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WO1995005081A1 - Compositions biocides contenant des composes organobores - Google Patents

Compositions biocides contenant des composes organobores Download PDF

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Publication number
WO1995005081A1
WO1995005081A1 PCT/GB1994/001810 GB9401810W WO9505081A1 WO 1995005081 A1 WO1995005081 A1 WO 1995005081A1 GB 9401810 W GB9401810 W GB 9401810W WO 9505081 A1 WO9505081 A1 WO 9505081A1
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WO
WIPO (PCT)
Prior art keywords
boronic acid
carbon atoms
optionally substituted
composition according
organoboron compound
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/GB1994/001810
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English (en)
Inventor
Jeffrey Douglas Lloyd
Allison Kathleen Deane-Wray
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.)
US Borax Inc
Original Assignee
US Borax Inc
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
Application filed by US Borax Inc filed Critical US Borax Inc
Priority to AU73902/94A priority Critical patent/AU7390294A/en
Publication of WO1995005081A1 publication Critical patent/WO1995005081A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents

Definitions

  • BIOCIDAL COMPOSITIONS CONTAINING ORGANOBORON COMPOUNDS This invention relates to a liquid biocidal or preservative composition containing an organoboron compound, particularly for the control of pests, including insects, fungi and bacteria, that can cause considerable damage to organic substrates that support biological growth, especially timber.
  • the invention also provides a method for protecting a porous substrate with a cellulosic base, such as timber, particle board and chipboard, from deterioration caused by insects, fungi and bacteria.
  • Inorganic borates have been used as active ingredients in timber preservation for many years and show activity against fungi and insects such as white and brown rots, beetles and termites.
  • US-A-4,719,110 describes solutions containing inorganic borate preservatives, such as borax and sodium polyborates, that are applied to unseasoned timber by dipping for a period sufficient to allow diffusion of the borate into the wood.
  • borate compositions are their efficacy as preservatives allied to low mammalian toxicity. This makes them safe to handle both before and after application. For this reason they are preferred in many applications to compositions containing more toxic combinations such as chromium, arsenic and chlorinated phenols.
  • Stable organoboron compounds namely boronic, diboronic and borinic acids are known and can be synthesised by methods known to the art.
  • boronic acids are inhibitors of the activity of proteolytic enzymes as used, for example, in liquid detergents.
  • PCT patent application PCT/US92/03372 published as WO 92/19707, describes the use of aryl boronic acids, substituted at the 3- position relative to boron, as an inhibitor of proteolytic enzymes in liquid detergent compositions to protect enzymes in the compositions. The inhibition is reversible upon dilution with water and the enzyme's activity is regained, as happens in a washing cycle.
  • certain boronic, diboronic and borinic acids have biocidal activity showing greater efficacy against certain organisms such as Reticulitermes santonensis than that found with inorganic borates previously described.
  • liquid biocidal or preservative composition which is enzyme free and comprises,
  • R, and R 3 which may be the same or different, each represents an optionally substituted alkyl, cycloalkyl, aralkyl or aryl group of up to 20 carbon atoms, which can have a monocyclic or fused ring structure of up to 18 ring carbon atoms; an optionally substituted heterocyclic group containing at least one nitrogen, oxygen or sulphur heteroatom, which can have a monocyclic or fused ring structure of up to 17 ring carbon atoms; or an optionally substituted quinoid group, which can have a monocyclic or fused ring structure of up to 18 ring carbon atoms, R 2 and R 4 , which may be the same or different, each represents a divalent group of the formula
  • each X which may be the same or different, is hydrogen, optionally substituted alkyl of up to 6 carbon atoms, optionally substituted aryl, hydroxy or a derivative thereof, halogen, optionally substituted amino, nitro, thiol or a derivative thereof, aldehyde, carboxylic acid or salt or ester thereof, sulphonate or phosphonate, and o, p and q, which may be the same or different, are each 0, 1 or 2, and m and n, which may be the same or different, are each 0 or 1, or a salt of such an organoboron compound; (ii) at least one surfactant; and (iii) an aqueous or organic solvent or carrier.
  • the present invention additionally provides a method of treating a porous cellulosic substrate to protect it from deterioration caused by insects, fungi or bacteria which comprises impregnating said porous substrate with liquid composition comprising,
  • an aqueous or organic solvent or carrier (ii) an aqueous or organic solvent or carrier.
  • the present invention also provides the use of an organoboron compound of formula (I) , (II) or (III) as a biocide or preservative, for example for a porous cellulosic substrate.
  • Each R 2 group may be the same or different from any other R 2 group.
  • Each R 4 group may be the same or different from any other R « group.
  • the organoboron compound is of formula (I) or (II) in which m and n are each zero and Rj and R 3 , which may be the same or different, are each an optionally substituted group selected from alkyl of up to 10 carbon atoms, cycloalkyl of up to 8 carbon atoms, aralkyl of up to 16 carbon atoms wherein the aryl moiety has up to 12 carbon atoms and the alkyl moiety has up to 4 carbon atoms or a nitrogen- or sulphur-containing heterocyclic group.
  • Suitable optional substituents are at least one atom or group selected from halogen, C-.-C 4 alkyl, C,-C 4 alkoxy and trifluoromethyl.
  • Suitable salts of the organoboron compounds of formula (I) , (II) and (III) are sodium, potassium, copper, zinc, barium, magnesium, calcium, iron, manganese, cobalt, nickel or silver salts.
  • Borates are well known to undergo chelate complex formation with compounds containing polyols and it is believed that such complexation with compounds of biological importance is the mechanism by which inorganic borates act as biocides and wood preservatives.
  • the compounds used as active ingredient in the compositions of the invention are thought to undergo a similar interaction with polyols and additionally have further advantages which will become apparent, that lead to greater efficacy in certain situations over inorganic borates previously used.
  • the organoboron compounds used according to the invention have a low solubility in water and, when using water as a carrier, they may be dissolved in an organic solvent and further diluted with water in the presence of at least one surfactant, as an emulsion, microemulsion, liquid crystal phase or liquid crystal phase dispersion.
  • the biocidal compositions of the invention typically contain up to 10% by weight of the organoboron compound as the biocidally active ingredient. Preferably there is from 0.5 to 5.0%, more preferably about 1.0%, of active ingredient.
  • These compositions are preferably prepared in situ by diluting a concentrate with water.
  • the concentrate may contain up to 60% by weight of the organoboron compound.
  • the content of the organoboron compound in concentrates is in the order of 10% by weight.
  • the concentrate is in the form of a microemulsion. Methods for preparing icroemulsions using one or more surfactant are known to those skilled in the art.
  • 1 part by weight of octylboronic acid can be dissolved in 10 parts by weight of an organic solvent such as petroleum distillate or kerosene, 8 parts by weight of an ionic surfactant such as an alkyl benzene sulphonate, and 12 parts of a co- surfactant such as a C 4 -C 6 alcohol are added.
  • the mixture is agitated to form a microemulsion useful for treating wood on dilution with 170 parts of water.
  • Part of the water can be used in making the concentrate to ease blending on dilution with further water.
  • surfactants or a surfactant plus a co-surfactant are used.
  • These can be mixtures of high and low hydrophile-lipophile balance (HLB) non-ionic surfactants such as ethoxylated alcohols and nonylphenols or anionic/non-ionic mixtures such as low HLB ethoxylated non-ionic surfactants with ionic surfactants, for example, alkylaryl sulphonates, alkyl sulphates, fatty acid salts in combination with co-surfactants such as short to medium chain alcohols.
  • HLB hydrophile-lipophile balance
  • ionic surfactants for example, alkylaryl sulphonates, alkyl sulphates, fatty acid salts in combination with co-surfactants such as short to medium chain alcohols.
  • the solvent in which the organoboron compounds are usually dissolved may be one or a mixture of a range of solvents, including white spirit, kerosene, aromatic esters or
  • products containing amounts of, or comprising entirely, surfactant liquid crystal phases are produced which have customised rheological properties such as viscoelasticity, which is useful to suspend particulates in the formulation.
  • surfactant concentrations are in the order of 10-20% by weight of the product.
  • Preferred surfactants include a phosphate ester plus an ethoxylated ionic or pairs of high and low HLB non-ionics.
  • stable emulsions can be formulated using between 0.5 and 5.0% by weight surfactant based on the weight of emulsified solvent in the concentrate.
  • a wide range of surfactants or surfactant combinations may be used which may be anionic, cationic, non-ionic or zwitterionic.
  • a typical example is a nonylphenol ethoxylate with between 7 and 14 moles ethylene oxide. Up to 80% by weight of solvent containing the dissolved organoboron compound can be incorporated into the emulsion.
  • biocidal compositions can be prepared as suspensions incorporating a suitable thickening agent such as a carboxymethyl cellulose or a xanthan gum.
  • a suitable thickening agent such as a carboxymethyl cellulose or a xanthan gum.
  • the liquid compositions of the invention can be applied to a porous substrate by simple brushing, dipping or spraying techniques. If desired, vacuum or pressure application can be used to promote penetration of the substrate by the liquid composition.
  • the organoboron compounds used in the compositions of the invention can be prepared by known methods. For example, the hydroboration of unsaturated materials, i.e. alkenes and alkynes, using either catecholborane (1,3,2- benzodioxaborole) or dichloroborane-dimethyl sulphide complex as the hydroborating agent is described in J. Amer. Chem. Soc, 97 (18), 1975, 5249-5255. Catecholborane reacts rapidly with the alkenes and alkynes at 100° and 70°C respectively, to give corresponding alkyl- and alkenylcatecholboranes in high yield.
  • the borinic acids for use according to the invention are preferably prepared by Grignard synthesis with a ratio of Grignard reagent to borate of 2:1.
  • Diboronic acids are prepared by selecting the appropriate Grignard reagent and proceeding according to the methods for Grignard synthesis of boronic acids.
  • a Grignard reagent was prepared by the slow dropwise addition of 1-bromonaphthalene (10.4g, 0.05M) in sodium dried ether (50ml) to magnesium turnings (1.2g, 0.05M) also in sodium dried ether (50ml) . The reaction was encouraged by the addition of a small crystal of iodine.
  • Tri-n-butyl borate (11.5g, 0.05M) in sodium dried ether (50ml) was cooled to -70°C.
  • the Grignard reagent was added dropwise over a period of two hours to the borate solution; the temperature of the reaction was maintained at -70°C throughout the addition.
  • the reaction mixture was then allowed to warm to room temperature overnight.
  • the mixture (an orange solution) was hydrolysed by the dropwise addition of dilute sulphuric acid (10%) .
  • the ether layer was separated and the aqueous layer extracted with ether (2x3Oml) . The fractions were combined and the ether removed.
  • Diphenylborinic acid was prepared using essentially the same method as for 1-naphthalene boronic acid.
  • the Grignard reagent was prepared from bro Beingzene and magnesium turnings. However, two moles of Grignard reagent were used per one mole of tri-n-butylborate.
  • the borinic acid so formed was isolated by reaction with ethanolamine thus yielding the diphenyl borinic acid, ethanolamine complex ((C 6 H 5 ) 2 BO.CH 2 CH 2 NH 2 ) which is easier to handle.
  • the melting point of the complex was 192-194°C.
  • 2-vinylnaphthalene (0.05M) was dissolved in dichloro ethane (50ml) .
  • Dichloroborane dimethyl sulphide complex (5.8ml, 0.05M) was then added to the 2-vinylnaphthalene solution with stirring. The reaction mixture was refluxed for four hours.
  • treatment solutions of the active ingredient sodium octaborate or phenyl boronic acid dissolved in water were prepared. 1 ml of each treatment solution was spread on a dried 9 cm Whatman No. 4 filter paper (a simulated wood substrate) in a 9 cm Petri dish to provide concentrations of 18 mg and 1.8 mg active ingredient per gram of dried substrate, and the substrate allowed to dry. Each set of test plates was prepared in duplicate. 15 worker termites were then placed on each substrate, which had been moistened with water. The test plates were incubated at 90% ⁇ 5% RH and at 28°C + l ⁇ C. Each test plate was checked daily, at which time dead termites were removed and the substrate re-moistened with water as necessary.
  • Example 1 The tests of Example 1 were repeated for a number of organoboron compounds over a different set of concentration ranges. In this example, however, a variable number of termites was used (17 to 22 in each test plate) , and the active ingredient was dissolved in ethanol rather than water. Furthermore 2 ml of minimal salts nutrient solution as described in Bravery A.F., J. of Science of Food and Agriculture, vol 19, p 133-135 (1968), was added to each substrate prior to the addition of the active ingredient.
  • Tables 2 to 8 illustrate the use of organoboron compounds in accordance with the present invention.
  • Table 8 illustrates the use of sodium octaborate.
  • a 4 wt % malt/2 wt % agar solid medium containing a phenyl or substituted phenyl boronic acid at various concentrations were used to assess the growth of representative fungal decay basidiomycetes.
  • Test plates containing the solid media were inoculated with 8mm plugs of actively growing Coniophora souna (FPRL HE) (cp) or Coriolus versicolor (FPRL 28A) (cv) fungi and incubated at a temperature of 22 ⁇ 1°C. Radial growth was observed over a period of 23 days. The results have been expressed as colony size against time and are shown in Table 9.
  • the retentions were chosen to give results for the sodium octaborate at the highest retention, against the test organisms and to specifically determine the toxic thresholds of the organoboron compounds. Solubility of the active ingredient was achieved in this case by using ethanol as a cosolvent with water and 0.05% sodium dpdecyl sulphate. Treatment was carried out in small glass vessels containing the preservative mixtures. The blocks were immersed in the treatment solutions and treated under vacuum for one hour, followed by two hours under atmospheric pressure. Eighteen replicate blocks were treated in each solution; six for each of the exposure conditions used.
  • the blocks were weighed to determine preservative uptake and then stored at room temperature for twenty four hours in air-tight containers. The lids were then removed gradually over a five day period and the blocks were turned over on their supports every twenty four hours. The presence of a xylene vapour source prevented mould growth on the blocks during drying.
  • the blocks were sterilised by gamma radiation.
  • Cultures of Coriolus versicolor (FPRL 28A) were grown on 4% malt extract 2% agar plates at 22"C, and used to inoculate the test plates. When the cultures had covered about 95% of each plate, the mini blocks were placed on top of mesh supports (to avoid waterlogging of the wood) in the plates. Two plates with three blocks were used for each of the different treatment sets. A third set of blocks was placed on the supports over uninoculated plates as controls and used to correct the final weight losses. The plates were then incubated at 22°C ( ⁇ 1°C) for a period of seven weeks.
  • boron retentions were determined in both the exposed and unexposed samples to enable a determination of preservative loss, by diffusion, out of the half coupons.
  • the retention found for exposed and non-exposed samples are given in Table 11 along with the amount of boron in the exposed samples expressed as a percentage of the amount of boron in the unexposed samples. It can be seen that the sodium octaborate retention was determined to be from 2.6 to 7.3% of its original retention compared to the phenyl boronic acid retention which was determined to be about from 16.6 to 25.9% of its original retention. Leaching of boron wood preservatives in the past has always been a perceived problem. This situation is considerably alleviated using the organoboron compounds of the present invention.

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

Abstract

L'invention concerne une composition biocide ou protectrice liquide, dépourvue d'enzyme, qui comprend 1) en guise d'ingrédient actif, au moins un acide borinique, boronique ou diboronique, 2) au moins un agent tensio-actif, et 3) un solvant ou vecteur aqueux ou organique. Une telle composition liquide protège très efficacement des substrats poreux, cellulosiques notamment, tels que le bois d'÷uvre, contre les attaques de champignons, de bactéries ou d'insectes.
PCT/GB1994/001810 1993-08-19 1994-08-18 Compositions biocides contenant des composes organobores Ceased WO1995005081A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU73902/94A AU7390294A (en) 1993-08-19 1994-08-18 Biocidal compositions containing organoboron compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9317297A GB2281210A (en) 1993-08-19 1993-08-19 Biocidal compositions containing organoboron compounds
GB9317297.1 1993-08-19

Publications (1)

Publication Number Publication Date
WO1995005081A1 true WO1995005081A1 (fr) 1995-02-23

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PCT/GB1994/001810 Ceased WO1995005081A1 (fr) 1993-08-19 1994-08-18 Compositions biocides contenant des composes organobores

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AU (1) AU7390294A (fr)
GB (1) GB2281210A (fr)
WO (1) WO1995005081A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1416799A4 (fr) * 2001-07-23 2004-11-10 Univ Ramot Methodes et compositions de traitement des infections fongiques
RU2552691C1 (ru) * 2014-04-22 2015-06-10 Ирина Васильевна Степина Биоогнезащитный состав афб
US9095141B2 (en) 2012-07-31 2015-08-04 Empire Technology Development Llc Antifouling compositions including dioxaborinanes and uses thereof
US9290598B2 (en) 2012-03-29 2016-03-22 Empire Technology Development Llc Dioxaborinane co-polymers and uses thereof
US9352485B2 (en) 2012-03-23 2016-05-31 Empire Technology Development Llc Dioxaborinanes and uses thereof
CN111357759A (zh) * 2020-04-08 2020-07-03 兰州大学 一种有机硼酸类化合物在农业病害防治中的应用
CN116970384A (zh) * 2022-04-22 2023-10-31 中国科学院理化技术研究所 磷光染料及含磷光染料的三重防伪光子晶体薄膜，制备及应用
CN117260913A (zh) * 2023-10-24 2023-12-22 江苏零界科技集团有限公司 一种用于木材表面的防腐防霉液及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5834415A (en) * 1994-04-26 1998-11-10 Novo Nordisk A/S Naphthalene boronic acids
WO2012137164A1 (fr) * 2011-04-07 2012-10-11 Biolinerx Ltd. Compositions antimicrobiennes, compositions antibiofilms et leurs utilisations
WO2012137166A1 (fr) * 2011-04-07 2012-10-11 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. Composé d'oxoborolidine et ses utilisations
CN105209556B (zh) * 2013-03-15 2017-11-14 英派尔科技开发有限公司 含硼化合物和其用途

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US3090801A (en) * 1956-07-06 1963-05-21 American Potash & Chem Corp Aryl polyboronic acids and esters and process for their preparation
US3092652A (en) * 1959-01-16 1963-06-04 American Potash & Chem Corp Preparation of aryldihaloboranes and poly (dihaloborano) benzenes
WO1988004601A1 (fr) * 1986-12-19 1988-06-30 Laporte Industries Limited Agents de conservation du bois
WO1989003287A1 (fr) * 1987-10-13 1989-04-20 Manchem Limited Element de protection contenant des composes de bore organique et leur utilisation
WO1990000959A1 (fr) * 1988-07-21 1990-02-08 Imperial College Of Science, Technology & Medicine Traitement du bois et de materiaux a base de bois

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BR9205958A (pt) * 1991-04-30 1994-09-27 Procter & Gamble Detergentes líquidos com ácido aril borônico

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Publication number Priority date Publication date Assignee Title
US3090801A (en) * 1956-07-06 1963-05-21 American Potash & Chem Corp Aryl polyboronic acids and esters and process for their preparation
US3092652A (en) * 1959-01-16 1963-06-04 American Potash & Chem Corp Preparation of aryldihaloboranes and poly (dihaloborano) benzenes
WO1988004601A1 (fr) * 1986-12-19 1988-06-30 Laporte Industries Limited Agents de conservation du bois
WO1989003287A1 (fr) * 1987-10-13 1989-04-20 Manchem Limited Element de protection contenant des composes de bore organique et leur utilisation
WO1990000959A1 (fr) * 1988-07-21 1990-02-08 Imperial College Of Science, Technology & Medicine Traitement du bois et de materiaux a base de bois

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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CHEMICAL ABSTRACTS, Columbus, Ohio, US; *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1416799A4 (fr) * 2001-07-23 2004-11-10 Univ Ramot Methodes et compositions de traitement des infections fongiques
US7825104B2 (en) 2001-07-23 2010-11-02 Ramot At Tel Aviv University Ltd. Methods and compositions for treating fungal infections
US9352485B2 (en) 2012-03-23 2016-05-31 Empire Technology Development Llc Dioxaborinanes and uses thereof
US9290598B2 (en) 2012-03-29 2016-03-22 Empire Technology Development Llc Dioxaborinane co-polymers and uses thereof
US9095141B2 (en) 2012-07-31 2015-08-04 Empire Technology Development Llc Antifouling compositions including dioxaborinanes and uses thereof
RU2552691C1 (ru) * 2014-04-22 2015-06-10 Ирина Васильевна Степина Биоогнезащитный состав афб
CN111357759A (zh) * 2020-04-08 2020-07-03 兰州大学 一种有机硼酸类化合物在农业病害防治中的应用
CN116970384A (zh) * 2022-04-22 2023-10-31 中国科学院理化技术研究所 磷光染料及含磷光染料的三重防伪光子晶体薄膜，制备及应用
CN117260913A (zh) * 2023-10-24 2023-12-22 江苏零界科技集团有限公司 一种用于木材表面的防腐防霉液及其制备方法

Also Published As

Publication number Publication date
GB2281210A (en) 1995-03-01
GB9317297D0 (en) 1993-10-06
AU7390294A (en) 1995-03-14

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