JPH0347242B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention generally relates to the use and use of 1-iodo-substituted alkyne (carbamate) urethanes as repellents and poisons for aquatic invertebrate control. Compositions containing these compounds also form part of the invention. U.S. Pat. No. 3,923,870 describes a method for the synthesis of urethanes of 1-halogen-substituted alkynes and their fungicidal activity and use in compositions and various substrates as fungicides. U.S. Pat. No. 4,276,211 describes the use of 1-halogen-substituted alkyne urethanes and mixtures of this compound with epoxides to create color-stabilizing fungicides for coating applications. Certain carbamates are used as insecticides and herbicides. Insecticide Seven (carbamyl or naphthyl methyl carbamate) is 1 to 100 ppm
It is known to have algaecide activity in the range of (100μg/ml). However, testing at 100 ppm only reduced the sterile cultivation population of Chlorella pyrenoidosa by 30%. (Christy's “Pesticide”
Microbiology (1969)) Zectran, a mexacarbamate formulation, is said to prevent photosynthesis in blue-green algae (bacteria).However, in 'normal' spray use it did not harm aquatic algae. Synder 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, are Profuam, chloroprofuam, and Barban (trade names) reduce the growth of blue-green algae by 50% in the range of 0.3 to 70 ppm (Hill and Wright, 1978). Barban has been tested. It did not inhibit growth in all algae species. Like Seven and Zectran, phenyl carbamates are not structurally 1-halogen-substituted alkyne urethanes. Compounds and compositions used against aquatic pests contain copper, tin, and zinc. compounds such as creosote, halogenated phenols, etc.Cheap copper, tin and zinc oxides are used because of their low cost rather than their high activity.For specific organisms or groups of organisms, more expensive oxides are used because of their high activity. Organometallic compounds are used. Each of the known poisons has its own unique spectra of bactericidal activity and most have drawbacks, including environmental concerns. The use of mercury compounds as conventional marine and water intoxicants is also known. These have limited efficacy and have toxicity drawbacks. Tributyltin oxide has been used, but it is relatively expensive for this purpose and has stability problems when exposed to the outside world. Although the compounds have been used in limited applications in lakes, ponds, and stagnant bodies of water, until recently there has been little recognition of the need for algaecides in coatings. Chlorine was known to be able to be applied to water towers, such as cooling towers and water storage towers, but this caused problems with pigmented coatings and membranes, resulting in low algae-killing activity and stability issues with membranes. Materials such as sodium hypochlorite or sodium hypochlorite are used specifically as algaecides, but these materials are currently not available for use by environmental protection agencies and would probably be environmentally hazardous if used. Book The object of the invention is generally aquatic invertebrates, including, but not limited to, aquatic protozoa, hydrozoa, bryozoans, planaria, barnacles, snails, snails, clams, tunicates, and tunicates. The purpose of this invention is to use 1-halogen-substituted alkyne urethanes as repellents and poisons for the control and extermination of these animals. Another object is to describe compositions for aquatic invertebrate control, including, but not limited to, coating compositions, protective compositions, and the like. Furthermore, other purposes include paints, coatings, pawl materials, linings,
Encapsulants, sprays, lacquers, finishing compositions, abrasives, wood, mortar, concrete, cement,
It relates to the use of this composition in and/or with fillers, molding compositions, waxes, resins, polymers, fibers, etc. for aquatic invertebrate control. The present invention relates to the use of 1-halogen substituted alkynes in urethanes for repelling, inhibiting and inhibiting the growth of aquatic invertebrates and for combating the existing presence of such animals. These compounds are known to have pesticidal and toxic activity and have the general formula:

[Formula] (R is a substituted or unsubstituted alkyne having 1 to 20 carbon atoms and 1 to 3 bonds corresponding to m and n,
a 1-iodo-substituted alkyne representing a group selected from the group consisting of aryl, aralkyl, alkaryl, and cycloalkyne groups, and m and n represent integers from 1 to 3 and may be the same or different; It is a derivative. These compounds have been shown to have many advantages as algaecides for the control and control of various aquatic invertebrates. They are very stable when mixed into aqueous and non-aqueous compositions, including seawater, and only deactivate and/or when exposed to high temperatures for long periods of time.
Disassemble. They are also said to be relatively harmless to useful motile vertebrates. These compounds are also used in animals, birds, field animals,
It has minimal toxicity to livestock and humans. Their use in the compositions described herein, therefore, requires no more than common good handling practice and the precautions taken when handling commercially available household and marine disinfectants and poisons. good. The urethane compound can be mixed with other fungicides as desired to extend and improve its activity and extend its range of use against aquatic invertebrates. Compositions in which the compounds are used may include a relatively wide range of ingredients well known in the art. In many cases these will be used in seawater. Compounds useful in the present invention, when commonly used as anthelmintics or poisons, are used in concentrations of about 0.001 to about 12.0% by weight, depending on the stability of the compound in the composition and whether the medium used is aqueous or non-aqueous, if any. It depends. Sometimes the compounds can be used beforehand as a dispersion. Alternatively, the compound may be made into a solution or dispersion and then added to the aqueous medium used. For example, 3-iodo-2-propynyl-n-butyl carbamate has been found to be soluble in water at concentrations of about 150-200 ppm. In all cases, it is necessary to use an effective amount (concentration) of urethane to control and/or kill the particular species that is being avoided, suppressed, or exterminated. For example, in some cases it is necessary to use up to about 15% by weight of the compound to control certain harmful marine animals, although lower concentrations can also be effective as repellents. The 1-halogen-substituted alkyne urethanes, dissolved or dissolved in water, for the applications described herein can be used in various compositions, paints, coatings, including wood and mortars, which require protection and freedom from marine animals. It can be mixed with or applied to pawl materials, fillers, etc. 1-Halogen-substituted alkyne urethanes have inhibitory activity against aquatic species found in the sea, fresh water, land, and air. They are active in species found in water cooling towers, clogged irrigation ditches, and growing on mortar and wood, and are particularly valuable agents when used for these purposes. The compositions include, for example, all types of water-based latex paints, including acrylic and PVA latex paints and chlorinated rubber-vinyl paints, oil-alkyd paints, oil-based colorant-pigmented paints and protective and other compositions, rubber and (or) asphalt-containing membranes, inorganic and polymeric pawl materials, molding materials, encapsulants, silicone compositions, aqueous and non-aqueous liquid compositions suitable for coating, dipping and/or jetting, and others for the wide range of uses of these materials. It may be a composition of. This anthelmintic and toxic compound is especially suitable for use in obstruction problems in ditches, irrigation canals, water pipes, and around docks and moorings and in areas where it is particularly troublesome and difficult to control ships and marine animals. I know it's valuable. 1-Halogen-substituted alkyne urethanes have a unique spectrum of activity against aquatic pests associated with biophores. They are active against aquatic vertebrates that bore into wood and are repellent to other aquatic vertebrates. Aquatic vertebrates that exhibit avoidance responses are desirable species that escape to safety. These are also the undesirable species that settle on unprotected substrates such as wood, resins, fibrous materials, hair, wool, paper and paper substitutes. Particularly of this class, the urethane compound 3-iodo-2-propynyl-n-butyl carbamate (known as Polyphaes, a product of Troy Chemical Company) has been shown to be very effective and useful both as an anthelmintic and as a poison. There is. 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 integers from 1 to 3 and may be the same or different)
- A new urethane family of iodohydroxyalkynes has been found to be very effective. The individual types tested are fully described in the examples as indicated by the data. The compounds were highly effective at repelling and killing the test species. The examples below are for illustrative purposes only. The values and test results in the table are intended to illustrate the use of the compounds as pesticides and poisons for aquatic vertebrates, and are not intended to limit the invention thereto or to limit the use of the compounds and compositions to aquatic vertebrates or to any particular class of aquatic vertebrates. There is no intention to be limited to the activity or to the specific amount or concentration of carbamate used to inhibit the test species. It is well known in this field that it is usually easier to avoid animals than to eliminate existing or growing animals. It is also well known that it is easier to suppress small populations of marine animals than large populations. Time is also an important factor. Example 1 Agnotobiotic cultures of protozoa were obtained from the Ward Natural Science Facility in Lochiester, New York. For the experiments described below, cultures were transferred to a new medium and incubated at ambient temperature for a suitable period of time, and growth was examined microscopically to determine the effect of the compound and/or composition. A known amount of properly grown new culture was used as inoculum. Depending on the study type, inoculated tubes were filled with liquid medium and/or sterile water (control). 3
-Iodo-2-propynyl-n-butyl A known amount of an aqueous solution containing carbamate was added and the concentration of carbamate was calculated from the total amount. The test cultures were incubated for an appropriate period of time and then examined microscopically. Active protozoa were also observed in the control article at low concentrations of the compound(s) tested. The absence of protozoa indicated that the concentration had made protozoa extinct. The protozoa used in this study are commonly found in a wide variety of aquatic ecosystems. The majority of protozoa and most common taxa were represented in the study. The result is:

[Table] Additionally, these carbamate compounds generally exhibit varying degrees of toxicity and repellency to motile aquatic animals. The fact that the compound also exhibits repellent properties limits and modifies its toxic effects, so a large amount of water is usually included, which acts as an effective diluent. Example 2 Protozoa axenic cultures were obtained from either the Ward Natural Science Facility or the American Type Culture Collection. Cultures were transferred to new media and incubated at appropriate temperatures and times, and growth was examined microscopically.
A known amount of new culture, which had been tested to show adequate growth, was used as the inoculum. Depending on the type, the tube containing the inoculum was topped with a known amount of sterile agar (slope) and sterile liquid medium and/or sterile water (control). Known amount of 3-iodo-2-propynyl-
An aqueous n-butyl carbamate solution was added, and the carbamate concentration was calculated from the total liquid volume. The amount of agar was ignored during calculations. The value obtained from the calculation therefore represents the highest amount of contact during the test. Test cultures were incubated at appropriate temperatures for appropriate times and examined microscopically. Active protozoa were also observed at weak (low or inadequate) concentrations in the controls. The absence of protozoa indicated that the concentration effectively killed protozoa. As mentioned above, protozoa are pathogenic in invertebrates and/or vertebrates. In one case (Tosypanosoma cyclopus), the pathogen came from monkeys and was a potential human pathogen. The test results were as follows.

[Table] Mu
Example 3 The reptile Aurelia aurita sp. was obtained from the Marine Biological Laboratory in Utsudhor, Masachi, Yusetsu. This species was kept in well-aerated glass tanks with gravel filters, limestone sand bottoms, and wood chips as attachment surfaces. substituted iodoalkynes,
(3-iodo-2-propynyl-n-butyl
A carbamate) solution was prepared in artificial seawater and the test was conducted in a 1.5 tank. This tank was the same as the holding tank except that no seawater was allowed to pass through and ventilation was provided through small air holes. Animals were tested in solution over the weekend (2.5 days).
Animals that died from the solution showed no avoidance response when touched and were immediately destroyed. Surviving animals showed avoidance responses and moved around when returned to the holding tank. The minimum concentration to kill toxic Aurelia aurita is 3-iod-
2-propynyl-n-butyl carbamate
It was 10 ppm (20 μg/ml). The following compounds were also found to be equivalent to or slightly less toxic than Aurelia aurita: 4-iodo-3-butynyl methyl carbamate 3-iodo-2-propynyl cyclohexyl carbamate 3-iodo-2-propynyl-n-octyl carbamate 3- iodo-2-propynyl-phenyl carbamate 3-iodo-2-propynyl-4-chlorophenyl carbamate di(3-iodo-2-propynyl) 4,4'-
Diphenylmethane carbamate 3-iodo-2-propynyl benzyl carbamate. Example 4 Hydroids belonging to the genera Obelia and Tubularia were tested as described in Example 1. However, the hydroid was attached to seaweed placed in a test glass tank. Obelia and Tubularia are the lowest concentrations tested
Killed by 1 ppm (1 μg/ml) carbamate. A suitable control without carbamate contained viable hydroids at the end of the experiment. Example 5 Two species of bryozoans were grown and tested as described in Example 1. The first type came from the Marine Biological Laboratory and was 3-iodo-2-propynyl-n-butyl carbamate 5ppm (5μ
g/ml). The second type was obtained from Cape Fire Biological Supply Co., Southport, North Carolina, and contained 25 ppm (25 μg/ml).
3-iodo-2-propynyl-n-butyl
Died from carbamate. Example 6 Three nematode media (Ward Natural Science Facility)
-Iodo-2-propynyl-n-butyl was mixed with an aqueous carbamate solution (100 ppm) in various proportions in test tubes with screw caps. Carbamate concentrations were prepared at 10, 20, 30, 40 and 50 ppm. A control product was prepared by mixing the medium and distilled water.
Each tube was inoculated with 1 drop of activated Tarbatrix aceti broth (Ward's) and incubated for 7 days. Active animals were found in the control and 10 ppm. Nematodes were killed at 20 ppm and above, and no animals were visible microscopically in the solution at that concentration. The following compounds were also found to be equally or somewhat less toxic to T. acetyl: 4-iodo-3-butynyl methyl carbamate 3-iodo-2-propynyl-cyclohexyl carbamate 3-iodo-2-propynyl-n-octyl carbamate 3-iodo-2-propynyl-phenyl carbamate 3-iodo-2-propynyl-4-chlorophenyl carbamate di(3-iodo-2-propynyl) 4,4'-
Diphenylmethane carbamate 3-iodo-2-propynyl benzyl carbamate. Example 7 Isopod that bores holes in trees - Suceloma quadridemtum - cape species Huiya Biological
Its sensitivity to 3-iodo-2-propynyl-n-butyl carbamate obtained from Supply Company was tested. A 10.0 ml solution was prepared in a test tube and the animal was placed in the tube. The minimum concentration of carbamates that kill Suceroma quatridentum is 30 ppm (30 μg/
ml). Example 8 Three cultures of different genera and species representing different planarians were obtained from the Ward Natural Science Facility. The animal was transferred to a test tube containing an aqueous solution of 3-iodo-2-propynyl-n-butyl-carbamate. Carbamate 0, (distilled water control product),
Five animals were used for each tube at 10, 18, 25 and 31 ppm concentrations. All animals belonging to three genera survived in the control steam water. At concentrations of 10 ppm and above, all were killed within 2 hours. The following compounds were also found to be equivalent or somewhat less toxic to the genus Planaria: 4-iodo-3-butynyl methyl carbamate 3-iodo-2-propynyl cyclohexyl carbamate 3-iodo-2-propynyl- n-octyl carbamate 3-iodo-2-propynyl phenyl carbamate 3-iodo-2-propynyl-4-chlorophenyl carbamate di(3-iodo-2-propynyl) 4,4'-
Diphenylmethane Carbamate 3-Iodo-2-Propynyl Benzyl Carbamate Example 9 Barnacles belonging to the genus Balanus thiasamaras and Polycytes were obtained from Marine Biological Laboratory, Cape Fire Biological Supply Co., and Diem Cultivars, Fort Plug, California. I got it. These animals were tested as described in Example 1. The results of this experiment are shown in the following table:

[Table] Jirasu
Cancer Neck Burner Polishitespoli 50.0
Cruz Melas
Example 10 Two planks (6″ wide x 4″ thick) with live worms (Toledo bunkies) were obtained from Cape Fire Biological Supply Company. Cut the board into 1-foot lengths and add a total of 80 pieces each of 3-iodo-2-propynyl-n-into artificial seawater or seawater.
It was placed in a bucket containing either a saturated solution of butyl carbamate. After 5 days, the boards were opened with a hammer and chisel. In the control product without carbamate, 5 caterpillars were alive, but in the control product containing carbamate saturated solution, all 7 caterpillars were dead. Example 11 A total of 100 Limnolia were removed from culture and placed in each 500 ml beaker. The beaker was filled with 0% Oaksbury Bay seawater (control with acetone).
1, 5, 10, 25 and 50 ppm of 3-iod-2
-Propynyl-n-butyl carbamate was added. The beakers were examined after 24, 48, and 96 hours to count the number of dead Limnolia. The values were examined statistically and the LC50 was calculated to be 18.6 ppm with a 95% confidence limit of 16, 86 to 20, 59 ppm. The result is:

[Table] Example 12 Three species of snails were obtained from the natural science facility in Ward. The two species are of the genus Ampuraria (Ward No. 87
W4121) and Planorbis (Ward's No.87
W4161) and one species was not identified. (Ward No.87 W4101). Three snails were used for each test in aqueous 3-iodo-2-propynyl-n-butyl carbamate solution. Test concentrations are carbamate 0 (distilled water control product), 5, 10, 15, 20,
and 25ppm liquid. When snails were placed in the test solution for 24 hours, all snails survived at 0 and 5 ppm carbamate. carbamate
At 10 ppm and above, all snails died. The following compounds were found to be approximately as toxic as Ward's No. 87 W4101: 4-iodo-3-butynyl methyl carbamate 3-iodo-2-propynyl cyclohexyl carbamate 3-iodo-2-propynyl-n- Octyl Carbamate 3-iodo-2-propynyl-phenyl Carbamate 3-iodo-2-propynyl-4-chlorophenyl Carbamate di(3-iodo-2-propynyl) 4',4'-
Diphenylmethane carbamate 3-iodo-2-propynyl benzyl carbamate. Example 13 Two 5-gallon tubs were enclosed and divided vertically into two halves. Half of the first tub was painted with an unprotected oil alkyd paint, and half of the second tub was painted with the same paint. The other half of the tubs were each coated with the above paint containing the equivalent of 6 pounds of 3-iodo-2-propynyl-n-butyl carbamate per 100 gallons of this paint. The paint was allowed to dry for 4 days. The tubs were filled to about 2/3 with water and 10 planorbis snails were released into each tub.
Snails were obtained from the Ward Natural Science Facility, Lochiester, New York. I kept the snails in a bucket overnight and examined their distribution. In the tub that did not contain carbamate, the snails were randomly distributed between the coated and uncoated surfaces. In the tub coated with carbamate-containing paint, the snails exhibited repellent responses and avoided the carbamate-containing paint. They found only the unpainted side of the tub. This example shows that carbamate materials are repelled by snails and are useful as such in membrane and resin compositions. Example 14 Freshwater mussels (Unio spp.) were obtained from the Ward Natural Science Facility. The experimental procedure was as described in Example 1, except that sand was used as the bottom material and fresh water was used instead of seawater. Mussels show a repellent response and close their shells to remove carbamates.
It was able to survive for 24 hours even at 100ppm. Example 15 Total volume of 100 ml of 3-iodo-2-propynyl-
Boofura was placed in an aqueous n-butyl carbamate solution. Boofura in a solution with a concentration of 8ppm (8μg/ml)
Died within 24 hours. The pigeons survived in the lower concentration solution and the control solution. Example 16 The sensitivity of the tunicate Stiera partita to carbamates was tested as described in Example 1.
Stiera partita was obtained from Cape Huia Biological Supply Company. The lowest concentration at which animals died was 25 ppm. Tunicates are usually classified as urochordates, which are considered lower vertebrates rather than invertebrates. Example 17 A 3-iodo-2-propynyl-n-butyl carbamate congener was tested on Acorn barnacles belonging to the species Balanus evernius, commonly referred to as Iveolive barnacles. The method of use was as described in Example 1, and the results are shown in the table below.

TABLE The above examples encompass a wide range of aquatic pests known to be associated with both biofouling and/or wood destruction in saltwater environments.
The organisms killed were generally sessile pests. The potentially desirable motile invertebrates were repelled by the 1-halogen-substituted alkyne urethane. However, as a result of this avoidance response, undesirable organisms are also repelled, thereby protecting the surface from this undesirable destructive activity. This coating is in no way limited to the invertebrates described in the examples above. This range of activity indicates that many other invertebrates can be suppressed by the use of 1-halogen-substituted alkynes in urethanes. The present invention is also expected to encompass the control of lower vertebrate pests that are often colonized and included in biofouling. For example, Example 10 contains actual experimental results clearly demonstrating the activity of 1-halogen-substituted alkyne urethanes on this group. The anthelmintic toxic solutions used in these experiments were made in one or two ways. The first method is the compound 0.100PH
was dissolved in distilled water in a 1000 ml volumetric flask, and the mixture was diluted with water to a fixed amount. This liquid is a compound
Contains 100ppm and was later diluted. The second method is carried out by dissolving 1.00 g of the compound in acetone in a 100 ml volumetric flask to obtain a solution containing 10,000 ppm of the compound.
Dilutions were made in either fresh or seawater as necessary and indicated. When using the second method to prepare test solutions, appropriate control solutions containing the same amount of acetone were used.

Claims (1)

[Claims] 1 Formula: (In the formula, R has 1 to 20 carbon atoms, and m and n
represents a group selected from the group consisting of substituted or unsubstituted alkyl, aryl, aralkyl, alkaryl and cycloalkyl groups having 1 to 3 bonds corresponding to , and m and n represent integers of 1 to 3. (can be the same or different)
-A repellent, suppressor or exterminator for aquatic invertebrates containing a urethane of a halogen-substituted alkyne as an active ingredient.