US3266981A - Biologically toxic compositions containing boron-phenol complexes and methods - Google Patents

Biologically toxic compositions containing boron-phenol complexes and methods Download PDF

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US3266981A
US3266981A US425609A US42560965A US3266981A US 3266981 A US3266981 A US 3266981A US 425609 A US425609 A US 425609A US 42560965 A US42560965 A US 42560965A US 3266981 A US3266981 A US 3266981A
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David R Stern
Friedrich J Weck
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American Potash and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/08—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing boron
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • C10L1/303—Organic compounds compounds not mentioned before (complexes) derived from metals boron compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/38—Aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy

Definitions

  • This invention relates, in general, to biologically toxic compositions and to methods of combating biological growth. More specifically, the biologically toxic compositions comprise a major amount of inert matter and an effective amount of certain toxic ontho-substituted-phenol complexes.
  • substratum as used in this specification and in the appended claims means any substance which it is desired to protect from undesired biological growth and which is capable of retaining on its surface or within itself, or both, a toxic amount of the biological toxicants which are more specifically described hereafter.
  • the term includes liquids, powders, granular material, unitary solids, emulsions, solutions, dispersions, and heterogeneous systems such as a liquid-liquid, liquid-solid, or solidsolid type.
  • the biologically toxic compositions according to this invention are comprised of a major proportion of (A) a substratum and (B) a toxic amount of an orthosubstituted-phenol complex.
  • the ortho-substituted-phenol complex portion of these compositions comprises phenols having the formulas:
  • R can be any of the substituents, chlorine, fluorine, bromine, iodine, alkyl, cycloalkyl or aryl; R can be any of chlorine, fluorine, bromine, iodine, alkyl, cycloalkyl or aryl, with the provision that only one of R and R can be halogen on any given com- 3,266,981 August 16, 1966 pound; R can be any of hydrogen, alkyl, cycloalkyl or aryl substituents; M can be any of the alkali metals, lithium, sodium, potassium, rubidium, or cesium; or ammonium.
  • R or R When one of R or R is a halogen, the other can be an alkyl or cycloalkyl group containing from 4 to 24 carbon atoms or an aryl group containing from 6 to 24 carbon atoms.
  • R nor R When neither R nor R is a halogen, either one can be an alkyl group having from 2 to 22 carbon atoms, a cycloalkyl substituent having from 4 to 22 carbon atoms or an aryl group having from 6 to 22 carbon atoms, provided that there is a total of between 8 and 24 carbon atoms present in the two substituents combined.
  • R When R is not hydrogen, it can be either an alkyl group containing from 1 to 7 carbon atoms, a cycloalkyl group containing from 4 to 7 carbon atoms or an aryl group containing from 6 to 10 carbon atoms.
  • the total number of carbon atoms in the R and R substituents combined is at least 4 when one of these substituents is halogen and at least 8 when neither R nor R is halogen.
  • the method of inhibiting or substantially minimizing the growth of biological material on a substratum comprises providing such substratum with an amount of'the above described toxicants sufficient to render the resultant substratum-toxicant composite, toxic to biological material.
  • the toxicant may be associated with it by, for example, mixing, blending, shaking, or by like means.
  • the substratum is a liquid or an emulsion
  • toxicant can be associated with it by dispersing, dissolving, or suspending the compound in the liquid or emulsion.
  • the toxicant can be associated with it in many ways such as, for example, by dusting or spraying the toxicant onto the surface of the solid either with or without a solvent or diluent; or by soaking the unitary solid in a large body of liquid containing dissolved toxicant for a period of [time sutficient to impregnate the solid with the desired concentration of toxicant; and the like.
  • Pressure impregnation techniques also can be used, employing a pressure chamber in which the toxicant is introduced at elevated temperatures, either as a vapor or as a liquid entrained in another vapor such as toxicant-in-steam, and the like.
  • Hardenable coatings such as paints, enamels, varnishes, and like surface coatings can be associated with the toxicant by dispersing, grinding into, polymerizing or dissolving the toxic compounds in the fluid coating before the latter has hardened or by spraying or dusting the toxic compounds on the coating after it has been applied to a surface.
  • the substituents R, R and R of the ortho-substitutedphenol complex portion (B) of the composition preferably are chosen so that the resulting toxicant is compatible with the desired substratum portioii (A).
  • R should be a low molecular weight substituent such as methyl
  • R should be halogen or a low molecular weight alkyl
  • R should be either hydrogen or a low molecular weight substituent such as methyl.
  • R should be a large substituent such as octyl or nonyl, while the selection of R and R is not critical.
  • This invention is particularly useful in preventing the growth of undesirable biological matter in liquid hydrocarbons.
  • an aqueous phase to form in contact with a liquid hydrocarbon, due to absorption and condensation of atmospheric moisture.
  • liquid hydrocarbons are almost always in contact with an aqueous phase.
  • Certain micro-organisms live in this aqueous phase and feed on the hydrocarbon.
  • the interface between the aque- 011s and hydrocarbon phases is often covered with a growth of micro-organisms.
  • An eifective amount of toxicant dissolved in the hydrocarbon phase substantially inhibits the growth of these micro-organisms.
  • normally liquid hydrocarbon as used in the instant specification and in the appended claims includes gasoline, kerosene, naphtha, gas oil, cylinder stock, diesel fuel, jet fuel, heating oil, and the like. Normally, these hydrocarbons contain an average of from about four to fourteen carbon atoms, have a specific gravity or from about 0.6 to 0.95, an average molecular weight of from about 60 to 250, and an average boiling point of from about 40 F. to 700 F. Average boiling point is defined as the temperature of the boiling mixture of hydrocarbons when one half by weight of the hydrocarbons have been distilled olf. In general, any hydrocarbon material from the lightest liquids through waxy solids to highly polymeric solids can be protected from attack by biological material, according to this invention.
  • This invention is also useful in preventing the growth of undesirable biological material on cellulosic substratum.
  • Cellulosic materials which can be provided with a toxic amount of the herein described toxicants, in accordance with this invention, include cellulosic films and filaments, fabrics, paper, Wood, various compositions including wood in one form or another, such as compositions iCOlltaining wood fibres in a matrix of some other material and the like. These cellulosic materials can be provided with a toxic amount of these compounds by any of the procedures described above, including particularly, impregnating as by soaking, treating the surface of the cellulosic materials, by spraying or dusting, and coating the surface with other compositions containing the toxic compounds such as varnishes, lacquers, calcimine, oil and water base paints, paper coatings of various kinds, and the like.
  • the toxic compounds such as varnishes, lacquers, calcimine, oil and water base paints, paper coatings of various kinds, and the like.
  • the preferred cellulosic material is wood. Wooden articles provided with a toxic amount of the above described toxicants are extremely resistant to wood destroying fungus and insects. Many different types of wood can be protected in this manner. Thus, pine, fir, hickory, mahogany, oak, ash, spruce, birch, aspen, maple and the like, can be protected from insects and micro organisms by providing them with a toxic amount of these compounds.
  • Wood can be provided with these compounds by any of the conventional, well-known procedures for impregnating woods with preservatives.
  • These toxicants which are boron complexes, can be introduced into the wood as complexes or the complex can be tor-med in situ in the wood [by reaction between the corresponding ortho-alcoh'ol-phenol and boric acid or some other soluble boron compound. This reaction can be accomplished, for example, by first impregnating the wood with one reactant, followed by a second impregnation with the other reactant.
  • Various other agents can be employed with the toxicants, for example, surfactants which aid the penenation of the toxicant into the wood can be used.
  • the toxicants can be in- :orporated in wood in an amount ranging from about ).1 percent by weight to about 0.05 percent by weight. It will be understood that the concentration of toxicant ormally will be greatest at the surface of the wood and vill decrease progressively with increasing depth into he wood.- For this reason, the surface of the wood is iften provided with an excess of toxicant so that the inerior will contain an effective amount of the compound.
  • a further aspect of this invention comprises the proision of a toxic amount of the herein described toxicants with various substratum-surface coating compositions.
  • the toxicants can be incorporated in a substratum such as paint to render the paint resistant to the growth of biological materials.
  • a substratum such as paint to render the paint resistant to the growth of biological materials.
  • the paints, according to this invention, which can be provided with a toxic amount of toxicant are comprised primarily of pigment and vehicle.
  • the volatile constituents in the paint vehicle include, for example, hydrocarbons such as aliphatic and mineral spirit cuts, aromatics such as toluene and xylene, lacquer solvents, for example, esters such as butyl acetate, and ketones such as methylethylketone, mixtures of two or more vehicles, and the like.
  • the non-volatile portions of the vehicle can include, for example, natural drying oils such as linseed oil, synthetic resins such as glycerol phthalate or phenol-formaldehyde, lacquers which dry by solvent evaporation such as nitrocellulose and other thermoplastic resins, materials such as silicones, mixtures of two or more non-volatile vehicles, and the like.
  • the pigment portion of the paint can be either inorganic or organic, including, for example, chalk, cadmium yellow, bone black, azurite, litharge, mica, ochre yellow, pumice, white lead, zinc white, talc, red lead, silica, and the like. These pigments may be used singly or in mixtures of two or more.
  • the gloss of the particular paint is conveniently regulated by adjusting the proportion of pigment contained therein. In general, the lower the amount of pigment, provided it is present in a quantity adequate to provide adequate covering, the glossier the paint.
  • the toxicants can be incorporated in paint in an amount ranging from about 0.1 percent by weight to about 0.05 percent by weight.
  • these toxicants are used in anti-fouling marine paints to prevent the growth of various marine life on boat hulls, they are provided in relatively large amounts, for example, in excess of about 4 percent.
  • the biological toxicants used in the present invention are stable compounds which range from viscous liquids to crystalline 0r glassy solids. They are soluble in a wide range of solvents and as herein described, can advantageously be tailored to fit the solubility problems attendant the particular susbtratum involved. These ortho-substituted-phenol complexes can be advantageously employed for a variety of commercial and industrial purposes, but they are particularly useful as biological toxicants. When used as biological toxicants, they are effective at a concentration from as low as about one part per million parts of substratum up to a concentration of about 1,000 parts per million parts of substratum.
  • the ortho-alcohol-phenols used in the preparation of the toxicants used in this invention can be prepared conveniently by the reaction of a phenol having the formula:
  • aldhyde having the formula:
  • R CHO In the above formulas R, R and R have the values set forth above. This reaction is carried out in the presence of an alkaline catalyst. If an alkaline borate is used, the boron complex is produced. Treatment of the boron complex with acid will destroy the complex and produce the corresponding ortho-alcohol-phenol. This preparation is described in more detail in assignees copending application Ser. No. 118,526, filed June 21, 1961.
  • the boron complex formed, as illustrated above, may be conveniently treated with a quantity of a dilute mineral acid to break the complex and release the compound of this invention.
  • the other alkali metals such as lithium, potassium, rubidium, and cesium may be used as well as the ammonium ion.
  • Example I This example illustrates the preparation of a toxicant additive: 2-chloro-4-tertiarybutyl-6-methylolphenol.
  • a solution of 50 gm. of sodium hydroxide (1.25 mols) and 62 gm. of boric acid (1 mol) in 500 ml. of water is added to 181 gm. of raw 2-chloro-4-tertiarybutylphenol (approximately 0.9 mol) and heated while vigorously stirring. When a temperature of 65 C. is reached, the addition of 100 ml. of a 36.1% aqueous solution of formaldehyde is begun. The initially milky mixture clears after about minutes. The addition of formaldehyde is finished after two hours. After a third hour, the mixture turns cloudy and solidifies slowly while forming a soft crystalline mass.
  • reaction mixture After standing overnight, the reaction mixture is repulped in 5 liters of cold water for the removal of the water-soluble components, and 205 gm. of a white, flaky material is obtained by vacuum filtration. After repulping in 600 ml. of benzene for the removal of the organic impurities, 95 gm. of a white crsytalline material (borate complex) are obtained. The melting point is over 350 F. The crystals are tested for boron content by suspending one gram of the material in 30 ml. of benzene and contacting the suspension three times with 60 ml. of 0.1 N sulfuric acid, thus stripping the chelate of boron ions.
  • the boron content of the aqueous phase is then determined by titration with alkali in the presence of mannitol (Scotts Standard Methods of Chemical Analysis I, 5th edition, New York, D. Van Nostrand Publishing Co., 1939, p. 170). Boron equivalent to 30.5 ml. 0.1 N boric acid is found in the aqueous phase, and indicates that the precipitate consists of a mixture of monoand di-saligenin borate complexes, as can be concluded from the following calculations.
  • One gm. of the di-saligenin complex corresponds to 0.0021 mol for which the boron content should be equivalent of 21 ml. of 0.1 N boric acid.
  • the precipitate consists of a mixture of monoand di-saligenin borate complexes.
  • the estimate-d conversion of phenol to saligenin is 90%.
  • Example 11 A water-hydrocarbon system is prepared using diesel fuel and sea water.
  • the fuel has an average of 12 carbon atoms, a specific gravity of 0.85, an average molecular weight of 170, and an average boiling point of 500 F.
  • the toxicant additive (the sodium salt of the boron complex of 2-chloro-4-nony1-6-methylolphenol) is dissolved in the hydrocarbon to produce a solution containing 0.005% of the toxicant in the hydrocarbon. Water containing the fungus, Hormodendron, is introduced into the hydrocarbon.
  • Example 111 Two specimens of pine wood (Pinus radiata, such as are found in Australia and New Zealand) measuring x 4" x 18 are treated as follows:
  • the first specimen is impregnated by pressure injection with a saturated aqueous solution of the sodium salt of the boron complex of 2-butyl-4-butyl-6-( l-hydroxyethyl)-phenol.
  • the second specimen is untreated.
  • the two specimens are inoculated with the fungus Lensite trabea.
  • the inoculated ends of the two specimens are buried in loose sandy soil to a depth of six inches and allowed to stand undisturbed.
  • the specimens are then carefully removed from the soil and cleaned.
  • the untreated specimen shows extensive deterioration while the treated specimen is substantially unchanged except for slight discoloration due to contact with the soil.
  • Example IV A quantity of interior flat oil paint is prepared containing 65% pigment, 14% non-volatile vehicle, which is primarily treated dryingoil, 21% turpentine solvent and 0.25% of the ammonium salt of the boron complex of 2-chlor0-4-nonyl-6-methylolphenol.
  • a line is drawn on a piece of 12 in. x 12 in. plywood so that it divides the surface into two halves, each measuring 6 in. x 12 in. One half of the plywood is given two coats of the complex-containing paint, while the other half is given two coats of the paint which contains no complex.
  • a culture medium is prepared containing the organism Aspergz'llus niger in a medium having the composition:
  • Sucrose and agar 7 The culture medium is seeded with spores of Aspergillus niger and incubated for 46 hours at 25 to 27 C., and 80 to 85% relative humidity, after which period of time the white mycelial stage of the mold is extended over the entire surface of the agar.
  • the painted plywood specimen is dipped in water and placed painted side down on the white mycelial growth so that half of the culture medium is in contact with the complex-containing paint and the other half of the culture medium is in contact with the paint which contains no complex.
  • the whole specimen is further incubated while contact between the mold and painted surface is maintained.
  • the incubation is carried out at a temperature of 25 to 27 C., and 80% to 85% relative humidity for a period of 7 days.
  • the control sample of paint which contains no complex, shows substantial growth of dark sporulating mold growing on and in contact with the painted surface.
  • the complexcontaining paint shows substantially no evidence of dark sporulating mold either on or in contact with the painted surface.
  • Suitable inert carriers for use in this invention include, for example, finely divided talc, oil-in-Water emulsions, mineral spirits, finely divided bentonite, benzene, diatomaceous earth, carbontetrachloride, water and an inert wetting agent, acetone and the like.
  • organic substituents from which R, R and R can be selected can each be independently chosen from the following illustrative but not all inclusive list of organic substituents: alkyl substituents such as ethyl, methyl, isoamyl, neopentyl, decyl, hexyl, propyl, Z-methylpentyl, S-methylhexyl, pentyl, dodecyl, butyl; cycloalkyl substituents such as cyclopentyl, cyclohexyl, cycloheptyl, pmethylcyclohexyl, 3-ethylcyclopentyl, 3,5-dimethylcyclopentyl, cyclobutyl; aryl substituents such as 2,4-xylyl, rn-cumenyl, phenyl, mesityl, biphenylyl, naphthyl, indanyl, tolyl and the like.
  • R is an organic group, preferably it will be an alkyl group having from 1 to 3 carbon atoms or a phenyl group.
  • Preferred ortho-substituted-phenol complexes are those wherein R is an alkyl or cycloalkyl substituent having from 4 to 12 carbon atoms, R is a halogen atom and R is hydrogen or an alkyl substituent containing 1 to 3 carbon atoms.
  • R is an alkyl or cycloalkyl substituent having from 4 to 12 carbon atoms
  • R is a halogen atom
  • R is hydrogen or an alkyl substituent containing 1 to 3 carbon atoms.
  • the most preferred ortho-substituted-phenols are the boron complexes of 2-chloro-4-isooctyl-G-methylolphenol.
  • the biological toxicants can be contacted with the substratum in any :one of several ways, for example, by mixing, dissolvini spraying and the like.
  • the toxicant can be associated with an inert carrier and the resultant composition can be contacted with the substratum.
  • his inert carrier can be liquid, solid or gaseous.
  • the toxioant can be dissolved or dispersed in a liquid inert carrier to form a toxioant-oarrier composition which is then applied to a substratum.
  • the toxicants can be prepared and supplied separate from or in combination with a carrier.
  • T-hese toxicants find particular application in preventing mildew, for example, on leather and plastic goods. These toxic'ants are active against fungi, bacteria, algae and protozoa.
  • composition of matter comprising (A) a major proportion of -a substratum and (B) a toxic amount of a compound selected from the ⁇ group consisting of (1) a compound having the formula:
  • R and R are each independently selected from the group consisting of 'halogen, alkyl, cycloal'kyl and aryl substituents; one of said -R and R being halogen; the rtotal number of carbon atoms in said R and R substituents combined being from 4 to 24;
  • R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 atoms;
  • (0) M is selected from the group consisting of alkali metal and ammonium.
  • a biologically toxic composition of matter comprising- (A) a major proportion *of a zfinely divided solid and (B) a toxic amount of a compound selected from the group consisting of (1) a compound having the formula:
  • R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl "and aryl substituents; one of said Rand R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
  • R is selected from the group consisting of hydrogen, 'alkyl substituents containing from 1 to 7 carbon 'atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to carbon atoms;
  • (c) M is selected from the group consisting of alkali metal and ammonium.
  • a biologically toxic composition of matter comprising (A) a major proportion of a unitary solid and (B) a toxic amount of a compound selected from the group consisting of (1) a compound having the formula:
  • R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl substituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
  • R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
  • (c) M is selected from the group consisting of alkali metal and ammonium.
  • a biologically toxic composition of matter comprising (A) a major proportion of a liquid and (B) a toxic amount of a compound selected from the group consisting of (1) a compound having the formula:
  • R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl substituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
  • R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
  • (0) M is selected from the group consisting of alkali metal and ammonium.
  • a biologically toxic composition of matter comprising (A) a major proportion of a liquid hydrocarbon and (B) a toxic amount of a compound selected from the group consisting of (1) .a compound having the formula:
  • R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl substituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
  • R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
  • (0) M is selected from the group consisting of alkali metal and ammonium.
  • a biologically toxic composition of matter comprising- (A) a major proportion of a surface coating composition and (B) a toxic amount of a biologically toxic compound selected from the group consisting of (1) a compound having the formula:
  • R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl su-bstituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
  • R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
  • (0) M is selected from the group consisting of alkali metal and ammonium.
  • a biologically toxic composition of matter comprising- (A) a major proportion of a cellulosic substance and (B) a toxic amount of a biologically toxic compound selected from the group consisting of (1) a compound having the formula:
  • R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl substituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
  • R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
  • (0) M is selected from the group consisting of alkali metal and ammonium.
  • R -0 ⁇ OH M (3110 OH R2 and mixtures thereof, wherein and mixtures thereof, wherein and mixtures thereof, wherein (a) R and R are each independently selected from the group consisting of halogen, 'alkyl, cycloalkyl and aryl suhstituents; one of said Rand R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
  • R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
  • (c) M is selected from the group consisting of alkali metal and ammonium.
  • a biologically toxic composition of matter comprising- (A) a major proportion of an inert carrier and (B) a toxic amount of a compound selected from the group consisting of (1) a compound having the formula:
  • R and 'R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl substituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
  • R is selected from the group consisting of hydrogen, a'lkyl su-bstituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to '10 carbon atoms;
  • (c) M is selected from the group consisting of alkali metal and ammonium.
  • R and R are each independently selected from the group consisting of halogen, alkyl, cycloa-lkyl and aryl s-ubstituents; one of said R and R being halogen; the total number of carbon atoms in said R and R 'substituents combined being from 4 to 24;
  • R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from *6 to 10 carbon atoms;
  • (c) M is selected from the group consisting of alkali metal and ammonium.
  • composition of matter comprising (A) a major proportion of a substratum and ('B) a toxic amount of a compound having the formula:

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Description

lim -18929 or: it; age/H United St:
BIOLOGICALLY TOXIC COMPOSITIONS CONTAIN- IN( BORON-PHENOL COMPLEXES AND METH- OD David R. Stern, Fullerton, and Friedrich I. Weck, Hacienda Heights, Caiif., assignors to American Potash & Chemical Corporation, Los Angeles, Calif., a corporation of Delaware No Drawing. Filed Jan. 14, 1965, Ser. No. 425,609
12 Claims. (Cl. 16730) This is a continuation-in-part of application Serial Number 187,943, filed April 16, 1962, now abandoned.
This invention relates, in general, to biologically toxic compositions and to methods of combating biological growth. More specifically, the biologically toxic compositions comprise a major amount of inert matter and an effective amount of certain toxic ontho-substituted-phenol complexes.
Considerable difiiculty has been experienced in trying to obtain broad protection against undesirable biological growth through the use of a single biological toxicant The use of a single toxicant capable of inhibiting undesirable biological growth is highly desirable because it re duces the number of toxic ingredients required in biologically toxic compositions.
Further, previous biological toxicants have been limited in the scope of their usefulness because they were compatible or could be rendered compatible with only a limited number of substratum.
The term substratum as used in this specification and in the appended claims means any substance which it is desired to protect from undesired biological growth and which is capable of retaining on its surface or within itself, or both, a toxic amount of the biological toxicants which are more specifically described hereafter. The term includes liquids, powders, granular material, unitary solids, emulsions, solutions, dispersions, and heterogeneous systems such as a liquid-liquid, liquid-solid, or solidsolid type.
Broadly, the biologically toxic compositions according to this invention are comprised of a major proportion of (A) a substratum and (B) a toxic amount of an orthosubstituted-phenol complex. The ortho-substituted-phenol complex portion of these compositions comprises phenols having the formulas:
R1 I'M R -o oa M \B/ on on I 0 R2 R2 (1) CH /B\ M 0 OH R2 (11) These phenol complexes may be used singly or in combinations of two or more.
In the above formulae, R can be any of the substituents, chlorine, fluorine, bromine, iodine, alkyl, cycloalkyl or aryl; R can be any of chlorine, fluorine, bromine, iodine, alkyl, cycloalkyl or aryl, with the provision that only one of R and R can be halogen on any given com- 3,266,981 August 16, 1966 pound; R can be any of hydrogen, alkyl, cycloalkyl or aryl substituents; M can be any of the alkali metals, lithium, sodium, potassium, rubidium, or cesium; or ammonium. When one of R or R is a halogen, the other can be an alkyl or cycloalkyl group containing from 4 to 24 carbon atoms or an aryl group containing from 6 to 24 carbon atoms. When neither R nor R is a halogen, either one can be an alkyl group having from 2 to 22 carbon atoms, a cycloalkyl substituent having from 4 to 22 carbon atoms or an aryl group having from 6 to 22 carbon atoms, provided that there is a total of between 8 and 24 carbon atoms present in the two substituents combined. When R is not hydrogen, it can be either an alkyl group containing from 1 to 7 carbon atoms, a cycloalkyl group containing from 4 to 7 carbon atoms or an aryl group containing from 6 to 10 carbon atoms. Thus, the total number of carbon atoms in the R and R substituents combined is at least 4 when one of these substituents is halogen and at least 8 when neither R nor R is halogen.
The method of inhibiting or substantially minimizing the growth of biological material on a substratum, comprises providing such substratum with an amount of'the above described toxicants sufficient to render the resultant substratum-toxicant composite, toxic to biological material.,
When the substratum is a finely divided solid or powder such as talc, clay, bentonite, or the like, the toxicant may be associated with it by, for example, mixing, blending, shaking, or by like means.
When the substratum is a liquid or an emulsion, the,
toxicant can be associated with it by dispersing, dissolving, or suspending the compound in the liquid or emulsion.
When the substratum is a unitary solid such as wood, fabric, fur, leather, organic plastic materials, or the like, the toxicant can be associated with it in many ways such as, for example, by dusting or spraying the toxicant onto the surface of the solid either with or without a solvent or diluent; or by soaking the unitary solid in a large body of liquid containing dissolved toxicant for a period of [time sutficient to impregnate the solid with the desired concentration of toxicant; and the like. Pressure impregnation techniques also can be used, employing a pressure chamber in which the toxicant is introduced at elevated temperatures, either as a vapor or as a liquid entrained in another vapor such as toxicant-in-steam, and the like.
Hardenable coatings such as paints, enamels, varnishes, and like surface coatings can be associated with the toxicant by dispersing, grinding into, polymerizing or dissolving the toxic compounds in the fluid coating before the latter has hardened or by spraying or dusting the toxic compounds on the coating after it has been applied to a surface.
The substituents R, R and R of the ortho-substitutedphenol complex portion (B) of the composition, preferably are chosen so that the resulting toxicant is compatible with the desired substratum portioii (A). Thus, if the substratum is water, R should be a low molecular weight substituent such as methyl, R should be halogen or a low molecular weight alkyl and R should be either hydrogen or a low molecular weight substituent such as methyl. If the substratum is a liquid hydrocarbon, R should be a large substituent such as octyl or nonyl, while the selection of R and R is not critical.
This invention is particularly useful in preventing the growth of undesirable biological matter in liquid hydrocarbons. There is .a tendency for an aqueous phase to form in contact with a liquid hydrocarbon, due to absorption and condensation of atmospheric moisture. For this reason, during storage, liquid hydrocarbons are almost always in contact with an aqueous phase. Certain micro-organisms live in this aqueous phase and feed on the hydrocarbon. Thus, the interface between the aque- 011s and hydrocarbon phases is often covered with a growth of micro-organisms. An eifective amount of toxicant dissolved in the hydrocarbon phase substantially inhibits the growth of these micro-organisms.
The term normally liquid hydrocarbon as used in the instant specification and in the appended claims includes gasoline, kerosene, naphtha, gas oil, cylinder stock, diesel fuel, jet fuel, heating oil, and the like. Normally, these hydrocarbons contain an average of from about four to fourteen carbon atoms, have a specific gravity or from about 0.6 to 0.95, an average molecular weight of from about 60 to 250, and an average boiling point of from about 40 F. to 700 F. Average boiling point is defined as the temperature of the boiling mixture of hydrocarbons when one half by weight of the hydrocarbons have been distilled olf. In general, any hydrocarbon material from the lightest liquids through waxy solids to highly polymeric solids can be protected from attack by biological material, according to this invention.
This invention is also useful in preventing the growth of undesirable biological material on cellulosic substratum.
Cellulosic materials which can be provided with a toxic amount of the herein described toxicants, in accordance with this invention, include cellulosic films and filaments, fabrics, paper, Wood, various compositions including wood in one form or another, such as compositions iCOlltaining wood fibres in a matrix of some other material and the like. These cellulosic materials can be provided with a toxic amount of these compounds by any of the procedures described above, including particularly, impregnating as by soaking, treating the surface of the cellulosic materials, by spraying or dusting, and coating the surface with other compositions containing the toxic compounds such as varnishes, lacquers, calcimine, oil and water base paints, paper coatings of various kinds, and the like.
' The preferred cellulosic material, according to this invention, is wood. Wooden articles provided with a toxic amount of the above described toxicants are extremely resistant to wood destroying fungus and insects. Many different types of wood can be protected in this manner. Thus, pine, fir, hickory, mahogany, oak, ash, spruce, birch, aspen, maple and the like, can be protected from insects and micro organisms by providing them with a toxic amount of these compounds.
Wood can be provided with these compounds by any of the conventional, well-known procedures for impregnating woods with preservatives. These toxicants, which are boron complexes, can be introduced into the wood as complexes or the complex can be tor-med in situ in the wood [by reaction between the corresponding ortho-alcoh'ol-phenol and boric acid or some other soluble boron compound. This reaction can be accomplished, for example, by first impregnating the wood with one reactant, followed by a second impregnation with the other reactant. Various other agents can be employed with the toxicants, for example, surfactants which aid the penenation of the toxicant into the wood can be used.
According to this invention, the toxicants can be in- :orporated in wood in an amount ranging from about ).1 percent by weight to about 0.05 percent by weight. it will be understood that the concentration of toxicant ormally will be greatest at the surface of the wood and vill decrease progressively with increasing depth into he wood.- For this reason, the surface of the wood is iften provided with an excess of toxicant so that the inerior will contain an effective amount of the compound.
A further aspect of this invention comprises the proision of a toxic amount of the herein described toxicants with various substratum-surface coating compositions. The toxicants can be incorporated in a substratum such as paint to render the paint resistant to the growth of biological materials. These paints find particular utility when applied below the water line on the hulls of seagoing vessels, where their anti-fouling properties are particularly valuable.
The paints, according to this invention, which can be provided with a toxic amount of toxicant are comprised primarily of pigment and vehicle.
The volatile constituents in the paint vehicle include, for example, hydrocarbons such as aliphatic and mineral spirit cuts, aromatics such as toluene and xylene, lacquer solvents, for example, esters such as butyl acetate, and ketones such as methylethylketone, mixtures of two or more vehicles, and the like. The non-volatile portions of the vehicle can include, for example, natural drying oils such as linseed oil, synthetic resins such as glycerol phthalate or phenol-formaldehyde, lacquers which dry by solvent evaporation such as nitrocellulose and other thermoplastic resins, materials such as silicones, mixtures of two or more non-volatile vehicles, and the like. The pigment portion of the paint can be either inorganic or organic, including, for example, chalk, cadmium yellow, bone black, azurite, litharge, mica, ochre yellow, pumice, white lead, zinc white, talc, red lead, silica, and the like. These pigments may be used singly or in mixtures of two or more.
The gloss of the particular paint is conveniently regulated by adjusting the proportion of pigment contained therein. In general, the lower the amount of pigment, provided it is present in a quantity suficient to provide adequate covering, the glossier the paint.
According to this invention the toxicants can be incorporated in paint in an amount ranging from about 0.1 percent by weight to about 0.05 percent by weight. When these toxicants are used in anti-fouling marine paints to prevent the growth of various marine life on boat hulls, they are provided in relatively large amounts, for example, in excess of about 4 percent.
The biological toxicants used in the present invention are stable compounds which range from viscous liquids to crystalline 0r glassy solids. They are soluble in a wide range of solvents and as herein described, can advantageously be tailored to fit the solubility problems attendant the particular susbtratum involved. These ortho-substituted-phenol complexes can be advantageously employed for a variety of commercial and industrial purposes, but they are particularly useful as biological toxicants. When used as biological toxicants, they are effective at a concentration from as low as about one part per million parts of substratum up to a concentration of about 1,000 parts per million parts of substratum.
The ortho-alcohol-phenols used in the preparation of the toxicants used in this invention can be prepared conveniently by the reaction of a phenol having the formula:
with an aldhyde having the formula:
R CHO In the above formulas R, R and R have the values set forth above. This reaction is carried out in the presence of an alkaline catalyst. If an alkaline borate is used, the boron complex is produced. Treatment of the boron complex with acid will destroy the complex and produce the corresponding ortho-alcohol-phenol. This preparation is described in more detail in assignees copending application Ser. No. 118,526, filed June 21, 1961.
Thus, when the reaction is carried out in the presence C r-C of an alkaline borate, such as sodium borate, a novel boron complex forms substantially as follows:
He r; 2 2RCHO NaBOz :2
The boron complex formed, as illustrated above, may be conveniently treated with a quantity of a dilute mineral acid to break the complex and release the compound of this invention. In carrying out these reactions, in addition to the sodium ion, the other alkali metals such as lithium, potassium, rubidium, and cesium may be used as well as the ammonium ion.
In the specification, claims and following specific examples, all parts and percentages are by weight unless otherwise indicated. The following examples are set forth to further illustrate and not to limit the invention:
Example I This example illustrates the preparation of a toxicant additive: 2-chloro-4-tertiarybutyl-6-methylolphenol.
A solution of 50 gm. of sodium hydroxide (1.25 mols) and 62 gm. of boric acid (1 mol) in 500 ml. of water is added to 181 gm. of raw 2-chloro-4-tertiarybutylphenol (approximately 0.9 mol) and heated while vigorously stirring. When a temperature of 65 C. is reached, the addition of 100 ml. of a 36.1% aqueous solution of formaldehyde is begun. The initially milky mixture clears after about minutes. The addition of formaldehyde is finished after two hours. After a third hour, the mixture turns cloudy and solidifies slowly while forming a soft crystalline mass. After standing overnight, the reaction mixture is repulped in 5 liters of cold water for the removal of the water-soluble components, and 205 gm. of a white, flaky material is obtained by vacuum filtration. After repulping in 600 ml. of benzene for the removal of the organic impurities, 95 gm. of a white crsytalline material (borate complex) are obtained. The melting point is over 350 F. The crystals are tested for boron content by suspending one gram of the material in 30 ml. of benzene and contacting the suspension three times with 60 ml. of 0.1 N sulfuric acid, thus stripping the chelate of boron ions. The boron content of the aqueous phase is then determined by titration with alkali in the presence of mannitol (Scotts Standard Methods of Chemical Analysis I, 5th edition, New York, D. Van Nostrand Publishing Co., 1939, p. 170). Boron equivalent to 30.5 ml. 0.1 N boric acid is found in the aqueous phase, and indicates that the precipitate consists of a mixture of monoand di-saligenin borate complexes, as can be concluded from the following calculations.
(a) The mono-saligenin borate complex:
One gm. of the above complex represents 0.0036 mol Na= C11H1504C1N3B M01 wt. =280.498 Percent B, calculated=3.86
(b) The di-saligenin borate complex: C1 G1 I I CH3 Mol wt. =459.153
B CH3 Percent B, calcu1ated=2.35
CHsO OCH:
for which the boron content should be equivalent to 36 ml. of 0.1 N boric acid.
One gm. of the di-saligenin complex corresponds to 0.0021 mol for which the boron content should be equivalent of 21 ml. of 0.1 N boric acid.
Since the titrated equivalent of the one gm. sample obtained by synthesis represents a value between these calculatd figures, it can be concluded that the precipitate consists of a mixture of monoand di-saligenin borate complexes. The estimate-d conversion of phenol to saligenin is 90%.
Example 11 A water-hydrocarbon system is prepared using diesel fuel and sea water. The fuel has an average of 12 carbon atoms, a specific gravity of 0.85, an average molecular weight of 170, and an average boiling point of 500 F. The toxicant additive (the sodium salt of the boron complex of 2-chloro-4-nony1-6-methylolphenol) is dissolved in the hydrocarbon to produce a solution containing 0.005% of the toxicant in the hydrocarbon. Water containing the fungus, Hormodendron, is introduced into the hydrocarbon.
After constant agitation for a period of 7 days at a temperature of F., under the same conditions, a substantially identical water-hydrocarbon system containing no toxicant shows-a substantial growth of micro-organisms while the solution containing the toxicant shows no discernible evidence of micro-organisms. The conditions of sea water and constant agitation used in this example, closely approximate those present in a ship at sea which contains fuel in storage.
Example 111 Two specimens of pine wood (Pinus radiata, such as are found in Australia and New Zealand) measuring x 4" x 18 are treated as follows:
The first specimen is impregnated by pressure injection with a saturated aqueous solution of the sodium salt of the boron complex of 2-butyl-4-butyl-6-( l-hydroxyethyl)-phenol. The second specimen is untreated.
The two specimens are inoculated with the fungus Lensite trabea.
The inoculated ends of the two specimens are buried in loose sandy soil to a depth of six inches and allowed to stand undisturbed. The specimens are then carefully removed from the soil and cleaned. The untreated specimen shows extensive deterioration while the treated specimen is substantially unchanged except for slight discoloration due to contact with the soil.
Example IV A quantity of interior flat oil paint is prepared containing 65% pigment, 14% non-volatile vehicle, which is primarily treated dryingoil, 21% turpentine solvent and 0.25% of the ammonium salt of the boron complex of 2-chlor0-4-nonyl-6-methylolphenol.
A second quantity of paint having substantially the same composition except that it contains no 2-chloro- 4-nonyl-6-methy1olphenol complex, is prepared.
A line is drawn on a piece of 12 in. x 12 in. plywood so that it divides the surface into two halves, each measuring 6 in. x 12 in. One half of the plywood is given two coats of the complex-containing paint, while the other half is given two coats of the paint which contains no complex.
A culture medium is prepared containing the organism Aspergz'llus niger in a medium having the composition:
Sucrose and agar 7 The culture medium is seeded with spores of Aspergillus niger and incubated for 46 hours at 25 to 27 C., and 80 to 85% relative humidity, after which period of time the white mycelial stage of the mold is extended over the entire surface of the agar.
The painted plywood specimen is dipped in water and placed painted side down on the white mycelial growth so that half of the culture medium is in contact with the complex-containing paint and the other half of the culture medium is in contact with the paint which contains no complex. The whole specimen is further incubated while contact between the mold and painted surface is maintained.
The incubation is carried out at a temperature of 25 to 27 C., and 80% to 85% relative humidity for a period of 7 days. After this period of time, the control sample of paint, which contains no complex, shows substantial growth of dark sporulating mold growing on and in contact with the painted surface. The complexcontaining paint shows substantially no evidence of dark sporulating mold either on or in contact with the painted surface.
Suitable inert carriers for use in this invention include, for example, finely divided talc, oil-in-Water emulsions, mineral spirits, finely divided bentonite, benzene, diatomaceous earth, carbontetrachloride, water and an inert wetting agent, acetone and the like.
Satisfactory results are also obtainable by substituting any one or more of the following complexes in the above examples: the potassium salt of the boron complex of 2-chloro-4-(1,1,3,3-tetramethyl'butyl) 6-methylolphenol, the sodium salt of the boron complex of 2,4-di(tertiaryamyl)-6-methylolphenol, the lithium salt of the boron complex of 2-bromo-4-cumenyl-6-(1-hydr0xyethyl)- phenol, the ammonium salt of the boron complex of 2-iodo- 4-benzyl-6-(1-hydroxy-2-phenylethyl)-phenol, the rubidium salt of the boron complex of 2-fluoro-4-isoamyl-6- methylolphenol, the cesium salt of the boron complex of 2-nonyl-4-iodo-6-(1-hydroxyethyl)-phenol, the sodium salt of the boron complex of 2-methyl-4-pentadecyl-6-(l-hydroxy-2-cyclopentylethyl)-phenol, the ammonium salt of the boron complex of 2-cyclohexyl-4-cyclohexyl-6-methylolphenol, mixtures of two or more of these toxicants and the like. It will be understood that these boron complexes are generally present as a mixture of complexes having one and two substituted phenols per boron atom.
The organic substituents from which R, R and R can be selected can each be independently chosen from the following illustrative but not all inclusive list of organic substituents: alkyl substituents such as ethyl, methyl, isoamyl, neopentyl, decyl, hexyl, propyl, Z-methylpentyl, S-methylhexyl, pentyl, dodecyl, butyl; cycloalkyl substituents such as cyclopentyl, cyclohexyl, cycloheptyl, pmethylcyclohexyl, 3-ethylcyclopentyl, 3,5-dimethylcyclopentyl, cyclobutyl; aryl substituents such as 2,4-xylyl, rn-cumenyl, phenyl, mesityl, biphenylyl, naphthyl, indanyl, tolyl and the like.
If R is an organic group, preferably it will be an alkyl group having from 1 to 3 carbon atoms or a phenyl group. Organic substituents having more than these preferred limits of carbon atoms at this particular position, tend to provide more steric hindrance than is desirable for the formation of boron complexes or other reactions.
Preferred ortho-substituted-phenol complexes according to this invention, are those wherein R is an alkyl or cycloalkyl substituent having from 4 to 12 carbon atoms, R is a halogen atom and R is hydrogen or an alkyl substituent containing 1 to 3 carbon atoms. These pretferred compounds are soluble in and compatible with a wide range of solvents and are very toxic to a wide range of biological materials.
The most preferred ortho-substituted-phenols are the boron complexes of 2-chloro-4-isooctyl-G-methylolphenol.
As indicated bereinabove, the biological toxicants can be contacted with the substratum in any :one of several ways, for example, by mixing, dissolvini spraying and the like. Moreover, if desired, the toxicant can be associated with an inert carrier and the resultant composition can be contacted with the substratum. 'I his inert carrier can be liquid, solid or gaseous. Thus, the toxioant can be dissolved or dispersed in a liquid inert carrier to form a toxioant-oarrier composition which is then applied to a substratum. It will be understood that the toxicants can be prepared and supplied separate from or in combination with a carrier.
While the biological toxicants used in this invention are broadly toxic to all types of biological growth, they are particularly useful in combating micro-organisms and insects such as termites, mosquitos and moths. T-hese toxicants find particular application in preventing mildew, for example, on leather and plastic goods. These toxic'ants are active against fungi, bacteria, algae and protozoa.
As will be understood by those skilled in the art, what has been described is the preferred embodiment of the invention. However, many modifications, changes, and substitutions can be made therein without departing from the scope and spirit of the following claims.
We claim:
1. A composition of matter comprising (A) a major proportion of -a substratum and (B) a toxic amount of a compound selected from the \group consisting of (1) a compound having the formula:
OCIEH 2 (2) a compound having the formula:
R O OH ]3 M (1110 OH in and mixtures thereof, wherein (a) R and R are each independently selected from the group consisting of 'halogen, alkyl, cycloal'kyl and aryl substituents; one of said -R and R being halogen; the rtotal number of carbon atoms in said R and R substituents combined being from 4 to 24;
(b) R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 atoms;
(0) M is selected from the group consisting of alkali metal and ammonium.
2. A biologically toxic composition of matter compris- (A) a major proportion *of a zfinely divided solid and (B) a toxic amount of a compound selected from the group consisting of (1) a compound having the formula:
Rx I
h/ in and mixtures thereof, wherein (a) R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl "and aryl substituents; one of said Rand R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
(b) R is selected from the group consisting of hydrogen, 'alkyl substituents containing from 1 to 7 carbon 'atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to carbon atoms;
(c) M is selected from the group consisting of alkali metal and ammonium.
3. A biologically toxic composition of matter comprising (A) a major proportion of a unitary solid and (B) a toxic amount of a compound selected from the group consisting of (1) a compound having the formula:
(2) a compound having the formula:
and mixtures thereof, wherein (a) R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl substituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
('b) R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
(c) M is selected from the group consisting of alkali metal and ammonium.
4. A biologically toxic composition of matter comprising (A) a major proportion of a liquid and (B) a toxic amount of a compound selected from the group consisting of (1) a compound having the formula:
(2) a compound having the formula:
and mixtures thereof, wherein (a) R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl substituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
(b) R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
(0) M is selected from the group consisting of alkali metal and ammonium.
5. A biologically toxic composition of matter comprising (A) a major proportion of a liquid hydrocarbon and (B) a toxic amount of a compound selected from the group consisting of (1) .a compound having the formula:
(2) a compound having the formula:
and mixtures thereof, wherein .(a) R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl substituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
(b) R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
(0) M is selected from the group consisting of alkali metal and ammonium.
6. A biologically toxic composition of matter compris- (A) a major proportion of a surface coating composition and (B) a toxic amount of a biologically toxic compound selected from the group consisting of (1) a compound having the formula:
11 (2) a compound having the formula:
R- OH and mixtures thereof, wherein (a) R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl su-bstituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
(b) R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
(0) M is selected from the group consisting of alkali metal and ammonium.
7. A biologically toxic composition of matter compris- (A) a major proportion of a cellulosic substance and (B) a toxic amount of a biologically toxic compound selected from the group consisting of (1) a compound having the formula:
(2) a compound having the formula:
n-C -o OH I 0110 la and mixtures thereof, wherein (a) R and R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl substituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
(b) R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
(0) M is selected from the group consisting of alkali metal and ammonium.
(2) a compound having the formula:
R1 R1 l I R o o-n M I 3110 O(|3H R2 R1 (2) a compound having the formula:
R -0\ OH M (3110 OH R2 and mixtures thereof, wherein and mixtures thereof, wherein (a) R and R are each independently selected from the group consisting of halogen, 'alkyl, cycloalkyl and aryl suhstituents; one of said Rand R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
(b) R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to 10 carbon atoms;
(c) M is selected from the group consisting of alkali metal and ammonium.
8. A biologically toxic composition of matter compris- (A) a major proportion of an inert carrier and (B) a toxic amount of a compound selected from the group consisting of (1) a compound having the formula:
Ilii If! R o 0 -11 M I pno \O(|3H (a) R and 'R are each independently selected from the group consisting of halogen, alkyl, cycloalkyl and aryl substituents; one of said R and R being halogen; the total number of carbon atoms in said R and R substituents combined being from 4 to 24;
(b) R is selected from the group consisting of hydrogen, a'lkyl su-bstituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from 6 to '10 carbon atoms;
(c) M is selected from the group consisting of alkali metal and ammonium.
group consisting of 1) a com-pound having the formula:
Manama/A 4 13 (2) a compound having the formula:
B M 0110 \OH and mixtures thereof, wherein (a) R and "R are each independently selected from the group consisting of halogen, alkyl, cycloa-lkyl and aryl s-ubstituents; one of said R and R being halogen; the total number of carbon atoms in said R and R 'substituents combined being from 4 to 24;
( b) R is selected from the group consisting of hydrogen, alkyl substituents containing from 1 to 7 carbon atoms, cycloalkyl substituents containing from 4 to 7 carbon atoms and aryl substituents containing from *6 to 10 carbon atoms;
(c) M is selected from the group consisting of alkali metal and ammonium.
11. A composition of matter comprising (A) a major proportion of a substratum and ('B) a toxic amount of a compound having the formula:
CH3 CH3 C 3 3 mula:
References Cited by the Examiner UNITED STATES PATENTS 8/ 1936 Honel 260619 X 7/1941 Perkins 260-619 6/ 1946 DAlelio 260--619 3/ 1953 Moyle et a1. 260-621 6/195-8' Garner 260-462 4/1959 Lowe 260 462 111/ 1960 Boyer t16738.7 6/ 1961 'Leshin 260621 4/1962 Morris et a1 260-621 4/ 1963 Roberts 260-623 FOREIGN PATENTS 11/ 8 Canada.
5/1953 Germany.
JULIAN S. LEVITT, Primary Examiner. GEORGE A. MENTIS, Assistant Examiner.

Claims (1)

  1. 9. A METHOD OF COMBATING THE GROWTH OF BIOLOGICAL MATERIAL CHARACTERIZED BY CONTACTING SAID BIOLOICAL MATERIAL WITH A TOXIC AMOUNT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) A COMPOUND HAVING THE FORMULA:
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Cited By (5)

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US3839073A (en) * 1970-04-20 1974-10-01 Koppers Co Inc Aesthetic wood product
EP0361892A2 (en) * 1988-09-28 1990-04-04 Chemicca Limited Improvements in or relating to preservatives and/or biocides
USRE37133E1 (en) * 1988-09-28 2001-04-10 Fernz Timber Protection Limited Method of preparing a borate organic complex anion containing salt compositions
JP2011508736A (en) * 2007-12-27 2011-03-17 ビーエーエスエフ ソシエタス・ヨーロピア Spiro compounds
GB2628617A (en) * 2023-03-30 2024-10-02 Sumitomo Chemical Co Compound

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US2049447A (en) * 1927-08-06 1936-08-04 Beck Koller & Company Inc Condensation products and process for preparing same
US2247404A (en) * 1939-03-24 1941-07-01 Dow Chemical Co Aralkyl polyhydric phenol
US2394754A (en) * 1938-11-23 1946-02-12 Gen Electric Substituted phenols
US2630458A (en) * 1951-06-26 1953-03-03 Dow Chemical Co 3-alkyl-2,2'-dihydroxy-3',5,5'-trihalodiphenylmethanes
DE876492C (en) * 1951-08-24 1953-05-15 Boehringer Sohn Ingelheim Pest control
US2839564A (en) * 1952-02-21 1958-06-17 Shell Dev Cyclic esters of boric acid
CA566310A (en) * 1958-11-18 E. Nagy Daniel Borate complexes of methylol phenols
US2883412A (en) * 1954-12-27 1959-04-21 California Research Corp P-xylylenediamine salts of glycol boric acids
US2961373A (en) * 1959-05-07 1960-11-22 Richardson Co Fungicidal and bactericidal agent
US2987497A (en) * 1958-12-24 1961-06-06 Goodyear Tire & Rubber Vulcanization of butyl rubber with 2, 6-dimethylol-3, 5-dimethyl-4-chlorophenol, andvulcanizate obtained thereby
US3030428A (en) * 1962-04-17 Hydroxybenzyl alcohol production
US3086061A (en) * 1959-11-12 1963-04-16 Goodyear Tire & Rubber Process for the manufacture of 2, 6-dimethylol-3, 5-dimethyl-4-chlorophenol

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CA566310A (en) * 1958-11-18 E. Nagy Daniel Borate complexes of methylol phenols
US3030428A (en) * 1962-04-17 Hydroxybenzyl alcohol production
US2049447A (en) * 1927-08-06 1936-08-04 Beck Koller & Company Inc Condensation products and process for preparing same
US2394754A (en) * 1938-11-23 1946-02-12 Gen Electric Substituted phenols
US2247404A (en) * 1939-03-24 1941-07-01 Dow Chemical Co Aralkyl polyhydric phenol
US2630458A (en) * 1951-06-26 1953-03-03 Dow Chemical Co 3-alkyl-2,2'-dihydroxy-3',5,5'-trihalodiphenylmethanes
DE876492C (en) * 1951-08-24 1953-05-15 Boehringer Sohn Ingelheim Pest control
US2839564A (en) * 1952-02-21 1958-06-17 Shell Dev Cyclic esters of boric acid
US2883412A (en) * 1954-12-27 1959-04-21 California Research Corp P-xylylenediamine salts of glycol boric acids
US2987497A (en) * 1958-12-24 1961-06-06 Goodyear Tire & Rubber Vulcanization of butyl rubber with 2, 6-dimethylol-3, 5-dimethyl-4-chlorophenol, andvulcanizate obtained thereby
US2961373A (en) * 1959-05-07 1960-11-22 Richardson Co Fungicidal and bactericidal agent
US3086061A (en) * 1959-11-12 1963-04-16 Goodyear Tire & Rubber Process for the manufacture of 2, 6-dimethylol-3, 5-dimethyl-4-chlorophenol

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839073A (en) * 1970-04-20 1974-10-01 Koppers Co Inc Aesthetic wood product
EP0361892A2 (en) * 1988-09-28 1990-04-04 Chemicca Limited Improvements in or relating to preservatives and/or biocides
EP0361892A3 (en) * 1988-09-28 1991-09-04 Chemicca Limited Improvements in or relating to preservatives and/or biocides
US5221758A (en) * 1988-09-28 1993-06-22 Maynard Nigel P Method of preparing a borate organic complex anion containing salt composition
USRE37133E1 (en) * 1988-09-28 2001-04-10 Fernz Timber Protection Limited Method of preparing a borate organic complex anion containing salt compositions
JP2011508736A (en) * 2007-12-27 2011-03-17 ビーエーエスエフ ソシエタス・ヨーロピア Spiro compounds
GB2628617A (en) * 2023-03-30 2024-10-02 Sumitomo Chemical Co Compound

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