WO2008058490A1 - Composés complexes d'acide borique, d'acide salicylique ou de ses dérivés et d'argent, leur procédé de préparation et une préparation contenant ces composés pour éradiquer les moisissures, les mycètes et les insectes ligniperdus - Google Patents

Composés complexes d'acide borique, d'acide salicylique ou de ses dérivés et d'argent, leur procédé de préparation et une préparation contenant ces composés pour éradiquer les moisissures, les mycètes et les insectes ligniperdus Download PDF

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Publication number
WO2008058490A1
WO2008058490A1 PCT/CZ2007/000101 CZ2007000101W WO2008058490A1 WO 2008058490 A1 WO2008058490 A1 WO 2008058490A1 CZ 2007000101 W CZ2007000101 W CZ 2007000101W WO 2008058490 A1 WO2008058490 A1 WO 2008058490A1
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WO
WIPO (PCT)
Prior art keywords
preparation
solution
silver
salicylic acid
water
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Application number
PCT/CZ2007/000101
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English (en)
Inventor
Radim Hrdina
Marcela HRDINOVÁ
Ladislav Burgert
Václav BURES
Henryk Lewandowski
Romana SULÁKOVÁ
Original Assignee
Univerzita Pardubice
Kubi Spol. S R.O.
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Application filed by Univerzita Pardubice, Kubi Spol. S R.O. filed Critical Univerzita Pardubice
Publication of WO2008058490A1 publication Critical patent/WO2008058490A1/fr

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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
    • C07F5/022—Boron compounds without C-boron linkages

Definitions

  • the invention relates to novel complex compounds of boric acid, salicylic acid or its derivatives and silver, method of their preparation, and a preparation containing these compounds for use against moulds, fungi and ligniperdous insects.
  • Silver and its compounds are very efficient preparations against moulds and fungi or general disinfectants.
  • the mechanism of action of silver, which is applied mainly in colloidal form, is not fully understood.
  • the univalent silver compounds it is known that the efficient concentrations of these ions begin as low as in the region of 10 ⁇ 12 mol.drrr 3 (for overview of silver and its compounds see e.g., Comprehensive Inorganic Chemistry, vol. 3, J. C. Bailar, Jr. et al., Eds., Pergamon Press, Oxford, 1973).
  • Commercially available are also organometallic compounds of silver which exhibit these properties, too.
  • metal-free derivatives of both series exhibit biological effects, e.g., 4-aminosalicylic acid has strong antibacterial effects (for overview of these compounds see e.g., The Merck Index, An Encyclopedia of Chemicals, Drugs, and Biologicals, 12 th edition, Merck Research Laboratories, 1996), which can probably be ascribed to the formation of the zwitterionic form ( + H 3 N-C 6 H 3 (OH)-COO ⁇ ).
  • the drawback of the compounds A and B consists in that they actually are pigments, which poorly penetrate into the substrate treated and can be easily removed from its surface.
  • boric acid or its salt are efficient preparations against ligniperdous (wood-destroying) insects; these compounds act as protecting agents against moulds, fungi and ligniperdous insects also in nature (e.g., in roots of plants).
  • the disadvantage of both these boron compounds is that they are soluble in water, so that the protection of a material that is exposed to the action of water is not long- lasting.
  • esters of boric acid e.g., the ester of boric acid and glycerol, which have similar effects and are less soluble in water and readily soluble in ethanol (Sciarra, Elliot, J. Am. Pharm. Assoc. (Sci. Ed.) 49, 116 (1960)).
  • their biological efficiency, particularly against moulds is low, and the mould will be destroyed neither by boric acid nor by borax once the substrate has already been attacked by the mould.
  • Boric acid (H 3 BO 3 ) is known to be a weak monoprotic acid of a limited solubility in water, which does not act as a proton donor but acts as a Lewis acid.
  • Salicylic acid or its derivatives form tetrahedral complexes with boric acid at the ratio of 1 : 1 or 2 : 1 (see Reaction in the boric acid-salicylic acid system.
  • Distinct disinfecting effects are also exhibited by cationic, i.e. basic dyestuffs, in which the chromophore carries a positive charge counterbalanced by a simple anion.
  • cationic i.e. basic dyestuffs
  • the best known representatives e.g., are Crystal violet and Gentian violet (for a toxicological study, see H. C. Hodge et a/., Toxicol. Appl. Pharmacol. 22, 1 (1972)).
  • these compounds bind to phosphate group, thereby preventing the formation of adenosine triphosphate and, hence, the nutrition of the cell.
  • All tetraalkyl- or tetraaryl-ammonium compounds i.e.
  • the drawback of the solutions known so far consists either in the insolubility of the active components and the prevention of the saturation of the material treated, or - on the contrary, - in their high solubility and readily washing out from the material treated.
  • individual components possess specific activities, i.e. they are only efficient against some kinds of pest microorganisms, as described herein above.
  • Object of the present invention are new complex compounds of boric acid, salicylic acid or its derivatives and silver of general formula I,
  • Object of the invention is further a method of preparation of the complex compound of general formula I, consisting in preparation of a solution of one molar unit of boric acid and two molar units of salicylic acid or its derivative in a polar solvent under stirring, whereas the concentration of salicylic acid or its derivative in the solution is in the range of 0.2-50 % wt.
  • the solution is prepared at the temperature ranging from 0 0 C to the boiling point of the polar solvent used, then one molar unit of silver nitrate is added with stirring into the solution of boric acid and salicylic acid or its derivative, and the resulting solution is cooled to the temperature of 0-25 0 C, and the formed precipitate of the complex compound is then collected by filtration and dried at the temperature of 25-80 0 C.
  • the solution of boric acid and salicylic acid or its derivative in the polar solvent is prepared at room temperature.
  • the polar solvent is selected from the group comprising water, ethanol, propan-1-ol, propan-2-ol, acetone or their mixtures.
  • silver nitrate is added in the form of a solution having the silver nitrate concentration in the range of 0.2-91 % wt. in a solvent selected from the group comprising water, ethanol or their mixtures, prepared at the temperature ranging from 0 0 C to the boiling temperature of the solvent used.
  • a solvent selected from the group comprising water, ethanol or their mixtures, prepared at the temperature ranging from 0 0 C to the boiling temperature of the solvent used.
  • the solution of silver nitrate is prepared at room temperature.
  • silver nitrate is added in the form of a solid substance.
  • Object of the invention is further a preparation for killing moulds, fungi and ligniperdous insects, which contains as an active agent at least one complex compound of general formula I, solvents and optionally suitable auxiliary substances.
  • the above described compounds of general formula I are insoluble in water. On the other hand, they are soluble in mixtures of water and alcohol, the solubility in alcohol being the higher, the longer the aliphatic chain R is. Hence, they are applied in the form of these solutions, wherein the active agent (complex compound I) penetrates by diffusion into the material treated. After a certain period of time, the complex compound I is gradually decomposed and silver is produced by the reduction (ethanol acts on Ag + as a reducing agent); the silver in atomic form is then evenly distributed throughout the material, which brings very high biological efficiency with it. Of course, silver is also insoluble in water; therefore, it cannot be washed out from the treated material by water or by organic solvents. Boric acid and salicylic acid or its derivative has fungicidal effects in the material treated, too. Thus, the preparation acts not only as a preventive protection of the material, but also as a highly efficient killer of harmful micro-organisms.
  • the preparation according to this invention contains a mixture of water and C 2 to C 3 alcohol as the solvent.
  • the preparation according to this invention contains dyestuffs and stabilisers as accompanying substances.
  • a dyestuff exhibiting disinfectant effects e.g., a basic dyestuff such as, e.g., Crystal violet or Malachite green, is used.
  • the preparation according to this invention can be stabilised by an addition of hydrogen peroxide.
  • Hydrogen peroxide prevents the reduction and the formation of silver in the solution.
  • This preferred preparation is prepared by first preparing the required hydrogen peroxide solution in water and then adding alcohol and finally adding the complex compound of general formula I.
  • the preparation of this invention contains 0.001- 10 % wt. of the complex compound of general formula I, 25 - 98 % wt. of C 2 to C 3 alcohol, and 2 - 75 % wt. of water, and optionally further auxiliary substances, such as dyestuffs and stabilisers.
  • the preparation of this invention further contains 0.01 - 5 % wt. of a dyestuff.
  • a dyestuff exhibiting disinfecting effects e.g., a basic dyestuff such as, e.g., Crystal violet or Malachite green can be used as the dyestuff.
  • a basic dyestuff such as, e.g., Crystal violet or Malachite green
  • the preparation of this invention can be stabilised by the addition of up to 0.6 % wt. of hydrogen peroxide, with regard to the weight of water in the preparation.
  • the preparation according to this invention can be used, e.g., for killing of moulds in households, or for preventive protection of wood, plaster or other materials that can be attacked by moulds, fungi or ligniperdous (wood-destroying) insects.
  • the colourless preparation can be advantageously used for protection of plaster before decorating the walls or for protection of wood before coating with coloured coating composition itself.
  • the 1 H and 13 C NMR spectra were measured with Bruker AVANCE 500 apparatus in VUOS a.s., Pardubice, at 500.13 MHz ( 1 H) and at 125.76 MHz ( 13 C), respectively.
  • the 11 B NMR spectra were measured with Bruker AMX 360 apparatus at 115.55 MHz. The samples were dissolved in DMSO-D 6 .
  • the 1 H and 13 C chemical shifts were assigned by means of two-dimensional spectra ( 1 H 1 1 H-COSY, 1 H 1 13 C-HSQC and 1 H 1 13 C-HMBC).
  • the infrared spectra were measured with FTIR - 8400S Fourier Transform Infrared Spectrophotometer Shimadzu. The samples were measured in solid state as KBr tablets. Approximately 20 mg sample and 60 mg KBr was ground in an agate mortar and compressed in a hydraulic press.
  • reaction medium water/ethanol
  • the silver nitrate solution is poured into the latter solution with stirring.
  • complex compound I-2 was confirmed by infrared spectroscopy, showing new peaks in spectrum, with frequencies 991 and 968 crrf 1 v(B(OX) 4 ) " as , characteristic of tetragonal arrangement.
  • the below-given IR spectrum was identical for samples of complex compounds I-2 prepared according to both Example 3 and Example 4.
  • the reaction temperature is kept at 60 0 C, and the pH value is kept at 6-7 throughout the reaction by additions of the 10% aqueous solution of NaOH.
  • the reaction lasts 5 hours, and the progress of acetylation is monitored by means of the test with the Ehrlich reagent.
  • reaction mixture After 5 min intensive stirring mixture at the low temperature, the reaction mixture is filtered through a sintered glass filter No. 2, the filter cake is washed with 20 cm 3 acetone and transferred into the pre- prepared solution of 4-amino-2-hydroxybenzoic acid.
  • the reaction mixture is stirred at room temperature for 30 min. The reaction then continues at the temperature of 60 0 C for another 3 hours.
  • the pH value is decreased from 6 to 3.0 by addition of concentrated (35%) HCI.
  • the formed precipitate is collected by suction on a B ⁇ chner funnel.
  • the reaction mixture is cooled to the temperature of 0 - 5 0 C, the precipitate of the complex compound I-4 is collected by filtration and dried at the temperature of 40 °C.
  • a mixture of 40 g water and 10 g 3% H 2 O 2 is prepared and 50 g denatured ethanol (96%) is added, then 0.4 g complex compound of silver of the formula 1-1 is dissolved in this mixture with stirring.
  • the resulting solution is very suitable for eradication (killing) of moulds in households (e.g. on damp walls) or for preventive protection of wood, e.g. window frames.
  • the preparation is also very suitable as disinfectant. It is suitable to consume the liquid preparation within 2 years after mixing the components.
  • the content of silver in the final preparation is 0.0936 % wt., relative to the overall mass of the preparation.
  • the content of boron in the preparation is 0.0102 % by wt.
  • the liquid preparation must be consumed within 24 hours after mixing the components.
  • the content of silver in the preparation is 0.0768 g, which represents 0.0765 % wt, with regard to the overall mass of the preparation.
  • the content of boron is 0.01024 g (i.e. 0.01 % wt.).
  • the liquid preparation must be consumed within 24 hours after mixing of the components.
  • the content of silver in the preparation is 0.085 g, which represents 0.085 % wt., with regard to the overall mass of the preparation.
  • the content of boron in the preparation is 0.0085 g (i.e. 0.0085 % by wt.).
  • the liquid preparation must be consumed within 24 hours after the mixing of the components.
  • the content of silver in the preparation is 0.01 g, which represents 0.01 % wt., with regard to the overall mass of the preparation.
  • the content of boron in the preparation is 0.001 g (i.e. 0.001 % wt.).
  • the liquid preparation must be consumed within 24 hours after mixing of the components.
  • the content of silver in the preparation is 0.035 g, which represents 0.035 % wt., with regard to the overall mass of the preparation.
  • the content of boron in the preparation is 0.0035 g (i.e. 0.0035 % wt.).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Abstract

La présente invention concerne des composés complexes d'acide borique, d'acide salicylique ou de ses dérivés et d'argent, répondant à la formule générale (I), dans laquelle X = H, NH2, NHC(=O)R, où le groupe R représente H ou généralement un groupe alkyle en C1 à C8, et leur procédé de préparation, consistant à préparer une solution d'acide borique (une unité molaire) et d'acide salicylique (deux unités molaires) ou de son dérivé dans un solvant polaire, la concentration en acide salicylique ou en son dérivé dans la solution étant dans la gamme de 0,2 à 50 % en poids, et la solution est préparée à une température dans la gamme allant de 0 °C à la température d'ébullition du solvant polaire utilisé ; dans cette solution d'acide borique et d'acide salicylique ou de son dérivé dans le solvant polaire, on ajoute une unité molaire de nitrate d'argent sous agitation, la solution résultante est refroidie à une température dans la gamme de 0 à 25 °C, et le précipité blanc formé du composé complexe est ensuite recueilli par filtration et séché à une température dans la gamme de 25 à 80 °C. La présente invention concerne également une préparation contenant ces composés complexes pour éradiquer les moisissures, les mycètes et les insectes ligniperdus.
PCT/CZ2007/000101 2006-11-15 2007-11-09 Composés complexes d'acide borique, d'acide salicylique ou de ses dérivés et d'argent, leur procédé de préparation et une préparation contenant ces composés pour éradiquer les moisissures, les mycètes et les insectes ligniperdus WO2008058490A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZPV2006-716 2006-11-15
CZ20060716A CZ300772B6 (cs) 2006-11-15 2006-11-15 Komplexní slouceniny kyseliny borité, kyseliny salicylové nebo jejích derivátu a stríbra, zpusob jejich prípravy a prípravek pro hubení plísní, hub a drevokazného hmyzu, obsahující tyto slouceniny

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011056168A1 (fr) * 2009-11-03 2011-05-12 Biosyb Pharmaceuticals Procédés et compositions antimicrobiens
JP2013503122A (ja) * 2009-08-26 2013-01-31 ビーエーエスエフ ソシエタス・ヨーロピア 抗微生物性アミノサリチル酸誘導体
WO2013152125A1 (fr) * 2012-04-03 2013-10-10 Solutions Biomed, Llc Composition de désinfectant à base d'argent avec coloration réduite
WO2016061059A1 (fr) * 2014-10-13 2016-04-21 University Of Central Florida Research Foundation, Inc. Compositions agrochimiques et procédés de préparation et d'utilisation de celles-ci
WO2016192831A1 (fr) 2015-05-29 2016-12-08 Merck Patent Gmbh Compositions d'anions et de cations ayant une activité pharmacologique
WO2018159640A1 (fr) * 2017-02-28 2018-09-07 富士フイルム株式会社 Composition durcissable, plaque originale pour plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, et composé

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013503122A (ja) * 2009-08-26 2013-01-31 ビーエーエスエフ ソシエタス・ヨーロピア 抗微生物性アミノサリチル酸誘導体
WO2011056168A1 (fr) * 2009-11-03 2011-05-12 Biosyb Pharmaceuticals Procédés et compositions antimicrobiens
WO2013152125A1 (fr) * 2012-04-03 2013-10-10 Solutions Biomed, Llc Composition de désinfectant à base d'argent avec coloration réduite
WO2016061059A1 (fr) * 2014-10-13 2016-04-21 University Of Central Florida Research Foundation, Inc. Compositions agrochimiques et procédés de préparation et d'utilisation de celles-ci
US11083201B2 (en) 2014-10-13 2021-08-10 University Of Central Florida Research Foundation, Inc. Agrichemical compositions and methods of making and using same
WO2016192831A1 (fr) 2015-05-29 2016-12-08 Merck Patent Gmbh Compositions d'anions et de cations ayant une activité pharmacologique
WO2018159640A1 (fr) * 2017-02-28 2018-09-07 富士フイルム株式会社 Composition durcissable, plaque originale pour plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, et composé
CN110382558A (zh) * 2017-02-28 2019-10-25 富士胶片株式会社 固化性组合物、平版印刷版原版、平版印刷版的制作方法及化合物
JPWO2018159640A1 (ja) * 2017-02-28 2020-03-12 富士フイルム株式会社 硬化性組成物、平版印刷版原版、平版印刷版の作製方法、及び、化合物
JP7062635B2 (ja) 2017-02-28 2022-05-06 富士フイルム株式会社 硬化性組成物、平版印刷版原版、平版印刷版の作製方法、及び、化合物
US11333977B2 (en) 2017-02-28 2022-05-17 Fujifilm Corporation Curable composition, lithographic printing plate precursor, method for producing lithographic printing plate, and compound

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