JPS59122459A - Benzamidine compound and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is lower alkyl; X is lower alkyl or halogen; Y is lower alyl, halogen, lower alkoxy or nitro; n and m are 0, 1 or 2). EXAMPLE:N,N-Diethyl N'-benzylthiocarboxybenzamidine. USE:An agricultural and horticultural fungicide having extremely remarkable controlling effect to parasitic pathogenic fungi of various crops. It has extremely low phytotoxicity to crops and toxicity to man and animal. PROCESS:The compound of formula I can be prepared easily by reacting the benzamidine compound of formula II with chlorothioformic acid S-benzyl ester of formula III in an organic solvent such as benzene in the presence of a dehydrochlorination agent such as pyridine at 0-60 deg.C.

Description

Detailed Description of the Invention The present invention is based on the general formula () (wherein R represents a lower alkyl group, X represents a lower alkyl group or a halogen atom, and Y represents a lower alkyl group, a halogen atom, or a lower alkoxy group). or a nitro group, and n and m are 0.1 or 2), and these benzamidine compounds are used as active ingredients. This article relates to agricultural and horticultural fungicides (2,).

Conventionally, various organic mercury agents have been used as fungicides for agriculture and horticulture.

Arsenic agents and other agents were often used, but these agents later became problematic due to residual contamination of the soil, toxicity to humans and livestock, and persistence, and their use is now restricted. In recent years, pathogens of various crops, especially powdery mildew,
Gray mold, rice blast.

Drug-resistant bacteria are emerging in pathogens such as sclerotia.

Drugs that have been used for many years have reduced their disease control effects. For these reasons, the development of new types of agricultural and horticultural fungicides is expected.

The present inventors searched for the bactericidal effects of nine different compounds with the aim of developing new agricultural and horticultural fungicides. As a result, they succeeded in synthesizing a new benzamidine compound represented by the above general formula, and also discovered that these benzamidine compounds have extremely excellent control effects against pathogenic bacteria parasitic on various crops.9 The present invention completed.

In the above general formula, the lower alkyl groups represented by R,
The halogen atom represented by χ and Y may be any of chlorine, bromine, fluorine and iodine. , and the lower alkoxy group represented by Y is methoxy.

Examples include lower alkoxy groups having 1 to 4 carbon atoms such as ethoxy, propoxy, and butoxy.

The benzamidine compound of the present invention exhibits an excellent control effect on powdery mildew of various crops, even at a lower dose than commercially available drugs, and also exhibits a highly effective control effect on other diseases such as botrytis, anthracnose, rice blast, and sesame leaf blight. , soft rot.

It also has an excellent control effect against pathogenic bacteria such as bacterial leaf blight, sclerotium, and sclerotium, and has extremely low chemical damage to crops and toxicity to humans and livestock.

It has the above general formula in the present invention. Specific examples of benzamidine compounds are shown in Table 1.

(4) Table 1 (5) Continuation of Table 1 (6) (7) Continuation of Table 1 (8) The benzamidine compound in the present invention is 9 For example, benzamidine and chlorothioformate S-
It can be easily synthesized by reacting with benzyl ester.

(However, in the reaction formula, R, X, Y, n and m have the same meanings as above.)

This reaction is carried out in the presence of tertiary amines such as pyridine, triethylamine and dimethylaniline, dehydrochlorination agents such as caustic soda and potassium carbonate.

It can be carried out in an organic solvent such as ethyl ether, benzene, toluene, dichloroethane and chloroform at a temperature of 0 to 60°C. Chloro(9) Thioformate S-benzyl ester is benzamidine 1
05 to 5 moles can be used, and the dehydrochlorination agent can be used in an amount of 05 to 10 moles per mole of benzamidines.
Preferably, moles are used.

Synthesis Example I Synthesis of N,N-diethyl N'-pendylthiocarboxypenzamidine (compound number l) N,N-diethylbenzamidine 8.1 g (0,0
4,6 mol) and triethylamine 5.1y (0,0
5 mol), toluene 150 m/! Add
dichlorothi, t-formic acid s-benzyl ester 100 under cooling
g (0,046 mol) dissolved in 30 ml of toluene was slowly added dropwise using a dropping funnel. During this time, the reaction solution was vigorously stirred. After stirring for 3 hours after the completion of the dropwise addition, the reaction solution was returned to room temperature to complete the 9 reactions, and further stirred for 1 hour. After completion of the reaction, the precipitated salt was separated from P, and the toluene layer of the solution was treated with a 2N aqueous hydrochloric acid solution, and then washed with water until it became neutral. Next, the toluene layer was dried over anhydrous magnesium sulfate, and then the solvent was removed using an evaporator (10) to precipitate crystals. After recrystallizing this crystal from a mixed solvent of ethyl ether and petroleum benzine, it was left in the refrigerator overnight to obtain the desired product 12.89 as a colorless prism crystal with a melting point of 50-52°C.0 Elemental analysis value (01gH220N2S ); Synthesis Example 2 N,N-diethylN'-hensylthiocarboxy0-
Synthesis of chlorbenzamidine (compound No. 11) Trichloromethyl chloroformate 6.1 g (0.03
1 mole) topendylmercabutane 5.5 g (0,044
A mixture of triethylamine 12.44 (0,1 mol) was dissolved in 200 ml of toluene and cooled with ice water.
23 mol) was added dropwise over 20 minutes, followed by stirring for 2 hours to synthesize S-benzyl chlorothioformate. 11.29 (0,053 mol) of N,N-diethyl 0-chlorobenzamidine was added dropwise to the reaction mixture, stirred for 1 hour, and then left overnight at room temperature. Next, the organic layer was washed with water, two volumes of hydrochloric acid, and water in this order, dried over anhydrous magnesium sulfate, and then the solvent was removed to obtain an oily liquid. This liquid was subjected to column chromatography (Fuco-gel C-30
Orange oil, refractive index n” 1.592
4.7 tons of the desired product, which is an orange oil having a concentration of 1, was obtained.

Elemental analysis value (as CI9H21ON2SCL); theoretical value 5.87 63.23 7.76 actual value 6.54
62.98 7.42 When the benzamidine compound represented by the above general formula in the present invention is used as an agricultural and horticultural fungicide.

In accordance with the customary practice of agricultural chemical formulations, inert solid carriers, liquid carriers, emulsifying dispersants, etc. are used to prepare 9 granules, fine granules, agents, powders, etc.
It can be used in any dosage form such as an aquarium, an emulsion tablet, an oil solution, an aerosol, or a smoke agent. Examples of these inert carriers include talc, clay, kaolin, diatomaceous earth, and white carbon. Calcium carbonate, potassium chlorate.

Saltpeter, wood flour, starch, nitrocellulose, gum arabic, vinyl chloride, carbon dioxide, freon.

Examples include propane and butane.

Further, auxiliary agents for formulation, such as spreading agents, dispersants, emulsifiers, etc., may be appropriately incorporated. Also herbicides, insecticides and other pesticides, urea, ammonium sulfate.

It can also be used by appropriately mixing it with ammonium phosphorus, potassium salt, other fertilizer substances, soil conditioners, etc.

The agricultural and horticultural fungicides of the present invention prepared in various formulations in this way are sprayed on the leaves and foliage of crops before or after disease outbreaks in rice fields or fields, for example.
Or, when treating the soil or water surface, the active ingredient should be 1 to 5000y per 10a, preferably 10
By casting ~1000 g, the disease can be effectively controlled (13).

Next, Examples of the agricultural and horticultural fungicide of the present invention will be shown. Parts in each example indicate parts by weight.

Example 1 20 parts of compound number 1, 5 parts of toxanone (trade name)
and 75 parts of xylene were mixed to obtain 100 parts of an emulsion.

Example 2 20 parts of compound No. 11, 1 part of Demol (trade name)
20 parts of white carbon, and 59 parts of Merck were mixed and ground to obtain 100 parts of an irrigation agent.

Example 3 2 parts of Compound No. 14 and 98 parts of talc were mixed to obtain 100 parts of a powder.

Example 4 10 parts of Compound No. 20, 15 parts of starch, 72 parts of bentonite, and 3 parts of sodium salt of lauryl alcohol sulfate were mixed and ground to obtain 1 granule and 100 parts of tablets.

Next, according to test examples, agricultural and horticultural sterilization (14) according to the present invention The pest control effect of the agent will be explained in detail.

Note that the sample drug number is the same as the number of the above compound example.

Test Example 1 Control test against cucumber udon blight. Cucumbers (variety: Sagami Hanshiro Bushei) were grown in cultivation pots with a diameter of 6 m, one plant per pot, and cucumber seeds were sown.
The drug prepared according to Example 1-j or Example 2 was diluted to have an active ingredient concentration of 1.000 ppm, and sprayed on the young seedlings in an amount of 20 m1' per pot.

After air-drying, each seedling was infected with cucumber powdery mildew fungus (Sph).
Aerotheca fuliginea) spore suspension (conidia collected from diseased leaves were diluted with distilled water and adjusted to 10 ml per field of view under a 150x optical microscope) was uniformly sprayed and inoculated. did. After inoculation, the seedlings were left in an isolated glass greenhouse.

The number of cucumber powdery mildew lesions that appeared on the first true leaves every 10 days was investigated, and the control rate of the test chemical was calculated using the 9th order calculation method. The results are shown in Table 2.

Trial example 2 Low concentration test against cucumber powdery mildew The drug manufactured according to Example 1 or Example 2 was diluted to give active ingredient concentrations of 200 ppm and 100 ppm.
and 201n per pot as 50 ppm! The test was conducted in the same manner as in Test Example 1, except that the particles were sprayed with .

The Ω control rate of each test agent was initially calculated using the same calculation method as in Test Example 1.

(1'7) Table 3 Gin (18) Test Example 3 Control test against rice sheath blight 10 grains each of paddy rice (variety: Nipponbare) were sown in cultivation pots with a diameter of 6 crn, and the rice grew 4 to 5 leaves. Example 1-! !
Manufactured in accordance with Example 2. Each test drug was diluted to give an active ingredient concentration of 500 ppm] and sprayed in 20 ml per pot, air-dried, and then inoculated with the inoculum. The inoculum is rice sheath blight (after culturing in the ground, the inoculum is diluted 5 times with rice husks and inoculated at the ground edge, and placed in a constant temperature and humidity infection box at a temperature of 25°C and humidity of 80%). This is the one that caused the disease.7 to 10 days after inoculation.
On the second day, the length of the lesions developed on the stems and leaves of the plants was measured, and the disease onset index was determined based on the following disease symptom criteria.

Judgment criteria for disease symptoms: No disease is observed at all: 0 (Number of rice bacteria: n): Very small signs of disease: 1 (
tr:n2)], those with lesions smaller than cm.
...2(p:n3) Those with lesions of 2tyn or less...3(#:n4) Those with lesions of 5crn or less...4(z:n5)1.0c
Those with lesions smaller than m...5 (rice bacterial count: n6
) Those with lesions of 10 Crn or more...6 (#
:n7) Next, based on this investigation, the control rate of each test chemical was calculated using a linear equation. The results are shown in Table 4.

Table 4 Test Example 4 Rice sesame leaf blight control effect test 10 grains each of paddy rice (variety: Nipponbare) were sown in cultivation pots with a diameter of 6 m.
When rice reaches the 4th to 5th leaf stage, the drug prepared according to Example 1 or 2 is diluted to an active ingredient concentration of 500.
20tn1 per needle as ppm. After spraying and air drying,
The inoculum was spray inoculated. The inoculum is rice sesame leaf blight fungus (Cochl, j, obol, us mlyabea).
nus) at 28°C for 10 days.

After culturing in rice straw decoction medium, it was examined using an optical microscope (magnification: 150
x) ■ A spore suspension adjusted to have a number of conidia of -5 per field of view. After inoculation 27℃, humidity 95
% in a constant temperature and humidity infection box for 2 days, and then the number of lesions that appeared on the second leaf was investigated.

The control rate of each test chemical was calculated using the same calculation method as Test Example 1. The results are shown in Table 5.

Table 5 Test Example 5 Control test against apple rot disease A drug manufactured according to Example 1 or Example 2 with an active ingredient concentration of
Apple trees (
10 cuttings of 7+4m long annual branches of Fuji (variety: Fuji)
Soaked for minutes. After air-drying, a piece of bark with a diameter of 5 m was punched out from the center of the cut branch using a hot corkpola.
Apple rot fungus (V
spore suspension (spore concentration 5 x 10'/
-) (22) was inoculated into the punched area. After inoculation, temperature 2.5℃ humidity (
After being left in a ff'70 greenhouse for 10 days, the length of the formed lesions was measured, and the control rate of each test chemical was calculated using the same calculation method as in Test Example 1.

The results are shown in Table 6.

Table 6; Topgin M; 1,2-bis(methoxycarbonylthioureido)benzene Test Example 6 Control test against tobacco powdery mildew Diameter 12
Tobacco seedlings (variety: MC-■) were grown in a cultivation pot of z, and when the number of leaves reached 4 to 5, Example 1-i was used only in Example 2.
Dilute the drug manufactured according to 7 to obtain an active ingredient concentration of 500.
As ppm] 50m1 per pot! Spread. Next, after air-drying, tobacco udon and disease bacteria (Erysiphe CC10h
OraCearu) spore suspension (a spore suspension prepared by diluting conidia collected from diseased leaves with distilled water and preparing 10 ml per field of view under an optical microscope at 150 magnification) was uniformly inoculated by spraying. .

After inoculation, the seedlings are left in an isolated glass greenhouse for about 1 hour.
After 4 days, we investigated the number of lesions of tobacco powder and disease that appeared.
The control rate of each test chemical was calculated using the same calculation method as Test Example 1.

The results are shown in Table 7.

Table 7 Patent applicant: Ube Industries Co., Ltd. (25)

Claims (1)

[Claims] (1) General formula (wherein R represents a lower alkyl group, or a lower alkyl group or)/a rogene atom, and Y represents a lower alkyl group, a halogen atom, or a lower alkoxy group It also represents a 1゛nitro group, and n and m are 0.1 and 2. ) A benzamidine compound represented by (2), general formula % formula % (1) (wherein R represents a lower alkyl group, X represents a lower alkyl group or a halogen atom, and Y represents a lower alkyl group, a halogen atom, a lower alkoxy group or a nitro An agricultural and horticultural fungicide characterized by containing a benzamidine compound represented by the following formula (where n and m are 0, 1 or 2) as an active ingredient.