GB2104516A - m-Alkyl phenol derivatives and their use in copper extraction - Google Patents
m-Alkyl phenol derivatives and their use in copper extraction Download PDFInfo
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Abstract
Compounds of the formula <IMAGE> in which: X represents a straight chain hydrocarbyl group containing from 9 to 17 carbon atoms; Y represents H or the group -CH=NOH, and Z represents H or the group -CN=NOH or the group -CPh=NOH, provided that at least one of Y and Z represents H; or such compound containing at least one electronegative substituent in the aromatic ring, may be prepared from anacardic acid and its analogues, and are useful for the extraction of copper from acidic aqueous solution.
Description
SPECIFICATION
Metal extraction
The compound (2-hydroxy 5-tertiary nonyl) acetophenone oxime which is commercially available in a hydrocarbon diluent, is useful for the extraction of copper from acidic media but is at present derived from petroleum the supply and price of which is liable to fluctuation.
Compounds have now been found which can extract relatively greater amounts of copper from acidic media and which can be produced from the replenishable source Cashew Nut-Shell Liquid (CNSL) and from relatedAnacardium species.
Accordingly the present invention comprises a compound of formula I.
wherein:
X represents a straight chain hydrocarbyl group containing from 9 to 17 carbon atoms; when Z represents hydrogen, Y represents the group -CH=NOH; and when Y represents hydrogen, Z represents the group -CH=NOH or-CPh=NOH.
Electronegative substituents, such as chloro, nitro and cyano groups, may also be present on the aromatic ring.
Compounds of formula 1 are preparable from the carbonyl precursors of the oximes by treatment with appropriate reagents e.g. hydroxylamine salts, typicallythe hydrochloride or sulphate in a solvent such as anhydrous pyridine, if necessary or preferred with the application of heat.
The present invention further includes within its scope carbonyl compounds IA which are compounds of formula I in which:
X represents a straight chain hydrocarbyl group containing from 9to 17 carbon atoms.
when Z represents hydrogen, Y represents-CHO and when Y represents hydrogen, Z represents-CHO or -COPh.
Aldehyde precursors for compounds I in which Y represents -CH= NOH may be produced for example from 15:0, 15:1 and/or 15:2 anacardic acid IB, which are compounds of formula I in which Z=H, Y=CO2H and X= C,sH27, C15H29 or C15H31 by various methods.
Such methods include (1) Reduction e.g. hydride reduction to the corres
ponding alcohol followed by oxidation thereof
to the aldehyde using for example periodate to
produce a spirodienone which is subsequently
ultraviolet irradiated or using pyridinium
chlorochromate or a pyridine/chromium triox
ide mixture or (2) conversion of the acid to the corresponding acid
chloride or anhydride or a mixture thereof by
treatment with e.g. thionyl chloride followed by
reduction of the product to the corresponding
aldehyde by means for example of a suitable
Rosenmund catalyst and hydrogen or by hyd
ride.
Anacardic acid is available from natural CNSL as a mixture comprising the compounds IB and it may be desirable to partly or fully reduce the C15 side chain to produce the 15:1 or 15:0 compound or a mixture of such compounds prior to conversion to the 15:1 or 15:0 oximes which are preferred extractants. Full or partial reduction may be accomplished by hydrogenation using for example a catalyst of the Raney orSabatiertype ora palladium catalyst whereas partial reduction to the 15:1 acid can be effected by diimide in a solvent such as ethanol, the diimide being generated in situ suitably from hydrazine hydrate and air.
Aldehyde precursors for compounds I wherein Z represents the group -CH= NOH may be produced by oxidation of the corresponding alcohol using for example the reagents hereinbefore described, the alcohol being obtainable by reduction, typically hydride reduction, of the corresponding acid. Such an acid can be produced for example by a Kolbe reaction of cardanol, IC a compound of formula I in which
Z=H, Y=H and X=C15H27, C15H29 or C15H31, or an alkali metal salt thereof with carbon dioxide.
The present invention also includes within its scope compounds ID offormula I in which Z repres ents -CO2H, Y represents hydrogen and X represents a straight chain hydrocarbyl group containing from 9 to 17 carbon atoms.
Alternatively, cardanol (IC) can be methylolated to produce a compound comprising a-CH2OH group at the ring position para to the side chain by treatment with an alkylmagnesium halide e.g. ethyl magnesium bromide to give the phenoxymagnesium halide derivative of cardanol followed by treatment thereof with paraformaldehyde in an aprotic solvent such as hexamethyl phosphorictriamide. The methylolated product can then of course be readily oxidised to the corresponding aldehyde by methods such as those hereinbefore described.
In a further method for production of aldehyde precursors for oximes of formula I in which Z represents-CH=NOH, cardanol is converted to the phenoxymagnesium halide derivative which is treated with ethylorthoformate in an aprotic solvent such as tetrahydrofu ran followed by hydrolysis of the intermediate acetal. In yet further methods for the production ofthe aldehyde cardanol, preferably 15:0 cardanol, isformylated by means of the Gatterman reaction, the product containing an impurity 3-pentadecyl-4-formyl phenol, or is subjected to the
Hoesch reaction.
The present invention also includes within its scope alcohols from which the hereinbefore described aldehydes may be obtained by oxidation thereof. Such alcohols, IE are compounds of formula
I, in which: Z represents-CH20H when Y represents hydrogen Y represents-CH2OH when Z represents hydrogen and X represents a straight chain hydrocarbyl group containing from 9 to 17 carbon atoms.
Electronegative ring substituents, such as chloro, nitro and cyano groups, enhance the chelation properties of the oxime product. Such substituents may be introduced, by conventional methods, onto the aromatic ring of eitherthe acid or the alcohol. Such substituted acids and alcohols are within the scope of the invention.
Cardanol is obtainable from Technical Cashew
Nut-Shell Liquid (CNSL) in which it is present in high concentration or Technical CNSL may be used per se generally after reduction for example as hereinbefore described for anacardic acid to give compounds containing 15:0 or 15:1 side chains or a mixture comprising such compounds.
Technical CNSL or cardanol may also be used as a starting material for the production of the ketone precursor or compounds I in which Z represents -CPh=NOH. After any desired reduction of the unsaturation in the side chain by methods such as those hereinbefore described, CNSL or Cardanol may be treated with a benzoyl halide, typically benzoyl chloride in the presence of a Lewis acid such as AICI3 under conditions appropriate for Friedel-Crafts reaction to yield the precursor.
Different species ofAnacardium yield anacardic acids containing hydrocarbyl side chains of different lengths. For example, an anacardic acid containing a C11 side chain may be obtained from theAnacardium giganteum, and particularly from the nut-shell of this species.
Extractants of formula 1 may be utilised for extraction of a metal such as copper by treatment of a solution or dispersion thereof in a water immiscible solvent (typically a non polar solvent such as kerosene), with a mildly acidic aqueous solution of the metal salt e.g. CuS04 which generally contains salts of other metals such as nickel. Following agitation of the two phase system to promote extraction
into the non-polar phase the phases are separated and the extracted metal salt is stripped therefrom, generally by treatment with an acid e.g. sulphuric
acid at a concentration greater than that present in the aqueous phase before extraction e.g. 1.5 molar or stronger sulphuric acid.The present invention is
illustrated by the following Examples:
Example 1 (15:0)-Anacardic aldoxime (6 Pentadecylsalicylaldoxime) (A) 15:0 AnacardicAlcohol Anacardicacid consisting of a mixture of (15:0), (15:1), (15:2) and (15:3) - anacardic acids is
extracted from natural cashew nut-shell liquid as
described in Tyman and Lam, J. Chem. Soc., Perkin
1, 1981, 1924 and is obtained as an oil in 69% yield.
The oil (309) in ethyl acetate (200 cm3) containing 10% palladium-carbon catalyst (3.09) is shaken with hydrogen at 15 Ib in-2 at ambient temperature. After absorption of hydrogen (3,530 cm3) the reduction is complete. The mixture is filtered to recover the catalyst and upon evaporation and recovery ofthe solvent, (15:0)-anacardic acid obtained in theoretical yield, m.p. 87-88".
(15:0)-Anacardicacid (5.29) in drytetrahydrofuran (60 cm3) is added dropwise over two hours to lithium aluminium hydride (2.59) suspended in tetrahydrofuran (25 cm3) and the stirred mixture is refluxed fortwo hours with monitoring by thin layer chromatography to indicate complete reduction. The excess hydride is decomposed by the addition of ethyl acetate and the acidified mixture is extracted with ether. Recovery gives a brown oil which upon crystallisation from light petroleum (40-60") yields (15:0)-anacardic alcohol (6-pentadecyisalicyl alcohol) as cream coloured crystals, m.p. 60-62" (4.059).
(B) 15:0AnacardicAldehyde
(15:0)-Anacardicalcohol (2.09) in methanol (30 cm3) is treated with a solution of sodium periodate (1.769) in water (10 cm3). After several minutes a thick yellow solid separates and the stirred mixture is warmed at 30"C for one hour to complete the reaction. Dilution with water and ethereal extraction gives a thick yellow oil which after crystallisation from light petroleum (40-60") affords the spirodienone, 8 - pentadecyl - 1 - oxaspiro (2.5) octa 5,7 - dien - 4 - one, m.p. 80-81"C (1.209).
The spirodienone (1.089) in ethanol is irradiated with ultraviolet light from a medium pressure
Hanovia photochemical reactor during three hours.
Concentration of the solution, ethereal extraction and crystallisation from light petroleum (40-60") gives pale yellow of (15:0)-anacardic aldehyde (6pentadecylsalicylaldehyde, h.p. 4547" (1.019).
(C) 15:0Anacardic aldoxime
(15:0)-Anacardicaldehyde (0.419) in pyridine (7 cm3) is heated at 100"C with hydroxylamine hydrochloride (0.7469). Oximation is complete after five hours and the mixture is diluted with water, acidified with hydrochloric acid and ethereally extracted.
Concentration of the dried ethereal solution gives a greyish oil which after crystallisation from light petroleum (40-60") furnished (15:0)-anacardic aldoxime as off-white prisms, m.p. 95-97", (0.349). Found: C, 75.45; H, 10.77; N, 3.80. C22H3702N requires C, 76.08;
H. 10.66; N, 4.03%. It had the expected'H NMR and
IR absorption spectra.
Example 2 15:0 Anacardic aldoxime
The oxime is produced as described in Example 1 from 15:0 Anacardic aldehyde produced by a procedure in which oxidation of (15:0)-anacardic alcohol (2.09) in dichloromethane (110 cm3) with pyridinium chlorochromate (5.50g), prepared from chromium trioxide and 6M hydrochloric acid is followed by addition at 0" of pyridine according to Corey and
Suggs (Tetrahedron Letters, 1975,2647), during 90 minutes at ambient temperature. Filtration of the reaction mixture, concentration of the filtrate and crystallisation gives (15:0)-anacardic aldehyde identical with the product from the process described in
Example 1.
Example 3
(A) 15:0Anacardic aldehyde
(15:0)-Anacardic acid (3.489) in light petroleum,
40-60"C (20 cm3) containing pyridine (0.029) is stirred
and treated with thionyl chloride (0.62 cm3) at 30".
After two hours the mixture which becomes almost clear is filtered and the filtrate concentrated to give
an oily product consisting of the acid chloride and the acid anhydride.
The crude product from two such reactions (59) in dryxylene (9.2 cm3) containing 5%-palladium barium sulphate catalyst (0.276g) and thiourea, catalyst poison, (0.0559) is heated at 140-150" and hydrogen passed into the mixture with the usual precautions. Hydrogen chloride soon appears in the exit gas and is collected in a water trap. When no more is produced the reaction is stopped, the reaction mixture is cooled, decolourising charcoal (lug) added and after filtration and concentration the residual material (4.609) is crystallised from light petroleum (40-60") to give (1 5:0)-anacardic aldehyde which is identical with the products from the reactions described in Examples 1 and 2.
(B) 15:0Anacardic aldoxime
The aldehyde is converted into the corresponding aldoxime as described in Example 1.
Example 4 (A) 15:0 Anacardic aldehyde A mixture of acid chloride and anhydride produced as described in Example 3 (1.0g), is reduced in diglyme (1.1 cm3 )at-75"C with a t-butanol/lithium aluminium hydride complex, obtained by reacting dryt-butanol (0.6g) with lithium aluminium hydride (0.106g) in dry ether (5.6 cm3) and dissolving the precipitate in diglyme (2.2 cm3), to give (15:0)-anacardic aldehyde which is purified by crystallisation to give (0.69g).
(B) 15:0Anacardicaldoxime is produced from the aldehyde as described in Example 1.
Example 5 4- Pentadecylsalicylaldoxime {{"15:0) - iso anacardic aldoxime") (A) 4 - Pentadecylsalicylic acid The unsaturated product "iso-anacardic acid" 4-pentadecylsalicylic acid from the Kolbe reaction of the sodium salt of cardanol with carbon dioxide is hydrogenated to give the saturated compound in the following manner.
The unsaturated acid, consisting of (15:0), (15:1), (15:2) and (15:3) constituents (209) in ethanol (150 cm3) containing 10% palladium-carbon catalyst (2.09) is hydrogenated until 2500 cm3 of hydrogen
has been absorbed. Filtration to recover the catalyst and concentration of the filtrate followed by crystal
lisation of the residual material gives 4-pentadecylsalicyclic acid, (1 5:0)-iso-anacardic acid
as greyish prisms, m.p. 96-97" (14.89).
(B) 4-Pentadecylsalicyl alcohol 4-Pentadecylsalicylic acid (5.29) in tetrahydrofu
ran (60 cm3) is slowly added to stirred lithium aluminium hydride (2.59) in drytetrahydrofuran (25 cm3) and the mixturethen stirred and refluxedfor five hours to complete the reduction. Work-up by
recovery of the tetrahydrofuran, addition of a little ethyl acetate to the cooled residual material, fol iowed by acidification and ethereal extraction yields the crude product which is crystallised from light petroleum (40-60") to give 4-pentadecylsalicyl alcohol as off-white prisms, m.p. 66-68", (4.059).
(C) 4-Pentadecylsalicylaldeh yde 4-Pentadecylsalicyl alcohols (1.549) in methanol (25 cm3) is treated with sodium periodate (1.309) in water (8 cm3). Athick yellow solid soon separates and the mixture is warmed to 30" during five hours to complete the reaction which is indicated by monitoring with thin layer chromatography. Dilution of the mixture with water and ethereal extraction followed by concentration of the ethereal layer and crystallisation of the residue from light petroleum (40-60") affords the "isomeric spiro epoxy dienone", m.p. 84-86"C, (0.82g).
Irradiation of the spirodienone (0.72g) in ethanol with ultraviolet light in an Hanovia photochemical reactor during three hours and recovery and crystallisation of the product from light petroleum (40-60") gives 4-pentadecylsalicylaldehyde as a pale yellow material, m.p. 50-54", (0.619).
(D) 4-Pentadecylsalicylaldoxime
Interaction of the aldehyde in pyridine solution with hydroxylamine hydrochloride at 100" during five hours yields 4-pentadecylsalicylaldoxime, "(1 5:0)-iso-anacardic aldoxime".
Example 6 (A) 4-Pentadecylsallcylaldeh yde Cardanol consisting of a mixture of (15:0) cardanol, (15:1 )-cardanol, (1 5:2)-cardanol and (1 5:3)-cardanol is obtained from the technical cashew nut-shell liquid by vacuum distillation in 70% yield.
The mixed material in ethanol containing 10% palladium-carbon catalyst is hydrogenated until absorption of hydrogen ceased and the side-chain has been saturated as revealed by argentation thin layer chromatography and H NMR absorption spectroscopy. The product is recovered by filtration, concentration of the filtrate and crystallisation of the residual material from light petroleum (40-60") to give (15:0)-cardanol, containing a little (15:0)-cardol.
(15:0)-Cardanol (10.29) is added to an equivalent proportion of ethyl magnesium bromide in dry ethereal solution of which is observed when evolution of ethane ceases. Ethyl orthoformate (10 cm3) is added and the ether removed by distillation so that the temperature rises to 1 00"C. After refluxing for three hours, the mixture is decomposed with dilute hydrochloric acid and warned to effect the hydrolysis of the intermediate acetal formed. Ethereal extraction and recovery gives a mixture of some unchanged (15:0)-cardanol and the formylated pro duct, 4-pentadecylsalicylaldehyde which is separated by chromatography.
(B) 4-Pen ta decylsalicylaldoxime The aldehyde is converted into the corresponding aldoxime by the process described in Example 5.
Example 7 (A) 4-Pentadecylsalicylaldeh yde Cardanol (2.09) is converted as described in
Example 6 to the phenoxy magnesium bromide derivative and refluxed in benzene (50 cm3) contain ing hexamethyl phosphoric triamide(1.2g) and paraformidehyde (0.679) for thee hours, Acidification and ethereal extraction followed by drying and concentration gives a pale brown oil consisting of some unchanged (15:0'-cardanol and 4-pentadecylsa Ecylaldehyde which are separated by chromatography.
(B) 4-Pentadecylsalicylaldoxime
The aldehyde is converted into the corresponding aldoxime by the process described in Example 5.
Example 8 2 - Hydroxy -4- pentadecyl benzopnenone ketoxime (A) 2 - hydroxy - 4 - pentadecylbenzophenone
(15:0)-Cardanol (2.09) in dry pyridine (5 cm3) ) is treated with benzoyl chloride (1.5 cm3) and the mixture warmed for five hours at 100"C. The cooled mix- ture is diluted with water, basified with dilute sodium hydroxide solution, and the precipitated (15:0)-cardanol benzoate collected by filtration, washed with water until neutral and dried to give 2.7859.
3-Pentadecylphenyl benzoate (1.366g) is finely powdered, mixed with pulverised an hydros aluminium chloride (0.616g) and the intimate mixture is heated to 165" during fifteen minutes. After hydrogen chloride evolution has ceased, the cooled mixture is treated with water, concentrated hydrochloric acid added, and the whole thoroughly stirred to decompose the aluminium complex. The product is ethereally extracted and the dried ethereal layer is concentrated to give the crude product (1.348g) which possesses a greenish ferric chloride reaction.
Chromatographic purification and crystallisation from light petroleum (40-60 ) affords 2 - hydroxy - 4 pentadecylbenzophenone, m.p. 46-47".
Moles of reagent oxime used
Equivalent to moles copper
Equivalent tog copper
Max. theoretical loading
Copper extracted (g)
Copper initially present (g)
% copper extracted
%theoretical loading of copper
% recovery of copper
Both reagents are stable to the acidic conditions of recovery as assessed by thin layer chromatography.
Example 10
In an extraction process similar to that of Example 9 in which nickel chloride is present with coppersul- phate in equimolarstrength, analysis by atomic
absorption indicates that anacardic aldoxime (like the ketoxime reagent) extracts copper specifically.
Claims (5)
1. A compound useful for extraction of copper from acidic media of the formula
(B) 2-hydroxy 2- hydroxy-4-pentadecylbenzophenone ketoxime
Conversion to
2 - hydro - 4 - pentadecylbenzophenone oxime is effected in pyridine solution with hydroxylamine hydrochloride as described in
Example 1 or 5 to give the product, m.p. 51-3"C.
Example 9
The extraction properties of (15:0)-anacardic aldoxime for copper irons are compared with those of the commercial extractant, the oxime of 2 - acetyl 4 - nonyl phenol (SME 529). The following solutions are used.
A Standard copper sulphate solution,5.71 5g/litre of CuSO4- 5H2O B Anaca rdic aldoxime, 1.25% w/w,
3.6 x 10 3 moles/100 cm3 of petroleum (100-120)
C 2-Acetyl-4-nonyl phenolketoxime, 1.25%w/w,
4. A method according to claim 2 substantially as hereinbefore described with reference to Example 9 or 10.
4.5 x 10cm- moles/100 cm of petroleum
(100-120")
D 1.50 M aqueous sulphuric acid.
Solution B (20 cm3) is thoroughly mixed with Solution A (10 cm3) and similarly Solution C (20 cm3) is mixed with Solution A (10 cm3). Excess of copper ion is present to ensure, if possible, maximum loading of oxime compounds. The pH was
5. Both solutions are thoroughly shaken and after emulsion separation has occurred, the lower copper sulphate aqueous layer is removed and analysed for copper sulphate by iodometrictitration. The following results at the extraction stage are obtained on the basis that 1 g atom of copper is associated with 2 moles of the oxime derivative. Each of the organic solutions are finally washed with Solution D (2 x 10 cm3) to recover the copper extracted.
Anacardic
Aldoxime
7.20x104 9.00x104
3.60x104 4.50x104
2.29x102 2.86x102
2.29x102 2.86x102
2.33x102 1.27x102
5.715x102 5.715x102
40.7 22.2
100 44.4
91 100
in which:
X represents a straight chain hydrocarbyl group containing from 9 to 17 carbon atoms;
Y represents H or the group - CH= NOH, and
Z represents H or the group - CH=NOH or the group - CPh= NOH, provided that at least one of Y and Z
represents H; or such compound containing at least one electronegative substituent in the aromatic ring.
2. A method of extracting copper from an acidic aqueous solution containing copper comprising:
treating such a solution with a solution of a com
pound according to claim 1 in a water immiscible solvent;
separating the aqueous phase from the water
immiscible phase; and
extracting the copper from the water immiscible
phase.
3. A compound substantially as hereinbefore described with reference to any of the Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08220097A GB2104516B (en) | 1981-07-13 | 1982-07-09 | M-alkylphenol derivatives and their use in copper extraction |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8121526 | 1981-07-13 | ||
| GB08220097A GB2104516B (en) | 1981-07-13 | 1982-07-09 | M-alkylphenol derivatives and their use in copper extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2104516A true GB2104516A (en) | 1983-03-09 |
| GB2104516B GB2104516B (en) | 1985-12-04 |
Family
ID=26280103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08220097A Expired GB2104516B (en) | 1981-07-13 | 1982-07-09 | M-alkylphenol derivatives and their use in copper extraction |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2104516B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0166151A1 (en) * | 1984-06-25 | 1986-01-02 | AlliedSignal Inc. | Novel extractants and method for the recovery of palladium |
| US4578250A (en) * | 1984-07-02 | 1986-03-25 | Allied Corporation | Method for the recovery of palladium |
| US4697038A (en) * | 1983-10-24 | 1987-09-29 | 501 Brunel University | Metal extraction using a novel group of compounds and chemical purification method |
| US4705896A (en) * | 1984-06-25 | 1987-11-10 | Allied Corporation | Novel extractants for the recovery of palladium |
| EP0529870A2 (en) * | 1991-08-23 | 1993-03-03 | Zeneca Limited | Preparation of 2-hydroxyarylaldehydes |
| EP0583910A1 (en) * | 1992-08-20 | 1994-02-23 | Zeneca Limited | Method for the preparation of 2-hydroxyarylaldehydes |
| TR26222A (en) * | 1991-08-23 | 1995-02-15 | Ici Plc | METHOD FOR THE PREPARATION OF HYDROXYARILALDEHIDES |
| EP1058676A2 (en) * | 1998-02-27 | 2000-12-13 | Conselho Nacional de Desenvolvimento Cientifico e Technologico - CNPQ | Process for preparation of oximes and resulting products |
| WO2002028862A2 (en) * | 2000-10-02 | 2002-04-11 | Emory University | Triptolide analogs for the treatment of autoimmune and inflammatory disorders |
| GB2407813A (en) * | 2003-05-15 | 2005-05-11 | John Henry Paul Tyman | The solvent extraction of borates by complexation with 1,3- and 1,2-diols derived by semi-synthesis and by separation from natural phenolic lipids |
| RU2499063C2 (en) * | 2012-01-23 | 2013-11-20 | Лидия Алексеевна Воропанова | Extraction of zinc ions from water solutions with vegetable oils |
| CN115716779A (en) * | 2022-11-28 | 2023-02-28 | 南京工业大学 | Cardanol-based bisphenol as well as preparation method and application thereof |
-
1982
- 1982-07-09 GB GB08220097A patent/GB2104516B/en not_active Expired
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4697038A (en) * | 1983-10-24 | 1987-09-29 | 501 Brunel University | Metal extraction using a novel group of compounds and chemical purification method |
| EP0166151A1 (en) * | 1984-06-25 | 1986-01-02 | AlliedSignal Inc. | Novel extractants and method for the recovery of palladium |
| US4705896A (en) * | 1984-06-25 | 1987-11-10 | Allied Corporation | Novel extractants for the recovery of palladium |
| US4578250A (en) * | 1984-07-02 | 1986-03-25 | Allied Corporation | Method for the recovery of palladium |
| CN1035813C (en) * | 1991-08-23 | 1997-09-10 | 曾尼卡有限公司 | Chemical process |
| EP0529870A3 (en) * | 1991-08-23 | 1993-04-14 | Zeneca Limited | Preparation of 2-hydroxyarylaldehydes |
| US5260487A (en) * | 1991-08-23 | 1993-11-09 | Imperial Chemical Industries Plc | Process for the preparation of 2-hydroxyarylaldehydes |
| TR26222A (en) * | 1991-08-23 | 1995-02-15 | Ici Plc | METHOD FOR THE PREPARATION OF HYDROXYARILALDEHIDES |
| EP0529870A2 (en) * | 1991-08-23 | 1993-03-03 | Zeneca Limited | Preparation of 2-hydroxyarylaldehydes |
| EP0583910A1 (en) * | 1992-08-20 | 1994-02-23 | Zeneca Limited | Method for the preparation of 2-hydroxyarylaldehydes |
| US5354920A (en) * | 1992-08-20 | 1994-10-11 | Zeneca Limited | Chemical process for the preparation of a 2-hydroxyarylaldehyde |
| EP1058676A2 (en) * | 1998-02-27 | 2000-12-13 | Conselho Nacional de Desenvolvimento Cientifico e Technologico - CNPQ | Process for preparation of oximes and resulting products |
| EP1058676A4 (en) * | 1998-02-27 | 2001-08-29 | Conselho Nacional Cnpq | Process for preparation of oximes and resulting products |
| WO2002028862A2 (en) * | 2000-10-02 | 2002-04-11 | Emory University | Triptolide analogs for the treatment of autoimmune and inflammatory disorders |
| WO2002028862A3 (en) * | 2000-10-02 | 2002-09-12 | Univ Emory | Triptolide analogs for the treatment of autoimmune and inflammatory disorders |
| US6777441B2 (en) | 2000-10-02 | 2004-08-17 | Emory University | Triptolide analogs for the treatment of autoimmune and inflammatory disorders |
| EP1659125A1 (en) | 2000-10-02 | 2006-05-24 | Emory University | Triptolide analogs for the treatment of autoimmune and inflammatory disorders |
| US7557139B2 (en) | 2000-10-02 | 2009-07-07 | Emory University | Triptolide analogs for the treatment of autoimmune and inflammatory disorders |
| US8193249B2 (en) | 2000-10-02 | 2012-06-05 | Emory University | Triptolide analogs for the treatment of autoimmune and inflammatory disorders |
| GB2407813A (en) * | 2003-05-15 | 2005-05-11 | John Henry Paul Tyman | The solvent extraction of borates by complexation with 1,3- and 1,2-diols derived by semi-synthesis and by separation from natural phenolic lipids |
| RU2499063C2 (en) * | 2012-01-23 | 2013-11-20 | Лидия Алексеевна Воропанова | Extraction of zinc ions from water solutions with vegetable oils |
| CN115716779A (en) * | 2022-11-28 | 2023-02-28 | 南京工业大学 | Cardanol-based bisphenol as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2104516B (en) | 1985-12-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |