US3307970A - Preparations for the production of metal 8-hydroxy quinolinates and process for utilizing same - Google Patents

Preparations for the production of metal 8-hydroxy quinolinates and process for utilizing same Download PDF

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US3307970A
US3307970A US187999A US18799961A US3307970A US 3307970 A US3307970 A US 3307970A US 187999 A US187999 A US 187999A US 18799961 A US18799961 A US 18799961A US 3307970 A US3307970 A US 3307970A
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copper
metal
gms
quinolinolate
solution
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Grier Nathaniel
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Merck and Co Inc
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Merck and Co Inc
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Priority to US187999A priority patent/US3307970A/en
Priority to DE1962M0065147 priority patent/DE1284019C2/de
Priority to DE19621444098 priority patent/DE1444098A1/de
Priority to BR144976/62A priority patent/BR6244976D0/pt
Priority to GB45169/62A priority patent/GB1032051A/en
Priority to SE12877/62A priority patent/SE324363B/xx
Priority to ES283065A priority patent/ES283065A1/es
Priority to BE625529A priority patent/BE625529A/fr
Priority to FR917220A priority patent/FR1359124A/fr
Priority to NO146656A priority patent/NO116714B/no
Priority to CH1410162A priority patent/CH432118A/de
Priority to NO16062165A priority patent/NO124648B/no
Priority to SE13900/66A priority patent/SE327964B/xx
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    • 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
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • 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
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C07D215/30—Metal salts; Chelates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/40—Six-membered ring containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/30—Heterocyclic compounds

Definitions

  • This invention relates to the preparation of non-alkali metal, and particularly insoluble metal S-quinolinolates (8-hydroxyquinolinates), and especially to a process for the in situ deposition of true non-alkali metal 8-quinolinolates from a single treating or impregnating solution, and to antimicrobial compositions containing or giving rise to such metal 8-quinolinolates.
  • the invention relates to processes and compositions utilizing or containing esters of 8-quinolinol for binding non-alkali metals for the purpose of depositing insoluble non-alkali metal 8-quinolinolates in fibrous or porous materials to render them proof against attack by fungi and bacteria and/ or active to reduce the ozone content in their vicinity and thereby protect vegetation subject to attack by ozone, for eliminating undesirable catalytic effects of metals in various materials like lubricating oils, plastic compositions, and the like and for other purposes requiring the conversion of a soluble nonalkali metal compound into a form which is insoluble in aqueous and organic solvents, or substantially so in organic solvents.
  • the metal salts of S-quinolinol have found extensive use in many industries for the prevention or control of microbial activity.
  • Cellulosic materials such as textiles, wood, paper and cordage have been treated with these compounds to prevent destruction by bacterial and fungal attack.
  • a wide variety of plant diseases including those of fruits and vegetables, caused by bacteria and fungi have been brought under control by the use of various metal S-quinolinolates.
  • Some of the properties of these salts which have made them outstanding are high anti-microbial activity, low toxicity to human beings, stability to heat, light, and water leaching, as well as lack of odor.
  • non-alkali metal 8-quinolinolates also known as oxinates
  • oxinates are quantitatively insoluble in water and most are practically completely insoluble in many organic solvents.
  • many of the desirable properties of the salts are lost in'the so-called solubilization techniques employed heretofore.
  • the known solubilizing procedures do not produce true non-alkali metal S-quinolinolates but rather compounds containing other radicals in addition to those of the metal and quinolinol.
  • quaternary ammoni um compounds are first caused to form salts with 8-hydroxyquinoline, and these salts are then chemically reacted with non-alkali metal soaps of water-insoluble organic carboxylic acids in an organic solvent solution to yield a metal complex of the quaternary ammonium-8- hydroxyquinoline compound.
  • the primary objective in providing soluble forms of the metal quinolinolates is to achieve complete penetration of the substances to be protected against microbial attack.
  • the importance of this is at once realized, for example, in the mildewproofing of heavy webbing such as is used in parachute harnesses.
  • Surface or partial protection by the use of dispersions of the insoluble metal quinolinolates is unsatisfactory; while treatment in two baths to effect metathetical precipitation of the insoluble compound can lead to failure because of incomplete impregnation.
  • fibrous material such as fabrics, yarn, paper, wood, cordage, leather, and other cellulosic and non-cellulosic materials
  • tht metal quinolinolates will still be formed and deposited.
  • esterification of the phenolic hydroxyl of 8-quinolinol would prevent the formation of metal quinolinolates by reaction with, for example, organic acid salts of the metals.
  • organic acid salts of the metals for example, organic acid salts of the metals.
  • the esters of 8-quinolinol react with metal salts to form true metal quinolinolates over a wide temperature range, from such low temperatures as 10 C., to about 200 C., or to a temperature just short of the decomposition temperature, the reaction rate varying with the concentration of reactants, the nature of the acid radicals, the solvents, and the temperature.
  • the fabric After being subjected to the action of squeeze rolls, the fabric was then conducted through a second bath containing a solution of B-hydroxyquinoline in water with a small amount of acetic or other aliphatic acid or any other water-miscible solvent, such as an aliphatic alcohol. This caused a practically immediate precipitation of copper 8-hydroxyquinolinate in the fabric.
  • the fabric was then passed through a drier in which the acetic acid and water were evaporated and also any additional solvent that was employed, such as the alcohol.
  • One aspect of the present invention is based on my discovery that the metathetical reaction between an ester of S-quinolinol and a metal salt in an organic solvent is an unusually slow one, and in the case of most metal salts, precipitation of the metal oxinate does not begin for a number of hours, in many cases 18 to 24 hours or longer. This aliords adequate time, after a mixture of the reactants in an organic solvent has been prepared, for the solution to be used for impregnating fibrous or porous materials, and for any batch solution to be exhausted before precipitation occurs in the bath.
  • the impregnated material After the impregnated material has passed through the bath and, if desired, through squeeze rolls, it can be allowed to dry at room temperature; after a number of hours, formation of the insoluble oxinate within the impregnated material will occur. In commercial practice, however, it is preferred to heat the treated material in order to speed the deposition of the oxinate and the removal of the solvents together with the formed other product of the reaction.
  • the present invention accordingly for the first time provides a single bath treatment for the deposition of insoluble metal oxinates within fibrous material and out of an organic solvent.
  • Me metal (monovalent or polyvalent, monovalent being shown in (a) and (b));
  • R and R' a hydrocarbon radical, or a substituted hydrocarbon radical, including alkyl groups of 1 to 22. carbon atoms; cycloaliphatic, such as cyclopentyl and e elahexyl; aromatic, like phenyl, hydroxy phenyl, and other substituted phenyl groups; aralkyl, like benzyl, phenylpropyl; and heterocyclic, like f-uryl, etc.
  • the acid component of the ester canbelong to the parafiin or fatty acid series, from the simplest; formic, to extremely long branched and unbranched, chain types, such as acetic, propionic, octoic, and uudecylic and including the saturated acids derived from animal and vegetable oils and fats, and by the hydrogenation of unsaturated acids, such as lauric, myristic, palmitic, steario and arachidic.
  • Unsaturated acids are equally suitable, including those derived from vegetable and animal fats and oils, like undecylenic, oleic, linoleic, linolenic and palmitoleic acids, and also maleic, fumaric, cinriamic; aconitic.
  • Polycarboxylic acids can also be employed; such as oxalic, malonic, succinic, glutaric, sebacic, phthalic and its isomers.
  • acids that can be used are benzoic, phenylacetic and phenylpropionic acids, tall oil acids, acidic petroleum products such as naphthenic acid, hydrogenated or partially hydrogenated; and substituted acids such as glycollic, citric, tartaric, salicylic and acetylsalicylic. It is not necessary to employ pure acids; impure acids and mixtures of acids are readily usable. In general, any acid can be used which can form an ester with a phenol, which ester is soluble in some organic solvent.
  • the metal salts employed can be those whose acid groups are the same as those which form the oxine ester; however, the acids used for the metal salt syntheses can be different from those which form the esters.
  • the use of salts of inorganic acids is possible, e.g., cupric chloride, but salts of organic acids are preferred.
  • metal quinolinolates can also be accomplished by the use of metal salts derived from the acidic enols of ketones such as 1,3- and 1,4-diketones of, for example, the following types:
  • R-(fi-CHr-(fi-R, R-fi-CH2CHz-(fi-R quinolinolates can be utilized to react with the esters of S-quinolinol.
  • the S-quinolinol ester and the metal salt are brought together preferably in solvents which give complete solutions.
  • the ratio of reactants can be stoichiometric, that is, for each metal valence equivalent contained in the metal salt there is added one mole of 8-quinolinol ester equivalent.
  • An excess of either reactant may be used in those applications where the presence of, for example, excess metal salt is desired. Titration of the reactants with each other can be readily run to determine stoichiometric quantities.
  • the esters need not be pure or free from acid, and similarly the metal salts can be used with or without excess acid. In certain applications where an excess of acid may be of advantage, as in the use of stearic acid for imparting water repellency, it has been found that the formation of the metallic quinolinolate is not prevented by its presence.
  • the reactants that is, the metal salt and theester of 8-quinolinol
  • the reactants may be brought together in the absence of solvents and physically mixed; or in those instances where the ester is a liquid at moderate temperatures, the reactants can be blended to yield a solution which, on chilling, solidifies. Even in this type of solid composition, the formation of the metal quinolinolate takes place, the rate of reaction being easily varied by the choice of ester and metal salt.
  • a further advantage of this invention lies in the ability to use a mixture of metal salts with a given ester or mixtures of esters so that mixed metal quinolinolates can be prepared simultaneously.
  • a mixture of metal salts with a given ester or mixtures of esters so that mixed metal quinolinolates can be prepared simultaneously.
  • cobalt or manganous S-quinolinolates have proved effective anti-ozonants for the protection of tobacco plants when tobacco shade cloth is treated with them. From a single bath containing both metals as salts and toget-her with various esters of 8-quinolinol, the in situ deposition of both metallic quinolinolates is easily accomplished.
  • esters of 8-quinolinol can be prepared separately from the metal salts needed to yield the metal quinolinolates, the danger of destruction by oxidation is avoided. No inert atmosphere is required, and the components can be brought together under the mildest of conditions when necessary, to yield the metal quinolinolates.
  • the present invention has also made possible the preparation of metal quinolinolates, the synthesis of which has not been possible heretofore.
  • mercuric S-quinolinolate of the composition (C H ON) Hg has never been satisfactorily prepared, products of varying composition being obtained prior to the present invention.
  • An example showing the ease of obtaining such a compound by this invention is presented hereinbelow.
  • the present invention is applicable to the esters of the various position isomers of S-quinolinol, such as the 2-, 5-, 6-, and 7-quinolinols, as well as to the esters of their lower alkyl, halo, lower .alkyl-halo, cyano, and amino derivatives, such as 4-met-hyl-8-hydroxy-, 4-methyl-2-hydroxy-, 2-methyl-4-hydroxy-, 5,7- dichloro-, dibromoand diiodo-8-hydroxy-, and S-ethyl- 7-bromo-8-hydroxy-quinolines, 4-cyanoand 7-cyano-8- hydroxy-, and Z-amino-8-hydroxy-quinolines, the 8-quinolinol is the preferred hydroxyqui'noline and the invention will be further described specifically by the use of such compound.
  • the speed of the reaction can be controlled not only by way of the temperature but also by other measures.
  • greater dilution of the solutions of the reactants will generally increase the precipitation time, and vice versa; while addition of an alcohol such as a lower alkyl- 01, like ethanol, propanol, isopropanol and butanol, will tend to speed the precipitation, apparently by accelerating the breakdown of the oxine ester.
  • the concentration of the reactants in the organic solvent can be controlled within certain limits.
  • the concentration of the reactants in the organic solvent can be controlled within certain limits.
  • many of the mixtures of a metal salt of an organic carboxylic acid and of an organic acid ester of hydroxyquinolinol will be stable for about 48 hours.
  • the process described herein is the first to produce many of the metal oxinates in crystalline condition; for example, the copper oxinate.
  • Such crystalline oxinates can be employed as pigments in paints and other coating compositions.
  • Some of the salts like the zinc salts, are fluorescent, and it appears that precipitation from a non-aqueous solvent aids in preserving the fluorescence.
  • the metal salt and the oxine ester will in many cases react with each other even when mixed in the dry condition to produce the insoluble metal oxinate.
  • This resin or wax can serve the useful .purpose of rendering the impregnated fabric or other material at least partially water-repellent. If desired, the resin or wax can be leached from the fabric or other material by a suitable solvent after the metal oxinate has been precipitated.
  • EXAMPLE 1 11.9 gms. S-quinolyl propionate and 23 gms. copper 2-ethylhexoate (8% copper) were dissolved at room temperature in 65 gms. mineral spirits to give a clear solution. In less than 24 hours at room temperature, copper 8-quinolinolate was produce-d and precipitated in the form of needles. Analysis of the precipitate for copper and 8-hydroxyquinoline confirmed the identification in addition to ther distinguishing properties.
  • Example 1 The preparation of the solution as in Example 1 was carried out using well-dried equipment. Again, copper 8- quinolinolate was obtained in excellent yield after 2 minutes heating at l125 C., and also in less than 24 hours at room temperature.
  • EXAMPLE 3 11.3 gms. 8-quinolyl propionate and 23 gms. copper 2- ethylhexoate were dissolved in 61.2 gms. xylene at room temperature to give a clear solution. There were then added 3.9 gms. propionic anhydride to act as an acceptor for water. In les than 18 hours at room temperature, copper 8-quinolinolate precipitated in good yield. Elevated temperatures, 110 125 0, caused immediate precipitation.
  • EXAMPLE 5 The same amounts of reactants as Example 4 were dissolved in 5 gms. of xylene instead of 65 gms. of xylene at room temperature. In less than 18 hours, because of the higher concentration than in Example 4, copper 8- quinolinolate formed in relatively large quantity.
  • EXAMPLE 6A The presence of a large excess of acid surprisingly does not increase the stability of the ester in the presence of the metal salt, as shown by the following:
  • EXAMPLE 6B 12 gms. 8-quinolyl propionate, 24 gms. 2-ethylhexoie acid, 23 gms. copper 2-ethylhexoate (8% copper), and 41 gms. xylene were mixed together at room temperature to give a clear solution. On standing, there gradually deposited copper B-quinolinolate.
  • EXAMPLE 6C 12 gms. S-quinolyl propionate, 65 gms. propionic acid and 23 gms. copper Z-ethylhexo'ate (8% copper) were mixed together at room temperature to give a clear solution. Even at room temperature, there gradually precipitated copper 8-quinolinolate.
  • EXAMPLE 6D 12 gms. 8-quinolyl propionate, 12 gms. propionic acid, 20 gms. methyl dihydroabietate and 33 gms. xylene were mixed at room temperature to give a clear solution. Finally, 23 gms. copper 2-ethylhexoate (8% copper) were added. The resultant clear solution gradually deposited copper 8-quinolinolate on standing.
  • EXAMPLE 7 Some of the commonly employed types of compounds used as plasticizers and water-proofing materials, as in fabric finishing, are esters. It was desirable to determine whether there would be competition in the metal catalyzed ester cleavage between these esters and the oxine ester.
  • the alcohol components of these esters ranged from the butyl to tridecyl, and included cyclic and alicyclic alcohols. In no case was there any interference with the metal-catalyzed cleavage of the oxine ester to yield the copper S-quinolinolate.
  • ethyl 2,2-dimethyl-4,-cyclohexane-dione oarboxylate was prepared, using gentle warming. Then, 23 gms. copper 2-ethylhexoate (8% copper) were added. In less than 24 hours the viscous solution deposited copper 8-quinolinolate.
  • EXAMPLE 9 18.2 gms. S-Iauroyloxyquinoline and 23 gms. copper 2-ethylhexoate (8% copper) were mixed at room temperature to give a clear solution. On heating at 90-100 C., rapid precipitation of the copper 8-quino1inolate occurred. 50 ml. of xylene were added and the mixture heated at 100 C.; no solution took place. Pure copper 8-quinolinolate was easily isolated.
  • EXAMPLE 10 14 gms. S-quinolyl benzoate were dissolved in 70 gms. xylene by warming. Next, 22 gms. copper 2-ethylhexoate (8% copper) were added. On heating at 95 C., heavy precipitation of copper 8-quinolinola-te resulted.
  • EXAMPLE 1 1 38 gms. S-quinolyl stearate, 46 gms. copper 2-ethylhexoate (8% copper) and 116 gms. mineral spirits were mixed at room temperature to give 'a clear solution. In one-half hour at 95 0, heavy crystallization of copper 8-quinolinolate was observed.
  • EXAMPLE 12 A solution of 16 g. S-quinolyl 2-ethylhexoate in 40 g. 2-ethylhexoic acid was mixed with 23 g. copper 2-ethylhexoate (8% copper) to give a clear solution. On standing for a period of several days at room temperature, gradual precipitation of copper-S-quinolinolate occurred. A ten-fold dilution with mineral spirits showed the same behavior.
  • a solution of 16 g. 8-quinolyl 2-ethylhexoate in 10 g. 2-ethylhexoic acid was mixed with 23 g. copper 2-ethylhexoate (8% copper) to give a clear solution at room temperature. It gradually deposited copper 8-quinolinolate on standing at room temperature. Heating at 95 C. caused rapid precipitation.
  • esters of oxine enumerated in the examples there were used the phthalate, maleate, oleate, furoate, citrate, naphthenate, sebacate, butyrate, mixed fatty acid esters with palmitic and stearic acids, linoleic and linolenic acids, tall oil acids, malonate, phenylacetate, cinnamate, para-nitrobenzoate, and other organic carboxylic acids.
  • palmitic and stearic acids palmitic and stearic acids
  • linoleic and linolenic acids tall oil acids
  • malonate phenylacetate
  • cinnamate para-nitrobenzoate
  • other organic carboxylic acids In no instance was there failure of cleavage in the presence of soluble copper salts to yield the copper oxinate.
  • copper salts utilized were the propionate, naphthenate, oleate, resinate (salts of rosin acids), 2-ethylhexoate, stearate, ethyl acet-oacetate, ethyl benzoylacetate, laurate, linoleate, succinate, phthalate, and decanoate.
  • EXAMPLE 13 12.5 gms. 8-quinolyl Z-ethylhexoate and 12.5 gms. zinc naphthenate (8% zinc) were dissolved in 25 gms. mineral spirits at room temperature to give a clear light amber solution. On standing at room temperature, in less than 18 hours a voluminous zinc oxinate precipitated. It failed to dissolve on heating.
  • EXAMPLE 14 14 gms. 8-quinolyl stearate were dissolved in 24 gms. mineral spirits with gentle heating. The solution was cooled to room temperature and 12.5 gms. zinc naphthenate (8% zinc) were added. On heating at 110 C., there was complete precipitation of zinc oxinate in less than 1 minute. Further heating even at higher tempera tures failed to effect solution of the precipitate.
  • EXAMPLE 16 68.5 gms. S-quinolyl propionate were dissolved in 515 gms. mineral spirits with gentle warming. There were then added 167 gms. cobalt naphthenate (6% cobalt). In less than 1 minute at 1.15 C, the solution gave rise to a very heavy precipitate of cobalt quinolinolate. At room temperature, the freshly prepared solution showed precipitation of cobalt quinolinolate within one-half hour.
  • EXAMPLE 17 137 gms. 8-quinolyl Z-ethylhexoate were dissolved in 200 gms. mineral spirits at room temperature. Upon the addition of 167 gms. cobalt naphthenate (6% cobalt) and heating at 100 C., cobalt quinolinolate formed in less than two minutes as an insoluble precipitate in large amount.
  • EXAMPLE l9 10.6 gms. magnesium stearate were dissolved in ml. xylene with gentle warming. Then 8.4 gms. of 8- quinolyl propionate were added, which dissolved rapidly. The resultant solution slowly deposited magnesium oxinate at room temperature and very rapidly at with the prior development of an intense lemon yellow color. Further heating failed to dissolve the precipitate.
  • EXAMPLE 20 In a similar procedure using tallates, ricinoleates, naphthenates, octoates, oleates and other salts of such metals as cerium, zirconium, ferric iron, lead, calcium, barium, mercuric mercury, manganese, cadmium, nickel, silver, bismuth and tin, the corresponding metalloquino- Iinolates readily formed. In some instances there was rapid precipitation on heating: In other cases where the metalloquinolinolate was soluble in the solvents employed, a marked color change was noted.
  • a solution was prepared at room temperature from 10 gms. mercuric Z-ethylhexoate (37% Hg), 10 g. 8- quinolyl Z-ethylhexoate and 60 gms. mineral spirits. A clear, light yellow color was noted. On heating, at C. for less than 2 minutes, a deep red color followed by the precipitation of mercuric oxinate was observed. The solution which remained at room tem- 13 perat'ure gave a further quantity of the same product in 72 hours.
  • EXAMPLE 21 50 gms. 8-quinolyl benzoate, 100 gms. calcium naphthenate (4% calcium) and 750 gms. mineral spirits were heated to give a clear solution. Within 2 minutes at temperatures above 100 C. complete precipitation of calcium oxinate resulted.
  • EXAMPLE 22 16.7 gms. zirconium naphthenate (6% Zr), 8.9 gms. S-quinolyl propionate and 47 gms. mineral spirits dissolved on gentle warming to give a light greenish yellow solution. In less than 1 minute at 135 C. a rapid color change occurred denoting the formation of zirconium oxinate. 7
  • EXAMPLE 23 EXAMPLE 24 16.7 gms. ceric naphthenate (6% cerium), 5.8 gms. 8-quinolyl propionate and 29 gms. mineral spirits gave a clear solution on mixing. Heating at 105 C. gave heavy precipitation of ceric oxinate.
  • EXAMPLE 25 25.8 gms. commercial copper tallate (7% Cu), 16 gms. 8-quinolyl 2-ethylhexoate, and 58 gms. mineral spirits were mixed at room temperature to give a clear deep green solution. In less than two minutes of heating at 125 C., the initially clear solution became a thick paste due to the precipitation of copper S-quinolinolate.
  • EXAMPLE 26 gms. lead octoate (24% Pb), 7.0 gms. 8-quinolyl octoate and 80 gms. mineral spirits were mixed at room temperatures to give a'clear solution. An aliquot was heated to boiling for a few minutes. A very sharp color change denoted the liberation of oxine from the esterified compound and consequent lead oxinate formation. The remainder of the initial solution showed the same transformation at room temperatures in 2448 hours.
  • EXAMPLE 27 32 ml. of manganese naphthenatae (commercial), containing 6% manganese, 35 ml. of S-qinolyl 2-ethylhexoate and 200 m1. of mineral spirits were mixed at room temperature to give a clear solution. Heating at 125 C. for '2-5 minutes caused a very marked color change, again 14 due to the release of oxine from the ester and formation of the oxinate.
  • the oxine esters can be employed also for protecting various coatings for wires, and particularly for underground cables, against fungal and bacterial attack.
  • a known wire-coating composition composed of linseed oil, zinc oxide, and neoprene rubber, which is thermocured at about 290 F.
  • the oxine ester such as the stearate, oleate or 2-ethylhexoate (octoate)
  • the oxine ester will bind the metal of the metal compound employed as the catalyst and thus form the antifungal and antibacterial metal oxinate.
  • EXAMPLE 29 46 gms. cop-per octoate (containing 8% copper), 33 gms. 8-quinolyl 2-ethylhexoate, 23 gms. 2-ethyl hexoic acid, 60 gms. diethyl amine and 30 gms. of mineral spirits were mixed at room temperature to give a clear solution. On heating the solution for 1530 minutes at -100 C., copper 8-quinolinolate precipitated. An aliquot of the unheated solution, allowed to stand at room temperature, deposited copper 8-quinolinolate in 24 hours.
  • Metal alcoholates and metal phenates can be employed in the above example to yield the metal 8-hydroxyquinolinates.
  • these starting compounds are copper ethylate and copper and calcium phenates. Copper ammonium salts, and also copper amino complexes in non-aqueous solvents, will precipitate the copper oxinate on reaction with the oxine ester.
  • Organic metal compounds that are not strictly salts but which are soluble in a solvent in which the oxine ester is also soluble may also be used, such as calcium and magnesium di-(lower alkyl) malonate esters, whose formulas can be written as follows:
  • alkyl stands for lower alkyl, such as methyl, ethyl, propyl, butyl, etc.
  • Me represents the metal, preferably calcium and magnesium.
  • metal enolates can be employed, such as copper acetyl acetone, and also salts, preferably the copper salts of beta-ketoesters, such as methyl 3-keto-butyrate and ethyl 3-keto hexoate and octoate and other lower alkyl keto-esters.
  • esters of oxine in place of the specific esters of oxine named in the above examples, other esters, and also the corresponding esters and other esters of derivatives of oxine, such as the propionic, 2-ethylhexoic and undecylenic acid esters of 5,7-dichloro-8-hydroxyquinoline, can be employed.
  • the preferred hyd-roxyquinoline esters are generally those of 2-ethylhexoic acid, naphthenic acid, and the acids obtainable from animal and vegetable fats and oils, particularly oleic and stearic acids.
  • Benzene, xylene, and toluene have a slight solvent action on certain of the metal 8-quinolinolates, while mineral spirits and other saturated aliphatic hydrocarbons generally have the least solvent action.
  • Aluminum forms an oxinate which is quite soluble in organic solvents, but oxinate of this metal as well as of the other non-alkali metals is quite insoluble in water.
  • This procedure will remove all of the salt from a fabric treated either "by the known two-bath method wherein the fabric is first passed through a solution containing a soluble copper salt and then through a solution of S-hydroxyquinoline, and/or by the so-called single bath method wherein there is employed a solu-bilized copper 8- quinolinolate. It is also the method employed in testing fabrics which have been treated with a dispersion of copper 8-quinolinolate.
  • the extractions remove 100% of the copper compound in the fabric, but when the same test is applied to fabrics treated to deposit copper S-quinolinolate therein in accordance with the present invention, only about of the copper salt is extracted, where 1% of the salt has been deposited, as is required by certain Government specifications. Heating with 10% sulfuric acid for a much longer time is required to remove substantially all of the copper salt from tfabric treated in accordance with my invention. This difference is probably due to the fact that in my process, by reason of the fact that the solution contains both re- :acting substances when it is absonbed by the fibers, precipitation occurs uniformly throughout the interior of the fibers, as well as upon their surfaces.
  • the simultaneous formation of the anhydride when the metal compound is in the form of a carboxylic acid salt affects or modifies the nature of the deposition of the copper oxinate and possibly other oxinates, and the manner in which they are :absorbed or adsorbed by the fibers.
  • the extraction test establishes a far greater permanence of the deposit effected by the present invention than is obtainable by prior protcedures.
  • a paint or other coating composition contains a metal salt dissolved in the vehicle
  • the composition can be rendered mildew-proof either by the direct addition of an oxine ester to the paint by the manufacturer, or the ester can be supplied to the purchaser of the paint to be added immediately before use of the paint or other coating composition.
  • the coating composition does not contain a non-alkali metal salt in solution
  • the salt can be added to the composition by the manufacturer or by the user just prior to use, along with the oxine ester.
  • the amount of oxine ester that is added, with or without the added metal salt need be no more than 1% of the total weight of the paint, a quantity ranging between to by weight of the coating composition being usually sufificient.
  • the oxine esters of saturated acids such as the 2- ethylhexoic, myristic, palmitic, stearic and other higher molecular weight fatty acids which are not subject to oxidation.
  • the amount of the ester should be that sufficient to bind the metal compounds normally occurring in lubricating oils and will ordinarily amount to no more than about /,,0% to 1 of the weight of the oil.
  • the anhydrides produced in the above-described reactions are usually of benefit in the process, since they are capable of reacting with cellulosic fibers to produce, for example, cellulose esters which are more water-repellent than the original cellulosic fabric or other material.
  • My process accordingly reduces or even eliminates the need for treatment of a fabric to render it water-repellent, as in the case of tent material, parachutes, and the like.
  • the present invention provides a process whereby true non-alkali metal S-quinolinolates can be precipitated out of a single treating solution by taking advantage of the fact that the re action between the metal salt, preferably of an organic acid, and the ester of 8-quinolinol proceeds so slowly that precipitation will not ordinarily occur for quite a number of hours at room temperature, so that the complete batch of a mixture of the reactants can be exhausted in impregnating a fibrous or porous material before precipitation sets in within the fibers or the interstices of the material being treated.
  • the precipitation of the metal S-quinolinolates can be accelerated by heating to any elevated temperature below the decomposition point; usually temperatures of to C. will be adequate.
  • the procedure of the present invention has, in addition to the advantages above mentioned, the further advantage that the oxine ester is usually soluble in all of the solvents in which the metal salt is soluble, whereas the presolubilized mixtures of the prior art are usually limited in their solubility, for example, to solubility in xylene or mineral spirits. As shown by the foregoing, the present process can be conducted even without the use of any solvent.
  • non-alkali metal S-quinolinolates which comprises reacting an ester of 8-quinolinol with a salt of a non-alkali metal in the absence of sufficient water to cause substantial hydrolysis of the ester before it reacts with the metal salt.
  • ester group and the metal salt are derived from aliphatic or cycloaliphatic carboxylic acids.
  • metal of said metal salt is aluminum, beryllium, magnesium, calcuim, strontium, barium, lead, zinc, mercury, tin, iron, nickel, cobalt, manganese, chromium, copper, cadmium, silver, thallium, zirconium or cerium.
  • ester group is propionate, Z-ethyl hexoate, lauryloxy, stearate or benzoate and the metal salt is the metal 2-ethyl hexoate, naphthenate or stearate.

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NL286201D NL286201A (forum.php) 1961-11-30
US187999A US3307970A (en) 1961-11-30 1961-11-30 Preparations for the production of metal 8-hydroxy quinolinates and process for utilizing same
DE19621444098 DE1444098A1 (de) 1961-11-30 1962-11-27 Verfahren zur Herstellung von Metallchinolinolaten mit Ausnahme der Alkalimetallderivate und diese enthaltende Zusammensetzungen
BR144976/62A BR6244976D0 (pt) 1961-11-30 1962-11-27 Processo para preparar e utilizar quinolinolatos de metal nao alcalino e preparacao assim obtida
DE1962M0065147 DE1284019C2 (de) 1961-11-30 1962-11-27 Verfahren zum Schutz von Schmieroelen gegen die stoerende Wirkung von darin enthaltenen Metallionen
SE12877/62A SE324363B (forum.php) 1961-11-30 1962-11-29
GB45169/62A GB1032051A (en) 1961-11-30 1962-11-29 Methods for preparing and utilizing non-alkali metal quinolinolates and preparations obtained therein
ES283065A ES283065A1 (es) 1961-11-30 1962-11-29 Procedimiento para preparar quinolcinolatos de metales no alcalinos
BE625529A BE625529A (fr) 1961-11-30 1962-11-30 Procédé de préparation de 8-hydroxy-quinoléinates métalliques.
FR917220A FR1359124A (fr) 1961-11-30 1962-11-30 Procédé de préparation de 8-hydroxy-quinoléinates métalliques
NO146656A NO116714B (forum.php) 1961-11-30 1962-11-30
CH1410162A CH432118A (de) 1961-11-30 1962-11-30 Verfahren zum Schützen von Textilien gegen Pilz- und Bakterienbefall
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622377A (en) * 1969-08-27 1971-11-23 Us Agriculture Process for applying copper 8-quinolinolate to cellulosics from solvent system
US3872128A (en) * 1972-03-08 1975-03-18 Union Carbide Corp Antimicrobial hydroxy quinoline, ethylene-acrylic polymer compositions
US3895013A (en) * 1971-10-20 1975-07-15 Pechiney Ugine Kuhlmann Hydroxyquinoline derivative
US4431553A (en) * 1980-12-30 1984-02-14 Autoipari Kutato Intezet Lubricant composition containing metal oxyquinolinate
US20120205597A1 (en) * 2011-02-14 2012-08-16 Manoharan S Sundar Zinc chalcogenides, doped zinc chalcogenides, and methods of making
CN110476988A (zh) * 2019-09-17 2019-11-22 嘉兴市世诚科技有限公司 一种防治农作物细菌性病害的杀菌组合物及其用途

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2030033A (en) * 1933-06-10 1936-02-04 Standard Oil Co Treatment of cracked petroleum distillates
US2255597A (en) * 1939-11-10 1941-09-09 Du Pont Stabilization of organic substances
US2298640A (en) * 1942-05-13 1942-10-13 Lubri Zol Corp Lubricating composition
US2363778A (en) * 1942-12-01 1944-11-28 Du Pont Stabilization of organic substances
US2372588A (en) * 1940-06-19 1945-03-27 Shell Dev Compounded mineral oil
US2381863A (en) * 1943-05-01 1945-08-14 Monsanto Chemicals Method of fungusproofing textiles
US2523114A (en) * 1949-01-22 1950-09-19 Standard Oil Dev Co Methoxy dicyclopentadiene mercuric chloride for controlling parasites
US2526948A (en) * 1945-10-23 1950-10-24 Phillips Petroleum Co Process of treating textiles with half-acid amide derivatives
US2608556A (en) * 1950-07-10 1952-08-26 Scient Oil Compounding Company Preparation of a soluble metal quinolinolate
US2666058A (en) * 1950-05-16 1954-01-12 Ciba Pharm Prod Inc Undecylenic acid esters of 8-hydroxyquinolines
US2745832A (en) * 1954-03-08 1956-05-15 Nuodex Products Co Inc Metal quinolinolates and methods of making the same
US2755280A (en) * 1952-02-29 1956-07-17 Geigy Chem Corp Solubilization of metallic-8-quinolinolates
US2799615A (en) * 1953-05-23 1957-07-16 Riedel De Haen Ag Process of preparing fungicidal 8-hydroxyquinoline compositions
US2895837A (en) * 1956-12-26 1959-07-21 Cfmc New complex solutions and dispersions and process for their preparation
US2979434A (en) * 1953-12-07 1961-04-11 Monsanto Chemicals Polyamine nematocides
US2991183A (en) * 1958-01-02 1961-07-04 Metalsalts Corp Fungicidal and bactericidal compositions
US3002882A (en) * 1958-07-28 1961-10-03 Tno Systemically working agent for combating micro-organisms
US3017362A (en) * 1958-06-12 1962-01-16 Universal Oil Prod Co Hydrocarbon oil composition
US3031402A (en) * 1959-07-27 1962-04-24 Sinclair Refining Co Lubricant composition

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2030033A (en) * 1933-06-10 1936-02-04 Standard Oil Co Treatment of cracked petroleum distillates
US2255597A (en) * 1939-11-10 1941-09-09 Du Pont Stabilization of organic substances
US2372588A (en) * 1940-06-19 1945-03-27 Shell Dev Compounded mineral oil
US2298640A (en) * 1942-05-13 1942-10-13 Lubri Zol Corp Lubricating composition
US2363778A (en) * 1942-12-01 1944-11-28 Du Pont Stabilization of organic substances
US2381863A (en) * 1943-05-01 1945-08-14 Monsanto Chemicals Method of fungusproofing textiles
US2526948A (en) * 1945-10-23 1950-10-24 Phillips Petroleum Co Process of treating textiles with half-acid amide derivatives
US2523114A (en) * 1949-01-22 1950-09-19 Standard Oil Dev Co Methoxy dicyclopentadiene mercuric chloride for controlling parasites
US2666058A (en) * 1950-05-16 1954-01-12 Ciba Pharm Prod Inc Undecylenic acid esters of 8-hydroxyquinolines
US2608556A (en) * 1950-07-10 1952-08-26 Scient Oil Compounding Company Preparation of a soluble metal quinolinolate
US2755280A (en) * 1952-02-29 1956-07-17 Geigy Chem Corp Solubilization of metallic-8-quinolinolates
US2799615A (en) * 1953-05-23 1957-07-16 Riedel De Haen Ag Process of preparing fungicidal 8-hydroxyquinoline compositions
US2979434A (en) * 1953-12-07 1961-04-11 Monsanto Chemicals Polyamine nematocides
US2745832A (en) * 1954-03-08 1956-05-15 Nuodex Products Co Inc Metal quinolinolates and methods of making the same
US2895837A (en) * 1956-12-26 1959-07-21 Cfmc New complex solutions and dispersions and process for their preparation
US2991183A (en) * 1958-01-02 1961-07-04 Metalsalts Corp Fungicidal and bactericidal compositions
US3017362A (en) * 1958-06-12 1962-01-16 Universal Oil Prod Co Hydrocarbon oil composition
US3002882A (en) * 1958-07-28 1961-10-03 Tno Systemically working agent for combating micro-organisms
US3031402A (en) * 1959-07-27 1962-04-24 Sinclair Refining Co Lubricant composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622377A (en) * 1969-08-27 1971-11-23 Us Agriculture Process for applying copper 8-quinolinolate to cellulosics from solvent system
US3895013A (en) * 1971-10-20 1975-07-15 Pechiney Ugine Kuhlmann Hydroxyquinoline derivative
US3872128A (en) * 1972-03-08 1975-03-18 Union Carbide Corp Antimicrobial hydroxy quinoline, ethylene-acrylic polymer compositions
US4431553A (en) * 1980-12-30 1984-02-14 Autoipari Kutato Intezet Lubricant composition containing metal oxyquinolinate
US20120205597A1 (en) * 2011-02-14 2012-08-16 Manoharan S Sundar Zinc chalcogenides, doped zinc chalcogenides, and methods of making
US8801972B2 (en) * 2011-02-14 2014-08-12 Indian Institute Of Technology Kanpur Zinc chalcogenides, doped zinc chalcogenides, and methods of making
CN110476988A (zh) * 2019-09-17 2019-11-22 嘉兴市世诚科技有限公司 一种防治农作物细菌性病害的杀菌组合物及其用途

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SE327964B (forum.php) 1970-09-07
ES283065A1 (es) 1963-05-01
DE1284019B (de) 1968-11-28
BR6244976D0 (pt) 1973-05-15
FR1359124A (fr) 1964-04-24
SE324363B (forum.php) 1970-06-01
CH432118A (de) 1967-09-15
GB1032051A (en) 1966-06-08
NL286201A (forum.php)
BE625529A (fr) 1963-03-15
CH1410162A4 (forum.php) 1966-09-30
NO116714B (forum.php) 1969-05-12
DE1444098A1 (de) 1970-01-22

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