EP0594583A1 - Composition et emploi de 3-thio-2-propynenitriles a substitution en tant qu'antimicrobien industriel - Google Patents

Composition et emploi de 3-thio-2-propynenitriles a substitution en tant qu'antimicrobien industriel

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Publication number
EP0594583A1
EP0594583A1 EP91903461A EP91903461A EP0594583A1 EP 0594583 A1 EP0594583 A1 EP 0594583A1 EP 91903461 A EP91903461 A EP 91903461A EP 91903461 A EP91903461 A EP 91903461A EP 0594583 A1 EP0594583 A1 EP 0594583A1
Authority
EP
European Patent Office
Prior art keywords
thio
chloro
propenenitrile
propynenitrile
methylthio
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.)
Withdrawn
Application number
EP91903461A
Other languages
German (de)
English (en)
Other versions
EP0594583A4 (fr
Inventor
Connie I. Deford
Charles D. Gartner
Kalakota S. Reddy
John K. Swayze
David E. Wallick
Warren L. Treptow
George A. Paul
Billy R. Hardas
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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 US07/633,866 external-priority patent/US5126349A/en
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0594583A4 publication Critical patent/EP0594583A4/fr
Publication of EP0594583A1 publication Critical patent/EP0594583A1/fr
Withdrawn legal-status Critical Current

Links

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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • 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
    • A01N37/36—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 containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur atom

Definitions

  • the field of this invention is novel compounds which are useful as antimicrobials.
  • X is a free or esterified carboxy group and B is a substituted tetrazolyl or thiadiazolyl radical or a heterobicyclic ring.
  • B is a substituted tetrazolyl or thiadiazolyl radical or a heterobicyclic ring.
  • X is a halogen and R is a lower alkyl, aryl, aralkyl, heterocyclo, or a thiocarbonyl group.
  • R is a lower alkyl, aryl, aralkyl, heterocyclo, or a thiocarbonyl group.
  • n ew antimicrobial agents The desirability of identifying or discovering n ew antimicrobial agents is widely recognized for several reasons. These include the development of microbe strains resistant to known antimicrobials, the occurrence of undesirable interactions of certain known antimicrobials with the medium or product in which the antimicrobial is used, and high toxicity of certain known antimicrobials to certain non-target organisms such as mammals.
  • the present invention solves this problem by disclosing a new compound which may be employed as an antimicrobial.
  • the present invention is a compound corresponding to the formula: R-S-C ⁇ C-C ⁇ N *
  • R is an alkyl, cyclic alkyl, aryl, or heterocyclo group.
  • the invention also includes a method of making such substituted 3-thio-2-propynenitriles of the same formula, and con-positions containing said compounds and the use of such compositions as antimicrobials in industrial or commercial uses.
  • the compounds of this invention are useful as 0 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, stiampoos, 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 0 cooling towers and pulp and paper mills.
  • the present invention is also directed to a 0 process of using such substituted 3-thio-2-propy- nenitriles of the same formula as above, as an antimicrobial agent.
  • This, process is a method for inhibiting microorganisms, particularly bacteria, fungi, and algae which comprises contacting said microorganisms - . -
  • the antimicrobial compounds of this invention may be added directly to aqueous formulations susceptible to microbial growth, either undiluted or dissolved in organic solvents like glycols, alcohols, or acetone. They may also be added alone or in combination with other preservatives.
  • alkyl is employed to designate straight chain and branched chain alkyls. Such alkyls may be with or without substituents, such as cyclic alkyl, aryl, alkoxy or halogen. Preferably, the term “alkyl” is employed to designate straight chain alkyls of 1 to 18 carbon atoms and branched chain alkyls of 3 to 18 carbon atoms.
  • alkyl is employed to designate straight chain alkyls of 1 to 12 carbon atoms, such as methyl, ethyl, propyl, butyl, decyl, or dodecyl and branched chain alkyls of 3 to 12 carbon atoms, such as isopropyl or tertiary butyl.
  • cyclic alkyl is employed to designate a closed-ring alkyl structure. Such cyclic alkyls may be with or without substituents, such as alkyl, aryl, alkoxy or halogen.
  • cyclic alkyl is employed to designate cyclic alkyls of 3 to 8 carbon atoms.
  • cyclic alkyl is employed to designate cyclic alkyls of 3 to 6 carbon atoms, such as cyclopentyl or cyclohexyl.
  • aryl is employed to designate groups which have the ring structure characteristic of benzene, wherein the ring may be with or without substituents such as alkyl, cyclic alkyl, alkoxy, or halogen.
  • the aryl ring may also be a fused ring, 'wherein the ring may have one or more of its sides in common with another ring.
  • the aryl ring has no more than three substituents.
  • the aryl is phenyl, naphthyl, or chlorophenyl.
  • heterocyclo is employed to designate a closed-ring structure containing at least one ring carbon, in which one or more of the atoms in the ring is an element other than carbon. Such heterocyclos may be
  • the heterocyclo ring may also be a fused ring, wherein the ring may have one or more of its sides in common with another ring.
  • the closed-ring structure will consist of 5 0 or 6 atoms.
  • the non-carbon ring atom or atoms will be nitrogen, oxygen or sulfur.
  • the ring has no more than three substituents.
  • the heterocyclo is thiazolyl, triazolyl, imidazolyl, or pyrimidyl.
  • the term "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 organisms. Typically, this
  • the compounds of this invention may be added as a liquid concentrate or diluted with additional liquid to produce the ultimate treating composition, wherein the liquid could be water or an organic solvent such as glycols, alcohols, or acetone.
  • inhibitors refer to suppression, control, stasis, kill or any other interference with the normal life processes of microorganisms that is adverse to such microorganisms.
  • R is an alkyl, cyclic alkyl, aryl, or heterocyclo group, which is used as a precursor to produce a like-substituted 3-thio-2-propynenitrile.
  • like-substituted 3-thio-2-propynenitrile refers to a 3-thio-2-propynenitrile of the formula:
  • R is an alkyl, cyclic alkyl, aryl, or heterocyclo group, but wherein R is identical to the R of the appropriately substituted 2-chloro-3-thio- -2-propenenitrile used as a precursor to produce the " like-substituted 3-thio-2-propynenitrile.
  • 2-chloro-3-methylthio-2-propenenitrile is an appropriately substituted 2-chloro-3-thio- -2-propenenitrile which is used as a precursor to produce 3-methylthio-2-propynenitrile, the like-substituted 3-thio-2-propynenitrile.
  • the compounds of the present invention can be prepared by the reaction of an appropriately substituted 2-chloro-3-thio-2-propenenitrile precursor with basic aqueous solution (such as sodium hydroxide solution).
  • basic aqueous solution such as sodium hydroxide solution
  • the appropriately substituted 2-chloro-3-thio-2-propenenitrile precursor and the basic aqueous solution are mixed together in substantially equimolar amounts.
  • the general reaction scheme is as follows:
  • a preferred method of preparing the compounds of the present invention is to carry out the dehydrochlorination of the appropriately substituted 2-chloro-3-thio-2-propenenitrile precursor at a temperature below ambient, in the presence of water and an inert, water-miscible solvent such ,as tetrahydrofuran, dioxane, isopropanol, polyglycols and their ethers, or dimethylformamide, with the subsequent addition of a known Lewis base such as an alkaline earth metal hydroxide.
  • Lewis base refers to compounds that form a covalerit bond by donating a pair of electrons, with neutralization resulting from a reaction between the base and an acid with formation of a covalent bond.
  • reaction rate of this preferred method of preparing the compounds of the present invention is conveniently controlled by the rate of base addition coupled with external cooling. Room temperature, however, may be used as the starting reaction temperature to increase the reaction rate.
  • the reaction may also be accelerated by increasing the amount of inert, water-miscible solvent. An increase in the amount of inert, water-miscible solvent also makes the reaction mixture more homogeneous.
  • Advantages of using this preferred method of preparing the compounds of the present invention include mild reaction conditions, a high yield reaction, relatively inexpensive reagents, and a short reaction time.
  • a solvent extraction step can be eliminated because a desired product may be directly formulated as compared to a reaction process that uses a water- -immiscible solvent to isolate the desired product.
  • the reaction yield of this preferred method is also sufficiently high such that purification of a desired final product may not be required.
  • Tetraethylene glycol for example, is a common formulating solvent for paints, pigment slurries, latexes, and metal working fluids.
  • tetraethylene glycol as the inert, water-miscible solvent in the dehydrochlorination reaction, a desired composition may be directly formulated which could be
  • a paint used directly into: a paint, pigment slurry, latex, or metal working fluid product.
  • 2-chloro-3-thio-2-propenenitrile precursor begins with the chlorination of acrylonitrile ' to form
  • the 2,3-dichloroaorylonitrile reacts with an alkaline earth metal salt df an appropriate mercaptan to form the appropriately substituted 2-chloro-3-thio- -2-propenenitrile precursor in alkanols or aprotic solvents.
  • the reaction temperature, stoichiometries, and mode of addition are important to obtain acceptable isolated yields (greater than 85 percent from 2,3-dichloroacrylonitrile).
  • An aqueous NaOH solution is produced by mixing 1N NaOH (22.5 ml) with water (40 ml). This NaOH solution is added to the addition funnel.
  • the aqueous NaOH solution is added to the flask over a 20-hour period while maintaining the solution at room temperature or below. A temperature between zero and 5°C is preferred.
  • the reaction mixture is cooled to 5°C.
  • Dichloromethane (30 ml) is added to the reaction mixture.
  • the two-phase system is agitated and then transferred to a separatory funnel.
  • the dichloromethane phase is removed and the dichloromethane is vacuum distilled off.
  • the remaining material weighs 1.70 g.
  • Gas chromatographic analysis (GC) of the residue reveals 71 percent by area 3-methy;lthio-2-propynenitrile. A calculated overall yield of 64 percent is achieved.
  • the crude reaction product is purified by column chromatography yielding 3-methylthio- -2-propynenitrile in greater than 99 percent purity (by GC).
  • the structure identity is confirmed by proton ( ⁇ ) and carbon nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR) and gas chromatography/mass spectrometry (GC/MS).
  • the dichloromethane extract is dried over anhydrous sodium sulfate, filtered and concentrated on a rotary evaporator to yield 6.8 g of dark brown oil.
  • the dark 0 brown oil is purified by silica gel flash column chromatography to give 4.0 g of 3-ethylthio-
  • the compounds of the present invention are useful because of their antimicrobial activity and can be used as antibacterial and/or antifungal agents. c Their effectiveness varies with the concentration of the compound used and the particular organisms to be controlled. While not all compounds are effective at the same concentrations, all the compounds of the present invention are useful as antimicrobial agents in
  • the antimicrobial activity of the compounds of the present invention is demonstrated by the following techniques.
  • the minimum inhibitory concentration . (MIC) for the compounds listed in Table I 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 0.04M 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 115°C. The test tubes containing the agar are cooled in a water bath until the temperature of the agar is 48°C.
  • test compound is added (except in the controls where no compound is' added) to the respective test tubes so that the final concentrations are 500, 250, 100, 50, 25, 10, 5, 2.5, 1.0 and zero parts per million of the test compound in the agar, thus having a known concentration of test compound dispersed therein.
  • the contents of the test tubes are then transferred to respective petri 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 bacteria in tubes containing nutrient broth for 24 hours at 30°C in a shaker. Dilutions of each of the 24 hour-cultures are made so that nine separate suspensions (one for each of the nine test bacteria) are made, each containing 10" colony forming units (CFU) per ml of suspension of a particular bacteria. Aliquots of 0.3 ml of each of the bacterial suspensions are used to fill the individual wells of Steer's Replicator.
  • 0.3 ml was used to fill three wells (i.e., three wells of 0.3 ml each) so that for the nine different bacteria, 27 wells are filled.
  • 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 respective bacteria.
  • 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 ethanol (TRITON ® X-100, a trademark of Rohm & Haas Company) to the agar slant of yeast or fungi. The sterile saline/octylphenoxy polyethoxy ethanol solution is then agitated with a sterile swab to suspend the microorganism grown on the slant.
  • octylphenoxy polyethoxy ethanol TRITON ® X-100, a trademark of Rohm & Haas Company
  • Each resulting suspension is diluted into sterile saline (1 part suspension: 9 parts sterile saline). Aliquots of these dilutions are placed in individual wells of Steer's Replicator ' and petri plates inoculated as previously described. The petri plates are incubated at 30°C and read after 48 hours for yeast and 72 hours for fungi.
  • Table II 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 II
  • Pseudomonas aeruginosa 10145 Pseudomonas aeruginosa (PRD-10) 15442
  • Staphylococcus aureus (Sa) 6538 Yeast/Fungi
  • DOWICIL ® 75 >500 >500 >500 500 >500 >500 >500 A 2.5 0.50 0.25 0.50 0.25 2.5 0.50
  • the ability of the compounds of Table I to serve as preservatives in a variety of formulated industrial, household, and commercial products is tested using a Multiple Challenge Test Protocol.
  • the formulations include a styrene-butadiene latex, a tape joint, a hand lotion, and a shampoo.
  • the styrene-butadiene latex test formulation used is Latex DL 238A, available from The Dow Chemical Company.
  • the compositions of the tape joint, hand lotion and shampoo test formulations can be found in Tables V-VII. TABLE V Tape Joint Test Formulation
  • the formulations are separated into 50 g aliquots and placed in sterile bottles. An appropriate amount of a fresh one percent stock solution of the test compound in acetone-water is added to achieve the desired final concentrations. A small portion of each of the test formulations is streaked onto Tryptic Soy Agar (TSA) petri plates using sterile cotton swabs to ensure that the formulations are sterile. If the formulation is sterile, then it is inoculated with 0.1 ml of a mixture of equal aliquots of the 24 hour cultures of each of the bacterial organisms listed in Table II. The test formulations are then incubated at 30°C.
  • TSA Tryptic Soy Agar
  • each sample is streaked onto a TSA petri plate using a sterile swab. All plates are then incubated at 30°C for 48 hours and then rated for microbial growth using the rating system listed in Table VIII. Samples with a rating of 3 or less are reinoculated as described in the procedure for the first inoculation. Samples with a rating of 4 or greater are not reinoculated but after another 24 hours are restreaked on TSA agar.
  • MEC Minimum Effective Concentration
  • the compounds of the invention are added at concentrations of at least 0.002 percent by weight. This effectiveness can be compared to that of the commercial standard (DOWICIL ® 75) in a tape joint compound, under the conditions of the Multiple Challenge
  • 2-chloro-3-thio- -2-propenenitrile will generally exist as a reaction product with both an E isomer and a Z isomer, as shown below, wherein R is as defined hereinabove.
  • the ratio of E isomer to Z isomer of an appropriately substituted 2-chloro-3-thio-2-propenenitrile reaction product is largely dependent on the reaction process and conditions employed to produce the appropriately substituted 2-chloro-3-thio-2-propenenitrile.
  • an appropriately substituted 2-chloro-3-thio- -2-propenenitrile reaction product will generally exist with 50 to 10 weight percent E isomer and 50 to 90 weight percent Z isomer, based on a total weight of the appropriately substituted 2-chloro-3-thio- -2-propenenitrile.
  • a typical appropriately substituted 2-chloro-3-thio-2-propenenitrile reaction product will generally exist with 25 weight percent E isomer and 75 weight percent Z isomer.
  • the Z isomer of an appropriately substituted 2-chloro-3-thio- -2-propenenitrile precursor may degrade in situ to a like-substituted 3-thio-2-propynenitrile.
  • the half-life for the degradation of the Z isomer of 2-chloro- -3-methylthio-2-propenenitrile to 3-methylthio- -2-propynenitrile has been found, for example, to be approximately two days at pH 9 and approximately two months at pH 7.
  • the Z isomer of 2-chloro-3-methylthio-2-propenenitrile has antimicrobial activity which is essentially equivalent to 3-methylthio-2-propynenitrile (Compound A) and 25-50 times greater than the E isomer of 2-chloro- ° -3-methylthio-2-propenenitrile (Compound H) at a pH of 8.2, due to the partial conversion of the Z isomer to 3-methylthio-2-propynenitrile.
  • the compounds of the present invention may degrade at a pH of 7 or above over an extended time period to compounds which are less antimicrobially active than the original compounds of the present invention.
  • 3-methylthio-2-propynenitrile is observed to decompose in a basic solution to several compounds, one of which is 3.3-bis(methylthio)propenenitrile, represented below, which is virtually inactive as an antimicrobial.
  • Antimicrobial compositions containing both an appropriately substituted 2-chloro-3-thio- -2-propenenitrile precursor and a like-substituted " 3-thio-2-propynenitrile are formulated.
  • Such antimicrobial compositions generally exhibit an increased potency of antimicrobial activity as compared to the appropriately substituted 2-chloro-3-thio- -2-propenenitrile precursor alone and also result in a more stable level of the like-substituted 3-thio-2-propynenitrile than the like-substituted 3-thio-2-propynenitrile alone, thus generally resulting in greater antimicrobial activity over an extended time period.
  • Such an antimicrobial composition containing both an appropriately substituted 2-chloro-3-thio- -2-propenenitrile precursor and a lik ⁇ -substituted 3-thio-2-propynenitrile will contain between 50-95 weight percent, preferably between 80-90 weight percent, of the appropriately substituted 2-chloro- -3-thio-2-propenenitrile precursor and between 50-5 weight percent, preferably between 20-10 weight percent, of the like-substituted 3-thio- -2-propynenitrile, based on a total weight of the appropriately substituted 2-chloro-3-thio- -2-propenenitrile precursor and the like-substituted 3-thio-2-propynenitrile.
  • a mixture of an appropriately substituted 2-chloro-3-thio-2-propenenitrile precursor and the like- -substituted 3-thio-2-propynenitrile, or a mixture of two or more such appropriately substituted ⁇ 2-chloro- -3-thio-2-propenenitriles precursors and the like-substituted 3-thio-2-.propynenitr.iles, must be present in an antimicrobial composition in an amount needed to be antimicrobially effective so as to exhibit inhibition of selected organisms.
  • 3-thio-2-propynenitrile will be present in the mixture in antimicrobially effective amounts.
  • the amounts of each of the appropriately substituted 2-chloro-3-thio-2-propenenitrile precursor and the like-substituted 3-thio-2-propynenitrile used in the mixture will generally be less than the amount of the appropriately substituted 2-chloro-3-thio- -2-propenenitrile precursor and the like-substituted 3-thio-2-propynenitrile needed when used separately to achieve the same level of both short- and long-term antimicrobial activity as the mixture.
  • the amount of such a mixture to be used varies from 1 part per million (ppm) to 5000 ppm by weight. Such amounts vary depending upon the particular mixture tested and organism treated. Also, the exact concentration of the mixtures to be added in the treatment of industrial and consumer formulations may vary within a product type depending upon the components of the formulation. In such formulations, the mixtures of this invention may be added as a liquid concentrate or diluted with additional liquid to produce the ultimate treating composition, wherein the liquid could be water or an organic solvent like glycols, alcohols, or acetone.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On a préparé des 3-thio-2-propynenitriles à substitution, correspondant à la formule: R-S-C=C-C=N, dans laquelle R représente un groupe alkyle, alkyle cyclique, aryle ou hétérocyclo. On a découvert que ces composés présentent un degré élevé d'activité antimicrobienne dans des applications industrielles et commerciales. On utilise des compositions contenant lesdits composés dans ces applications.
EP91903461A 1990-01-12 1991-01-11 Composition et emploi de 3-thio-2-propynenitriles a substitution en tant qu'antimicrobien industriel Withdrawn EP0594583A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US46408590A 1990-01-12 1990-01-12
US464085 1990-01-12
US07/633,866 US5126349A (en) 1990-01-12 1990-12-26 Composition and use of substituted 3-thio-2-propynenitriles as an industrial antimicrobial
US633866 1990-12-26
PCT/US1991/000262 WO1991011503A1 (fr) 1990-01-12 1991-01-11 Composition et emploi de 3-thio-2-propynenitriles a substitution en tant qu'antimicrobien industriel

Publications (2)

Publication Number Publication Date
EP0594583A4 EP0594583A4 (fr) 1993-04-20
EP0594583A1 true EP0594583A1 (fr) 1994-05-04

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EP (1) EP0594583A1 (fr)
JP (1) JPH05504767A (fr)
AU (1) AU7226591A (fr)
BR (1) BR9105938A (fr)
CA (1) CA2073458A1 (fr)
WO (1) WO1991011503A1 (fr)

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CN113508823A (zh) * 2021-04-26 2021-10-19 天津市汉邦植物保护剂有限责任公司 含有吲哚丁酸、氨基寡糖素的深绿木霉可分散油悬浮剂及制备方法及其对病原线虫防控应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3140306A (en) * 1957-02-21 1964-07-07 Monsanto Co Method of making aliphatic and aromatic thio and sulfonyl chloro- and bromoalkanenitriles
IT1075277B (it) * 1977-02-11 1985-04-22 Erba Carlo Spa Derivati insaturi e epossidici dell'acio 7-acilamido-3-cefem-4-carbossilico e procedimento per la loro preparazione
US4238405A (en) * 1977-09-19 1980-12-09 Stauffer Chemical Company Fungicidal 1,2-dichlorocyanovinyl compounds
EP0104432A2 (fr) * 1982-08-25 1984-04-04 Teijin Limited Herbicide et régulateur de la croissance des plantes comprenant un composé alpha-bêta insaturé
DK163000C (da) * 1982-09-30 1992-06-01 Shionogi & Co Analogifremgangsmaade til fremstilling af vinylthioacetamido-1-dethia-1-oxa-cephalosporinderivater

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO9111503A1 *

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BR9105938A (pt) 1992-11-10
CA2073458A1 (fr) 1991-07-13
WO1991011503A1 (fr) 1991-08-08
EP0594583A4 (fr) 1993-04-20
JPH05504767A (ja) 1993-07-22
AU7226591A (en) 1991-08-21

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