JPH04210952A - Guanidine derivative and agricultural and horticultural germicide - Google Patents

Abstract

PURPOSE:To obtain a new guanidine derivative useful as an active ingredient of agricultural and horticultural germicides having high activity and safety. CONSTITUTION:A compound, e.g. 1,3-dibenzyl-1,3-diisopropyl-2-phenylguanidine expressed by formula I [R is H, 1-10C alkyl, lower alkenyl, lower alkynyl, 5-6C cycloalkyl-lower alkyl or 5-7C cycloalkyl which may have a lower alkyl; X is H, halogen, lower(halo)alkyl or lower(halo)alkoxy; Y is H, halogen, lower alkyl or lower alkoxy; R1 and R2 are H or methyl; l, m and n are 1 or 2, except when R, X, Y, R1 and R2 are simultaneously H and l is 1]. The above-mentioned compound is obtained by reacting phenyl isocyanide dichloride expressed by formula II with an amine derivative expressed by formula III in the presence of an acid binder in an organic solvent.

Description

[Detailed description of the invention] purpose of invention 1) Industrial application field The present invention relates to novel guanidine derivatives.

More specifically, it relates to an agricultural and horticultural fungicide containing a guanidine derivative represented by the following general formula (and Mk!, a conductor) as active ingredients.

Therefore, the present invention is applicable to the fields of chemical industry, agriculture and horticulture,
Especially made of pesticides;? It is useful in the i-industry field.

2) Prior art] There are some literature descriptions regarding guanidine in Lema. For example, Japanese Patent Publication No. 43-29742 describes a method for producing substituted guanidine represented by the following general formula.

1'2\R' / 2\ / R'3 (wherein, R'1 represents an aromatic group, a substituted aromatic group, etc., and R'
' or R'3 represents a hydrogen atom, an aromatic group, a substituted aromatic group, or the like. ) Furthermore, Japanese Patent Publication No. 50-9846 describes that guanidine represented by the following general formula has insecticidal, acaricidal and plant disease control activities.

R'4 (In the formula, X'1 represents a hydrogen atom or a chlorine atom, and R'4 represents a benzylamino group, etc.) 3) The known guanidine of the problem yA to be solved by the invention is a sterilizer for agricultural and horticultural use. The activity as an agent is not recognized or high, and there is a 'L blindness to crops, so it is not practical. On the other hand, various drugs have been used to treat downy mildew, late blight, powdery mildew, rust, etc., which are important diseases of fruit trees, vegetables, and grains, but all of them have problems due to drug resistance. Ability to use: The ability to use it has been lost or its use has been restricted. Therefore, in these fields, the emergence of new fungicides with different skeletons from conventional drugs is a major 3IW.
3, and the present invention aims to solve these problems.

Structure of the Invention 1) Means for Solving the Problems In order to achieve the above object, the present inventors have synthesized a large number of compounds and have studied their usefulness. ! ! ',investigated. As a result, we succeeded in synthesizing guanidine derivatives represented by the following general formula (1), and found that these derivatives are novel compounds of the literature and have high activity and safety as agricultural and horticultural fungicides. I discovered that.

Therefore, the present invention first focuses on the following general formula (1) (wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a lower alkenyl group, a lower alkynyl group, and a group having 5 to 6 carbon atoms). represents a cycloalkyl lower alkyl group, or represents a cycloalkyl group having 5 to 7 carbon atoms which may be substituted with a lower alkyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower represents a haloalkyl group or a lower haloalkoxy group, Y represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group,
R and R2 represent a hydrogen atom or a methyl group, and Ill
, m and n represent an integer of 1 or 2. However, R,
, Y, R and R2 are all hydrogen atoms, except when p is 1 (.).

The lower alkyl group referred to herein is an alkyl group containing 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 5e
Examples include c-butyl group, tert-butyl group, pentyl group, and hexyl group.

When R is a lower alkenyl group, it is an alkenyl group containing 2 to 6 carbon atoms, such as vinyl group, allyl group, 1-propen-2-yl group, butenyl group, pentenyl group, hexenyl group, etc. be.

When R is a lower alkynyl group, it is an alkynyl group containing 2 to 4 carbon atoms, such as ethynytL, 77,
These include propargyl group, 1-propyn.2-yl group, butynyl group, and the like.

When X and Y are lower alkoxy groups, they are alkoxy groups containing 1 to 5 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, and the like.

Examples of R being a cycloalkyl lower alkyl group include cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl.

R has 5 or more carbon atoms, which may be substituted with a lower alkyl group
Examples of 7 cycloalkyl groups include methyl, ethyl, n-propyl or 1so-propyl,
Examples include cyclopentyl, cyclohexyl, and cyclohebutyl substituted with n-butyl or the like.

Second, the present invention is an agricultural and horticultural fungicide characterized by containing the guanidine irises conductor of the general formula CI) as an active ingredient.

Next, specific examples of the compounds of the present invention represented by general formula (1) are shown in Table 1.

In addition, Compound Arashi is also referred to in the following Examples and Test Examples.

2) Action The compound of the present invention represented by general formula (1) is a compound Ii. This compound of general formula (1) acts as an active ingredient of l1liZ artistic fungicide.

3) Example (Part 1) Method for producing the compound of the present invention The compound of general formula (1) according to the present invention can be produced by the method described below. That is, it can be produced by reacting phenyl isocyanide dichloride represented by general formula (II) with an amine derivative represented by general formula (m).

p (b) (III) (wherein, R, x, Y, R, R2, i' 1m, n
has the same meaning as above. ) This condensation reaction is usually carried out in an organic solvent. Usable solvents include hydrocarbons such as toluene and hexane, halogenated hydrocarbons such as chloroform and chlorobenzene, ethers such as ethyl ether, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, methanol, These include alcohols such as ethanol and dimethyl sulfoxide.

Since the compound of formula (m) is a basic substance, the acid binder can be substituted by using an excess amount, but inorganic bases such as sodium hydride, sodium amide, sodium hydroxide, potassium carbonate, triethylamine, pyridine, etc. It is also possible to use organic bases.

Although the reaction proceeds at room temperature, the reaction time can be shortened by heating up to the boiling point of the solvent. After the reaction is completed, if salts of the acid binder are present, the desired product can be obtained by separating them in a furnace and distilling off the solvent. The compound of the present invention can also be obtained by adding water and an organic solvent such as benzene, toluene, tetrahydrofuran, or chloroform, separating the desired product, and distilling off the solvent.

Note that the compounds of formula (I) and formula (m), which are starting materials, are both known compounds. Examples of production by the second method are shown in Examples 1 to 4.

In a 500 ml four-loaf flask was added 59.6 ml of N-isopropylhennolamine and 20 ml of acetonitrile.
After cooling with water, 17.4 g of phenyl isocyanide dichloride (17.4 g') was added dropwise. After the dropwise addition, the mixture was stirred at 50°C for 3 hours. After cooling, the precipitated salt was separated from the furnace, the quenched solution was concentrated, water and toluene were added to the residue, the toluene layer was washed with 1N aqueous hydrochloric acid (7), and after washing and concentrated under reduced pressure, the title compound was obtained as a pale yellow oil. 36.7g was obtained. When this was purified by silica gel column chromatography using a hexane-acetone mixed solvent, it became a 23° colorless oil (yield: 24.5 g), n D -, 5
847 was shown.

Example 21,3-di/Clobene Ru 1.3-di500
N-cyclopentyl-4 in a 4-bottle flask with 1 ml volume of El.
- 48.2 g of difluoromethoquinhensylamine,
) 2 g of ethylamine, 2. and 200 ml of dioxane were added thereto, and 17.4 g of phenylisonanidodichloride was added dropwise while cooling with water. After the dropwise addition, the mixture was stirred and refluxed for 2 hours. After cooling, the same treatment as in Example 1 was performed to obtain 53.6 g of the title compound as pale brown crystals. When this was recrystallized from a hexane-ethyl acetate mixed solvent, white crystals were obtained (yield: 28.
2g) and showed a melting point of 86.5-Bε°C.

Production of Nα56) 31.1 g of N-methyl-4-chlorobenzylamine and 200 g of 7cetonitrile were placed in a 500 ml volume Q four-bottle flask.
After cooling with water, 202 g of 2,6-methylphenyl isocyanide dichloride was added dropwise.

After the dropwise addition, the mixture was stirred at 50°C for 3 hours. After cooling, treatment was carried out in the same manner as in Example 1, and the W combination compound was converted into a pale yellow oil.
7.4g was obtained. When this was purified by silica gel chromatography using a hexane-acetone mixed solution, it became a colorless oil (yield: 130.3 g), n23
-1.5fi03 is shown t2.

Production: 37.8 g of N-cyclohequinolbenzylamine, 20 g of triethylamine in a 4-bottle flask with a capacity of 500 ml.
2g of dioxane and 200ml of dioxane were added thereto, and 18.81r of 4-methylphenylisocyanide dichloride was added dropwise under water cooling. After the dropwise addition, the mixture was stirred and refluxed for 2 hours. After cooling, the mixture was treated in the same manner as in Example 1, yielding 25.6 riQ of the title compound as light brown crystals. When this was recrystallized from a hexane-ethyl acetate mixed solvent, white crystals (yield: 13.4 g) were obtained.
The melting point is 128~! It showed 30"C.

Further, the R horticultural fungicide of the present invention can be used by formulating the compound of general formula (1) according to a conventional formulation. That is, by blending the compound of general formula (1) with appropriate carriers and auxiliary agents, such as surfactants, binders, stabilizers, etc., it is possible to prepare wettable powders, emulsions, liquids, sols (flowables), and oils. , powder, DL (driftless) powder, fine granules, coarse powder, etc. The content of the compound of the present invention in these preparations includes wettable powders, emulsions, solutions,
In the case of sol and oil agents, it can be contained in the range of 1 to 9,096 degrees (weight% 2 or less), and in the case of powders, DL powders, fine granules, and coarse powders, it can be contained in the range of 05 to 100 degrees.

The method of using the agricultural and horticultural fungicide of the present invention is generally as follows. In other words, wettable powders, liquids, emulsions, and sols (
For flowable agents) and oil agents, add 500 to 20 with water.
The active ingredient is generally 1 to 110,000 when diluted to 1:00.
It is made into a solution with a concentration of pp. And per lO are,
This diluted solution is 50-3001), usually 100-20
A dose of 0g is sprayed on the stems and leaves of the plant where the disease occurs.

In addition, liquids, emulsions, and sol (flowables) can be used as concentrated liquids without diluting them with water, or by diluting them up to 10 times with water. UL
V spraying agent), 50-3000ml per 107-h
amount will be sprayed using helicopters, etc.

In addition, for powders, DL powders, fine granules, and coarse powders, 2 to 5 damas per 10 ares (approximately 50 to 500 g as active ingredient amount)
is applied to the foliage, soil surface, inside the soil, or water surface of the plant where the disease occurs.

A method for formulating the compound of the present invention of general formula (1) as an agricultural and horticultural fungicide is shown in Examples 5 to 8 below.

Example 5 2 parts of the powder compound N11I3, 1 part of PAP (physical property modifier 9) and 97 parts of clay were mixed uniformly,
Grinding yields a powder containing 2% of the active ingredient.

Example 6 20 parts of the compound of wettable powder compound N121, 3 parts of potassium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 72 parts of white clay were mixed uniformly and ground to obtain water containing 20% of the active ingredient. Obtain Japanese medicine.

Example 7 Emulsion Compound Arashi 3 Compound 30 parts, Methyl Utyl Katone 4
By mixing and dissolving 0 parts of polyoxyethylene nonylphenyl ether and 30 parts of polyoxyethylene nonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained.

Example 8 40 parts of sol compound 25, 2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate,
1 part of 7゛cetoxypropyl cellulose and 55 parts of water are uniformly mixed to obtain a sol containing 40% of the active ingredient.

Effects of the Invention The novel compound of the present invention is useful as an agricultural and horticultural fungicide because it exhibits high control effects against downy mildew, late blight, powdery mildew, and rust, which are FFI-required diseases of fruit trees, vegetables, and grains. It is.

Next, the usefulness and specific examples of the compound of the present invention represented by the general formula (1) are shown in Test Examples 1 to 4.

Test example 1 Cucumber downy mildew control effect test! ! 20 ml of a predetermined concentration chemical solution of a hydrating powder prepared according to Example 6 was sprayed onto cucumber seedlings (product fi = Sagami Hanshiro) at the S2B stage that were cultivated indoors in clay pots with a diameter of 9C111. Then, with a damp brush, remove the mildew fungus (Pseuclopero).
Spores were scraped off from diseased leaves of Nospora cubensis and suspended in an aqueous solution of a spreading agent (polyoxyethylene alkyl ether) 5 (ippa).

Then, the spore concentration was adjusted to 5×10 6 spores/ml, and a spore suspension of cucumber downy mildew was inoculated by spraying one day after the chemical spraying. Then, it was left standing at a temperature of 20° C. and 100% humidity for 2 days to cause cucumber downy mildew to develop.

Six days after inoculation, the lesion area ratio (%) per 16 was investigated,
The control value (%) was calculated using the following formula.

This test was conducted twice per ll&liquid concentration section, and the average control value (%) was determined and the evaluation value was determined according to the following criteria.

In addition, chemical damage to cucumbers was investigated according to the following criteria. The results are shown in Table 2.

In addition, the evaluation value of bactericidal effect and the investigation index of drug damage are similarly used in Test Examples 2 to 4 below.
less than 209ci 4, 3: high 2: slightly]: only 0, none Table 2 Table 2 (continued) Table 2 (continued) Table 2 (with vc) Table 2 (continued) Table 2 ( (Continued) Table 2 (Continued) Comparative drug A showing average disease area ratio:
Compound described in Publication No. 846) Comparative drug B: N (generic name: chlorothalonil) Test example 2 Tomato late blight control efficacy test Tomatoes grown in soil in a vinyl pot with a diameter of 9 cm in a greenhouse (variety Nitoko K) Example 6 on the fifth leaf stage seedlings of
A diluted solution of a predetermined concentration of a hydrating powder prepared according to the method was sprayed in an amount of 30 ml per 3 pots using a zero-dynamic spraying device. On the day after the drug treatment, on pre-sliced potato pieces,
Tomato Phytophthora blight bacteria (Phytopht) cultured at 0°C for 3 days
hora 1nfestans) was removed (adjusted so that the zoosporangium concentration was 10 5 /ml), and sprayed and inoculated onto tomatoes using a spray gun. Then, after storing for 5 days at 20℃ and 7g in 100% humidity, the disease area ratio (%) was investigated for the 1st to 4th true leaves.
The average percentage of diseased area was determined, and the control reef (%) was calculated from the comparison with the non-spread area.

This test was conducted twice in one chemical concentration area, and the average control value (%) was determined and converted into an evaluation value. In addition, phytotoxicity to tomatoes was investigated using the same criteria as in Test Example 1. The results are shown in Table 3.

Control defects (%) - Table 3 Table 3 (continued) Table 3 (continued) Table 3 (continued) ';j43 Table (continued) Table 3 (continued) Table 3 (continued) Note 1) Comparison Drugs A and B are the same compounds shown in Table 2.

Note 2) The numbers in parentheses for non-sprayed plots indicate the average percentage of diseased area per leaf.

Test Example 3 Effect on preventing two diseases of barley udon: Prepared according to Example 6 on the first leaf plot of barley (product!: Azuma Golden) cultivated in soil in a 21A greenhouse on an unglazed burnt site with a diameter of 9cI11. After spraying 10ml of a predetermined concentration of hydrating powder and leaving it overnight,
c gramins: Elisifue graminis)
The spore suspension was inoculated by spraying. Seven days after inoculation, the number of lesions of barley powdery mildew was investigated, and the control value (%) was calculated using the following formula and converted into an evaluation value.

In addition, the degree of drug damage to barley was investigated using the same criteria as in Test Example 1, and displayed. The results are shown in Table 4.

Table 4 Table 4 (continued) ′:jS4 Table (continued) Table 4 (vL) Table 4 (continued) Table 4 (continued) Table 4 (with vc) It is.

Note 2) The numbers in parentheses for non-sprayed plots indicate the number of lesions per leaf.

Comparative drug C: (generic name: chinomethionate) Test example 4 Wheat rot disease control effect test Cultivated in soil in a clay pot with a wide diameter of 9 cIn in a greenhouse! It': Wheat seedlings at the single-leaf stage (Product Ff: A Cup No. 61) according to Example 6! A predetermined concentration diluted solution of a wettable powder made from Al was sprayed in an amount of 20 ml per three pots. 1 day later
The fungus rot fungus (P) that has been formed on the wheat leaves
uccinia recondita nibukucinia
Tween 2 [1 [
The spore suspension was suspended in sterile water supplemented with 50pp of polyoxyethylene sorbitan monolaurate manufactured by Kao Soap Co., Ltd., and the spore suspension was sprayed and inoculated on the leaves to be treated. After keeping the plants at a constant temperature, they were transferred to a greenhouse at 20°C to encourage disease onset. Ten days after inoculation, the plants were taken out, and the number of diseased diaspores per leaf was evaluated, and the control value (%) was calculated using the following formula: This test was conducted using 3 pots per chemical solution S level, and the average control value was calculated and converted into an evaluation value.The degree of chemical damage to wheat was determined using the same IL standard as in Test Example 1.
examined and displayed.

The results are shown in Table 5.

Control value (%) - Table 5 Table 5 (continued) Table 5 (continued) FSS table (vc) Table 5 (continued) Table 5 (continued) Table 5 (a) Note 1) Comparison Drug A is identical to the compound shown in Table 2.

Note 2) The numbers in parentheses for non-sprayed plots indicate the number of lesions per leaf.

Comparative drugs.

S 1 Patent applicant: Hokuko Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1) General formula (1) (1) (wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a lower alkenyl group, a lower alkynyl group, or a carbon number 5 to 6)
cycloalkyllower alkyl group, or a cycloalkyl group having 5 to 7 carbon atoms which may be substituted with a lower alkyl group, where X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, represents a lower haloalkyl group or a lower haloalkoxy group, Y represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, R and R2 represent a hydrogen atom or a methyl group,
plm and n represent an integer of 1 or 2. However, R,
Excluding the case where X, Y, R and R2 are all hydrogen atoms and are g or 1. ) Guanidine derivatives represented by 2) In the general formula (1), R represents cycloalkyl having 5 to 6 carbon atoms, X represents a halogen atom, a lower alkyl group or a lower alkoxy group, Y represents a hydrogen atom, and R and R2 represent The guanidine derivative according to claim 1, which represents a hydrogen atom, and l, m and n are 1. 3) General formula (2, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a lower alkenyl group, a lower alkynyl group, a carbon number 5 to 6
represents a cycloalkyl lower alkyl group, or represents a 7-cycloalkyl group having 5 to 7 carbon atoms which may be substituted with a lower alkyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group. , lower l\roalkyl group or lower I-roalkoxy group, Y represents a hydrogen atom, halogen atom, lower alkyl group or lower alkoxy group, R and R2 represent a hydrogen atom or a methyl group, plm and n represent Indicates an integer of 1 or 2. R, X, Y, R and R2 are all hydrogen atoms and g is 1
except in the case of 1. An agricultural and horticultural fungicide characterized by containing a guanidine derivative represented by ) as an active ingredient. 4) In the general formula (1), R represents a carbon alkyl group having 5 to 6 carbon atoms, X represents a halogen atom, a lower alkyl group, or a lower alkoxy group, Y represents a hydrogen atom, and R and R2 represent The agricultural and horticultural fungicide according to claim 3, which contains a guanidine derivative representing a hydrogen atom and having plm and n of 1 as an active ingredient.