JPS6340164B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to molluscicides, particularly to synergistic molluscicide mixtures that suppress mollusc growth and life. Many terrestrial and aquatic mollusks, including snails and slugs, pose economic and sanitary problems throughout the world. Snails belonging to the class Gastropoda, which includes both shelled and shellless snails, are extremely harmful to plants as they devour a wide variety of useful agricultural plants. Even more harmful is the role they play in the life cycle of many tropical and subtropical infectious diseases. Millions of people and countless animals in all parts of the world are suffering from this epidemic. Snails play an important role in the growth cycle of the parasites involved in this infectious disease. The larval stage of the parasite develops and emerges with the snail. The larvae enter warm-blooded animals where they mature into adults. The adult worms in turn lay eggs, which are carried by the bloodstream to organs that are absolutely necessary for sustaining life within the animal body. Finally, the egg finds its way back to the snail through the sewage and the cycle begins again. Thus one snail will become the ancestor of countless new snails each year. For example, snails of the genera Oncomelania, Australorbis and Rubinus are intermediate hosts for schistosomes. Similarly, snails of the genus Limnaea are intermediate hosts of liver flukes. These snails especially cause debilitating problems in humans. Schistosomiasis in particular has long been endemic in many parts of the world and is even on the rise. Although various methods have been proposed to eradicate schistosomiasis and other infectious diseases of this type, eradication of the intermediate host snail with toxic chemicals remains the most effective means of preventing transmission of many tropical and subtropical infectious diseases. It seems to be a quick and effective method. However, many chemicals useful for eradicating molluscs such as snails (molluscicides) have certain drawbacks. In some cases they are difficult to manufacture and in some habitats commercial compositions cannot be effectively dispersed. In other cases, the chemicals themselves are irritating and dangerous to handle, or require the use of relatively large amounts. In other cases, it is necessary to preabsorb it into soil or other organic matter. In addition, recently commercially available mollusc eradicators have high pH.
is ineffective in the environment, corrodes the device, or its activity is reduced by sunlight. Finally, some eradicators are sufficiently active but at low PH they become inactive and/or do not kill snail eggs. Therefore, there is a need for an effective mollusc killer that can directly and reliably eradicate snail eggs when applied to snails or their habitat without these side effects. According to the present invention, a neomollusc combating mixture has been discovered which exhibits synergistic activity against snails and related molluscs. Molluscs have a structure: O,O-dialkyl-O-(3
-benzothiene glyoxylonitrile oximino) phosphate with well-known molluscum-killing agents, such as 2,5-bis(1-aziridinyl)-p-benzoquinone (hereinafter referred to as ABQ), N-tritylmorpholine, nicrosamide [N-( 2′-chloro-
4'-nitrophenyl)-5-chlorosalicylamide], pentachlorophenol, triphenyltin acetate, 3,5-dibromo-N-(4-bromophenyl)-2-hydroxybenzamide, etc. with a synergistic effect. Essentially inhibited by the action of things. For the purposes of the present invention, "well-known" mollusc killers also include mixtures of the above-mentioned known substances. Mollusc eradicating activity has been recognized for all of these compounds except for . However, according to the present invention, a mixture with at least one other mollusc killer exhibits a strong synergistic effect, resulting in a more effective product for eradicating snails at low concentrations. The combined properties of the mollusc killer compositions of the present invention, including the mollusc killer compositions of the present invention, result in a more effective and complete means of killing snails and their eggs, while requiring the use of smaller amounts of each component. The neo-mollusc eradication mixture also eradicates molluscs in a very short time. Animals generally die within 24 hours after treating molluscs or their habitat with a neomollusc eradication mixture. The effect of the mixture of these two molluscum killers is therefore synergistic, making it a very practical means of mollusc eradication. The mollusc combating mixture according to the invention is very simply prepared by mixing the individual components with the desired properties.
For example, by mixing the desired amount of a second standard molluscum killer and applying the mixture to the molluscs and/or their habitat, or in a diluent or carrier in a tank or equipment for treating them. Add it. The two mollusc killers can be mixed with each other in various proportions. For example, they can be mixed in equal amounts or in ratios where one is twice or half the weight of the other. A typical example is 0.020ppm in new molluscum eradicators and other
Good results are obtained using 0.01ppm. The mixture that has generally been found to be most effective is a mixture of equal parts of and other mollusc killers. The following examples illustrate the invention and its features in various mollusk treatments. Example 1 3-Benzothienglyoxylonitrile oxime A solution of 3 g of sodium dissolved in 200 ml of ethanol was cooled with ice, and 20 g of 3-benzothiophene acetonitrile was added dropwise thereto, followed by 12.4 g of butyl nitrite. After adding 300 ml of diethyl ether over 30 minutes while stirring the mixture, the mixture was filtered.
A mixture of oxime salts (15g) was then used.
A small amount of the salt sample was dissolved in water and the solution was made acidic with 6N hydrochloric acid. The mixture was filtered, washed with water and dried. Recrystallization from benzene gave a light brown solid. melting point
142−148℃. It was identified as 3-benzothiene glyoxylonitrile oxime by trace analysis. Example 2 O,O-diethyl-O-(3-benzothiene glyoxylonitrile oximino)phosphate A mixture containing 11.15 g of 3-benzothiene glyoxylonitrile sodium salt in 100 ml of acetone was stirred and 7.74 g of diethyl chlorophosphate was added. added. The mixture was stirred for 1 hour and then evaporated to dryness in vacuo. 100 ml of water was added and the mixture was extracted several times with ether. The ether extracts were combined, washed with water, and dried over magnesium sulfate. The desiccant was removed and the solution was concentrated to dryness. Recrystallization from pentane gave 11.6 g of O,O-diethyl-O-(3-benzothienglyoxylonitrileoximino)phosphate. Melting point 70-72℃. The O,O-dimethyl, O,O-dipropyl or O,O-dibutyl congeners of this compound can be prepared in the same manner by substituting equimolar amounts of other dialkylchlorophosphates for the above diethylchlorophosphate. . Example 3 1,4-Diaziridinobenzoquinone A mixture of 50 g of cuprous acetate in 500 ml of methanol was added to ethyleneimine while keeping the mixture at 20-25°C in an ice bath.
It turned into a slurry weighing 54g. After passing air through the blue solution, a solution containing 27.0 g of 4-benzoquinone in 1000 ml of methanol was added while maintaining the same temperature. After stirring for 30 minutes, the orange product was filtered and washed with methanol and water. The product, dried in vacuum in an oven, was identified by microanalysis as 1,4-diaziridino-p-benzoquinone. Melting point 208-210°C (decomposition) Example 4 Adult and larval (A&J) or newly hatched (NH) mollusc eradication mixtures of (R=ethyl) and B. glabrata (snail) of the invention
The effects on the same structure were compared with those of related congeners with the same structure. In a number of simultaneous tests, a new mixed mollusc killer was prepared by mixing equal amounts of (R=ethyl). The water used with the test molluscum killer was dechlorinated tap water (DTW) with a pH of 7.0 and a temperature of 24°C. The tested snails were exposed to the test compounds for 24 hours, harvested for 24 hours, and then washed with DTW. The test results are as follows.

[Table] Chill)

Claims (1)

[Claims] 1 Formula: (wherein R is lower alkyl having 1-4 carbon atoms) O,O-dialkyl-O-(3-benzothienglyoxylonitrileoximino)phosphate and a well-known mollusc killer on a weight basis. A method for combating molluscs, characterized in that a composition effective for eradicating molluscs containing a ratio between 2:1 and 1:2 is applied to molluscs or their habitat. 2. The method of claim 1, wherein said ratio is about 1:1. 3. The method of claim 1, wherein said known molluscicide is 2,5-bis(1-aziridinyl)-p-benzoquinone. 4 the alkyl is ethyl and the mollusc killer is 2,5-bis(1-aziridinyl)-
The method according to claim 1, wherein the p-benzoquinone is p-benzoquinone. 5. The method of claim 4, wherein said phosphate and said benzoquinone are included in a weight ratio of about 1:1. 6 Formula as active ingredient: (wherein R is lower alkyl having 1-4 carbon atoms) O,O-dialkyl-O-(3-benzothienglyoxylonitrileoximino)phosphate and a well-known mollusc killer on a weight basis. A composition for combating molluscs, characterized in that it contains a ratio of between 2:1 and 1:2. 7. The composition of claim 6, wherein said known mollusc killer is 2,5-bis(1-aziridinyl)-p-benzoquinone. 8 The above O,O-dialkyl-O-(3-benzothienglyoxylonitrileoximino)phosphate and the above 2,5-bis(1-aziridinyl)
8. The composition of claim 7, wherein the active ingredient is in a weight ratio of about 1:1 with -p-benzoquinone. 9. A composition according to claim 8, wherein the active ingredient is mixed with a liquid or solid diluent. 10 The diluent dilutes the active ingredient mixture by 1-5
A composition according to claim 9, which is an emulsifiable concentrate containing % by weight.