JPS62228001A - Agricultural germicide - Google Patents

Abstract

PURPOSE:An agricultural germicide, containing a chromone compound and having antimicrobial activity against Pellicularia sasaki of rice plants as well as Piricularia oryzae, Leptosphaeria salvinii, Cochliobolus miyabeanus, Gibberella fujikuroi and further Phytophthora infestans of cucumbers, Sclerotinia sclerotiorum of kidney beans, etc., without phytotoxicity. CONSTITUTION:An agricultural germicide obtained by containing a compound expressed by the formula (R1 and R2 are amino group which may be substituted; ring A is benzene ring which may be substituted) as an active ingredient. The above-mentioned germicide is capable of readily and precisely exhibiting improved action and effect at a low cost ad hardly causing side effects. The content of the active ingredient in the above-mentioned formulation is preferably 10-90% for an emulsion, wettable powder, etc., 0.1-10% for oil, dust, etc., and 5-50% for granule. For the emulsion, wettable powder, etc., the formulation is suitably diluted further with water (e.g. 50-5,000 times), etc.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a new agricultural fungicide.

(Conventional technology) Regarding rice cultivation, in recent years, advances in technological reforms such as mechanization and labor-saving, as well as the development of ridges and waterways, have gradually reduced the incidence of leaf blight, one of the three major rice cultivation diseases. On the other hand, sheath blight, along with rice blast, is becoming more and more popular.A variety of drugs are being researched and tested to control this important disease, sheath blight. Santesata.

(Problems to be Solved by the Invention) As a result of our dedicated research aimed at controlling sheath blight, the present inventors discovered that a chromone compound, which has a completely different structure from the previously known fungicidal compounds, is superior. The present invention was completed based on these new findings.

(Means for Solving the Problems) The present invention provides an agricultural fungicide containing a chromone represented by the general formula [wherein R1 and R2 represent an optionally substituted Zene ring]. It is related to.

Chromone is a common name for 4-oxo-4H-1-benzopyran, but "chromone" is used in the final document. In the chromone compound of the present invention represented by the general formula CD, since R1 and R2 represent an optionally substituted amino group, the uncompound is 2-aminochromone-3-
They can be collectively referred to as carboxamide derivatives.

Even if R1 is substituted in compound [I], and R
4 are the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a phenylargyl group, a phenyl group, an acyl group, a substituted oxycarbonyl group or a carbamoyl group, or R3 and R4 together represent an alkylene group ], and R3 and R4
is a hydrogen atom.

Alkyl group, anru group, substituted okynecarbonyl group.

A carbamoyl group is preferred.

In the substituents R3 and R4, the alkyl group is a low 1-chain or branched argyl group having 1 to 4 carbon atoms (hereinafter, 0
1-4 alkyl group.

Such 01-4 alkyl group is methyl.

Mention may be made of ethyl, n-propyl, isopropyl, n-butyl, isophthyl, 5ec-butyl and tert-butyl. As the 01-4 alkyl group, methyl and ethyl are particularly preferred.

In the substituent R3, R, the cycloalkyl group has 3 carbon atoms.
・It refers to an alicyclic hydrocarbon group of ~6 (hereinafter sometimes abbreviated as a 03-6 chloroalkyl group). C3-6 like this
Examples of the ncroalkyl group include noklopipyr, cyclobutyl, nclopentyl, cyclohexynyl, and the like.

The alkyl group of the phenylalkyl group in the single substituents R3 and R4 is preferably the above-mentioned C1-4 alkyl group. Examples of such phenyl 01-4 alkyl groups include hata, benzyl, 1-phenylethyl, and 2-phenylethyl. The phenyl group of the phenyl C1-4 alkyl group may have a substituent as described later.

In the substituents R3 and R4, the phenyl group and the phenyl group of the above phenyl01-4 alkyl group may have one to several, preferably one to three substituents. Examples of such substituents include 01-4 argyl groups, hydroxyl groups, halogen atoms, and halogenated 01-2 alkyl groups. Examples of the 01-4 alkyl include those mentioned above, examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and examples of the halogenated C1-2 alkyl group include fluoromethyl, difluoromethyl, trifluoromethyl, and chloromethyl. Each is specific (- can be mentioned.

In the substituents R3 and R4, the acyl group is an alkanoyl group,
Refers to benzoyl group or phenylalkanoyl group. The alkanoyl group refers to a linear or branched aliphatic acyl group having 2 to 5 carbon atoms (hereinafter sometimes abbreviated as C2-5 alkanoyl group). Examples of such C2-5 alkanoyl groups include acetyl, phthalocyanyl, phthyryl, etc., and acetyl is particularly preferred.The alkanoyl group of the phenylalkanoyl group is preferably the above-mentioned C2-5 alkanoyl group. Examples of the phenyl C2-5 alkanoyl group include phenylacetyl.

Examples include 2-phenylph"ropionyl, s-phenylpropionyl, etc. The above-mentioned benzoyl group and phenyl C2,5 alkanoyl group have one to several phenyl groups,
Preferably, it may have 1 to 3 substituents. Examples of such substituents include the C1-4 alkyl group and halogen atom already mentioned as substituents on the phenyl group in substituents R3 and R4.

Also mentioned here are halogenated 01-2 alkyl groups. 01-4 alkyl group, halogen atom, halogenated C
Specific examples of the 1,2 alkyl group include those mentioned above.

Substituents R8 and R4 refer to a substituted oquinecarbonyl group, haalcoquine, carbonyl group, phenylalkoxycarbonyl group or phenoxycarbonyl group. The alkoxycarbonyl group is preferably a C1-4 alkoxy group, which will be described later as a substituent on the 6-benzene ring. Examples of such C1,4 alkoxy-carbonyl groups include methoxycarbonyl, ethquincarbonyl, propoxycarbonyl, butoxycarbonyl, and methoxycarbonyl and ethoxycarbonyl are particularly preferred. As the phenylalkyl group of the phenylalkoxycarbonyl group, the above-mentioned phenyl C
1-4 alkyl groups are preferred. Such phenyl C1,4
Examples of the alkoxycarbonyl group include benzyloxycarbonyl, 2-phenylethyloxycarbonyl, and the like. The phenyl group of the above-mentioned phenyl C1-4 alkoxycarbonyl group and fenoquine carbonyl group may have one to several substituents, preferably one to three substituents. C1, which has already been mentioned as such a substituent
~4 alkyl group.

Eight halogen atoms, halogenated 01-2 alkyl groups, etc. are also mentioned here. Specific examples of the 01-4 alkyl group, the halogen atom, and the halogenated 01-2 alkyl group include those mentioned above.

In the substituents R3 and R4, the carbamoyl group may have one or two substituents bonded to the nitrogen atom. Examples of such substituents include the above-mentioned 01-4 alkyl group and phenyl C1-4 alkyl group.

Examples include phenyl group. C1-4 alkyl group.

Specific examples of the phenyl 01N4 alkyl group and specific examples of the substituents of the phenynyl group are those mentioned above. As the carbamoyl group having a substituent, N-methylcarbamoyl and N-ethylcarbamoyl are particularly preferred.

When substituents R3 and R4 together represent an alkylene group, the alkylene group has 3 to 5 carbon atoms (hereinafter referred to as 03
~5 alkylene group) represents table-yl, pyrrolidin-1-yl, hyhelicin-1-yl, etc.

Even if R2 in compound [I] is substituted and R
6 are the same or different and each represents a hydrogen atom or an alkyl group. It is preferable that at least one of R5 and R6 is a hydrogen atom. Furthermore, it is particularly preferable that R5 and R6 are both hydrogen atoms.

In the substituents R5 and R6, the alkyl group is the substituent R3゜R
The 01-4 alkyl groups mentioned above are mentioned here as well. Specific examples of the C1-4 alkyl group include those mentioned above.

It represents a good benzene ring, and when it is substituted, the substitution position is 5,6° of the chromone ring as shown in the formula below. , 8th place.

When substituted, the number of substituents is 1 to 4, and 1 to 2
These are more preferred, and those mono-substituted at the 6-position or di-substituted at the 6.8-position are particularly preferred.

When it has two or more substituents, those substituents may be the same or different.

For example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a phenylalkyl group, a phenyl group, an acyl group, a hydroxyl group, an alkokene group, a mercapto group,
Alkylthio group, halogen atom.

Alkyl groups include nitro group, amino group, monoalkylamino group, dialkylamino group, etc.

An alkoxy group and a halogen atom are preferred.

The alkyl group as a substituent on the benzene ring is a linear or branched lower alkyl group having a prime number of 1 to 10 (hereinafter, 0
Sometimes abbreviated as 1-1o alkyl group].
Examples of such C1-1o alkyl groups include methyl, ethyl, n-propyl, and isopropyl.

n-butyl, isobutyl, 5ec-butyl, tert
-butyl, n-pentyl, impentyl, 2-methylbutyl, l-methylbutel, 1,2-dimethyl 10 pyru,
Examples include 1,1-dimethyl 10-pyl, neopentyl, n-hexyl, l-ethyl-1-methylglopyl, 1,1-dimethylbutyl, l,1,2-trimethylpropyl, heptyl, octyl, nonyl, and denyl. 01～
1o Among the alkyl groups, those having 3 to 8 carbon atoms (hereinafter sometimes abbreviated as C3,,8 alkyl group) are preferred, and those in which a C3 to 8 alkyl group is monosubstituted at the 6th position are preferred. Looks likeable. Specifically, C-enlarged l'-isoprofine, isobutyl, 5eC-buty/L/, ter
t-butyl, 1,1-dimethylglobil, 1-ethyl-
1-methylglobil, 1,1-dimethylbutyl, 1,1
, 2-trimethylpropyl or the like is even more preferred. Those in which an alkyl group having 4 carbon atoms, that is, a butyl group, is monosubstituted with 6 acetic acid are particularly preferred;
The most preferred is one in which 5ec-butyl or tert-butyl is monosubstituted at the position.

The alkenyl group as a substituent on the benzene ring is a linear or branched lower alkenyl group having 2 to 6 carbon atoms (hereinafter referred to as
(sometimes abbreviated as C2-6 alkenyl group). Examples of such C2-6 alkynyl groups include vinyl, allyl, 1-propenyl, methallyl, butenyl, and 1-propenyl.
-ethylvinyl, 1°1-dimethylvinyl, 1-methyl-2-propenyl, and the like.

The alkynyl group as a substituent on the benzene ring is a linear or branched lower alkynyl group having 2 to 6 carbon atoms (hereinafter referred to as
(sometimes abbreviated as C2-6 alkynyl group). Examples of such 02-6T + niso groups include ethynyl, propynyl, butynyl fz, and the like.

Cycloalkyl group, phenylalkyl group, phenyl group as a substituent on the benzene ring R3, R
The 03-6 cycloalkyl group, the phenyl C1-4 alkyl group (which may have a substituent), and the phenyl group (which may have a substituent) mentioned above as 4 are also mentioned here. C3~, ncroalkyl group, phenyl C1,,
As specific examples of the +4 alkyl group and phenyl group, those mentioned above can be mentioned here as well.

The acyl group as a substituent on the benzene ring is a substituent R3,
The acyl groups mentioned above as R4, ie, the C2-5 alkanoyl group, the benzoyl group, and the phenyl C2-5 alkanoyl group (which may have a substituent) are mentioned here as well. Furthermore, a formyl group can also be mentioned. Specific examples of the C2-5 alkanoyl group and phenyl C2-5 alkanoyl group and the specific list of substituents for the phenyl group are those mentioned above.

The alkoxy group as a substituent on the benzene ring is a linear or branched alkoxy group having 1 to 4 carbon atoms (hereinafter referred to as C1
(sometimes abbreviated as ~4 alkoxy group). Such Cel4 alkoxy groups include methquine, ethoxy, n-propoxy, impropoxy, n-butoxy, imbutoxy, 5ec-butoxy and tert-butoxy.

The alkylthio group as a substituent on the benzene ring is a linear or branched alkylthio group having 4 to 4 carbon atoms (hereinafter referred to as
01-4 alkylthio group). Examples of such C□-4 alkylthio groups include methylthio and ethylthio.

Examples include propylthio and butylthio.

When a rogen atom is used as a substituent on a benzene ring, it also refers to fluorine, chlorine, bromine, iodine, etc.

These halogen atoms are mono-substituted at the 6-position, or 6.8
It is more preferable to use di-substitution at this position.

a monoalkylamino group as a substituent on the benzene ring,
Examples of the alkyl group of the dialkylamino group include the 01-4 alkyl groups described above as substituents R3 and R4. Examples of such mono-01-4 alkylamino groups and di-C1-4 alkylamino groups include N-methylamino, N-ethylamino, N-propylamine, N-butylamino,
N, N-dimethylamino, N, N-diethylamino, N
-Ethyl-N-methylamine and the like.

Substituent on benzene ring is 5, 6, 6, 7 or 7,
When two substituents are present at the 8-position, these two substituents may combine to form an alkylene group, alkenylene group, or alkadienylene group.

The alkylene group here represents an alkylene group having 3 or 4 carbon atoms, ie, trimethylene and tetramethylene. The alkenylene group is an alkenylene group having 3 or 4 carbon atoms, that is, -CH2CH=CH-.

-CH2CH2CH=CH->j and -CH2CH=CH
Represents CH2-. Al sword dininylene group::! Knee CH
= represents CHCH=CH-.

In this book, chromonization &
Material: 8 L' of foreign salt. Examples of the salt of compound CI] include acid addition salts and salts with bases. Acid addition salts are salts formed when the compound El] has a basic group, such as a basic amino group, monoalkylamino group, or dialkylamino group. Compounds: As acid addition salts: Acid addition salts and non-acid addition salts are listed. Examples of finite acid addition salts include formate, acetate,
Specific examples include trifluoroacetates, oxalates, nicotinates, paratoluenesulfone, and picrates. Specific examples of liquid-free acid addition salts include L hydrochloride, sulfur salt, phosphate, and the like.

Salt with a base: A salt that can be formed when compound [I] has an acidic group, such as an acidic hydroxyl group or a mercapto group. The salts of compound El] with bases include finite base salts and infinite base salts. Specific examples of the finite base salt include triethylamine salt, pyrinone salt, and diazavinclononane salt. Specific examples of inorganic base salts include sodium salts, potassium salts, calcium salts, etc.

In the general formula C1), it is shown in the test results as follows: Nisani Ruri=mono-ka-5 Yo.

Go; Leaf stone disease 1. It has a beneficial effect on 轡, Muromoya, and other diseases:/C.

Compound CI) in which R1 and R2 are both amine groups (hereinafter sometimes abbreviated as compound CIo)
Some of these are Yoneguchi patent confectionery 3,932゜466 No. 2
：、Bi=Fuji Publications Publication No. 111071 (Sho 58)) The former two are anti-allergic; however,
2 and anti-asthma; 2. Regarding the action, although mutual allergy is described in the latter category, there is no mention of its activity as an agricultural chemical in the article 9.

Mono-compounds/mono-compounds [In the formula, R'1 and R'2 are respectively the above-mentioned R1 and R'2].
As in 2, an optionally substituted amino group is a good benzene ring. However, when R'1 and R'2 are both amino groups, ■ is a benzene ring substituted with an alkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a fluorine atom, a bromine atom, or an iodine atom. The range of chromone compounds represented by However, the compounds within the range of the above general formula [1'] are not disclosed in the above-mentioned US patents and Japanese patent publications, especially in the implementation series, and there is no description of specific compounds.
Therefore, the scope of the above general formula [1'] is a new group of compounds in which specific compounds have been synthesized for the first time by the present invention and have been completed as an invention for the first time.

171 Compound CI of the present invention is a compound in which R1 and R2 are both amino groups, that is, 2-aminochromone-3-carboxamides (to), and a compound in which at least one of R1 and R2 is substituted with an amine group (hereinafter referred to as , compound [■′]
(sometimes abbreviated as ) and can be produced by the reaction route shown in the following formula.

In the alkyl group, R and R each represent an optionally substituted amino group like R1 and R2 above, and at least one of Rτ and R represents a substituted amine group] Each step is described below. will be explained in detail.

Method A: (U'J (Io) This method is a method for producing a compound (To) by reacting chromone-3-carbonitrile (ff) with hydroxylamine in the presence of water in an acidic manner.

It is convenient to use a salt of hydroxylamine used in the reaction, such as its hydrochloride, but the reaction may also be carried out by adding an excess of acid, such as hydrochloric acid.
Usually about 1 to 2 moles are used per 1 mole of the starting compound [''].The amount of water used in the reaction is an equimolar amount to a large excess of the compound [■].The reaction is carried out according to the general Q. It is preferable to carry out the reaction in an organic solvent such as methanol, ethanol, n-propanol alcohols, dimethylformamide, dimethyl sulfoxide, etc.
− is used. There is no particular restriction on the reaction temperature, but it is usually 50
Temperatures ranging from °C to around the boiling point of the solvent used, and reaction times of several minutes to several days are often used. After the reaction is complete, conventional isolation and cleanliness procedures such as solvent extraction, crystallization,
The desired product ([o,
) can be obtained.

Note that the starting compound [■] can be easily produced by a known method or a method similar thereto.

Method: (U)-(II)=CrV)-[:Io]
This law is A, S! The reaction of = is carried out stepwise to form the compound (I
o,) is a method of manufacturing. That is, first, starting compound (II) is reacted with water in the presence of a base to produce 2-aminochromone-3-carboxamides [■]. Examples of the base used in the reaction include organic amines such as ethylamine, n-dipropylamine, n-butylamine, and benzylamine.

Primary amines such as aniline and dimethylamine.

diethylamine, dipropylamine, dibutylamine,
Secondary amines such as morpholine, piperidine, and pyrrolidine, tertiary -20= amines such as triethylamine, heterocyclic bases such as imidazole and 2-methylimidasonyl, aqueous ammonia, ammonium acetate,
Ammonium carbonate, sodium carbonate.

Examples include inorganic bases such as sodium bicarbonate. These bases can be used in a catalytic amount to a large excess, and are not particularly limited.

The reaction is generally preferably carried out in a water-miscible solvent;
For example, dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, formic acid, acetic acid, propionic acid, and any organic acids.

Examples include ethers such as tetrahydrofuran and dioxane, and alcohols such as methanol, ethanol, propatool, and butanol. There are no particular restrictions on the reaction temperature, reaction time, or other reaction conditions;
Generally, the reaction is carried out for several minutes to three hours at a temperature of about 'C.

By reacting the f-hybrid compound CLI thus obtained with hydroxylamine, 2-aminochromone-8-carbonitrile (IVJ) is obtained.The hydroxylamine used in the reaction is a salt thereof, for example, a hydrochloride. However, the reaction may be carried out by adding an excess amount of acid, such as hydrochloric acid, and usually about 1 to 2 moles are used per 3 i moles of the compound ['x3]. Examples of solvents include methanol and ethanol.

Examples include alcohols such as n-propatol, dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, and organic acids such as formic acid, acetic acid, and propionic acid. Although there is no particular restriction on the reaction temperature, conditions are generally used, ranging from 50'C to around the boiling point of the solvent used, and the reaction time is often from several minutes to several days.

By reacting the thus obtained compound CIV) with water, the target compound [IO3] can be obtained.

To react a compound (IVJ with water, it is generally necessary to react it with an excess of inorganic acid, such as sulfuric acid, cynic acid, hydrochloric acid, etc.
The reaction is carried out by heating to 00'C, and the reaction time is appropriately selected depending on the reagent used.

The above 2-aminochromone-43-carbonitrile C
N] can also be obtained by reacting malondinitrile with acetylsalicyloyl chloride [v] in the presence of a base. Examples of the base used in this reaction include organic bases such as triethylamine, sodium methoxide, and sodium ethoxide, sodium hydride, and sodium hydroxide.

Examples include inorganic bases such as potassium hydroxide, sodium amide, and potassium amide. The reaction is usually carried out in a solvent, such as water.

Examples include benzene, toluene, tetrahydrofuran, and dimethylformamide. The amount of malondinitrile used per 1 mol of compound [v] is usually about 1 to 3 mol, and the amount of base used is about 1.1 to 3.3 mol.

The reaction temperature is not particularly limited, but is usually from 50°C to a temperature near the boiling point used. Also, the reaction time is several minutes ~
Conditions of several tens of hours are frequently used.

In addition, 2-aminochromone-3-carbonitrile (I
Y) can also be obtained by reacting malondinitrile with salicylic acid esters (Vl) in the presence of a base, particularly a strong base. The base used in the reaction is preferably a strong base such as sodium hydride, sodium amide, potassium amide, sodium methoxide, or sodium ethoxide. The reaction is usually carried out in a solvent,
Examples of such solvents include benzene, toluene, tetrahydrofuran, dimethylformamide, and dimethylsulfoxide. The amount of malondinitrile used per 31 moles of the compound (VT) is usually about 1 to 3 moles, and the amount of base used is about 1.1 to 3.3 moles.

The reaction temperature is not particularly limited, but is usually from 50°C to a temperature near the boiling point of the solvent used. Conditions in which the reaction time is still several minutes to several tens of hours are often used.

Note that salicylic acid-induced JE (Vl and (VT,l) can be easily produced by a known method or a method analogous thereto.

Method C: (To)-(I″) 2-aminochromone-3 obtained by the three-prong method or method B
- This is a method for producing compound [I'] by reacting carboxamides [■o] with a substituent-introducing reagent according to a conventional method. Here, examples of the substituent-introducing reagent include f-hyde compound [I
'], when R1 and/or R'2 is an amine group substituted with an alkyl group, the alkylating agent is 'f(t,
When is an amine group substituted with an acyl group, examples thereof include acylating agents.

The substituent introduction reaction in this method is a usual alkylation or acylation of an amine or amide using an alkylating agent or an acylating agent, and can be carried out according to a conventional method. Below, the benzene ring which may have the general formula as U] is R'3
represents an alkyl group or an acyl group] In the case of alkylation, for example, in the case of alkylation, Examples of introduction reagents include general formulas R', X (R'',
An alkylating agent represented by '=alkyl group) is used. In the alkylating agents R' and X, X is a halogen atom, particularly chlorine, bromine, and iodine. In addition, the alkylating agent R''3X is a sulfuric acid ester (R'30)2SO2
or sulfonic acid ester R', 0'-8o2・R [in the formula,
R can also be used as an alkyl group or an optionally substituted phenyl group. When X is...a rogen atom, 2-aminochromone-3-carboxamides (T
o) is reacted with an alkyl halide.

In this case, a base may be present together. Examples of the base include potassium carbonate, sodium hydroxide, etc.
machine base, triethylamine, pyridine.

Diethylaniline.

An organic base such as DB(J) is used.

□□□□□□□□□ Reactions are usually carried out in a solvent. As the solvent, common finite solvents such as water (71), benzene, toluene, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran, etc. are used alone or in combination. In addition, when the base and solvent are used, for example, pyridine, Diethylaniline, etc. may be used. Among these solvents, toluene, dimethylformamide, tetrahydrofuran, pyridine, etc. are preferable. 18 IC) +/shi, 'J-! -J shi(+
f l , 2-~2 + 7shi<'I January"t 3-
s, E-Improvement Packaging)
The amount of base is 1 to 20 mol, preferably 1.5 mol to 1 mol.
~2.5 moles are used. The solvent is 1 to 1 per 1 g of raw material.
00 minutes and then stir to dry. The reaction temperature is usually -20 to 200°C, preferably -5 to 150°C. The reaction time depends on the raw material compound (Ll clause, type of reagent,
It depends on the salt species, the solvent species, their amounts, and the reaction temperature, but it usually ends in 5 minutes to 48 hours. Extraction, crystals (H.

Which is convenient (2) is used. As an acid halide,
Amber, bromide, etc. are used. When using an acid halide as a reagent, a base is usually used and the reaction is carried out in an anhydrous solvent. Here, as the base, the above-mentioned groups used in the case of alkylation (2) can be mentioned as they are here. Examples of the anhydrous solvent used include benzene, toluene, dimethylformamide, dimethylacetamide,
Anhydrous organic solvents such as tetrahydrofuran are used. Pyridine can also be used as both a base and a solvent.

Diethylaniline and the like are sometimes used.

Among these solvents, toluene, dimethylformamide, tetrahydrofuran, and pyridine are preferred. 12 halides per mole of raw material f arsenide [L]
)~107ru, 躬)L(/yoha2~λmonoshi/f-
Measure IR. (Basic Umekushi raw material for river fhi compound [L)
] The amount of base is 1 to 20 mol, preferably 1 to 1 mol.
．． 5 to 2.5 moles are used. The solvent is almost 1 g thick;
The reaction proceeds by adding and stirring the mixture.The reaction temperature is usually -20 to 200℃, preferably -5 to 15℃.The reaction time depends on the raw material compound [type of Ll, type of reagent , the type of base, the type of solvent and their amounts, and the reaction temperature (=therefore, it is not constant, but it usually ends in 5 minutes to 48 hours.

Further, when an acid anhydride is used as a reagent, the above steps are usually carried out in an anhydrous solvent, but a large amount of the acid anhydride may also be used as a solvent. The use of a base may accelerate the reaction. As such bases, finite bases such as pyridine and diethylaniline are used, and the base compound rz
, t 1 mol (usually 1 to 10 mol, preferably 1 to 2 mol per 2 mols).

When carrying out the reaction using a solvent, the solvent should be 1/\1
] Noankarorojin) 0\\Uashi/Shikaii, f;, rf
l knee work ≠ Hiro・沁U medium 6° ゛゛゛;
Rishin 21-' Shiru Ushi 09 Cry #, 1+, ¥7Tj
, J Toy ((kai) Th(Ll I>l;hshi-(1
~100m1. Preferably 2 to 20 ml is used. The reaction proceeds from step 2 by dissolving the f-hybrid compound [I0] in an acid anhydride or a mixture of an acid anhydride and a solvent (= after dissolving, adding a base if necessary and stirring. The reaction temperature is usually -20 to 20 °C.
It is carried out at 0°C, preferably -5 to 150°C.

The degree and window time are the Harabuchi compound [LE's inverted term, and the reagent's turbid term.

Although the type of base, the type of solvent and their temperature, and the reaction temperature are not constant, the reaction is usually completed in 5 minutes to 48 hours. ■all■Countriesm1■I--■-■■After the reaction is completed, use conventional fluorescence separation methods such as solvent extraction, crystallization, and recrystallization.

The desired product can be obtained by chromatography, etc.

A method for producing a compound represented by the following general formula, in which a benzene ring may be substituted and R'5 represents an alkyl group, will now be described.

As the substituent introducing reagent (alkylating agent), the alkylating agent R', X (
The same alkyl halides as for R', ≧alkyl group, X = halogen atom) are used here as well, and as base a strong base such as, for example, sodium hydride is used. Here, too, the reaction is usually carried out in a solvent, and the solvent used here also includes the alkylating agent for the amino group at the 2-position. The alkyl halide is used in an amount of 1 to 10 moles, preferably 1.2 to 2 moles, per 1031 moles of the raw material compound.

A base such as sodium hydride is a raw material with 1 hydride [o]
1 to 20 moles per mole, preferably 1.5 to 2.
Use 5 moles. Solvent: 1-100r per 1g of raw material
ttl preferably 2 to 20 rrtl is used. The reaction proceeds by dissolving the compound (Io) in a solvent, then adding and stirring the alkyl rogenide and a strong base such as sodium hydride.The reaction temperature is usually -20 to 200°C.
It is preferably carried out at -5 to 150'C.

Although the reaction time varies depending on the type of raw material compound (ro), the type of reagent, the type of strong base, the type and amount of solvent, and the reaction temperature, the reaction is usually completed in 5 minutes to 48 hours. After the reaction is completed, the desired product can be obtained by conventional isolation and purification methods such as bath medium extraction, crystallization, recrystallization, and chromatography.

The structural formula and melting point of some of the compounds (1) of the present invention are shown in the following table.

Among the compounds [I] of the present invention, for example, 2-amino-6
-sec-butylchromone-3-carboxamide (compound number 7), 2-amino-6-tert-butylchromone-3-carboxamide (compound number 8), etc. are particularly known for their disease control activity.

The chromone compound CD according to the present invention has strong antibacterial activity against a wide range of plant pathogenic bacteria, especially fungi.
For example, when applied as a fungicide for paddy fields,
Blast disease doctor, micrococcal fungus.

It has strong double-play killing power against sesame leaf blight, baka-seed disease, etc. Furthermore, it has strong antibacterial activity not only against pathogenic bacteria in greens, but also against pathogenic bacteria that cause disease in many crops such as turmeric. For example, it has antibacterial activity against cucumber gray blight fungi, vegetable mycobacterium, and strawberry gray blight fungi.

The compound [■] of the present invention shows remarkable efficacy against the bakanae disease fungus, but
There are very few drugs that are effective against the Akainae disease bacterium, and with the emergence of bacteria resistant to Benlate T agents that have been used in the past, compound (r) is attracting attention. In addition, the best effect can be obtained when used as a seed disinfection method against the bakanae disease fungus.

In addition, the compound [■] of the present invention not only has the therapeutic ability to inhibit the spread of diseased plants by treating it, but also has the therapeutic ability to inhibit the spread of diseased plants by treating it with non-diseased plants.
It also has the preventive ability to prevent pathogen infection and protect the plant body. As a treatment method, even if it is simply sprayed on the stems and leaves of the plant body, due to its strong penetrating properties, it is absorbed into the plant body, moves through the body, and is widely distributed, and has the ability to maintain the concentration necessary for plant protection. have

Although all of the present compounds (1,) have strong bactericidal activity, they have low skin dander irritation and oral toxicity to warm-blooded animals, and have little impact on the environment such as fish toxicity. Furthermore, it does not cause any phytotoxicity to various crops, or is extremely invasive, and has no effect on subsequent growth or yield. It is presumed that this is because this compound (Il) has a strong affinity for plants and has moderate chemical stability. In other words, it is assumed that this compound (Il) has a strong affinity for plants and has moderate chemical stability. It is estimated that the chromone compound [+] according to the present invention gradually deactivates.
can be said to be a group of compounds with extremely excellent qualities as multi-purpose agricultural fungicides.

The agricultural fungicide of the present invention is one of the compounds of the general formula [1].
Of course, you can use only the seeds, but you can also use two or more songs. In addition, the compound of the present invention [1] (hereinafter sometimes referred to as an active ingredient) itself may be used alone, or, if necessary, various natural products.

It may also contain additives, solvents, etc. To explain in more detail, the active ingredient is used as a solid formulation for a long period of time.
It may be used for sustained efficacy purposes and may be dissolved or dispersed in a suitable liquid carrier (e.g., two-part formulation) or in a suitable solid carrier (e.g., a diluent,
It is mixed with or adsorbed to (massifying agent), and further (
2. Emulsifier 1. Dispersing agent, suspending agent, spreading agent, penetrating agent,
Wetting agent.

A mucilage, a stabilizer, etc. may be added to form an appropriate dosage form such as an oil solution, an emulsion, a wettable powder, a suspension, a single powder, a single fine granule, or a spray.

Examples of such solvents include water, alcohols (
For example, methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol, etc.), ketones (for example, acetone).

methyl ethyl ketone, etc.), ethers (e.g., dioxane, tetrahydrofuran, cellosolve, etc.), aliphatic carbons (e.g., gasoline, kerosene, kerosene, fuel oil, machine oil, etc.), aromatic hydrocarbons (e.g., benzene, ,toluene.

xylene, solvent naphtha, methylnaphthalene, etc.)
and other organic bases (e.g. pyridine).

aldehyde collidine, etc.), halogenated hydrocarbons (e.g., chloroform, 4-1 arsenic carbon, etc.).

acid amides (e.g. dimethylformamide),
Esters (e.g., ethyl acetate, butyl acetate, glycerin ester of fatty acids, etc.), nitriles (e.g., acetonitrile, etc.), sulfur-containing compounds (e.g., dimethyl sulfoxide, tetramethylene sulfone, etc.) are used. However, in general, it is preferable to use it by dissolving it in a water-soluble solvent such as glycols, dimethylformamide, dimethyl sulfoxide, or water.

In addition, solid carriers such as diluents and thickeners include, for example, vegetable powders (eg, rice bran, soybean flour).

(tobacco powder, wheat flour, wood flour, etc.), mineral powders (e.g., clays such as kaolin, bentonite, calcium phosphate, acid clay, talcs such as talcum powder, waxite powder,
Silicas such as diatomaceous earth and Kumohi powder), alumina, sulfur powder, activated carbon, etc. are also used, and these can be used alone or in combination of two or more.

In addition, sulfuric esters of soaps and higher alcohols can be used as emulsifiers, spreading agents, penetrating agents and dispersants.

Alkyl sulfonic acid, alkylaryl sulfonic acid, quaternary ammonium salt, oxyalkyl amine 7, fat e
l Ester, polyalkylene oxide type. Surfactants such as anhydrosorbitol-based surfactants are widely used, and it is generally preferable to include them in the formulation at an amount of 0.2 to 10% (% is by weight, the same applies hereinafter).If necessary, casein, gelatin, etc. .

Starch, alginic acid, agar, CMC, polyvinyl alcohol, pine oil, Nukaura, bentonite, Fresol soap, etc. may also be used. Also, necessary (two corresponding III: , 1
disinfectants (e.g. organochlorine disinfectants, pJJ+J
Non-based disinfectant. Nzimidazole fungicide, copper fungicide.

Organic sulfur fungicides, phenolic fungicides, antibiotics, etc.), insecticides (natural insecticides, carbamate insecticides, organophosphorus insecticides, etc.), acaricides, nematicides, herbicides, plants Growth regulators, stabilizers, synergists, attractants, repellents, fragrances, plant nutrients.

Fertilizer, various amino acids, low-molecular or high-molecular phosphates, etc. may be mixed as appropriate.

method (manufactured by mixing the two.
W? The content of active ingredients in Ji'-based pest control agents is approximately 10 to 90% for emulsions and irrigation agents, approximately 0.1 to 10% for oils and powders, and approximately 5% for granules. ~50% 9 is appropriate.

Note that emulsions, irrigation agents, and the like are preferably further diluted (for example, 50 to 5000 times) with water and the like before being sprayed.

The amount of active ingredients to be used, the amount of mixture with the emetic agent, and the ratio of these ingredients will depend on the growth stage of the target plant,
Although it varies depending on various conditions such as the growth situation, the type of disease, the condition of one drop, the timing and method of application of the drug, in general, the amount of active ingredient should be about 10 to 300 g per 10 are (2 adjustments may be made). , the concentration used is:
The active ingredient may be in the range of 10 to 11,000 pp, and the method of use may be by spraying, dusting, irrigating, or coating the seeds. However, the amount, concentration, or method of use does not impose any limitations on the present invention.

(Action, Effect) The plant disease control agent of the present invention has very few side effects,
It is extremely useful in the industry because it is simple, inexpensive, and provides excellent action and effects.

(Examples, test examples) Next, Examples and Test Examples are shown.

Example 1 2-methylamino-6-tert-butylchromone-3
-Synthesis of carboxamide (Compound No. 29) 1.3'7 of 2-amino-5-tert-butylchromone-3-carboxamide (Compound No. 8) was dissolved in 25 scraps of tetrahydrofuran, and 066 g of tert-butoxypotassium was added thereto. Ta. Then, while stirring while keeping the temperature below 10°C, a solution of 0.37 ml of iodine (himethyl) and 1 t:2 of tetrahydrofuran was gradually added dropwise. After the dropwise addition was completed, the mixture was heated at room temperature for 1 hour, and then at 50°C for 2 hours.
Stir for a while, then add 0.5 m of 1-himethyl iodine.
1 was added and boiled under reflux for 17 hours. After cooling, the precipitated inorganic salts were filtered off, and the filtrate was concentrated under reduced pressure. The residue was dissolved in chloroform, washed with water, dehydrated, and concentrated.

The residue was subjected to column chromatography using silica gel (elution 11).
ffichloroform:ethanol=20:1. V/V)
Upon purification, crystal 06□ with a melting point of 237-240C was obtained.

Example 2 Synthesis of 2-acetamidochromone-3-carboxamide (Compound No. 30) 0.51i7 of 2-aminochromone-3-carboxamide (Compound No. 1) was added to 5Mi of pyridine, and to this was added 1.0:l of acetic anhydride. added. The crystals were dissolved by heating to 50'C and allowed to cool. Concentration under reduced pressure and recrystallization of the residue from ethyl acetate gave crystals with a melting point of 360° C. (decomposition).
429 was obtained.

Example 3 2-Ethoxycarbonylamino-6-tert-ph'thylchromone-3-carboxamide ((Higosu number 35)
Synthesis of 2-Amino-6-tert-butylchromone-3-carboxamide (Compound No. 8) 1.5 g and 0.94 ml of triethylamine were processed into 20 ml of toluene, = 43- 0.74' of ethyl chlorocarbonate while stirring at room temperature. A solution of 7 dissolved in 5 ml of toluene was gradually added (1 drop).

After the addition was completed, stirring was continued for 1 hour, and the precipitated crystals were collected by filtration, washed with water, and dried. When this was recrystallized from toluene, crystals with a melting point of 194-196°C were obtained.

Example 4 2-(N-methylcarbamoyl)amino-6-tert
-butylchromone-3-carboxamide (compound no. 3
Synthesis of 6) 2-Amino-6-tert-butylchromone-3-carboxamide (compound number 8) L5'l' was dissolved in 20ml of tetrahydrofuran, and triethyl/I/7
Then, 0.6 ml of methyl isocyanate was gradually added dropwise while stirring at room temperature.

After the addition was completed, the mixture was boiled under reflux for 8 days. During this time, 0.6 ml of methyl isocyanate was added four more times.

The residue was dissolved in chloroform and washed with water to precipitate crystals. The crystals were collected by filtration and recrystallized from methanol to give a solution with a melting point of 300°C, 2.7
, also a, 3s, q (+ dashi mousse nolinoshi 1/7;
Bow - gold side.

44-Example 5 Synthesis of 2-amino-6-sec-butylchromone-3-carboxamide (Compound No. 7) 6-sec-butylchromone-3-carbonitrile 38 g, hydroxylamine hydrochloride 1.4 g.

A mixture of 66 mL of ethanol and 1 mρ of water was added to 48
Heat to reflux with stirring for an hour. Cold soaked.

When the precipitate is collected by filtration and recrystallized from 1-chloroform, the melting point
0.7 g of crystals at 193-195°C were obtained.

Example 6 Synthesis of 2-amino-6-tart-butylchromone-3-carboxamide (compound number 8) 6-tert-butylchromone-3-carbonitrile 2.8 g, hydroxylamine hydrochloride 1.1 g, ethanol 5
0m12. The mixture of 1.2 mff of water was heated under reflux with stirring for 45 hours. After cooling, the precipitate was collected by filtration and recrystallized from ethyl acetate to obtain 1.27 g of crystals with a melting point of 245-247°C.

Example 7 Compound (3) 50%, sodium ligninsulfonate 2
%, white carbon 3%, polyoxyethylene alkyl allyl ether 5q6. A hydrating agent made by mixing 40% clay. Dilute it 1,000 to 3,000 times with water and spray 10 to 201 times per are.

Example 8 Compound (s) s%, aluminum stearate 0.1
%, a powder made by mixing 96.9% clay. 3 per a
Spray directly from C109 to 5009.

Example 9 Compound (7) 5%, gum arabic 5o6. bentonai)
Granules made by mixing and granulating 30% talc and 60q6 talc. 5009 directly from aooq per a (-apply.

Example 10 Compound (31) 20Q6. An emulsion containing xylene (75 eV) and polyoxyethylene alkylaryl ether (5 eV). Dilute 40 to 2000 times with water and spray directly (= 1nl per a).

Example 11 Compound (20) 30%, sodium ligninsulfonate 5o6. A hydrating agent made by mixing and pulverizing 5% polyoxyethylene alkyl ether and 60% clay.

Dilute 40 to 2,000 times with water and spray directly at 101/a.

Example 12 Compound (500o6. Granules that can be granulated by adding water to a mixture of 5% sodium ligninsulfonate and 85% bentonite. Directly apply 500g of 800Q to a per a.

Test Example 1 Multiply dilution method using agar medium (from 2) An antibacterial activity test was performed on a representative target compound (1 compound number (indicated in 2) listed in the text) and a control compound according to the following procedure, and the results were are summarized in the table below.

(1), Assay medium Glucose broth agar medium (2)
, drug preparation Test compound or control compound 40 capes N,
Dissolved in a mixture of 0.5 m of N-dimethylformamide and 9.5 d of acetone, diluted with sterile water to 1000 μg and 7 ml (the concentration in the medium is 1/1).
0) Do.

(3), Test bacteria 1) Pyricularia oryza x
aoryzae) I FO5279, rice blast fungus 2) Helmintosporium sigmoideum (Hel
minthosporium sigmoideum
) IF04867, Rice micrococcal rot fungus 3) Helmintosporium oryzae sesame leaf blight fungus 4) Pellicularia
asasakii) IP06830. Rice sheath blight disease garden (4), control compound control f-hi compound 1: Japanese Patent Publication 1985-485
50 of the compound of Example 1 chromone-3-carpoxanilide (melting point, 217-21
8.5°C) Control compound 2: Japanese Patent Publication No. 49-4507
Compound 1 of Example 2 of Japanese Patent Application Publication No. 49-45074 Compound 2 of Example 1 2-M-F-lucromone-8-(p-talolocarpoxanilide) (melting point 18 o'C ) (5), Inoculation method Plot point 4 is agar plate containing mycelia and other test bacteria are inoculated with bacterial solution (6), culture plot point 1.2 is inoculated at 28°C for 4 days, bacterial infection 3.4
for 3 days at 28°C (7).
, 'd) was calculated.

(8), test results Note: - means "not tested".

Test Example 2 The effect of controlling rice blast disease when sprayed on foliage was investigated using the following test method, and the results are summarized in the table below. In addition, the test compound No. 1 is indicated by the compound number in the text.

l Test method: 1. Pathogen: Pyricularia oryzae 2. Test plants: 9 rice varieties, No. 4, 9G + 10 pots, approx. 3
28 seedlings 3, inoculation: natural infection from leaves damaged by blast disease 4, chemical treatment: test sample-51 prepared by the method of Example 10 = Compound (31) diluted to a predetermined concentration and sprayed, 0.2
Spreading agent (Dyne, trade name, manufactured by Takeda Pharmaceutical) was added at a rate of 28% and sprayed 28 days after the start of inoculation. The other test compounds and control compounds were the same as in Example 10, with a compound content of 20%.

An emulsion containing 75% xylene and 5% phosphoryoxyethylene argylaryl ether was prepared in the same manner (double spraying).

5. Ward system 21 wards 2 pots 6. Preparation: Issued by the Japan Plant Protection Association 7 days after inoculation (8,4
9, 2, 15) The investigation was conducted according to "Basic layer J of leaf blast attack area rate" (pages 4-7) of "Standards for pest and disease outbreak investigation".

■ Test Results: Test Example 3 The effect of controlling rice sheath blight was investigated using the following test method, and the results are summarized in the table below. In addition, the test compound (compound) is shown under the compound column in the main text.

l Test method: 1. Pathogen: Bellicularia sasakii (Rhizoctonia
Sorani-Sasaki type) (pelli-curaria 5
asakii (Rhizoctonia solan)
i5asakii type)] 2, Test plants:
1 rice variety Kinnanpu, 90 pots, 3 plants, 80-90 days old, 3 seedlings, Inoculation: Cultured on potato sucrose agar medium at 28℃ for 2 days, punch out the periphery of the bacterial flora with a cork pole with a diameter of IQa + In. Insertion inoculation into rice ground storage, 2 days until post-inoculation survey
It was kept at 5-35°C and 70-100% RH.

4. Chemical treatment: Based on Test Example 2, sprinkled with air, then inoculated 5. District system: 1 area, 2 pots 6. Survey: 10 days after inoculation, the height from the ground to the top of the lesion was measured. , the lesion expansion rate was calculated based on the ratio to the untreated area.

■ Test Results: Test Example 4 A representative compound of the present invention (indicated by the compound number stated in the main text) and a control compound were tested against Tokainae disease fungus in the following manner, and the results are summarized in the table below.

(1) Test method: Seed sterilization of Niigata early paddy naturally infected with Horse Seedling Disease concavity is carried out in the usual manner. In other words, dry rice is mixed with a chemical solution.
After soaking for 4 hours and disinfecting, air dry and then soak in water. Next, the disinfectant seeds are sown and the seedlings are raised. Seed amount is 1
Ratio of 20I/box (60
30°C).

Commercially available granular coral clay was used for the floor.

(2) Occurrence status of bakanae disease: Severe outbreak (3) Preparation of drug solution: Dissolve the test compound or control compound in water to a predetermined concentration.

(4) Section division: 1/8 box per section, 2 repetitions (5) Investigation: 14 days after sowing, 100 to 140 plants per section were investigated for the presence or absence of disease.

(6) Control compound: benlate T hydrate The color components are 20% benomyl and 20% thiuram.

(8) Discussion

Claims (1)

[Claims] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are optionally substituted amino groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ An agricultural fungicide containing a chromone compound represented by the following formula: