JPH049766B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to algae growth inhibitors. U.S. Pat. No. 3,923,870 describes a method for synthesizing urethanes of 1-halogen-substituted alkynes, their fungicidal activity, compositions as fungicides, and various substrates. U.S. Pat. No. 4,276,211 describes the use of 1-halogen-substituted alkyl urethanes and mixtures of this compound with epoxides to create color-stabilizing fungicides for coating applications. Certain carbamates are used as insecticides and herbicides. The insecticide Seven (carbamyl or naphthyl methyl carbamate) has a concentration of 1 to 100 ppm (μ
It is known to have algae-killing properties in the range (g/ml).
However, testing at 100 ppm only reduced the sterile cultivation population of Chlorella pyrenoidosa by 30%. (Christy's “Pesticide Microbiology”
(1969)) “Zectran” mexacarbamate formulation is said to prevent photosynthesis of blue-green algae (bacteria). However, in "normal" spray use it did not harm the aquatic algae. (Sinder and Siyaridan, 1974) This formulation, Zectran, was not intended to be used as an algaecide and is therefore not particularly useful for this purpose. Phenyl carbamates, often used as herbicides, have shown activity against blue-green algae (bacteria). Brofuam, chloroprofuam and Verban (trade names) reduce green grass growth by 50% at concentrations ranging from 0.3 to 70 ppm. (Results of Hill and Wright (1978)). Barban did not suppress growth in all species tested. Like Seven and Zectran, phenyl carbamates are not structurally 1-halogen-substituted alkyne urethanes. The use of mercury compounds with limited efficacy and toxicity drawbacks is also known. Although copper compounds are active and can be used, they have the disadvantage of coloring in many applications. Tributyltin oxide has been used, but it is expensive for this purpose and has stability problems when exposed to the outside. Although various compounds have been used in limited applications in lakes, ponds, and stagnant waters, until recently there has been little recognition of the need for algaecides in coatings. It has been known that certain compositions containing materials such as zinc oxide can be "smeared", but this presents problems with pigmented coatings and membranes, low algicidal activity and stability problems with membranes. Materials such as chlorine or sodium hypochlorite are used in special applications in water towers, such as cooling towers and water storage towers. However, these materials are currently not available for use by environmental protection agencies and would likely be environmentally hazardous if used. An object of the present invention is to provide an algal growth inhibitor. Algal growth inhibitors (also referred to as algaecides) can be used in the form of compositions such as coating compositions, protective compositions, decorative compositions, etc., and can be used in paints, coatings, pawls, linings, etc. , encapsulants, sprays, lacquers, finishes, compositions, abrasives, wood, mortar, concrete, cement, fillers, molding compositions, waxes, resins, polymers, fibers, etc. in various forms. I can do it. The present invention relates to the use of 1-halogen-substituted alkyne urethanes to inhibit or prevent the growth of algae and to eliminate algae that have already grown. The compound discovered to have algaecide activity according to the present invention has the general formula: (However, in the formula, R is selected from substituted or unsubstituted alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkyl, and cycloalkenyl groups having 1 to 20 carbon atoms and 1 to 3 bonds corresponding to m. and m and n
is an integer from 1 to 3 regardless of each other).
Iodo-substituted alkyne derivatives. These compounds were found to have many advantages as algaecide agents in controlling and exterminating many types of algae. In the present invention, the algae growth inhibitor also includes the extermination of algae. It is very stable when mixed into aqueous and non-aqueous compositions, losing activity and/or decomposing only when exposed to high temperatures for extended periods of time. The compound has low toxicity to animals, birds and other field animals, livestock and humans. Therefore, use of the algaecide composition requires only the usual handling methods and care taken in handling and using commercially available household disinfectants. Laboratory tests have shown that the urethane compounds of the present invention can be mixed with other fungicides to improve their activity and broaden their range of applications. Compositions in which the compounds of the invention are used may include a relatively wide variety of ingredients well known in the art. The compounds of the present invention are generally used as algaecides in amounts ranging from 0.01 to
A concentration of 12.0% by weight is used, depending on the stability of the composition used, whether aqueous or non-aqueous in some cases. In some cases, the compounds are used as premixed dispersions. It may also be prepared as a solution or dispersion and then added to the final protective composition. For example, 3-iodo-2-propynyl-N-butyl carbamate (Polyphase) was found to be water soluble at concentrations of about 150-200 ppm. Amount (concentration) of urethane effective in all cases to control or exterminate algae(s) or the like.
need to be used. For example, in some cases it may be necessary to use up to about 40% by weight of the compound to control and/or kill algae in a fully grown state. When used as an algaecide, 1-halogen-substituted alkyne urethanes dissolved or solvated in water and various organic solvents are effective against algae containing wood and mortar, most paints, coatings, pawls, fillers, etc. It can be mixed into a wide variety of compositions requiring protection from the growth of cerebrospinal fluids. When used as algaecides, 1-halogen-substituted alkyne urethanes are effective as algaecides and in controlling algae that grow in seawater, fresh water, land, and air. It is also effective against species found in water cooling towers, clogged irrigation ditches, and growing on mortar and wood, making it a particularly valuable agent when used against these. The compositions include, for example, all types of water-based latex paints, including acrylic and PVA latex paints and chlorinated rubber-vinyl paints, oil-alkyl paints, oil-based colorant-pigmented paints and protective and decorative compositions, rubber. and/or asphalts for roof coverings, inorganic and polymeric pawl materials, molding materials, encapsulants, silicone compositions, aqueous and non-aqueous liquid compositions suitable for application, dipping or spraying and other applications for a wide range of applications of these materials. It may also be a protective composition. These algicidal compounds have also been found to be of particular value in the problem of clogging of irrigation ditches, ditches, and pipes, particularly in troublesome Batraeuspermium (red algae) problems. In addition, this algaecide compound was added to one of the Deinophyci species.
Or it can be used to prevent so-called "red tide" problems commonly caused by two or more algae. The compounds can also be used for odor control by preventing, suppressing and/or eradicating algae populations in water, such as in irrigation systems, water towers, sewage circulation systems, and similar water storage and transportation systems. Among these types, the urethane compound 3-iodo-2-propynyl-N-butylcarbamate (known as Polyphase, a product of Troy Chemical Company) is particularly effective and convenient as an algaecide. In other features of the invention the formula: (wherein R is selected from the group consisting of aralkyl and substituted aryl groups, and m and n are independent integers from 1 to 3) It was found to be very effective as an algaecide. Algae that can be effectively treated with the compounds and compositions of the present invention include Chlorophyta (green algae), Chrysophyta (yellow-green algae), Cyanophyta (blue-green algae or bacteria), Euglenophyta (Euglenodes), Phiophyta (brown algae) and Rhodophyta (red algae). ), but these groups and the species within them are not the only algae for which the compounds and compositions are effective. Algae used in testing the algae inhibiting and algaecide activity of compounds and compositions were obtained from Wards Natural Science Institute, Lochiester, New York. The individual algae tested are fully described in the Examples. As the results showed, the compound was very effective in inhibiting the growth of the algae tested. The examples below are for illustrative purposes only. The numbers and test results in the table are intended to illustrate the use of the compounds and various coating compositions containing them, and do not limit the invention thereto or to the algicidal activity of the compounds and compositions. There is no intention to limit the type of algae or the specific amount or concentration of algaecide used to control the test algae. It is well known in the field that it is usually easier to prevent or suppress the growth of algae than to eliminate them if they are already growing. It is also known that it is easier to control small populations of algae than large populations. Examples include in particular the algicidal properties of the compounds and compositions containing them, particularly those species that are protected by thick capsules and those that reproduce rapidly in dense colonies;
It is intended to illustrate the efficacy results of the composition against, for example, Sitnema species with thick capsules and Nostok species that grow in dense clumps. Example 1 Preparation of hydroxy-iodo-propyne p-chlorophenyl urethane Hydroxyiodopropyne in ether (IC
A 70% solution of 0.2 mol of ≡C-CH ₂ OH) was dried over anhydrous sodium sulfate and mixed with 0.2 mol of p-chlorophenyl isocyanate and a few drops of dibutyltin dilaurate were added as a catalyst. An exothermic reaction occurred. The mixture was refluxed to complete the reaction. After filtration, 21 g of pale cream-colored precipitate was obtained. Melting point 95−100
℃. Evaporation from the clear liquid gave an additional 22 g of precipitate.
Melting point 93-95℃. Iodine = 36.8% (theoretical value 37.8%) Example 2 Preparation of 3-methylphenyl urethane from hydroxy-iodo-propyne The product preparation reaction of Example 1 was repeated except that m-tolyl isocyanate was used in place of p-chlorophenyl isocyanate. First, remove a small amount of impurities and leave it in a refrigerator overnight to separate the product from the reaction mixture and form light cream-colored crystals.
I gained 37g. Melting point: 93℃. Iodine = 39.97% (theoretical value 40.2%) Example 3 Production of mixed diurethane of hydroxy-iodopropyne and toluene diisocyanate

[Formula] [80% 2,4- and 20% 2,6-tolyl] Hydroxyiodopropyne and Mondilleur TD-30 (trade name) manufactured by Mobay Chemical Company
80% of toluene diisocyanate known as
The 2,4- and 20% 2,6-mixed isomers were reacted in a molar ratio of 2.15 moles of HIP (hydroxyiodopropyne) per mole of diisocyanate. 60 g of 72% HIP solution in ether and 200 g of methylene chloride;
After mixing with dibutyltin dilaurate 1/3 c.c., gently add Mongiur TD-30 for 50 minutes.
Added 19.2g. After the addition was complete, the mixture was refluxed and about 250 g of methylene chloride was added as needed to disperse the precipitate. The reaction mixture was heated at reflux for 2.5 hours and left overnight. The next day, I obtained 51g of cream-colored powder. Melting point 174-177℃. Example 4 Preparation of diurethane from hydroxy-iodopropyne and 4,4'-methylene diphenyl isocyanate The product preparation reaction of Example 3 was repeated, except that the isocyanate used was 4, obtained from Mobay Chemical Company under the trade name Mongieur M.
It was 4'-methylene diphenyl isocyanate. The reaction product of 39 g of HIP and 25 g of Mongiur M was 55.5 g of a cream colored powder with a melting point of 165-168 DEG C. and an iodine content of 40% (41.4% theoretical). Example 5 Hydroxy-iodopropyne and toluene 2,
Diurethane production from 4-diisocyanate This product was made by the method of Example 3.
However, toluene 2,4-diisocyanate (Mobay Chemical Co., Ltd. trade name: Mongiur TDS) was used. Product yield 52g cream colored powder, melting point approx.
181−184℃. Iodine content 47% (theoretical value = 47.2%) Example 6 Preparation of benzyl urethane of hydroxy-iodopropyne 14.6 g of HIP was dissolved in 20 c.c. of ether, and 0.1 cc of dibutyltin dilaurate was added. To this was added 16.7 g of benzyl isocyanate over 30 minutes.
The temperature rose to 39°C due to an exothermic reaction, and precipitation occurred. After mixing for an additional 30 minutes, the reaction mixture was filtered and washed with ether to yield 20.5 g of a cream colored powder. Melting point 107-110℃.
The product was slurried in ether to give 17.5 g of faint cream colored crystals. Melting point 112−
113℃. Iodine = 39.4% (theoretical 40.3%) Example 7 Various nutrient solutions, such as Bristol's solution, Etre Schleiber's solution, soil-water media and other liquid media, were added to 100 μg/ml of 1 in screw cap tubes. −
Iodo-2-propynyl N-butyl carbamate (trade name: Polyphaes, manufactured by Troy Chemical Company)
and an appropriate amount of an aqueous solution containing. The tubes were inoculated with an active culture of Carteria sp., Chlamydomonas sp., Eudrina sp., Haematococcus sp., Pandorina sp., Vulvochus sp. or other algal species that grow well on the medium. A control sample was created by mixing the medium with water and inoculating it with algae species. For example, the following mixture was prepared, inoculated with Prolocentrium, and charged with Polyphaes.

[Table] Tubes inoculated with Prolocentrium were incubated at approximately 20°C for 2 days under a cool white fluorescent light (40W) and examined microscopically. Live (motile) cells were found in both control tubes without polyphases and tubes containing 5 μg/ml of polyphases. polyphase 10μ
No viable cells were observed in tubes containing g/ml and above. If green algal species were used as inoculum, bleaching (bleaching or disappearance of green color) could be used to test for toxic amounts of polyphaes on the algae. Microscopic examination, bleaching, or both were used in this type of study. The results using this method for all single cell and/or microscopic algae tested are shown in Table 2 below. Example 8 Solutions were made as described in Example 7, but without inoculum, the final volume in each case was 10 ml. The inoculum consists of fibers of algae species such as Spirodilla and Sitnema, large seaweed strips such as Uruvua, and clusters of species the size of a poplar such as Nostok. fiber. Small amounts of water adhering to the debris and mass were ignored. Whitening was used to test polyphaes algae removal activity. Both freshwater and saltwater species were tested as described in Examples 7 and 8 and are summarized in Table 2. Polyphaes showed good algicidal activity against both groups of organisms. Seaweeds were separated as shown in Table 3. Polyphaes and its congeners could be used to treat seawater flowers such as "red tide". Because Polyphaes is water soluble at approximately 175 ppm (μg/ml) and because congeners with varying water solubility are available, we conclude that a saturated water column solution contains sufficient fungicide to control the most formidable algae. .

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[Table] Example 9 Schreicher and Schünel analysis paper (#740-
E, diameter 1/2" = 12 mm) was immersed in a 1-40% aqueous solution of the test compound dissolved in acetone. A push pin "T" was used in the center to hold each paper in place during soaking and drying. Cork board The treated paper was air-dried by fixing it with a "T" pin. Protease agar plates were prepared and seeded with Chlorella pylenoidosa "lawn" from a sterile culture.
A treated, air-dried paper containing Polyphaes or its congeners listed in Table 4 was placed in the center of each board. The Petri dish was placed under a cool white fluorescent light (40W) at ambient temperature (approximately 20
℃) until algae grew (about 6 days).
The size of the inhibition zone was measured (mm) from the edge of the paper to the edge of algae growth. The results obtained are shown in Table 5. The compound of the present invention, a 1-iodo-substituted alkyne urethane, was highly toxic to Chlorella pyrenoidosa. These compounds, including polyphaes, have therefore been shown to be toxic to algae from a wide range of breeding grounds and from each major division occupying a wide range of known algal species.

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[Table] Example 10 Blends of latex paints, oil alkyd paints, and oil-based colorants from commercially available materials (the blends are shown in Table 7 below).
8 and 9) were made. Polyphaes was added at amounts of 2.4 and 6 pounds per 100 gallons. Paper was coated or treated with the formulation and the polyphase-free control, dried and cut into 12 mm diameter disks. This disk was placed on a proteose agar-containing plate seeded with Chlorella pyrenoidosa grass and cultured as in Example 9. The zone of inhibition was measured as in Example 9. The test results are shown in Table 6. It was observed that a small area of inhibition was obtained in the control product that did not contain polyphaes. The abnormality was caused by solvents and disinfectants commonly added to paints and other films to protect them from bacteria. However, after use as a membrane, these toxic agents weathered away, leaving an unprotected membrane. A large area of inhibition was observed in the polyphaes-protected membrane. These results clearly demonstrate the increased and long-lasting protection of Polyphaes use.

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[Table] On Carbide product name)

[Table] Example 11 Polyphaes in roof covering material at 0.1 to 1.0%
(approximately equal to 1 to 10 pounds per 100 gallons). A roof coating called Tray Coat (trade name) (its composition is shown in Table 10 with and without Polyface) was applied onto a standard 1″ x 3″ glass microscope slide, allowed to dry for 2 days, and then soaked with distilled water for 3 days. I drifted away. Membranes were cut from the slides with a razor blade and placed on Proteose agar overlaid with a lawn of Chlorella pyrenoidosa cells. Plates were incubated and examined under cool white fluorescent light (40 W) for 2 days. A green "lawn" of algae cells was seen growing to the edge of the polyphaes-free control membrane. Growth on the surface of the control membrane was also observed. (as seen in reflected light)
However, no growth was observed under membrane samples containing 0.4% or more polyphases. Furthermore, an inhibition zone with a width of 0.5 to 4.0 mm was observed around the protective film. Table 10 Roof Coating Composition Tray Coat (trade name, Tray Coat Co., Columbia, South Carolina) is a protective roof coating with the following composition: Ibs of material /100 gallons Ethylene Glycol 23.3 Natrasol 250HR (trade name, Hercules Co., Ltd.) 4.0 Wednesday 197.6 Nopco NXZ (Diamond Shamlok product name) 93.2 Tamol 250 (Rohm & Haas product name)
4.7 Calcium carbonate 93.2 Titanium dioxide 65.3 pounds of material /100 gallons Talc 279.5 Acrylic latex resin 442.6 26 Baume's ammonia water 1.9 Troysan ^* 174 (trade name of Troy Chemical Co.) 2.5 *Troysan 174 is a volatile sterilizer for preserving can contents. It is a drug. EXAMPLE 12 A commercially available rubberized asphalt roof covering having the composition shown in Table 11 was mixed with a Troysan® Polyphase AF-1 formulation. The active polyphase content of this formulation is 40%
The remaining inert ingredient is the solvent. The mixture contains Polyphaes AF-1 at 0.0, 0.5, 1.0, 1.5 and 2.0%
The active polyphases contained were 0.0, 0.2, 0.4, 0.6 and 0.8% by weight. These samples were spread onto glass slides with a wooden spatula and allowed to dry for 3 days. The membrane was cut from the slide with a razor blade and placed smooth side down on the surface of a proteose agar plate seeded with Chlorella pyrenoidosa. The samples were incubated at ambient temperature (approximately 22°C) for 7 days under a 40W white fluorescent light. Chlorella pyrenoidosa grew below and above the surface of the control sample without polyphaes.
The Pyrenodosa was suppressed and did not grow under the surface of all concentration samples containing polyphaes.
An inhibitory range was observed for active polyphases at 0.6 and 0.8%. Table 11 Rubberized Asphalt Roof Covering Composition Materials % Asphalt 50 Attutagel (Engelhard Industries trade name) Thickening agent 15 Kraton Rubber (Siel Oil trade name) <5 Lecithin and surfactants <1 Aromatic process oil <5 High Flush Naphtha 24-25 Example 13 Polyphase 0.0 per 100ml in ethanol,
Solutions containing 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0 g were prepared and transferred to an "Omit" air dispenser and sprayed onto the proteose agar surface in a Petri dish. Proteose agar was previously inoculated with Chlorella pyrenoidosa to grow a "lawn" of cells on the surface. Petri dishes were incubated for one week at ambient temperature (approximately 22°C) under a 40W white fluorescent light. Chlorella pyrenoidosa grew on the agar surface sprayed with polyphaes-free ethanol. At polyphase concentrations of 0.1 and 0.2 g/100 ml, some point growth occurred. polyphas 0.4
At concentrations of g/100ml and above, no growth was observed on the plates.

Claims (1)

[Claims] 1 Formula: (wherein R is a group consisting of substituted or unsubstituted alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkyl, and cycloalkenyl groups having 1 to 20 carbon atoms and 1 to 3 bonds corresponding to m) and m and n represent integers from 1 to 3, and may be the same or different. agent. 2. The algae growth inhibitor according to claim 1, wherein m in the formula of the urethane compound is 1. 3. The algae growth inhibitor according to claim 1, wherein n in the formula of the urethane compound is 1. 4. The algae growth inhibitor according to claim 1, wherein R in the formula of the urethane compound is an aralkyl group or a substituted aryl group.