JPS5810545A - N-methylbenzyl-haloacetamide derivative, its preparation, agricultural and gardening fungicide comprising it as active ingredient - Google Patents

Abstract

NEW MATERIAL:An N-methylbenzyl-haloacetamide derivative shown by the formulaI(R is R or CH3; X is Cl, Br, or I; Y and Z are CH3, OCH3, or Cl. EXAMPLE:N-(3,4-Dichloro-alpha'-methylbenzyl)-alpha-bromo-tert-butyl-ac etamide. USE:An agricultural and gardening fungicide exhibiting strong germicidal effect and long-term prolonged effect on pathogenic germs such as Phycomycetes, Asycomycetes, Basidiomycetes, Fungi imperfecti, etc., especially on blast of rice plant, having low toxicity to men, beasts, and fishes, and no remaining properties in crops. PROCESS:A haloacetic acid deivative shown by the formula II or its reactive drivative is reacted with a methylbenzylamine drivative shown by the formula III, to give a compound shown by the formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention Fi%-methylbenzyl-halo-7 cetami V! The present invention relates to a derivative, a method for producing the compound, and a fungicide for common use in farms containing the compound as an active ingredient. of.

X is a chlorine atom, a bromine atom or an iodine atom, and Y and 2 are the same or different.

Represents a methyl group, methoxy group, or chlorine atom. ] An N-methylbenzylvaroatamide derivative represented by the general formula [Otori] [wherein R and X are as defined above] or a reactive derivative thereof, and a haloacetic acid derivative represented by the general formula [Otori] [In the formula, Y and 2 are as defined above. , method for producing acetamide derivatives, and (3) N-methylbenzi J represented by general formula CI)
This is a fungicide for common use in farms, which is characterized by a germ containing lehaloacetamide as an active ingredient.In recent years, the simplification of work has become an extremely important factor due to the work situation in business. There is a need for the development of drugs that can reduce the number of applications for protecting useful crops from diseases, that is, drugs that have a high residual effect over a long period of time after only one application, and that can simplify the application method. Furthermore, environmental pollution caused by pesticides has become an important problem, and it is well known that pesticides that are low in toxicity to humans, livestock, and fish and that decompose quickly are in great demand.

The inventors of the present invention took the above points into consideration and conducted repeated research, and found that
The compound of the present invention represented by the general formula (1) has a strong bactericidal effect against pathogenic microorganisms that cause great damage to agricultural crop cultivation, such as algae, ascomycetes, basidiomycetes, deuteromycetes, and other bacteria. It was found that

Among them, it has been found that the compound of the present invention has particularly high efficacy against rice blast, which is an important disease of rice.

Furthermore, it was surprisingly discovered that the compound of the present invention exhibits a long-term residual copper property, which is absent from known blast fungicides.
The present invention was completed. This fact is a completely new fact that could not have been expected from the action and usage characteristics of conventional rice blast killing steel.

On the other hand, the toxicity to mixed-breed animals such as mice, rats, dogs, and chickens, as well as to fish such as carp and Japanese medaka, is extremely weak, and the compounds of the present invention have almost no residue in crops. Good to say.

The compound of the present invention is conceptually included in the general formula described in JP-A No. 34-24133, but there is no example of the compound in this document, and the compound is not used as an agricultural or horticultural fungicide. No description was found regarding the usefulness, etc., and the present inventors are the first to discover new findings regarding the compound of the present invention. In addition, 1998-341-30θj describes an α-octahecarboxylic acid derivative having a somewhat similar structure to the compound of the present invention as a wood preservative. however,
As shown in the Examples, the compound of the present invention has far superior efficacy as a fungicide for Honkien strawberries than the Crest compound.

The present invention was completed based on the above-mentioned new findings, and (
1) relates to the N-methylbenzyl-haloacetamide derivative represented by the general formula (1), Cs) relates to its production method, and (6) relates to the N-methylbenzyl-haloacetamide derivative represented by the general formula (1).
This is an Ik horticultural fungicide characterized by containing a methylbenzyl haloacetamide derivative as an active ingredient.

In the present invention (1), a preferred synthetic or common disinfectant is one in which R in the general formula (1) is a hydrogen atom, X is a chlorine atom or a bromine atom, and Y and 2 are a methyl group or a chlorine atom. It is. Particularly preferred are N-(j,Ill-dichloro-α'-methylbenzyl)-α-bromo-tart-butylacetamide and N-(3,Ill-dichloro-α'-methylbenzyl)-α-bromo- Tart-butylacetamide can be mentioned.

Further, the compound of the present invention has asymmetric carbon atoms in the acid site and the amine site, and there are a total of q types of optical isomers, and it goes without saying that the present invention also includes these optical isomers.

In the present invention (j), the methylbenzylamine derivative represented by the general formula (Ill) 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, acetic acid,
Ketones such as ton, methyl ethyl ketone, and methyl isobutyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile, and dimethyl sulfnoxide, dimethyl formamide, dissolved or suspended in water, etc., or preferably without a solvent. Benzene VCs
Therefore, θ, tl~/, 5 equivalents, preferably θ, j~/
,/equivalent of the acetic acid haze conductor or its reactive derivative is added to the compound represented by the general formula (U). A haloacetic acid derivative represented by the general formula (If) or its reactive derivative is dissolved or suspended in the above-mentioned solvents, or a methylbenzyl 7t derivative represented by the general formula [Gate] is added and reacted with a hot solvent/vehicle. It is also possible to do this.

The reaction can be carried out at any temperature from the solid point of the solvent to the boiling point, preferably from θ°C to the boiling point of the solvent, and can be heated or cooled as necessary.

The haloacetic acid derivative represented by the general formula (II) or its reactive derivative to be used includes the corresponding carboxylic acid,
Acid anhydrides, acid chlorides, acid bromides, carboxylic acid esters, etc. are possible, and depending on the yakuchiacetic acid derivative represented by the general formula (II) used or its reactive derivative, a suitable reaction aid, For example, for the corresponding carboxylic acid,
For example, dicyclohexylcarbodiimide, phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, thionyl chloride, sodium hydroxide, potassium hydroxide, sodium ethylate, sodium methylate, triethylamine, and lysine.
quinoline, inquinoline, N,N-dimethylaniline,
M, N-jethylaniline, y-methylmol phosphorus, etc.
In the case of the corresponding acid chlorides or bromides, for example sodium hydroxide, potassium hydroxide, sodium ethylate, sodium methylate, triethylamine, pyridine, quinoline, inquinoline, N,N-dimethylaniline, N,M- Diethylaniline, y-methylmorpholine, sodium acetate, etc., preferably triethylamine in a catalytic amount/, 3 equivalents, preferably 0.9j'W'
The reaction can be carried out with or without the use of ,/equivalents. 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 N-methylbenzyl-
The heroaceta IL derivative can be obtained with good purity and high yield. This product can be further purified by recrystallization with benzene, toluene, methyl alcohol, ethyl alcohol, chloroform di9 isopropyl ether, etc.

When the compound of the present invention is used as a IIkIs British fungicide, it may be used as a raw material or in the form that is commonly used, that is, a single powder.

The compound of the present invention in each formulation can be used in any formulation such as fine granules, wettable powders, emulsions, and oils.
The weight ratio can be adjusted within the range of θ, - to 10, preferably θ, - to lO. When the compound of the present invention is applied, the range is 101 to 1000 Y per /θ area in terms of the amount of active ingredient.

4!1! It is desirable to use the product appropriately depending on its purpose.

In preparing these pharmaceutical products, the carrier may be either solid or liquid. Solids include vegetable carriers (e.g., wheat flour, tobacco stalk flour, soybean flour, walnut shell flour, wood flour, sawdust, bran, bark powder, cellulose powder, residues from extracts of plant extracts, and textile products (9 and 1). Paper, cardboard, Furugire), crushed synthetic resins, clays (e.g. kaolin, bentonite, hostile clay), talc, and other inorganic minerals (e.g. pyrophyllite, sericite, pumice, **'e powder, activated carbon) ) and other fine powders or powders, chemical fertilizers (such as Min'an, Lin'an, and Ni'an).

Mineral water, Flucours (eg methyl alcohol, ethyl alcohol), ketones (eg acetone, methyl ethyl ketone) as liquid carriers.

Eta 31 II! (Even if F is ethyl ether, dioxane, cellosolve, or tetrahydropurofuran).

Aromatic hydrocarbons II (eg benzene, toluene, xylene, methylnaphthalene), [H[hydrogens (eg gasoline, kerosene, kerosene)].

esters, nitriles, and amides (eg methylformamide, dimethylanilinyl').

Halogenated hydrocarbons (e.g. dichloroethane).

Trichlorethylene, carbon tetrachloride), etc. can be used.
Next, examples of surfactants are alkyl sulfate h@,
yh-tei Rusul sulfate, fluoryl aryl sulfonate, 1g of polyethylene glycol ethers, polyhydric alcohol ester, etc. as a fixing agent or dispersant that can be used in the present invention. ,casein.

Gelatin, starch powder, OMO, arabicum, algin, lignin sulfnate, bentonite, molasses, polyvinyl alcohol, pine oil.

Examples of stabilizers include PAP (isopropyl phosphate), TOP (licresyl wood sulfate), tall oil, epoxidized oil, various surfactants, various fat powders, and esthetics. In addition, this drug can be used in combination with other drugs, such as kasugamycin, polyoxin, validamycin, 2,6-dichrono-1-darnitroaniline, zinc ethylene bisdithiocarbamate, co, 1It-dichloro- 6-(0-chloroanilino)-3-triazine, 0. 〇-dimethyl 0-(J-methyl d-nitro 7
Enyl) Kimoto lotioate, iron methylarsonate-”
e Corbis(3-ethoxycarbonyl-thioureiF)benzene, /, -bis(3-medoxylponyl-2-thioureido)benyne, methyl /-(butylcarbamoyl)-2-benzimidazole carbamate, Tetrachloroisophthalonitrile, IPN, die 7
Zinone, malathion, BRIC, chlorzenamidine.

M-(J,j-dichlorophenyl)-/, -1-dimethylcyclopropane-/, -1-dicarboximide, (to)
-/-(,2,4I-dichlorophenyl)-da,dadimethyl-(/,,2,4I-tri7zol-/-yl)-/-penten-3-ol, 4I-chloro-3-
Methylbenzothiazolone, 8-n-butyl-8-
7<Laterxybutyl benzyl dithiocarbonimidate, 0.0-dimethyl-〇-(J,4-cycloruder-methylphenyl) methoxyrothioate, DCPA
, bench 1 curve, OAT, o, o-diinpropyl S-benzylthiosulphate, 0-ethyl S, 8
-Diphenylthio wood sulfate, diimpropyl /,
3-Dithiolane-1-ylidene qnate, 0.0-dimethyl 8-(N-methylcarbamoylmethyl) dithiocysulfate, 0,0-dimethyl 0-(p-cyanophenyl)thiocysulfate, ethyl p-cyanophenyl Phenylhydranothioate, -methoxyda H-/
, 3. ．． It can be used in combination with 2-benzodioxa, phosphorus, 11-sulfur, etc., and neither of them will destroy the control effect of each single agent. However, it is also possible to use it in combination with other agricultural chemicals such as nematicides and acaricides, or fertilizers. The types of additives to the inventive compound and the mixed gold wire are not limited to these, and can be varied within a wide range.

In addition, the compound name is shown by the number of the example below (Table 7).

Formulation Example/Powder 0.2 parts of the compound of the present invention) and 99.8 parts of clay are thoroughly ground and mixed to obtain a powder with a base ingredient content of θ, 2%.
When used, it may be applied or mixed with soil.

Formulation Example - Emulsion 6 parts of the compound of the present invention (1) J, 55 parts of Kijirole and 0 part of Nlupol/Xθ (registered trademark of Toho Chemical Co., Ltd.) are mixed to obtain an emulsion with a main ingredient content of 596. When used, it may be diluted with water or applied directly.

Formulation Example 3 Wettable powder Compound of the present invention <g) tra part, wetting agent (alkylbenzenesulfonate type) 5 parts and white carbon lj
Thoroughly pulverize and mix the parts to obtain a hydrating agent with a base ingredient content of 10%. When used, it may be diluted with water or mixed with soil.

Formulation Example 2 Pulling agent: 15 parts of the compound of the present invention (RI) pulverized with a jet mill to less than Jμ, 6 parts of a dispersant (polyoxyethylene nonylphenol ether), 6 parts of a dispersion stabilizer (carboxymethylcellulose), and 6 parts of water. If the parts are stirred and mixed, and further dispersed and mixed evenly with this Mogenai ν1, the main ingredient content λ
! -obtain a sol. When used, it may be diluted with water or applied as is.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these examples.

Example/Production method N (3r a-dichloro-α'-methylbenzyl)
-α-bromo-t@rt-butylacetamide r-〇θI
In the IIq neck flask, benzene/θθd1J,! -Dichloro-α-methylbenzylamine (7.9f) and triethylamine/Jf were charged, and -, /f α-bromo-tart-butylacetyl chloride was added dropwise while 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 the desired title compound 3. /9 f
I got it.

Melting point elemental analysis value o(d a(@m<qa, J'B
r(9J 4cL(i) Calculated value IIJ, Io
11.911 3.12 2/, 77 /9.3
/(014HIBNOBrO12 0 Actual value 41jf, 9.2 4,9j J, 47
Examples of compounds obtained in this manner are listed in Table 1.

The compounds used as controls for the Examples are shown in Table 1.

Table 2 *) Compound M described in JP-A-Sho st, -it, tsJ publication
) Examples of compounds described in JP-A-5A-SθθS - Rice blast control test Chemical foliar application test (preventive spraying) Rice grown in a 9m flowerpot (Kinki No. 33 61-j leaf stage)
A test compound in the form of an emulsion prepared according to the above formulation example was sprayed using a spray gun at a ratio of /3d//pot. Seven days after spraying, this pathogen (PyrtcuLaria o
ryza) was spray-inoculated, and the temperature was -μ~24°.
Placed in a constant temperature room with C1 humidity of 9θ or more, and after another 9 days,
The disease severity was determined by the percentage of lesion area, and the control effect was investigated.

The results are shown in Table @3. The control value was calculated using the following formula.

@3 Table 1 < 11-Emulsion) Example 3 Rice blast control test Chemical foliar application test (residual spraying)? 1 Rice grown in a flower pot (Kinki No. 33, Q - 3 leaf stage) K The test compounds prepared in the order of emulsion form according to the above formulation example were sprayed using a spray gun at a ratio of /3d//pot. . Nine days after spraying, Pyriaularia o
The spore liquid of ryzae l was spray inoculated, placed in a thermostatic chamber with a temperature of -l-colo°C1 humidity t9θh or higher, and further inoculated with VCl1.
The severity of the disease was determined by the percentage of lesion area after 1 day, and the control effect was investigated.

The results are shown below. The control value was calculated in the same manner as in Example.

Table l (% visit to q) Example q Cucumber and disease control test Chemical foliar application test 911!11 Cucumber (variety: Sumo Hanshiro) grown in a flower pot Cotyledon K, emulsion prepared according to the above formulation example The test compound of the form was sprayed at a rate of isd//pot. Five days after spraying, this pathogen (P8-@udopernospora δ
Spray inoculation with conidial liquid of ubeneis ). The mice were placed under busy conditions of θ゛C1 and then placed under fluorescent lamp illumination at -θ°C for ~3 days to develop the disease. The degree of disease severity was determined by the percentage of lesion area, and the control effect was examined. The results are shown in Table 5. The control value was calculated in the same manner as in Example.

Section S Table East Tetrachloroisophthalonitrile (73 hydrating powder)
Example J Cucumber anthracnose control test A test compound in the form of an emulsion prepared according to the Mayuki formulation example was applied to cucumbers (variety: Sumo Hanshiro, Daiichi True Leaf) grown in a 9 cm flower pot using a spray gun. It was sprayed at a ratio of 3θ−//pot.

Seven days after spraying, this pathogen IC! ollstotriah
um lagenarium) was spray inoculated and placed in a constant temperature room at -4°C and humidity of 9θ coefficient or higher. After sunset, the disease severity was determined by the lesion area ratio and the control effect was calculated. The results are shown in Table 6.

Table 6

Claims (1)

[Claims] (/) General formula [In the formula, R is a hydrogen atom or a methyl group, X is a chlorine atom, a bromine atom, or an iodine atom,! and 2 represent the same or different groups, methyl group, methoxy group or chlorine atom. ] An N-methylbenzyruhaloacetami Pal conductor represented by: (To) The methylbenzyl-haloacetamide p derivative according to claim 7, wherein P is a hydrogen atom, X is a chlorine atom or a bromine atom, and Y and 2 are a methyl group or a chlorine atom. s body. (JPN-(2,lI-dichloro-α'-methylbenzyl)-α-butylacetamidyl)-
a-bromo-t@rt-butylacetami [wherein Ra hydrogen atom or methyl group]. X represents a chlorine atom, a bromine atom, or a single elementary atom
] An acetic acid derivative or its reactive I conductor represented by the general formula [formula, in,! and 2 are the same but different. Represents a methyl group, a methoxy group, or a chlorine atom. ] N-methylbenzyl-/XQ acetamide represented by the general formula [wherein R, x and Y are as defined above] Method for producing derivatives 0 (4) General formula [wherein R is a hydrogen atom or a methyl group, X is a chlorine atom, a bromine atom or an iodine atom, and Y and 2 are the same or different ones. Represents a methyl group, methoxy group, or chlorine atom. ] Agricultural product 1Ill characterized in that it contains the N-methylbenzyl-halo-7cetamide derivative shown as an active ingredient.
British carbonicide 0