JPS58157708A - Safe herbicidal composition - Google Patents

Abstract

PURPOSE:A herbicidal composition, containing a compound obtained by reacting menadione hydrogensulfite with a pyridyl, pyrimidinylthiazoline or purine compound in a carbamate herbicide, and capable of suppressing the toxic action on fishes and shellfishes while retaining the herbicidal effect thereof. CONSTITUTION:A safe herbicidal composition containing a compound obtained by reacting menadione hydrogensulfite with a pyridyl compound, preferably having hydroxy or amino group substituted at the 2-position and an alkyl and/or amino group substituted at the 4- and/or 6-position, e.g. nicotinic acid, a pyrimidinylthiazoline compound, e.g. thiamine, or purine compound, e.g. adenine, in an amount of preferably 0.1-5.0wt% based on the active constituent for suppressing the toxic action of the thiolcarbamate herbicide having the hemorrhagic toxic action on fishes and shellfishes.

Description

DETAILED DESCRIPTION OF THE INVENTION Paddy field herbicides have been used since the 1960s, and since then their herbicidal spectrum and acute toxicity to fish and shellfish have been improved. However, as rice field herbicides have rapidly become popular in recent years, they are temporarily used over a wide range of areas, so herbicides remain in the soil for quite a long time in the same water system of the rice field where they are used, albeit at low concentrations. It has been pointed out that the chronic effects on aquatic animals cannot be ignored because they persist in water. For example, among various herbicides, molinate (S-ethylhequinahydro IH-azepine-1-carbothio-1.), a thiol carbamate herbicide, is one of them, and its acute toxicity to carp (
48-hour T L m = 48-hour half-lethal concentration) is 3
4 p p IT+, and has been evaluated as one of the safest agricultural chemicals. However, the half-lethal concentration in the #&21-day long-term exposure test (subacute fish toxicity test) is said to be approximately 0.2 ppm, which is considered a problem. The cause of death due to long-term exposure is believed to be hemorrhagic anemia due to various disorders of the crocodile capillaries. (197
March 12, 2007 Fish Disease Research Colloquium, Fish Disease Symposium Abstracts P2-3).

On the other hand, looking at Japan's agricultural system, most farmers are part-time farmers, so there is a need for labor savings, and the role of agricultural machinery, pests, and weed control in today's farming operations is important.

Conventionally, vitamins such as vitamin P have been used as preventive and therapeutic agents for hemorrhagic diseases in the pharmaceutical industry and the poultry feed industry.

As an example of application to fish, there are three types of vitamins in the group.
It has been reported that adding molinate to feed can suppress hemorrhagic anemia and mortality caused by molinate.

(Mie University Fisheries Research Institute Report No. 5 P129-153 19
1978). There are also vitamin groups (Ki, 3. and 5.
Menasotone, 2-methyl-1,4-naphthoquinone oxide, menadione bisulfite alkali metal salt) are directly introduced into the carp farm (JP-A-56104805), or menadione bisulfite alkali metal salt (hereinafter abbreviated as MSB) is used for weeding. Method of blending into a drug (Japanese Patent Application Laid-open No. 56-6390
5) has been proposed.

The fate of the active ingredients of sprayed herbicides in the natural world is extremely complex, but broadly speaking, soil adsorption at the spraying point, absorption by plants, metabolic decomposition, biodegradation by microorganisms, and chemical reactions. decomposition, photodecomposition by sunlight, volatilization into the atmosphere, and runoff into rivers and oceans. Although most of the herbicide disappears due to natural purification near the spraying point, some of it disappears due to surface runoff from rainfall, overflow of rice fields, and water leakage, regardless of whether it is applied to non-agricultural land, fields, or rice fields. It is thought that these substances may travel through agricultural waterways, rivers, etc. to reservoir ponds, aquaculture ponds, or the ocean, where they may have an impact on aquatic animals.

As a practical method for suppressing the harmful effects of such herbicide components, we investigated a method of incorporating harmful effect suppressing substances into herbicidal compositions. In this case, in order to achieve the objective, the compounded harmful effect suppressing substance must not be decomposed until the herbicide is used and must coexist with the herbicide component. Among the harmful effect suppressing substances that have been disclosed so far, MSB, which is incorporated into herbicide compositions, is quite unstable;
It was difficult to store the formulation for long periods of time.

Therefore, the present inventors investigated compounds derived from menadione, and found that the compound obtained by reacting menadione bisulfite with pyridyl, pyrimidinyl, thiazoline, or purine compounds has a specific resistance to thiol carbamate herbicides. The present invention was completed based on the discovery that these compounds have high stability in formulations, and that by incorporating them into thiol carbamate herbicides, it is possible to maintain the herbicidal effect while suppressing harmful effects on seafood.

The present invention combines a compound obtained by reacting menadione bisulfite with a pyridyl, pyrimidinyl, or thiazoline purine compound to a thiol carbamate herbicide that has a hemorrhagic harmful effect on seafood.
This is a thiol carbamate herbicide composition that is highly stable, maintains herbicidal effects, and has suppressed harmful effects on seafood.

The thiol carbamate herbicide of the present invention is a herbicide having a hemorrhagic harmful effect on seafood such as molinate (S-ethyl-hexahydro-I H-azebin-1-carbothioate).

Menadione bisulfite and pyridyl used in the present invention,
The compound obtained by reacting with a pyrimidinyl or purine compound is an aqueous solution of menadione bisulfite with an alkali metal salt, such as sodium chloride, lithium, potassium, etc., and a pyridyl compound, such as nicotinic acid, nicotinamide, or a pyrimidinyl compound, such as dimethylpyridine. A compound obtained by mixing midinol, diaminopyrimidinol, a thiazoline compound such as thiamine, a purine compound such as adenine, etc. with a hydrochloric acid solution in a conventional manner, filtering and drying the precipitate, and comprising menadione sulfite. Hydrogen nicotinamide (hereinafter abbreviated as MNB), menadione bisulfite dimethylpyrimidinol (hereinafter abbreviated as MPB)
, menadione hydrogen sulfite adenine, etc. (for example, US Pat. No. 3,328,169, JP-A-5
5-27180, etc.), and MNB, MPB, etc. are copper,
It can also be used in combination with organic/inorganic hematopoietic agents such as iron, microvascular strengthening agents such as rutin and reserpine, blood pressure lowering agents, analgesics, etc.

The herbicide composition of the present invention is formulated by blending the above-mentioned menadione bisulfite derivative, which is the harmful effect suppressing substance of the present invention, with the pesticide active ingredient in the process of manufacturing general pesticide formulations, and is then formulated into a suitable formulation such as granules or powders. It can be made into a dosage form.

The amount of the menadione bisulfite derivative is generally about 0.01 to 20% by weight, preferably 0.1 to 20% by weight based on the active ingredient.
It is 5.0% by weight.

Next, examples of the present invention and test examples showing the effects thereof will be given.

Example 1 Method for producing a preparation containing menadione bisulfite derivative Sodium alkylbenzenesulfonate 5g 1 clay 500
g and 480 g of bentonite were uniformly mixed, an aqueous solution of 15 g of calcium lignin sulfonate dissolved in 200 rr+j2 of water was added thereto, the mixture was kneaded, and the mixture was extruded through a screen with a pore diameter of 1 to form granules. After grading and drying, use a sieve to remove 0.
Base grains were obtained by adjusting the grain size to a range of 5 to 1.2 mm. 24.7 g of molinate to 2.75 g of base grain.

Molinate granules (sample A) were obtained by impregnating and coating with 0.3 g of MPB. Similarly, a molinate granule of the present invention (sample B) containing MNB instead of MPB was obtained.

Example 2 Storage stability test of menadione bisulfite derivative in formulation Sample A of the herbicide composition of the present invention manufactured according to Example 1
and B. As a control, MSB was used instead of MPB in Example 1.
A molinate granule (sample C) blended with the following and a molinate granule (sample D) produced in the same manner as in Example 1 without the addition of an adverse effect inhibitor were manufactured, and for each sample, the following The test was conducted.

Samples A, B, and C were placed in a 100 m 11 wide-mouth amber bottle, sealed tightly, and placed in a constant temperature bath at 40° C. for 30 days to conduct an abuse test. Sampled on 15th day 1.30th day 1,
The menadione content in the formulation was measured according to the method specified by the Ministry of Agriculture, Forestry and Fisheries (Feed Additives Ingredient Standards, 1st Edition, published March 25, 1980).

The results are shown below.

Table 1/ρ Menadione sulfite derivatives (MPB, M
NB) has been shown to be more stable than conventional menadione sulfite (MSB).

Example 3 Fish toxicity test of a preparation containing menadione hydrogen sulfite derivative etc. 6 g each of test samples A and B of the present invention produced according to Example I and test samples C and D produced as controls were added to 11 g of water.
In addition, the mixture was stirred and suspended to obtain a stock solution for fish toxicity testing. When this stock solution is diluted 1000 times, the concentration of molinate in water will be 0.5 ppm, and the concentration of menadione hydrogen sulfite derivative etc. in water will be 5 ppm. Prepare five 50β test tanks made entirely of glass, fill each of the four tanks with 5mA of the above stock solution for fish toxicity test, add water, and test 50I! The remaining one was used as a blank test by adding only water and 50β. After adjusting the water temperature in each tank to 25°C, the test fry (
Body length: 5cm.

Fifteen (15) young carp (weighing 3 g) were placed in each pot. The water in the tank is 1
The entire amount was replaced twice a week, and the water temperature was maintained at 25°C ± 1°C during the test period.

The test period was 21 days, during which time pellet-shaped feed (manufactured by Nisshin Seifun fil [compound feed for carp breeding - Mizuha breeding Yo 4]) was given in an amount equivalent to 0.5% of body weight. Mortality rate and hematocrit value (hereinafter abbreviated as "H") were used to judge the effectiveness in the fish toxicity test. Here, the hematocrit value is a term used in clinical tests, etc., and is the volume percentage of red blood cells in the blood, and a value of 20 or more has been proposed as a normal value for fish. Next, the test results are shown.

/2 Table 2/This shows that the fish toxicity of molinate can be reduced by incorporating tumenadione bisulfite derivatives etc. into molinate preparations.

Example 4 Molinae containing a menadione hydrogen sulfite derivative; Fish toxicity test using the formulation that was subjected to the abuse test Example 3 A fish toxicity test was conducted in the same manner. The results are shown below.

/q Table 3/ The products of the present invention (specimen A, B) are the conventional disclosed products (specimen C)
Or it shows that it is superior to additive-free (sample D).

Example 5 Medicinal efficacy/toxicity test The sample used in Example 4 was 115,000 Wagnerbo,
Tests on phytotoxicity and medicinal efficacy were conducted on paddy rice and Novieum, a paddy field weed, using the same method. Samples A and B were equivalent to sample D (conventional product), and no problems were observed. Ta.

As shown in the above examples, the MPB according to the present invention,
It is clear that MNB and the like have higher stability in products than conventionally disclosed MSB and the like, and therefore have a superior fish toxicity reducing effect.

Patent applicant: Mikasa Chemical Industry Co., Ltd. Agent: Ito Okimo (2 idiots) /・to

Claims (1)

[Claims] 1. A compound obtained by reacting menadione bisulfite with pyridyl, pyrimidinylthiazoline, or a purine compound is blended into a thiol carbamate herbicide that has a visible harmful effect on fish and shellfish. A safe herbicide composition. 2. The herbicidal composition according to claim 1, wherein the pyridyl compound is nicotinic acid or a derivative thereof. 3. The weed killer according to claim 1, wherein the hyrimidinyl compound is substituted with a hydroxy group or an amino group at the 2-position, and an alkyl group and/or an amino group at the 4-position and/or the 6-position. agent composition. 4. The herbicidal composition according to claim 1qi, wherein the thiazoline compound is thiamine. 5. The herbicidal composition according to claim 1, wherein the purine compound is adenine.