WO1996019464A1 - 2-(thiocyanatomethylthio)-1,3,4-oxadiazoles a substitution en 5 servant d'antimicrobiens et d'agents antisalissure - Google Patents

2-(thiocyanatomethylthio)-1,3,4-oxadiazoles a substitution en 5 servant d'antimicrobiens et d'agents antisalissure Download PDF

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Publication number
WO1996019464A1
WO1996019464A1 PCT/US1995/013493 US9513493W WO9619464A1 WO 1996019464 A1 WO1996019464 A1 WO 1996019464A1 US 9513493 W US9513493 W US 9513493W WO 9619464 A1 WO9619464 A1 WO 9619464A1
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WO
WIPO (PCT)
Prior art keywords
compound
oxadιazole
composition
oxadiazole
thιomethylthιocyanate
Prior art date
Application number
PCT/US1995/013493
Other languages
English (en)
Inventor
Duane R. Romer
Ravi B. Shankar
R. Garth Pews
Original Assignee
The Dow Chemical Company
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 The Dow Chemical Company filed Critical The Dow Chemical Company
Publication of WO1996019464A1 publication Critical patent/WO1996019464A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
    • C07D271/113—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • 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
    • A01N43/82—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 three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic

Definitions

  • the present invention is directed to 5-substituted-2-(thiomethylthiocyanate)- -1 ,3,4-oxadiazole compounds, compositions containing said compounds, their preparation and their use as antimicrobial agents and marine antifoulants.
  • U.S. Patent 3,888,869 discloses the compound 2,5-bis(thiocyanatomethylthio)- -1 ,3,4-thiadiazole, corresponding to the formula
  • German Patent 2541 388 discloses compounds corresponding to the formula
  • R represents C ⁇ C ⁇ straight or branched chained alkyl and X is oxygen or sulfur
  • X is oxygen or sulfur
  • the present invention is directed to 5-substituted-2-(thiomethylth ⁇ ocyanate)- -1 ,3,4-oxadiazole compounds corresponding to the formula:
  • n X represents -Br, -Cl, -F, -NO. or -CH.. and n is 0, 1 or 2
  • antimicrobial compositions of the present invention can also be employed to treat surfaces exposed to a marine environment in which marine organisms grow to prevent 5 the growth of said marine organisms on said surfaces
  • alkali metal is employed to designate sodium, potassium, lithium or cesium
  • halo is employed to designate bromo, chloro, fluoro or lodo 0
  • certain specific alkali metals, halo groups and specific solvents are set forth These representations are only presented for convenience and are not to be considered as an indication that these specific representations are the only groups or materials which can be employed
  • the reactions as set forth below and in the specific examples can all be carried out at room temperature in the presence of 5 conventional reaction mediums, such as for example, a 70 percent ethanol/30 percent water mixture
  • the 5-subst ⁇ tuted-2-(th ⁇ omethylth ⁇ ocyanate)-1 ,3,4-oxad ⁇ azole compounds of the present invention may be prepared by the reaction of an appropriate 5-subst ⁇ tuted 2-(halomethylth ⁇ o)-1 ,3,4-oxad ⁇ azole with an alkali metal th ⁇ ocyanate (AMSCN) in a reaction 0 medium
  • AMSCN alkali metal th ⁇ ocyanate
  • R represents furanyl, py ⁇ dyl, or phenyl
  • the oxadiazole reacta ⁇ t such as for example, a 2-(halomethylthiol)-5-(furanyl, pyridyl, or phenyl)-1,3,4-oxadiazole and the alkali metal thiocyanate, for example, potassium thiocyanate are typically mixed together in substantially equimolar amounts in the presence of a polar, aprotic solvent, such as, for example, dimethylformamide or dimethylsulfoxide.
  • the reactions are typically carried out at a temperature of from 30 to 100°C.
  • the reactants may be added to the reaction mixture in any order of addition; conventionally they are added as a solution in the solvent used for the reaction. Subsequent to the addition of the reactants, the mixing of the reaction mixture will typically be allowed to continue over a period of from 1 to 24 hours.
  • reaction product resulting from the furanyl or pyridyl reactants are usually isolated by first concentrating the mixture to dryness and the taking up the residue in a solvent such as methylene chloride and washing the mixture with water and then with brine. The mixture is dried (usually over anhydrous sodium sulfate) and concentrated to give the desired product.
  • reaction product resulting from the phenyl reactants may be isolated by adding a 3 to 10 volume excess of water which will precipitate the desired product. Filtration followed by washing and drying yields the desired compounds of the present invention.
  • the 5-phenyl compounds of the present invention may also be prepared by the reaction of an appropriately substituted 5-phenyl-1 ,3,4-oxadiazole-2-thiol corresponding to the formula:
  • the 5-(furanyl, thiofuranyl or pyr ⁇ dyl)-1 ,3,4-oxad ⁇ azol-2-th ⁇ ols used as a starting reactant can be conveniently prepared from the appropriate acylhydrazide
  • the amount of the reactants to be employed is not critical In most cases, it is preferred to employ substantially equimolar amounts of the reactants. Depending upon the specific type of reaction taking place, it may be beneficial that a given one of the reactants be present in a slight excess to obtain the highest yield of the desired product
  • the desired product can be separated from the reaction product of the above preparative procedures employing conventional separatory procedures known to those skilled in the art including steps of solvent extraction, filtration, water washing, column chromatography, neutralization, acidification, crystallization and distillation Since the hereinabove and hereinafter set forth compound preparation procedures employ only standard chemistry practices and it is known that slightly different reactants can require slightly different reaction parameters from those for other reactants, it is to be understood that minor modifications to the reaction parameters set forth such as the choice of the specific solvent or reaction medium employed, the use of an excess of one reactant, the use of a catalyst, the use of high temperature and/or high pressure equipment, high speed mixing and other such conventional changes are within the scope of the present invention.
  • Triethylamine (1 1 5 g, 0 1 14 mol) was added dropwise to a solution of 5-(2- -th ⁇ ofuranyl)-1 ,3-4-oxad ⁇ azole-2-th ⁇ ol (12 O g, 0 065 mol) and bromochloromethane (12 6 g, 0 0978 mol) in methylene chloride (150 mL) and the resulting solution was stirred overnight (about 16 hours) at room temperature The reaction mixture was washed with 1 M HCI (2X 50 mL) followed by a saturated aqueous sodium bicarbonate solution and then with brine The mixture was then dried over sodium sulfate and concentrated to give 13 3 g (88 percent yield) of 2-(chloromethylth ⁇ o)-5-th ⁇ ofuranyl-1 3-4-oxad ⁇ azole as a viscous oil The oil was dissolved in DMF (50 mL) and KSCN ( 1 1 1 g, 0 1 14 mol) was added
  • Example I The preparative procedure of Example I was used to react 2-(chloromethylthio)-5-(4-methylphenyl)-1 ,3,4-oxidiazole and potassium thiocyanate in dimethylformamide. The product was crystallized from ethanol and recovered in a yield of 90 percent of theoretical as a white solid which melted at 1 16-1 17°C.
  • Example II The preparative procedure of Example I is used to react 2-(chloromethylth ⁇ o)-5-(2-chlorophenyl)-1 ,3,4-oxad ⁇ azole and potassium thiocyanate in dimethylformamide
  • Example IX The preparative procedure of Example I is used to react 2-(chloromethylth ⁇ ol)-5-(4-n ⁇ trophenyl)-1 ,3,4-oxad ⁇ azole and potassium thiocyanate in dimethylformamide
  • Example IX Preparation
  • a mixture was prepared by adding triethylamine (2 6 g, 0 026 mol) in CH2CI2 (5 mL) dropwise to a slurry of 5-phenyl- 1 ,3, 4-oxad ⁇ azol-2-th ⁇ ol (3 O g, 0 017 mol) and bromochloromethane (2.8 g, 0.021 mol) in CH 2 Cl2 (30 mL) at 0°C. The resulting mixture is stirred overnight at room temperature. The reaction mixture is washed with 20 mL of 1 M HCI, then with 20 mL of aHC ⁇ 3 and 20 mL of brine.
  • Example VI The preparative procedure of Example VI is used to react 5-(4- -chlorophenyl)-1 ,3,4-oxadiazol-2-thiol and bromochloromethane
  • Example XII Preparation of 2-(Chloromethylthio)-5-(2-chlorophenyl)-1 ,3,4-oxadiazole
  • Example VI The preparative procedure of Example VI is used to react 5-(2- -chlorophenyl)-1 ,3,4-oxadiazol-2-thiol and bromochloromethane.
  • the recovered product is obtained in a yield of 53 percent of theoretical as a yellow oil, which slowly solidified upon standing.
  • Example VI The preparative procedure of Example VI is used to react 5-(4- -nitrophenyl)-1 ,3,4-oxadiazol-2-thiol and bromochloromethane. The recovered product is obtained in a yield of 77 percent of theoretical as a yellow solid.
  • 'H NMR 300 MHz, CDCI.
  • 1 C NMR 75 MHz, CDCI,) ⁇ 164.48, 162.39, 149.30, 128.42, 127.49, 124.21 , 45.06.
  • the compounds of this invention are useful as antimicrobial additives to such industrial products as styrene-butadiene latexes used for paper coatings, paints, inks, adhesives, soaps, cutting oils, textiles, and paper and pigment slurries.
  • the compounds are also useful as antimicrobial additives in such personal care products as hand creams, lotions, shampoos, and hand soaps.
  • a further advantage of this invention is its cost-effectiveness for applications which need to have an antimicrobial continuously replenished, such as in cooling towers and pulp and paper mills.
  • the present invention is also directed to a method for inhibiting microorganisms which comprises contacting said microorganisms or habitat thereof with an effecti e amount of the compounds of this invention.
  • the antimicrobial compounds of this invention may be added directly to aqueous formulations susceptible to microbial growth, either undiluted or dissolved, in inert diluents such as organic solvents such as glycols, alcohols, or acetone. They may also be added alone or in combination with other preservatives.
  • inert diluents such as organic solvents such as glycols, alcohols, or acetone. They may also be added alone or in combination with other preservatives.
  • organic solvents such as glycols, alcohols, or acetone.
  • microorganism is meant to refer to bacteria, fungi, viruses, algae, subviral agents and protozoa.
  • the term "antimicrobially-effective amount” refers to that amount of one or a mixture of two or more of the compounds, or of a composition comprising such compound or compounds, of this invention needed to exhibit inhibition of selected microorganisms. Typically, this amount varies from providing 1 part per million (ppm) to 5,000 ppm by weight of the compound to a microbial habitat being contacted with the compound. Such amounts vary depending upon the particular compound tested and microorganism treated. Also, the exact concentration of the compounds to be added in the treatment of industrial and consumer formulations may vary within a product type depending upon the components of the formulation. A preferred effective amount of the compound is from 1 ppm to 500 ppm, more preferably from 1 ppm to 50 ppm by weight, of a microbial habitat.
  • microbial habitat refers to a place or type of site where a microorganism naturally or normally lives or grows.
  • a microbial habitat will be an area that comprises a moisture, nutrient, and/or an oxygen source such as, for example, a cooling water tower or an air washing system.
  • inhibitors refer to the suppression, stasis, kill, or any other interference with the normal life processes of microorganisms that is adverse to such microorganisms, so as to destroy or irreversibly inactivate existing microorganisms and/or prevent or control their future growth and reproduction
  • the antimicrobial activity of the compounds of the present invention is demonstrated by the following techniques.
  • the minimum inhibitory concentration (MIC) for the compounds of the present invention is determined for 9 bacteria, using nutrient agar; and 7 yeast and fungi, using malt yeast agar.
  • a one percent solution of the test compound is prepared in a mixture of acetone and water.
  • Nutrient agar is prepared at pH 6.8, representing a neutral medium, and at pH 8 2, representing an alkaline medium.
  • the nutrient agars are prepared by adding 23 g of nutrient agar to one-liter of deionized water
  • the alkaline medium is prepared by adjusting a 0.04 M solution of N-[tris-(hydroxymethyl)methyl]-glycine buffered deionized water with concentrated sodium hydroxide to a pH of 8.5.
  • Malt yeast agar is prepared by adding 3 g yeast extract and 45 g malt agar per liter of deionized water. The specific agar is dispensed in 30 mL aliquots into 25 x 200 mm test tubes, capped and autoclaved for 15 minutes at 1 15°C. The test
  • test tubes 1 o therein.
  • the contents of the test tubes are then transferred to respecti e petn plates After drying for 24 hours, the petri plates containing nutrient agar are inoculated with bacteria and those containing malt yeast agar are inoculated with yeast and fungi.
  • the inoculation with bacteria is accomplished by using the following procedure. Twenty-four hour-cultures of each of the bacteria are prepared by incubating the respective
  • the Steer's Replicator is then used to inoculate both the neutral and alkaline pH nutrient agar petri plates.
  • the inoculated petri plates are incubated at 30°C for 48 hours and then read to determine if the test compound which is incorporated into the agar prevented growth of the
  • the inoculation with the yeast and fungi is accomplished as follows Cultures of yeast and fungi are incubated for seven days on malt yeast agar at 30°C. These cultures are used to prepare suspensions by the following procedure. A suspension of each organism is prepared by adding 10 mL of sterile saline and 10 microliters of octylphenoxy polyethoxy
  • Table I lists the bacteria, yeast and fungi used in the MIC test described above along with their respective American Type Culture Collection (ATCC) identification numbers. TABLE I
  • Tables II and III the MIC values of the compounds of the present invention as compared to the MIC of a standard commercial preservative (with 1-(3-chloroallyl)-3,5,7-t ⁇ aza- -1-azon ⁇ aadamantane chloride as the active agent, and referred to in Tables II and III as "STANDARD") are set forth for the bacteria organisms and yeast/fungi organisms which are listed in Table I. 0
  • the present invention is also directed to a method for inhibiting marine organisms.
  • marine organisms is meant to include marine animals, such as barnacles, serpulid, bryozoa, oysters and hydroids, and marine plahts, such as green algae and brown algae.
  • the method for inhibiting marine organisms comprises contacting a surface exposed to a marine environment in which marine organisms grow with a marine antifouhng effective amount of the compound of this invention.
  • the term "marine antifouling effective amount” refers to that amount of one or a mixture of two or more of the compounds of this invention needed to exhibit inhibition of selected marine organisms Typically, this amount vanes from providing 1 weight percent to 30 weight percent of the compound to a marine antifouling composition which is used to treat a surface exposed to a marine environment in which marine organisms live or grow. Such amounts vary depending upon the particular compound tested and marine organism to be treated Also, the exact concentration of the compounds to be added in the preparation of industrial and consumer formulations may vary within a product type depending upon the components of the formulation A composition comprising a marine antifouling effective amount of the compound will also comprise an inert diluent which may be, for example, in the form of a paint. Particularly preferred are those paints having a vinyl resin binder such as, for example, a plasticized polyvinyl chloride or a polyvinyl chloride-polyvinyl acetate type.
  • the term “marine antifouling effective amount” refers to that amount
  • binders are formulated as latexes or emulsions.
  • the compound of the present invention is preferably used in an amount from 1 to 30 weight percent and, most preferably, from 10 to 25 weight percent.
  • epoxy and polyurethane binder paints containing the compound may also be useful. Coatings and films prepared from paints comprising the compound of the present invention typically remain
  • a surface exposed to a marine environment refers to a surface where a marine organism naturally or normally lives or grows Typically, such a surface will be an area
  • Typical surfaces include, for example, a ship hull.
  • the marine antifouling activity of the compounds of the present invention is demonstrated by the following techniques.
  • Test panels are prepared from clear, rigid polyvinyl chloride film that is
  • test panels 20 0.381 x 10 3 m thick and has one textured surface
  • the test panels are 0.1524 m by 0.1524 m squares that have 0 00635 m holes punched at corners on 0.127 m centers.
  • a 0.102 square template, with a 0.067 m diameter hole at the center, is attached to the center of the textured surface of the test panels.
  • a candidate marine antifoulant compound (1 0 g) is stirred into a resinous latex
  • test panels are prepared for each candidate marine antifoulant compound
  • Two control test panels are also prepared by only treating with the resinous latex binder.
  • One test panel of each candidate marine surfactant compound is attached over a white background
  • the second test panel is attached over a black background to the underside of the exposure support apparatus
  • the exposure support apparatus is placed horizontally 0 0254 m under a marine surface with the white background topside facing up
  • the exposure support apparatus is exposed to the marine environment for both 6 and 10 weeks during which time the control test panels become substantially covered with mature marine organism growth on both the topside and underside exposures.
  • each test panel After being removed from the exposure support apparatus, each test panel is inspected and rated for marine organism growth on both the treated and untreated areas of
  • test panel 5 The marine organisms present on the treated and untreated areas are noted. The presence of algae spores and bacterial slime are noted but not included in rating each test panel. The test panels are rated on a scale from 10 (representing completely free of marine organism growth) to 0 (representing completely covered with marine organism growth). In Table IV, the marine antifouling rating values for some of the active
  • test panels were prepared using tributyl tin oxide, a known marine antifouling compound.
  • One set of such panels used the tributyl tin oxide in a commercially available ship-hull paint (referred to in Table IV as "STANDARD II ") which was employed in the

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  • Wood Science & Technology (AREA)
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  • Pest Control & Pesticides (AREA)
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Abstract

Préparation de 2-(thiocyanatométhylthio)-1,3,4-oxadiazoles substitués correspondant à la formule (I) où R désigne (a), (b), (c) ou (d), où X désigne -Br, -Cl, -F, -NO2 ou -CH3 et où n est égal à 0, à 1 ou à 2. On a constaté que ces compositions possèdent des propriétés antimicrobiennes et antisalissure marine dans des applications industrielles et commerciales. Des compositions contenant ces composés sont employées.
PCT/US1995/013493 1994-12-21 1995-10-10 2-(thiocyanatomethylthio)-1,3,4-oxadiazoles a substitution en 5 servant d'antimicrobiens et d'agents antisalissure WO1996019464A1 (fr)

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US36049294A 1994-12-21 1994-12-21
US08/360,492 1994-12-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998001035A1 (fr) * 1996-07-10 1998-01-15 The Dow Chemical Company Utilisation de 5-alkyle-1,3,4-oxadiazol(et thiadiazol)-2-thiomethylthiocyanates comme agents antifouling marins
WO1998001037A2 (fr) * 1996-07-10 1998-01-15 The Dow Chemical Company Thiocyanomethyloxo (et thiocyanothiomethyl)-1,2,3-benzatriazin-4(3h)ones, compositions les contenant et leur utilisation comme agents antimicrobiens et agents antifouling marins

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2211008A5 (fr) * 1972-12-18 1974-07-12 Pepro
DE2541388A1 (de) * 1975-09-17 1977-03-31 Hoechst Ag 2-rhodanmethylmercapto-1,3,4-oxdiazole und -1,3,4-thiadiazole, verfahren zu ihrer herstellung und ihre verwendung als fungizide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2211008A5 (fr) * 1972-12-18 1974-07-12 Pepro
DE2541388A1 (de) * 1975-09-17 1977-03-31 Hoechst Ag 2-rhodanmethylmercapto-1,3,4-oxdiazole und -1,3,4-thiadiazole, verfahren zu ihrer herstellung und ihre verwendung als fungizide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A.G.M. WILLEMS ET AL.: "The chemistry and fungicidal and phytotoxic properties of heterocyclic sulfonyl-, sulfinyl-, and thio-methyl thiocyanates", RECUEIL DES TRAVAUX CHIMIQUES DES PAYS-BAS, vol. 90, no. 1, THE HAGUE NL, pages 97 - 104 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998001035A1 (fr) * 1996-07-10 1998-01-15 The Dow Chemical Company Utilisation de 5-alkyle-1,3,4-oxadiazol(et thiadiazol)-2-thiomethylthiocyanates comme agents antifouling marins
WO1998001037A2 (fr) * 1996-07-10 1998-01-15 The Dow Chemical Company Thiocyanomethyloxo (et thiocyanothiomethyl)-1,2,3-benzatriazin-4(3h)ones, compositions les contenant et leur utilisation comme agents antimicrobiens et agents antifouling marins
WO1998001037A3 (fr) * 1996-07-10 1998-05-22 Dow Chemical Co Thiocyanomethyloxo (et thiocyanothiomethyl)-1,2,3-benzatriazin-4(3h)ones, compositions les contenant et leur utilisation comme agents antimicrobiens et agents antifouling marins

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