WO1993007251A1 - Composition anti-microbienne - Google Patents

Composition anti-microbienne Download PDF

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Publication number
WO1993007251A1
WO1993007251A1 PCT/US1992/006695 US9206695W WO9307251A1 WO 1993007251 A1 WO1993007251 A1 WO 1993007251A1 US 9206695 W US9206695 W US 9206695W WO 9307251 A1 WO9307251 A1 WO 9307251A1
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WO
WIPO (PCT)
Prior art keywords
blend
compound
composition according
weight
composition
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.)
Ceased
Application number
PCT/US1992/006695
Other languages
English (en)
Inventor
John J. Merianos
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.)
ISP Investments LLC
Original Assignee
ISP Investments LLC
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 claimed from US07/772,182 external-priority patent/US5196135A/en
Priority claimed from US07/772,409 external-priority patent/US5216030A/en
Priority claimed from US07/783,017 external-priority patent/US5242684A/en
Application filed by ISP Investments LLC filed Critical ISP Investments LLC
Priority to EP19920917984 priority Critical patent/EP0607162A4/fr
Publication of WO1993007251A1 publication Critical patent/WO1993007251A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds

Definitions

  • antimicrobial compositions comprising:
  • R ⁇ and R 2 are independently C 12 or C 14 -alky1;
  • X is a halogen such as Cl, Br or I;
  • compositions exhibit excellent antibacterial activity, low toxicity, water solubility and a low irritation effect on the skin of the user.
  • the several bis-quaternary ammonium compounds which comprise the blend composition (a) are made by reacting one mole of a selected dihalo compound selected from:
  • X is a halide such as Cl, Br and I, with 2 moles of dodecyldimethyl a ine, tetradecyldimethylamine or predetermined mixtures thereof.
  • a typical reaction is the following:
  • a reaction mixture of one mole of dodecyldimethyla ine, one mole of the tetradecyldimethylamine and one mole of the selected dichloro compound will provide the following blend compositions:
  • Another way of introducing the quaternary nitrogen into the polymer structure is by using monomers with functionality, either tertiary amine or reactive alkylating groups which are quaternizable.
  • the following vinyl ammonium monomers can be copolymerized with vinyl pyrrolidone by solution polymerization in isopropyl alcohol or by precipitation polymerization in cyclohexane or heptane and under conditions to provide low molecular weight copolymers, i.e. about 10,000 to about 20,000, suitable for coprecipitation or admixture with the blend of bis-quaternary ammonium compounds.
  • a preferred copolymer is the copolymer of vinylpyrrolidone and MAPTAC, which is known as GAFQUAT ® HS-100 resin (ISP) , and is supplied as a 20% aqueous solution.
  • the coprecipitate product comprising the blend composition and copolymer usually is prepared by reacting predetermined amounts of a dilute aqueous solution of the blend composition and copolymer, usually from 90:10 to 10:90 wt. ratio of each, respectfully, and removing the solvent.
  • the desired coprecipitate is formed as a solid product.
  • the antimicrobial compositions of the invention may be used as such; however, preferably they are admixed with inert materials as pharmaceutical and cosmetic formulations, e.g. in the form of powders, solutions, lotions, suspensions and the like. Typical inert additives include water, alcohols, starch, and the like. Active ingredients also may be included in the product, if desired.
  • coprecipitate form of the antibacterial product of the invention is favored, admixtures of the blend and copolymer also may be used to prepare commercial compositions.
  • the antimicrobial activity of the products herein are represented by their Minimum Inhibitory Concentration (MIC) against E.Coli, a Gram negative microorganism. Their effect on skin is indicated by an Irritation Index.
  • MIC Minimum Inhibitory Concentration
  • Irritation Index an Irritation Index
  • the antibacterial activity of the compositions of the invention are up to 12.5 times more favorable than the individual compounds of the blend; the product containing the D blend shows only 1/3 to 1/4 as much irritation to the skin as the H and L blend products, respectively; and the blends are 5-20 less toxic than the individual compounds in the blends.
  • the antimicrobial blend composition of bis-quaternary ammonium compounds is selected from those represented by the formula
  • R j L and R are independently C 12 or
  • X ⁇ is a halogen such as Cl, Br or I; and in the weight ratio of about 25% of the compound where both R. ⁇ and R 2 are C 12 -alkyl;
  • the blend composition with polyvinylpyrrolidone usually is prepared by reacting a dilute solution of the blend composition in alcohol or water, preferably methanol, with a dilute solution of the bisquat blend composition in the same solvent, and removing the solvent to form the desired coprecipitate solid product.
  • the blend coprecipitate compositions of the invention are prepared by refluxing the selected dichloro compound, the amines, and an alkali metal halide, in alcoholic solution, removing the solvent, precipitating the blend of bisquats in an organic solvent in substantially quantitative yield, and reacting a solution of the thus-prepared bisquat in methanol or water with a solution of soluble polyvinylpyrrolidone in the same solvent, and removing the solvent under reduced pressure to form the solid coprecipitate product.
  • blend compositions with polyvinylpyrrolidone exhibit an enhanced antimicrobial activity and reduced toxicity as compared to the individual compounds therein. Furthermore, they show excellent solubility in water, and less irritation to the user, as compared to the blend composition itself, that is, without polyvinylpyrrolidone.
  • the antimicrobial compositions of the invention may be used as such, or, preferably, admixed with an inactive or inert component to prepare pharmaceutical formulations such as powders, solutions, lotions, suspensions and the like. Typical additives include water, alcohols, starch, etc. Other active ingredients may be included if desired.
  • coprecipitate form is favored, mixtures of the blend composition and polyvinylpyrrolidone may be used as well.
  • Typical antimicrobial activities represented by their Minimum Inhibitory Concentration (MIC) , against E.Coli, a gram negative microorganism, is presented in the Table below for both the individual compounds in blend composition D and the D, H and L blend compositions with polyvinylpyrrolidone at different relative amounts of the compounds therein (as measured in a 10% active solution) .
  • MIC Minimum Inhibitory Concentration
  • compositions of the invention also have increased water solubility than blends without PVP.
  • the LD 50 toxicity of the D blend-PVP compositions above also is reduced by a factor of 5-6 as compared to the individual compounds in the blend, furthermore they exhibit a substantially reduced irritation to the skin as compared to the individual compounds or the blend without PVP.
  • the blend composition comprised 25% by weight of A, 50% by weight of B and 25% by weight of C compounds.
  • Typical antimicrobial activities represented by their Minimum Inhibitory Concentration (MIC) against E.Coli, a gram negative microorganism, is presented in the Table below for both the individual compounds in blend composition D and the blend composition itself, with PVP, with different relative amounts of the A, B and C compounds therein (as measured in a 10% active solution) .
  • MIC Minimum Inhibitory Concentration
  • the MIC values of the D blend compositions in the TABLE are up to 25 times more favorable than the individual compounds in the blend.
  • the LDt jQ toxicity of the blend composition D (without PVP) above also is observed to be reduced by a factor of 5-6 as compared to the individual compounds.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • Medicinal Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicinal Preparation (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Une composition anti-microbienne non irritante et à faible toxicité comprend un mélange de plusieurs composés ammonium bi-quaternaires facultativement coprécipités (1) avec un copolymère de vinylpyrrolidone et un monomère d'ammonium quaternaire acrylamide ou vinyle, ou (2) avec du polyvinylpyrrolidone.
PCT/US1992/006695 1991-10-07 1992-08-12 Composition anti-microbienne Ceased WO1993007251A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19920917984 EP0607162A4 (fr) 1991-10-07 1992-08-12 Composition anti-microbienne.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US772,182 1991-10-07
US07/772,182 US5196135A (en) 1991-10-07 1991-10-07 Antimicrobial, low toxicity, blend composition of bis-quaternary ammonium compounds
US07/772,409 US5216030A (en) 1991-10-07 1991-10-07 Antimicrobial, low toxicity, blend composition of bis-quaternary ammonium compounds and polyvinylpyrrolidone
US772,409 1991-10-07
US783,017 1991-10-25
US07/783,017 US5242684A (en) 1991-10-25 1991-10-25 Antimicrobial, low toxicity, non-irritating composition comprising a blend of bis-quaternary ammonium compounds coprecipitated with a copolymer of vinylpyrrolidone and an acrylamido or vinyl quaternary ammonium monomer

Publications (1)

Publication Number Publication Date
WO1993007251A1 true WO1993007251A1 (fr) 1993-04-15

Family

ID=27419681

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/006695 Ceased WO1993007251A1 (fr) 1991-10-07 1992-08-12 Composition anti-microbienne

Country Status (4)

Country Link
EP (1) EP0607162A4 (fr)
AU (1) AU2461892A (fr)
CA (1) CA2120335A1 (fr)
WO (1) WO1993007251A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5536494A (en) * 1994-10-04 1996-07-16 Alcon Laboratories, Inc. Polyethylene oxide-containing quaternary ammunium polymers and pharmaceutical compositions containing an antimicrobial amount of same
EP0859547A4 (fr) * 1995-06-07 2000-12-20 Surmodics Inc Enrobages rendant les virus inactifs

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5085860A (en) * 1989-11-20 1992-02-04 L'oreal Reducing composition for the permanent deformation of hair containing as a reducing agent, an amino mercaptoalkylamide or a salt thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2194906A (en) * 1936-04-11 1940-03-26 Ig Farbenindustrie Ag Nitrogenous condensation product and process of producing same
US2933529A (en) * 1956-01-09 1960-04-19 Rohm & Haas Symmetrical diquaternary ammonium compounds
CH409985A (de) * 1961-11-03 1966-03-31 Robapharm Ag Verfahren zur Herstellung von neuen heterocyclischen Ammoniumverbindungen
US3525793A (en) * 1969-06-30 1970-08-25 Millmaster Onyx Corp Microbiocidal quaternary ammonium compounds containing synergistic blends of alkyl groups

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5085860A (en) * 1989-11-20 1992-02-04 L'oreal Reducing composition for the permanent deformation of hair containing as a reducing agent, an amino mercaptoalkylamide or a salt thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DEVINSKY et al., 41 Chemical Papers 803 (1987), see p. 803-14. *
Disinfectants, Sterilization and Preservatives, 1991, JOHN L. MERIANOS, "Quaternary Ammonium Antimicrobial Compounds", pp. 225-52, see pp. 230. *
See also references of EP0607162A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5536494A (en) * 1994-10-04 1996-07-16 Alcon Laboratories, Inc. Polyethylene oxide-containing quaternary ammunium polymers and pharmaceutical compositions containing an antimicrobial amount of same
EP0859547A4 (fr) * 1995-06-07 2000-12-20 Surmodics Inc Enrobages rendant les virus inactifs

Also Published As

Publication number Publication date
EP0607162A1 (fr) 1994-07-27
AU2461892A (en) 1993-05-03
CA2120335A1 (fr) 1993-04-15
EP0607162A4 (fr) 1994-11-17

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