JPS59122460A - Benzamidine compound and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is H, lower alkyl or halogen; n is 1 or 2; when n is 1, M is lower alkyl, benzyl, lower alkenyl or halogenated benzyl, and when n is 2, M is metal selected from Ni, Co and Zn). EXAMPLE:N,N-Diethyl-N'-n-propyldithiocarboxybenzamidine. USE:An agricultural and horticultural fungicide having extremely remarkable controlling effect to the pathogenic fungi of various crops (e.g. pathogen of powdery mildew). It has extremely low phytotoxicity to crops and toxicity to man and animal. PROCESS:The compound of formula III can be prepared by reacting the benzamidine compound of formula II with CS2 in a concentrated aqueous solution of caustic soda at -5-+40 deg.C, and reacting the resultant sodium amidinodithioate optionally after separating from the reaction system, with a mineral acid salt, etc. at 0-50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (wherein X represents a hydrogen atom, a lower alkyl group or a halogen atom, and n represents 1 or 2).

When n is 1, M represents a lower alkyl group, a lower alkenyl group, a Hensyl group or a halogenated benzyl group, and n
When is 2, it indicates a metal selected from nickel, cobalt and zinc. ), and these benzamidine compounds are used as active ingredients.

This is a dl related to agricultural and horticultural fungicides.

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

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

Drug-resistant bacteria have emerged among the pathogens associated with sclerotia disease.

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 discovered that these benzamidine compounds have extremely excellent control effects against pathogenic bacteria parasitic on various crops. L. completed the invention.

(3) In the above general formula, the lower alkyl groups represented by X and M include methyl, ethyl, n(or 1)-
X
The halogen atom represented by and the halogen atom in the halogenated benzyl group represented by M include chlorine,
Any of bromine, fluorine and iodine may be used, and M
The lower alkenyl group represented by has 3 to 5 carbon atoms.
Preferably.

The benzamidine compound of the present invention exhibits a unilateral control effect on powdery mildew of various crops, even at a lower dose than commercially available drugs, and also exhibits a unilateral 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 rot, and has extremely low toxicity to crops and 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) (6) Continuation of Table 1 (7) Continuation of Table 1 The benzamidine compound in the present invention can be synthesized, for example, by the following method.

According to the following formula, benzamidines and carbon disulfide are reacted in a concentrated aqueous solution of caustic soda to synthesize sodium ami(8) dinodithioate.

This reaction is carried out in water or dilute aqueous alcohol solution.

It can be carried out at a temperature of -5 to 40°C.

Next, from this reaction system, sodium amidinodithioate is isolated or without isolation, lower alkyl halide, lower alkenyl halide.

(Halogenation) By reacting with halides such as benzyl halide or mineral salts of nickel, cobalt, and zinc such as hydrochloric acid, sulfuric acid, and nitric acid at a temperature of 0 to 50°C, various benzamidine compounds of the present invention can be obtained. be synthesized. This reaction can also be carried out using water and dilute aqueous alcohol solutions.

Synthesis Example I Synthesis of N,N-diethyl-N'-n-propyldithiocarboxybenzamidine (compound (9) of compound number 3) N,N-diethylbenzamidine F+, Oy ('0
．． 028 mol) and 2.3 g (0,030 mol) of carbon disulfide
Add 50 d of water to the mixture of (mol), and while stirring vigorously under ice-water cooling, add 1.3 g of caustic soda (o, 032
An aqueous solution prepared by dissolving mol) in water was added dropwise. During this time, the reaction solution gradually turned orange.

After stirring for 1 hour, 3.52 (a, 4 mol of oz) of n-propyl bromide was added dropwise (the reaction solution turned yellow) and the mixture was stirred for 30 minutes. The reaction solution was diluted with chloroform 6
The extract was extracted with 0+++/, neutralized with 2N hydrochloric acid, washed with water, dried over anhydrous sodium sulfate, and the solvent chloroform was removed under reduced pressure to obtain an oily substance.

This oil was isolated by column chromatography (using Wako Gel C-200) using benzene as a solvent.

Orange oil object 4 with refractive index n281.6160
．． 3g was obtained.

NMR spectrum (in deuterochloroform); δ value (ppm
): 1.0(t, 3H, -BCH2CH2CH3
)1.1-1.5(6H, -N-(CH2CH3)2
)(lO) 1.7(m, 2H, -8CH2CH2CH3)31(t
,2H,-5c)(2cT(,,aH3)3.2-4.
．． 0 (4H, -N -(0H2CT(3),, )'
7.5 (5H, -@ Synthesis Example 2 Synthesis of N,N-diethyl-N'-hensyldithiocarboxybenzamidine (compound No. 8) N,N-diethylbenzamidine 5y (0,028 mol) and Carbon disulfide 2.3 g, (0,030 mol)
To the mixture, 40 me of water was added, and while stirring vigorously under cooling, 5 g of an aqueous solution containing 1.3 g of caustic soda (0.032 mol) was slowly added dropwise, followed by stirring for 1 hour. Then benzyl bromide 4. , 9 g (0,028 mol) was added dropwise, followed by stirring for 1.5 hours. The reaction solution was extracted with 60 me of chloroform, neutralized with 2N hydrochloric acid, washed with water, dried over anhydrous sodium sulfate, and chloroform was removed under reduced pressure to obtain an oil. This oily substance was isolated by column chromatography (using Wako Gel C-200) using a benzene solvent to obtain the desired product 2.72 as an orange clear substance having a refractive index n'' of 6540.

NMR spectrum (in deuterochloroform); δ value (ppm
): 1.0 to 1.6 (6H, -N-(c) (2c
! (,,)2)3.1~:<,9(4H,-N-(aH
2cH3)2)4.4 (S, 2H,i(G7.2~7.7(lOH,O2) Synthesis Example 3 Nickel bis(N,N-ethylbenzamicino N'
-carbodithioate) (compound number 10) 2.1 p (0.05 mol) of caustic soda and 3.2 ml of water
8.8 f (0.05 mol) of N,N-diethylbenzamidine was added to the aqueous solution dissolved in the solution, and while stirring vigorously at room temperature, the reaction temperature was kept below 40°C.
6 # (0.06 mol) was added dropwise. After about 30 minutes, the precipitated crystals were suction filtered, and the crystal residue was dissolved in ethyl ether 3
0m/! Wash twice with yellow crystals of sodium-N,N
-diethylbenzamidino-N/-dithioate 11.
Obtained 8t. Next, this crystalline substance 11.8IP (0,043
mol) was dissolved in 200 mp of water, and 50 - of an aqueous solution containing 5.6 f (0,022 mol) of nickel sulfate hexahydrate was added under stirring at room temperature. The precipitated crystals were collected, washed with water, and dried under reduced pressure at a temperature of 80°C to obtain a decomposition point of 184-189°C.
9.3 tons of the target material was obtained as a brick-red powder crystal having the following properties.

Elemental analysis value (as C, 2H3oN4S4N 1); H
(4) 0(@N(→ S (@N i (!@Theoretical value) 3.39 51.34 9.9B 22.8 1
0.4 Actual value 5.2B 49,84 9.63 2
1.4 10.8 Synthesis Example 4 Synthesis of zinc bis(N,N-diethylbenzamidino-N'-carbodithioate) (compound No. 11) Add 2.1II (0.05 mol) of caustic soda and 3.1II (0.05 mol) of water. 2 m
After dissolving in l, N,N-diethylbenzamidine 8
．． 8 g (0.05 mol) was added to the room temperature with strong stirring while maintaining the reaction temperature below 40°C.
, 06 mol) was added dropwise.

(13) After 40 minutes, the precipitated crystals were suctioned and filtered, and after sufficiently removing water, the crystals were mixed with ethyl ether (30 m/!). The solution was washed twice with sodium chloride and yellow crystals of sodium-N,N-diethylbenzamidino-N'-dithioate 12.1f were obtained. 1 g (o, o45 mol) of this crystalline substance lz was mixed with 200 fn1. Dissolved in zinc sulfate heptahydrate f3.3g (0022 mol)
50ml of an aqueous solution containing was added dropwise.

The precipitated crystals were collected, thoroughly washed with water, and then dried under reduced pressure at a temperature of 50°C to obtain the desired product 9.61 as a yellow powder crystal having a melting point of 96 to 98°C.

Elemental analysis value (as 024H36N484 Z n);
H(@OC@N(@S(@Z)
n (%) Theoretical value 5.32 50. '73 9.8
6 22.5 11.5 Actual value 5.20 50.2B
9.64 22°3 11.7 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 agrochemical formulations, inert solid carriers, liquid carriers, emulsifying dispersants, etc. are used to produce single granules, fine granules, powders, water consolation tablets, emulsion tablets, oil solutions, air seals (14), smoking agents, etc. It can be used in any dosage form. These inert carriers include, for example, talc, clay, kaolin, diatomaceous earth, white carbon, calcium carbonate, potassium chlorate.

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

Examples include propane and butane.

Auxiliary agents such as a spreading agent, a dispersing agent, an emulsifier, etc. can be appropriately added to the formulation. 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 paddy field fields, for example,
Or, when treating the soil or water surface, the active ingredient should be 1 to 5000y per 10a, preferably 10
By throwing ~1.000 ft, diseases can be effectively controlled.

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. 8, 1 part of Demol (trade name), 20 parts of white carbon, and 59 parts of talc were mixed and ground to obtain 100 parts of an irrigation agent.

Example 3 2 parts of Compound No. 18 and 98 parts of talc were mixed to obtain 100 parts of a powder.

Example 4 10 parts of Compound No. 22, 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, the pesticidal effect of the agricultural and horticultural fungicide according to the present invention will be specifically explained using test examples.

k The sample drug number is the same as the number of the preformed compound example.

Test Example 1 Control test against cucumber powder disease Diameter 6
Cultivate cucumbers (variety: Sagami Hanjiro Seishi) one per pot in a 2-m cultivation pot, and sow cucumber seeds to produce 15-day-old seedlings according to Example 1 or Example 2. The drug was diluted to an active ingredient concentration of 1000 ppm and sprayed 20 times per needle. After air-drying, each seedling was infected with Kicuri udon and disease bacteria (Sphaer O↑, haCa).
fu T j gi, nea ) spore suspension (conidia collected from diseased leaves were diluted with distilled water and analyzed with an optical microscope 1.
A spore suspension (adjusted to 10 spores per field of view under 50x magnification) was uniformly sprayed and inoculated. After inoculation, the young seedlings were left in an isolated glass greenhouse, and the number of lesions of Kikucuri powdery mildew that appeared on the first true leaves was investigated after about 10 days.The control of the test chemical was calculated using the following formula. The rate was calculated. The results are shown in Table 2.

(17) Table 2 (18) Test Example 2 Low Concentration Test Example for Cucumber Powdery Mildew], -itake The drug manufactured according to Example 2 was diluted to give an active ingredient concentration of 200 ppm and 100 ppm.
In addition to spraying 20 ml per pot at 50 ppm and 50 ppm, the test was conducted in the same manner as in Test Example 1.

Test Example] The control rate of each test chemical was calculated using the same calculation method as in -.

The results are shown in Table 3.

Table 3 *: N,N-diethyl N'-ethylthiocarboxybenzamidine Test Example 3 Control test against apple rot disease Example 1 A drug prepared according to Example 2 was used at an active ingredient concentration of 1-000 ppm. Cuttings of annual branches of an apple tree (variety: Fuji) cut into 7 cm pieces were immersed in diluted weeping solution for 10 minutes. After air-drying, a 5 mx diameter bark was punched out from the central part of the cutting using a hot cork pom, and a spore suspension of apple rot fungus (Valsamali), which had been previously cultured in PDA medium, was added to the bark.
A spore concentration of 5×10′/me 2 ) was inoculated into the punched site. After inoculation, the seeds were left in a greenhouse at a temperature of 25° C. and a humidity of 70% for 10 days, and then the length of the formed lesions was measured, and the control rate of each test agent was calculated using the same calculation method as in Test Example 1.

The results are shown in Table 4.

/ 7-' (21) Table 4*; Topgin M, 1,2-bis(methoxycarbonylthioureido)benzene test example 4 Control test against tobacco powdery mildew Diameter 12
Example or Example 2 Tobacco seedlings (variety: MC-1) were grown in crn cultivation pots, and when 9 true leaves had grown to 4 to 5 leaves.
Dilute the drug manufactured according to the method to obtain an active ingredient concentration of 500 p.
50 ml of water was applied per pot as pm. Next, after air-drying tobacco powder, a spore suspension of the diseased fungus ((22) Erys+he clchoracearum) (conidia collected from diseased leaves was diluted with distilled water and prepared to have 10 conidia per field of view under an optical microscope at 150x magnification). The spore suspension) was uniformly inoculated by spraying.

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

The results are shown in Table 5.

Table 5

Claims (1)

[Claims] (1) General formula (wherein X represents a hydrogen atom, a lower alkyl group, or a halogen atom, n represents 1 or 2, and M represents a lower alkyl group when n is ]-) , lower alkenyl group, Hensyl M Dimension * Iti indicates a halogenated benzyl group, and n is 2
indicates a metal selected from nickel, cobalt and zinc. ) A benzamidine compound represented by (2), General formula (1) (wherein, group, benzyl group-1: ta indicates a halogenated benzyl group, and when n is 2, it indicates a metal selected from nickel, cobalt, and zinc. A fungicide for agricultural and horticultural use.