US3247051A - Method of protection against growth of microorganisms with organo-bismuth compound - Google Patents

Method of protection against growth of microorganisms with organo-bismuth compound Download PDF

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Publication number
US3247051A
US3247051A US244252A US24425262A US3247051A US 3247051 A US3247051 A US 3247051A US 244252 A US244252 A US 244252A US 24425262 A US24425262 A US 24425262A US 3247051 A US3247051 A US 3247051A
Authority
US
United States
Prior art keywords
bismuth
tri
compound
microorganisms
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US244252A
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English (en)
Inventor
John R Leebrick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Primerica Inc
Original Assignee
Metal and Thermit Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL301743D priority Critical patent/NL301743A/xx
Application filed by Metal and Thermit Corp filed Critical Metal and Thermit Corp
Priority to US244252A priority patent/US3247051A/en
Priority to GB46719/63A priority patent/GB1000755A/en
Priority to DEM59144A priority patent/DE1266449B/de
Priority to CH283567A priority patent/CH463192A/de
Priority to CH1516563A priority patent/CH479242A/de
Application granted granted Critical
Publication of US3247051A publication Critical patent/US3247051A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/94—Bismuth compounds
    • 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
    • A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms

Definitions

  • This invention relates to methods of preventing and inhibiting the growth of microorganisms including bacteria and to compositions of matter utilized in these methods.
  • the invention also relates to materials which have been made resistant to attack by microorganisms such as bacteria.
  • the method of this invention for protecting a medium susceptible to attack by microorganisms comprises applying to the locus to be protected, an effective amount of R Bi wherein R is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, and cycloalkenyl.
  • R may be alkyl, cycloalkyl, alkenyl, cycloalkenyl, or alkynyl, including such groups when inertly substituted.
  • R When R is alkyl, it may include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-amyl, n-octyl, Z-ethylhexyl, etc. as well as substituted alkyls including phenyl ethyl, b-enzyl, etc.
  • Typical alkenyl groups which may be employed may include vinyl, 2- propenyl (i.e., allyl), l-propenyl, l-butenyl, Z-butenyl, etc. as well as inertly substituted alkcnyl groups typified by 4-phcnyl, buten-l-yl, etc.
  • cycloalkyl groups may include cyclohcxyl, cycloheptyl, cyclooctyl as well as incrtly substituted eycloalkyl groups including 2-methyl cycloheptyl, 3-butyl cyclohexyl, 3-methyl cyclohexyl, etc.
  • Typical aikynyl groups which may be employed include propyn-l-yl, propyn-Z-yl, butyn-l-yl, phenlethyn-yl, ethynyl.etc.
  • R may be an alkyl group having from three to eight carbon atoms, e.g., n-propyl, i-propyl, n-butyl, i-butyl, n-amyl, n-hexyl, 2-ethylhexyl, cyclohexyl, and octyl.
  • the preferred R may be butyl,
  • Typical specific compounds which maybe employed in practice of this invention may include trimethyl bismuth, triethyl bismuth tri-n-propyl bismuth, tri-i-propyl bismuth, tri-n-butyl bismuth, tri-i-butyl bismuth, tri-n-amyl bismuth, tri-i-amyl bismuth, tri-n-hexyl bismuth, tri-cyclohexyl bismuth, tri-n-heptyl bismuth, tri-eycloheptyl bismuth, tri-moctyl bismuth, tri-Z-ethylhexyl bismuth, tri-ndecyl bismuth, tri-tetradecyl bismuth, tri-vinyl bismuth, tri-allyl bismuth, tri-cyclohexenyl bismuth, tripropynyl bismuth, and triphenylcthynyl bismuth.
  • Preferred compounds may include those wherein R may have from about three to about eight carbon atoms.
  • Typical specific preferred compounds include trin-butyl bismuth, tri-n-octyl bismuth, tri-n-propyl bismuth, tricyclohexyl bismuth, and tri-n-hexyl bismuth.
  • These compounds may be available or may be readily made in the laboratory. For example, they may be made by the reaction of bismuth trichloride with, e.g., the appropriate Grignard reagent.
  • bismuth compounds R Bi may be used to control a wide range of microorganisms including bacteria.
  • the compounds of this invention are highly effective against a wide spectrum of bacteria including Gram negative and Gram positive bacteria.
  • Typical Gram positive bacteria against which the technique of this invention may be particularly effective may include S. aureus.
  • Typical Gram negative bacteria which may be controlled in accordance with certain aspects of this invention may include A. aerogenes and P. aeruginosa. It is a particular feature of this invention that in accordance with certain aspects it may be used to control fungi including C. nlbicans, A. flaws, and
  • these microorganisms and preferably bacteria may be controlled in a wide variety of loci. It is possible according to this invention to treat plastics, textiles, paper products, paints, and other specific materials which may serve as media in which microorganisms may grow. Plastics, textiles, paper products, and paints may be illustrative of the materials which are rendered resistant to attack when treated by applying the bismuth compound to the surface and/or by incorporation therein.
  • the plastics in massive and in fiber form may include urethanes, halogenated polymers and copolymers such as polyvinyl chloride and polyvinyl chloride-polyvinyl acetate copolymers, polyesters, polyamides, polyolefins, and natural or synthetic rubbers, etc.
  • Natural fiber products that may be protected may include paper products, hemp, and felts. Paints may be protected during storage and after application. Typical paints may include interior and exterior vinyl latex and alkyd paints, non-synthetic fiat natural paints, acrylic paints, and anti-fouling paints containing acrylic and vinyl components.
  • the process of this invention may be used in preserving adhesives; in secondary oil recovery processes; in paper mill slime control processes; and in controlling S.
  • novel compositions of this invention may be active components of detergent sanitizers and may be used for this and other purposes in the form of an aerosol material. They may also be used to protect plants and other growths against attack by microorganisms.
  • the preferred formulations prepared in accordance therewith possess an unexpectedly high activity against Gram negative bacteria. It will be obvious to those skilled in the art that prior art bactericides possess little or no activity against Gram negative bacteria when used in concentrations at which the preferred formulations of this invention (i.e., those containing tri-n-butyl bismuth) may control a wide range of biocidal targets including Gram negative bacteria. For example in a comparison by means of a Broth Dilution Test against phenyl mercury acetate (a typical active prior art bactericide), it was found that tri-n-butyl bismuth was about four times as effective as phenyl mercury acetate as noted in the table.
  • the method of this invention may be effected by using the noted compound R 81 in solid, liquid, or gaseous (including spray) formulations which preferably may include a carrier or diluent. It may, for example, be carried out by applying the compound to the surface of the material to be protected and/or admixing the compound with the material to be protected during the fabrication of said material.
  • the compounds may be used per se, particularly when they are incorporated into the material during preparation or fabrication. Many materials, particularly fibrous products such as textiles, may be treated by applying the compound to the surface by dipping, padding, spraying, etc.
  • Liquid compositions may be utilized in which the compound is dissolved and/or suspended in a solvent.
  • Solid compositions may be utilized in which the compound is mixed with a carrier or diluent.
  • the carrier may be inert, such as talc, clay, diatomaceous earth, flour, etc., or it may have activity such as that shown by the quaternary ammonium compounds.
  • the liquid formulations of the emulsion type may often include a dispersing agent such as an anionic, cationic, or nonionic surface active agent.
  • the compounds may be formulated with other active materials such as the triorganotins, pentachlorophenyl, copper-8-quinolinolate, bisphenols, o-phenylphenol, and polybrominated salicylanilides.
  • the amount of the active compound R Bi present in the total composition may be sufiicent to provide and effective amount at the locus to be protected against the appropriate microorganism. Typically such contained amounts may range from very low concentrations typically 0.001% or 0.002% up to 90%-l00%.
  • the carrier is a solid, e.g., talc
  • the compound may be present in amount of %-50%, say 20% of the total; when the carrier is a liquid, e.g., isopropanol-Frcon (under pressure), the compound may be present in an amount of 0.0l%1%, say 0.05%.
  • concentrations may permit attainment on or in the medium susceptible to attack at the locus to be protected, of effective amounts. Such amounts may be, e.g., in water treatment, 1-100 ppm. or in plastic treatment, 10-2000 p.p.m., etc.
  • Illustrative of the compositions containing the active bismuth compound may be those of Examples 1-4.
  • a standard paint, Sunoco PVA paint was mixed with the amount of trin-bu'tyl bismuth noted in column 1 of Table IV and applied to 10 mm. filter paper discs.
  • Example 5 Parts by weight Tri-cyclohexyl bismuth M
  • organobismuth compounds as defined herein can be employed in the compositions and methods of the invention to protect a wide variety of materials and living organisms that are susceptible to attack by microorganisms.
  • the invention includes all such modifications as come within the scope of the appended claims.
  • the method for protecting plastics, textiles, natural fibers materials, adhesives, oil wells, paper mills, and has pitals from attack by Gram negative bacteria, Gram positive bacteria and fungi which comprises applying to the locus to be protected an eiicctive amount of a compound RgBi wherein R is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, and cyloalkenyl.
  • a composition active against microorganisms comprising an inert carrier; and as the active component 0.01 to 50% by weight of the composition of a bismuth compound R Bi wherein R is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, and cycloalkenyl; and a dispersing agent.
  • composition active against microorganisms as claimed in claim 8 wherein said compound is tri-n-octyl bismuth.
  • a composition active against microorganisms comprising a solid carrier and as the active component a fungicidal amount of a bismuth compound RgBl wherein R is selected from the group consisting of alkyl, alkenyl alkynyl, cycloalkyl, and cycloalkenyl.
  • a composition active against microorganisms comprising a solid carrier and as the active component, a bismuth compound R Bi wherein R is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, and cycloalkenyl, said bismuth compound being present in the amount of 5-50% by weight of the total composition.
  • the method for protecting a medium from attack by fungi which comprises applying to the locus to be protected, an effective amount of a compound R Bi wherein R is selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, and cycloalkenyl.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paints Or Removers (AREA)
US244252A 1962-12-13 1962-12-13 Method of protection against growth of microorganisms with organo-bismuth compound Expired - Lifetime US3247051A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL301743D NL301743A (nl) 1962-12-13
US244252A US3247051A (en) 1962-12-13 1962-12-13 Method of protection against growth of microorganisms with organo-bismuth compound
GB46719/63A GB1000755A (en) 1962-12-13 1963-11-26 Antimicrobial agents
DEM59144A DE1266449B (de) 1962-12-13 1963-12-04 Verfahren zur Hemmung bzw. Verhinderung des Wachstums von Bakterien und Pilzen
CH283567A CH463192A (de) 1962-12-13 1963-12-11 Verfahren zum Schützen eines Substrates ausserhalb der Textilindustrie gegen den Angriff von Mikroorganismen
CH1516563A CH479242A (de) 1962-12-13 1963-12-11 Verfahren zum Schützen von nichtkeratinhaltigen Textilien gegen den Angriff durch Mikroorganismen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US244252A US3247051A (en) 1962-12-13 1962-12-13 Method of protection against growth of microorganisms with organo-bismuth compound

Publications (1)

Publication Number Publication Date
US3247051A true US3247051A (en) 1966-04-19

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US244252A Expired - Lifetime US3247051A (en) 1962-12-13 1962-12-13 Method of protection against growth of microorganisms with organo-bismuth compound

Country Status (5)

Country Link
US (1) US3247051A (nl)
CH (2) CH479242A (nl)
DE (1) DE1266449B (nl)
GB (1) GB1000755A (nl)
NL (1) NL301743A (nl)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4033915A (en) * 1974-08-02 1977-07-05 Montedison Fibre S.P.A. Flame-extinguishing polyolefin compositions
US4748113A (en) * 1985-06-13 1988-05-31 Marshall Barry J Compositions and methods for the diagnosis of gastrointestinal disorders involving urease
US5256684A (en) * 1985-06-13 1993-10-26 The Procter & Gamble Company Methods and compositions for the treatment of gastrointestinal disorders
US5601848A (en) * 1985-06-13 1997-02-11 The Procter & Gamble Company Methods for the treatment of gastrointestinal disorders
US6258376B1 (en) 1994-05-02 2001-07-10 Josman Laboratories, Inc. Method of making chewing gum containing colloidal bismuth subcitrate
US6372784B1 (en) 1995-02-07 2002-04-16 Josman Laboratories, Inc. Bismuth-containing compounds in topical dosage forms for treatment of corneal and dermal wounds
US6379651B1 (en) 1995-02-07 2002-04-30 Josman Laboratories Oral-topical dosage forms for delivering antibacterials/antibiotics to oral cavity to eradicate H. pylori as a concomitant treatment for peptic ulcers and other gastro-intestinal diseases
US6426085B1 (en) 1994-05-02 2002-07-30 Josman Laboratories Inc. Use of bismuth-containing compounds in topical oral dosage forms for the treatment of halitosis
US20030082664A1 (en) * 2001-10-15 2003-05-01 Kimberly-Clark Worldwide, Inc. System for the detection of urease and method for using same
US20030118517A1 (en) * 1994-05-02 2003-06-26 Athanikar Narayan K. Topical oral dosage forms containing bismuth compounds
US6929926B2 (en) 2001-10-15 2005-08-16 Barry J. Marshall Composition for the detection of gastrointestinal disorders

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4033915A (en) * 1974-08-02 1977-07-05 Montedison Fibre S.P.A. Flame-extinguishing polyolefin compositions
US4748113A (en) * 1985-06-13 1988-05-31 Marshall Barry J Compositions and methods for the diagnosis of gastrointestinal disorders involving urease
US5256684A (en) * 1985-06-13 1993-10-26 The Procter & Gamble Company Methods and compositions for the treatment of gastrointestinal disorders
US5601848A (en) * 1985-06-13 1997-02-11 The Procter & Gamble Company Methods for the treatment of gastrointestinal disorders
US20030118517A1 (en) * 1994-05-02 2003-06-26 Athanikar Narayan K. Topical oral dosage forms containing bismuth compounds
US6426085B1 (en) 1994-05-02 2002-07-30 Josman Laboratories Inc. Use of bismuth-containing compounds in topical oral dosage forms for the treatment of halitosis
US6258376B1 (en) 1994-05-02 2001-07-10 Josman Laboratories, Inc. Method of making chewing gum containing colloidal bismuth subcitrate
US6616938B2 (en) 1994-05-02 2003-09-09 Josman Laboratories, Inc. Method of making chewing gum containing colloidal bismuth subcitrate
US6902738B2 (en) 1994-05-02 2005-06-07 Josman Laboratories, Inc. Topical oral dosage forms containing bismuth compounds
US20060088481A1 (en) * 1994-05-02 2006-04-27 Athanikar Narayan K Topical oral dosage forms containing bismuth compounds
US6372784B1 (en) 1995-02-07 2002-04-16 Josman Laboratories, Inc. Bismuth-containing compounds in topical dosage forms for treatment of corneal and dermal wounds
US6379651B1 (en) 1995-02-07 2002-04-30 Josman Laboratories Oral-topical dosage forms for delivering antibacterials/antibiotics to oral cavity to eradicate H. pylori as a concomitant treatment for peptic ulcers and other gastro-intestinal diseases
US20030082664A1 (en) * 2001-10-15 2003-05-01 Kimberly-Clark Worldwide, Inc. System for the detection of urease and method for using same
US6929926B2 (en) 2001-10-15 2005-08-16 Barry J. Marshall Composition for the detection of gastrointestinal disorders
US7008777B2 (en) 2001-10-15 2006-03-07 Barry J. Marshall System for the detection of urease and method for using same

Also Published As

Publication number Publication date
CH463192A (de) 1968-09-30
NL301743A (nl)
DE1266449B (de) 1968-04-18
CH1516563A4 (nl) 1969-03-31
CH479242A (de) 1969-11-28
GB1000755A (en) 1965-08-11

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