KR960005424B1 - Agricultural composition - Google Patents

Abstract

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Description

[Name of invention]

Agricultural composition

Detailed description of the invention

The present invention provides (1) boron oxide and / or boron oxide complex, (2) 4,6-dimethyl-2- [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine or salt thereof, and ( And 3) a stabilized agricultural composition, characterized in that it is composed of an organophosphorus compound. The invention also relates to a method of making said agricultural composition.

Generally, agricultural compositions include those in which agriculturally single active ingredient efficacy is expected; Those containing two or more different agriculturally active ingredients intended to obtain a broad spectrum of antimicrobial efficacy compared to a composition comprising a single active ingredient or to save labor by simultaneously controlling various plant pests and pathogenic microorganisms. Can be classified as

In particular, agricultural compositions comprising two or more agriculturally active ingredients in combination have been widely used in the field of pesticides today. However, the period from the manufacturing process to the consumption process was too long, as can be seen in most agricultural compositions. In this case, during the storage period, the agriculturally active ingredients tend to decompose sometimes, causing them to lose their biological activity or cause phytotoxic effects.

4,6-dimethyl-2- [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine (hereinafter sometimes referred to as compound M) having the formula: Pyricularia oryzae Cavara and sesame seed It is known to have agriculturally good antimicrobial activity, in particular good antimicrobial activity, which shows a strong inhibitory effect against a broad spectrum of plant pathogens including Cochliobolus miyabeanus Drechsler (Japanese Patent Publication No. 61-21551, USP No. 4341782, Taiwan Patent No. 15338, Korean Patent Nos. 19952 and 19953, EPC 19450).

O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphothioate (hereinafter, sometimes simply MEP) having the following formula for the control of rice extinction and chiro suppressalis walker Several organophosphorus compounds have been commonly used.

However, an agricultural composition containing both compound M and an organophosphorus compound such as MEP, and having a practically useful anti-foil fever and anti-leaf spot disease effect and control effect against Chiro suppressalis Walker, anchovy, stink bug, etc. Nothing is known about.

Moreover, in the agricultural composition containing compound M and the organophosphorus compound, two component compounds influence mutual stability.

On the other hand, there has been a continuing strong demand for the development of compositions which exhibit the biological activity of two-component compounds containing pesticidal organophosphorus compounds such as Compound M and MEP which have excellent anti-febrile action.

However, the inventors have found that mixing the organophosphorus compound with compound M results in the decomposition of the two active compounds, and compositions containing both components do not exhibit biological activity during long-term storage. As shown in the reference example described later, it is found that the aging of the organophosphorus compound is particularly remarkable.

In addition, although isopropyl acid phosphate and fatty acids are known as stabilizers of organophosphorus compounds, the addition of such conventional organophosphorus compound stabilizers does not help any stability of the composition (Reference Examples 2 and 4-13). The addition of strong acids, such as sulfonic acid compounds, can prevent the decomposition of organophosphorus compounds, but compound M decomposes substantially and loses its activity (Reference Example 3). Thus, there have been such problems to be solved.

It is an object of the present invention to provide a highly stabilized agricultural composition containing Compound M or a salt thereof and an organophosphorus compound, wherein the decomposition of the bicomponent compound is inhibited to the maximum extent possible.

The present inventors have conducted intensive studies to overcome the above-mentioned problems and to provide a stable agricultural composition comprising these two compounds M and organophosphorus compounds. This study has yielded unexpected results that the degradation of organophosphorus compounds can be specifically inhibited by incorporating boron oxide or boron oxide complex into a composition containing organophosphorus compound and compound M without involving decomposition of compound M.

Therefore, the present invention relates to a stable agricultural composition composed of (1) compound M or a salt thereof, (2) organophosphorus compound, (3) boron oxide and / or boron oxide complex.

In the agricultural composition of the present invention, the compound M useful as an active ingredient for rice blasting or the like is used by itself or in the form of a salt with an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like or an organic acid such as acetic acid, citric acid, tartaric acid or the like. Can be used. Compound M and its salts can be prepared, for example, by the method of the above-mentioned US Patent No. 44341782 (Japanese Patent Publication No. 61-21551, Taiwan Patent No. 15338, Korean Patent No. 19952 and 19953, European Patent No. 19450).

The organophosphorus compounds used according to the invention can be selected from a wide variety of species. For example, the following compounds can be used conventionally.

(1) O, O-diethyl O- (3-methyl-4-nitrophenyl) phosphorothionate (MEP)

(2) S- [α- (ethoxycarbonyl) benzyl] O, O-dimethyl phosphorothioolothionate (hereinafter sometimes abbreviated simply as PAP)

(3) O, O-dimethyl O-methylthio-m-tolylphosphorothionate (hereinafter sometimes abbreviated simply as MPP)

(4) O-ethyl S, S-diphenyl phosphorodithiolate (common name: EDDP)

(5) O-2-diethylamino-4-methyl-6-pyrimidinyl O, O-dimethyl phosphorothionate (common name: pyrimifos-methyl)

(6) S-1,2-bis (ethoxycarbonyl) ethyl O, O-dimethyl phosphorodithiolate (common name: malathion)

(7) S-2-ethylsulfinyl-methylethyl dimethylphosphothiolate (common name: ESP)

(8) S- (N-formyl-N-methylcarbamoylmethyl) dimethyl phosphorothiolothionate (common name: formomothione)

(9) S- (2-ethylthioethyl) dimethyl phosphorothiolothionate (common name: thiometone)

(10) S-[(2-methoxy-5-oxo-1,3,5-thiadiazolin-4-yl) methyl] dimethyl phosphorothiolothionate (common name: DMTP)

(11) 2,2-dichlorovinyl dimethyl phosphate (common name: DDVP)

(12) (E) -1-methyl-2- (methylcarbamoyl) vinyl dimethyl phosphate (common name: monocrotophosph)

(13) 1,2-dibromono-2,2-dichloroethyl dimethyl phosphate (common name: BRP)

(14) 2-Chloro-1- (2,4,5-trichlorophenyl) -vinyl dimethyl phosphate (common name: CVMP)

(15) 2-chloro-1- (2,4-dichlorophenyl) vinyl dimethyl phosphate (common name: dimethyl bean force)

(16) O, S-dimethyl N-acetylphosphoamidothiolate (common name: acetate)

(17) Dimethyl 2,2,2-trichloro-1-hydroxyethyl phosphonate (common name: DEP)

Among the organophosphorus compounds described above, a dimethyl phosphate compound having the following partial structural formula is suitably used in the present invention.

In addition, O, O-dimethylphosphorothionate compound having the following partial structural formula:

O, O-dimethylphosphorothiolothionate compound having the following partial structural formula:

Particularly advantageously used in the agricultural composition of the present invention in view of the stabilization efficiency by boron oxide and / or boron oxide complex. Therefore, the above-described MEP, PAP, MPP and the like are suitably used.

However, the organophosphorus compound used in the present invention is not limited to the above-mentioned kind.

The ratio of organophosphorus compound: compound M is in the range of about 2: 1-1: 5 by weight, preferably in the range of about 2: 1-1: 2 by weight.

The boron oxide composite that can be used in the present invention can be, for example only B ₂ O ₃ -Al ₂ O ₃ or B ₂ O ₃ -TiO ₂ . The ratio of boron oxide or its complex: compound M or salt thereof is in the weight ratio range of about 20: 1-1: 10, preferably in the range of about 10: 1-1: 4 weight ratio.

It is an object of the present invention to provide a method for producing a stabilized agricultural composition.

Agricultural compositions according to the invention may be prepared according to conventional procedures.

According to the method for preparing a stabilized agricultural composition, the composition comprises the above-mentioned constituents, namely (1) Compound M or salts thereof, (2) organophosphorus compounds and (3) boron oxide and / or boron oxide complex And, if desired, (4) mixing the carriers, if desired, by pulverizing the mixture and converting the mixture into solid preparations such as powders, wettable powders, emulsifiable concentrates, fine granules, granules and the like. It can be prepared by formulating according to. Examples of solid preparation carriers include vegetable powders (e.g. soybean powder, tobacco powder, flour, sawdust), mineral powders (e.g. clay such as kaolin, bentonite, acid clay, etc. Talc and: diatomaceous earth (e.g., silica, such as radiolite), mica powder, and the like), calcium carbonate, sulfur powder, activated carbon and the like. Such carriers may be used alone or in combination.

In such a production method, an appropriate amount of an antioxidant (for example, dibutylhydroxytoluene, 4,4'-thiobis-6-t-butyl-3-methyl-phenol, etc.), a dispersant (for example, ethylene Glycols, glycerin, etc.), surfactants (eg, ligninsulfonates, alkylbenzenesulfonates, polyoxyethylene alkylaryl ethers, alkylnaphthalenesulfonates, etc.), flow aids (eg, white carbon, etc.), preservatives, Synergists and the like can be incorporated. In the case of powder, for example, a fluid-free powder (DL powder) can be made by incorporating another additive (for example, liquid paraffin) that exhibits a flow reducing effect.

In addition to the above-mentioned 4,6-dimethyl-2- [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine or salts thereof and organophosphorus compounds, other agriculturally active substances are incorporated into the agricultural composition of the present invention. Can be. As such other agriculturally active substances, insecticides (eg 2-secondarybutylphenyl-N-methylcarbamate (BPMC, phenobucarb), captal, benzel tower, etc.), fungicides [eg 4,5 , 6,7-tetrachlorophthalide (phthalide), blastosidine S benzyl aminobenzenesulfonate, 3'-isopropoxy-2-methylbenz anilide, validamycin A, tricyclazole, etc.] This may be incorporated in an appropriate amount that does not adversely affect the effects of the present invention. For example, above all, Compound M exhibits potent inhibitory and therapeutic activity against Pyricularia oryzae, phthalides and Chilo suppressalis Walkers, extinct, etc. By using a combination of excellent MEP for the control of the agricultural composition can be provided that enables excellent simultaneous control against pests and pathogens and their diseases. Moreover, in the present invention, the addition of BPMC effective against extinction and larvae to the compound M, phthalide and MEP combinations above yields a very stabilized agricultural composition exhibiting a broad spectrum of pesticidal and bactericidal spectra.

When the composition is formulated with a carrier and other component materials, the preferred proportion of compound M, based on 100 parts by weight of the composition, is about 10-90 parts by weight for emulsifiable concentrates or wettable powders, and for oil preparations and powders. About 0.0001-50 parts by weight, and about 0.1-50 parts by weight for granules. In the case of powder, it is more effective when there are many ratios of about 0.001-20 weight part. However, these ratios are not necessarily critical.

Emulsifiable concentrates and wettable powders are preferably diluted (e.g., 50-5000 times) with a diluent such as water when in use. The present invention comprises 4,6-dimethyl-2- [1- (o-zolyl) -1-ethylidenehydrazino] pyrimidine or salt thereof, organophosphorus compound, boron oxide and / or boron oxide complex and carrier The present invention relates to a method for controlling pests and pathogens against rice in rice fields, which is composed of spraying a stabilized agricultural composition on rice fields.

The optimal amount of active compound, the combination with other active agents, the proportion thereof, etc. depend on the condition and growth stage of the crop to be protected, the type of disease to be controlled, the prevalence, the season of use and the usage. Generally speaking, however, the recommended dosage of the active compound (compound M plus the organophosphorus compound) is about 1-300 g per 10 ars of rice. As for the concentration used, the concentration of the active compound should be in the range of 10-1000 ppm. As a use method, spraying, spraying, sprinkling, powder coating to a seed is mentioned. If stability to the crop is to be ensured, the present invention is independent of the dose, the concentration used or the method of use.

The agricultural composition of the present invention comprising boron oxide or a composite thereof as a stabilizer is highly stable. More specifically, for example, as evident from the stability test data below, the degradation of the agriculturally active ingredients of the composition is significant compared to that of compositions containing any conventional stabilizer such as isopropyl acid phosphate and linoleic acid. Is suppressed. Therefore, even after long-term storage, the composition of the present invention exhibits excellent activity, that is, the organophosphorus compound in the composition is protected without degradation and maintains high insecticidal action, and other components 4,6-dimethyl-2- [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine is also intact and protected to maintain antifebrile and antispot disease activity. The following examples and reference examples are intended to illustrate the invention in more detail, and are not intended to limit the invention. In the examples described below, "parts" mean "parts by weight".

Example 1

2 parts compound M, 3 parts MEP, 0.5 parts tricyclazole, 10 parts boron oxide and 84.5 parts clay are weighed and mixed in a ceramic mortar. The whole amount is mixed again in a flash mixer to produce a powder.

Example 2

Using 2 parts of compound M, 3 parts of MEP, 1.5 parts of phthalide, 5 parts of boron oxide, and 88.5 parts of clay, the procedure of Example 1 was followed to yield a powder.

Example 3

2 parts of compound M, 3 parts of MEP, 10 parts of boron oxide-aluminum oxide composite, 85 parts of clay are weighed and mixed in a ceramic mortar. The whole amount is remixed in a flash mixer to produce a powder.

Example 4

2 parts of compound M, 3 parts of MEP, 10 parts of boron oxide-titanium dioxide composite, 85 parts of clay are weighed and mixed in a ceramic mortar. The whole amount is remixed in a flash mixer to produce a powder.

Example 5

2 parts of compound M, 3 parts of MPP, 5 parts of boron oxide, and 90 parts of clay are weighed and mixed in a ceramic mortar. The whole amount is remixed in a flash mixer to produce a powder.

Example 6

2 parts of compound M, 3 parts of PAP, 5 parts of boron oxide and 90 parts of clay are weighed and mixed in a ceramic mortar. The whole amount is remixed in a flash mixer to produce a powder.

Example 7

2 parts of compound M, 3 parts of MEP, 1.5 parts of phthalide, 10 parts of boron oxide, 5 parts of white carbon, 0.5 parts of isopropyl acid phosphate and 76 parts of clay are weighed and mixed in a ceramic mortar. The whole amount is remixed in a flash mixer to produce a powder.

Example 8

15 parts Compound M, 15 parts MEP, 10 parts phthalide, 10 parts boron oxide, 10 parts BPMC, 10 parts Newkalgen NV 410, 20 parts white carbon, 0.5 parts surfactant STP-800, 1.5 parts Dikssol WK, Radiolite # 200 Eight parts are weighed and placed in a ceramic mortar and mixed.

The whole amount is ground with a mill having a screen-diameter of 1 mm to obtain a wettable powder.

Example 9

15 parts of compound M, 20 parts of MEP, 15 parts of boron oxide, 20 parts of white carbon, 14 parts of Newkalgen NV 410, 0.5 parts of surfactant STP-800, 1.5 parts of Dikssol WK, 14 parts of Radiolite # 200 are weighed and mixed in a ceramic mortar . The whole amount is pulverized by a screen-diameter 1 mm mill to obtain a wettable powder.

The surfactants STP-800, Dikssol W-K, Newkalgen, Radiolite # 200 used in the above examples are as follows:

Surfactant STP-800 (nonionic surfactant, commercially available from Sanyo Chemical Industries).

Dikssol W-K (anionic surfactant, commercially available from Dai-Ichi Koqyo Seiyaku).

Newkalgen (nonionic surfactant, commercially available from Takemoto Oil and Fat Company).

Radiolite # 200 (diatomaceous earth, commercial item of Showa Chemical).

Reference Example 1

2 parts compound M, 3 parts MEP and 95 parts clay are weighed and mixed in a ceramic mortar. The whole amount is mixed again in a flash mixer to yield a powder.

Reference Example 2

Powder is computed by performing the procedure of Reference Example 1 using 2 parts compound M, 3 parts MEP, 1 part isopropyl acid phosphate, and 94 parts clay.

Reference Example 3

Using 2 parts compound M, 3 parts MEP, 5 parts benzenesulfonic acid and 90 parts clay, powder is computed by performing the procedure of the reference example 1.

Reference Example 4

The powder is computed by performing the procedure of the reference example 1 using 2 parts compound M, 3 parts MEP, 2 parts linoleic acid, and 93 parts clay.

Reference Example 5

Using 2 parts compound M, 3 parts MEP, 10 parts boric acid, 85 parts clay, powder is computed by performing the procedure of the reference example 1.

Reference Example 6

Powder is computed by performing the procedure of the reference example 1 using 2 parts compound M, 3 parts MEP, 10 parts manganese borate (II), and 85 parts clay.

Reference Example 7

Using 2 parts compound M, 3 parts MEP, 10 parts titanium dioxide and 85 parts clay, powder is computed by performing the procedure of the reference example 1.

Reference Example 8

Using 2 parts compound M, 3 parts MEP, 10 parts nickel monoxide and 85 parts clay, powder is computed by performing the procedure of the reference example 1.

Reference Example 9

Using 2 parts compound M, 3 parts MEP, 10 parts nickel monoxide and 85 parts clay, powder is computed by performing the procedure of the reference example 1.

Reference Example 10

Powder is computed by performing the procedure of the reference example 1 using 2 parts compound M, 3 parts MEP, 10 parts calcium oxide, and 85 parts clay.

Reference Example 11

Using 2 parts compound M, 3 parts MEP, 10 parts bismuth oxide and 85 parts clay, powder is computed by performing the procedure of the reference example 1.

Reference Example 12

Using 2 parts compound M, 3 parts PAP, 1 part isopropyl acid, 94 parts clay, powder is computed by performing the procedure of the reference example 1.

Reference Example 13

Powder is computed by performing the procedure of Reference Example 1 using 2 parts compound M, 3 parts MPP, 1 part isopropyl acid phosphate, and 94 parts clay.

[Test Example]

Each 20 g of the composition prepared in Example 1-9 and Reference Example 1-13 was placed in a glass bottle, and the stopper was tightly closed and maintained at 40 ° C. for 30 days. Each composition sample was then taken out of the bottle and the amount of active material was measured by high performance liquid chromatography. Degradation rate (%) was calculated according to the following formula.

The results are shown in Table 1.

TABLE 1

Claims (14)

Agricultural composition comprising 4,6-dimethyl-2 [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine or a salt thereof, an organophosphorus compound and boron oxide and / or boron oxide complex. The compound of claim 1, wherein the organophosphorus compound has an O, O-dimethyl phosphorothionate compound having the following substructure formula (I) or an O, O-dimethyl phosphorothiolothionate having the following substructure formula (II) Agricultural composition that is a compound.

The agricultural composition according to claim 1, wherein the organophosphorus compound is O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothionate. The agricultural composition of claim 1, wherein the organophosphorus compound is O, O-dimethyl-O-o-methylthio-m-tolyl phosphorothionate. The agricultural composition according to claim 1, wherein the organophosphorus compound is S- [α- (ethoxycarbonyl) benzyl] O, O-dimethyl phosphorothiolothionate. The agricultural composition of claim 1, wherein the agricultural composition is in powder form. The agricultural composition of claim 1, wherein the agricultural composition is a wettable powder. The amount of boron oxide and / or its complex relative to 4,6-dimethyl-2- [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine or its salt is 4, Agricultural composition in the range of about 0.1-20 parts by weight per 1 part by weight of 6-dimethyl-2- (1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine or salt thereof. The amount of the compound which is organic to 4,6-dimethyl-2- [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine or a salt thereof is 4,6-dimethyl-2. An agricultural composition in the range of about 0.2-2 parts by weight per 1 part by weight of [1- (o-tolyl) -1-ethylidene hydrazino] pyrimidine or salt thereof. The amount of 4,6-dimethyl-2- [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine or salt thereof relative to the entire composition is about 0.001 per 100 parts by weight of the total composition. Agricultural composition is -50 parts by weight. The agricultural composition of claim 1, wherein the agricultural composition additionally comprises o-secondarybutylphenyl-N-methylcarbamate. The agricultural composition of claim 1, wherein the agricultural composition additionally comprises o-secondarybutylphenyl-N-methylcarbamate and 4,5,6,7-tetraphthalide. 4,6-dimethyl-2- [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine or a salt thereof; Organophosphorus compounds; Boron oxide and / or boron oxide complexes; And mixing the carrier, to produce a stabilized agricultural composition. 4,6-dimethyl-2- [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine or a salt thereof; Organophosphorus compounds; Boron oxide and / or boron oxide complex and; A compound comprising a stabilized agricultural composition containing a carrier for use in paddy fields and organophosphorus with 4,6-dimethyl-2- [1- (o-tolyl) -1-ethylidenehydrazino] pyrimidine or salts thereof A method for controlling pests and pathogens against rice in paddy fields in which the total amount of is in the range of 1-300 g per 10 paddy fields.