JPH0140801B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an agricultural and horticultural fungicide containing an N-methylbenzyl-haloacetamide derivative as an active ingredient. More specifically, the present invention is based on the general formula [] [In the formula, R is a hydrogen atom or a methyl group,
represents a chlorine atom, bromine atom or iodine atom, Y
represents a methyl group, a methoxy group, a fluorine atom or a bromine atom. ] This is an agricultural and horticultural fungicide characterized by containing the N-methylbenzyl-haloacetamide derivative shown below as an active ingredient. In recent years, the simplification of work has become an extremely important factor due to the work situation in agriculture. In agriculture, which protects useful crops from diseases, there is a need for the development of drugs that can reduce the number of applications, that is, have a high residual effect over a long period of time after a single application, and that can simplify the application method. Furthermore, environmental pollution caused by agriculture has become an important issue, and it is well known that agriculture that is low in toxicity to humans, livestock, and fish and that decomposes quickly is in great demand. Taking the above points into consideration, the present inventors conducted repeated research and found that the compound represented by the general formula
For example, it has a strong bactericidal effect against algal fungi, ascomycetes, basidiomycetes, deuteromycetes, and other bacteria, and is especially effective against blast disease, which is an important disease of rice.As a result of further studies, The present invention was completed based on the discovery that it also exhibits a long-term residual effect that is not found in known blast fungicides. 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 to fish such as carp and Japanese medaka, is extremely low, and it can be said that there is almost no residue in crops. The compound represented by the general formula [] is conceptually included in the general formula described in JP-A No. 56-26853, but there is no example of this compound in that document, and it is used in agriculture and horticulture. There is also no mention of its usefulness as a disinfectant. Also, JP-A-54
Publication No. 5005 describes α-halocarboxylic acid derivatives whose structure is somewhat similar to the compound used in the present invention as a wood preservative. However, as shown in the Examples, the compound used in the present invention has far superior efficacy as an agricultural and horticultural fungicide than the compound described in the above-mentioned publication. In the present invention, preferable synthetic or agricultural and horticultural disinfectants are those in which R in the general formula [] is a hydrogen atom, X is a chlorine atom or a bromine atom,
Y is a methyl group, a methoxy group or a bromine atom. Particularly preferred are those in which R is a hydrogen atom, X is a bromine atom, and Y is a 4-methyl group, 4-methoxy group, or 4-bromine atom. Further, the compound used in the present invention has an asymmetric carbon in the acid site and the amine site, and there are a total of four types of isomers, and it goes without saying that these are also included in the present invention. A compound represented by the general formula [] is a compound represented by the general formula [In the formula, Y represents the same meaning as above. ] The methylbenzylamine derivative represented by is mixed with a suitable solvent such as hydrocarbons such as benzene, toluene, xylene, chlorobenzene, methylene chloride,
Halogenated hydrocarbons such as chloroform and carbon tetrachloride, 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, and acetic acid. Dissolve or suspend in esters such as ethyl, nitriles such as acetonitrile, dimethyl sulfoxide, dimethyl formamide, water, etc., or without a solvent, preferably in benzene, to give an amount of 0.4 to 1.5 equivalents, preferably is 0.5~1.1
General formula for equivalent weight [In the formula, R and X have the same meanings as above. ] Add the haloacetic acid derivative shown in or its reactive derivative. Alternatively, the reaction may be carried out by dissolving or suspending the haloacetic acid derivative represented by the general formula [] or its reactive derivative in the above-mentioned solvents, or by adding the methylbenzylamine derivative represented by the general formula [] without a solvent. is also possible. 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. 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, phosphorus chloride, in the case of the corresponding carboxylic acid, etc. Thionyl, sodium hydroxide, potassium hydroxide, sodium ethylate, sodium methylate, triethylamine,
Pyridine, quinoline, isoquinoline, N,N-
Dimethylaniline, N,N-diethylaniline,
In the case of the corresponding acid chloride or acid bromide such as N-methylmorpholine, 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 0.95 to 1.1 The reaction can be carried out with or without equivalent amounts. After the reaction is completed, the reaction aid or its reaction product is removed by filtration or washing with water, and the solvent is distilled off to obtain the desired compound. When the compound represented by the general formula [] is used as a fungicide for agricultural and horticultural purposes, it may be used as a raw material or in the commonly used forms, such as powders, granules, fine granules, and hydrated agents, suspensions, emulsions,
Any formulation form such as an oil solution can be used. The compound of the present invention in each formulation form has a weight ratio of 0.1
It can be blended in a range of 99.9%, preferably 0.2 to 80%. When applying the agricultural and horticultural fungicide of the present invention, the amount of active ingredient is 10 per 10 ares.
g to 1000 g. The carrier used in the present invention may be either solid or liquid. Solids include vegetable 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), paper, Furugire), crushed synthetic resins, clays (e.g. kaolin, bentonite, acid clay),
Fine powders or powders such as talc, other inorganic minerals (e.g. pyrophyllite, sericite, pumice, sulfur powder, activated carbon), fine powders of chemical fertilizers (e.g. ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride), etc. I can give it to you. 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),
Examples include esters, nitriles, acid amides (eg, methylformamide, dimethylacetamide), and halogenated hydrocarbons (eg, dichloroethane, trichloroethylene, carbon tetrachloride). Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, and polyhydric alcohol esters. Further, as fixing agents and dispersing agents that can be used in the present invention, casein, gelatin, starch powder, CMC, gum arabic, alginic acid, lignin sulfonate, bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc. can be,
Examples of the stabilizer include PAP (isopropyl phosphate), TCP (tricresyl phosphate), tall oil, epoxidized oil, various surfactants, and various fatty acids or esters thereof. 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 methylarsonate, 1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 1,2-bis(3-methoxycarbonyl-2-thioureido)benzel, 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-penten-3-ol, 4-chloro-
3-Methylbenzothiazolone, S-normal-butyl-S-paratertiary-butylbenzyldithiocarbonimidate, 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
-Dithiolane-2-ylidenemalonate, O,O
-Dimethyl S-(N-methylcarbamoylmethyl)dithiophosphate, O,O-dimethyl O-
It can be used in combination with (p-cyanophenyl)thiophosphate, ethyl p-cyanophenyl phenylphosphonothioate, 2-methoxy-4H-1,3,2-benzodioxaphosphorine-2-sulfide, etc. None of these methods will reduce 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 or fertilizers such as nematicides, acaricides, and herbicides. The present invention will be described in more detail below with reference to formulation examples, but the types and mixing ratios of additives to 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 compound (2) and 99.8 parts of clay are thoroughly ground and mixed to obtain a powder with a base ingredient content of 0.2%. When used, it may be applied as is or mixed with soil. Formulation Example 2 Emulsion If you mix 25 parts of compound (4), 55 parts of xylol and 20 parts of Solpol 1200 (registered trademark name of Toho Chemical),
An emulsion with a base agent content of 25% is obtained. When using,
It may be diluted with water or applied as is. Formulation Example 3 Wettable powder 80 parts of compound (7), 5 parts of wetting agent (alkylbenzene sulfonate type) and 15 parts of white carbon are thoroughly ground and mixed to obtain a wettable powder with a base ingredient content of 80%. When used, it may be diluted with water or mixed with soil. Formulation Example 4 Sol 25 parts of compound (7) ground to 5μ or less using a diet mill, 5 parts of a dispersant (polyoxyethylene nonylphenol ether), 5 parts of a dispersion stabilizer (carboxymethyl cellulose), and 65 parts of water are stirred. By mixing and further uniformly dispersing and mixing using a homogenizer, a sol with a base ingredient content of 25% is obtained. When used, it may be applied after diluting with water, or it may be applied as is. Next, a manufacturing example will be given as a reference example. Reference example N-(p-bromo-α-methylbenzyl)-α
-Bromo-tert-butylacetamide 200ml 4-necked flask was charged with 100ml of benzene, 2.0g of p-bromo-α-methylbenzylamine and 1.2g of triethylamine, and 2.1g of α-bromo-tert-butylacetyl chloride was added dropwise with stirring at room temperature. did.
After the dropwise addition was completed, the reaction solution was stirred for 8 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 8.2 g of the desired title compound. Examples of the compounds obtained as described above are listed in Table 1.

Table 2 Compounds used as controls for Examples are shown in Table 2.

[Table] Example 1 Rice blast control test Chemical foliar application test (preventive spraying) Rice grown in 9 cm flower pots (Kinki No. 33, 4-
5 leaf stage), use a spray gun to spray 15 ml/1 of the test compound in emulsion form prepared according to Formulation Example 2 above.
Sprayed at the rate of 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 3. 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 x 100 (%)

【table】

[Table] * O, O-diisopropyl S-benzyl thiophosphate (48% emulsion) Example 2 Rice blast control test Chemical foliar application test (residual spraying) Rice grown in a 9 cm flower pot (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. Four days 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 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 1.

[Table] Example 3 Downy mildew control test on cucumber Foliar application test 15 ml of the test compound in the form of an emulsion prepared according to Formulation Example 2 was applied to the cotyledons of cucumber (variety: Sagami Hanshiro) grown in a 9 cm flowerpot. Sprayed at a rate of 1/1 pot. Five days after spraying, this pathogen (Pseudopernospora
The conidial liquid of M. cubensis was inoculated by spraying and left under humid conditions at 20°C for 3 days, and then left undisturbed for 2 to 3 days under fluorescent lamp illumination at 20°C to induce disease. The degree of onset of the disease is
The disease severity was determined by the percentage of lesion area, and the control effect was investigated. The results are shown in Table 5. The control value was calculated in the same manner as in Example 1.

[Table] Hydrating agent)
Example 4 Apple scab control test Apple seedlings (variety: Kunimitsu, second true leaf) grown in 9 cm flower pots were sprayed with the test compound in the form of an emulsion prepared according to Formulation Example 2 at a rate of 30 ml/pot. did. One day after spraying, this pathogen (Venturia
Inaequalis) was spray-inoculated with a spore solution at 15℃ and humidity.
Placed in a constant temperature room of 90% or higher for 3 days, then heated to 15℃
The disease was allowed to develop under fluorescent lighting for 10 days. The degree of disease onset was determined by the lesion area ratio, and the control effect was examined. The results are shown in Table 6. Note that the control value was calculated in the same manner as in Example 1.

[Table] Agent)

Claims (1)

[Claims] 1. General formula [In the formula, R is a hydrogen atom or a methyl group,
represents a chlorine atom, bromine atom or iodine atom, Y
represents a methyl group, a methoxy group, a fluorine atom or a bromine atom. ] An agricultural and horticultural fungicide characterized by containing the following N-methylbenzyl-haloacetamide derivative as an active ingredient.