EP0900189A1 - 2-hydroxy-5-alkyl-beta-methylstyrene et procede de preparation d'hydroxyarylaldehydes a partir de cette substance - Google Patents

2-hydroxy-5-alkyl-beta-methylstyrene et procede de preparation d'hydroxyarylaldehydes a partir de cette substance

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Publication number
EP0900189A1
EP0900189A1 EP97920075A EP97920075A EP0900189A1 EP 0900189 A1 EP0900189 A1 EP 0900189A1 EP 97920075 A EP97920075 A EP 97920075A EP 97920075 A EP97920075 A EP 97920075A EP 0900189 A1 EP0900189 A1 EP 0900189A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
allyl
substituted
phenol
hydroxy
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP97920075A
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German (de)
English (en)
Other versions
EP0900189A4 (fr
Inventor
Leroy Krbechek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Corp
Original Assignee
Henkel Corp
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 Henkel Corp filed Critical Henkel Corp
Publication of EP0900189A1 publication Critical patent/EP0900189A1/fr
Publication of EP0900189A4 publication Critical patent/EP0900189A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring
    • C07C39/19—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • 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
    • C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
    • 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
    • C07C45/673—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 by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
    • C07C69/157—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols containing six-membered aromatic rings

Definitions

  • This invention relates to a process for the preparation of hydroxyarylaldehydes from 4-alkylphenols by a new route.
  • the invention further relates to the novel compositions that are prepared from the 4- alkylphenols.
  • hydroxyarylaldehydes are particularly useful as intermediates in the preparation of oximes which find utility as metal extractants.
  • the end compounds produced by the processes of the present invention are particularly useful as intermediates for the production of oximes that in turn are useful for the extraction of copper and other metals from aqueous solutions.
  • the metal extractant is dissolved in a solvent, and is contacted with an aqueous metal solution to form a complex with the metal which is soluble in an organic solvent.
  • the organic phase is then separated from the aqueous phase and the metal is stripped from the organic phase, usually by means of an acid.
  • the water immiscible solvents usually employed for this purpose are hydrocarbon solvents such as the petroleum-derived liquid hydrocarbons, either straight chain or branched, such as kerosene, fuel oil, etc.
  • Various aromatic solvents may also be used, such as, for example, benzene, toluene, xylene and other aromatic solvents, particularly those derived from petroleum processing which may contain alkyl substituted aromatic materials.
  • the chlorinated hydrocarbons may also be used and in some instances may improve solubility.
  • both the unsubstituted and the chlorinated solvents are contemplated by the term "liquid hydrocarbon".
  • the extractants that are made from the intermediates that are produced by the processes of the present invention are characterized as having sufficient solubility in one or more of the above solvents or mixtures thereof to make about a 2% solution, and they are essentially insoluble or immiscible with water. At the same time, they each should form a complex with a metal, such as copper, which complex, likewise, is soluble in the organic solvent to at least the extent of about 2% by weight.
  • a metal such as copper
  • oxime extractants are often produced by reacting an organic carbonyl compound such as an aldehyde or ketone with hydroxylamine, usually generated from a hydroxylamine salt such as hydroxylammonium sulfate or hydroxylammonium chloride.
  • the oximes such as the hydroxy aryl ketoximes and hydroxy aryl aldoximes, which are substantially insoluble in water but soluble in water-immiscible organic solvents, such as kerosene, are useful in solvent extraction processes for the recovery of metals, particularly copper, from aqueous solutions.
  • U.S. Pat. No. 4,507,268 describes a number of such oxime reagents prepared from ketones and aldehydes, and the use thereof in liquid/liquid extraction processes.
  • Reagents frequently employed in commercial processes for copper recovery are included among those offered by Henkel Corporation under the LIX® trademark, viz., LIX®63, LIX®65N, LIX®64, LIX®64N, LIX®70, LIX®71, LIX®73, LIX®34, LIX®54, LIX®605, LIX®617, LIX®622 and LIX®6022, LIX®860, LIX®984, LIX®973, and LIX®84.
  • LIX®63 extractant includes, in addition to a liquid hydrocarbon diluent, an aliphatic ⁇ - hydroxy oxime extractant (5,8-diethyl-7-hydroxy-dodecan- 6-oxime) of the type illustrated in Swanson U.S. Pat. No. 3,224,873.
  • the LIX®65N extractant includes an alkyl substituted hydroxy benzophenone oxime (2-hydroxy-5-nonyl benzophenone oxime) as set out in Swanson U.S. Pat. No. 3,592,775.
  • the LIX®64 extractant and the LIX®64N extractant incorporate benzophenone oxime extractants (2- hydroxy-5-dodecyl benzophenone oxime and 2-hydroxy-5- nonyl benzophenone oxime, respectively) in combination with an aliphatic ⁇ -hydroxy oxime as described in U.S. Pat. No. 3,423,449.
  • Formulation of the LIX®70 extractant involves the combination of a benzophenone oxime extractant containing an electron withdrawing substituent (2-hydroxy-3-chloro- 5-nonyl benzophenone oxime) with an aliphatic ⁇ -hydroxy oxime.
  • the LIX®71 and LIX®73 formulations both include a mixture of two benzophenone oximes, one of which has an electron withdrawing substituent (i.e., a mixture of 2- hydroxy-5-nonyl benzophenone oxime and 2-hydroxy-3- chloro-5-nonyl benzophenone oxime) with the latter reagent further including an aliphatic ⁇ -hydroxy oxime.
  • the LIX®34 extractant and the LIX®54 extractant incorporate alkaryl sulfonamido quinoline and ⁇ -diketone extractants, respectively.
  • the LIX®605 extractant, the LIX®617 extractant, the LIX®622 extractant, and the LIX®6022 extractant employ alkyl substituted hydroxy benzaldoxime (salicylaldoxime) extractants according to Parrish, J. South African Chem. Inst. , 23, pp. 129-135 (1970).
  • the LIX®605 extractant and the LIX®617 extractant include 2-hydroxy- 5-nonyl benzaldoxime extractants with, respectively, nonylphenol and tridecanol additives.
  • the LIX®622 extractant and the LIX®6022 extractant comprise fomulations of 2-hydroxy-5-dodecyl benzaldoxime and a tridecanol additive in approximately 4:1 and 1:1 w/w ratios, respectively.
  • Acorga PT-5050 extractant is offered for sale by Acorga, Ltd., Hamilton, Bermuda, as a formulation comprising 2-hydroxy-5-nonyl benzaldoxime and a tridecanol additive in an approximately 2:1 w/w ratio. See also, Ackerley et al., U.S. Pat. No. 4,020,105; Ackerley et al., U.S. Pat. No. 4,020,106; and Dalton, U.S. Pat. No. 4,142,952.
  • the hydroxyarylaldehydes may be prepared by a number of routes.
  • a summary and review of the synthesis of aromatic hydroxyarylaldehydes may be found in H. Fiege, K. Wedemehyer, K.A. Bauer, A. Krève and R.G. Molleken, Fragrance Flavor Subst. Proc. Int. Haarmann Reimer Symp. 2nd, 1979 (Publ. 1980), pp. 63-73, which discusses in particular three processes of preparation.
  • a second industrially useful approach involves condensation of the phenol with formaldehyde followed by oxidation with oxygen and a catalyst. While reasonable yields of salicylaldehyde are obtained, the process consists of two steps and involves the use of expensive catalysts. Illustrative of some of the patents relating to this process are U.S. Pat. Nos. 3,173,956, 3,321,526, 3,673,257, 3,780,110, 4,026,950 and 4,190,605. Other variations have been introduced. One which is described in U.S. Pat. No. 4,151,201, involves heating paraformaldehyde with phenol in the presence of anhydrous stannous chloride and pyridine. A second, which is described in U.S. Pat. No.
  • 4,085,146 directed specifically towards production of alkylsalicylaldehydes, involves formation of a Mannich base, followed by oxidation and hydrolysis to the alkyl- salicylaldehyde. While good yields are said to be obtained, the process is economically burdensome due to the number of steps involved.
  • the invention relates to novel processes for the production of substituted hydroxyarylaldehydes (substituted salicylaldeydes) which, after oximation, are useful metal extractants.
  • the invention relates to novel precursors that are produced during the reaction steps of the above preferred embodiment processes. More specifically, the invention relates to precursors that are useful in the synthesis of hydroxyarylaldehydes, such as, for example, 4-isoalkylphenyl allyl ethers; 2-allyl- 4-isoalkylphenols; and 2-hydrox ⁇ -5-isoalkyl-beta- methylstyrenes. In another and related embodiment, the invention relates to processes for making each of these and other novel precursors useful in the production of hydroxyarylaldehydes, and particularly, 5-alkyl salicylaldehydes.
  • the invention relates to a process comprising the ozonization of solutions of 2-hydroxy-5-alkyl-beta-methylstyrenes, whereby substantial amounts of 5-alkyl-substituted salicylaldehydes are formed, and from which the desired metal extractants may be produced by oximation.
  • Figure 1 is a schematic diagram illustrating new processes for the preparation of substituted hydroxyaryl aldehydes, especially alkyl substituted salicylaldehydes that are useful Intermediates in the production of metal extractants.
  • the process of the invention uses 4-alkylphenols as starting materials.
  • the starting materials are 4-isoalkylphenols.
  • the alkyl moiety in the starting material can be a straight chain alkyl, or other alkyl isomer. In the following discussion, for simplicity's sake, it is generally assumed that preferred starting materials are used.
  • the 4-alkylphenols are and can be manufactured by the alkylation of phenol with olefins as shown as a first reaction step in Figure 1 of the drawing.
  • Suitable olefins are: octenes; nonenes including tripropylenes; decenes; undecenes; dodecenes including triisobutylenes; tetraisopropylenes; tridecenes; and so on. Since the preferred alkyl-substituted salicylaldehydes are those with isoalkyl substitution, it is preferred that this step produce a 4-isoalkyl phenol, such as, for example, a phenol substituted in the 4 position with an isononyl or an isododecyl substituent.
  • the alkylphenols are then alkylated at the phenolic oxygen atom with allyl derivatives, to produce the corresponding allyl ethers (I), preferably the 4-isoalkylphenyl allyl ethers (I).
  • the allyl ethers are rearranged via the classical Claisen rearrangement, by heating to a temperature in the range from about 140°C to about 220°C, to the corresponding 2-allyl-4-alkylphenols (II), which are then isomerized to 2-hydroxy-5-alkyl beta-methylstyrenes (III).
  • the acetate functionality is not affected by the ozonolysis, but the beta-methylstyrene substituent is converted to an aldehyde group, -CHO, and the acetate group can then be removed by hydrolysis.
  • the final product is a 5-alkyl salicylaldehyde, again present as the major component.
  • the alkyl substituted benzaldehydes per se or their hydrolysates are substituted salicylaldehydes, which, after oximation, are useful metal extractants.
  • the ozonolysis can be carried out in a number of solvents including alcohols such as methanol, ethanol or isopropanol; ketones such as acetone; hydrocarbons such as toluene or heptane; carboxylic acids such as acetic acid; esters such as butyl acetate, and ethers such as dimethoxyethane or tetrahydrofuran.
  • solvents including alcohols such as methanol, ethanol or isopropanol; ketones such as acetone; hydrocarbons such as toluene or heptane; carboxylic acids such as acetic acid; esters such as butyl acetate, and ethers such as dimethoxyethane or tetrahydrofuran.
  • allyl compounds such as allyl bromide, allyl iodide, and allyl sulfate can be used as well as corresponding substituted allyl compounds.
  • Ruthenium acetylacetonate a precious metal complex, was used to isomerize precursor II.
  • Other precious metal complexes or supported precious metal catalysts may be used to isomerize precursor II. For instance, five percent ruthenium on carbon may be used instead of ruthenium acetylacetonate.
  • Example 1 describes the preparation of the 4- alkylphenyl allyl ether of Product I.
  • Example 2 describes the preparation of Product II, a 2-allyl-4- alkylphenol, from Product I.
  • Example 3 describes the production of a beta-methylstyrene.
  • Examples 4-10 each describe one of the steps that were used to make the desired final desired product, a substituted salicylaldehyde. Lastly, the oximation of Product IV is described in
  • Example 1 Preparation of p-isododecylphenyl allyl ether (I) 273 grams (1.042M) p-isododecylphenol in 300 ml of toluene, 17.7 grams of tetra butyl ammonium hydrogen sulfate, and 395 grams of 50% NaOH aqueous solution were reacted together to give a semisolid material; and then heated to 60°C, when this initial reaction product became fluid.
  • the temperature of the mixture was then held at 75°C for 8 hours. During this period of time, periodic TLC analyses indicated that the content of unreacted isododecylphenol gradually decreased. At the four hour mark, the TLC analysis indicated that a trace of the isododecylphenol remained. GC/IR revealed that the product was mostly the 4-isododecylphenyl allyl ether, together with the unreacted isododecylphenol, and a small amount of ortho isododecylphenol. The reaction mixture, at the end of the 8 hours of maintained temperature, was washed with water, then washed with sulfuric acid, then again with water. The reaction had not gone to completion.
  • the resulting reaction mixture was distilled and a fraction was taken in a temperature range of 150°C-155°C at 90 micrometers pressure, to produce 93g of distillate material.
  • This distillate material upon analysis by GC/IR, appeared to be about 95% 2-hydroxy 5-isododecyl beta-methylstyrene.
  • Example 4 Ozonolysis in the Presence of Glacial Acetic Acid
  • TLC thin layer chromatography
  • the resultant mixture was reduced with Zn dust to reduce any peroxides, hydroperoxides, ozonides, etc., by stirring for 15 minutes at 40°-45°C.
  • Example 5 Ozonolysis of Compound IV in Methanol The ozonolysis was repeated by bubbling gaseous ozone through a solution of 6.25 grams of compound IV in about 150 ml of methanol.
  • the ozonized solution was reduced with 0.1 molar sodium thiosulfate and the product isolated to yield 6.0 grams of material.
  • Analysis by TLC showed the major component present to be DSA.
  • Analysis by IR showed the product to contain about 67% DSA.
  • Example 6 Ozonolysis of Compound IV in Acetone The ozonolysis was conducted on a solution of 6.10 grams of compound IV in about 150 ml of acetone. The product was isolated, with a yield of 6.0 grams of product, which also was rich in DSA by TLC analysis. Analysis by IR showed that the product contained about 77% DSA.
  • Example 8 Ozonolysis of Compound IV in Heptane The ozonolysis was conducted on a solution of 6.07 grams of compound IV in about 150 ml of heptane. The product was isolated, with a yield of 6.8 grams of residue which is rich in DSA by TLC analysis. Analysis by IR showed that the product contained about 54.5% DSA.
  • Step 1 In the first phase of this example, a solution consisting of 6.9 grams of 2-acetoxy-5-isododecyl-beta- methylstyrene, compound VI, in about 150 ml of glacial acetic acid, was ozonized by passing gaseous ozone through the solution at about 20°C, until no more starting material was detected by TLC. The reaction mixture was reduced with zinc dust at 40°-45°C for about 15 minutes.
  • the resultant mixture was then diluted with water, extracted two times with toluene and the combined toluene, extracts washed two times with water. The volatiles were then removed at reduced pressure to leave 6.7 grams of residue.
  • Step 2 In the second phase of this example, the crude product residue from Step 1 was stirred at room temperature for 48 hours in about 50 ml of methanol which contained 2.4 grams of 50% sodium hydroxide. The reaction mixture was then acidified with aqueous sulfuric acid and extracted two times with toluene.
  • reaction mixture was then diluted with water and extracted with toluene. This toluene extract was washed two times with water before the toluene was removed at reduced pressure to leave 2.64 grams of residue. Analysis by IR showed the oximation to be substantially complete.
  • the remaining oxime was dissolved in 48 ml of SX-11 kerosene. This kerosene solution was shaken for 10 minutes with 25 ml aqueous copper sulfate solution which contained 7.01 grams of copper per liter. After extraction of the copper, the aqueous raffinate contained only 0.74 grams of copper per liter.
  • alkyl substituents on the ring of both the intermediate compounds with the production of which this invention is concerned, and the final oxime extractants themselves, is to enhance solubility in organic solvents. Consequently, the alkyl substitution preferably consists of a substituent inserted or attached to the ring at one location, providing a long chain that will enhance solubility, and that preferably is an isoalkyl, to optimize solubility. Since the size of the alkyl substituent increases the molecular weight of the metal extractant, the shorter the chain the better, consistent with enhanced solubility.
  • compositions of the invention can be represented as follows:
  • R isohexyl or isononyl
  • R' isopentyl or isooctyl
  • Z allyl or 2 propenyl.
  • R" is a straight chain octyl, nonyl or decyl alkyl and wherein R" is attached to the ring by way of any carbon atom making up R".
  • Other products of the invention include the use of a totally branched octyl substituent (i.e., 1,1,3,3-tetra methyl butyl) or a highly branched nonyl or a highly branched decyl substituent and mixtures thereof.
  • a totally branched octyl substituent i.e., 1,1,3,3-tetra methyl butyl
  • a highly branched nonyl or a highly branched decyl substituent and mixtures thereof.
  • salicylaldehydes that can be produced by the invention provide, at present, relatively inexpensive materials for oximation, for the production of metal extractants.
  • the initial raw materials are readily available and the reaction steps of the present invention are straightforward.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de fabrication d'un salicylaldéhyde à substitution alkyle dans lequel la substitution alkyle porte sur au moins 3 atomes de carbone par molécule, et de préférence un nombre inférieur ou égal à 25, consistant à ozonoliser un 2-hydroxy béta-méthylstyrène substitué par alkyle, cette substitution par alkyle portant sur au moins 3 atomes de carbone par molécule. Après oximation des produits, on obtient des substances d'extraction du métal utiles, en particulier pour l'extraction du cuivre.
EP97920075A 1996-04-23 1997-04-10 2-hydroxy-5-alkyl-beta-methylstyrene et procede de preparation d'hydroxyarylaldehydes a partir de cette substance Withdrawn EP0900189A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US63586596A 1996-04-23 1996-04-23
US635865 1996-04-23
US67012796A 1996-06-25 1996-06-25
US670127 1996-06-25
PCT/US1997/005503 WO1997040004A1 (fr) 1996-04-23 1997-04-10 2-hydroxy-5-alkyl-beta-methylstyrene et procede de preparation d'hydroxyarylaldehydes a partir de cette substance

Publications (2)

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EP0900189A1 true EP0900189A1 (fr) 1999-03-10
EP0900189A4 EP0900189A4 (fr) 2000-01-26

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EP97920075A Withdrawn EP0900189A4 (fr) 1996-04-23 1997-04-10 2-hydroxy-5-alkyl-beta-methylstyrene et procede de preparation d'hydroxyarylaldehydes a partir de cette substance

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Country Link
EP (1) EP0900189A4 (fr)
AU (1) AU725614B2 (fr)
PE (1) PE24298A1 (fr)
WO (1) WO1997040004A1 (fr)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1532295A (en) * 1976-07-29 1978-11-15 British Petroleum Co Process for the removal of metals from organic solutions
JPS5426900A (en) * 1977-08-01 1979-02-28 Armstrong Cork Co Curable aryloxyphosphazen polymer
DE4104835A1 (de) * 1990-02-23 1991-08-29 Basf Ag Verfahren zur herstellung von salicylaldehyd

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
R. E. FORD ET AL.: "Synthesis and quantitative structure-activity relationships of antiallergic 2-hydroxy-N-1H-tetrazol-5-ylbenzamides" J.MED.CHEM., vol. 29, 1986, page 538-549 XP002109293 *
See also references of WO9740004A1 *

Also Published As

Publication number Publication date
PE24298A1 (es) 1998-05-26
EP0900189A4 (fr) 2000-01-26
WO1997040004A1 (fr) 1997-10-30
AU2435797A (en) 1997-11-12
AU725614B2 (en) 2000-10-12

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