JPH0140821B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an N-methylbenzyl-haloacetamide derivative, a method for producing the same, and an agricultural and horticultural fungicide containing the compound as an active ingredient. More specifically, the present invention includes (1) General formula [] [In the formula, R is a hydrogen atom or a methyl group,
X represents a halogen atom, and Y represents a cyano group or a nitro group. ] N-methylbenzyl-haloacetamide derivative represented by (2) General formula [] In the formula, R and X are as described above. ]
A haloacetic acid derivative or its reactive derivative represented by the general formula [] [In the formula, Y is as described above.] ] A method for producing an N-methylbenzyl haloacetamide derivative represented by the general formula [I], which is characterized by reacting the N-methylbenzyl haloacetamide derivative represented by the general formula [I] with a methylbenzylamine derivative represented by the general formula [] in an organic solvent; This is an agricultural and horticultural fungicide characterized by containing the following N-methylbenzyl-haloacetamide derivative as an active ingredient. In recent years, due to the working conditions in agriculture, there has been a demand for the development of chemicals that can simplify the work and can be used in all situations. For example, in terms of work simplification, we are looking for drugs that have a long-lasting and high residual effect after one application, and in terms of usage methods, we are looking for foliar applications such as powders, emulsions, wettable powders, fine granules, powders, emulsions, etc. There is a strong need for highly effective agricultural chemicals that can be applied to the water or soil using wettable powders, surface-spreading oils, granules, etc., ie, highly effective agricultural chemicals that can be used easily and in a wide variety of ways. Furthermore, environmental pollution caused by agricultural chemicals has become an important problem, and it is well known that agricultural chemicals that are low in toxicity to humans, livestock, and fish and that decompose quickly are in great demand. The present inventors took the above points into consideration and conducted repeated research, and found that the compound of the present invention represented by the general formula Fungi, Basidiomycetes,
It was found that it has strong efficacy against Deuteromycetes and other bacteria. Among these, the compound of the present invention is highly effective in controlling blast disease, which is an important disease of rice, and due to the properties of the compound of the present invention, it can be used in all situations, namely, three application methods: foliar treatment, water surface treatment, and soil treatment. They discovered that it is possible and has a high pesticidal effect. Furthermore, it was surprisingly discovered that this compound exhibits an immediate and long-term residual effect that is not found in known foliar-, water-, or soil-applied blast fungicides, and thus completed the present invention. be. This fact is completely unexpected from the action and usage characteristics of conventional blast fungicides. On the other hand, the toxicity to warm-blooded animals such as mice, rats, dogs, and chickens, as well as fish such as carp and Japanese medaka, is extremely weak, and the residue of this compound in crops can be said to be almost nil. Although the compound of the present invention is a new compound,
No. 5005 describes an α-halocarboxylic acid derivative having a structure somewhat similar to the compound of the present invention as a wood preservative. However, as shown in the following examples, the compound of the present invention has far superior efficacy as an agricultural and horticultural fungicide than the literature compound. The present invention was completed based on the above-mentioned new knowledge, and (1) relates to the N-methylbenzyl-haloacetamide derivative itself represented by the general formula [], (2) relates to its production method, and (3) ) is an agricultural and horticultural fungicide characterized by containing an N-methylbenzyl-haloacetamide derivative represented by the general formula [ ] as an active ingredient. In the present invention (1), the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
Preferred synthetic or agricultural and horticultural disinfectants are those in the general formula [] where R is a hydrogen atom, X is a chlorine atom, bromine atom or iodine atom, and Y is a cyano group or a nitro group. Particularly preferably, R is a hydrogen atom, X is a bromine atom,
Examples include those in which Y is a cyano group or a nitro group. In producing the compound of the present invention, the haloacetic acid derivative represented by the general formula [] which is the starting material is, for example, J.Am.Chem.Soc., 55 , 4209.
(1933). Furthermore, the methylbenzylamine derivative represented by the general formula [] is described in, for example, J.Am.
It can be easily synthesized by the method described in Chem.Soc., 58 , 1808 (1936). Furthermore, the compound of the present invention has an asymmetric carbon in the acid site and the amine site, and there are a total of four types of optical isomers, but it goes without saying that the present invention includes not only ceramiforms but also optical isomers. stomach. In the present invention (2), the methylbenzylamine derivative represented by the general formula [] is generally used in a suitable solvent such as hydrocarbons such as benzene, toluene, and xylene, chlorobenzene, methylene chloride, chloroform, and carbon tetrachloride. Halogenated hydrocarbons, ethers such as diisopropyl ether, tetrahydrofuran and dioxane, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, acetonitrile nitriles such as dimethylsulfoxide, dimethylformamide, preferably dissolved in benzene, to give an amount of 0.4 to 1.5 equivalents, preferably 0.5 to 1.1 equivalents of the haloacetic acid derivative represented by the general formula [] or its reactivity. Add derivative. It is also possible to carry out the reaction by dissolving the haloacetic acid derivative represented by the general formula [] or its reactive derivative in the above-mentioned solvents and adding the methylbenzylamine derivative represented by the general formula []. The reaction can be carried out at any temperature from the freezing point to the boiling point of the solvent, preferably from 0° C. to the boiling point of the solvent, and can be heated or cooled as necessary. The haloacetic acid derivatives or reactive derivatives thereof represented by the general formula [] to be used can be the corresponding carboxylic acids, acid anhydrides, acid chlorides, acid bromides, and carboxylic acid esters. ] Depending on the haloacetic acid derivative or its reactive derivative, suitable reaction auxiliaries, such as dicyclohexylcarbodiimide, phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, thionyl chloride in the case of the corresponding carboxylic acid; , sodium hydroxide, potassium hydroxide, sodium ethylate,
Sodium methylate, triethylamine, pyridine, quinoline, isoquinoline, N,N-dimethylaniline, N,N-diethylaniline, N-methylmorpholine, etc. In the case of the corresponding acid chloride or acid bromide, for example, sodium hydroxide,
Potassium hydroxide, sodium ethylate, sodium methylate, triethylamine, pyridine,
Quinoline, isoquinoline, N,N-dimethylaniline, N,N-diethylaniline, N-methylmorpholine, sodium acetate, etc., preferably triethylamine in a catalytic amount to 1.5 equivalents, preferably
The reaction can be carried out with or without 0.95 to 1.1 equivalents. After the reaction is complete, the reaction aid or its reaction product is removed by filtration or washing with water, and the solvent is distilled off to obtain the N-methylbenzyl-haloacetamide derivative represented by the general formula [] with good purity and high yield. can get. This product can be further purified by recrystallization with benzene, toluene, methyl alcohol, ethyl alcohol, chloroform, diisopropyl ether, etc. When using the compound of the present invention as an agricultural and horticultural fungicide, it may be used as a raw material or in any of the commonly used forms, such as powders, fine granules, wettable powders, emulsions, and oils. It can also be used in pharmaceutical form. The weight ratio of the compound of the present invention in each formulation is 0.1 to
It can be blended within a range of 99.9%, preferably
It is 0.2-80%. When applying the compound of the present invention,
The range is from 10g to 1000g per 10are. It is desirable to use various products as appropriate depending on their purpose. In preparing these pharmaceutical products, the carrier may be either solid or liquid. Solids include value-based physical carriers (e.g., wheat flour, tobacco stem flour, soybean flour, walnut shell flour, wood flour, sawdust, bran, bark powder,
Cellulose powder, residue after extracting plant extracts, textile products (e.g. paper, cardboard, seri), crushed synthetic resins, clays (e.g. kaolin, bentonite, acid clay) talc, other inorganic minerals (e.g. pyrophyllite, seri) Examples include fine powders or pulverulent substances such as chlorine, pumice, sulfur powder, activated carbon), and fine powders of chemical fertilizers (for example, ammonium sulfate, ammonium phosphorus, ammonium sulfate, urea, and ammonium chloride). Liquid carriers include water, alcohols (e.g. methyl alcohol, ethyl alcohol), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. ethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene). , toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, kerosene), esters, nitriles, acid amides (e.g. methylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane) , trichlorethylene, carbon tetrachloride), etc. Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, and polyhydric alcohol esters. In addition, examples of fixing agents that can be used in the present invention include casein, gelatin, starch powder, CMC, gum arabic, alginic acid, lignin sulfonate, bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc. There are stabilizers such as
Examples include PAP (isopropyl phosphate), TCP (tricresyl phosphate), tall oil, epoxidized oil, various surfactants, and various fatty acids or their esters. Furthermore, this drug can be used in combination with other drugs. For example, kasugamycin, polyoxin, validamycin, 2,6-dichlor-4-
Nitroaniline, zinc ethylene bisdithiocarbamate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate, iron methylluarsonate ,1,2-
Bis(3-ethoxycarbonyl-2-thioureido)benzene, 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene, methyl 1
-(Butylcarbamoyl)-2-benzimidazole carbamate, tetrachloroisophthalonitrile, EPN, diazinon, malathion,
BPMC, chlorphenamidine, N-(3.5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, (E)-1-
(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-benten-3-ol, 4-chloro-
3-Methylbenzothiazolone, S-Normal-Butyl-S-Balata Sharybutylbenzyldithiocarbonimidate, O,O-Dimethyl-O
-(2,6-dichloro-4-methylphenyl)phosphorothioate, DCPA, Benthiocarb,
CAT, O,O-diisopropyl S-benzylthiophosphate, O-ethyl S,S-diphenylthiophosphate, diisopropyl 1,3-dithiolan-2-ylidenemalonate, O,O-dimethyl S-(N -Methylcarbamoylmethyl)dithiophosphate, O,O-dimethyl O-(p-
cyanophenyl) thiophosphate, ethyl p-
Cyanophenyl phenyl phosphonothioate, 2
It can be used in combination with -methoxy-4H-1,3,2-benzodioxaphosphorine-2-sulfite, etc., without reducing the control effect of each single agent. Therefore, it is possible to simultaneously control two or more types of pests and weeds, and it is also possible to use it in combination with other agricultural chemicals such as nematicides and acaricides, or fertilizers. The present invention will be explained in more detail below with reference to formulation examples, but the types and mixing ratios of additives to the compounds of the present invention are not limited to these and can be varied within a wide range. The compound names are indicated by the numbers listed in the examples (Table 1) below. Formulation Example 1 Powder 0.2 parts of the compound of the present invention (2) and 99.8 parts of clay are thoroughly ground and mixed to obtain a powder containing 0.2% of the main ingredient.
When used, it may be applied as is or mixed with soil. Formulation Example 2 Emulsion 25 parts of the compound of the present invention (3), 55 parts of xylene and 20 parts of Solpol 1200 (Toho Chemical registered trademark) are mixed to obtain an emulsion with a base agent content of 25%. When used, it may be diluted with water or applied as is. Formulation Example 3 Wettable powder: 80 parts of the compound of the present invention (5), 5 parts of wetting agent (alkylbenzene sulfonate type), and white carbon
By thoroughly grinding and mixing 15 parts, a wettable powder with a base ingredient content of 80% can be obtained. When used, it may be diluted with water or mixed with soil. Formulation Example 4 Granules Spray 10 parts of the compound of the present invention (2) on 90 parts of bentonite sized to 16-32 mesh, and let it soak in for 10 parts.
Obtain % granules. When used, it may be applied after diluting with water, or it may be applied as is. Formulation Example 5 Water Surface Floating Granules 10 parts of the compound (3) of the present invention was blown onto 85 parts of pumice sized to a size of 16 to 32 meshes to soak it in, and then 5 parts of liquid balafine was blown on to soak it in, resulting in 10% floating on the water surface. Obtain type granules. When using, apply as is. Formulation Example 6 Surface-applied granules 77 parts of silica sand prepared by sizing 16 to 32 meshes of 10 parts of the compound of the present invention (1) and PVA (polyvinyl alcohol)
Mix by wiping with 3 parts of a 10% aqueous solution, add 10 parts of white carbon, and mix to obtain 10% surface-applied granules. When using, apply as is. Formulation Example 7 Granules 10 parts of the compound of the present invention (2) was mixed with 30 parts of bentonite, 1 part of calcium lignin sulfonate, 0.1 part of sodium lauryl sulfate, and 58.9 parts of clay, mixed with water, and then passed through a φ7 mm screen. Extrude, size, and dry to obtain 10% granules. When used, it may be diluted with water or applied as is. Formulation Example 8 Water surface spreading oil 1 part of the compound (3) of the present invention, 10 parts of polyoxypropylene glycol monoether and 89 parts of kerosene are mixed to obtain a 1% water surface spreading oil. When using, apply as is. Formulation Example 9 Sol Compound (2) of the present invention is pulverized with a diet mill to a size of 5μ or less, 25 parts, dispersant (polyoxyethylene nonylphenol ether) 5 parts, dispersion stabilizer (carboxymethyl cellulose) 5 parts, and water 65 parts. A 25% sol can be obtained by stirring and mixing and then uniformly dispersing and mixing with a homogenizer. When used, it may be diluted with water or applied as is. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these. Example 1 Production method N-(p-cyano-α-methylbenzyl)-α
100 ml of benzene, 2.9 g of p-cyano-α-methylbenzylamine and 3.0 g of triethylamine were placed in a 200 ml 4-necked flask containing bromo-tert-butylacetamide, and 4.3 g of α-bromo tert-butylacetyl chloride was added dropwise with stirring at room temperature. .
After the dropwise addition was completed, the reaction solution was stirred for 5 hours. After the reaction was completed, the reaction solution was washed with water to remove triethylamine hydrochloride, the benzene layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized from diisopropyl ether to obtain 4.7 g of the desired title compound. Melting point 126.5-128℃ Elemental analysis value C(%) H(%) N(%) Br(%) Calculated value 55.74 5.93 8.67 24.72 (as C ₁₅ H ₁₉ N ₂ OBr) Actual value 55.79 6.08 8.41 24.65 As above. Examples of the compounds obtained are listed in Table 1.

[Table] Compounds used as controls in Examples are shown below.

【table】

[Table] Example 2 Rice blast control test Chemical foliar application test (preventive spraying) Rice cultivated in a 9 cm flowerpot (Kinki No. 33, 4-5)
During the leaf stage), the test compound in the form of an emulsion prepared according to Formulation Example 2 was sprayed using a spray gun at a rate of 15 ml/pot. One day after spraying, the spore liquid of this pathogen (pyricularia oryzae) was spray inoculated.
The plants were placed in a constant temperature room at 24 to 26°C and a humidity of 90% or higher, and after 4 days, the disease severity was determined by the lesion area ratio and the control effect was examined. The results are shown in Table 2. The control value was calculated using the following formula. Control value = Disease severity in untreated area - Disease severity in treated area / Disease severity in untreated area × 100 (%)

[Table] Example 3 Rice blast control test Chemical foliar application test (residual spraying) Rice grown in a 9 cm flowerpot (Kinki No. 33, 4-5)
During the leaf stage), the test compound in the form of an emulsion prepared according to Formulation Example 2 was sprayed using a spray gun at a rate of 15 ml/pot. 4 days after spraying, the spore liquid of this pathogenic bacterium ((pyricuiaria oryzae)) was spray inoculated.
The plants were placed in a constant temperature room at 24-26°C and a humidity of 90% or more, and after 4 days, the degree of disease was determined by the percentage of lesion area and the control effect was examined. The results are shown in Table 3. The control value was calculated in the same manner as in Example 2.

[Table] Example 4 Rice blast control test Chemical surface application test Granule form prepared according to Formulation Example 4 on rice (Kinki No. 33, 5-6 leaf stage) submerged and cultured in a 1/5000a Wagner pot. The test compound was applied to the water surface. The granules were uniformly applied to the water surface at an amount of 500 g of active ingredient per 10 ares, and the water was kept at a depth of 4 to 5 cm in a greenhouse until inoculation with the pathogen. This pathogenic bacterium (pyricularia
oryzae) and placed in a constant temperature room at 24-26°C and a humidity of 90% or more, and after 4 days, the degree of disease was determined by the percentage of lesion area and the control effect was examined. The results are shown in Table 4. The control value was calculated in the same manner as in Example 2.

【table】

[Table] Example 5 Rice blast control test Chemical soil application test Rice grown in 1/5000a Wagner pot (Kinki
No. 33, 5th to 6th leaf stage), a test compound in the form of an emulsion prepared according to Formulation Example 2 was applied to the soil. The emulsion was diluted with water and applied uniformly to the soil surface at an amount of 500 g of active ingredient per 10 ares.
4 and 30 days after application, spray inoculation with spore liquid of this pathogen (Pyricularia oryzae),
The plants were placed in a constant temperature room at 24-26°C and a humidity of 90% or more, and after 4 days, the degree of disease was determined by the percentage of lesion area and the control effect was examined. The results are shown in Table 2. The control value was calculated in the same manner as in Example 2.

[Table] Example 6 Rice blast control test Chemical seedling box application test The above formulation example was applied to rice (Kinki No. 33, 3-leaf stage) grown in a seedling box measuring 30 x 60 x 3 (cm) in length x width x height. 50 g of the test compound in granule form prepared according to 7 was uniformly dispersed. After 24 hours of dusting, the seedlings were placed in soil (1 x 1
x 3cm) and transplanted into a 1/5000a Wagner pot with soil still attached. 45 days after transplantation, the spore solution of this pathogen (Pyricularia oryzae) was spray inoculated and placed in a constant temperature room at 24-26°C and humidity of 90% or higher.Four days later, the disease severity was determined by the lesion area ratio and the control effect was investigated. . The results are shown in Table 6. The control value was calculated in the same manner as in Example 2.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R is a hydrogen atom or a methyl group,
represents a halogen atom, and Y represents a cyano group or a nitro group. ] An N-methylbenzyl-haloacetamide derivative represented by: 2. The N-methylbenzyl-haloacetamide derivative according to claim 1, wherein R is a hydrogen atom, X is a chlorine atom, a bromine atom, or an iodine atom, and Y is a cyano group or a nitro group. 3. The N-methylbenzyl-haloacetamide derivative according to claim 2, wherein R is a hydrogen atom, X is a bromine atom, and Y is a cyano group or a nitro group. 4 General formula [In the formula, R is a hydrogen atom or a methyl group,
represents a halogen atom. ] Haloacetic acid derivative or its reactive derivative and general formula [In the formula, Y represents a cyano group or a nitro group. ] A general formula characterized by reacting a methylbenzylamine derivative represented by in an organic solvent. [In the formula, R, X and Y are as described above.] ] A method for producing an N-methylbenzyl-haloacetamide derivative represented by: 5 General formula [In the formula, R is a hydrogen atom or a methyl group,
represents a halogen atom, and Y represents a cyano group or a nitro group. ] An agricultural and horticultural fungicide characterized by containing the following N-methylbenzyl-haloacetamide derivative as an active ingredient.