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United States Patent Office Patented Apr 3,179,676 United States Patent Office Patented Apr. 20, 1965 2 drocarbon radicals including alkyl, aryl, aralkyl, alkaryl, 3,179,676 and cycloaliphatic hydrocarbon radicals. The hydro ORGANOTNORGANOPHOSPHORUS COM carbyl substituent represented by each of the symbols R' POUNDS AND A METHOD FOR PREPAIR and R' in the above recited formulae will normally con ING THE SAME Charles J. Stern, Jr., Westfield, N.J., assignor to Nease tain from 1 to 20 carbon atoms. This is, of course, par Chemical Company, Inc., State College, Pa., a corpo ticularly true where R is an alkyl radical, for example. ration of Pennsylvania Where R is an aryl, aralkyl or alkaryl radical, the num No Drawing. Fied Mar. 28, 1961, Ser. No. 98,789 ber of carbon atoms may be in the range of 6 to 20 car 10 Clains. (C. 260-429.7) bon atoms; and where R' is a cycloaliphatic radical, 3 to O 20 carbon atoms circumscribes the proper range. Where This invention relates to novel biocidal compounds and R’ is a heterocyclic radical, the number of carbon atoms to methods for the preparation thereof. More particular may be in the range of 12 to 20 carbonatoms, as well. ly, the present invention relates to novel highly effective Each of the radicals represented by R contains from 1 fungicidal and bactericidal organotin-organophosphorus to 12 carbon atoms with the sum of the carbon atoms compounds which are advantageously combined with 5 of the R substituents attached to each stannic moiety paints and plastic formulations and which are, in addi being within the range of 8 to 14. tion, useful in the treatment of paper, cloth, leather, wood, The preferred biocidal compounds of the invention are and other fibrous and insulating materials, to render these embraced by the formula: materials resistant to deterioration caused by bacteria and fungi; and to methods for the preparation thereof. 20 Fungicidal and bactericidal compositions employed heretofore have been known to present one or a plurality wherein R is butyl and R' is a member selected from of difficulties. Thus, for example, fungicidal and fungi the group consisting of alkyl and hydroxyalkyl radicals static chlorinated phenols are normally highly toxic, neces containing from 1 to 7 carbon atoms, a phenyl radical and sitating special handling. In addition, they cause dis a trihaloalkyl radical, and preferably a trichloroalkyl coloration of plastics and paint films; are corrosive to moiety, such astrichloromethyl. metals; and are usually ineffective at low treatment levels. IIIustrative of the biocidal compounds embraced by the Similarly, fungicidal mercapto-dicarboximide compounds above general formulae are tributyltin-di(hydroxy when used in clear formulations of coatings and plastics, methyl)phosphinate, di(tributyltin) hydroxymethyl phos reduce the heat and light-stability thereof and are, in addi 30 phonate, di(tributyltin)trichloromethyl phosphonate, tri tion, malodorous. In like manner, many copper-contain butyltin-di(hydroxyheptyl)phosphinate, tributyltin-dihexyl ing fungicides result in high treatment costs; discoloration phosphinate, diethylmonobutyltin - di(hydroxymethyl) of the paints and plastics in which they are incorporated; phosphinate, di-(dimethylmonoheptyltin) hydroxymethyl are effective over an abbreviated period of time; and in phosphonate, di - (diethylmonononyltin)trichloromethyl volve difficulty in formulation because of poor solubility 35 phosphonate, dimethylmonododecyltin - di(hydroxyhep characteristics. Phenyl mercurials are also employed as tyl)phosphinate, tripropyltin-dihexyl phosphinate, tribu biocidal agents and yet are uneconomic, highly toxic, tyltin-diphenyl phosphinate, and di(tributyltin) phenyl corrosive to metals, and prohibited in certain military phosphonate. specifications for plastic materials. The term “biocidal' as employed throughout this specific Accordingly, it is an object of the present invention to 40 cation is intended to designate, as indicated hereinabove, provide novel thermally stable biocidal organotin-organo an agent characterized by a fungicidal, fungistatic, bac phosphorus compounds which are particularly effective in tericidal, and/or bacteriostatic activity. the inhibition and destruction of fungi and bacteria; and In their pure state, the compounds of the invention are which are readily incorporated in a wide range of resins, normally colorless or slightly colored, viscous liquids or paints and plasticizers, as well as cloth, leather, Wood and white crystalline or amorphous solids. To facilitate han the like and which are stable against oxidation by air and diling of these compounds for use as biocidal agents, they are resistant to hydrolysis under all conditions of manu may be furnished as solutions in the usual organic sol facture, storage, and use. The organotin-organophos vents and plasticizers. Stable water dispersions of these phorus compounds provided by the practice and within compounds may also be utilized. m the purview of the present invention are characterized, 50 The aforesaid compounds are prepared by reaction of in addition, by low vapor pressure, non-corrosivity to a trialkyltin oxide with an organic phosphinic acid oran metals and solubility in polar and non-polar solvents de E. phosphonic acid, which is included in the for pending upon the nature of the organic Substituents. a The novel biocidal compounds of the invention are represented by the general formulae: 55 O and (RSnO) --Ra O and 60 O R--orOH (RSnO)-P-R’ OR wherein each of R, R', and n has the value attributed to it hereinabove. wherein R is a substituted or unsubstituted alkyl radical; 65 Illustrative of the alkyl stannic oxide components emi R’ is a heterocyclic radical or a substituted or unsub ployed as reactants herein are bis-tributyltin oxide, bis stituted hydrocarbyl radical; R' is a heterocyclic radical, diethylmonobutyltin oxide, bis-dimethylmonoheptyltin a substituted or unsubstituted hydrocarbyl radical, a hy oxide, bis-diethylmononyltin oxide, bis-dimethylmonodo drogen atom or the radical of any compound capable of decyltin oxide, and bis-tripropyltin oxide. reacting with an acidic hydrogen; and n is an integer from 70 Representative phosphinic and phosphonic acid react 1 to 2 inclusive. The term "hydrocarbyl radical' as em ants are di(hydroxymethyl)phosphinic acid, hydroxy ployed herein is intended to encompass monovalent hy methylphosphonic acid, trichloromethyl phosphonic acid, 3,179,6?6 3. 4. di(hydroxyheptyl) phospinic acid, dihexyl phosphinic acid, pounds of the invention together with those known hith phenyl phosphinic acid, and phenyl phosphonic acid. erto employed in this test procedure are listed in Table II. The proportions of organotin and organophosphorus reactants are normally determined by the number of hy TABLE II droxy substituents attached to the phosphorus nucleus of the organophosphorus reactant. Thus the molar propor Fungistatic Compounds tions of reactants where the alkyl stannic oxide is being Tributyltin-di(hydroxymethyl)phosphinate. reacted with a phosphonic acid is at least 1:2 and may be Bis-Tributylti-hydroxymethylphosphonate. in the ratio of 1:1 respectively; whereas when the organo Tributyltin-di(hydroxyheptyl)phosphigiate.Bis-Tributyltin-trichloromethylphosphonate. phosphorus compound is a phosphinic acid the ratio of Tributyltin-di(hexyl)phosphinate. trialkyltin oxide to phosphinic acid is normally 1:2 respec 2,2'-Dihydroxy-5,5-dichlorodiphenyl methane. tively. While ambient temperatures, i.e. 25 C., may be N-Trichloromethyl2,2'-Methylene-3,4,6-trichlorophenol. mercapto-4-cyclohexene-1,2-dicar .. boxinide. employed to effect the reaction herein described, the re Dodecyl dimethyl benzyl ammonium cyclopentane action proceeds more efficaciously at elevated tempera carboxylate salt. Phenyl mercuric composition (Corobex CpV, a trade. tures of 100° C. and higher but at a point below the de name). composition point of the reactants and reaction product. 2,4-Dichloro-6-(o-chloroanilino)-s-triazene. A reaction temperature within the range of 125° C. to Trichlorophenyl acetate. 160° C. is preferred. Petlopmeta-xylenolhall0). derivative (Ottacide P, a trade The compounds of the invention formed in the manner Control sample (containing no fungist3t). described hereinabove are capable of inhibiting the growth of a wide spectrum of microorganisms at comparatively 20 The ingredients were thoroughly dry blended and placed low concentrations. The activity of these compounds in on a laboratory roll mill and milled for three minutes at controlling fungal and bacterial growth has been deter 320 F. The mill gauge was set at 0.040 inch and the mined by the following test procedure. Malt agar solu material removed from the mill and cooled. Discs, 15 tions containing known concentrations (0.1, 0.2, 0.5, 1, mm. in diameter of polyvinyl chloride film composition, 2, and 5 parts per million based on tin content only of each containing a fungistat of Table in the concentra each of the compounds, tributyltin-di(hydroxymethyl) tion recited therein, and a control disc of the aforesaid phosphinate, bis-tributyltin-hydroxymethyl phosphonate, film and dimensions were placed in an agar medium, bis-tributyltin-trichloromethyl phosphonate, tributyltin seeded with a suspension of spores and fragments of three di(hydroxyheptyl) phosphinate, and tributyltin-dihexyl 30 fungi, Aspergillus niger, Aspergillus flavus and Tricho phosphinate were inoculated with the fungus spores and derma sp. and incubated at 25° C. for a period of fifteen bacteria recited in Table I. The inoculated
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