JPS58103350A - N-(alpha-methylbenzyl)-t-butylhaloacetamide derivative, its preparation, and agricultural and gardening fungicide containing it as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formulaI(X is halogen; R is lower alkyl; Y is halogen, methyl, cyano, methoxy, or nitro; m is 1 or 2). EXAMPLE:N-Methyl-N-(alpha-methyl-4-bromobenzyl)-alpha-bromo-t-butylace tamide. USE:An agricultural and gardening fungicide. Showing high controlling effect especially on blast of rice plant. It may be blended with other pesticide, insecticide, etc. and used. PROCESS:A t-butylhaloacetic acid shown by the formula II or its reactive derivative (e.g., corresponding carboxylic acid, acid anhydride, acid chloride, carboxylic acid ester, etc.) is reacted with an alpha-methylbenzylamine derivative shown by the formula III in a solvent such as benzene, etc. at 0 deg.C- the boiling point of the solvent, to give a compound shown by the formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [I] [wherein, N-(a-methylbenzyl)-@w-butyl haloacetamide derivative (hereinafter referred to as the compound of the present invention),
The method for producing the same and the preparation of agricultural chemicals containing these ingredients as ingredients.

a-halocarbonate amide derivatives of al species, such as N
-<Kl-methylbenzyl)bromoacedeamide and N-
Benzyl-a-bromopropionamide is a special introduction 54-
6006, it is known that it can be used as a wood preservative.

However, this document does not mention whether or not these compounds can be used as agricultural chemicals.

The present inventors have discovered that the compound of the present invention represented by the general formula CI) has a high control effect on plant diseases, such as diseases of rice and soybean, and rice blast disease, and has developed the present invention. It was completed.

In the present invention, the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom, or a chlorine atom.

The lower alkyl group represents a methyl group, an ether group, an n-propyl group, a tSO-propyl group, a s-butyl group, and the like.

Preferred carbonicides for agricultural TGG+M are those of the general formula (
In I), X is a chlorine atom, a bromine atom, or a chlorine atom;
Bromine atom, cyano group, methoxy group or nitro group,
Difficulty is 1 or more! An example is an integer of . 411
Preferably, X is a bromine atom, 凰 is a methyl group or an ethyl group, ■ is a chlorine atom or a bromine atom, and n
It is possible to name something for which is an integer of 1 or 2.

The compound of the present invention has the general formula [1 [) % formula % [1] [wherein, X has the same meaning as described above]. ]
-Butylhaloacetic acid or its reactive derivative and general formula [
1] [In the formula, 凰, Y and RAN have the same meanings as above. ] It is produced by reacting with the a-methylbenzylamine derivative represented by the following: In this case, the a-methylbenzylamine derivative represented by general formula Ethers such as water bulk, diisobuyl ether, tetrahydro7rane, dioxane, alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and esters such as ethyl acetate. , nitriles such as acetonitrile, and further dimethyl sulfoxide, dimethyl formamide, dissolved in water, or suspended, or without SS, preferably dissolved in benzene, 0.4 to 1.6 equivalents, Preferably, the reaction is carried out by adding 0.6 to 1.1 molar amount of t-butyl haloacetic acid represented by the general formula (1) or a reactive derivative thereof, or conversely, t-butyl haloacetic acid represented by the general formula [II] The reaction is carried out by dissolving or suspending acetic acid or its reactive derivative as described above, or by adding an a-methylbenzylane haze conductor represented by the general formula [111] in an llI4 solvent.

The reaction can be carried out at any temperature from the freezing point to the boiling point of the solvent, preferably at a temperature from 0° C. to the boiling point of the solvent.

The t-butylhaloacetic acid or its reactive derivative represented by the general formula [I] refers to the corresponding carboxylic acid, acid anhydride,
Acid chlorides, acid bromides, carboxylic acid esters, etc.
Suitable reaction auxiliaries, such as for example dicyclohexylcarbodiimide, phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, thionyl chloride, sodium hydroxide, potassium hydroxide, sodium ethyl chloride, in the case of the corresponding carboxylic acids; In the case of acid chlorides or acid bromides, for example, sodium hydroxide, Potassium hydroxide, sodium ethylate, sodium methylate, triethylamine, pyridine, quinoline, isoquinoline, N,N-dimethylaniline, N,N-diethylaniline, N-methylsulfoline,
The reaction can be carried out with or without using a catalytic amount of sodium acetate, preferably triethylamine, in an amount of 1.8 to 1.8 degrees, preferably 0.96 to 1.1 degrees. After the reaction is completed, the reaction product of the reaction aid is removed by filtration or washing with water, and am is distilled off to obtain N-(a-methylbenzyl)-1 represented by the general formula [1]. −
Butyl Haloa ordered amide derivatives are wiped out. This product can be purified by crystallization by recrystallization with beneine, toluene, methyl alcohol, ethyl alcohol, chloroform, etc., or by column chromatography.

The t-butyl acetic acid represented by the general formula (1), which is a starting material, is, for example, J, Am, Cham, 8oc.

ss, 4gos (tsss) 5clli! I'm glad that I can get it using the method described. Also, a represented by general formula (1)
-Methylbenzylamine derivatives are, for example, J-mu, O
hem.

8oo, 615L! It can be obtained by the method described in J. O. (1989).

Next, a manufacturing example will be shown.

Production example N-methyl-N-(a-methyl-4-bromobenzyl)
-a-Bromo-1-butylacetamide 200 mg in 40 flasks, benzene 161) wl, N
4.8 f of +a-dimethyl-4-bromobenzylamine and 2.4 t of triethylamine were charged, and 4.3 F of a-bromo-t-butylacetyl chloride was added dropwise while stirring at room temperature.

After the dropwise addition was completed, the reaction solution was stirred for 6 hours. After the reaction 1
The reaction solution was washed with water to remove triethylamine hydrochloride, and the benzene layer was washed with anhydrous sulfuric acid.

After drying with thorium, the solvent was distilled off under reduced pressure.

The obtained residue was recrystallized from diisopropyl ether to obtain 6.7t of the desired title compound.

Melting point 110-112℃ Elemental analysis Brightness Gp4 H@) 8% Br$1 Calculated value 4
1.06 6.41 1.68 4a8@(C1sHs
*As NOBtm) Actual value 411.89 &4? IIJII 4
6. il HatakeNext, specific examples of the compounds of the present invention are shown in Table 1.

Table 111 When the compound of the present invention is used as an agricultural OII soil pesticide, it may be used as it is without adding any other ingredients;
Alternatively, preparations can be made by mixing with solid carriers, liquid carriers, surfactants, and other auxiliary ingredients for formulations, such as dressings, granules, wettable powders, sols, emulsions, fine granules, aqueous solutions, oils, tablets, etc. Aerosol or Flowable 1IRi may be used.

Each preparation can contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 80,00 stems, preferably 8.6 to 80,0 stems.

These preparations can be prepared according to conventional methods. In this case, solid carriers include vegetable carriers (e.g., wheat flour, tobacco stem powder, soybean flour, walnut shell powder, wood flour, sawdust, bran, bark powder, grain powder, residue after extracting plant extracts), Matoiyushoku (e.g. paper, cardboard, Furugire), Mikikurasei-guri, clay III (e.g. kaolin,
bentonite, acid clay), talcs, fine powders or powders of their inorganic minerals (e.g. pyrophyllite, sericite, sulfur powder, activated carbon), chemical fertilizers (e.g. ammonium sulfate, ammonium phosphorus, ammonium nitrate, Examples include fine powders such as ammonium chloride and ammonium chloride. Liquid carriers include water, alcohols (e.g., methyl alcohol, ethyl alcohol), ketones (e.g., methyl alcohol, methyl ethyl ketone), ethers (e.g., ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons. @ (e.g. benzene, toluene, xylene, methylnaphthalene)
, 11 aliphatic 1 to hydrogenide II (e.g. gasoline, kerosene, kerosene), esters, nitriles, acid ates (e.g. methylformamide, dimethylacetamide),
Examples include halogenated hydrocarbons (eg dichloroethane, trichloroethylene, 181 carbon chloride), and the like. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, and polyhydric alcohol esters. In addition, fixing agents and dispersants that can be used include casein, gelatin, starch 1000M
O, gum arabic, alginic acid, lignin sulfonate, bentonite, sugar, polyvinyl alcohol, pine oil, agar, etc. Stabilizers include, for example, FiF.
(isopropyl phosphate), TOP (licresyl phosphate), tall oil, epoxy Kamiike, various surfactants,
Examples include fatty acids and their esters.

Furthermore, the compounds of the present invention can be used in combination with fungicides, insecticides, insecticides, acaricides, pest repellents, plant growth regulators, herbicides, fertilizers, or fertilizers. .

Examples of formulations are shown below. The compound salt is the 1st m compound number [
It is shown by In addition, a part means a part by weight.

Formulation Example 111 Agent Compound of the Invention (4) 0.1! A 0.2% powder can be obtained by thoroughly mixing the eta part and the clay eta part. When used, it may be applied as is or may be mixed with soil.

Formulation Example 2 Emulsion Compound of the present invention <r> 0 parts, cyclohexanone 70
Department and Tsuru 4-ru Is! 00 (Toho Chemical Co., Ltd. genuine name)
By mixing 20 parts, a 101 emulsion is obtained. When used, it may be diluted with water or applied as is.

Formulation Example 8 Wettable powder 80 parts of the compound of the present invention (1), 6 parts of wet rolling (alkylbenzene sulfonate) and 16 parts of white carbon are thoroughly pulverized and mixed to obtain a wettable powder of 80%. Use Iε
In some cases, it may be applied diluted with water or mixed with soil.

Formulation Example 4 Sol Compound (1) of the present invention is pulverized to 6μ or less using gel! ! 6 parts of dispersant (polyoxyethylene nonylphenol ether), 6 parts of dispersion stabilizer (carboxymethyl chloride), and 66 parts of water are stirred and warmed, and then uniformly dispersed and warmed with a homogenizer to obtain a 26% sol. is obtained. When used, it may be diluted with water or applied as is.

A test example will be shown to specifically demonstrate the effectiveness of the frozen compound of the present invention as a pesticide for agricultural use.

The compounds used as controls in the test examples are as shown below.

Related compounds rice I11% allowed 11! , No. 864,679. Compound described in JP-A No. 1864-6005 Test Example 1 Rice blast control test Chemical surface application test (preventive spraying) Rice grown in flower pots (Kinki No. 88., No. 4- FIII period) before li! A water-diluted emulsion solution prepared according to the preparation method was sprayed using a spray gun so that the drug solution was sufficiently attached. After 4 days, the degree of disease was determined by the direct accumulation ratio of lesions.
The pesticidal effect was investigated. The results are shown in Table 2. The disease severity and control value were calculated using the following formula.

(Incidence index) (Initiation condition 1I) No bacterial flora or lesions are observed on the O11 surface.

os i* Bacterial flora or lesions are observed in less than 5% of the upper leaf area of the screen.

1 Warm or lesions are observed on less than 20% of the leaf area on 11 sides.

2. 1 Warm or lesions are observed on the leaf surface in less than 6011 of the leaf area.

4 Cao II with a leaf surface area of 6011 or more!
Or notice lesions.

Ayu IPIN of S treatment 1 Table 112 *O,O-diisopropyl 8-benzyl thiophosphate (48 emulsion) Test example 2 Rice blast control test Chemical foliar application test (residual spraying) Rice grown in a 9eIm flowerpot ( Kinki No. 88, 4th to 6th leaf stage], a water diluted emulsion prepared according to Formulation Example 2 was sprayed using a spray gun so that the chemical solution was sufficiently attached to the leaf surface. 4 days after spraying. Pyrloula
Inoculated with spore liquid of Ria oryxa, 24-2
Place in a constant temperature room at 6℃ and humidity of 9011 or higher, and then heat for 48 hours.
The severity of the disease was determined by the ratio of the area of post-lesion, and the control effect was investigated. The results are shown in No. **. The control value was calculated in the same manner as in Test Example 1.

Test Example 8 Cucumber anthracnose control test 9am Cucumber grown in a flower pot (Sagami Hanshiro Daiichimoto II)
) before 1i! A water diluted emulsion prepared according to Formulation Example 2 was sprayed using a spray gun so that the chemical solution was sufficiently adhered to the bare surface.

One day after spraying, pathogenic bacteria (Oolle Sotrichum)
lags-n@rium) was inoculated with S, placed in a thermostatic chamber at 24℃ and a temperature of 90% or higher, and further incubated for 4 hours.
After a day, the disease severity was determined by the lesion area ratio, and the control effect was examined. The results are shown in Table 4. The control value was calculated in the same manner as in Test Example 1.

Table 4

Claims (1)

[Claims] [In the formula, X is a halogen atom, R is a lower alkyl group,
Y represents a halogen atom, a methyl group, a cyano group, a methoxy group, or a nitro group, and n represents l- or an arbitrary number. ? N-(#-methylbenzyl)-1-butylha, aacedo(do derivative) represented by (')X is a chlorine atom, a bromine atom or a sulfur atom,
1 is a methyl group or an ethyl group, I is a chlorine atom, a bromine atom, a cyano group, a methoxy group or a nitro group, nbsi
or N as set forth in claim 1, which is an integer of meaning.
-(a-methylbenzyl)-butyl haloacetamide derivative. (8) General formula % formula % [In the formula, X represents a halogen atom. ] and lt-
Butylhaloacetic acid moiety → or its reactive derivative and the general formula [In the formula, 凰 represents a lower alkyl group, M represents a halogen atom, methyl group, cyano group, methoxy group or nitro group, n
is an integer of 1 or 2. ] General formula an alkyl group,
Y represents a halogen atom, a methyl group, a cyano group, a methoxy group, or a nitro group, and n represents an integer of 1 or 2. ] A method for producing an N-(a-methylbenzyl)-1-butylhaloacetamide derivative represented by: (4) General formula [wherein, X is a halogen atom, and 凰 is a lower atom]
'k and 1 represent a halogen atom, a methyl group, a cyano group, a methoxy group, or a nitro group, and U represents an integer of 1 or 2. ] A carbonicide for agricultural roofing, characterized by containing an N-(a-methylbenzyl)-butylhaloacetamide derivative represented by the following as an active ingredient.