JP2008088161A - Phenylguanidine derivative or salt thereof and pest control agent containing the same as active ingredient - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pest control agent having a high, stable pest control effect. <P>SOLUTION: A phenylguanidine derivative represented by formula (I) and salts thereof are provided. (Wherein, R<SP>1</SP>represents H, an alkyl or a cycloalkyl; R<SP>2</SP>represents H, an optionally substituted phenyl, an optionally substituted arylalkyl, nitro, cyano or the like; R<SP>3</SP>and R<SP>4</SP>may be the same or different and represent H, an alkyl, an alkenyl, an alkynyl or the like; R<SP>5</SP>represents H, a halogen, an alkyl, an alkoxy or hydroxy; A represents O, S or NR<SP>6</SP>; X represents NR<SP>6</SP>, NR<SP>6</SP>-Ak<SP>c</SP>-NR<SP>6</SP>or the like; and Ak<SP>a</SP>, Ak<SP>b</SP>and Ak<SP>c</SP>independently represent an alkylene). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel phenylguanidine derivative having a pest control effect or a salt thereof. Moreover, it is related with the pest control agent which contains them as an active ingredient.

  A compound in which the guanidine moiety of the phenylguanidine derivative of the present invention is amidine is described in Patent Document 1. However, the phenylguanidine derivative of the present invention is not known.

International Publication WO2003 / 074476

  Many agricultural and horticultural fungicides provided in the past have their characteristics in controlling the phytopathogenic fungi, and some of them have a slightly inferior therapeutic effect or a relatively residual effect compared to the preventive effect. Depending on the application situation, it may show only a practically insufficient control effect against phytopathogenic fungi. Accordingly, there is a demand for the creation of new compounds having a powerful plant pathogen control effect.

  As a result of researches to solve the above-mentioned problems, the present inventors have used various compounds represented by the formula (I) as active ingredients, thereby causing various diseases, particularly wheat powdery mildew, red rust, The present inventors completed the present invention by obtaining the knowledge that gray mold disease; sclerotia of legumes; excellent control effect against downy mildew, plague, and anthracnose of vegetables. That is, the present invention relates to the formula (I)

[Wherein R ¹ is a hydrogen atom, alkyl or cycloalkyl; R ² is a hydrogen atom, phenyl optionally substituted with D, arylalkyl optionally substituted with D, nitro, cyano, NR ⁷ R ⁸ CONR ⁷ R ⁸ , OR ⁷ , SO ₂ R ⁹ , COR ⁹ or COOR ⁹ ; R ³ and R ⁴ are each independently a hydrogen atom, alkyl, alkenyl or alkynyl, or R ³ and R ⁴ Together may form a nitrogen-containing saturated monocyclic heterocycle with the adjacent nitrogen atom; R ⁵ is a hydrogen atom, halogen, alkyl, alkoxy or hydroxy; A is an oxygen atom, sulfur atom or NR ⁶ ; X is NR ⁶ , NR ⁶ -Ak ^c -NR ⁶ or

（式中、Ｙ¹及びＹ²はそれぞれ同一でも異なっていてもよく、ハロゲン若しくはアルコキシで置換されてもよいＣ_1-4低級アルキレンであり；Ｚは窒素原子又はＣＨである）であり；Ｒ⁶は水素原子又はアルキルであり；Ｒ⁷及びＲ⁸は各々独立に、水素原子、Ｃ_1-6アルキル又はＣ_1-6ハロアルキルであり；Ｒ⁹はＣ_1-6アルキル又はＣ_1-6ハロアルキルであり；Ak^a、Ak^b及びAk^ｃは各々独立に、アルキレンであり；Ｄはハロゲン、アルキル、アルコキシ、ハロアルキル又はハロアルコキシである]で表されるフェニルグアニジン誘導体又はその塩、並びにそれらを有効成分として含有する有害生物防除剤に関する。

Wherein Y ¹ and Y ² may be the same or different and each is a C _1-4 lower alkylene which may be substituted with halogen or alkoxy; Z is a nitrogen atom or CH; ⁶ is a hydrogen atom or alkyl; R ⁷ and R ⁸ are each independently a hydrogen atom, C _1-6 alkyl or C _1-6 haloalkyl; R ⁹ is C _1-6 alkyl or C _1-6 haloalkyl Ak ^a , Ak ^b and Ak ^c are each independently alkylene; D is halogen, alkyl, alkoxy, haloalkyl or haloalkoxy], and a phenylguanidine derivative represented by The present invention relates to a pest control agent contained as a component.

Two R ¹ , R ² , R ³ , R ⁴ , R ⁵ and A contained in the formula (I) are the same substituent.

Examples of the alkyl or alkyl moiety contained in the formula (I) include linear or branched C _1-6 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl.

Examples of the cycloalkyl or cycloalkyl moiety contained in the formula (I) include C _3-6 cycloalkyl such as cyclopropyl, cyclopentyl, cyclohexyl and the like.

  Examples of the alkenyl or alkenyl moiety contained in the formula (I) include linear or branched ones having 2 to 7 carbon atoms such as vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 1,3- Examples include butadienyl, 1-hexenyl, 1-heptenyl and the like. The alkynyl or alkynyl moiety contained in the formula (I) is a straight chain or branched chain having 2 to 7 carbon atoms such as ethynyl, 2-butynyl, 2-pentynyl, 3-hexynyl, 4-dimethyl. -2-pentynyl and the like.

  As the halogen contained in the formula (I), fluorine, chlorine, bromine or iodine is used, and for example, fluorine, chlorine or bromine is preferably used.

Examples of the alkoxy or alkoxy moiety contained in the formula (I) include linear or branched C _1-6 alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.

The nitrogen-containing saturated monocyclic heterocycle formed by R ³ and R ⁴ together in the formula (I) together with the adjacent nitrogen atom may optionally contain a hetero atom other than nitrogen. . Among them, a 5- or 6-membered nitrogen-containing saturated monocyclic heterocyclic ring which may contain S and / or O is desirable, for example, a 5-membered saturated monocyclic ring such as pyrrolidinyl, imidazolidinyl, pyrazolidinyl, triazolidinyl, thiadiazolidinyl, etc. Formula heterocycles; saturated monocyclic 6-membered heterocycles such as piperidinyl, morpholinyl, piperazinyl and the like.

  Examples of the salt of the compound of the formula (I) include generally known salts of basic groups such as amino groups. Such salts include, for example, salts with mineral acids such as hydrochloric acid, hydrobromic acid and sulfuric acid; organic carboxylic acids such as tartaric acid, formic acid, acetic acid, citric acid, fumaric acid, maleic acid, trichloroacetic acid and trifluoroacetic acid. And salts with acids; and salts with sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, mesitylenesulfonic acid and naphthalenesulfonic acid.

  The phenylguanidine derivative represented by the formula (I) or a salt thereof exhibits an excellent effect as an active ingredient of agricultural and horticultural fungicides and / or antifungal agents.

Among the phenylguanidine derivatives or salts thereof of the present invention, desirable embodiments are described below. In addition, the compound of following (2) points out the compound of a postscript formula (I-1).
(1) A phenylguanidine derivative of the formula (I) or a salt thereof.
(2) The phenylguanidine derivative or a salt thereof according to (1), wherein R ³ and R ⁴ are hydrogen atoms.
(3) The phenylguanidine derivative or a salt thereof according to (1), wherein R ¹ , R ³ and R ⁴ are hydrogen atoms.
(4) R ¹ is a hydrogen atom; R ² is a hydrogen atom, dimethylamino or nitro; R ³ and R ⁴ are hydrogen atoms; A is an oxygen atom or NR ⁶ ; X is NR ⁶ ; The phenylguanidine derivative or a salt thereof according to (1), which is NR ⁶ -Ak ^c -NR ⁶ , a piperidinyl group or a piperazinyl group.
(5) The phenylguanidine derivative or a salt thereof according to (4), wherein R ² is a hydrogen atom or nitro; A is an oxygen atom; and X is —NH, a piperidinyl group or a piperazinyl group.

The compound of Formula (I) can be manufactured by the method according to the manufacturing method [1]-[3] shown below, the synthesis example 1 and the synthesis example 2 which are mentioned later.
Manufacturing method [1]
Among the compounds of formula (I), the compound of formula (I-1) can be produced by the method shown in the following flow (in the flow, R ¹ , R ² , R ⁵ , A, Ak ^a , Ak ^b and X is as described above, R ^{1 ′} is alkyl or cycloalkyl, PG represents an amino protecting group, and Hal represents halogen)

  The compound of formula (III-1) is obtained by reducing the nitro group in the compound of formula (II) to an amino group. As a method for reducing a nitro group to an amino group, various methods can be mentioned. Specifically, (a) catalytic hydrogenation reaction using metal catalysts, (b) methods using sulfides (dimethyl sulfide, diphenyl sulfide, etc.), (c) metal hydrides (sodium borohydride, lithium aluminum hydride, etc.) And (d) a method of reacting with a metal such as zinc or iron under acidic conditions. The catalytic hydrogenation reaction with a metal catalyst in (a) is usually performed by using platinum, platinum oxide, platinum black, Raney nickel, palladium, palladium carbon, rhodium, rhodium-alumina, etc. as a catalyst in a hydrogen atmosphere. Can do.

  The above reduction reaction can usually be performed in the presence of a solvent. The solvent may be any solvent as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and cyclohexane; dioxane, tetrahydrofuran, Ethers such as diethyl ether and dimethoxyethane; esters such as methyl acetate and ethyl acetate; polar aprotic solvents such as dimethylacetamide, dimethylformamide and N-methylpyrrolidone; methanol, ethanol, propanol and t-butanol 1 type, or 2 or more types can be suitably selected from water etc .; This reaction can be carried out usually at 0 to 150 ° C., preferably 0 to 80 ° C., and the reaction time can be usually about 0.5 to 96 hours, preferably about 0.5 to 48 hours.

The compound of the formula (III-2) is obtained by reacting the compound of the formula (III-1) with a compound represented by R ^{1 ′} -Hal in the presence of a base and a solvent. Examples of the base include inorganic bases such as sodium carbonate and potassium carbonate; organic amines such as triethylamine, tributylamine, diisopropylethylamine, pyrrolidine, and piperidine. The amount of the base used may be a ratio of 2 mol or more with respect to 1 mol of the compound of the formula (III-1), and is preferably a ratio of 2 to 5 mol. The solvent may be any solvent that is inert to the reaction, for example, ethers such as dioxane, tetrahydrofuran, diethyl ether and dimethoxyethane; polar aprotic such as dimethylformamide, acetonitrile and propionitrile. 1 type or 2 types or more can be suitably selected from a solvent;

A compound of formula (IV) is obtained by reacting a compound of formula (III) with isothiocyanate (PG-NCS). Specific examples of the isothiocyanate that can be used include ethoxycarbonyl isothiocyanate and benzyloxycarbonyl isothiocyanate. This reaction can be performed by a method of converting a normal amino compound into thiourea. In addition, this reaction can be performed in the presence of a solvent that does not adversely influence the reaction. For example, alcohols such as methanol, ethanol, n-propanol, i-propanol; diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, Ethers such as dimethoxyethane and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride; aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene, and toluene; Nitriles such as acetonitrile; N, N-dimethylformamide; N, N-dimethylacetamide; The amount of isothiocyanate that can be used in this reaction may be 2 to 100 moles, preferably 2 to 10 moles, per mole of the compound of formula (III). The compound of formula (III) includes the compound of formula (III-1) and the compound of formula (III-2).

The compound of the formula (V) is obtained by reacting the compound of the formula (IV) with a primary amine compound represented by R ² NH ₂ in the presence of a condensing agent and subjecting it to desulfurization treatment. This reaction can be performed according to, for example, a method of converting thiourea to a guanidine derivative described in WO2004 / 037166 and the like. Examples of the condensing agent that can be used in this reaction include N, N′-dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, and the amount used thereof is 1 mol of the compound of formula (IV). The ratio may be 2 to 100 moles, preferably 4 to 10 moles. This reaction can be carried out in the presence of a solvent that does not adversely influence the reaction, for example, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether; dichloromethane, chloroform, carbon tetrachloride, etc. Halogenated hydrocarbons; aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene, toluene; nitriles such as acetonitrile; N, N-dimethylformamide; N, N-dimethylacetamide; 1-ethyl-3- (3 -Dimethylaminopropyl) carbodiimide;

The compound of the formula (I-1) can be produced by reacting the compound of the formula (V) with a deprotecting group. This reaction can be performed by a general method. The protecting group represented by PG may be a common amino protecting group, and examples thereof include t-butoxycarbonyl, benzyloxycarbonyl, ethoxycarbonyl, benzoyl and the like.

Manufacturing method [2]
The compound of the formula (I-2) can be produced by the method shown in the following flow (in the flow, R ¹ , R ⁵ , A, Ak ^a , Ak ^b , X and PG are as described above).

The compound of the formula (VI) can be obtained by guanidinating the compound of the formula (III) described in the production method [1] in the presence of a reaction reagent. The method of guanidinolation can be produced according to the method described in Journal of Organic Chemistry (1998), 3804. This reaction can be carried out in the presence of a solvent that does not adversely influence the reaction. For example, alcohols such as methanol, ethanol, n-propanol, i-propanol; diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane Ethers such as diethylene glycol dimethyl ether; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene and toluene; nitriles such as acetonitrile; N, N-dimethylformamide N, N-dimethylacetamide; and the like can be used. The reaction reagent used in the reaction is a combination of a compound represented by the following formula (1) (wherein Tf represents trifluoromethanesulfonyl) and a base; a compound represented by the following formula (2); And a combination of a compound represented by 3), a condensing agent, and a base. Examples of the compound represented by the following formula (1) include N, N′-di-t-butoxycarbonyl-N ″ -trifluoromethanesulfonylguanidine. Examples of the compound represented by the following formula (2) include N, N′-bis-t-butoxycarbonyl-1H-pyrazole-1-carboxyamidine. Examples of the compound represented by the following formula (3) include N, N′-di-t-butoxycarbonyl-N ″ -thiourea. Examples of the condensing agent include those exemplified in the production method [1].

  Examples of the base that can be used in these reactions include inorganic bases such as sodium carbonate and potassium carbonate; organic amines such as triethylamine, tributylamine, diisopropylethylamine, pyrrolidine, and piperidine. The amount of the base used may be a ratio of 2 mol or more per 1 mol of the compound of formula (IV), and is preferably a ratio of 2-5 mol. This reaction can be carried out usually at 0 to 150 ° C., preferably 0 to 80 ° C., and the reaction time can be usually about 0.5 to 96 hours, preferably about 0.5 to 48 hours.

The compound of formula (I-2) can be obtained by reacting the deprotecting group from the compound of formula (VI). This reaction can be carried out according to the reaction for obtaining the compound of the formula (I-1) from the compound of the formula (V) in the production method [1].

Manufacturing method [3]
The compound of the formula (I) can be produced by the method shown in the following flow (in the flow, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , A, Ak ^a , Ak ^b , X and PG are the same as those described above. And Ph represents phenyl).

The compound of formula (I) can be obtained by reacting the compound of formula (III) described in the production method [1] with cyanamide (NH ₂ CN) or a nitroso compound represented by formula (VII). Examples of the base that can be used in this reaction include inorganic bases such as sodium carbonate and potassium carbonate; organic amines such as triethylamine, tributylamine, diisopropylethylamine, pyrrolidine, and piperidine; A ratio of 2 moles or more per mole of the compound of III) is sufficient, and a ratio of 2 to 5 moles is desirable. This reaction is usually carried out at 0 to 200 ° C., preferably at room temperature to 100 ° C. for 1 to 24 hours.

  When cyanamide is reacted with the compound of formula (III), the reaction is carried out under acidic conditions using an acid. As the acid, for example, mineral acids such as hydrochloric acid, hydrobromic acid and nitric acid can be used. The amount of the acid used is desirably 2 to 100 moles per mole of the compound of formula (III). This reaction can be carried out in the presence of a solvent that does not adversely influence the reaction. For example, alcohols such as methanol, ethanol, n-propanol, i-propanol; water; As cyanamide, anhydrous cyanamide, cyanamide 50% aqueous solution, or the like can be used. The amount of cyanamide used may be 2 to 100 moles per mole of the compound of formula (III), and is preferably 2 to 20 moles.

  When the compound of formula (III) is reacted with the nitroso compound represented by formula (VII), the reaction can be carried out under neutral conditions. Examples of the solvent that can be used in this case include ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and diethylene glycol dimethyl ether, and water. The amount of the nitroso compound used may be 2 to 100 moles per mole of the compound of formula (III), and is preferably 2 to 10 moles.

  The compound of formula (IX) can be obtained by guanidinating a compound of formula (III) and a compound of formula (VIII) in the presence of an organic base. The method of guanidinolation can be performed according to the method of the above production method [2]. Examples of the organic base that can be used in this reaction include organic amines such as triethylamine, tributylamine, diisopropylethylamine, pyrrolidine, and piperidine. The organic base may be used in an amount of 2 mol or more, preferably 2 to 5 mol, per mol of the compound of formula (III).

A compound of formula (I) can be obtained by reacting a compound of formula (IX) with a compound represented by R ³ R ⁴ NH. This reaction can be performed according to the method of the above production method [1]. This reaction is desirably performed in the presence of the organic base described above, but when the compound represented by R ³ R ⁴ NH is used in a large excess, the organic base need not be used.

Intermediate Production Method The compound of formula (II), which is a raw material compound of the above production method [1], conformed to the following flows (1) to (8) or the description in (1) and (2) of Synthesis Example 1 below. (In the flow, R ⁵ , R ⁶ , A, Ak ^a , Ak ^b , Ak ^c , X, Y ¹ , Y ² and PG are as described above, and L is a leaving group). In addition, although various things are mentioned as a leaving group in each flow, Halogens, such as chlorine and a bromine, are mentioned.

Flow (1)
The compound of the formula (XI) can be produced by azidating a compound of the formula (X) in the presence of an azidating agent. A solvent is used for this reaction, and the solvent is not particularly limited as long as it does not adversely affect the reaction, but alcohols such as methanol and ethanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; diethyl ether and diisopropyl ether Ethers such as ethyl acetate and methyl acetate; aromatic hydrocarbons such as benzene and toluene; nitriles such as acetonitrile; N, N-dimethylformamide; N , N-dimethylacetamide; dimethyl sulfoxide; Examples of the azidating agent used in this reaction include sodium azide, lithium azide, barium azide, cesium azide, and trimethylsilyl azide. The ratio is preferably 1 to 5 moles. This reaction may be carried out at 0 to 200 ° C., preferably 0 to 150 ° C. for 1 minute to 24 hours.

  The amine compound of formula (XII) can be prepared by reducing the compound of formula (XI). Reduction methods include: (a) catalytic hydrogenation reaction with metal catalyst, (b) subsequent hydrolysis reaction with triphenylphosphine, (c) reaction with sodium borohydride, (d) reaction with inorganic and organic mercaptans. Etc.

  The compound of the formula (XIV) can be obtained by performing a dehydration condensation reaction between the amine compound of the formula (XII) and the compound of the formula (XIII) in the presence of a dehydrating agent. The solvent that can be used in this reaction can be carried out in the presence of a solvent that does not adversely influence the reaction. For example, alcohols such as methanol, ethanol, n-propanol and i-propanol; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane and diethylene glycol dimethyl ether; halogenated carbonization such as dichloromethane, chloroform and carbon tetrachloride Hydrogens; aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene and toluene; nitriles such as acetonitrile; and the like can be used. Examples of the dehydrating agent that can be used in this reaction include anhydrous magnesium sulfate, calcium chloride, molecular sieves, etc., and the amount thereof is 1 to 50 times (W / W) with respect to the amine compound of the formula (XII). The amount is preferably 1 to 10 times (W / W). This reaction may be carried out at 0 to 200 ° C., preferably 0 to 150 ° C. for 1 to 24 hours.

The compound of formula (II) is obtained by reducing the compound of formula (XIV). The solvent that can be used in this reaction can be carried out in the presence of a solvent that does not adversely influence the reaction. For example, alcohols such as methanol, ethanol, n-propanol and i-propanol; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane and diethylene glycol dimethyl ether; halogenated carbonization such as dichloromethane, chloroform and carbon tetrachloride Hydrogens; aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene and toluene; nitriles such as acetonitrile; N, N-dimethylformamide; N, N-dimethylacetamide;

Examples of the reducing agent used in this reaction include boron hydride compounds such as borane, dialkylborane, sodium borohydride, lithium borohydride, potassium borohydride, calcium borohydride, sodium triacetoxyborohydride; hydrogenation And aluminum hydride compounds such as aluminum lithium and diisobutylaluminum hydride; metal hydrides such as tin hydride compounds; and the like. The amount used varies depending on the type of the reducing agent. For example, in the case of a borohydride compound, it may be a ratio of 0.25 times mole or more, preferably 1 to 5 moles per mole of the compound of the formula (XIV). The molar ratio.

Flow (2)
The compound of formula (II) is obtained by reacting the compound of formula (XII) with the compound of formula (XV) in the presence of a base. Examples of the base include inorganic bases such as sodium carbonate and potassium carbonate; organic amines such as triethylamine, tributylamine, diisopropylethylamine, pyrrolidine, and piperidine. In this reaction, a solvent that does not adversely influence the reaction is used. For example, alcohols such as methanol, ethanol, n-propanol, i-propanol; diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, etc. Ethers; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene and toluene; nitriles such as acetonitrile; N, N-dimethylformamide; N, N -Dimethylacetamide; dimethylsulfoxide; and the like can be used. The amount of the base used may be a ratio of 1 mol or more per 1 mol of the compound of the formula (XII), and is preferably a ratio of 1 to 5 mol.

Flow (3)
A compound of formula (XVII) is obtained by reacting a compound of formula (X), a compound of formula (XV) and a compound of formula (XVI) in the presence of a base. Examples of the base used in this reaction include inorganic bases such as sodium carbonate and potassium carbonate; organic amines such as triethylamine, tributylamine, diisopropylethylamine, pyrrolidine, and piperidine. In this reaction, a solvent that does not adversely influence the reaction is used. For example, alcohols such as methanol, ethanol, n-propanol, i-propanol; diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, etc. Ethers; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene and toluene; nitriles such as acetonitrile; N, N-dimethylformamide; N, N -Dimethylacetamide; dimethylsulfoxide; and the like can be used.

  The compound of formula (II) is obtained by hydrolyzing the compound of formula (XVII) in the presence of an acid or a base. In this reaction, a solvent that does not adversely influence the reaction is used. For example, alcohols such as methanol, ethanol, n-propanol, i-propanol; diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, etc. Ethers; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; water; Examples of the acid that can be used in this reaction include mineral acids such as hydrochloric acid, hydrobromic acid, and sulfuric acid, and the amount used is preferably 1 to 100 times mole. Examples of the base used in this reaction include alkali metals such as sodium hydroxide, potassium hydroxide, and barium hydroxide, and hydroxides of alkaline earth metals. It may be -1000 times mole, and it is desirable that it is a ratio of 1-10 moles. These reactions are usually carried out at 0 to 200 ° C., preferably 0 to 150 ° C. for 1 to 24 hours.

Flow (4)
The compound of formula (II) is obtained by reacting the compound of formula (X), the compound of formula (XV) and the compound of formula (XVIII) in the presence of a base. This reaction can be carried out under the same reaction conditions as in the first half of the flow (3).

Flow (5)
A compound of formula (XXI) is obtained by reacting a compound of formula (XIX) with a compound of formula (XX-1) or a compound of formula (XX-2). The reaction between the compound of formula (XIX) and the compound of formula (XX-1) is a condensation reaction. As a reaction reagent used in this condensation reaction, phosphines such as triphenylphosphine and diazocarboxylic acid esters such as ethyl diazocarboxylate can be used. In this reaction, a solvent that does not adversely influence the reaction is used, for example, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether; aromatic carbonization such as benzene, chlorobenzene, nitrobenzene, toluene, etc. Hydrogens; etc. can be used. The protecting group used as PG may be a general amine protecting group, and examples thereof include a t-butoxycarbonyl group and a benzyloxycarbonyl group.
The reaction of the compound of formula (XIX) and the compound of formula (XX-2) can be carried out according to the method of flow (2).

  A compound of formula (XXII) can be produced by reacting a deprotecting group from a compound of formula (XXI). This reaction can be performed according to the said manufacturing method [1]. Deprotection can be performed by a general method.

The compound of formula (II-1) can be obtained by reacting the compound of formula (XXII) with the compound of formula (XV) in the presence of a base. This reaction can be performed according to the method of the flow (2) described above.

Flow (6)
A compound of formula (XXIII) can be produced by reacting a compound of formula (X) with a compound of formula (XX-3) in the presence of a base. This reaction can be performed according to the method of the flow (2) described above.
The compound of the formula (II-1) can be obtained by reacting the compound of the formula (XXIII) with the compound of the formula (XIX). The reaction follows the method of flow (5).

Flow (7)
The compound of formula (XXIV) is obtained by converting the hydroxyl group of the compound of formula (XXIII) into a leaving group. Examples of the conversion method to the leaving group include (a) synthesis using hydrogen halide; (b) synthesis using phosphorus trihalide; (c) synthesis using thionyl chloride and thionyl bromide; ) Synthesis using triphenylphosphine and CX ₄ ; (e) Synthesis using methanesulfonyl chloride, p-toluenesulfonyl chloride, or trifluoromethanesulfonic anhydride and base to convert to sulfonic acid ester.
The compound of formula (II-1) can be obtained by reacting the compound of formula (XXIV) with the compound of formula (XIX). The method conforms to the method of flow (2).

Flow (8)
The compound of the formula (XXVI-1) or the formula (XXVI-2) is obtained by mixing a compound of the formula (XXV-1) or the formula (XXV-2) with a compound of the formula (X) of 2 moles or more in the presence of a base. It is obtained by reacting. In this reaction, a solvent that does not adversely affect the reaction is used. Alcohols such as methanol and ethanol; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and diethylene glycol dimethyl ether; aromatics such as benzene and toluene Nitriles such as acetonitrile; N, N-dimethylformamide; N, N-dimethylacetamide; dimethyl sulfoxide and the like. Examples of the base used in this reaction include inorganic bases such as sodium hydride, sodium carbonate and potassium carbonate; organic amines such as triethylamine, tributylamine and diisopropylethylamine. The amount of the base used may be a ratio of 2 times mol or more with respect to 1 mol of the compound of the formula (X), and preferably 2 to 5 mol. This reaction may be carried out at 0 to 200 ° C., preferably 0 to 150 ° C. for 1 minute to 24 hours.

  The phenylguanidine derivative represented by the formula (I) or a salt thereof (hereinafter abbreviated as the present compound) is useful as an active ingredient of a pest control agent such as an agricultural and horticultural fungicide and / or an antifungal agent. In particular, it is useful as an active ingredient of agricultural and horticultural fungicides. Examples of agricultural and horticultural fungicides include rice blast disease, sesame leaf blight, coat blight; wheat powdery mildew, red mold disease, rust disease, snow rot, naked smut, eye coat disease, leaves Blight, dry blight; citrus black spot, common scab; apple monilia, powdery mildew, spotted leaf disease, black scab; pear black scab, black spot; peach ash, black spot, Phomopsis rot; grape black rot, late rot, powdery mildew, downy mildew; oyster anthracnose, leaf fall; cucurbit anthracnose, powdery mildew, vine blight, downy mildew; Tomato ring mold disease, leaf mold disease, plague; black crab disease of cruciferous vegetables, summer plague of potato, plague; strawberry powdery mildew; for the prevention of diseases such as gray mold disease and mycorrhizal disease of various crops It is valid. In particular, it exhibits excellent control effects on wheat powder and vegetables against powdery mildew and rice blast. It is also effective in controlling soil diseases caused by phytopathogenic fungi such as Fusarium, Psium, Rhizoctonia, Verticillium, and Plasmodiohora. Antifungal agents are effective against, for example, Candida, Cryptococcus, Aspergillus, Staphylococcus, and Trichophyton.

  The compound of the present invention is usually prepared by mixing the compound with various agricultural adjuvants, powders, granules, granule wettable powders, wettable powders, aqueous suspensions, oily suspensions, aqueous solvents, emulsions, It can be used in various forms such as liquids, pastes, aerosols, microdispersions, etc., but it can be made into any conventional form used in the art as long as it meets the purpose of the present invention. it can. Adjuvants used in the formulation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch, etc. Solvent such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, alcohol; fatty acid salt, benzoic acid Acid salt, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, alcohol Sulfate ester salt, alkyl sulfonate salt, alkyl aryl sulfonate salt, aryl sulfonate salt, lignin sulfonate salt, alkyl diphenyl ether disulfonate salt, polystyrene sulfonate salt, alkyl phosphate ester salt, alkyl aryl phosphate salt, styryl aryl Phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate , Anionic surfactants such as naphthalenesulfonic acid formalin condensate salts and spreading agents; sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid polyglycerides , Fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyoxyethylene fatty acid ester , Nonionic surfactants and spreading agents such as polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid ester; olive oil, kapok oil, castor oil, palm Oil, coconut oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, cutting oil, liquid Examples include vegetable oils such as paraffin and mineral oils. These adjuvants can be selected from those known in the art without departing from the object of the present invention. In addition, various commonly used adjuvants such as a bulking agent, thickener, anti-settling agent, antifreezing agent, dispersion stabilizer, safener, and antifungal agent can also be used. The compounding ratio of the compound of the present invention and various adjuvants is generally 0.005: 99.995 to 95: 5, preferably 0.2: 99.8 to 90:10. In actual use of these preparations, they can be used as they are, or diluted to a predetermined concentration with a diluent such as water, and various spreaders can be added as necessary.

  The concentration of the compound of the present invention varies depending on the target crop, method of use, formulation, application rate, etc., and cannot be defined unconditionally, but in the case of foliar treatment, it is usually 0.1 to 10,000 ppm, preferably 1 to 2,000 ppm. In the case of soil treatment, it is usually 10 to 100,000 g / ha, preferably 200 to 20,000 g / ha.

  The compound of the present invention is generally applied for application of its various preparations or dilutions thereof, that is, spraying (eg spraying, spraying, misting, atomizing, dusting, water surface application, etc.), soil application (Mixing, irrigation, etc.), surface application (application, powder coating, coating, etc.) can be performed. It can also be applied by the so-called ultra low volume application method (ultra low volume). In this method, it is possible to contain 100% of the active ingredient.

  The compound of the present invention may be used in combination with other agricultural chemicals such as fungicides, insecticides, acaricides, nematicides, antiviral agents, attractants, herbicides, plant growth preparations, etc. In this case, a more excellent effect may be exhibited.

In the above-mentioned other agricultural chemicals, the active ingredient compound of a fungicide (generic name; including some pending applications). The pending application means the generic name before being approved by the ISO (International Organization for Standardization). And the like below), for example, ananilinopyrimidinamine compounds such as mepanipyrim, pyrimethanil, cyprodinil;
Pyridinamine compounds such as fluazinam;
Triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanil, cyproconazole cyproconazole), tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole, o Oxpoconazole fumarate, sipconazole, prothioconazole, triadimenol, flutriafol, difenoconazole , Fluquinconazole, fenbuconazole, bromuconazole, diniconazole, tricyclazole, probenazole, cimeconazole, pefurazoate, ipconazole, ipconazole ), Azole compounds such as imibenconazole;
Quinoxaline compounds such as quinomethionate;
Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram;
Organochlorine compounds such as fthalide, chlorothalonil, quintozene;
Imidazole compounds such as benomyl, thiophanate-Methyl, carbendazim, thiabendazole, fuberiazole, cyazofamid;
Cyanoacetamide compounds such as cymoxanil;
Metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, offurace, benalaxyl, benalaxyl-M, also known as Kiraraxyl, hiralaxyl ), Phenylamide compounds such as furalaxyl, cyprofuram;
Sulfenic acid compounds such as dichlofluanid;
Copper-based compounds such as cupric hydroxide and oxine copper;
Isoxazole compounds such as hymexazol;
Fosetyl-aluminum (fosetyl-Al), Turkish phosmethyl (tolcofos-Methyl), S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate, edifenphos, Organophosphorus compounds such as iprobenfos;
N-halogenothioalkyl compounds such as captan, captafol, folpet;
Dicarboximide compounds such as procymidone, iprodione, vinclozolin;
Benzanilide compounds such as flutolanil, mepronil, zoxamid, tiadinil;
Anilide compounds such as carboxin, oxycarboxin, thifluzamide, penthiopyrad, boscalid;
Piperazine compounds such as triforine;
Pyridine compounds such as pyrifenox;
Carbinol compounds such as fenarimol, flutriafol;
Piperidine compounds such as fenpropidine;
Morpholine compounds such as fenpropimorph, spiroxamine, and triridemorph;
Organotin compounds such as fentin hydroxide and fentin acetate;
Urea-based compounds such as pencycuron;
Synamic acid compounds such as dimethomorph, flumorph;
Phenyl carbamate compounds such as dietofencarb;
Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
Azoxystrobin, kresoxim-Methyl, metminomino, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin , Strobilurin compounds such as pyraclostrobin, fluoxastrobin;
Oxazolidinone compounds such as famoxadone;
Thiazole carboxamide compounds such as ethaboxam;
Silylamide compounds such as silthiopham;
Amino acid amide carbamate compounds such as iprovalicarb, benchthiavalicarb-isopropyl;
Imidazolidine compounds such as fenamidone;
Hydroxyanilide compounds such as fenhexamid;
Benzenesulfonamide compounds such as flusulfamid;
Oxime ether compounds such as cyflufenamid;
Phenoxyamide compounds such as fenoxanil;
Atraquinone compounds;
Crotonic acid compounds;
Antibiotics such as validamycin, kasugamycin, polyoxins;
Guanidine compounds such as iminoctadine;
Other compounds include isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, metam-sodium ), Nicobifen, metrafenone, UBF-307, diclocymet, proquinazid, amisulbrom (aka amibromdole), KIF-7767 (KUF-1204, pyribencarb methyl, mepyricarb) Syngenta 446510 (mandipropamid, dipromandamid), fluopicolide, carpropamid, BCF051, BCM061, BCM062 and the like.

In the above-mentioned other pesticides, as an insecticide, acaricide, or nematicide, that is, an active ingredient compound of a pesticide (generic name; including some pending applications), for example, profenofos, dichlorvos ( dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos-methyl, acephate, prothiofos, fothhiazate, phosphocarb, phosphocarb, cadusafos), disulfoton, chlorpyrifos, demeton-S-methyl, dimethoate, metamidophos, imicyafos, isoxathion, isoxathion, isofenphos , Etion, etrim Etrimfos, quinalphos, dimethylvinphos, sulprofos, thiometon, bamidothion, pyraclofos, pyridaphenthion, pirimiphos-methyl, propiphos-methyl (propaphos), hosalon (phosalone), formothion, malathion, tetrachlovinphos, chlorfenvinphos, cyanophos, trichlorfon, methidathion, Phenthoate, ESP, azinphos-methyl, fenthion, heptenophos, methoxychlor, parathion, monocrotophos, parathion-methyl, terbufos (Terbufos), Phospha Dong (phospamidon), phosmet (phosmet), organic phosphoric acid ester compounds such as folate (phorate);
Carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, fenobucarb Carbamates such as carbosulfan, benfuracarb, bendiocarb, furathiocab, isoprocarb, metolcarb, xylylcarb, XMC, fenothiocarb Compound;
Nereistoxin derivatives such as cartap, thiocyclam, bensultap, sodium thiosultap-sodium;
Organochlorine compounds such as dicophor, tetradifon, endosulfan, dienochlor, dieldrin;
Organometallic compounds such as fenbutatin oxide and cyhexatin;
Fenvalerate, permethrin, cypermethrin, deltamethrin, cyhalothrin, tefluthrin, etofenprox, flufenprox, fenpropatrin ( fenpropathrin), bifenthrin, imidate, cyfluthrin, flucythrinate, fluvalinate, cycloprothrin, lambda-cyhalothrin, pyrethrin ( pyrethrins), esfenvalerate, tetramethrin, resmethrin, protrifenbute, zeta-cypermethrin, acrinathrin, alpha sipe Lumethrin (alpha-cypermethrin), allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin, Pyrethroid compounds such as beta-cypermethrin, beta-cyfluthrin, metofluthrin;
Diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, lufenuron, novaluron, triflumuron, hexaflumuron, hexaflumuron Benzoylurea compounds such as (bistrifluron), nobifluuron, fluazuron;
Juvenile hormone-like compounds such as metoprene, pyriproxyfen, fenoxycarb, diofenolan;
Pyridazinone compounds such as pyridaben;
Pyrazole compounds such as fenpyroximate, fipronil, tebufenpyrad, ethiprole, tolfenpyrad, acetoprole, pyrafluprole, pyriprole;
Imidacloprid, nitenpyram, acetamiprid, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran, dinotefuranoid, dinotefuranoid
Hydrazine compounds such as tebufenozide, methoxyfenozide, chromafenozide, halofenozide;
Pyridine compounds such as Pyridaryl, flonicamid and the like;
Tetronic acid compounds such as spirodiclofen;
Strobilurin compounds such as fluacrypyrin;
Pyridinamine compounds such as flufenerim;
Dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, hydrazone compounds, and other compounds include buprofezin, hexythiazox, amitraz, chlordimeform, silafluofen ), Triazamate, pymetrozine, pyrimidifen, chlorfenapyr, indoxacarb, acequinocyl, etoxazole, cyromazine, 1,3-dichloropropene (1,3-dichloropropene), diafenthiuron, benclothiaz, flufenerim, pyridalyl, spirodiclofen, bifenazate (b ifenazate, spirotetramat, propargite, verbutin, spiromesifen, thiazolylcinnanonitrile, amidoflumet, flubendiamide, clofente Clofentezine metaflumizone, chlorantraniliprole, cyflumetofen, cyenopyrafen, pyrifluquinazone, fenazaquin, pyazaben, pyridaben, pyridaben, pyridaben, pyridaben Compounds such as chlorobenzoate, sulfluramid, metaldehyde, ryanodine; AKD-1022, IKA-2000 and the like. Furthermore, Bacillus thuringienses aizawai, Bacillus thuringienses kurstaki, Bacillus thuringienses israelensis, Bacillus thuringienses japonensis, Bacillus thuringienses tenebrionis or crystalline protein toxins produced by Bacillus thuringienses, entomopathogenic fungi, nematode pathogenic fungi, etc. Microbial pesticides, such as avermectin, milbemectin, milbemycin, spinosad, emamectin benzoate, ivermectin, lepimectin, spinetorum, spinetoram, It can also be used in combination with antibiotics such as abamectin and emamectin; natural products such as azadirachtin and rotenone; and repellents such as deet.

Next, although the specific synthesis | combination of the phenylguanidine derivative of this invention and its intermediate for manufacture, and the test example concerning this invention are described, this invention is not limited to these.
Synthesis example 1
1,1 '-(4,4'-(3,3 '-(piperazine-1,4-diyl) bis (propane-3,1-diyl)) bis (oxy) bis (4,1-phenylene)) Synthesis of diguanidine hydrochloride (hydrochloride of compound No. 2)

(1) Synthesis of 1- (3-bromopropyloxy) -4-nitrobenzene
6 g of 4-nitrophenol was dissolved in 60 ml of 2-butanone, 8.94 g of potassium carbonate and 9.54 g of 1,3 dibromopropane were added, and the mixture was stirred at 70 ° C. for 13 hours. After cooling to room temperature, the insoluble material was filtered off through celite, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent n-hexane / ethyl acetate = 92/8). Bromopropyloxy) -4-nitrobenzene (5.71 g) was obtained.

(2) Synthesis of 1,4-bis (3- (4-nitrophenoxy) propyl) piperazine Piperazine 0,82 g was dissolved in 6 ml of dimethyl sulfoxide, 8 ml of N, N-diisopropylethylamine, 1- (3-bromopropyloxy ) -4-nitrobenzene (5.21 g) was added, and the mixture was stirred at 100 ° C. for 6 hours. After cooling to room temperature, the precipitate was filtered and washed with hexane and diethyl ether. The washed precipitate was purified by silica gel column chromatography (eluent: ethyl acetate / methanol = 70/30) to obtain 2.73 g of 1,4-bis (3- (4-nitrophenoxy) propyl) piperazine.

(3) t-Butyl (4,4 '-(3,3'-(piperazine-1,4-diyl) bis (propane-3,1-diyl) bis (oxy) bis (4,1-phenylene)) Synthesis of bis (azanediyl) bis ((t-butylcarbonylamino) methane-1-yl-1-ylidene) dicarbamate
0.77 g of 1,4-bis (3- (4-nitrophenoxy) propyl) piperazine was suspended in 20 ml of methanol, 0.05 g of palladium carbon was added, the reaction system was replaced with hydrogen, and the mixture was stirred at room temperature for 15 hours. Insoluble matters were filtered off from the reaction mixture with celite. After concentration, 10 ml of dichloromethane and 2 ml of methanol were added to the residue, and 1.29 g of N, N′-di-t-butoxycarbonyl-N ″ -trifluoromethanesulfonylguanidine and 0.38 of triethylamine were added. g was added and stirred at room temperature for 1 hour and under reflux for 4 hours. After cooling to room temperature, the reaction solution was poured into water and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent ethyl acetate / methanol = 95/5) and t-butyl (4,4 ′-(3,3 ′-(piperazine-1,4-diyl) bis (propane- 0.79 g of 3,1-diyl) bis (oxy) bis (4,1-phenylene)) bis (azanediyl) bis ((t-butylcarbonylamino) methane-1-yl-1-ylidene) dicarbamate was obtained.

(4) t-Butyl (4,4 '-(3,3'-(piperazine-1,4-diyl) bis (propane-3,1-diyl) bis (oxy) bis (4,1-phenylene)) Bis (azanediyl) bis ((t-butylcarbonylamino) methane-1-yl-1-ylidene) dicarbamate (0.29 g) was dissolved in ethanol, and hydrogen chloride gas was blown into it, followed by stirring at room temperature for 2 days. The solvent was distilled off and the precipitated crystals were washed with diethyl ether and dried to obtain 0.10 g of the desired product.

Synthesis example 2
(1,1 '-(4,4'-(4,4'-Azandiylbis (butane-4,1-diyl) bis (oxy)) bis (4,1-phenylene)) diguanidine) hydrochloride (Compound No. .8 hydrochloride) (1) Synthesis of 1- (4-bromobutoxy) -4-nitrobenzene In the same manner as in the synthesis method 1 (1), 1- (4-bromobutoxy) -4- Nitrobenzene was obtained.

(2) Synthesis of t-butyl bis (4- (4-nitrophenoxy) butyl) carbamate
1.05 g of 1- (4-bromobutoxy) -4-nitrobenzene was dissolved in 10 ml of N, N-dimethylformamide, 0.3 g of sodium azide was added, and the mixture was stirred at room temperature for 13 hours. The reaction mixture was poured into water and extracted with diethyl ether. The organic layer was dried over sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The residue was dissolved in 10 ml of tetrahydrofuran and 1 ml of water, 1.37 g of triphenylphosphine was added, and the mixture was stirred at room temperature for 12 hours. After concentration of the reaction solution, the residue was dissolved in 10 ml of N, N-dimethylformamide, 1.06 g of 1- (4-bromobutoxy) -4-nitrobenzene and 0.53 g of potassium carbonate were added, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent ethyl acetate / methanol = 60/40). The obtained crude product of bis (4- (4-nitrophenoxy) butyl) amine was dissolved in 10 ml of methylene chloride, 0.13 g of triethylamine and 0.28 g of di-t-butylbutyl dicarbonate were added, and the mixture was stirred at room temperature for 12 hours. did. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent hexane / ethyl acetate = 75/25) to obtain 0.5 g of t-butyl bis (4- (4-nitrophenoxy) butyl) carbamate.
(3) From the t-butyl bis (4- (4-nitrophenoxy) butyl) carbamate, t-butyl (4,4 ′-(4,4 ′-( t-Butoxycarbonylazanediyl) bis (4,1-phenylene)) bis (azanediyl) bis ((t-butoxycarbonylamino) methane-1-yl-1-ylidene) dicarbamate was obtained from this, and Synthesis Example 1 In the same manner as in (4), 0.20 g of the desired product was obtained.

  The compounds of the formula (I-1) are shown in Table 1 as the compounds of the formula (I). These compounds can be produced by the production methods [1] to [3], intermediate production methods, and methods according to Synthesis Examples 1 and 2. Table 2 shows the salts of the compounds obtained by synthesis and their physical properties. The mp (melting point) in the physical properties column was measured using a melting point measuring device (YANACO MP-J3) or an automatic melting point measuring device (METTLER FP62 manufactured by METTLER TOLEDO).

Below, the test example of this invention composition is described. In each test, the control index followed the following criteria.
[Control index] [Disease severity: Visual observation]
5: No lesion or sporulation is observed.
4: The lesion length, the number of lesions, or the sporulation area is less than 10% of the untreated area.
3: The lesion length, the number of lesions, or the sporulation area is less than 40% of the untreated area.
2: The lesion length, the number of lesions, or the sporulation area is less than 70% of the untreated area.
1: The lesion length, the number of lesions, or the spore formation area is 70% or more of the untreated section.

Test Example 1 (Wheat powdery mildew prevention effect test)
Growing wheat (variety: Norin 61) in a 7.5cm diameter plastic pot, and spraying 10ml of chemical solution with phenylguanidine derivative of formula (I) or its salt adjusted to a predetermined concentration when reaching 1.5 leaf stage Sprayed with a gun. After the chemical solution was dried (on the day of treatment), conidia of powdery mildew ( Erysiphe graminis ) were sprinkled and inoculated, and kept in a constant temperature room at 20 ° C. The spore formation area was investigated 6 to 7 days after the inoculation, and the control index was determined according to the evaluation criteria. When tested with respect to the hydrochloride of Compound No. 6, the hydrochloride of Compound No. 8, the trifluoroacetate of Compound No. 8, the hydrochloride of Compound No. 21, and the hydrochloride of Compound No. 24, it was controlled at 400 ppm. An effect of index 4 or higher was shown.

Test Example 2 (Injury gray mold prevention effect test)
Growing green beans (variety: Taishokin) in a 15 cm diameter plastic pot, and when the true leaves are fully developed, spray 10 ml of a chemical solution adjusted to the prescribed concentration of the phenylguanidine derivative of formula (I) or its salt. did. After the drug solution is dried (on the day of treatment or the next day), inoculate a spore suspension of potato ( Botrytis cinerea ) (potato / glucose broth diluted to 50% (V / V) with water) at 20 ° C. Kept in a constant temperature room. The lesion length (mm) was examined 3 days after the inoculation, and the control index was determined according to the above evaluation criteria. Compound No. 8 hydrochloride, No. 8 trifluoroacetate salt, Compound No. 10 hydrochloride, Compound No. 24 hydrochloride, Compound No. 25 hydrochloride and Compound No. 26 hydrochloride When tested, it showed an effect of a control index of 4 or more at 200 ppm.

Test Example 3 (Test for preventing kidney bean nuclear disease)
Growing green beans (variety: Taishokin) in a 15 cm diameter plastic pot, and when the true leaves are fully developed, spray 10 ml of a chemical solution adjusted to the prescribed concentration of the phenylguanidine derivative of formula (I) or its salt. did. After the chemical solution was dried (on the day of treatment or the next day), a flora disc of Sclerotinia sclerotiorum was inoculated and kept in a constant temperature room at 20 ° C. The lesion length (mm) was examined 3 days after the inoculation, and the control index was determined according to the above evaluation criteria. When tested with respect to the hydrochloride salt of Compound No. 8, the trifluoroacetate salt of Compound No. 11, the hydrochloride salt of Compound No. 17, and the hydrochloride salt of Compound No. 24, an effect of a control index of 4 or more was exhibited at 200 ppm. .

Test Example 4 (Cucumber anthrax prevention effect test)
Cucumber (variety: Sagamihanjiro) is cultivated in a 7.5cm diameter plastic pot, and when the 1.5 leaf stage is reached, spray 10ml of a chemical solution in which the phenylguanidine derivative of formula (I) or a salt thereof is adjusted to a predetermined concentration. Sprayed with a gun. After the chemical solution was dried (on the day of treatment), a conidial spore suspension of Colletotrichum lagenarium was spray-inoculated, kept in an inoculation box at 20 ° C. for 48 hours, and then kept in a constant temperature room at 20 ° C. The lesion area was examined 6 to 8 days after the inoculation, and the control index was determined according to the above evaluation criteria. Tested on the hydrochloride of Compound No. 2, the hydrochloride of Compound No. 8, the hydrochloride of Compound No. 10, the hydrochloride of Compound No. 17, the hydrochloride of Compound No. 21, and the hydrochloride of Compound No. 28 As a result, an effect of controlling index 4 or more was shown at 200 ppm.

Test Example 5 (Tomato ring disease prevention effect test)
Cultivate tomato (variety: Ponterosa) in a 7.5cm diameter plastic pot, and when the 4th leaf stage is reached, spray 10ml of a chemical solution with the phenylguanidine derivative of formula (I) or its salt adjusted to the prescribed concentration. did. After the chemical solution was dried (on the day of treatment), a conidial spore suspension of Alternaria solani was spray-inoculated, kept in an inoculation box at 25 ° C. for 4 days, and then kept in a constant temperature room at 20 ° C. The lesion area was examined 5 to 7 days after the inoculation, and the control index was determined according to the evaluation criteria. Tested on the hydrochloride of Compound No. 2, the hydrochloride of Compound No. 6, the hydrochloride of Compound No. 8, the hydrochloride of Compound No. 10, the hydrochloride of Compound No. 13, and the hydrochloride of Compound No. 21 As a result, the effect of controlling index 4 or more was shown at 400 ppm.

Formulation Example 1
(1) Compound of the present invention 20 parts by weight (2) 72 parts by weight of clay (3) Sodium lignin sulfonate 8 parts by weight or more is uniformly mixed to obtain a wettable powder.

Formulation Example 2
(1) Compound of the present invention 5 parts by weight (2) Talc 95 parts by weight or more is uniformly mixed to obtain a powder.

Formulation Example 3
(1) Compound of the present invention 20 parts by weight (2) N, N'-dimethylacetamide 20 parts by weight (3) Polyoxyethylene alkylphenyl ether 10 parts by weight (4) Xylene 50 parts by weight or more are uniformly mixed and dissolved To make an emulsion.

Formulation Example 4
(1) Clay 68 parts by weight (2) Lignin sulfonic acid soda 2 parts by weight (3) Polyoxyethylene alkylaryl sulfate 5 parts by weight (4) Fine powder silica A mixture of each component of 25 parts by weight or more and the compound of the present invention Mix at a weight ratio of 4: 1 to make a wettable powder.

Formulation Example 5
(1) Compound of the present invention 50 parts by weight (2) Oxidated polyalkylphenyl phosphate triethanolamine 2 parts by weight (3) Silicone 0.2 parts by weight (4) Water 47.8 parts by weight or more uniformly (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are further added to the mixed and pulverized stock solution, and the mixture is uniformly mixed, granulated and dried to obtain a granulated wettable powder.

Formulation Example 6
(1) Compound of the present invention 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Polyoxyethylene phosphate ester 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight (1)- (3) is uniformly mixed in advance and diluted with an appropriate amount of acetone, and then sprayed onto (4) to remove the acetone and form granules.

Formulation Example 7
(1) Compound of the present invention 2.5 parts by weight (2) N-methyl-2-pyrrolidone 2.5 parts by weight (3) Soybean oil 95.0 parts by weight or more are uniformly mixed and dissolved to give a trace amount of spray. (ultra low volume formulation).

Formulation Example 8
(1) Compound of the present invention 20 parts by weight (2) Oxidated polyalkylphenyl phosphate triethanolamine 2 parts by weight (3) Silicone 0.2 part by weight (4) Xanthan gum 0.1 part by weight (5) Ethylene glycol 5 Part by weight (6) Water 72.7 parts by weight or more are uniformly mixed and pulverized to obtain an aqueous suspension.

Claims (9)

Formula (I):

[Wherein R ¹ is a hydrogen atom, alkyl or cycloalkyl; R ² is a hydrogen atom, phenyl optionally substituted with D, arylalkyl optionally substituted with D, nitro, cyano, NR ⁷ R ⁸ CONR ⁷ R ⁸ , OR ⁷ , SO ₂ R ⁹ , COR ⁹ or COOR ⁹ ; R ³ and R ⁴ are each independently a hydrogen atom, alkyl, alkenyl or alkynyl, or R ³ and R ⁴ Together may form a nitrogen-containing saturated monocyclic heterocycle with the adjacent nitrogen atom; R ⁵ is a hydrogen atom, halogen, alkyl, alkoxy or hydroxy; A is an oxygen atom, sulfur atom or NR ⁶ ; X is NR ⁶ , NR ⁶ -Ak ^c -NR ⁶ or

Wherein Y ¹ and Y ² may be the same or different and each is a C _1-4 lower alkylene which may be substituted with halogen or alkoxy; Z is a nitrogen atom or CH; ⁶ is a hydrogen atom or alkyl; R ⁷ and R ⁸ are each independently a hydrogen atom, C _1-6 alkyl or C _1-6 haloalkyl; R ⁹ is C _1-6 alkyl or C _1-6 haloalkyl Ak ^a , Ak ^b and Ak ^c are each independently alkylene; D is halogen, alkyl, alkoxy, haloalkyl or haloalkoxy], or a salt thereof. The phenylguanidine derivative or a salt thereof according to claim 1, wherein R ³ and R ⁴ are hydrogen atoms. The phenylguanidine derivative or a salt thereof according to claim 1, wherein R ¹ , R ³ and R ⁴ are hydrogen atoms. R ¹ is a hydrogen atom; R ² is a hydrogen atom, dimethylamino or nitro; R ³ and R ⁴ are hydrogen atoms; A is an oxygen atom or NR ⁶ ; X is NR ⁶ , NR ^6- The phenylguanidine derivative or a salt thereof according to claim 1, which is Ak ^c -NR ⁶ , a piperidinyl group or a piperazinyl group. The phenylguanidine derivative or a salt thereof according to claim 4, wherein R ² is a hydrogen atom or nitro; A is an oxygen atom; and X is -NH, a piperidinyl group or a piperazinyl group. The pest control agent which contains the phenylguanidine derivative or its salt in any one of Claims 1-5 as an active ingredient. An agricultural and horticultural fungicide containing the phenylguanidine derivative or a salt thereof according to any one of claims 1 to 5 as an active ingredient. The antifungal agent which contains the phenylguanidine derivative or its salt in any one of Claims 1-5 as an active ingredient. A method for controlling plant diseases, which comprises applying the phenylguanidine derivative or salt thereof according to any one of claims 1 to 5 to an agricultural or horticultural plant.