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WO2006085859A1 - Compositions a effet biocide - Google Patents

Compositions a effet biocide Download PDF

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Publication number
WO2006085859A1
WO2006085859A1 PCT/US2005/003671 US2005003671W WO2006085859A1 WO 2006085859 A1 WO2006085859 A1 WO 2006085859A1 US 2005003671 W US2005003671 W US 2005003671W WO 2006085859 A1 WO2006085859 A1 WO 2006085859A1
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WO
WIPO (PCT)
Prior art keywords
biocidal
composition
anion
biocidal composition
cation
Prior art date
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Application number
PCT/US2005/003671
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English (en)
Inventor
Richard F. Stockel
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Individual
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Individual
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Priority to PCT/US2005/003671 priority Critical patent/WO2006085859A1/fr
Publication of WO2006085859A1 publication Critical patent/WO2006085859A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof

Definitions

  • This invention relates to new biocidal complexes prepared by metathesis synthesis involving either a monomelic or polymeric cationic biocide reacted with the anionic form of a monomelic or polymeric biocide.
  • These complexes tend to have low water solubility therefore for many, but not all applications it is necessary to prepare emulsions or microemulsions to obtain a stable aqueous solution, or the biocidal compositions can be dissolved in an organic solvent.
  • Organic solvents rather than water, can also be utilized in carrying out metathesis reactions provide the starting reactants have some degree of solubility, and the complex product or by-product precipitate from solution as formed to shift the reaction equilibrium to the right.
  • bioactive complexes of this invention can also be synthesized by a straightforward acid-base reaction. This involves the direct combination of a free base bioactive molecule containing at least one or more nitrogen atom having a pair of free electrons with a bioactive molecule capable of donating a proton to form the complexes of this invention.
  • This synthetic route is particularly useful, when preparing complexes of anti-fungal compounds known as azoles and certain amine containing antibiotics having the ability of being protonated respectively.
  • the following reaction serves as an illustration. Chlorhexidine + undecylenic acid chlorhexidium
  • acidic proton transferable molecules include organic phosphoric, phosphonic, phosphinic acids; organic sulfonic or sulfinic acids and the like.
  • the bioactive acid component In order for the acid-base process to work, the bioactive acid component must have a transferable proton to a basic bioactive nitrogen compound having a lone pair of electrons.
  • the reaction is usually conducted in refluxing alcohol (C1-C4), aqueous alcoholic solutions or aprotic dipolar solvents.
  • the effectiveness of individual biologically active compounds can be enhanced by the formation of these complexes as described by this invention.
  • a bioactive cation with a bioactive anion improves the overall biological activity depending on the application.
  • This invention has other important safety and toxicity implications because the resulting complex can be composed of either EPA or FDA approved materials.
  • One parameter, which is important in determining the rate of kill is the dissociation constant of the biocidal complex. Other factors are the ionization and permeability of the complex.
  • U.S. 5,575,993 discloses compositions of polyionenes with anionic biological species.
  • my invention is not anticipated by 993' since the two are significantly different from each other. These differences are clearly delineated in 993 ' whereby only part of the polyionene anion is replaced by a bioactive species, from about 0.005 to about 0.33 or 0.50 degree of substitution depending on the specific polyionene used. All of the resulting compositions are very soluble in water, unlike the compositions of my invention, prior to solubilization with the assistance of surfactants and cosolvents. i he invention will be illustrated by the following examples, which, it will be understood are not intended to be limiting, but merely illustrative.
  • Gemini quats e.g., ethanediyl - ⁇ , w- bis (dodecyldimethyl) ammonium halide
  • Azoles are either triazoles or imidazoles
  • cyproconazole fenbuconazole, tebuconazole, penconazole, tetraconazole
  • Representative cationic monomeric or polymeric biocides included biguanides, guanidines, amidines, quaternaries, polyionenes, phosphoniums, sulfoniums, Gemini quats, amine containing dendrimers, amine containing antibiotics, azoles or any other biocidal cationic moieties.
  • these cationic antimicrobial agents can be other salts besides the hydrochloride.
  • Some examples are hydroxy carboxylic acids, amino acids, sulfonates, and phosphates to name just a few examples.
  • One skilled in organic chemistry could find other suitable substitutes.
  • polymeric species useful for carrying out this invention could be further modified by varying the repeating units or by end capping.
  • U.S. 4,891,423 and 5,741,886 are examples of further enhancing the antimicrobial activities of phmb. Other such examples for different polymeric systems also exist.
  • bioactive anions represent a partial list of actives, which can be utilized in this invention. Knowledgeable persons familiar with biocides can conjure other possible anionics substitutes. In keeping with the spirit of this invention, the list below is illustrative as working examples to achieve very broad antimicrobial activity for a variety of applications.
  • the preferred surfactants which form microemulsions or emulsions with the compositions of this invention, are by and large, either of the amphoteric and non-ionic type, or combinations thereof.
  • Highly charged anionic surfactants have the potential to reduce the overall bioactivity of these complexes by causing some degree of precipitation, thereby lessening its effective.
  • amphoteric Surfactants that carry a positive charge in strongly acidic media, carry a negative charge in strongly basic media, and form zwitterionic species at intermediate pH's are amphoteric.
  • the preferred pH range for the stability and effectiveness is from about 5.0 to about 9.0. Under this pH range the amphoteric surfactant is mostly or fully in the zwitter (overall neutral charge) form, therby negating any dilution of bioactivity of the compositions of this invention.
  • amphoteric surfactants useful for preparing microemulsions or emulsions for the complexes of this invention. These are:
  • Nonionic surfactants have also been found to be useful to form small particle micelles for these complexes. These can be classified as the following:
  • alkanolamides a. alkanolamides b. ethoxylated (propoxylated) amides
  • esters a. ethoxylated (propoxylated) carboxylic acids b. ethoxylated (propoxylated) glycerides c. glycol esters (and derivatives) d. mono (di) glycerides e. polyglycerol esterts f. polyhydric alcohol esters and ethers g. sorbitan / sorbital esters h. di (tri) esters of phosphoric acid
  • Ethers a. ethoxylated (propoxylated) alcohol b. ethoxylated (propoxylated) lanolin c. ethoxylated (propoxylated) polysiloxanes d. ethoxylated-propoxylated block copolymers
  • Two suitable cationic surfactants include D,L-2-pyrrolidone-5-carboxylic acid salt of ethyl-N-cocoyl-L-arginate (CAE), marketed by Ajinomto and cocamidopropyl, cocamidopropyl PG dimonium chloride phosphate (PTC), marketed by Uniqema, and the like.
  • CAE ethyl-N-cocoyl-L-arginate
  • PTC cocamidopropyl PG dimonium chloride phosphate
  • an effective surfactant system will differ to some degree for each biocidal complex.
  • the choice will depend on the surfactants hydrophilic- lipophilic balance (HLB) to form a stable small particle micelle in an aqueous or aqueous cosolvent medium solution.
  • HLB hydrophilic- lipophilic balance
  • the combination of two or more amphoteric or a amphoteric-nonionic system or two or more nonionic surfactants can also be utilized to achieve satisfactory results.
  • an appropriate solvent is required to solublize the biocidal composition in order to form an emulsion, or a microemulsion.
  • the latter usually needs a cosolvent.
  • the concentration of water is about or greater than 70 weight percent of the total solvents present. It is also preferable to have at least 10 weight percent or greater of actives present in the concentrate.
  • aprotic dipolar solvent in part, or in toto.
  • these types of solvents are dimethyl formamide, dimethyl sulfoxide, N-methylpyrrolidone, gamma butylrolactone, morpholine N-oxide, or dimethyl-2-piperidone and the like.
  • Other useful solvents found are mono/di/tri phosphates or mixtures thereof.
  • the complex has considerable hydrophobic functionality e.g., stearates it may be necessary to use aromatic solvents like toluene or xylene in part or in toto.
  • aromatic solvents like toluene or xylene in part or in toto.
  • the total amounts of any of the solvents in preparing microemulsions should be kept to a minimum.
  • About 30 weight percent of the concentrate represents the upper limit. With 10 weight percent or more preferred. These percentages are based only on the total weight of all the solvents present in the concentrate including water.
  • a second criteria for the selection of a water-solvent system for these complexes is dependent on the specific application. If the intended use is for human or animal applications then the solvents should have a safe toxicity/irritation profile.
  • Bioactive molecules are produced using the ultimate green chemistry approach.
  • Water is the solvent of choice, by-products are harmless salts and yields are excellent to quantitative.
  • the reactants are only slightly soluble in water, alcohols or other solvents can be used if the product precipitates from solution.
  • the appropriate cationic moiety is reacted with the desired anionic moiety in water.
  • concentration of reactants can vary from 20 to about 60 weight percent of the total solution. The reaction takes place at room temperature, and is generally completed within one hour. However, it should be noted that metathesis reactions can be successfully carried out in non-aqueous solvents as well.
  • the final product is readily removed by decantation, dried in an oven, and generally can be used as is certain applications.
  • the acid component In order for the acid-base synthesis to give good yields, the acid component must have a transferable proton (pka) to a basic molecule (pkb).
  • the reaction is usually conducted in refluxing from 1 to 10 hours in alcohol (C 1 -C 4 ) or aqueous alcoholic solutions.
  • the product is isolated after evaporating off the solvent(s). Recrystallization or chromatographic purification is preferred, if necessary.
  • the complex is dissolved in the minimum amount of a solvent with the appropriate Hildebrand solubility parameter.
  • the solubility parameter is a numerical value that indicates the relative solvency behavior of a specific solvent.
  • Hildebrand solubility parameters from about 8.5 to about 22.0 are suitable for solubilization of the complexes of this invention.
  • the correct solvent for solubilization will be on the low side, if the bonding has more co valency, and if the boding is more ionic, then the proper solvent will have a much higher value.
  • Combinations of solvents are also useful in preparing emulsions or microemulsions.
  • amphoteric or non-ionic is added to the dissolved complex.
  • Combinations of the above type surfactants can also be utilized.
  • the complex-solvent-surfactant is then diluted with water to the active concentration required for the particular application to form an emulsion or microemulsion depending on the micellar size and choice of solvents / cosolvents.
  • the bacteriostatic activity of several complexes was investigated by testing at 0.1 weight percent using Oxioid No. 2 nutrient broth and inoculating the broth with 1 ml of a 24 hour broth culture of the test organisms after incubation at the optimum growth temperature of the organism for 48 hours.
  • Dolvionene 6.6-triclosan polyionene 6.6 is prepared from tetramethyl hexamethylenediamine and 1 ,6-dichloro-hyxamethylene.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (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)

Abstract

L’invention concerne des compositions à effet biocide formées par métathèse de cations bioactifs monomères ou polymères avec des anions bioactifs monomères ou polymères, afin de former des complexes sensiblement insolubles dans l’eau. Ces composés ou polymères uniques et innovants sont efficaces contre une large variété d’espèces microbiennes.
PCT/US2005/003671 2005-01-31 2005-01-31 Compositions a effet biocide Ceased WO2006085859A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2005/003671 WO2006085859A1 (fr) 2005-01-31 2005-01-31 Compositions a effet biocide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2005/003671 WO2006085859A1 (fr) 2005-01-31 2005-01-31 Compositions a effet biocide

Publications (1)

Publication Number Publication Date
WO2006085859A1 true WO2006085859A1 (fr) 2006-08-17

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PCT/US2005/003671 Ceased WO2006085859A1 (fr) 2005-01-31 2005-01-31 Compositions a effet biocide

Country Status (1)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009020689A1 (fr) * 2007-08-08 2009-02-12 General Electric Company Procédé de lutte contre des protozoaires abritant des bactéries

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3825560A (en) * 1969-12-30 1974-07-23 Y Sasaki N-monoacyl derivatives of arginine
US4980067A (en) * 1985-07-23 1990-12-25 Cuno, Inc. Polyionene-transformed microporous membrane
US5019096A (en) * 1988-02-11 1991-05-28 Trustees Of Columbia University In The City Of New York Infection-resistant compositions, medical devices and surfaces and methods for preparing and using same
WO1992001380A1 (fr) * 1990-07-18 1992-02-06 Imperial Chemical Industries Plc Composition biocide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3825560A (en) * 1969-12-30 1974-07-23 Y Sasaki N-monoacyl derivatives of arginine
US4980067A (en) * 1985-07-23 1990-12-25 Cuno, Inc. Polyionene-transformed microporous membrane
US5019096A (en) * 1988-02-11 1991-05-28 Trustees Of Columbia University In The City Of New York Infection-resistant compositions, medical devices and surfaces and methods for preparing and using same
WO1992001380A1 (fr) * 1990-07-18 1992-02-06 Imperial Chemical Industries Plc Composition biocide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009020689A1 (fr) * 2007-08-08 2009-02-12 General Electric Company Procédé de lutte contre des protozoaires abritant des bactéries

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