-2°C (R 418), crystallized.
  • Anal. Calc. for C 23 H 18 N 2 O 6 C:66.02, H:4.34, N:6.70. Found: C:65.93, H:4.40, N:6.66.
  • 1,4-Bis (2-cyano-8-quinolinyloxy) butane was prepared by the method described in example 1 using 1,4-dibromobutane in place of 1,3-propanediol ditosylate. Yield: 75%, m.p. 233°C (DMF).
  • Anal. Calc. for C 24 H 18 O 2 N 4 C:73.08, H:4.60, N.14.21. Found: C:72.92, H:4.59, N.14.17.
  • 1,8-Bis (2-cyano-8-quinolinyloxy) octane was prepared by the method described in example 1 using 1,8-dibromooctane in place of 1,3-propanediol ditosylate. Yield: 98%, m.p. 166168.5°C (CH 3 CN).
  • Anal. Calc. for C 28 H 26 O 2 N 4 C:74.64, H:5.82. Found: C:73.61, H:5.76.
  • 1,10-Bis(2-cyano-8-quinolinyloxy) decane was prepared by the method described in example 1 using 1,10-decanediol ditosylate (E.J.P. Fear, J. Thrower and J. Veitch, J. Chem. Soc. (1958) 1325) in place of 1,3-propanediol ditosylate. Yield: 59%, m.p. 150-5°C (toluene).
  • Anal. Calc. for C 30 H 30 N 4 O 2 C:75.29, H:6.32, N:11.71. Found: C:75.3, H:6.3, N:11.6.
  • 1,10-Bis(2-carboxy-8-quinolinyloxy) decane (R 516) was obtained by hydrolysis of the nitrile with KOH in glycol at 135140°C for 15 h. Yield: 72%, m.p. 172-8°C (CH 3 COOH-H 2 O and CHCl 3 ). Methyl ester: M.p. 114-5°C.
  • Anal. Calc. for C 32 H 36 N 2 O 6 C:70.57, H:6.66, N:5.14. Found: C: 70.50, H: 6.62, N:5.09.
  • 1,8-Bis(2-cyano-8-quinolinyloxy)-3,6-dioxaoctane was obtained by the method described in example 1 using triethyleneglycol ditosylate in place of 1,3-propanediol ditosylate. Yield: 60%, m.p. 143-6°C (toluene) Anal. Calc. for C 26 H 22 N 4 O 4 : C:68.7, H:4.9, N:12.3, O:14.1. Found: C:68.5,
  • 1,8-Bis(2-carboxy-8-quinolinyloxy)-3,6-dioxaoctane (R 492) was obtained by hydrolysis of the nitrile with Claisen's alkali: H 2 O 2:1 at 80°C for 27 h. Yield: 70%, m.p. 148-9°C (EtOH).
  • 1,11-Bis(2-cyano-8-quinolinyloxy)-3,6,9-trioxaundecane was obtained by the method described in example 1 using tetraethyleneglycol ditosylate in place of 1,3-propanediol ditosylate. Yield: 68%, m.p. 137-140°C (toluene).
  • Anal. Calc. for C 28 H 26 N 4 O 5 C:67.5, H:5.3, N:11.2. Found: C: 68.0 , H: 5.3,
  • 1,11-Bis(2-carboxy-8-quinolinyloxy)-3,6,9-trioxaundecane (R 536) was obtained by hydrolysis of the nitrile with KOH in EtOH:H 2 O 1:1 at 80°C during 66 h. Yield: 87%, m.p. 132 ⁇
  • 1,8-Bis(2-cyano-8-quinolinyloxy)-3,6-dioxa-4-(1-decyl) octane was obtained by the method described in example 1 using 1,2-bis(2-hydroxyethoxy) dodecane ditosylate (M.Cinquini and P. Tundo, Synthesis (1976) 516) in place of 1,3-propanediol ditosylate. Yield: 80% (oil) .
  • 1,8-[2-Cyano-7-(3-(5,5,7,7-tetramethyl-l-octenyl))-8-quinolinyloxy]octane was prepared from 7-[3-(5,5,7,7-tetramethyll-octenyl)]-8-hydroxyquinoline-2-carbonitrile (SE patent application 8206378-5) (19.09 g, 56.7 mmol), 1,8-dibromooctane (8.02 g, 29.5 mmol) and K 2 CO 3 (8.15 g, 59 mmol) in DMF (75 ml) at 75°C during 18 h. The product was isolated by toluene extraction and purified by chromatagraphy on silica gel with toluene: ethyl acetate 60:1 as eluant. Yield:
  • 1,11-Bis[2-cyano-7-(3-(5,5,7,7-tetramethyl-l-octenyl))-8quinolinyloxy]-3,6,9-trioxaundecane was prepared by the method described in example 10 using tetraethyleneglycol ditosylate in place of diethyleneglycol ditosylate. Yield: 77%.
  • 1,3-Bis(2-carbethoxy-4-hydroxy-8-quinolinyloxy) propane was prepared by the Conrad-Limpach-Knorr reaction (B. Riegel, C.J. Albisetti, G.R. Lappin and R.H. Baker, J. Amer. Chem. Soc. 68 (1946) 2685 and G.F. Lisk and G.W. Stacy, J. Amer. Chem. Soc. 68 (1946) 2686).
  • K 2 CO 3 (5.52 g, 40 mmol) was added to 2-nitrophenol (5.56 g, 40 mmol) in DMF (20 ml), 1,3dibromopropane was added and the reaction mixture kept at 70oC.
  • the 4-hydroxy compound was alkylated (K 2 CO 3 /DMF) with 1chloro-5,5,7,7-tetramethyl-2-octane at 85°C overnight.
  • the crude product was hydrolyzed with KOH-EtOH-H 2 O at reflux during 5 h.
  • 1,3-Bis[2-carboxy-4-(1-(5,5,7,7-tetramethyl-2octenyloxy))-8-quinolinyloxy]propane (R 794) precipitated on addition of water and dilute H 2 SO 4 to pH 3, 1.98 g (94% yield), m.p. 167-9°C
  • 1,2-Di(o-aminophenylthio) ethane (0.91 g, 3.3 mmol) and dimethyl acetylene dicarboxylate (0.95 ml, 7.0 mmol) were refluxed in methanol (30 ml) for one day. The solvent was evaporated and the residue was dissolved in ether-CH 2 Cl 2 and washed with 2M HCl. Recrystallization from methanol afforded the anilino butenedioate (1.37 g, 74% yield), m.p. 119°C.
  • aqueous solution of a mixture of equal parts of metal sulfates (Cu 2+ , Zn 2+ , Fe 2+ , Ni 2+ and Co 2+ ) was prepared by dissolving the metal salts in dilute sulfuric acid. The metal concentrations were kept around 2 mM and the pH of the solution was adjusted to about 2. A 10 mM solution of the appropriate reagent in chloroform was prepared and the two phases were agitated until equilibrium was reached. The two phases were then separated by centrifugation and the distribution of each metal between the two phases was determined. The percentage of metal ions extracted is given below.
  • Equal amounts of sulfate salts of metals (Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ and Cd 2+ ) were dissolved in dilute sulfuric acid at pH 4. This solution was equilibrated at 25°C with a chloroform solution of the ligand concerned. The two phases were separated and the distribution of each metal between the two phases was determined. The percentage of metal ions extracted from the water phase is given below.
  • a series of single metal sulfate solutions were prepared and contacted with a chloroform solution of R 488.
  • the equilibrium pH value of the aqueous phase was adjusted to a given value.
  • the amount of metal extracted at a given pH value was determined.
  • the pH 50 values (the pH value at which 50% of the metal is extracted) for each metal were calculated and are given below.
  • a plastic film containing the selective reagent dissolved in chloroform was placed between two solutions so that any transport of ions would occur only through the membrane.
  • the first solution contained the metal ions in acidic sulfate solution, while the second contained only concentrated sulfuric acid. Efter some time the metal ions were transfered from the feed solution into the sulfuric acid solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Novel quinoline compounds having the general formula I, wherein R3, R4, R5 and R6, which may differ or be identical, are selected from the group consisting of hydrogen, R and OR, X is selected from the group consisting of O and S, and A is selected from the group consisting of (CH2)n, CH2CH2(OCH2CH2)p and CH2CH2OCHRCH2, wherein n=2-10, and p=1-3. R is a lipophilizing hydrocarbon which may be aliphatic or aromatic, straight or branched, saturated or unsaturated. The compounds of the formula I may be used as chelate forming agents.

Description

NEWCHELATE FORMINGBISQUINOLINE COMPOUNDSANDPROCESSES FORRECOVERINGMETALS
The present invention relates to new organic bisquinoline compounds with chelate forming abilities. The new compounds are intended for use as key chemicals, e.g. reagents or specialty chemicals, in different technical processes.
An important feature of the new compounds is that they exhibit improved selectivity effects when binding to metal ions or ionic compounds such as solid or dissolved metal salts, minerals, and metal surfaces, when compared with previously known compounds. The improved selectivity applies especially to ions and ionic compounds of certain heavy metals, such as copper and zinc, over ions and ionic compounds of other metals and non-metals, such as ferrous and ferric ions. The compounds described in the present invention also exhibit selectivity for copper and zinc over cadmium, nickel, cobalt, chromium, manganese, alkali and alkaline earth metals.
In view of the technical and economical importance of heavy metals and their impact on the environment, selective processes for their recovery from low grade and/or complex deposits are of utmost importance.
Thus, one object of the present invention is to provide new chelate forming agents for selectively separating heavy metal ions or ionic compounds from a mixture of metal ions or ionic compounds.
Another feature is to provide a process for selectively separating heavy metal ions and ionic compounds from a mixture of metal ions and ionic compounds.
Since the new compounds are also excellent extraction agents, further objects of the invention are to provide new extracting agents and new extracting processes based on the use of the new bisquinoline compounds of the present invention. In particular this invention relates to processes for extracting metal ions from aqueous solutions, e.g. from aqueous solutions obtained on recovering metals from ores and from natural, industrial or urban effluents. The processes involve treatment of the aqueous solution with a water immiscible organic solution of the extracting agent or reagent of the invention and subsequent separation of the aqueous phase from the organic phase containing the complexed metal ions.
The new chelate forming agents are bisquinaldic acids which may be represented by the general formula I:
Figure imgf000004_0001
wherein R3, R4, R5 and R6, which may differ or be indentical, are selected from the group consisting of hydrogen, R and OR, X is selected from the group consisting of 0 and S, and A is selected from the group consisting of (CH2)n, CH2CH2(OCH2CH2)p and CH2CH2OCHRCH2, wherein n=2-10 and p=1-3. R is a lipophilizing hydrocarbon group which may be aliphatic or aromatic, straight or branched, saturated or unsaturated.
The chelate forming agent should preferably have at least one or two lipophilizing groups R and R should be an alkyl or alkenyl group with 3-24 carbon atoms, optimally 6-18. Suitable R groups are decyl, 3-(5,5,7,7-tetramethyt-loctenyl) and 1-(5,5,7,7-tetramethyl-2-octenyl) groups. The total number of carbon atoms in all R groups should not exceed 40.
The following list discloses some of the compounds according to the invention which have particularly interesting properties:
1,3-bis(2-carboxy-8-quinolinyloxy)propane,1,3-bis[2-carboxy4-(1-hexyloxy)-8-quinolinyloxy]propane, 1,3-bis[2-carboxy4- (1-dodecyloxy)-8-quinolinyloxy]propane, 1,3-bis[2-carboxy-4-(1-(5,5,7,7-tetramethyl-2-octenyloxy))-8-quinolinyloxy]propane, 1,4-bis(2-carboxy-8-quinolinyloxy)butane, 1,8-bis(2-carboxy-8-quinolinyloxy) octane, 1,8-bis (2-carboxy-8-quinolinyloxy)-3,6-dioxaoctane, 1,8-bis[2-carboxy-4-(1-(5,5,7,7tetramethyl-2-octenyloxy))-8-quinolinyloxy]-3,6-dioxaoctane, 1,8-bis[2-carboxy-3-(1-propyl)-4-(1-(5,5,7,7-tetramethyl-2octenyloxy))-8-quinolinyloxy]-3,6-dioxaoctane, 1,8-bis[2carboxy-3-(3-(5,5,7,7-tetramethyl-1-octenyl))-4-hexyloxy-8quinolinyloxy]-3,6-dioxaoctane, 1,8-bis[2-carboxy-5-(1hexyloxy) 8-quinolinyloxy]-3,6-dioxaoctane, 1,8-bis[2-carboxy-5-(1-dodecyloxy)-8-quinolinyloxy]-3,6-dioxaoctane, 1,8bis[2-carboxy-5-(1-(5,5,7,7-tetramethyl 1-octenyloxy))-8quinolinyloxy]-3,6-dioxaoctane, 1,8-bis[2-carboxy-5-(l-hexyloxy) -6-(5,5,7,7-tetramethyl-l-octenyl))-8-quinolinyloxy]3,6-dioxaoctane, 1,11-bis(2-carboxy-8-quinolinyloxy)-3,6,9trioxaundecane and 1,2-di[2-carboxy-4-(1-(5,5,7,7-tetramethyl-2-octenyloxy))-8-quinolinylthio)lethane
In brief, the improved selectivity of the new compounds according to the present invention can be ascribed to
a) the metal bonding groups in the reagent, that is the quinoline nitrogen and the carboxylic oxygen, and
b) special, so called primary, structure elements, the function of which is to direct and limit the coordination geometry of the metal complex by sterical influence. In addition to the primary structure elements, the function of which is common for all compounds according to the present invention, there are secondary structure elements which are decided by and adapted for the technical processes for which the compounds are intended. The secondary structure elements modify the physical properties of the compounds such as solubility, hydrophobicity etc., properties determining the distribution of the compounds between different phases in multiple phase systems such as oil/ water, solid phase/liquid phase. The secondary elements are designed and positioned so that they do not interfere with the function of the primary structure elements and with the bonding ability of the compounds.
An essential feature of the structure of the compounds of the invention is the primary structure element, the flexible molecular chain joining the two quinoline nuclei in the 8-positions. This chain should be an α,ω-bisoxy or -bisthio group with at least two carbon atoms.
Another essential feature of the present compounds is the lack of substituent in the 7-positions. It has been found that a substituent in this position dramatically decreases the extracting power. A possible theoretical explanation to this effect is that the substituent in the 7-position prevents complexation by sterical hindrance in the sensitive complex-binding area. The 7-positions must therefore be avoided when the secondary lipophilizing elements are introduced into the parent molecule.
The substituents in the 3-, 4-, 5- and 6-positions of the quinoline nuclei are not critical and are chosen to give sufficient lipophilicity to the reagent.
It is believed that the selectivity of the tetradentate bisquinaldic acids is related to their ability to disfavour the extraction of certain hexacoordinating metal ions such as Fe3+ and Fe2+ ions, while simultaneously enhancing the extraction of certain tetracoordinating metal ions such as Cu 2+ and Zn2+ ions.
This discriminating effect may be rationalized by the fact that in a one-to-one complex between a hexacoordinating metal ion and a tetradentate organic reagent, only four out of six ligand sites, which are occupied by hydrophilic inorganic ligands in the original aquo-complex, are replaced by the lipophilizing organic reagent. Such a mixed and consequently only partially lipophilized metal ion complex is then less likely to be extracted into an organic phase relative to the fully lipophilized one-to-one complex resulting from the complexation by the same tetradentate reagent with a tetracoordinating metal ion.
The tetradentate bisquinaldic acid derivatives of the present invention may be obtained by hydrolysis of the corresponding dinitriles, which are prepared by alkylation of 8hydroxyquinaldonitriles with the appropriate ditosylates or dihalides. The 8-hydroxyquinaldonitriles are synthesized from 8-hydroxyquinolines, which can be synthezised by literature methods or are commercially available. The 8-hydroxyquinolines are oxidized to the N-oxides, which are transformed into 8-hydroxy-l-methoxy-quinolinium methyl sulfates using dimethyl sulfate. Reaction with sodium cyanide gives 8-hydroxy-2-cyanoquinolines.
An alternative route for the preparation of the reagents involve alkylation of 2-nitrophenols or 2-aminothiophenols with an α,ω-dihalide and, after reduction of the former to the corresponding bis-aniline compound, reaction with diethyl oxalacetic acid sodium salt or dimethyl acetylene dicarboxylate, followed by 0-alkylation with an appropriate alkyl halide and hydrolysis of the ester groups.
The new quinaldic acids are excellent reagents for the solvent extraction of metal ions that can form a complex compound soluble in an organic solvent, in particular copper(II) and zinc (II) .
Any organic solvent or mixture of solvents may be used which is immiscible with water and chemically stable. Nonflammability and low toxicicy are desirable properties.
Modifiers such as long chain aliphatic alcohols, which improve solubility, phase separation and general extraction performance may be added, suitably in amounts from 0.4 to 20% by weight of the organic solvent. Emulsification may be reduced by the addition of surface active agents such as ethylene oxide/alkyl phenyl condensates. Solubility and extraction performance may be further enhanced by using mixtures of quinaldic acids with different lipophilizing substituents R3-R6 and A.
Since acid is liberated during the extraction process, it may be necessary to add alkali to maintain the pH of the aqueous phase at the proper level.
Generally solutions containing from 5 to 50% by weight of the quinaldic acids are most effective. The extraction is conveniently carried out at ambient or near ambient temperatures but elevated temperatures may sometimes be required to improve the solubility of the extracted complexes.
The process of the invention may be applied to aqueous leach solutions of minerals, scrap metal or other metai-containing by-products or residues obtained by treatment thereof with acids such as sulfuric, sulfurous, hydrochloric or nitric acids. The extraction may be performed in any pH range in which the metal hydroxides are not precipitated. The pH may be chosen in such a way that only the desired metal ion is extracted; a convenient pH range is 1-5.
The process is in general particularly suitable for the recovery of metals from solutions containing at least 5 g per litre.
The liquid-liquid contacting mixture should be mixed intimately to obtain maximum mass transfer. It should also be given a sufficiently long setting or quiescent period to allow the phases to separate. These conditions may be fulfilled by using mixer-settlers, differential contactors or centrifugal separators.
To recover the extracted metal from the chelate, the organic phase is stripped with a strong aqueous acid. The organic phase may then be conditioned in a wash step to remove complexed acid prior to the next loading step.
Due to the dependance on a constant distribution coefficient and on proper timing for phase separation, the extraction process is essentially a steady-state process and should be run as a continous, rather than batch, operation. If a series of mixer-settlers are used they should always be run with countercurrent flows for maximum efficiency.
The metal ion selectivities expressed by the present class of chelating compounds can be advantageously used in other separation processes such as liquid or solid supported membrane technique and ore flotation. The specific compounds used in these other separation methods are derived from parent structures possessing the same primary structural elements as described above, but with different secondary elements specifically adopted for the actual process.
The invention is illustrated but not limited by the following examples.
Example 1
8-Hydroxγquinoline (87 g, 0.6 mol) in acetic acid (180 ml) was heated to 65-70°C. 35% H2O2 (46 ml) was added and another two portions of 35% H2O2 (2 x 36 ml) were added after 1 h 20 min and 2 h 40 min respectively. The reaction mixture was kept at 65-70°C for 5 h and then left at room temperature overnight. Evaporation of the solvent gave 117 g of an oil which was partly dissolved in CH2Cl2 (0.6 1). This solution was washed with 10% Na2CO3 (100 + 50 ml) and dried. The solvent was evaporated and the residue extracted with boiling water (0.7 + 0.3 1). 8-Hydroxyquinoline-l-oxide precipitated as yellow crystals (24 g, 28%), m.p.130-7ºC
(A.N. Bhat and B.D. Jain, J. Scient. Ind. Res. 19B (1960)16 and K. Ramaiah and V.R. Srinivasan, Proc. Indian Acad. Sci. A55 (1962) 360).
Dimethyl sulfate (4-5% excess) was added to 8-hydroxyquinoline-l-oxide, (55 g, 0.34 mol) and the mixture was heated to 75ºC for 3.5 h. When the mixture was allowed to reach room temperature 8-hydroxy-l-methoxyquinolinium methyl sulfate slowly crystallized. The product was washed with ether and dissolved in water (200 ml). This solution was added to sodium cyanide (50 g, 1 mol) in water (200 ml) at -5ºC during 45 min. After stirring at 0°C for a further 2 h, a 1:1 mixture of acetic acid and water (100 ml) was added. The precipitate formed was filtered off, washed with water and dried
Recrystallization of the crude product (54 g) from petroleum ether 100-125ºC (1.6 1) with decolorizing carbon gave 8hydroxyquinoline-2-carbonitrile (47 g, 0.27 mol, 80%), m.p. 134-5 C (V.M. Dziomko, J.A. Krasavin and Yu. Radin, Chem. Abstr. 65 (1966) 5437, 7139).
8-Hydroxyquinoline-2-carbonitrile (3.40 g, 20 mmol) and potassium carbonate (3.04 g, 22 mmol) in dimethylformamide
(DMF) (35 ml) were stirred and heated to 75°C. 1,3-propanediol ditosylate was added during 25 min and the reaction was continued for an additional 20 h. The reaction mixture was cooled and poured into ice-water (300 ml). The precipipated product was filtered off and recrystallized to give 1,3-bis(2-cyano-8-quinolinyloxy) propane (62%), m.p. 221-4ºC (acetone). Anal. Calc. for C23H16N4O2: C:72.6, H: 4.2, N:14.7. Found: C:73.1, H:4.2, N:14.8.
The dinitrile was hydrolyzed to the dicarboxylic acid by potassium hydroxide (KOH) in aq. ethanol at 70ºC until the evolution of ammonia had ceased (40 h). The reaction mixture was poured into water, neutralized with 2M HCl, and the product, 1,3-bis(2-carboxy-8-quinolinyloxy) propane m.p. 181-2°C (R 418), crystallized. Anal. Calc. for C23H18N2O6: C:66.02, H:4.34, N:6.70. Found: C:65.93, H:4.40, N:6.66.
Example 2
1,4-Bis (2-cyano-8-quinolinyloxy) butane was prepared by the method described in example 1 using 1,4-dibromobutane in place of 1,3-propanediol ditosylate. Yield: 75%, m.p. 233°C (DMF). Anal. Calc. for C24H18O2N4: C:73.08, H:4.60, N.14.21. Found: C:72.92, H:4.59, N.14.17.
1,4-Bis(2-carboxy-8-quinolinyloxy)butane, m.p. 201-3ºC (MeOH) (R 432). Anal. Calc. for C24H20N2O6 : C: 66.66, H: 4.66, N:6.48. Found: C:66.57., H:4.66, N:6.39.
Example 3
1,8-Bis (2-cyano-8-quinolinyloxy) octane was prepared by the method described in example 1 using 1,8-dibromooctane in place of 1,3-propanediol ditosylate. Yield: 98%, m.p. 166168.5°C (CH3CN). Anal. Calc. for C28H26O2N4 : C:74.64, H:5.82. Found: C:73.61, H:5.76.
1,8-Bis(2-carboxy-8-quinolinyloxy) octane (R 488) was obtained by hydrolysis of the nitrile in 84% yield, m.p. 173-6°C (CH3COOH, H2O). Anal. Calc. for C28H28N2O6: C : 68.84, H: 5.78, N:5.74. Found: C:68.41, H:5.82, N:5.62. Example 4
1,10-Bis(2-cyano-8-quinolinyloxy) decane was prepared by the method described in example 1 using 1,10-decanediol ditosylate (E.J.P. Fear, J. Thrower and J. Veitch, J. Chem. Soc. (1958) 1325) in place of 1,3-propanediol ditosylate. Yield: 59%, m.p. 150-5°C (toluene). Anal. Calc. for C30H30N4O2: C:75.29, H:6.32, N:11.71. Found: C:75.3, H:6.3, N:11.6.
1,10-Bis(2-carboxy-8-quinolinyloxy) decane (R 516) was obtained by hydrolysis of the nitrile with KOH in glycol at 135140°C for 15 h. Yield: 72%, m.p. 172-8°C (CH3COOH-H2O and CHCl3). Methyl ester: M.p. 114-5°C. Anal. Calc. for C32H36N2O6: C:70.57, H:6.66, N:5.14. Found: C: 70.50, H: 6.62, N:5.09.
Example 5
1,5-Bis (2-cyano-8-quinolinyloxy)-3-oxapentane was obtained by the method described in example 1 using diethyleneglycol ditosylate (J. Dale and P.O. Kristansen, Acta Chem. Scand.
26 (1972) 1471) in place of 1,3-propanediol ditosylate.
Yield: 60%, m.p. 192-4°C (acetone). Anal. Calc. for
C24H18N4O3: C:70-23, H:4.42, N:13.65. Found: C:70.6, H:4.5, N:13.6.
1,5-Bis(2-carboxy-8-quinolinyloxy)-3-oxapentane (R 448) was obtained by hydrolysis of the nitrile with Claisen's alkali at 80°C for 1 week. Yield: 38%, m.p. 170-2°C (EtOH and benzene). Anal. Calc. for C24H20N2O7: C:64.3, H:4.5, N:6.3. Found: C:64.0, H:4.5, N:6.2.
Example 6
1,8-Bis(2-cyano-8-quinolinyloxy)-3,6-dioxaoctane was obtained by the method described in example 1 using triethyleneglycol ditosylate in place of 1,3-propanediol ditosylate. Yield: 60%, m.p. 143-6°C (toluene) Anal. Calc. for C26H22N4O4: C:68.7, H:4.9, N:12.3, O:14.1. Found: C:68.5,
H:4.9, N:12.3, 0: 13.9.
1,8-Bis(2-carboxy-8-quinolinyloxy)-3,6-dioxaoctane (R 492) was obtained by hydrolysis of the nitrile with Claisen's alkali: H2O 2:1 at 80°C for 27 h. Yield: 70%, m.p. 148-9°C (EtOH). Anal. Calc. for C26H24N2°8: C:63.4, H:4.9, N:5.7, 0:26.0. Found: C:63.4, H:4.9, N:5.6, 0:26.2.
Example 7
1,11-Bis(2-cyano-8-quinolinyloxy)-3,6,9-trioxaundecane was obtained by the method described in example 1 using tetraethyleneglycol ditosylate in place of 1,3-propanediol ditosylate. Yield: 68%, m.p. 137-140°C (toluene). Anal. Calc. for C28H26N4O5: C:67.5, H:5.3, N:11.2. Found: C: 68.0 , H: 5.3,
N:11.1.
1,11-Bis(2-carboxy-8-quinolinyloxy)-3,6,9-trioxaundecane (R 536) was obtained by hydrolysis of the nitrile with KOH in EtOH:H2O 1:1 at 80°C during 66 h. Yield: 87%, m.p. 132¬
5°C (benzene). Anal. Calc. for C28H28N2°9: C:62.7, H:5.3, N:5.2. Found: C:62.7, H:5.3, N:5.2.
Example 8
1,8-Bis(2-cyano-8-quinolinyloxy)-3,6-dioxa-4-(1-decyl) octane was obtained by the method described in example 1 using 1,2-bis(2-hydroxyethoxy) dodecane ditosylate (M.Cinquini and P. Tundo, Synthesis (1976) 516) in place of 1,3-propanediol ditosylate. Yield: 80% (oil) .
1,8-Bis(2-carboxy-8-quinolinyloxy)-3,6-dioxa-4-(1-decyl)octane (R 632) was obtained by hydrolysis of the nitrile with KOH in glycol for 10 days at 130°C. Yield: 41%, m.p. 93-7°C (EtOH). Example 9
1,8-[2-Cyano-7-(3-(5,5,7,7-tetramethyl-l-octenyl))-8-quinolinyloxy]octane was prepared from 7-[3-(5,5,7,7-tetramethyll-octenyl)]-8-hydroxyquinoline-2-carbonitrile (SE patent application 8206378-5) (19.09 g, 56.7 mmol), 1,8-dibromooctane (8.02 g, 29.5 mmol) and K2CO3 (8.15 g, 59 mmol) in DMF (75 ml) at 75°C during 18 h. The product was isolated by toluene extraction and purified by chromatagraphy on silica gel with toluene: ethyl acetate 60:1 as eluant. Yield:
19.95 g (90%). Anal. Calc. for C52H70N4O2: C:79.75, H:9.01, N:7.15. Found: C:79.65, H.-8.99, N:7.03.
The dinitrile (19.8 g, 25.3 mmol) was hydrolyzed with KOH (25 g) in ethanol (255 ml) at reflux during 17 h. Acidification and ether extraction yielded 19.8 g 1,8-[2-carboxy7-(3-(5,5,7,7-tetramethyl-l-octenyl))-8-quinolinyloxy]octane (R 821) (95% yield), m.p. 85-7°C. Anai. Calc. for C52H72N2O6: C:76.06, H:8.84, N:3.41. Found: C:76.06, H:8.81, N:3.30.
Example 10
7-[3-(5,5,7,7-Tetramethyl-l-octenyl)]-8-hydroxyquinoline2-carbonitrile (SE patent application 8206378-5) (1.02 g, 3.0 mmol) and K2CO3 (0.41 g, 3.0 mmol) in DMF (4.5 ml) were allowed to react with diethyleneglycol ditosylate (0.62 g, 1.5 mmol) during 4 h at 75°C. The product was worked up by ether extraction and purified by chromatography on silica gel, eluting with 0.5% EtOH in CH2Cl2 to give 0.93 g 1,5bis[2-cyano-7-(3-(5,5,7,7-tetramethyl-l-octenyl))quinolinyloxyl-3-oxapentane (83% yield), m.p. 91-6ºC.
The dinitrile (0.83 g, 1.12 mmol) was hydrolyzed with KOH (1.2 g) in ethanol (17 ml) for 20 h at 75-80°C. The resulting diacid was isolated by ether extraction after acidification. Yield: 0.83 g of 1,5-bis[2-carboxy-7- (3-(5,5,7,7tetramethyl-l-octenyl))quinolinyloxy]-3-oxapentane (R 781), (95%), m.p. 115-120°C (cyclohexane). Anal. Calc. for C48H64N2O7 : C:73.82, H:8.26, N:3.59. Found: C: 73.82, H: 8 . 24 , N:3.56.
Example 11
1,11-Bis[2-cyano-7-(3-(5,5,7,7-tetramethyl-l-octenyl))-8quinolinyloxy]-3,6,9-trioxaundecane was prepared by the method described in example 10 using tetraethyleneglycol ditosylate in place of diethyleneglycol ditosylate. Yield: 77%.
Hydrolysis with 10% KOH in EtOH gave 1,11-bis[2-carboxy-7(3-(5,5,7,7-tetramethyl-l-octenyl))-8-quinolinyloxy]-3,6,9trioxaundecane (R 869) in 90% yield.
Example 12
1,3-Bis(2-carbethoxy-4-hydroxy-8-quinolinyloxy) propane was prepared by the Conrad-Limpach-Knorr reaction (B. Riegel, C.J. Albisetti, G.R. Lappin and R.H. Baker, J. Amer. Chem. Soc. 68 (1946) 2685 and G.F. Lisk and G.W. Stacy, J. Amer. Chem. Soc. 68 (1946) 2686). K2CO3 (5.52 g, 40 mmol) was added to 2-nitrophenol (5.56 g, 40 mmol) in DMF (20 ml), 1,3dibromopropane was added and the reaction mixture kept at 70ºC. The reaction mixture was cooled and poured into water and recrystallized from ethanol to give 4.80 g (75% yield) of 1,3-di(o-nitrophenoxy) propane. This product was reduced with hydrazine (3 ml) and Pd(C) (0.2 g) in ethanol (150 ml) at reflux for 1.5 h. The resulting diamino compound was converted to the hydrochloride. 1,3-Di(o-aminophenoxy) propane hydrochloride (4.38 g, 13 mmol) was stirred at ambient temperature for two days with diethyloxalacetic acid sodium salt (5.56 g, 26.5 mmol), anhydrous Na2SO4 (5.8 g) and absolute alcohol (26 ml). Water was added and the product was extracted with ether. The ether phase was washed with 1M H2SO4, water and brine, yielding 6.60 g (85%) of the condensation product. This product was dissolved in diphenyl ether (15 ml) and the solution was added dropwise to 60 ml refluxing diphenyl ether during 7 min. Reflux was continued for an additional 8 min after which most of the solvent was distilled off at reduced pressure. Chromatography on silica gel with 5% EtOH in CH2Cl2 and recrystallization from methanol yielded 1.44 g (14% yield based om 2-nitrophenol), m.p. 191-2°C.
The 4-hydroxy compound was alkylated (K2CO3/DMF) with 1chloro-5,5,7,7-tetramethyl-2-octane at 85°C overnight. The crude product was hydrolyzed with KOH-EtOH-H2O at reflux during 5 h. 1,3-Bis[2-carboxy-4-(1-(5,5,7,7-tetramethyl-2octenyloxy))-8-quinolinyloxy]propane (R 794) precipitated on addition of water and dilute H2SO4 to pH 3, 1.98 g (94% yield), m.p. 167-9°C
Example 13
2-Nitrophenol (13.9 g, 0.10 mol) and K2CO3 (13.8 g, 0.10 mol) in DMF (50 ml) were stirred and heated to 85°C. Triethyleneglycol ditosylate (22.9 g, 50 ml) in DMF (45 ml) was added and the reaction was left for 22.5 h at 85ºC. The reaction mixture was worked up by addition of water and extraction with CH2Cl2. The organic phase was washed with 10% NaHCO3. The product (7.84 g, 10 mmol) was dissolved in ethanol (200 ml) and heated to reflux. Pd(C) (0.25 g) was added and then cautiously hydrazine (4 ml). Refluxing was continued for 2 h. Ethanol was removed by distillation and the product was converted to the hydrochloride (7.22 g, 89% yield). The hydrochloride (6.1 g, 15 mmol), diethyloxalacetic acid sodium salt (6.3 g, 30 mmol) and anhydrous Na2SO4 (6.6 g) were stirred in absolute alcohol (30 ml) at room temp, for 20 h. Water was added and the product was isolated by ether extraction. The ether phase was washed with 1M H2SO4, water and brine. Evaporation of the solvent yielded a yellow oil (8.06 g). Diphenyl ether (7 ml) was added to the oil and the solution was added dropwise to refluxing diphenyl ether (50 ml) during 4 min. Heating was continued for an additional 7 min, the solution was cooled and petroleum ether (75 ml b.p. 40-60°C) was added. The product, 1,8-bis(2-carbethoxy-4-hydroxy-8-quinolinyloxy)-3,6-dioxaoctane, crystallized. Recrystallization from methanol gave 2.87 g (33% yield), m.p. 141-2°C.
The 4-hydroxy compound (2.70 g, 4.66 mmol) was stirred at 60°C for 20 min with K2CO3 (1.40 g, 10.2 mmol) in DMF (20 ml). l-Chloro-5,5,7,7-tetramethyl-2-octene (2.13 g, 10.5 mmol) was added and the reaction was continued for 40 h at 60°C. Work-up by ether extraction and recrystallization from petroleum ether: ether 3:1 gave 3.20 g (75% yield) of the 4-alkoxy ester, m.p. 78-80°C.
This diethyl ester (3.10 g, 3.4 mmol) was hydrolyzed with KOH in aq. ethanol at reflux for 1 h to give 1,8-bis[2-carboxy-4-(1-(5,5,7,7-tetramethyl-2-octenyloxy))-8-quinolinyloxy]-3,6-dioxaoctane (R 856) (2.29 g, 79%), m.p. 93-100°C (EtOH). Anal. Calc. for C50H68N2O10.H2O: C:68.6, H:8.06,
N:3.2. Found: C:68.8, H:8.0, N:3.2.
Example 14
The hydrochloride of 1,2-di(o-aminophenylthio) ethane (R.D. Cannon, B. Chiswell and L.M. Venanzi, J. Chem. Soc. A (1967) 1277) (3.25 g, 10 mmol) was stirred with diethyloxalacetic acid sodium salt (4.20 g, 20 mmol), Na2SO4 (4.4 g) and absolute ethanol (20 ml) for two days yielding a partly crystalline product after workup. This product was mixed with diphenyl ether (10 ml) and added dropwise to refluxing diphenyl ether (70 ml) during 5 min. Reflux was continued for 10 min, the solution was cooled and petroleum ether (160 ml) was added. The precipitate formed was recrystallized from CHCl3 - toluene to give 1,2-di(2-carbethoxy-4-hydroxy-8quinolinylthio) ethane, m.p. 226-8°C (26% yield).
1,2-Di(o-aminophenylthio) ethane (0.91 g, 3.3 mmol) and dimethyl acetylene dicarboxylate (0.95 ml, 7.0 mmol) were refluxed in methanol (30 ml) for one day. The solvent was evaporated and the residue was dissolved in ether-CH2Cl2 and washed with 2M HCl. Recrystallization from methanol afforded the anilino butenedioate (1.37 g, 74% yield), m.p. 119°C. This product was cyclized in refluxing diphenyl ether as described above, to yield 1,2-di(2-carbomethoxy-4-hydroxy-8quinolinylthio) ethane (1.07 g, 87% yield), m.p. 238-240°C.
The methyl or ethyl ester (2.13 mmol) and K2CO3 (0.65 g, 4.7 mmol) was stirred in DMF (15 ml) at 70°C for 15 min. 1-Chloro-5,5,7,7-tetramethyl-2-octene (1.03 g, 5.11 mmol) was added and stirring was continued for 20 h. The mixture was cooled and poured into water. The product was filtered off and recrystallized from petroleum ether (b.p. 100-125ºC). Ethyl ester: yield 83% (1.51 g), m.p. 127-145°C.
The diester (1.76 mmol) was hydrolyzed with KOH (1 g), EtOH (20 ml) and H2O (4 ml) at reflux overnight. Addition of water and acidification gave 1.09 g 1,2-di[2-carboxy-4-(1(5,5,7,7-tetramethyl-2-octenyloxy))-8-quinolinylthio]ethane (R 800) (77% yield), m.p. 166-8°C (aq. acetic acid). Anal.
Calc. for C46H60N2O6S2.H2O: C:67.4, H:7.6, N:3.4. Found:
C:67.8, H:7.4, N:3.4.
Example 15
An aqueous solution of a mixture of equal parts of metal sulfates (Cu2+, Zn2+, Fe2+, Ni2+ and Co2+) was prepared by dissolving the metal salts in dilute sulfuric acid. The metal concentrations were kept around 2 mM and the pH of the solution was adjusted to about 2. A 10 mM solution of the appropriate reagent in chloroform was prepared and the two phases were agitated until equilibrium was reached. The two phases were then separated by centrifugation and the distribution of each metal between the two phases was determined. The percentage of metal ions extracted is given below.
Figure imgf000019_0001
Example 16
An aqueous sulfuric acid solution at pH 2 containing equal concentrations of metal sulfates (Cu 2+, Zn2+, Fe3+, Cd2+ and K+) was contacted with an equal volume of a chloroform solution of the appropriate ligand until equilibrium was reached. The two phases were separated and the distribution of each metal between the two phases was determined. The percentage of metal ions extracted from the water is given below.
Figure imgf000019_0002
Example 17
Equal amounts of sulfate salts of metals (Cu2+, Zn2+, Ni2+, Co2+ and Cd2+) were dissolved in dilute sulfuric acid at pH 4. This solution was equilibrated at 25°C with a chloroform solution of the ligand concerned. The two phases were separated and the distribution of each metal between the two phases was determined. The percentage of metal ions extracted from the water phase is given below.
Figure imgf000020_0001
Example 18
A mixture of equal amounts of metal sulfates (Cu 2+, Zn2+, Fe 2+ and Cd2+ was dissolved in sulfuric acid at different pH. The solution was equilibrated with chloroform solutions of the ligands concerned and the distribution of metals in the two phases was determined. The results are given below
(pHin = initial pH, pHeq = pH at equilibrium) .
Figure imgf000020_0002
Example 19
A mixture of equal amounts of metal sulfates (Co2+, Ni2+, Zn2+ and Cr3+) was dissolved in sulfuric acid at different pH. This solution was equilibrated with chloroform solutions of the ligands concerned and the distribution of metals between the two phases was determined. The results are given below (pHin = initial pH, pHeq = pH at equilibrium).
Figure imgf000021_0001
Example 20
A mixture of equal amount of metal sulfates (Mg 2+, Mn2+, Na + and Zn2+) was dissolved in sulfuric acid at different pH. This solution was equilibrated with chloroform solutions of the appropriate ligands and the amount of metals extracted from the water phase (in %) was determined. The results are given below (pHin = initial pH, pHeq = pH at equilibrium).
Figure imgf000021_0002
Example 21
A series of sulfuric acid solutions of single metal sulfates at pH 2 were shaken with equal volumes of chloroform solutions of the appropriate extractant. The percentage of metal removed from the water phase is given below.
Figure imgf000022_0001
Example 22
A series of sulfuric acid solution of single metal sulfates at pH 4 were shaken with equal volumes of chloroform solutions of the appropriate extractants. The percentage of metal removed from the water phase is given below.
Figure imgf000022_0002
Example 23
A series of single metal sulfate solutions were prepared and contacted with a chloroform solution of R 488. The equilibrium pH value of the aqueous phase was adjusted to a given value. The amount of metal extracted at a given pH value was determined. The pH50 values (the pH value at which 50% of the metal is extracted) for each metal were calculated and are given below.
Figure imgf000022_0003
Example 24
A plastic film containing the selective reagent dissolved in chloroform was placed between two solutions so that any transport of ions would occur only through the membrane. The first solution (feed solution) contained the metal ions in acidic sulfate solution, while the second contained only concentrated sulfuric acid. Efter some time the metal ions were transfered from the feed solution into the sulfuric acid solution.

Claims

1. New quinoline compounds characterized by the formula
Figure imgf000024_0001
wherein R3, R4, R5 and R6, which may differ or be identical, are selected from the group consisting of H, R and OR, wherein R is a lipophilizing group, X is selected from the group consisting of O and S, and A is selected from the group consisting of (CH2)n, CH2CH2(OCH2CH2)p and
CH2CH2OCHRCH2, wherein n is 2-10 and p is 1-3.
2. Compounds according to claim 1 characterized in that the lipophilizing group R is aliphatic or aromatic, saturated or unsaturated, straight or branched.
3. Compounds according to claim 1 or 2 characterized in that at least one lipophilizing group is present.
4. Compounds according to any of the claims 1-2 characterized in that two lipophilizing groups are present.
5. Compounds according to any of the preceding claims characterized in that R is selected from the group consisting of alkyl and alkenyl having 3-24, preferably 6-18, carbon atoms.
6. Compounds according to any of the preceding claims cha characterized in that the total number of carbon atoms in all the R groups does not exceed 40.
7. A mixture of quinoline compounds as claimed in any of the preceding claims.
8. A process for optionally selectively recovering metal values, from a mixture of metal ions or ionic compounds, characterized in that a quinoline compound or a mixture thereof as claimed in any of the preceding claims is used as a chelate forming agent.
9. A process for selectively separating copper and/or zinc metal values from a mixture of metal ions or ionic compounds, characterized in that a quinoline compounds or a mixture thereof as claimed in claims 1-7 is used as a chelate forming agent.
10. A process for extracting metal values from an aqueous solution characterized in that the aqueous phase is treated with a water-immiscible organic solution of a quinoline compound or a mixture thereof as claimed in claims 1-7, and that the organic phase containing the complexed metal ions is separated from the aqueous phase.
PCT/SE1983/000386 1982-11-10 1983-11-08 New chelate forming bisquinoline compounds and processes for recovering metals WO1984001946A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
SE8206377A SE8206377A0 (en) 1982-11-10 1982-11-10 New chelating biskinoline compounds

Publications (1)

Publication Number Publication Date
WO1984001946A1 true WO1984001946A1 (en) 1984-05-24

Family

ID=20348524

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1983/000386 WO1984001946A1 (en) 1982-11-10 1983-11-08 New chelate forming bisquinoline compounds and processes for recovering metals

Country Status (3)

Country Link
EP (1) EP0125276A1 (en)
SE (1) SE8206377A0 (en)
WO (1) WO1984001946A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995012580A1 (en) * 1993-11-03 1995-05-11 Centre National De La Recherche Scientifique Compounds derived from 8-hydroxy-quinoleine, chelating agents, iron complexes and utilizations
US6521574B1 (en) * 1995-06-08 2003-02-18 Kabushiki Kaisha Toshiba Copper-based metal polishing solution and method for manufacturing a semiconductor device
CN115772070A (en) * 2022-11-29 2023-03-10 亚培烯科技（杭州）有限公司 Polyether compound, preparation method thereof and air compressor oil prepared based on polyether compound

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6263539A (en) * 1985-09-14 1987-03-20 Agency Of Ind Science & Technol Polyether derivative useful as carrier for ion-selective electrode

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637476A (en) * 1969-09-11 1972-01-25 American Cyanamid Co Method of recovering metals
US3697400A (en) * 1971-02-17 1972-10-10 American Cyanamid Co Recovering metals by extraction with a quinaldinic acid and electrowinning from the stripped chelate
US3787418A (en) * 1971-02-17 1974-01-22 American Cyanamid Co 6-alkyl-3-methylquinaldinic acids
US3941793A (en) * 1972-08-04 1976-03-02 Imperial Chemical Industries Limited Quinoline 2 carboxylic acids used in metal extraction processes
US4045441A (en) * 1976-03-10 1977-08-30 Ashland Oil, Inc. 7-(Alpha-methyl-alpha-alkenyl)substituted 8-hydroxyquinolines and process for the preparation thereof
US4065455A (en) * 1974-03-04 1977-12-27 General Mills Chemicals, Inc. 5-Halogen-substituted 7 alkyl and 7-alkenyl 8-hydroxyquinolines
US4066652A (en) * 1973-09-12 1978-01-03 Ashland Oil, Inc. Substituted 8-hydroxyquinolines and process for the preparation thereof
EP0000457A1 (en) * 1977-07-13 1979-01-24 Rhone-Poulenc Specialites Chimiques Process for the recovery of gallium from very basic solutions by liquid/liquid extraction.
EP0004226A1 (en) * 1978-03-10 1979-09-19 Rhone-Poulenc Industries Process for separating elements in the group consisting of the lanthanides and yttrium

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637476A (en) * 1969-09-11 1972-01-25 American Cyanamid Co Method of recovering metals
US3697400A (en) * 1971-02-17 1972-10-10 American Cyanamid Co Recovering metals by extraction with a quinaldinic acid and electrowinning from the stripped chelate
US3787418A (en) * 1971-02-17 1974-01-22 American Cyanamid Co 6-alkyl-3-methylquinaldinic acids
US3941793A (en) * 1972-08-04 1976-03-02 Imperial Chemical Industries Limited Quinoline 2 carboxylic acids used in metal extraction processes
US4066652A (en) * 1973-09-12 1978-01-03 Ashland Oil, Inc. Substituted 8-hydroxyquinolines and process for the preparation thereof
US4065455A (en) * 1974-03-04 1977-12-27 General Mills Chemicals, Inc. 5-Halogen-substituted 7 alkyl and 7-alkenyl 8-hydroxyquinolines
US4045441A (en) * 1976-03-10 1977-08-30 Ashland Oil, Inc. 7-(Alpha-methyl-alpha-alkenyl)substituted 8-hydroxyquinolines and process for the preparation thereof
EP0000457A1 (en) * 1977-07-13 1979-01-24 Rhone-Poulenc Specialites Chimiques Process for the recovery of gallium from very basic solutions by liquid/liquid extraction.
EP0004226A1 (en) * 1978-03-10 1979-09-19 Rhone-Poulenc Industries Process for separating elements in the group consisting of the lanthanides and yttrium

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995012580A1 (en) * 1993-11-03 1995-05-11 Centre National De La Recherche Scientifique Compounds derived from 8-hydroxy-quinoleine, chelating agents, iron complexes and utilizations
FR2711991A1 (en) * 1993-11-03 1995-05-12 Centre Nat Rech Scient Compounds derived from 8-hydroxyquinoline, chelating agents, iron complexes and uses.
US6521574B1 (en) * 1995-06-08 2003-02-18 Kabushiki Kaisha Toshiba Copper-based metal polishing solution and method for manufacturing a semiconductor device
CN115772070A (en) * 2022-11-29 2023-03-10 亚培烯科技（杭州）有限公司 Polyether compound, preparation method thereof and air compressor oil prepared based on polyether compound
CN115772070B (en) * 2022-11-29 2024-01-02 亚培烯科技（杭州）有限公司 Polyether compound, preparation method thereof and air compressor oil prepared based on polyether compound

Also Published As

Publication number Publication date
SE8206377D0 (en) 1982-11-10
SE8206377L (en) 1900-01-01
EP0125276A1 (en) 1984-11-21
SE8206377A0 (en) 1984-05-11

Similar Documents

Publication Publication Date Title
US4923686A (en) Process for the extraction of metal values
US4039612A (en) Process for extracting cobalt, copper or zinc values using a 1-alkyl substituted benzimidazole
US4822880A (en) Process for the extraction of metal values and novel metal extractants
US3941793A (en) Quinoline 2 carboxylic acids used in metal extraction processes
WO1984001946A1 (en) New chelate forming bisquinoline compounds and processes for recovering metals
US3936494A (en) Naphthenohydroxamic acid preparation
US4123435A (en) Nitro-substituted benzoxazoles having utility as metallurgical extractants
US4317887A (en) Metal complexing polymers
US4739054A (en) Triazolopyrimidine extractants
EP0112617B1 (en) Process for the extraction of metal values and novel metal extractants
JPH11179104A (en) Transition metal extraction agent and method for extracting transition metal
EP0513966B1 (en) Bis-bibenzimidazole composition
US4777274A (en) Process for the selective preparation of isosorbide-2-mononitrate from isosorbide-2,5-dinitrate
CA1084505A (en) Certain sulfonamidoquinolines, metal complexes thereof, and solutions containing such sulfonamidoquinolines and metal complexes
EP0124577A1 (en) New chelate forming quinoline compounds and processes for recovering metals
AU631657B2 (en) Heterocyclic thione
US3268538A (en) 8-sulfonamidoquinolines
EP0033215A2 (en) Process for preparing anti-allergy naphthotriazoles
CA2450443C (en) Solvent extraction mixture for the purification of base metals
MXPA02001433A (en) Method for separating copper from iron.
GB2150133A (en) 1-substituted-1,2,4-triazoles and their use in the extraction of metal values
US3202689A (en) Process for separating copper values from cobalt and nickel values
CN114230514A (en) Method for synthesizing 3-fluoro-2-amino isonicotinic nitrile
EP0266450B1 (en) Process for the selective preparation of isosorbide-2-mononitrate from isosorbide-2,5-dinitrate
AU2002319832B2 (en) Solvent extraction mixture comprising substituted imidazole or benzimidazole for the purification of base metals

Legal Events

Date Code Title Description
AK Designated states

Designated state(s): US

AL Designated countries for regional patents

Designated state(s): AT BE CH DE FR GB LU NL SE