WO2018097172A1 - Phenylguanidine compound and fungicide - Google Patents

Abstract

The present invention provides: compounds represented by formula (IV) (in the formula, Ar represents a substituted or unsubstituted phenylene group; X and Z each independently represent a substituted or unsubstituted alkylene group, etc.; T^a and T^b each independently represent a single bond or a substituted or unsubstituted alkylene group; R³⁰ represents a hydrogen atom, etc.; G represents a single bond, a substituted or unsubstituted phenylene group, etc.; Y represents a divalent group represented by formula (IIa) (in the formula, R¹¹-R¹³ each independently represent a hydrogen atom, etc., and * represents a bonding position); and R¹-R⁸ each independently represent a hydrogen atom, etc.) or salts thereof; and plant disease control agents, etc., that contain these compounds or salts thereof.

Description

Phenylguanidine compounds and fungicides

The present invention relates to phenylguanidine compounds and fungicides. More specifically, the present invention relates to a novel phenylguanidine compound that has excellent bactericidal activity, is excellent in safety, and can be advantageously synthesized industrially, and a bactericidal agent or plant containing the phenylguanidine compound as an active ingredient It relates to a disease control agent.
This application claims priority on November 25, 2016 based on Japanese Patent Application No. 2016-229454 filed in Japan, the contents of which are incorporated herein by reference.

Patent Documents 1, 2, 3 or 4 state that certain arylamidine compounds have a fungal and plant disease control effect. And the antifungal agent and plant disease control agent etc. which contain this arylamidine compound as an active ingredient are proposed. Patent Document 5 states that certain phenylguanidine compounds have a pest control effect.

WO2013 / 062024A1 WO2006 / 011499A1 WO2007 / 074868A1 WO2003 / 074476A1 WO2008 / 029810A1

An object of the present invention is to provide a novel phenylguanidine compound that has excellent bactericidal activity, excellent safety, and can be advantageously synthesized industrially, and a bactericidal agent or plant disease containing the phenylguanidine compound as an active ingredient It is to provide a control agent.

The present invention includes the following aspects.
[1] A compound represented by the formula [IV] or a salt thereof.

In the formula [IV],
Ar represents a substituted or unsubstituted phenylene group.
X and Z each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene ^{group, -T a -O-T b -} , - T a -S-T ^b -or -T ^a -N (R ³⁰ ) -T ^b -is shown.
T ^a and T ^b each independently represent a single bond or a substituted or unsubstituted alkylene group, and R ³⁰ represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclyl group, or a hydroxyl group. Substituted or unsubstituted alkoxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted aryl A sulfonyl group, a substituted or unsubstituted heterocyclylsulfonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted heterocyclylcarbonyl group;
G represents a single bond, a substituted or unsubstituted phenylene group, —CH═CH—, —C≡C—, —O—, —S—, —SO—, —SO ₂ —, or —N (R ³¹ ). -Is shown. R ³¹ represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclyl group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryl Oxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted heterocyclylsulfonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted A substituted arylcarbonyl group or a substituted or unsubstituted heterocyclylcarbonyl group is shown.
Y represents a divalent group represented by the formula [IIa].

In the formula [IIa], R ¹¹ to R ¹³ are each independently a hydrogen atom, nitro group, cyano group, substituted or unsubstituted hydrocarbon group, substituted or unsubstituted heterocyclyl group, hydroxyl group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or An unsubstituted heterocyclylsulfonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted heterocyclylcarbonyl group is shown. R ¹² and R ¹³ , R ¹¹ and R ¹² , or R ¹¹ and R ¹³ may be combined to form a divalent organic group. The substituents on R ¹² and X may be combined to form a divalent organic group. * Indicates a binding position.
R ¹ to R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclyl group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group Substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted heterocyclylsulfonyl group, substituted or unsubstituted An alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted heterocyclylcarbonyl group;
R ¹ and R ² may be bonded together to form a 4- to 8-membered ring together with two nitrogen atoms to which they are bonded and one carbon atom to which the two nitrogen atoms are bonded; ² and R ³ may combine to form a 4- to 8-membered ring together with two nitrogen atoms to which they are bonded and one carbon atom to which the two nitrogen atoms are bonded, or R ³ And R ⁴ may combine to form a 4- to 8-membered ring together with one nitrogen atom to which they are bonded, or R ¹ and R ⁴ may combine to form two A 4- to 8-membered ring may be formed together with the nitrogen atom and one carbon atom to which the two nitrogen atoms are bonded.
R ⁶ and R ⁷ may be bonded to each other to form a 4- to 8-membered ring together with two nitrogen atoms to which they are bonded and one carbon atom to which the two nitrogen atoms are bonded. Or R ⁷ and R ⁸ may be bonded to form a 4- to 8-membered ring together with one nitrogen atom to which they are bonded, or R ⁵ and R ⁸ may be bonded to form A 4- to 8-membered ring may be formed together with one nitrogen atom to be bonded and one carbon atom to which the two nitrogen atoms are bonded.

[2] The compound or a salt thereof according to [1], wherein the compound represented by the formula [IV] is a compound represented by the formula [I].

In the formula [I], X, Y, Z, G, and R ¹ to R ⁸ have the same meaning as described above.
R is a C1-6 alkyl group, C3-8 cycloalkyl group, C6-10 aryl group, 3-6 membered heterocyclyl group, hydroxyl group, C1-6 alkoxy group, C6-10 aryloxy group, carboxyl group, halogeno group , C1-6 haloalkyl group, C6-10 haloaryl group, C1-6 haloalkoxy group, unsubstituted amino group, C1-6 alkylamino group, C6-10 arylamino group, C1-7 acylamino group, C1-6 alkoxy Carbonylamino group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C7-11 aralkylthio group, C1-6 alkylsulfinyl group, C6-10 arylsulfinyl group, heteroarylsulfinyl group, C7-11 An aralkylsulfinyl group, a C1-6 alkylsulfonyl group, 6-10 arylsulfonyl group, heterocyclylsulfonyl group, a cyano group, a nitro group.
n represents the number of R, and is an integer from 0 to 4.

[3] The compound or salt thereof according to [1] or [2], wherein X and Z are each independently a substituted or unsubstituted alkylene group, and G is —O—.

[4] A fungicide containing as an active ingredient at least one selected from the group consisting of the compound according to any one of [1] to [3] and a salt thereof.

[5] A plant disease control agent comprising as an active ingredient at least one selected from the group consisting of the compound according to any one of [1] to [3] above and a salt thereof.

The phenylguanidine compound (a compound represented by the formula [I] or a salt thereof) according to the present invention is excellent in bactericidal activity, excellent in safety, and can be synthesized industrially advantageously. The fungicide or plant disease control agent containing the phenylguanidine compound as an active ingredient is particularly excellent in the control value of plant diseases such as apple black spot, cucumber gray mold, wheat powdery mildew, tomato plague, wheat red rust. Yes.

First, in the present invention, the term “unsubstituted” means only a group serving as a mother nucleus. When there is no description of “substituted” and only the name of the group serving as the mother nucleus is used, it means “unsubstituted” unless otherwise specified.
On the other hand, the term “substituted” means that any hydrogen atom of the group serving as the mother nucleus is substituted with a group having the same or different structure from the mother nucleus. Accordingly, the “substituent” is another group bonded to a group serving as a mother nucleus. The number of substituents may be one, or two or more. Two or more substituents may be the same or different.
Terms such as “C1-6” indicate that the group serving as the mother nucleus has 1 to 6 carbon atoms. This number of carbon atoms does not include the number of carbon atoms in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group.

The “substituent” is not particularly limited as long as it is chemically acceptable and has the effects of the present invention. Examples of groups that can be “substituents” are shown below.
C1-6 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. An alkyl group;
Vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, etc. A C2-6 alkenyl group of
C2-6 alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group;
A C3-8 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group;
A C4-8 cycloalkenyl group such as a 2-cyclopentenyl group, a 3-cyclohexenyl group, a 4-cyclooctenyl group;

A C6-10 aryl group such as a phenyl group or a naphthyl group;
A C7-11 aralkyl group such as a benzyl group or a phenethyl group;
3-6 membered heterocyclyl group;
A C1-7 acyl group such as a formyl group, an acetyl group, a propionyl group, a benzoyl group, a cyclohexylcarbonyl group;

A hydroxyl group;
C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group;
C2-6 alkenyloxy groups such as vinyloxy group, allyloxy group, propenyloxy group, butenyloxy group;
C2-6 alkynyloxy groups such as ethynyloxy group and propargyloxy group;
C6-10 aryloxy groups such as phenoxy group and naphthoxy group;
A C7-11 aralkyloxy group such as a benzyloxy group or a phenethyloxy group;

C1-7 acyloxy groups such as formyloxy group, acetyloxy group, propionyloxy group, benzoyloxy group, cyclohexylcarbonyloxy group;
A C1-6 alkoxycarbonyl group such as a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group;
A C1-6 alkoxycarbonyloxy group such as a methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group;
Carboxyl group;

Halogeno groups such as fluoro, chloro, bromo and iodo groups;
C1-6 haloalkyl groups such as chloromethyl group, chloroethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, perfluoro-n-pentyl group;
A C2-6 haloalkenyl group such as a 2-chloro-1-propenyl group and a 2-fluoro-1-butenyl group;
A C2-6 haloalkynyl group such as 4,4-dichloro-1-butynyl group, 4-fluoro-1-pentynyl group, 5-bromo-2-pentynyl group;
C6-10 haloaryl group such as 4-chlorophenyl group, 4-fluorophenyl group, 2,4-dichlorophenyl group;
A C1-6 haloalkoxy group such as a trifluoromethoxy group, 2-chloro-n-propoxy group, 2,3-dichlorobutoxy group;
A C2-6 haloalkenyloxy group such as a 2-chloropropenyloxy group and a 3-bromobutenyloxy group;
C6-10 haloaryloxy groups such as 4-fluorophenyloxy group, 4-chloro-1-naphthoxy group;
C1-7 haloacyl groups such as chloroacetyl group, trifluoroacetyl group, trichloroacetyl group, 4-chlorobenzoyl group;

Unsubstituted amino group (group represented by NH ₂ );
A C1-6 alkylamino group such as a methylamino group, a dimethylamino group, a diethylamino group;
C6-10 arylamino groups such as anilino group and naphthylamino group;
A C7-11 aralkylamino group such as a benzylamino group or a phenethylamino group;
C1-7 acylamino groups such as formylamino group, acetylamino group, propanoylamino group, butyrylamino group, i-propylcarbonylamino group, benzoylamino group;
A C1-6 alkoxycarbonylamino group such as a methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group;
A substituted or unsubstituted aminocarbonyl group such as aminocarbonyl group, dimethylaminocarbonyl group, phenylaminocarbonyl group, N-phenyl-N-methylaminocarbonyl group;
Imino C1-6 alkyl groups such as iminomethyl, (1-imino) ethyl, (1-imino) -n-propyl;
N-hydroxy-iminomethyl group, (1- (N-hydroxy) -imino) ethyl group, (1- (N-hydroxy) -imino) propyl group, N-methoxy-iminomethyl group, (1- (N-methoxy) -Imino) substituted or unsubstituted N-hydroxyimino C1-6 alkyl group such as an ethyl group;

A mercapto group;
C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group;
A C6-10 arylthio group such as a phenylthio group or a naphthylthio group;
A heteroarylthio group such as a thiazolylthio group or a pyridylthio group;
A C7-11 aralkylthio group such as a benzylthio group or a phenethylthio group;
A C1-6 alkylsulfinyl group such as a methylsulfinyl group, an ethylsulfinyl group, a t-butylsulfinyl group;
A C6-10 arylsulfinyl group such as a phenylsulfinyl group;
Heteroarylsulfinyl groups such as thiazolylsulfinyl group, pyridylsulfinyl group;
A C7-11 aralkylsulfinyl group such as a benzylsulfinyl group or a phenethylsulfinyl group;
A C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a t-butylsulfonyl group;
A C6-10 arylsulfonyl group such as a phenylsulfonyl group;
A heteroarylsulfonyl group such as a thiazolylsulfonyl group or a pyridylsulfonyl group;
A C7-11 aralkylsulfonyl group such as a benzylsulfonyl group or a phenethylsulfonyl group;
An aminocarbonyloxy group;
A C1-6 alkylaminocarbonyloxy group such as an ethylaminocarbonyloxy group or a dimethylaminocarbonyloxy group;

A tri-C1-6 alkylsilyl group such as a trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group;
A triarylsilyl group such as a triphenylsilyl group;
Cyano group; Nitro group; Oxo group In these “substituents”, any hydrogen atom in the substituent may be substituted with a group having a different structure.

The “3- to 6-membered heterocyclyl group” includes 1 to 4 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom as ring constituent atoms. The heterocyclyl group may be monocyclic or polycyclic. In the polycyclic heterocyclyl group, if at least one ring is a hetero ring, the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring. Examples of the “3- to 6-membered heterocyclyl group” include a 3- to 6-membered saturated heterocyclyl group, a 5- to 6-membered heteroaryl group, and a 5- to 6-membered partially unsaturated heterocyclyl group.

Examples of the 3- to 6-membered saturated heterocyclyl group include aziridinyl group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, thiazolidinyl group, piperidyl group, piperazinyl group, morpholinyl group, dioxolanyl group and dioxanyl group.

Examples of 5-membered heteroaryl groups include pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, etc. Can do.
Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridanidyl group, and a triazinyl group.

The phenylguanidine compound of the present invention is a compound represented by the formula [IV] (hereinafter sometimes referred to as compound [IV]) or a salt thereof.

In formula [IV], Y represents a divalent group represented by formula [IIa].

In the formula [IIa], * represents a bonding position.
In the formula [IIa], R ¹¹ to R ¹³ are each independently a hydrogen atom, nitro group, cyano group, substituted or unsubstituted hydrocarbon group, substituted or unsubstituted heterocyclyl group, hydroxyl group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or An unsubstituted heterocyclylsulfonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted heterocyclylcarbonyl group is shown.

The substituents on R ¹² and X may be combined to form a divalent organic group (preferably a C1-3 alkylene group, more preferably an ethylene group).

The “hydrocarbon group” in R ¹¹ to R ¹³ is a group formed by elimination of one hydrogen atom in a hydrocarbon compound. Hydrocarbon compounds include saturated hydrocarbon compounds such as methane, ethane, propane, butane, pentane, hexane and heptane, unsaturated hydrocarbon compounds such as ethylene, acetylene and propylene, and alicyclic compounds such as cyclopentane, cyclohexane and cyclohexene. Examples thereof include hydrocarbon compounds, aromatic hydrocarbon compounds such as benzene and naphthalene. Among these, “hydrocarbon group” means methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group. A C1-6 alkyl group such as a n-hexyl group; or a C6-10 aryl group such as a phenyl group or a naphthyl group; a methyl group, an ethyl group, an n-propyl group, an i-propyl group, A C1-6 alkyl group such as n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group or the like or a phenyl group is more preferable.

The “heterocyclyl group” in R ¹¹ to R ¹³ is a group formed by removing one hydrogen atom from a heterocyclic compound. Heterocyclyl group includes aziridinyl group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, thiazolidinyl group, piperidyl group, piperazinyl group, morpholinyl group, dioxolanyl group, dioxanyl group, pyrrolyl group, furyl group, thienyl group, imidazolyl group, pyrazolyl group Oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, triazolyl group, oxadiazolyl group, thiadiazolyl group, tetrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridinyl group, triazinyl group and the like.

Examples of the “alkoxy group” in R ¹¹ to R ¹³ include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group and the like. C1-6 alkoxy groups are preferred.

Examples of the “alkoxycarbonyl group” in R ¹¹ to R ¹³ include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an s-butoxycarbonyl group, and an i-butoxycarbonyl group. Group, t-butoxycarbonyl group and the like, and a C1-6 alkoxycarbonyl group is preferable.

Examples of the “aryloxy group” in R ¹¹ to R ¹³ include a phenoxy group and a naphthoxy group, and a phenoxy group is preferable.

As the “substituted or unsubstituted amino group” in R ¹¹ to R ¹³ , an amino group (a group represented by NH ₂ ); a C1-6 alkylamino group such as a methylamino group, a dimethylamino group, and a diethylamino group; anilino Group, C6-10 arylamino group such as naphthylamino group; C7-11 aralkylamino group such as benzylamino group, phenethylamino group; formylamino group, acetylamino group, propanoylamino group, butyrylamino group, i-propylcarbonyl C1-7 acylamino groups such as amino group and benzoylamino group; C1-6 alkoxycarbonylamino groups such as methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group, etc. Can do.

Examples of the “alkylsulfonyl group” in R ¹¹ to R ¹³ include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, s-butylsulfonyl group, i-butylsulfonyl group. Group, t-butylsulfonyl group and the like, and a C1-6 alkylsulfonyl group is preferable.

Examples of the “arylsulfonyl group” in R ¹¹ to R ¹³ include a phenylsulfonyl group and a naphthylsulfonyl group, and a phenylsulfonyl group is preferable.

The “heterocyclylsulfonyl group” in R ¹¹ to R ¹³ includes an aziridinylsulfonyl group, an epoxysulfonyl group, a pyrrolidinylsulfonyl group, a tetrahydrofuranylsulfonyl group, a thiazolidinylsulfonyl group, a piperidylsulfonyl group, a piperazinylsulfonyl group. Group, morpholinylsulfonyl group, dioxolanylsulfonyl group, dioxanylsulfonyl group, pyrrolylsulfonyl group, furylsulfonyl group, thienylsulfonyl group, imidazolylsulfonyl group, pyrazolylsulfonyl group, oxazolylsulfonyl group, isoxazolyl Rusulfonyl group, thiazolylsulfonyl group, isothiazolylsulfonyl group, triazolylsulfonyl group, oxadiazolylsulfonyl group, thiadiazolylsulfonyl group, tetrazolylsulfonyl group, pyridyls Examples thereof include a sulfonyl group, a pyrazinylsulfonyl group, a pyrimidinylsulfonyl group, a pyridanidylsulfonyl group, and a triazinylsulfonyl group.

Examples of the “alkylcarbonyl group” in R ¹¹ to R ¹³ include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, s-butylcarbonyl group, i-butylcarbonyl Group, t-butylcarbonyl group and the like, and a C1-6 alkylcarbonyl group is preferable.

Examples of the “arylcarbonyl group” in R ¹¹ to R ¹³ include a phenylcarbonyl group and a naphthylcarbonyl group, and a phenylcarbonyl group is preferable.

Examples of the “heterocyclylcarbonyl group” in R ¹¹ to R ¹³ include aziridinylcarbonyl group, epoxycarbonyl group, pyrrolidinylcarbonyl group, tetrahydrofuranylcarbonyl group, thiazolidinylcarbonyl group, piperidylcarbonyl group, piperazinylcarbonyl Group, morpholinylcarbonyl group, dioxolanylcarbonyl group, dioxanylcarbonyl group, pyrrolylcarbonyl group, furylcarbonyl group, thienylcarbonyl group, imidazolylcarbonyl group, pyrazolylcarbonyl group, oxazolylcarbonyl group, isoxazolyl Rucarbonyl, thiazolylcarbonyl, isothiazolylcarbonyl, triazolylcarbonyl, oxadiazolylcarbonyl, thiadiazolylcarbonyl, tetrazolylcarbonyl, pyridylca Examples thereof include a rubonyl group, a pyrazinylcarbonyl group, a pyrimidinylcarbonyl group, a pyridanidylcarbonyl group, and a triazinylcarbonyl group.

R ¹¹ to R ¹³ are preferably hydrogen atoms.

In the formula [IIa], R ¹² and R ¹³ , R ¹¹ and R ¹² , or R ¹¹ and R ¹³ may be combined to form a divalent organic group. Examples of Y in which R ¹² and R ¹³ together form a divalent organic group include a divalent organic group represented by the formula [III].

In the formula [III], * indicates a bonding position.
In the formula [III], R ⁵¹ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted phenylene group.

^Examples of the “alkylene group” in R ⁵¹ include a methylene group, an ethylene group, a propane-1,3-diyl group (also known as trimethylene group), a propane-1,2-diyl group (also known as a propylene group), butane-1, 4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, Examples include octane-1,8-diyl group.

Examples of the “alkenylene group” for R ⁵¹ include an ethene-1,2-diyl group (—CH═CH—) group, a propenylene group, and a 2-butenylene group.

^Examples of the “phenylene group” for R ⁵¹ include 1,2-phenylene group.

Examples of the substituent on the “alkylene group” and “alkenylene group” in R ⁵¹ include a C1-6 alkyl group, a C6-10 aryl group, a hydroxyl group, a C1-6 alkoxy group, a C6-10 aryloxy group, a carboxyl group, Halogeno group, C1-6 haloalkyl group, C6-10 haloaryl group, C1-6 haloalkoxy group, amino group (group represented by NH ₂ ), C1-6 alkylamino group, C6-10 arylamino group, C1˜ 7 acylamino group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C1-6 alkylsulfinyl group, C1-6 alkylsulfonyl group, C6-10 arylsulfonyl group, heteroarylsulfonyl group, cyano group, An oxo group is preferred, a C1-6 alkyl group or a C6-10 aryl group (phenyl ) Is more preferable.

Examples of the substituent on the “phenylene group” in R ⁵¹ include a C1-6 alkyl group, a C3-8 cycloalkyl group, a C6-10 aryl group, a 3-6 membered heterocyclyl group, a hydroxyl group, a C1-6 alkoxy group, a C6 ~ 10 aryloxy group, carboxyl group, halogeno group, C1-6 haloalkyl group, C6-10 haloaryl group, C1-6 haloalkoxy group, amino group (group represented by NH ₂ ), C1-6 alkylamino group, C6-10 arylamino group, C1-7 acylamino group, C1-6 alkoxycarbonylamino group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C7-11 aralkylthio group, C1-6 alkylsulfinyl Group, C6-10 arylsulfinyl group, heteroarylsulfinyl group, C7-11 Lal Kill sulfinyl group, C1 ~ 6 alkylsulfonyl group, C6 ~ 10 arylsulfonyl group, heteroarylsulfonyl group, a cyano group, a nitro group is preferred.

R ⁵¹ is preferably an unsubstituted alkenylene group, more preferably an ethene-1,2-diyl group (—CH═CH—) group.

In the formula [III], each R ⁵⁰ independently represents a hydrogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclyl group, a hydroxyl group, a substituted or unsubstituted alkoxy group. Substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted A heterocyclylsulfonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted heterocyclylcarbonyl group;

In the formula [III], in R ⁵⁰ , “hydrocarbon group”, “heterocyclyl group”, “alkoxy group”, “alkoxycarbonyl group”, “aryloxy group”, “substituted or unsubstituted amino group”, “alkylsulfonyl” As the “group”, “arylsulfonyl group”, “heterocyclylsulfonyl group”, “alkylcarbonyl group”, “arylcarbonyl group”, and “heterocyclylcarbonyl group”, description of R ¹¹ to R ¹³ in the formula [IIa] The same thing as what was illustrated by can be mentioned, respectively.

R ⁵⁰ is preferably a hydrogen atom.

In the formula [IV], Ar represents a substituted or unsubstituted phenylene group.

Substituents on the “phenylene group” in Ar include a C1-6 alkyl group, a C3-8 cycloalkyl group, a C6-10 aryl group, a 3-6 membered heterocyclyl group, a hydroxyl group, a C1-6 alkoxy group, a C6— 10 aryloxy group, carboxyl group, halogeno group, C1-6 haloalkyl group, C6-10 haloaryl group, C1-6 haloalkoxy group, unsubstituted amino group, C1-6 alkylamino group, C6-10 arylamino group, C1-7 acylamino group, C1-6 alkoxycarbonylamino group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C7-11 aralkylthio group, C1-6 alkylsulfinyl group, C6-10 arylsulfinyl group Group, heteroarylsulfinyl group, C7-11 aralkyls Finiru group, C1 ~ 6 alkylsulfonyl group, C6 ~ 10 arylsulfonyl group, heterocyclylsulfonyl group, a cyano group, a nitro group is preferred.

Ar is preferably an unsubstituted phenylene group.

In the formula [IV], X and Z are each independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, —T ^a —O—T ^b —, — T ^a —S—T ^b — or —T ^a —N (R ³⁰ ) —T ^b — is shown. T ^a and T ^b each independently represent a single bond or a substituted or unsubstituted alkylene group, and R ³⁰ represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclyl group, hydroxyl group Group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted An arylsulfonyl group, a substituted or unsubstituted heterocyclylsulfonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted heterocyclylcarbonyl group is shown.

The “hydrocarbon group”, “heterocyclyl group”, “alkoxy group”, “alkoxycarbonyl group”, “aryloxy group”, “substituted or unsubstituted amino group”, “alkylsulfonyl group”, “arylsulfonyl” for R ³⁰ The “group”, “heterocyclylsulfonyl group”, “alkylcarbonyl group”, “arylcarbonyl group”, and “heterocyclylcarbonyl group” are the same as those exemplified in the description of R ¹¹ to R ¹³ in the formula [II]. You can list each one.

Examples of the “alkylene group” in X and Z include those exemplified in the description of R ⁵¹ in the formula [III], and a C1-10 alkylene group is preferable.

Examples of the “alkenylene group” for X and Z include the same ones as exemplified in the description of R ⁵¹ in the formula [III].

Examples of the “alkynylene group” in X and Z include an ethynylene group and a 2-butynylene group.

Examples of the substituent on the “alkylene group”, “alkenylene group” or “alkynylene group” in X and Z include a C1-6 alkyl group, a C6-10 aryl group, a hydroxyl group, a C1-6 alkoxy group, and a C6-10 aryl group. Oxy group, carboxyl group, halogeno group, C1-6 haloalkyl group, C6-10 haloaryl group, C1-6 haloalkoxy group, amino group (group represented by NH ₂ ), C1-6 alkylamino group, C6-10 Arylamino group, C1-7 acylamino group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C1-6 alkylsulfinyl group, C1-6 alkylsulfonyl group, C6-10 arylsulfonyl group, heteroaryl A sulfonyl group, a cyano group, and an oxo group are preferable, and a C1-6 alkyl group, More preferably Seo group, a methyl group, an oxo group is particularly preferable.

X is preferably a substituted or unsubstituted alkylene group.
Z is preferably a substituted or unsubstituted alkylene group, and more preferably an unsubstituted alkylene group.

In the formula [IV], G represents a single bond, a substituted or unsubstituted phenylene group, an ethene-1,2-diyl group (—CH═CH—), an ethyne-1,2-diyl group (—C≡C— ), Oxy group (—O—), thio group (—S—), sulfinyl group (—SO—), sulfonyl group (—SO ₂ —), or unsubstituted or N-substituted imino group (—N (R ³¹ )-).

Examples of the substituent on the “phenylene group” in G include the same ones as exemplified in the description of the substituent on the phenylene group in R ⁵¹ in the formula [III].

R ³¹ represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclyl group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryl Oxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted heterocyclylsulfonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted A substituted arylcarbonyl group or a substituted or unsubstituted heterocyclylcarbonyl group is shown.

The “hydrocarbon group”, “heterocyclyl group”, “alkoxy group”, “alkoxycarbonyl group”, “aryloxy group”, “substituted or unsubstituted amino group”, “alkylsulfonyl group”, “arylsulfonyl” in R ³¹ The “group”, “heterocyclylsulfonyl group”, “alkylcarbonyl group”, “arylcarbonyl group”, and “heterocyclylcarbonyl group” are the same as those exemplified in the description of R ¹¹ to R ¹³ in the formula [II]. You can list each one.

G is preferably a single bond, an oxy group (—O—) or a thio group (—S—), more preferably an oxy group (—O—).

In the formula [IV], R ¹ to R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclyl group, a hydroxyl group, a substituted or unsubstituted alkoxy group, substituted or unsubstituted Unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted heterocyclylsulfonyl group Represents a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted heterocyclylcarbonyl group.

“Hydrocarbon group”, “heterocyclyl group”, “alkoxy group”, “alkoxycarbonyl group”, “aryloxy group”, “substituted or unsubstituted amino group”, “alkylsulfonyl group” in R ¹ to R ⁸ , “Arylsulfonyl group”, “heterocyclylsulfonyl group”, “alkylcarbonyl group”, “arylcarbonyl group”, “heterocyclylcarbonyl group” are those exemplified in the description of R ¹¹ to R ^{13 in} formula [IIa] The same thing can be mentioned respectively.

The substituent on the “hydrocarbon group” in R ¹ to R ⁸ is preferably a C1-6 alkylamino group such as a methylamino group.

R ¹ to R ⁸ are preferably a hydrogen atom or a substituted or unsubstituted C 1-6 alkyl group.

R ¹ and R ² may be bonded together to form a 4- to 8-membered ring together with two nitrogen atoms to which they are bonded and one carbon atom to which the two nitrogen atoms are bonded; ² and R ³ may combine to form a 4- to 8-membered ring together with two nitrogen atoms to which they are bonded and one carbon atom to which the two nitrogen atoms are bonded, or R ³ And R ⁴ may combine to form a 4- to 8-membered ring together with one nitrogen atom to which they are bonded, or R ¹ and R ⁴ may combine to form two A 4- to 8-membered ring may be formed together with the nitrogen atom and one carbon atom to which the two nitrogen atoms are bonded.

As the 4- to 8-membered ring formed by combining R ¹ and R ² together with two nitrogen atoms to which they are bonded and one carbon atom to which the two nitrogen atoms are bonded, an imidazole ring is preferable.

Examples of the 4- to 8-membered ring formed by combining R ² and R ³ together with two nitrogen atoms to which they are bonded and one carbon atom to which the two nitrogen atoms are bonded include 1, 4, 5 The 6,6-tetrahydropyrimidine ring is preferred.

Attached R ⁶ and R ⁷ is may also form a 4-8-membered ring one of the carbon atoms together with which they are two nitrogen atoms and the two nitrogen atoms bonded respectively bonded, or R ⁷ and R ⁸ may be bonded to form a 4- to 8-membered ring together with one nitrogen atom to which they are bonded, or R ⁵ and R ⁸ are bonded to bond them. A 4- to 8-membered ring may be formed together with one nitrogen atom and one carbon atom to which the two nitrogen atoms are bonded.

The compound [IV] according to the present invention includes hydrates, various solvates and crystal polymorphs. Furthermore, the compound [IV] according to the present invention includes stereoisomers, tautomers and mixtures thereof based on asymmetric carbon atoms, double bonds and the like.

The salt of the compound [IV] according to the present invention is not particularly limited as long as it is an agro-horticulturally acceptable salt. For example, salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid, lactic acid, albesylic acid and isethionic acid; salts of alkali metals such as lithium, sodium and potassium; alkaline earth metals such as calcium and magnesium Salts; salts of transition metals such as iron and copper; salts of organic bases such as ammonia, triethylamine, tributylamine, pyridine, and hydrazine. The salt of compound [IV] can be obtained from compound [IV] by a known method.

The phenylguanidine compound of the present invention is preferably a compound represented by the formula [I].

In the formula [I], R ¹ to R ⁸ , G, X, Y, and Z have the same meaning as that in the formula [IV].

In the formula [I], R represents a C1-6 alkyl group, a C3-8 cycloalkyl group, a C6-10 aryl group, a 3-6 membered heterocyclyl group, a hydroxyl group, a C1-6 alkoxy group, a C6-10 aryloxy group. , Carboxyl group, halogeno group, C1-6 haloalkyl group, C6-10 haloaryl group, C1-6 haloalkoxy group, amino group (group represented by NH ₂ ), C1-6 alkylamino group, C6-10 arylamino Group, C1-7 acylamino group, C1-6 alkoxycarbonylamino group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C7-11 aralkylthio group, C1-6 alkylsulfinyl group, C6-10 Arylsulfinyl group, heteroarylsulfinyl group, C7-11 aralkylsulfinyl group, C1- Alkylsulfonyl group, C6 ~ 10 arylsulfonyl group, heterocyclylsulfonyl group, a cyano group, a nitro group. Any one of R ¹ to R ⁴ may be bonded to R to form a ring.

N represents the number of R and is an integer from 0 to 4.

N is preferably 0.

Next, production examples of the phenylguanidine compound and its salt of the present invention are shown. In addition, the manufacture example shown below is only for demonstrating this invention, and does not restrict | limit the scope of the present invention.

Production Example 1
The aniline (3) can be obtained by reacting the nitrophenol (1) with the halogen compound (2) and then reducing the nitro group. Compound (5) can be obtained by reacting the amino group of aniline (3) with compound (4). Compound (8) can be obtained by deprotecting protecting group P in compound (5) and then reacting with compound (7). The compound (10) according to the present invention can be obtained by reacting the compound (8) with the alcohol (9). In addition, the compound (11) according to the present invention can be obtained by deprotecting the t-butoxycarbonyl group in the compound (10).

In the formula, n, X and Z are the same as n, X and Z in [IV]. In the formula, R is the same as R in formula [I]. In the formula, Hal represents a halogeno group, P represents an alcohol protecting group, and Boc represents a t-butoxycarbonyl group.

Production Example 2
Compound (13) can be obtained by reacting the amino group of aniline (12) with compound (4). The acid halide (14) can be obtained by deprotecting the protecting group P in the compound (13) and then reacting with a halogenating agent. The compound (9) and the compound (15) can be led to the compound (16) by Mitsunobu reaction. The compound (17) according to the present invention can be obtained by reacting the compound (16) with the previously synthesized acid halide (14). Moreover, the compound (18) according to the present invention can be obtained by deprotecting the t-butoxycarbonyl group in the compound (17).

In the formula, n, X and Z are the same as n, X and Z in [IV]. In the formula, R is the same as R in formula [I]. In the formula, Hal represents a halogeno group, P represents a carboxylic acid protecting group, Boc represents a t-butoxycarbonyl group, and X ′ represents an alkylene group.

After completion of the synthesis reaction, the target product can be efficiently isolated by subjecting it to conventional post-treatment operations in organic synthetic chemistry and, if necessary, conventionally known separation and purification means.
The structure of the target product can be identified and confirmed by measuring ¹ H-NMR spectrum, IR spectrum, mass spectrum, elemental analysis, or the like.

The fungicide or plant disease control agent according to the present invention contains at least one selected from the group consisting of compound [IV] or a salt thereof as an active ingredient. The amount of the active ingredient contained in the fungicide or plant disease control agent of the present invention is preferably 0.01 to 90% by weight, more preferably 0.05 to 85% by weight, based on the whole preparation.

The fungicides or plant disease control agents of the present invention can be used in the form of agricultural chemicals, that is, in the form of agricultural chemical preparations such as wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, and granular wettable powders. can do.
Additives and carriers used in solid formulations include vegetable powders such as soybean flour and wheat flour, mineral fine powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, sodium benzoate, urea And organic and inorganic compounds such as mirabilite.
Solvents used in liquid formulations include kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water, etc. Can be mentioned.

Furthermore, in order to take a uniform and stable form in these preparations, a surfactant can be added as necessary.
The surfactant that can be added is not particularly limited. For example, alkyl phenyl ether added with polyoxyethylene, alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, sorbitan higher fatty acid ester added with polyoxyethylene, tristyryl added with polyoxyethylene Nonionic surfactants such as phenyl ether, sulfates of alkylphenyl ethers added with polyoxyethylene, alkylbenzene sulfonates, sulfates of higher alcohols, alkylnaphthalene sulfonates, polycarboxylates, lignin sulfones Acid salt, formaldehyde condensate of alkyl naphthalene sulfonate, and isobutylene-maleic anhydride copolymer.

The wettable powder, emulsion, flowable powder, aqueous solvent, or granular wettable powder thus obtained is diluted with water to a predetermined concentration and sprayed on plants as a solution, suspension or emulsion. Used in the method. Powders and granules are used as they are sprayed on plants.

The bactericidal agent or plant disease control agent of the present invention is used by seed treatment, foliage application, soil application or water surface application for the control of various diseases that occur during cultivation of agricultural and horticultural crops including flower buds, turf, and grass. Can do.

The application amount of the fungicide or plant disease control agent of the present invention varies depending on weather conditions, formulation form, application time, application method, application location, disease to be controlled, target crop, etc., but usually the amount of active ingredient per hectare The amount is preferably 1 to 1,000 g, more preferably 10 to 100 g.
When a wettable powder, emulsion, suspension, aqueous solvent, granular wettable powder or the like is diluted with water and applied, the applied concentration is preferably 1 to 1,000 ppm, more preferably 10 to 250 ppm.

The fungicides or plant disease control agents of the present invention can be applied to a wide variety of filamentous fungi such as algae (Oomycetes), Ascomycetes, incomplete fungi (Deuteromycetes), and basidiomycetes. It can be used to control plant diseases derived from bacteria belonging to Zygomycetes.

Examples of plant diseases and pathogens to be controlled are shown below.
Sugar beet: brown spot disease (Cercospora beticola), black root disease (Aphanomyces cochlioides), root rot (Thanatephorus cucumeris), leaf rot (Thanatephorus cucumeris), etc. ), Rust disease (Puccinia arachidis), withering disease (Pythium debaryanum), rust spot disease (Alternaria alternata), white silk disease (Sclerotium rolfsii) black astringency (Mycosphaerella berkeleyi), cucumber: powdery mildew (Sphaerotheca fuliginea), Downy mildew (Pseudoperonospora cubensis), vine blight (Mycosphaerella melonis), vine split disease (Fusarium oxysporum), mycorrhizal disease (Sclerotinia sclerotiorum), gray mold disease (Botrytis cinerea), anthracnose disease (Colletotrichum orbiculare), black star disease (Cladosporium cucumerinum), brown spot disease (Corynespora cassicola), seedling blight (Pythium debaryanam, Rhizoctonia solani Kuhn), homopsis root rot (Phomopsis sp.) Spot bacterial disease (Pseudomonas syringa) e pv. Lecrymans) Tomato: Gray mold disease (Botrytis cinerea), leaf mold disease (Cladosporium fulvum), plague (Phytophthora infestans), half body wilt disease (Verticillium albo-atrum), powdery mildew (Oidium neolycopersici), ring crest Diseases (Alternaria solani), Subtilis (Pseudocercospora fuligena), etc. Eggplant: Gray mold (Botrytis cinerea), Black blight (Corynespora melongenae), Powdery mildew (Erysiphe cichoracearum), Subtilis (Mycovellosiella nattrassii), Mycovellosiella nattrassii Strawberries: Botrytis cinerea, powdery mildew (Sohaerotheca humuli), anthracnose (Colletotrichum acutatum, Colletotrichum fragariae), plague (Phytophthora cactorum), soft rot (Rhizopus stoifer) (Fusarium oxysporum) Onions: gray rot (Botrytis allii), gray mold (Botrytis cinerea), white leaf blight (Botrytis squamosa), downy mildew (Peronospora d estructor), white plague (Phytophthora porri), etc. cabbage: root-knot disease (Plasmodiophora brassicae), soft rot disease (Erwinia carotovora), black rot disease (Xanthomonas campesrtis pv. campestris), black spot bacterial disease (Pseudomonas syringae pv. maculicalas, Pseudomonas syringae pv. alisalensis), downy mildew (Peronospora parasitica), mycorrhizal disease (Sclerotinia sclerotiorum), black soot disease (Alternaria brassicicola), gray mold disease (Botrytis cinerea), etc. Kidney: Sclerotinia sclerotiorum, gray mold Diseases (Botrytis cinerea), anthrax (Colletotrichum lindemuthianum), keratosis (Phaeoisariopsis griseola), etc.

Apple: powdery mildew (Podosphaera leucotricha), black spot disease (Venturia inaequalis), monilinia disease (Monilinia mali), black spot disease (Mycosphaerella pomi), rot disease (Valsa mali), spotted leaf disease (Alternaria mali), red star disease (Gymnosporangium) yamadae), ring rot (Botryosphaeria berengeriana), anthracnose (Glomerella cingulata, Colletotrichum acutatum), brown spot (Diplocarpon mali), soot spot (Zygophiala jamaicensis), soot spot (Gloeodes pomigena), purple coat rot (Helicobasidium mompa), gray mold disease (Botrytis cinerea), etc. Ume: Black rot (Cladosporium carpophilum), gray mold disease (Botrytis cinerea), gray star disease (Monilinia mumecola), etc. Oysters: powdery mildew (Phyllactinia kakicola), anthrax Diseases (Gloeosporium kaki), keratodeciduous leaf disease (Cercospora kaki), etc. Peach: Monilinia fructicola, black scab (Cladosporium carpophilum), homoposis rot (Phomopsis sp.), Perforation Almonds: Monilinia laxa, spot disease (Stigmina carpophila), black star disease (Cladosporium carpophilum), leaf blight disease (Polystigma rubrum), spotted leaf disease (Alternariaalternata), anthrax Diseases (Colletotrichum gloeospoides), etc. Sweet potato: Monilinia fructicola, anthracnose (Colletotrichum acutatum), black spot (Alternaria sp.), Larvae nuclear disease (Monilinia kusanoi), etc. Grapes: Gray mold disease (Botrytis) cinerea), powdery mildew (Uncinula necator), late rot (Glomerella cingulata, Colletotrichum acutatum), downy mildew (Plasmopara viticola), black mildew (Elsinoe ampelina), brown spot (Pseudocercospora vitis), black rot ( Guignardia bidwellii), white rot (Coniella castaneicola), etc. Pear: Venturia nashicola, Red Star Disease (Gymnosporangium asiaticum), Black Spot Disease (Alternaria kikuchiana), Ring Ring Disease (Botryosphaeria berengeriana) , Powdery mildew (Phyllactinia mali), blight (Phomopsis fukushii), brown spot disease (Stemphylium vesicarium), anthracnose (Glomerella cingulata), etc. Cha: Ringe leaf disease (Pestalotia theae), anthracnose (Colletotrichum theae- citrus: scab (Elsinoe fawcetti), blue mold (Penicillium italicum), green mold (Penicillium digitatum), gray mold (Botrytis cinerea), black spot (Diaporthe citri), scab (Xanthomonas campestris pv. Citri), powdery mildew (Oidium sp.), Etc.

Wheat: powdery mildew (Erysiphe graminis f.sp.Tritici), red mold (Gibberella zeae), red rust (Puccinia recondita), yellow rust (Puccinia striiformis), brown snow rot (Pythium iwayamai), red snow rot Disease (Monographella nivalis), eye spot disease (Pseudocercosporella herpotrichoides), leaf blight disease (Septoria tritici), blight disease (Leptosphaeria nodorum), snow rot microbe nuclear disease (Typhula incarnata), snow rot large fungus nuclear disease (Myriosclerotinia borealis) ), Withering disease (Gaeumanomyces graminis), ergot disease (Claviceps purpurea), black wilt (Tilletia caries), naked smut (Ustilago nuda), etc. Barley: Pyrenophora graminea, reticulosis (Pyrenophora teres) , Cloudy disease (Rhynchosporium secalis), Bare smut (Ustilago tritici, U.nuda), etc. Rice: Rice blast (Pyricularia oryzae), Rhizoctonia solani, Idiot seedling (Gibberella fujikuroi), Sesame leaf blight ( Cochliobolus miyabeanus , Seedling blight (Pythiumgraminicolum), White leaf blight (Xanthomonas oryzae), Seed blight (Burkholderia plantarii), Brown streak (Acidovorax avenae), Bacterial blight (Burkholderia glumae), Leprosy blight (Cercospora) oryzae), rice mildew (Ustilaginoidea virens), brown rice (Alternaria alternata, Curvularia intermedia), belly black rice (Alternaria padwickii), red rice (Epicoccam purpurascenns), etc. Tobacco: Sclerotinia sclerotiorum, powdery mildew ( Erysiphe cichoracearum), plague (Phytophthora nicotianae), etc. Tulip: Gray mold disease (Botrytis cinerea), etc. ), Large patch (Rhizoctonia solani), dollar spot (Sclerotinia homoeocarpa), blast (Pyricularia sp.), Red blight (Pythium aphanidermatum), Collagetotrichum graminicola, etc. Orchardgrass: powdery mildew (Erysiphe graminis), etc. Nuclear diseases (Sclerotinia sclerotiorum), anthracnose (Colletotrichum truncatum), gray mold (Botrytis cinerea), etc. (Fusarium oxysporum), Sigatoka disease (Mycosphaerella fijiensis, Mycosphaerella musicola), etc. Rapeseed: Mycorrhizal disease (Sclerotinia sclerotiorum), root rot (Phoma lingam), black spot disease (Alternaria brassicae), etc. Coffee: Rust (Hemileia vastatrix) Anthracnose (Colletotrichum coffeanum), brown eye disease (Cercospora coffeicola), etc. Sugarcane: Brown rust (Puccinia melanocephala) Corn: leprosy (Gloecercospora sorghi), rust (Puccinia sorghi), southern rust (Puccinia polysora), smut (Ustilago maydis), sesame leaf blight (Cochliobolus heterostrophus), soot rot (Setophaeria turcica), etc. Cotton: seedling blight (Pythium sp), rust (Phakopsora gossypii), mildew (Mycosphaerella areola), anthracnose (Glomerella gossypii), etc. It is a highly safe drug with low toxicity to warm-blooded animals.

The fungicides or plant disease control agents of the present invention are mixed or used in combination with other fungicides, insecticides / acaricides, nematicides, soil insecticides, insecticides, plant growth regulators, synergists, etc. May be.
An example is shown below.

Fungicide:
(1) Nucleic acid biosynthesis inhibitors:
(a) RNA polymerase I inhibitor: benalaxyl, benalaxyl-M, furaxyl, metalaxyl, metalaxyl-M, oxadixyl, cloziracone, off-race;
(b) adenosine deaminase inhibitor: bupilimate, dimethylylmol, ethylimol;
(c) DNA / RNA synthesis inhibitors: Himexazole, octirinone;
(d) DNA topoisomerase II inhibitor: Oxophosphate.

(2) Mitotic fission inhibitor and cell division inhibitor:
(a) β-tubulin polymerization inhibitors: benomyl, carbendazim, chlorphenazole, fuberidazole, thiabendazole, thiophanate, thiophanate methyl, dietofencarb, zoxamide, ethaboxam;
(b) Cell division inhibitor: Pencyclon;
(c) Delocalization inhibitor of spectrin-like protein: fluopicolide.

(3) Respiratory inhibitor:
(a) Complex I NADH oxidoreductase inhibitor: diflumetrim, tolfenpyrad;
(b) Complex II succinate dehydrogenase inhibitor: benodanyl, flutolanil, mepronil, isophetamide, fluopyram, fenfram, flumecyclox, carboxin, oxycarboxyl, tifluzamide, benzovindiflupyr, bixafen, floxapyroxad , Furametopyr, isopyrazam, penflufen, penthiopyrad, sedaxane, boscalid, pyraziflumide;
(c) Complex III ubiquinol oxidase Qo inhibitor: azoxystrobin, cumoxystrobin, cumethoxystrobin, enoxastrobin, fluphenoxystrobin, picoxystrobin, pyroxystrobin, pyraclostrobin, Pyramethostrobin, triclopyricarb, cresoxime-methyl, trifloxystrobin, dimoxystrobin, phenaminestrobin, metminostrobin, oryastrostrobin, famoxadone, floxastrobin, fenamidone, pyribencarb, mandestrobin;
(d) Complex III ubiquinol reductase Qi inhibitor: cyazofamide, amisulbrom;
(e) oxidative phosphorylation uncouplers: binapacryl, meptyldinocup, dinocup, fluazinam, ferrimzone;
(f) Oxidative phosphorylation inhibitor (inhibitor of ATP synthase): fentin acetate, fentin chloride, fentin hydroxide;
(g) ATP production inhibitor: silthiofam;
(h) Complex III: Qx (unknown) inhibitor of cytochrome bc1 (ubiquinone reductase): Amethoctrazine.

(4) Amino acid and protein synthesis inhibitors
(a) Methionine biosynthesis inhibitor: Andoprim, cyprodinil, mepanipyrim, pyrimethanil;
(b) Protein synthesis inhibitor: blasticidin-S, kasugamycin, kasugamycin hydrochloride, streptomycin, oxytetracycline.

(5) Signaling inhibitor:
(a) Signaling inhibitor: quinoxyphene, proquinazide;
(b) MAP / histidine kinase inhibitor in osmotic signal transduction: fenpicuronyl, fludioxonil, clozolinate, iprodione, procymidone, vinclozolin.

(6) Lipid and cell membrane synthesis inhibitors:
(a) Phospholipid biosynthesis, methyltransferase inhibitor: Edifenphos, iprobenphos, pyrazophos, isoprothiolane;
(b) lipid peroxidants: biphenyl, chloroneb, dichlorane, kinden, technazene, tolcrofosmethyl, etridiazole;
(c) Agents that act on cell membranes: iodocarb, propamocarb, propamocarb hydrochloride, propamocarbfocetylate, prothiocarb;
(d) Microorganisms that disrupt the pathogen cell membrane: Bacillus subtilis, Bacillus subtilis QST713 strain, Bacillus subtilis FZB24 strain, Bacillus subtilis MBI600 strain, Bacillus subtilis strain D747 strain;
(e) Agent that disturbs the cell membrane: An extract of Goseika Yupte (Tea Tree).

(7) Cell membrane sterol biosynthesis inhibitors:
(a) Demethylation inhibitor at the C14 position in sterol biosynthesis: trifolin, pyrifenox, pyrisoxazole, phenarimol, flurprimidol, nuarimol, imazalyl, imazalyl sulfate, oxpoconazole, pefazoate, prochloraz, triflumizole , Viniconazole, azaconazole, viteltanol, bromconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriazole, fluconazole, Fluconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanyl, penconazole, propiconazole , Fluquinconazole, simeconazole, tebuconazole, tetraconazole triadimefon, triadimenol, triticonazole, prothioconazole, voriconazole, main phen triflupromazine Kona tetrazole (mefentrifluconazole);
(b) Inhibitors of Δ14 reductase and Δ8 → Δ7-isomerase in sterol biosynthesis:
Aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
(c) 3-keto reductase inhibitors in C4 demethylation of sterol biosynthesis system: phenhexamide, fenpyrazamine;
(d) Sterol biosynthetic squalene epoxidase inhibitors: Pyributibalbu, Naftifine, Terbinafine

(8) Cell wall synthesis inhibition
(a) trehalase inhibitor: validamycin;
(b) chitin synthase inhibitor: polyoxin, polyoxorim;
(c) Cellulose synthase inhibitor: dimethomorph, furmorph, pyrimorph; benavalicarb, iprovaricarb, toluprocarb, varifenalate, mandipropamide.

(9) Melanin biosynthesis inhibitor
(a) Reductase inhibitors of melanin biosynthesis: fusaride, pyroxylone, tricyclazole;
(b) Dehydrase inhibitors of melanin biosynthesis: carpropamide, diclocimet, phenoxanyl.
(c) Other: Torprocarb

(10) Host plant resistance inducer:
(a) Agents acting on the salicylic acid synthesis pathway: Acibenzoral-S-methyl;
(b) Others: Probenazole, thiazinyl, isothianyl, laminarin, giant redbird extract.

(11) Agents with unknown activity: Simoxanyl, fosetylaluminum, phosphoric acid (phosphate), teclophthalam, triazoxide, fursulfamide, dichromedin, metasulfocarb, cyflufenamide, metolaphenone, pyriophenone, dodin, dodin free base, fluthianyl.

(12) Agents with multiple action points: copper (copper salt), Bordeaux liquid, copper hydroxide, copper naphthalate, copper oxide, copper oxychloride, copper sulfate, sulfur, sulfur products, calcium polysulfide, farbum, mancozeb, maneb, Mankappa, methylam, polycarbamate, propineb, thiram, dineb, ziram, captan, captahol, phorpet, chlorothalonil, dichlorfluanid, tolylfluanid, guazatine, iminoctadine acetate (iminoctadine triacetate), iminoctadine albecate (iminoctadine trialbesilate), anilazine, dithianone, quinomethionate, fluorimide.

(13) Other agents: DBEDC, fluorophorpet, guazatine acetate, bis (8-quinolinolato) copper (II), propamidine, chloropicrin, ciprofram, agrobacterium, betoxazine, diphenylamine, methyl isothiocyanate (MITC ), Mildeomycin, Capsaicin, Cufraneb, Cyprosulfamide, Dazomet, Debacarb, Dichlorophene, Diphenzoquat, Diphenzoquat methylsulfonate, Flumetober, Focetyl calcium, Focetyl sodium, Irumamycin, Natamycin, Nitrotal isopropyl , Oxamocarb, pyrrolnitrin, tebufloquine, torniphanide, zaliramide, Algophase, amicaliazole (Amicarthiazol), oxathiapiproline, methylam zinc, Nthiazole, trichlamide, uniconazole, mildeomycin, oxyfenthiin, picarbutrazox, fenpicoxamid, dichlobentiazox, quinofumelin.

Insecticides, acaricides, nematicides, soil insecticides:
(1) Acetylcholinesterase inhibitor:
(a) Carbamate series: Alanicarb, Aldicarb, Bengiocarb, Benfuracarb, Butcarboxyme, Butoxycarboxyme, Carbaryl, Carbofuran, Carbosulfan, Ethiophenecarb, Fenobucarb, Formethanate, Furatiocarb, Isoprocarb, Methiocarb, Mesomil, Oxamyl, Pirimicarb, Propoxyl Thiodicarb, thiophanox, triazamate, trimetacarb, XMC, xylylcarb, phenothiocarb, MIPC, MPMC, MTMC, aldoxicarb, alixicarb, aminocarb, bufencarb, cloetocarb, metam sodium, promecarb;

(b) Organophosphorus: Acephate, azamethiphos, azinephos-ethyl, azinephos-methyl, kazusafos, chlorethoxyphos, chlorfenvinphos, chlormefos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, Dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethione, etoprophos, famfur, phenamiphos, fenitrothion, fenthion, phostiazet, heptenophos, imisiaphos, isofenphos, isocarbophos, isoxathione, malathione, methalmethione, mecarbamethione Monocrotophos, nared, ometoate, oxydimethone-methyl, parathion, parathion-methyl, phentoe Folate, hosalon, phosmet, phosphamidone, phoxime, pyrimiphos-methyl, propenophos, propetamphos, prothiophos, pyracrofos, pyridafenthion, quinalphos, sulfotep, tebupyrine phos, temefos, terbufos, tetrachlorbinphos, thiomethone, triazophos, trichlorfos, bromomidion, bromomidion Ethyl, BRP, carbophenothion, cyanophenphos, CYAP, demeton-S-methylsulfone, diariphos, diclofenthion, dioxabenzophos, etrimphos, phensulfothion, flupyrazophos, phonofos, formomothion, phosmethylan, isazophos, iodofenphos, methacliphos , Pyrimifos-ethyl, phosphocarb, propaphos, protoate, sulprophos.

(2) GABA-agonist chloride channel antagonists: acetoprole, chlordane, endosulfan, ethiprole, fipronil, pyrafluprole, pyriprole, camfechlor, heptachlor, dienochlor.
(3) Sodium channel modulator: Acrinatrin, d-cis-trans allelesine, d-transareleslin, bifenthrin, bioareslin, bioareslin isomers, bioresmethrin, cycloprotorin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda- Cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, ciphenothrin [(1R) -trans isomer], deltamethrin, enpentrin [(EZ)-( 1R) -isomers], esfenvalerate, etofenprox, fenpropatoline, fenvalerate, flucitrinate, flumethrin, tau-fulvalinate, halfenprox, imiprothrin, cade Phosphorus, permethrin, phenothrin [(1R) -trans isomer], praretrin, pyrethram, resmethrin, silafluophene, tefluthrin, tetramethrin [(1R) -isomer], tralomethrin, transfluthrin, allethrin, pyrethrin, pyrethrin I, pyrethrin II , Profluthrin, dimefluthrin, bioethanomethrin, biopermethrin, transpermethrin, fenfluthrin, fenpyritrin, fulbrocitrinate, flufenprox, methfluthrin, protrifen butto, pyrethmethrin, terraretrin.

(4) Nicotinic acetylcholine receptor agonists: acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam, sulfoxafurol, nicotine, flupiradiflon.
(5) Nicotinic acetylcholine receptor allosteric modulator: spinetoram, spinosad.
(6) Chloride channel activator: abamectin, emamectin benzoate, lepimectin, milbemectin; ivermectin, selamectin, doramectin, eprinomectin, moxidectin, milbemycin, milbemycin oxime, nemadectin.
(7) Juvenile hormone-like substances: hydroprene, quinoprene, mesoprene, phenoxycarb, pyriproxyfen, diophenolan, epofenanane, triprene.
(8) Other non-specific inhibitors: methyl bromide, chloropicrin, sulfuryl fluoride, borax, tartar.
(9) Homogeneous selective feeding inhibitors: flonicamid, pymetrozine, pyrifluquinazone.

(10) Tick growth inhibitor: clofentezin, difluvidazine, hexythiazox, etoxazole.
(11) Microbial-derived insect midgut lining destroyer: Bacillus thuringiensis subsp. Isla elensis, Bacillus sphaericus, Bacillus thuringiensis subsp. Aisawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1 / Cry35Ab1.
(12) Mitochondrial ATP biosynthetic enzyme inhibitors: diafenthiuron, azocyclotin, cyhexatin, fenbutasine oxide, propargite, tetradiphone.
(13) Oxidative phosphorylation uncoupler: chlorfenapyr, sulfuramide, DNOC, binapacryl, dinobutone, dinocup
(14) Nicotinic acetylcholine receptor channel blocker: bensultap, cartap hydrochloride, nereistoxin, thiosultap monosodium salt, thiocyclam.
(15) Chitin synthesis inhibitor: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novallon, nobiflumuron, teflubenzuron, triflumuron, buprofezin, fluazuron.
(16) Diptera molting agent: cyromazine.
(17) Molting hormone receptor agonists: Chromafenozide, halofenozide, methoxyphenozide, tebufenozide.
(18) Octopamine receptor agonist: Amitraz, demiditraz, chlordimeform.
(19) Mitochondrial electron transport system complex III inhibitor: acequinosyl, fluacrylpyrim, hydramethylnon.
(20) Mitochondrial electron transport system complex I inhibitor: phenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, rotenone.

(21) Voltage-gated sodium channel blocker: indoxacarb, metaflumizone.
(22) Acetyl CoA carboxylase inhibitor: spirodiclofen, spiromesifen, spirotetramat.
(23) Mitochondrial electron transport complex IV inhibitor: Aluminum phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide.
(24) Mitochondrial electron transport system complex II inhibitor: Sienopyrafen, cyflumethofene, pivlumide.
(25) Ryanodine receptor modulator: chlorantraniliprole, cyantraniprole, fulvendiamide, cyclaniliprol, tetraniprolol.
(26) Mixed function oxidase inhibitor compound: Piperonyl butoxide.
(27) Latrophilin receptor agonist: depsipeptide, cyclic depsipeptide, 24-membered cyclic depsipeptide, emodepside.
(28) Other agents (unknown mechanism of action): azadirachtin, benzoximate, biphenazate, bromopropyrate, quinomethionate, cryolite, dicofol, pyridalyl, bencrothiaz, sulfur, amidoflumet, 1,3-dichloropropene, DCIP, Phenisobromolate, benzomate, metaldehyde, chlorbenzilate, clothiazoben, dicyclanyl, phenoxacrime, fentriphanyl, flubenzimine, fluphenazine, gossip lure, japonyla, methoxadiazone, petroleum, potassium oleate, tetrasul, trialacene, aphidopyropene (afidopyropen ), Flometokin, flufiprole, fluenesulfone, meperfluthrin, tetramethylfluthrin, tralopyril, dimefluthrin, methylneodeca Amide, fluralanel, afoxolanel, floxamethamide, 5- [5- (3,5-dichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] -2- (1H-1,2,4 -Triazol-1-yl) benzonitrile (CAS: 943137-49-3), brofuranilide, and other metadiamides.

(29) Anthelmintic:
(a) benzimidazole series: fenbendazole, albendazole, triclabendazole, oxybendazole, mebendazole, oxfendazole, perbendazole, fulbendazole, fevantel, netobimine, thiophanate, thiabendazole, canbendazole;
(b) salicylanilide series: closantel, oxyclozanide, rafoxanide, niclosamide;
(c) substituted phenols: nitroxinyl, nitroskanate;
(d) Pyrimidine series: Pirantel, Morantel;
(e) Imidazothiazole series: levamisole, tetramisol;
(f) Tetrahydropyrimidine series: praziquantel, epsiprantel;
(g) Other anthelmintic drugs: cyclodiene, riania, chlorthrone, metronidazole, demiditraz, piperazine, diethylcarbamazine, dichlorophen, monepantel, tribendimidine, amidantel, thiacetalamide, melolsamine, arsenamide.

Plant growth regulator:
Abscisic acid, kinetin, benzylaminopurine, 1,3-diphenylurea, forchlorfenuron, thidiazuron, chlorfenuron, dihydrozeatin, gibberellin A, gibberellin A4, gibberellin A7, gibberellin A3, 1-methylcyclopropane, N-acetyl Aminoethoxyvinylglycine (also known as abiglycine), aminooxyacetic acid, silver nitrate, cobalt chloride, IAA, 4-CPA, cloprop, 2,4-D, MCPB, indole-3-butyric acid, dichloroprop, phenothiol, 1 -Naphtylacetamide, Ethiclozate, Cloxiphonac, Maleic acid hydrazide, 2,3,5-Triiodobenzoic acid, Salicylic acid, Methyl salicylate, (-)-Jasmonic acid, Methyl jasmonate, (+)-Strigol, (+) -Deoxystri Lumpur, (+) - Orobankoru, (+) - Sorugorakuton, 4-oxo-4- (2-phenylethyl) amino acid; ethephon, chlormequat, mepiquat chloride, benzyl adenine, 5-aminolevulinic acid.

Next, the present invention will be described more specifically with reference to examples. It should be noted that the present invention is not limited by the following examples, and can of course be implemented with appropriate modifications within a range that can be adapted to the spirit of the present invention. To be included in the scope.

Example 1
(Step 1) Synthesis of tert-butyldimethyl- [3- (4-aminophenoxy) propoxy] silane <tert-Butyldimethyl- [3- (4-aminophenoxy) propoxy] silane>

To a solution of 4-nitrophenol (5.79 g) and (3-bromopropoxy) -tert-butyldimethylsilane (12.63 g) in N, N-dimethylformamide (108 mL) was added potassium carbonate (28.7 g) at room temperature. added. After stirring at 60 ° C. for 5 hours, the reaction mixture was cooled to room temperature. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed twice with water and once with saturated brine, then dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. Palladium carbon (10% wet, 1.30 g) was suspended in a solution of the obtained crude product in methanol (250 mL). The mixture was stirred at room temperature for 3 hours under a hydrogen atmosphere, and then filtered through celite. The filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the title compound (10.36 g, yield 89%).
¹ H NMR (CDCl ₃ ): δ = 0.03 (s, 6H), 0.88 (s, 9H), 1.93 (tt, 2H), 3.39 (br.s, 2H, NH ₂ ), 3.77 (t, 2H), 3.97 (t, 2H), 6.62 (d, 2H), 6.73 (d, 2H).

(Step 2) tert-butyl N-[(tert-butoxycarbonylamino)-[4- [3- [tert-butyl (dimethyl) silyl] oxypropoxy] aniline] methylene] carbamate <tert-Butyl N-[(tert -butoxycarbonylamino)-[4- [3- [tert-butyl (dimethyl) silyl] oxypropoxy] aniline] methylene] carbamate>

To a solution of tert-butyldimethyl- [3- (4-aminophenoxy) propoxy] silane (1.00 g) obtained in Step 1 in tetrahydrofuran (5 mL) at room temperature, N, N′-di-tert-butoxycarbonyl- 1H-pyrazole-1-carboxamidine (1.14 g) was added and stirred overnight at the same temperature. Thereafter, the reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the title compound (1.74 g, yield 94%).
¹ H NMR (CDCl ₃ ): δ = 0.04 (s, 6H), 0.89 (s, 9H), 1.49 (s, 9H), 1.53 (s, 9H), 1.96 (tt, 2H), 3.79 (t, 2H ), 4.03 (t, 2H), 6.85 (d, 2H), 7.46 (d, 2H).

(Step 3) tert-butyl N-[(tert-butoxycarbonylamino)-[4- (3-hydroxypropoxy) anilino] methylene] carbamate <tert-Butyl N-[(tert-butoxycarbonylamino)-[4- (3 -hydroxypropoxy) aniline] methylene] carbamate〉

Tert-butyl N-[(tert-butoxycarbonylamino)-[4- [3- [tert-butyl (dimethyl) silyl] oxypropoxy] aniline] methylene] carbamate (1.74 g) of tetrahydrofuran obtained in Step 2 To the (20 mL) solution, tetrabutylammonium fluoride (1M, 15 mL) was added at room temperature. Stir at room temperature overnight. The reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the title compound (0.76 g, yield 56%).
¹ H NMR (CDCl ₃ ): δ = 1.49 (s, 9H), 1.53 (s, 9H), 2.03 (tt, 2H), 4.11 (t, 2H), 6.87 (d, 2H), 7.48 (d, 2H ).

(Step 4) tert-Butyl N- [N, N′-bis (tert-butoxycarbonyl) carbamidoyl] -N- [3- [4-[[N, N′-bis (tert-butoxycarbonyl) carba Imidoyl] amino] phenoxy] propyl] carbamate <tert-Butyl N- [N, N'-bis (tert-butoxycarbonyl) carbamimidoyl] -N- [3- [4-[[N, N'-bis (tert- butoxycarbonyl) carbamimidoyl] amino] phenoxy] propyl] carbamate〉

Tert-Butyl N-[(tert-butoxycarbonylamino)-[4- (3-hydroxypropoxy) anilino] methylene] carbamate (0.76 g), 1,2,3-tri-tert- A solution of butoxycarbonyl-guanidine (2.00 g) and triphenylphosphine (0.59 g) in tetrahydrofuran (12 mL) was cooled to 0 ° C., and diethylazodicarboxylate in toluene (2.2 M, 1.0 mL) was added to the same solution. Added at warm. The reaction mixture was warmed to room temperature and stirred overnight. Then, the reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the title compound (0.63 g, yield 45%).
¹ H NMR (CDCl ₃ ): δ = 1.45-1.55 (m, 45H), 2.13 (tt, 2H), 3.96-4.06 (m, 2H), 6.83 (d, 2H), 7.45 (d, 2H).

(Step 5) tert-Butyl N- [8-[[N, N′-bis (tert-butoxycarbonyl) carbamidoyl] amino] octyl] -N- [N- [3- [4-[[N, N′-bis (tert-butoxycarbonyl) carbamidoyl] amino] phenoxy] propyl-butoxycarbonyl] carbamidoyl] amino] phenoxy] propyl <tert-Butyl N- [8-[[N, N'-bis ( tert-butoxycarbonyl) carbamimidoyl] amino] octyl] -N- [N- [3- [4-[[N, N'-bis (tert-butoxycarbonyl) carbamimidoyl] amino] phenoxy] propyl-butoxycarbonyl] carbamimidoyl] amino] phenoxy ] propyl>

Tert-Butyl N- [N, N′-bis (tert-butoxycarbonyl) carbamidoyl] -N- [3- [4-[[N, N′-bis (tert-butoxycarbonyl) obtained in Step 4 ) Carbamidoyl] amino] phenoxy] propyl] carbamate (0.63 g), tert-butyl N-[(tert-butoxycarbonylamino)-(8-hydroxyoctylamino) methylene] carbamate (0.54 g) and triphenyl A solution of phosphine (0.66 g) in toluene (12 mL) was cooled to 0 ° C., and di-2-methoxyethyl azodicarboxylate (0.59 g) was added. The mixture was warmed to room temperature and stirred overnight. Thereafter, the reaction mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain the title compound (Compound No. 1: 0.49 g, yield 53%).
¹ H NMR (CDCl ₃ ): δ = 1.20-1.37 (m, 10H), 1.43-1.55 (m, 65H), 2.13 (tt, 2H), 3.34-3.43 (m, 2H), 3.44-3.53 (m, 2H), 3.72 (t, 2H), 3.98 (t, 2H), 6.83 (d, 2H), 7.46 (d, 2H).

Example 2
Synthesis of 1- (8-guanidinooctyl) -3- [3- (4-guanidinophenoxy) propyl] guanidine <1- (8-guanidinooctyl) -3- [3- (4-guanidinophenoxy) propyl] guanidine> hydrochloride

Tert-Butyl N- [8-[[N, N′-bis (tert-butoxycarbonyl) carbamidoyl] amino] octyl] -N- [N- [3- [4- [obtained in Example 1 [N, N′-bis (tert-butoxycarbonyl) carbamidoyl] amino] phenoxy] propyl-butoxycarbonyl] carbamidoyl] amino] phenoxy] propyl (0.49 g) was dissolved in dichloromethane (6 mL) at room temperature. Trifluoroacetic acid (6 mL) was added. The reaction mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure, the resulting residue was dissolved in methanol (6 mL), and hydrogen chloride dioxane solution (4 M, 6 mL) was added. The reaction mixture was stirred overnight at room temperature. Thereafter, the reaction mixture was concentrated under reduced pressure to obtain the title compound (Compound No. 2: 0.79 g, quantitative).
¹ H NMR (CD ₃ OD): δ = 1.31-1.48 (m, 8H), 1.52-1.69 (m, 4H), 2.08 (tt, 2H), 3.10-3.26 (m, 4H), 3.39-3.48 (m , 2H), 4.11 (t, 2H), 7.05 (d, 2H), 7.22 (d, 2H).

Example 3
(Step 1) Synthesis of benzyl 2- (4-aminophenoxy) acetate <Benzyl 2- (4-aminophenoxy) acetate>

A solution of 4-aminophenol (1.53 g) in acetonitrile (180 mL) was cooled to 0 ° C., and benzyl bromoacetate (3.48 g) and cesium carbonate (5.70 g) were sequentially added. The reaction mixture was warmed to room temperature and stirred at the same temperature overnight. Thereafter, the reaction mixture was filtered through celite, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain the title compound (2.70 g, yield: 76%).
¹ H NMR (CDCl ₃ ): δ = 3.46 (br.s, 2H, NH ₂ ), 4.58 (s, 2H), 5.23 (s, 2H), 6.62 (d, 2H), 6.75 (d, 2H), 7.29-7.42 (m, 5H).

(Step 2) Benzyl 2- [4- [2,3-bis (tert-butoxycarbonyl) guanidino] phenoxy] acetate <Benzyl 2- [4- [2,3-bis (tert-butoxycarbonyl) guanidino] phenoxy] acetate >

To a solution of benzyl 2- (4-aminophenoxy) acetate (2.68 g) obtained in Step 1 in tetrahydrofuran (15 mL) at room temperature, N, N′-di-tert-butoxycarbonyl-1H-pyrazole-1-carboxamidine (3.36 g) was added. The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the title compound (4.97 g, yield 96%).
¹ H NMR (CDCl ₃ ): δ = 1.49 (s, 9H), 1.53 (s, 9H), 4.64 (s, 2H), 5.24 (s, 2H), 6.86 (d, 2H), 7.31-7.42 (m , 5H), 7.49 (d, 2H).

(Step 3) 2- [4- [2,3-Bis (tert-butoxycarbonyl) guanidino] phenoxy] acetic acid <2- [4- [2,3-Bis (tert-butoxycarbonyl) guanidine] phenoxy] acetic acid> Synthesis of

To a solution of benzyl 2- [4- [2,3-bis (tert-butoxycarbonyl) guanidino] phenoxy] acetate (4.96 g) obtained in step 2 in ethanol (50 mL) was added palladium carbon (10% wet, 1. 00 g) was suspended. After stirring at room temperature for 3 hours under a hydrogen atmosphere, the reaction mixture was filtered through celite. The filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the title compound (2.62 g, yield 64%).
¹ H NMR (CDCl ₃ ): δ = 1.45 (s, 9H), 1.54 (S, 9H), 4.42 (s, 2H), 6.89 (d, 2H), 7.36 (d, 2H).

(Step 4) tert-Butyl N- [8-[[N, N′-bis (tert-butoxycarbonyl) carbamidoyl] amino] octyl] -N- (N-tert-butoxycarbonylcarbamidoyl) carbamate < Synthesis of tert-Butyl N- [8-[[N, N'-bis (tert-butoxycarbonyl) carbamimidoyl] amino] octyl] -N- (N-tert-butoxycarbonylcarbamimidoyl) carbamate)

tert-Butyl N-[(tert-Butoxycarbonylamino)-(8-hydroxyoctylamino) methylene] carbamate (1.25 g), 1,3-bis (tert-butoxycarbonyl) guanidine (1.01 g) and tri A solution of phenylphosphine (1.27 g) in tetrahydrofuran (32 mL) was cooled to 0 ° C., and a toluene solution of diisopropyl azodicarboxylate (1.9 M, 2.6 mL) was added at the same temperature. The reaction mixture was warmed to room temperature and stirred overnight. Thereafter, the reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the title compound (1.22 g, yield 60%).
¹ H NMR (CDCl ₃ ): δ = 1.18-1.41 (m, 8H), 1.43-1.62 (m, 40H), 3.88 (t, 4H).

(Step 5) tert-Butyl N- [8-[[N, N'-bis (tert-butoxycarbonyl) carbamidoyl] amino] octyl] -N- [N- [2- [4-[[N, N'-bis (tert-butoxycarbonyl) carbamidoyl] amino] phenoxy] acetyl] -N'-tert-butoxycarbonyl-carbamidoyl] carbamate <tert-Butyl N- [8-[[N, N'- bis (tert-butoxycarbonyl) carbamimidoyl] amino] octyl] -N- [N- [2- [4-[[N, N'-bis (tert-butoxycarbonyl) carbamimidoyl] amino] phenoxy] acetyl] -N'-tert -butoxycarbonyl-carbamimidoyl] carbamate〉

2- [4- [2,3-bis (tert-butoxycarbonyl) guanidino] phenoxy] acetic acid (0.62 g) obtained in Step 3 was dissolved in dichloromethane (6 mL) and cooled to 0 ° C. Oxalyl chloride (0.19 g) was added dropwise thereto at 0 ° C., and then 2 drops of N, N-dimethylformamide were added. The mixture was stirred at room temperature for 1 hour and concentrated under reduced pressure to give the corresponding acid chloride.
Next, tert-butyl N- [8-[[N, N′-bis (tert-butoxycarbonyl) carbamidoyl] amino] octyl] -N- (N-tert-butoxycarbonylcarbamide) obtained in Step 4 Yl) carbamate (0.60 g) was dissolved in dichloromethane (6 mL), triethylamine (0.13 g) was added, and the mixture was cooled to 0 ° C. A dichloromethane (6 mL) solution of the acid chloride synthesized previously was added dropwise at the same temperature. The mixture was stirred overnight at room temperature while gradually raising the temperature. The reaction mixture was then poured into water and extracted with chloroform. The organic layers were combined, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the title compound (Compound No. 3: 0.27 g, yield 28%).
¹ H NMR (CDCl ₃ ): δ = 1.16-1.39 (m, 8H), 1.40-1.72 (m, 58H), 3.61-3.96 (m, 4H), 4.51 (br.s, 1H), 4.70 (br. s, 1H), 6.93 (d, 2H), 7.40-7.62 (m, 2H).
LC-MS: [M + Na] ⁺ = 1042.8

Example 4
N- [N- (8-guanidinooctyl) carbamidoyl] -2- (4-guanidinophenoxy) acetamide <N- [N- (8-guanidinooctyl) carbamimidoyl] -2- (4-guanidinophenoxy) acetamide> hydrochloride Synthesis of

Tert-Butyl N- [8-[[N, N'-bis (tert-butoxycarbonyl) carbamidoyl] amino] octyl] -N- [N- [2- [4- [obtained in Example 3 [N, N′-bis (tert-butoxycarbonyl) carbamidoyl] amino] phenoxy] acetyl] -N′-tert-butoxycarbonyl-carbamidoyl] carbamate (0.27 g) was dissolved in dichloromethane (8 mL). Trifluoroacetic acid (8 mL) was added at room temperature, and the mixture was stirred overnight at the same temperature. The reaction mixture was concentrated under reduced pressure, and the resulting residue was dissolved in methanol (8 mL), a hydrogen chloride dioxane solution (4 M, 8 mL) was added, and the mixture was further stirred overnight. Thereafter, the reaction mixture was concentrated under reduced pressure to obtain the title compound (Compound No. 4: 0.14 g, quantitative).
¹ H NMR (CD ₃ OD): δ = 1.35-1.50 (m, 8H), 1.60 (tt, 2H), 1.65 (tt, 2H), 3.17 (t, 2H), 3.35 (t, 2H), 4.81 ( s, 2H), 7.26 (d, 2H), 7.28 (d, 2H).

Example 5
(Step 1) Synthesis of tert-Butyl N-[[8-[[N, N′-bis (tert-butycarbonyl) carbamimidyl] amino] octanoylamino] -methylsulfanyl-methylene] carbamate

8-[[N, N′-Bis (tert-butoxycarbonyl) carbamimidyl] amino] octanoic acid (1.21 g), tert-Butyl N- (methylsulfonylcarbonidoyl) isopropyl amine (5) Dissolved in DMF (4 mL). This was cooled to 0 ° C., O- (7-azabenzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate (1.26 g) was added, and the temperature was raised to room temperature. The reaction was allowed to warm up overnight. Thereafter, the reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1.23 g of the title compound in a yield of 72%.
¹ H NMR (CDCl ₃ ): δ = 1.24-1.40 (m, 6H), 1.45-1.76 (m, 31H), 2.36-2.41 (m, 5H), 3 .88 (t, 2H).

(Step 2) tert-Butyl N-[[8-[[N, N'-bis (tert-butoxycarbonyl) carbamimidyl] amino] octanoylamino]-[3- (4-nitrophenoxy) propylamine] methylene] methylene]

The compound obtained in step 1 (1.23 g) was dissolved in THF (12 mL) and methanol (6 mL), and a solution of 3- (4-Nitrophenoxy) propan-1-amine (0.42 g) in THF (6 mL) was added. Added at room temperature. This was stirred at 50 ° C. overnight, cooled to room temperature, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.29 g of the title compound in a yield of 84%.
¹ H NMR (CDCl ₃ ): δ = 1.25-1.41 (m, 6H), 1.45-1.63 (m, 29H), 1.63-1.74 (m, 2H), 2 .13 (tt, 2H), 2.41 (t, 2H), 3.66 (dd, 2H), 3.89 (t, 2H), 4.15 (t, 2H), 7.01 (d, 2H), 8.20 (d, 2H).

(Step 3) Synthesis of tert-Butyl N-[[3- (4-aminophenoxy) propylamino]-[8-[[N, N'-bis (tert-butoxycarbonyl) carbamimidoyl] amino] octanoylamine] methylene]]

Palladium carbon (10% wet, 0.75 g) was suspended in a methanol (15 mL) solution of the compound obtained in step 2 (1.23 g), and a balloon filled with hydrogen gas was attached. This was stirred for 3 days at room temperature and then filtered through celite. The filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 0.86 g of the title compound in a yield of 70%.
¹ H NMR (CDCl ₃ ): δ = 1.24-1.40 (m, 6H), 1.44-1.62 (m, 29H), 1.63-1.72 (m, 2H), 2 .03 (tt, 2H), 2.40 (t, 2H), 3.43 (br.s, 2H, NH 2), 3.58-3.67 (m, 2H), 3.88 (t, 2H), 3.96 (t, 2H), 6.63 (d, 2H), 6.77 (d, 2H).

(Step 4) tert-Butyl N-[[8-[[N, N'-bis (tert-butycarbonyl) carbamimidyl] amino] octanoylamino]-[3- [4-[[N, N'-bis (tert- butoxycarbonyl) carbamidoyl] amino] phenoxy] propylamino] methylene] carbamate

N, N′-di-Boc-1H-pyrazole-1-carboxamidine (0.27 g) was added to a THF (16 mL) solution of the compound obtained in Step 3 (0.53 g) at room temperature, and the same temperature was maintained for 2 days. Stir. Thereafter, the reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 0.64 g of the title compound (Compound No. 47) in a yield of 90%.
¹ H NMR (CDCl ₃ ): δ = 1.26-1.41 (m, 6H), 1.44-1.74 (m, 49H), 2.01-2.11 (m, 2H), 2 .40 (t, 2H), 3.59-3.68 (m, 2H), 3.88 (t, 2H), 4.01 (t, 2H), 6.89 (d, 2H), 7. 48 (d, 2H).

Example 6
Synthesis of 8-guanidino-N- [N- [3- (4-guanidinophenoxy) propyl] carbamidoyl] octanamide hydrochloride

The compound (0.64 g) obtained in Example 5 was dissolved in dichloromethane (10 mL), trifluoroacetic acid (10 mL) was added at room temperature, and the mixture was stirred overnight at the same temperature. The reaction mixture was concentrated under reduced pressure, and the resulting residue was dissolved in methanol (10 mL), a hydrogen chloride dioxane solution (4 M, 10 mL) was added, and the mixture was stirred for 5 hr. Thereafter, the reaction mixture was concentrated under reduced pressure to obtain 0.40 g of the title compound (Compound No. 23) in a quantitative yield.
¹ H NMR (CD ₃ OD): δ = 1.34-1.46 (m, 6H), 1.52-1.76 (m, 4H), 2.16 (tt, 2H), 2.49 ( t, 2H), 3.17 (t, 2H), 3.55 (t, 2H), 4.15 (t, 2H), 7.08 (d, 2H), 7.22 (d, 2H).

Example 7
N- [8-[[N, N'-Bis (tert-butoxycarbonyl) carbamimidyl] amino] octyl] -N- [N- [3- [4-[[N, N'-bis (tert-butoxycarbonyl)- Synthesis of N-methyl-carbamidoyl] amino] phenoxy] propyl] -N, N'-bis (tert-butoxycarbonyl) carbamidoyl] carbamate

tert-Butyl N- [3- (4-aminophenoxy) propyl] -N- [N, N'-bis (tert-butoxycarbonyl) -N- [8-[[N-tert-butylcarbocarbonyl-N'-isopropoxycarbonyl-N'-isopropoxycarbonyl-N ] Amino] octyl] carbamidoyl] carbamate (360 mg) was dissolved in THF (3.5 mL), methanol (1.5 mL), tert-Butyl N- [N-tert-butylcarboylyl-C-methylsulfidylcarbonyl-carbonyl] -N-methyl-carbamate (149 mg) was added. The reaction mixture was heated to 50 ° C. and stirred at the same temperature for 7 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 147 mg of the title compound (Compound No. 45) in a yield of 32%.
¹ H NMR (CDCl ₃ ): δ = 1.2-1.34 (m, 8H), 1.46-1.60 (m, 63H), 1.62-1.70 (m, 2H), 2 10-2.19 (m, 2H), 3.21 (s, 2H), 3.49 (dd, 2H), 3.71 (dd, 2H), 3.88 (dd, 2H), 3. 97 (dd, 2H), 6.83 (d, 2H), 7.00 (d, 2H).

Example 8
(Step 1) Synthesis of tert-Butyl N- [N-tert-butoxycarbonyl-C-methylsulfanyl-carbonylimidyl] -N- [3- (3-nitrophenoxy) propyl] carbamate

1,3-Bis (t-butyoxycarbonyl) -2-methylisothiourea (3.81 g) was dissolved in DMF (50 mL) and cooled to 0 ° C. Sodium hydride (0.629 g) was added thereto and stirred at the same temperature for 30 minutes. Thereafter, 1- (3-Bromopropoxy) -3-nitro-benzene (4.43 g) was added and stirred at 50 ° C. overnight. The reaction mixture was then cooled to room temperature, water was added and extracted with ethyl acetate. The organic layer was washed twice with water and once with saturated brine, then dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 5.47 g of the title compound in a yield of 89%.
¹ H NMR (CDCl ₃ ): δ = 1.47 (s, 9H), 1.51 (s, 9H), 2.17-2.22 (m, 2H), 2.37 (s, 3H), 3.77 (t, 2H), 4.11 (t, 2H), 7.22 (dd, 1H), 7.41 (t, 1H), 7.72 (d, 1H), 7.81 (dd , 1H).

(Step 2) tert-Butyl N- [N- [8-[[N, N'-bis (tert-butoxycarbonyl) carbamimidoyl] amino] octyl] -N'-tert-butoxycarbonyl-carbamidoyl-carbamidyl-carbamidyl-carbamidyl-carbamidoyl Synthesis of (3-nitrophenoxy) propyl] carbamate

To a mixed solution of the compound obtained in Step 1 (2.67 g) in THF (21 mL) and methanol (9 mL) at room temperature, tert-Butyl N-[(8-aminocarboxylicamino)-(tert-butycarbonylamino) methylene] carbamate (1 .14 g) was added and stirred at 50 ° C. overnight. Thereafter, the reaction mixture was cooled to room temperature and concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 1.72 g of the title compound in a yield of 41%.
¹ H NMR (CDCl ₃ ): δ = 1.24-1.37 (m, 10H), 1.43-1.54 (m, 40H), 2.07-2.17 (m, 2H), 3 .17-3.25 (m, 2H), 3.33-3.44 (m, 2H), 3.85-3.95 (m, 2H), 4.07-4.10 (m, 2H) , 7.21 (dd, 1H), 7.41 (t, 1H), 7.71 (d, 1H), 7.82 (dd, 1H).

(Step 3) tert-Butyl N- [3- (3-aminophenoxy) propyl] -N- [N- [8-[[N, N′-bis (tert-butoxycarbonyl) carbamimidoyl] amino] octyl] -N ′ -Tert-butoxycarbonyl-carbamimidyl] carbamate synthesis

Palladium carbon (10% wet, 0.18 g) was suspended in a solution of the compound obtained in step 3 (1.72 g) in methanol (25 mL), and a balloon filled with hydrogen gas was attached. This was stirred overnight at room temperature and then filtered through celite. The filtrate was concentrated under reduced pressure, 1.20 g of the title compound, tert-Butyl N- [N- [8-[[N, N′-bis (tert-butoxycarbonyl) carbamidoyl] amino] octyl] -N′-tert- It was obtained as a mixture with butyoxycarbonyl-carbamidoyl] -N- [3- [3- (3- (methoxyamino) phenoxy] propy]] carbamate. The next reaction was carried out as a mixture.

(Step 4) tert-Butyl N- [N- [8-[[N, N'-bis (tert-butoxycarbonyl) carbamimidoyl] amino] octyl] -N'-tert-butoxycarbonyl-carbamidyl-carbamidyl-carbamidyl-carbamidyl-carbamidoyl [3-[[N, N'-bis (tert-butoxycarbonyl) carbamidoyl] amino] phenoxy] propyl] carbamate and tert-Butyl N- [N- [8-[[N, N'-bis (tert-butoxy) carbamidoyl] amino] octyl] -N'-tert-butoxycarbonyl-carbamidoyl] -N- [3- [3-[[N, N'-bis tert-butoxycarbonyl) carbamidoyl] -methoxy-amino] phenoxy] propyl] carbamate in a THF (10 mL) solution of the mixture (0.50 g) obtained in synthesis step 4 at room temperature with N, N′-di-Boc-1H -Pyrazole-1-carboxamidine (0.24 g) was added and stirred at the same temperature overnight. The reaction mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to isolate each of the title compounds.
tert-Butyl N- [N- [8-[[N, N′-bis (tert-butoxycarbonyl) carbamimidoyl] amino] octyl] -N′-tert-butoxycarbonyl-carbamidyl [3-N [ [N, N′-bis (tert-butoxycarbonyl) carbamidoyl] amino] phenoxy] propyl] carbamate (0.092 g, 14% yield) Compound No. 54

¹ H NMR (CDCl ₃ ): δ = 1.26-1.32 (m, 10H), 1.62-1.80 (m, 58H), 2.04-2.21 (m, 2H), 3 .16-3.25 (m, 2H), 3.35-3.43 (m, 2H), 3.84 (t, 2H), 3.98 (t, 2H), 6.63 (s, 1H) ), 7.16-7.25 (m, 3H).
tert-Butyl N- [N- [8-[[N, N′-bis (tert-butoxycarbonyl) carbamimidoyl] amino] octyl] -N′-tert-butoxycarbonyl-carbamidyl [3-N [ [N, N′-bis (tert-butyoxycarbonyl) carbamidoyl] -methoxy-amino] phenoxy] propyl] carbamate (0.184 g, yield 28%) Compound No. 55

¹ H NMR (CDCl ₃ ): δ = 1.24-1.31 (m, 8H), 1.65-1.46 (m, 58H), 2.07-2.12 (m, 2H), 3 .15-3.26 (m, 2H), 3.36-3.41 (m, 2H), 3.70 (s, 3H), 3.83-3.89 (m, 2H), 3.98 (T, 2H), 6.42 (s, 1H), 7.38-7.44 (m, 3H).

Example 9
(Step 1) tert-Butyl N-[(tert-butyoxycarbonylamino)-[4- [3- [2- (2,2,2-trifluoroacetyl) imino-1H-imidazol-3-yl] propoxy] anilino] methylene] synthesis of carbamate

tert-Butyl N-[[4- (3-bromopropoxy) anilino]-(tert-butoxycarbonylamino) methylene] carbamate (1.38 g) in DMF (30 mL) solution at room temperature with N- (1,3-dihydroimidazol-2 ylidene) -2,2,2-trifluoro-acetamide (0.57 g) and potassium carbonate (1.00 g) were added, and the mixture was stirred at 50 ° C. for 5 hours. The reaction solution was cooled to room temperature and filtered through Celite, and then the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain the title compound at 0.80 g in a yield of 55%.
¹ H NMR (CDCl ₃ ): δ = 1.50 (s, 9H), 1.54 (s, 9H), 2.22-2.31 (m, 2H), 3.93 (t, 2H), 4.22 (t, 2H), 6.64 (d, 1H), 6.77 (d, 1H), 6.83 (d, 2H), 7.48 (d, 2H).

(Step 2) tert-Butyl N-[[4- [3- [3- [8-[[N, N'-bis (tert-butoxycarbonyl) carbamimidoyl] amino] octyl] -2- (2,2,2 -Trifluoroacetyl) imino-imidazol-1-yl] propoxy] anilino]-(tert-butoxycarbonylamino) methylene] carbamate

The compound obtained in Step 1 (0.25 g) was dissolved in DMF (5 mL), and tert-butyl N-[(8-bromocarbonylamino)-(tert-butylcarboxylicamino) methylene] carbamate (0.24 g) and potassium carbonate (0.24 g) were dissolved. 0.17 g) was added at room temperature. This was heated to 50 ° C., stirred for 6 hours, and then cooled to room temperature. Thereafter, the mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to give the title compound in 0.20 g (yield 44%).
¹ H NMR (CDCl ₃ ): δ = 12-11-1.36 (m, 10H), 1.44-1.59 (m, 36H), 1.66-1.79 (m, 2H), 2 15-2.27 (m, 2H), 3.80-3.94 (m, 8H), 6.69 (s, 2H), 6.83 (d, 2H), 7.48 (d, 2H) ).

(Step 3) Synthesis of 1- [4- [3- [3- (8-Guanidinooctyl) -2-imino-imidazol-1-yl] propoxy] phenyl] guanidine hydrochloride

The compound obtained in step 2 (0.20 g) was dissolved in dichloromethane (2 mL), trifluoroacetic acid (2 mL) was added at room temperature, and the mixture was stirred overnight at the same temperature. The reaction mixture was concentrated under reduced pressure, and the resulting residue was dissolved in methanol (2 mL), hydrogen chloride dioxane solution (4M, 2 mL) was added, and the mixture was stirred for 4 hr. Thereafter, the reaction mixture was concentrated under reduced pressure to obtain 0.13 g of the title compound (Compound No. 10) in a quantitative yield.
¹ H NMR (CD ₃ OD): δ = 1.38 (m, 10H), 1.57-1.59 (m, 2H), 1.74 (m, 2H), 2.24 (t, 2H) 3.16 (t, 2H), 3.86 (t, 2H), 4.05-4.13 (m, 4H), 4.60 (m, 1H), 6.94-6.96 (m , 2H), 7.02 (d, 2H), 7.22 (d, 2H).

Table 1 shows some of the compounds of the present invention produced by the same method as in the above Examples. The production intermediates are shown in Table 2.

Formulation Example (Emulsion)
Compound of the present invention 5.0 parts by weight Polyoxyethylene sorbitan monolaurate 1.5 parts by weight Dimethylformamide 93.5 parts by weight The above components were mixed and dissolved to obtain an emulsion of 5% active ingredient.

Test example 1
(Apple black spot disease prevention test)
The emulsion prepared by the formulation of the preparation examples was diluted with water so that the active ingredient was 125 ppm. Subsequently, the diluted solution was sprayed on apple seedlings grown in a seedling pot (variety “Wang Lin”, 3-4 leaf stage). After air drying, conidia spores of Venturia inaequalis were inoculated and humidified, and then left in a wet chamber at 20 ° C. where light and darkness was repeated every 12 hours. Two weeks later, the appearance of lesions on the leaves was investigated (treatment section). In the same manner as in Test Example 1, the lesion appearance state on the leaf was compared with no treatment, and the control value was calculated.
Control value = 100- {area where lesions appear (treated area) / area where lesions appear (untreated area)} × 100

The compounds of Table 3 were subjected to the apple black scab control test. All the compounds exhibited a control value of 75 or more.

Test example 2
(Cucumber gray mold control test)
An emulsion was prepared in the same manner as in Test Example 1. The emulsion was diluted with water to an active ingredient of 125 ppm. Subsequently, the diluted solution was sprayed on cucumber seedlings grown in a seedling pot (variety “ground” system, cotyledon stage). After air drying, a conidial spore suspension of cucumber gray mold fungus (Botrytis cinerea) was inoculated dropwise and left in a wet chamber at 20 ° C. Four days later, the appearance of lesions on the leaves was examined (treatment area). In the same manner as in Test Example 1, the lesion appearance state on the leaf was compared with no treatment, and the control value was calculated.

The compounds of Table 4 were subjected to the cucumber gray mold control test. All the compounds exhibited a control value of 75 or more.

Test example 3
(Wheat powdery mildew control trial)
An emulsion was prepared in the same manner as in Test Example 1. The emulsion was diluted with water to an active ingredient of 125 ppm. Subsequently, the diluted solution was sprayed on wheat seedlings (variety “Chihoku”, 1-2 leaf stage) cultivated in a pot for raising seedlings. After air drying, conidia of wheat powdery mildew (Erysiphe graminis f.sp.tritici) were shaken off and inoculated, and left in a 20 ° C. greenhouse. Six days later, the appearance of lesions on the leaves was examined (treatment area). On the other hand, wheat was cultivated without spraying the diluted solution, and the lesion appearance state was similarly investigated (untreated section). A comparative study was conducted between the treated and untreated areas, and the control value was calculated.

The wheat powdery mildew control test was conducted on the compounds in Table 5. All the compounds exhibited a control value of 75 or more.

Test example 4
(Tomato plague control trial)
An emulsion was prepared in the same manner as in Test Example 1. The emulsion was diluted with water to an active ingredient of 125 ppm. Subsequently, the diluted solution was sprayed on tomato seedlings (variety “Regina”, 4-5 leaf stage) cultivated in a seedling pot. After air drying, a zoospore suspension of Phytophthora infestans was spray-inoculated and left in a wet chamber at 20 ° C. Four days later, the appearance of lesions on the leaves was examined (treatment area). In the same manner as in Test Example 1, the lesion appearance state on the leaf was compared with no treatment, and the control value was calculated.

The tomato plague control test was conducted on the compounds in Table 6. All the compounds exhibited a control value of 75 or more.

Test Example 5
(Wheat red rust prevention test)
An emulsion was prepared in the same manner as in Test Example 1. The emulsion was diluted with water to an active ingredient of 125 ppm. Subsequently, the diluted solution was sprayed on wheat seedlings (variety “Noribayashi No. 61”, 1-2 leaf stage) cultivated in a seedling pot. After air drying, summer spores of wheat rust (Puccinia recondita) were shaken off and inoculated, and left in a 20 ° C. greenhouse. After 12 days, the appearance of lesions on the leaves was examined (treatment area). In the same manner as in Test Example 1, the lesion appearance state on the leaf was compared with no treatment, and the control value was calculated.

The wheat red rust control test was conducted on the compounds in Table 7. All the compounds exhibited a control value of 75 or more.

Since the compounds selected at random from the compounds of the present invention have the effects as described above, the compounds of the present invention have effects such as bactericidal and plant disease control, including compounds that could not be exemplified. It can be understood that it is a compound.

Claims (5)

1. A compound represented by the formula [IV] or a salt thereof.
   

   

   In the formula [IV],
   Ar represents a substituted or unsubstituted phenylene group.
   X and Z each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene ^{group, -T a -O-T b -} , - T a -S-T ^b -or -T ^a -N (R ³⁰ ) -T ^b -is shown.
   T ^a and T ^b each independently represent a single bond or a substituted or unsubstituted alkylene group, and R ³⁰ represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclyl group, or a hydroxyl group. Substituted or unsubstituted alkoxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted aryl A sulfonyl group, a substituted or unsubstituted heterocyclylsulfonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted heterocyclylcarbonyl group;
   G represents a single bond, a substituted or unsubstituted phenylene group, —CH═CH—, —C≡C—, —O—, —S—, —SO—, —SO ₂ —, or —N (R ³¹ ). -Is shown. R ³¹ represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclyl group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryl Oxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted heterocyclylsulfonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted A substituted arylcarbonyl group or a substituted or unsubstituted heterocyclylcarbonyl group is shown.
   Y represents a divalent group represented by the formula [IIa].
   

   

   In the formula [IIa], R ¹¹ to R ¹³ are each independently a hydrogen atom, nitro group, cyano group, substituted or unsubstituted hydrocarbon group, substituted or unsubstituted heterocyclyl group, hydroxyl group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or An unsubstituted heterocyclylsulfonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted heterocyclylcarbonyl group is shown. R ¹² and R ¹³ , R ¹¹ and R ¹² , or R ¹¹ and R ¹³ may be combined to form a divalent organic group. The substituents on R ¹² and X may be combined to form a divalent organic group. * Indicates a binding position.
   R ¹ to R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclyl group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group Substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted heterocyclylsulfonyl group, substituted or unsubstituted An alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted heterocyclylcarbonyl group;
   R ¹ and R ² may be bonded together to form a 4- to 8-membered ring together with two nitrogen atoms to which they are bonded and one carbon atom to which the two nitrogen atoms are bonded; ² and R ³ may combine to form a 4- to 8-membered ring together with two nitrogen atoms to which they are bonded and one carbon atom to which the two nitrogen atoms are bonded, or R ³ And R ⁴ may combine to form a 4- to 8-membered ring together with one nitrogen atom to which they are bonded, or R ¹ and R ⁴ may combine to form two A 4- to 8-membered ring may be formed together with the nitrogen atom and one carbon atom to which the two nitrogen atoms are bonded.
   R ⁶ and R ⁷ may be bonded to each other to form a 4- to 8-membered ring together with two nitrogen atoms to which they are bonded and one carbon atom to which the two nitrogen atoms are bonded. Or R ⁷ and R ⁸ may be bonded to form a 4- to 8-membered ring together with one nitrogen atom to which they are bonded, or R ⁵ and R ⁸ may be bonded to form A 4- to 8-membered ring may be formed together with one nitrogen atom to be bonded and one carbon atom to which the two nitrogen atoms are bonded.
2. The compound or its salt of Claim 1 whose compound represented by Formula [IV] is a compound represented by Formula [I].
   

   

   In the formula [I], X, Y, Z, G, and R ¹ to R ⁸ have the same meaning as described above.
   R is a C1-6 alkyl group, C3-8 cycloalkyl group, C6-10 aryl group, 3-6 membered heterocyclyl group, hydroxyl group, C1-6 alkoxy group, C6-10 aryloxy group, carboxyl group, halogeno group , C1-6 haloalkyl group, C6-10 haloaryl group, C1-6 haloalkoxy group, unsubstituted amino group, C1-6 alkylamino group, C6-10 arylamino group, C1-7 acylamino group, C1-6 alkoxy Carbonylamino group, C1-6 alkylthio group, C6-10 arylthio group, heteroarylthio group, C7-11 aralkylthio group, C1-6 alkylsulfinyl group, C6-10 arylsulfinyl group, heteroarylsulfinyl group, C7-11 An aralkylsulfinyl group, a C1-6 alkylsulfonyl group, 6-10 arylsulfonyl group, heterocyclylsulfonyl group, a cyano group, a nitro group.
   n represents the number of R, and is an integer from 0 to 4.
3. The compound or a salt thereof according to claim 1 or 2, wherein X and Z are each independently a substituted or unsubstituted alkylene group, and G is -O-.
4. A fungicide containing as an active ingredient at least one selected from the group consisting of the compound according to any one of claims 1 to 3 and a salt thereof.
5. A plant disease control agent comprising as an active ingredient at least one selected from the group consisting of the compound according to any one of claims 1 to 3 and a salt thereof.