JPH0931069A - Thiazolecarboxylic acid derivative and plant disease injury controller - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thiazolecarboxylic acid derivative shown by a specific formula, exhibiting excellent control action on agricultural and horticultural disorder, not being observed to have phytotoxicity to useful crops, useful as an agricultural and horticultural fungicide. SOLUTION: This compound is shown by the formula (X is a halogen; W is O or S; R<1> is a 1-4C alkyl or a halogen; R<2> is OR<3> , N(R<4> )(R<5> ), N(R<6> )-[C(R<7> )(R<8> )]n -CO2 R<9> [R<3> is a 3-8C cycloalkyl, a substituted aryl, a substituted benzyl, etc.; R<4> is H or a 1-4C alkyl; R<5> is a (substituted) heteroaryl 1-4C alkyl, a (substituted) heterocyclic 1-4C alkyl, etc.; R<6> is H, a 1-4C alkyl, formyl, etc.; R<7> and R<8> are each H, a 1-6C alkyl or a (substituted) aryl; R<9> is H, a 1-4C alkyl, a (substituted) aryl 1-4C alkyl, etc.; (n) is (1-3)] such as 2- chloro-4-methyl-5-thiazolecarboxylic acid 2-phenylpropyl ester, etc. The compound, for example, is obtained by using a 2-halogeno-4-alkyl-5-thiazolecarboxylic acid as a starting substance.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel thiazolecarboxylic acid derivative, and a plant disease controlling agent, particularly a rice blast controlling agent, containing a thiazolecarboxylic acid derivative as an active ingredient.

[0002]

2. Description of the Related Art Among 2-halogeno-4-alkyl-5-thiazolecarboxylic acid derivatives, certain esters have a phytotoxicity-reducing action on herbicides.
It is described in Japanese Patent No. 48785.

Further, JP-A-6-80653 and JP-A-4-128275 describe that certain thiazolecarboxylic acid amides have herbicidal activity or insecticidal activity and acaricidal activity. However, the above-mentioned publication does not disclose any plant disease controlling activity. Further, Japanese Patent Laid-Open No. 2-149572 discloses the following formula:

[0004]

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Compounds having bactericidal activity have been disclosed. However, the structure of the thiazolecarboxylic acid derivative of the present invention and its plant disease controlling activity are not disclosed in the above publication.

[0006]

The existing fungicides for agricultural and horticultural use are not satisfactory in view of problems such as an increase in resistant bacteria and environmental safety, and their efficacy and residual effect, and they are not harmful to plant diseases. On the other hand, there is a demand for the development of a cheaper and more effective control agent.

[0007]

In view of such a situation, the present inventors have conducted various studies to develop a compound having excellent bactericidal activity, and as a result, the compound represented by the following formula [1]
The inventors have found that the thiazolecarboxylic acid derivative has excellent bactericidal activity and have reached the present invention. That is, the present invention
General formula [1]

[0008]

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[In the above formula, X represents a halogen atom, and W
Represents an oxygen atom or a sulfur atom, R¹Is C₁-C_FourA
R represents a alkyl group or a halogen atom, and R^TwoIs -OR^Three
Group, -N (R^Four) (R^Five) Group, -N (R⁶)-[C (R
⁷) (R⁸)]_n-CO_TwoR⁹Group, -N (R^Ten) -N
(R¹¹) (R¹²) Group, -N (R ¹³) (OR¹⁴) Group, -N
(R^Fifteen) SO_TwoR¹⁶Group, N (R¹⁷) SO_TwoN (R¹⁸)
(R¹⁹) Group, -SR²⁰Group, -OC (R^{twenty one}) (R^{twenty two}) CO
N (R^{twenty three}) (R^{twenty four}) Group or the following formula,

[0010]

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Represents a group represented by: R ³ is C ₃ -C ₈
Cycloalkyl group, substituted aryl group, substituted benzyl group,
An optionally substituted aryl C ₂ -C ₄ alkyl group,
Represents an optionally substituted aryl C ₂ -C ₄ alkenyl group, an optionally substituted heteroaryl C ₁ -C ₄ alkyl group or an optionally substituted heterocyclyl C ₁ -C ₄ alkyl group,

R ⁴ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, R ⁵ represents an optionally substituted heteroaryl C ₁ -C ₄ alkyl group, an optionally substituted heterocyclyl C _1- C ₄ alkyl group, optionally substituted aryl C ₂ -C ₄ alkenyl group, C ₁ -C ₄ alkylcarbonyl group, optionally substituted arylcarbonyl group, C ₁ -C ₄ alkoxycarbonyl group or substituted Optionally represents an aryl C ₁ -C ₄ alkoxycarbonyl group,

R ⁶ is a hydrogen atom, a C ₁ -C ₄ alkyl group,
Formyl group, C ₁ -C ₄ alkylcarbonyl group, optionally substituted arylcarbonyl group, C ₁ -C ₄ alkoxycarbonyl group or optionally substituted aryl C ₁ -C ₄ alkoxycarbonyl group,

R ⁷ and R ⁸ are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group (these R ⁷ and R ⁸ may be combined to form a cyclic alkyl group), and are substituted. An optionally substituted aryl group, an optionally substituted aryl C ₁ -C ₄ alkyl group or a C ₁ -C ₂ alkylthio C ₁ -C ₄ alkyl group, n represents 1, 2 or 3,

R ⁹ represents a hydrogen atom, a C ₁ -C ₄ alkyl group or an optionally substituted aryl C ₁ -C ₄ alkyl group, and R ¹⁰ represents a hydrogen atom, a C ₁ -C ₄ alkyl group, C
₂ -C ₄ alkenyl group, an aryl group which may be substituted, an optionally substituted aryl C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkylcarbonyl group, C ₁ -C ₄ alkoxycarbonyl group or a substituted Represents an optionally substituted aryl C ₁ -C ₄ alkoxycarbonyl group,

R ¹¹ and R ¹² are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group (these R ¹¹ and R ¹² may be taken together to form a cyclic alkyl group), or are substituted. Optionally substituted aryl group, optionally substituted aryl C ₁ -C ₄ alkyl group, formyl group, C ₁ -C ₄ alkylcarbonyl group, optionally substituted arylcarbonyl group, C ₁ -C ₄ alkoxycarbonyl A group or an optionally substituted aryl C ₁ -C ₄ alkoxycarbonyl group,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group (these R ¹³ and R ¹⁴ may combine together to form a cyclic alkyl group), C ₂ ~
C ₄ alkenyl, C ₂ -C ₄ alkynyl group, an aryl group which may be substituted, an optionally substituted aryl C ₁ -C ₄ alkyl group, formyl group, C ₁ -C ₄ alkylcarbonyl group, a substituted Represents an optionally substituted arylcarbonyl group, a C ₁ -C ₄ alkoxycarbonyl group or an optionally substituted aryl C ₁ -C ₄ alkoxycarbonyl group,

R^FifteenIs a hydrogen atom, C₁~ C_FourAlkyl group,
C_Two~ C_FourAlkenyl group, C_Two~ C _FourAlkynyl group, C
_Three~ C₈Cycloalkyl group, optionally substituted ant
C₁~ C_FourAlkyl group, C₁~ C_FourAn alkoxy group,
C_Two~ C_FourAlkenyloxy group, C_Two~ C_FourAlkynyl
An oxy group or an optionally substituted aryl C₁~ C
_FourRepresents an alkyloxy group, R¹⁶Is C₁~ C_FourAlkyl
Represents an optionally substituted aryl group,

R ¹⁷ is a C ₁ -C ₄ alkyl group, C ₃ -C ₈
Cycloalkyl group, C ₂ -C ₄ alkenyl group, C ₂ -C
₄ Alkynyl group, optionally substituted aryl C _1-
C ₄ alkyl group, C ₁ -C ₄ alkoxy, C ₂ -C ₄
An alkenyloxy group, a C ₂ -C ₄ alkynyloxy group or an optionally substituted aryl C ₁ -C ₄ alkyloxy group,

R¹⁸And R¹⁹Is independently C₁~
C₆Alkyl groups (these are R¹⁸, R ¹⁹Together, ring
A linear alkyl group may be formed), R²⁰Is hydrogen
Child, C₁~ C_FourAlkyl group or optionally substituted
Aryl C₁~ C_ThreeRepresents an alkyl group;^{twenty one}And R^{twenty two}
Are each independently a hydrogen atom or C₁~ C_FourAlkyl
Represents a group,

R ²³ and R ²⁴ are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group (these R ²³ and R ²⁴ may combine together to form a cyclic amino group), C ₂ -C _{4 represents an} alkenyl group, an optionally substituted aryl group, or an optionally substituted aryl C ₁ -C ₄ alkyl group,
R ²⁵ represents a hydrogen atom, a C ₁ -C ₄ alkyl group or an optionally substituted aryl C ₁ -C ₄ alkyl group,

R²⁶Is a hydrogen atom or C₁~ C_FourAlkyl
Represents a group, m represents 2, 3 to 5, and "substituted aryl"
The expression "group" refers to a cyano group as a substituent on the aryl ring.
Or C₁~ C_FourRepresents an alkoxy group, "substituted benzyl
The expression "group" means halogen atom, cyano group, nitro group, C
₁~ C _FourAlkyl group or C₁~ C_FourBy an alkoxy group
Represents a substituted benzyl group,

The expression "optionally substituted" represents, in addition to a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group as a substituent. , "Aryl" represents an aromatic compound such as benzene and naphthalene, and "heteroaryl" represents a 5-membered and 6-membered aromatic heterocycle such as pyridine, furan and thiophene.

The expression "heterocyclyl" refers to 5- and 6-membered non-aromatic heterocycles such as piperidine, morpholine, tetrahydrofuran, tetrahydrothiophene. ] And a plant disease containing the derivative as an active ingredient.

Further, in the present invention, in the above general formula [1], R ³ is a C ₄ -C ₈ alkyl group, a C ₄ -C ₈ haloalkyl group, a C ₂ -C ₄ alkenyl group, a C ₂ -C ₄ alkynyl. A group, a benzyl group or an aryl group (which may be substituted by halogen, lower alkyl, trifluoromethyl and nitro group), or

A plant disease controlling agent containing, as an active ingredient, one or more thiazolecarboxylic acid derivatives in which R ⁴ and R ⁵ are each independently a hydrogen atom or an optionally substituted aryl C ₁ -C ₄ alkyl group. It is a thing. In the compound of general formula [1],

The halogen atom of X is a fluorine atom,
A chlorine atom, a bromine atom or an iodine atom can be mentioned,
A chlorine atom or a bromine atom is particularly preferable. R ¹ C ₁ ~
The C ₄ alkyl group, a methyl group, an ethyl group, n- or i- propyl, n-, s-, i- or t-
A butyl group can be mentioned, but a methyl group is particularly preferable. Although W represents an oxygen atom or a sulfur atom, an oxygen atom is preferable.

R ² is -OR ³ group, -N (R ⁶ )-[C
(R ⁷ ) (R ⁸ )] _n —CO ₂ R ⁹ group, —N (R ¹⁰ ) —
^{N (R 11) (R 12} ) ^{group, -N (R 13) (OR} 14) group, -
N (R ¹⁷ ) SO ₂ N (R ¹⁸ ) (R ¹⁹ ) group or the following formula,

[0029]

[Chemical 6]

Is preferred. R ³ is a substituted aryl group, a substituted benzyl group or an optionally substituted aryl C ₂ -C
₄ Alkyl groups are preferred. R ⁴ is preferably a hydrogen atom.
R ⁵ is optionally substituted heterocyclyl C _1-
C ₄ alkyl group, optionally substituted aryl C ₂ ~
A C ₄ alkenyl group is preferred. R ⁶ is a hydrogen atom, C ₁ ~
C ₄ alkyl group, C ₁ -C ₄ alkoxycarbonyl group.

R ⁷ and R ⁸ are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group (these R ⁷ and R ⁸ may combine together to form a cyclic alkyl group), and are substituted. Optionally aryl C ₁ -C ₄ alkyl group or C ₁
~ C ₂ alkylthio C ₁ -C ₄ alkyl groups are preferred.
n is preferably 1 or 2. R ⁹ is preferably a C ₁ -C ₄ alkyl group. R ¹⁰ is preferably a hydrogen atom or a C ₁ -C ₄ alkyl group.

R ¹¹ and R ¹² are each independently preferably a hydrogen atom or a C ₁ -C ₆ alkyl group (these R ¹¹ and R ¹² may be combined to form a cyclic alkyl group). R ¹³ and R ¹⁴ are each independently a hydrogen atom, C ₁
~ C ₆ alkyl group (these are R ¹³ , R ¹⁴ together,
A cyclic alkyl group may be formed. ) Or optionally substituted aryl C ₁ -C ₄ alkyl groups are preferred.
R ^{15 to} R ¹⁹ are preferably hydrogen atoms or C _{1 to} C ₄ alkyl groups.

R²⁰Is C₁~ C_FourAlkyl groups are preferred.
R^{twenty one}, R^{twenty two}Is a hydrogen atom or C₁~ C _FourAlkyl group is preferred
Good. R^{twenty three}And R^{twenty four}Are each independently C₁~ C₆A
Rukiru group (these are R^{twenty three}, R^{twenty four}Together with the ring archi
May form a group). R^{twenty five}And R²⁶Is
C₁~ C_FourAlkyl groups are preferred. m is preferably 4 or 5
Good.

The definitions of each substituent and the like have the following meanings. The halogen atom means fluorine, chlorine, bromine and iodine, and examples of the C _{1 to} C ₄ alkyl group, the C _{3 to} C ₈ cycloalkyl group and the C _{1 to} C ₆ alkyl group include methyl, ethyl and n-. Or i-propyl, n-,
i-, s- or t-butyl, pentyl, hexyl,
Examples include cyclopropyl, cyclopentyl, cyclohexyl and the like.

Examples of the substituted aryl group include cyano-substituted phenyl, methoxy-substituted phenyl, cyano-substituted naphthyl, methoxy-substituted naphthyl, cyano-substituted anthranyl and the like. Examples of the substituted benzyl group include halogen-substituted benzyl and alkyl-substituted benzyl.
An optionally substituted aryl C ₂ -C ₄ alkyl group,
Examples of the optionally substituted aryl C ₁ -C ₄ alkyl group include benzyl, phenethyl, phenylpropyl, methylphenethyl and the like. Examples of the optionally substituted aryl C ₂ -C ₄ alkenyl group include styryl and cinnamyl.

Optionally substituted heteroaryl C ₁
-C ₄ alkyl group as the example furylmethyl, thienylmethyl group and the like. Examples of the optionally substituted heterocyclyl C ₁ -C ₄ alkyl group include:
Examples thereof include tetrahydrofurylmethyl and tetrahydrothienylmethyl groups. Examples of the C ₁ -C ₄ alkylcarbonyl group include acetyl, propionyl, methylpropionyl, pivaloyl and the like.

Examples of the C ₁ -C ₄ alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, n-butoxycarbonyl, t-butoxycarbonyl and the like. The optionally substituted aryl C ₁ -C ₄ alkoxycarbonyl group is, for example, benzyloxycarbonyl, p
-Methoxybenzyloxycarbonyl and the like.

Examples of the C ₁ -C ₂ alkylthio C ₁ -C ₄ alkyl group include methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl and the like. Examples of the optionally substituted arylcarbonyl group include benzoyl and halo-substituted benzoyl. The C ₂ -C ₄ alkenyl group such as allyl, crotyl, methallyl and the like.

Examples of the C ₂ -C ₄ alkynyl group include propargyl, methylpropargyl and the like. C
The ₁ -C ₄ alkoxy groups such as methoxy, ethoxy, n- or -i- propyloxy, n- butyloxy, and the like. Aryl groups include phenyl, naphthyl and anthranyl. Examples of the heteroaryl group include furan, thiophene, pyrazole, thiazole, indazole, pyridine, pyrimidine, triazine, benzofuran, indole and the like. Examples of the heterocyclyl group include oxirane, tetrahydrofuran, tetrahydrothiophene pyrrolidine, piperidine, morpholine and the like.

The compound according to the present invention has little or very little antibacterial action against rice blast fungus in a petri dish test. However, when sprayed directly on rice or applied on the surface of water, it exhibits an excellent rice blast control effect. That is, it is considered that the compound according to the present invention promotes the production of antibacterial substances in the rice body and imparts resistance to disease, thereby preventing the blast fungus from being infected and preventing the disease from occurring.

The compounds of the present invention represented by the formula [1] are shown in Tables 1 to 10. However, the compound of the present invention is not limited to these. In the table, Me represents a methyl group, Et an ethyl group, Pr a propyl group, Bu a butyl group, Pen a pentyl group, Hex a hexyl group, i an iso, s a secondary, and t Represents tertiary, Cyc represents cyclo, and Ph represents a phenyl group.

Further, Th represents a thienyl group, Fr represents a furyl group, Tht represents a tetrahydrothienyl group, and Thf represents a tetrahydrofuryl group. Table 1

[0043]

[Chemical 7]

[0044]

[Table 1] ─────────────────────────────────── Compound No. X R ³ ─────────────────────────────────── 1-1 Cl cyc-Pr 1-2 Cl 1 -Me-cyc-Pr 1-3 Cl cyc-Bu 1-4 Cl cyc-Pen 1-5 Cl cyc-Pen 1-6 Cl cyc-Hex 1-7 Cl CH ₂ -cyc-Pr 1-8 Cl CH ₂ -cyc-Pen 1-9 Cl CH ₂ -cyc-Hex 1-10 Cl Ph (4-CN) 1-11 Cl Ph (4-OMe) 1-12 Cl Ph [3,4- (OMe) ₂ ] 1 -13 Cl CH ₂ -Ph (4-Cl) 1-14 Cl CH ₂ -Ph (2,4-Cl ₂ ) 1-15 Cl CH ₂ -Ph (4-CN) 1-16 Cl CH ₂ -Ph ( 4-NO ₂ ) 1-17 Cl CH ₂ -Ph (4-Me) 1-18 Cl CH ₂ -Ph (4-Et) 1-19 Cl CH ₂ -Ph (4-i-Pr) 1-20 Cl CH ₂ -Ph (4-OMe) 1-21 Cl CH ₂ -Ph (4-OEt) 1-22 Cl (CH ₂ ) ₂ -Ph 1-23 Cl CH (CH ₃ ) -Ph ────── ─────────────────────────────

[0045]

[Table 2] Table 1 (continued) ─────────────────────────────────── Compound No. X R ³ ─────────────────────────────────── 1-24 Cl CH ₂ CH (CH ₃ )- Ph 1-25 Cl CH ₂ CH (CH ₃ ) -Ph (4-Me) 1-26 Cl CH ₂ CH (CH ₃ ) -Ph (4-Cl) 1-27 Cl CH ₂ CH = CH-Ph 1- 28 Cl CH ₂ -2-Th 1-29 Cl CH ₂ -3-Th 1-30 Cl CH ₂ -2-Fr 1-31 Cl CH ₂ -3-Fr 1-32 Cl CH ₂ -2-Tht 1- 33 Cl CH ₂ -3-Tht 1-34 Cl CH ₂ -2-Thf 1-35 Cl CH ₂ -3-Thf 1-36 Br cyc-Pr 1-37 Br 1-Me-cyc-Pr 1-38 Br cyc-Bu 1-39 Br cyc-Pen 1-40 Br cyc-Pen 1-41 Br cyc-Hex 1-42 Br CH ₂ -cyc-Pr 1-43 Br CH ₂ -cyc-Pen 1-44 Br CH ₂ -cyc-Hex 1-45 Br Ph (4-CN) ────────────────────────────────────

[0046]

[Table 3] Table 1 (continued) ─────────────────────────────────── Compound No. X R ³ ─────────────────────────────────── 1-46 Br Ph (4-OMe) 1- 47 Br Ph [3,4- (OMe) ₂ ] 1-48 Br CH ₂ -Ph (4-Cl) 1-49 Br CH ₂ -Ph (2,4-Cl ₂ ) 1-50 Br CH ₂ -Ph (4-CN) 1-51 Br CH ₂ -Ph (4-NO ₂ ) 1-52 Br CH ₂ -Ph (2-Me) 1-53 Br CH ₂ -Ph (4-Me) 1-54 Br CH ₂ -Ph (4-Et) 1-55 Br CH ₂ -Ph (4-OMe) 1-56 Br CH ₂ -Ph (4-OEt) 1-57 Br (CH ₂ ) ₂ -Ph 1-58 Br CH (CH ₃ ) -Ph 1-59 Br CH ₂ CH (CH ₃ ) -Ph 1-60 Br CH ₂ CH (CH ₃ ) -Ph (4-Me) 1-61 Br CH ₂ CH (CH ₃ ) -Ph (4-Cl) 1-62 Br CH ₂ CH = CH-Ph 1-63 Br CH ₂ -2-Th 1-64 Br CH ₂ -3-Th 1-65 Br CH ₂ -2-Fr 1-66 Br CH ₂ -3-Fr 1-67 Br CH ₂ -3-Thf ─────────────────────────────────── -Table 2

[0047]

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[0048]

[Table 4] ─────────────────────────────────── Compound No. WR ⁴ R ⁵ ─────────────────────────────────── 2-1 OH CH ₂ -2- Thf 2-2 OH CH ₂ -2-Fr 2-3 OH CH ₂ -2-Th 2-4 OH CH ₂ -CH = CH-Ph 2-5 OH COMe 2-6 OH COEt 2- 7 OH COPh 2-8 OH CO ₂ Me 2-9 OH CO ₂ Et 2-10 OH CO ₂ CH ₂ Ph 2-11 OH CO ₂ CH ₂ Ph (4-OMe) 2-12 O Me CH ₂ -2-Thf 2-13 O Me CH ₂ -2-Fr 2-14 O Me CH ₂ -2-Th 2-15 O Me CH ₂ -CH = CH-Ph 2-16 O Me COMe 2-17 O Me COEt 2-18 O Me COPh 2-19 O Me CO ₂ Me 2-20 O Me CO ₂ Et 2-21 O Me CO ₂ CH ₂ Ph 2-22 O Me CO ₂ CH ₂ Ph (4-OMe) 2-23 O Et CH ₂ -2-Thf ────────────────────────────────────

[0049]

[Table 5] Table 2 (continued) ─────────────────────────────────── Compound No. WR ⁴ R ⁵ ─────────────────────────────────── 2-24 O Et CH ₂ -2- Fr 2-25 O Et CH ₂ -2-Th 2-26 O Et CH ₂ -CH = CH-Ph 2-27 O Et COMe 2-28 O Et COEt 2-29 O Et COPh 2-30 O Et CO ₂ Me 2-31 O Et CO ₂ Et 2-32 O Et CO ₂ CH ₂ Ph 2-33 O Et CO ₂ CH ₂ Ph (4-OMe) 2-34 O Et CH ₂ -2-Thf 2-35 O Et CH ₂ -2-furyl 2-36 O Et CH ₂ -2-Th 2-37 O Et CH ₂ -CH = CH-Ph 2-38 O Et COMe 2-39 O Et COEt 2-40 O Et COPh 2- 41 O Et CO ₂ Me 2-42 O Et CO ₂ Et 2-43 O Et CO ₂ CH ₂ Ph 2-44 SH CH ₂ -2-Fr 2-45 SH CH ₂ -2-Th ──── ─────────────────────────────── Table 3

[0050]

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[0051]

[Table 6] ─────────────────────────────────── Compound No. R ⁶ Q R ⁹ ─────────────────────────────────── 3-1 H Q1 H 3-2 H Q1 Me 3-3 H Q1 Et 3-4 H Q2 H 3-5 H Q2 Me 3-6 H Q2 Et 3-7 H Q2 t-Bu 3-8 H Q2 CH ₂ Ph 3-9 H Q3 H 3- 10 H Q3 Me 3-11 H Q3 Et 3-12 H Q3 CH ₂ Ph 3-13 H Q4 H 3-14 H Q4 Me 3-15 H Q4 Et 3-16 H Q5 H 3-17 H Q5 Me 3- 18 H Q5 Et 3-19 H Q5 n-Pr 3-20 H Q5 t-Bu 3-21 H Q5 CH ₂ Ph 3-22 H Q6 H 3-23 H Q6 Me ─────────── ─────────────────────────

[0052]

[Table 7] Table 3 (continued) ─────────────────────────────────── Compound No. R ⁶ Q R ⁹ ─────────────────────────────────── 3-24 H Q6 Et 3-25 H Q6 n-Pr 3-26 H Q6 t-Bu 3-27 H Q6 CH ₂ Ph 3-28 H Q7 H 3-29 H Q7 Me 3-30 H Q7 Et 3-31 H Q7 CH ₂ Ph 3-32 H Q8 H 3-33 H Q8 Me 3-34 H Q8 Et 3-35 H Q8 CH ₂ Ph 3-36 H Q9 H 3-37 H Q9 Me 3-38 H Q9 Et 3-39 H Q9 CH ₂ Ph 3- 40 H Q10 H 3-41 H Q10 Me 3-42 H Q10 Et 3-43 H Q10 CH ₂ Ph 3-44 H Q11 H 3-45 H Q11 Me ─────────────── ─────────────────────

[0053]

[Table 8] Table 3 (continued) ──────────────────────────────────── Compound No. R ⁶ Q R ⁹ ─────────────────────────────────── 3-46 H Q11 Et 3-47 H Q11 CH ₂ Ph 3-48 H Q12 H 3-49 H Q12 Me 3-50 H Q12 Et 3-51 H Q12 CH ₂ Ph 3-52 H Q13 H 3-53 H Q13 Me 3-54 H Q13 Et 3- 55 H Q13 CH ₂ Ph 3-56 Me Q1 H 3-57 Me Q1 Me 3-58 Me Q1 Et 3-59 Me Q2 H 3-60 Me Q2 Me 3-61 Me Q2 Et 3-62 Me Q3 H 3- 63 Me Q3 Me 3-64 Me Q3 Et 3-65 Me Q4 H 3-66 Me Q4 Me 3-67 Me Q4 Et ────────────────────── ─────────────

[0054]

[Table 9] Table 3 (continued) ─────────────────────────────────── Compound No. R ⁶ Q R ⁹ ─────────────────────────────────── 3-68 Me Q5 H 3-69 Me Q5 Me 3-70 Me Q5 Et 3-71 Me Q6 H 3-72 Me Q6 Me 3-73 Me Q6 Et 3-74 Me Q7 H 3-75 Me Q7 Me 3-76 Me Q7 Et 3-77 Me Q8 H 3-78 Me Q8 Me 3-79 Me Q8 Et 3-80 Me Q9 H 3-81 Me Q9 Me 3-82 Me Q9 Et 3-83 Me Q10 H 3-84 Me Q10 Me 3-85 Me Q10 Et 3- 86 Me Q11 H 3-87 Me Q11 Me 3-88 Me Q11 Et 3-89 Me Q12 H ───────────────────────────── ───────

[0055]

[Table 10] Table 3 (continued) ─────────────────────────────────── Compound No. R ⁶ Q R ⁹ ─────────────────────────────────── 3-90 Me Q12 Me 3-91 Me Q12 Et 3-92 Me Q13 H 3-93 Me Q13 Me 3-94 Me Q13 Et ─────────────────────────────── In the above Table 3, Q1-Q13 represent the following structures.

[0056]

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Table 4

[0058]

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[0059]

[Table 11] ─────────────────────────────────── Compound No. R ¹⁰ R ¹¹ R ¹² ─────────────────────────────────── 4-1 H H H 4-2 Me H H 4-3 Et H H 4-4 n-Pr H H 4-5 i-Pr H H 4-6 CH ₂ CH = CH ₂ H H 4-7 Ph H H 4-8 CH ₂ Ph H H 4-9 H COMe H 4-10 Me COMe H 4-11 Et COMe H 4-12 n-Pr COMe H 4-13 i-Pr COMe H 4-14 CH ₂ CH = CH ₂ COMe H 4-15 Ph COMe H 4-16 CH ₂ Ph COMe H 4-17 H COMe H 4-18 Me CO ₂ Et H 4-19 Et CO ₂ Et H 4-20 n-Pr CO ₂ Et H 4-21 i-Pr CO ₂ Et H 4-22 CH ₂ CH = CH ₂ CO ₂ Et H 4-23 Ph CO ₂ Et H ───────────────────────────── ───────

[0060]

[Table 12] Table 4 (continued) ──────────────────────────────────── Compound No. R ¹⁰ R ¹¹ R ¹² ─────────────────────────────────── 4-24 CH ₂ Ph CO ₂ Et H 4-25 H CO ₂ t-Bu H 4-26 Me CO ₂ t-Bu H 4-27 Et CO ₂ t-Bu H 4-28 CH ₂ CH = CH ₂ CO ₂ t-Bu H 4-29 H Me H 4-30 H Et H 4-31 H n-Pr H 4-32 H i-Pr H 4-33 H CH ₂ CH = CH ₂ H 4-34 H Ph H 4-35 H CH ₂ Ph H 4 -36 CO ₂ Et Me H 4-37 CO ₂ Et Et H 4-38 CO ₂ Et n-Pr H 4-39 CO ₂ Et i-Pr H 4-40 CO ₂ Et CH ₂ CH = CH ₂ H 4- 41 CO ₂ Et Ph H 4-42 CO ₂ Et CH ₂ Ph H 4-43 Me Me H 4-44 H Me Me 4-45 H-(CH ₂ ) ₄ -──────────── ──────────────────────── Table 5

[0061]

[Chemical 12]

[0062]

[Table 13] ─────────────────────────────────── Compound No. R ¹³ R ¹⁴ ─────────────────────────────────── 5-1 H H 5-2 H Me 5 -3 H Et 5-4 H n-Pr 5-5 H i-Pr 5-6 H n-Bu 5-7 H i-Bu 5-8 H s-Bu 5-9 H CH ₂ CH = CH ₂ 5 -10 H CH ₂ CH = CHCl 5-11 H CH ₂ Ph 5-12 H CH (CH ₃ ) Ph 5-13 H CH ₂ CH (CH ₃ ) Ph 5-14 Me H 5-15 Me Me 5-16 Me Et 5-17 Me n-Pr 5-18 Me i-Pr 5-19 Me n-Bu 5-20 Me i-Bu 5-21 Me s-Bu 5-22 Me CH ₂ CH = CH ₂ 5-23 Me CH ₂ CH = CHCl ────────────────────────────────────

[0063]

[Table 14] Table 5 (continued) ─────────────────────────────────── Compound No. R ¹³ R ¹⁴ ─────────────────────────────────── 5-24 Me CH ₂ Ph 5-25 Me _{CH (CH 3) Ph 5-26 Me} CH 2 CH (CH 3) Ph 5-27 - (CH 2) 3 - 5-28 - (CH 2) 4 - 5-29 CO 2 Et H 5-30 CO 2 Et Me 5-31 CO ₂ Et Et 5-32 CO ₂ Et n-Pr 5-33 CO ₂ Et i-Pr 5-34 CO ₂ Et n-Bu 5-35 CO ₂ Et i-Bu 5-36 CO ₂ Et s-Bu 5-37 CO ₂ Et CH ₂ CH = CH ₂ 5-38 CO ₂ Et CH ₂ CH = CHCl 5-39 CO ₂ Et CH ₂ Ph 5-40 CO ₂ Et CH (CH ₃ ) Ph 5- 41 CO ₂ Et CH ₂ CH (CH ₃ ) Ph 5-42 COMe Me 5-43 COMe Et 5-44 COMe CH ₂ Ph 5-45 H CH ₂ C≡CH ───────────── ─────────────────────── Table 6

[0064]

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[0065]

[Table 15] ─────────────────────────────────── Compound No. R ¹⁵ R ¹⁶ ─────────────────────────────────── 6-1 H Me 6-2 Me Me 6 -3 Et Me 6-4 n-Pr Me 6-5 cyc-Pr Me 6-6 CH ₂ CH = CH ₂ Me 6-7 CH ₂ C ≡ CH Me 6-8 CH ₂ Ph Me 6-9 OMe Me 6 -10 OEt Me 6-11 OCH ₂ CH = CH ₂ Me 6-12 OCH ₂ Ph Me 6-13 H Et 6-14 Me Et 6-15 Et Et 6-16 n-Pr Et 6-17 cyc-Pr Et 6-18 CH ₂ CH = CH ₂ Et 6-19 CH ₂ C ≡CH Et 6-20 CH ₂ Ph Et 6-21 OMe Et 6-22 OEt Et 6-23 OCH ₂ CH = CH ₂ Et ──── ───────────────────────────────

[0066]

[Table 16] Table 6 (continued) ─────────────────────────────────── Compound No. R ¹⁵ R ¹⁶ ─────────────────────────────────── 6-24 OCH ₂ Ph Et 6-25 H Ph 6-26 Me Ph 6-27 Et Ph 6-28 n-Pr Ph 6-29 cyc-Pr Ph 6-30 CH ₂ CH = CH ₂ Ph 6-31 CH ₂ C ≡ CH Ph 6-32 CH ₂ Ph Ph 6-33 OMe Ph 6-34 OEt Ph 6-35 OCH ₂ CH = CH ₂ Ph 6-36 OCH ₂ Ph Ph 6-37 Me Ph (4-Cl) 6-38 Et Ph (4-Cl) 6- 39 cyc-Pr Ph (4-Cl) 6-40 CH ₂ CH = CH ₂ Ph (4-Cl) 6-41 CH ₂ C ≡ CH Ph (4-Cl) 6-42 CH ₂ Ph Ph (4-Cl ) 6-43 OMe Ph (4-Cl) 6-44 OEt Ph (4-Cl) 6-45 OCH ₂ CH = CH ₂ Ph (4-Cl) ─────────────── ───────────────────── Table 7

[0067]

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[0068]

[Table 17] ─────────────────────────────────── Compound No. R ¹⁷ R ¹⁸ R ¹⁹ ─────────────────────────────────── 7-1 H Me Me 7-2 Me Me Me 7-3 Et Me Me 7-4 n-Pr Me Me 7-5 cyc-Pr Me Me 7-6 CH ₂ CH = CH ₂ Me Me 7-7 CH ₂ C ≡ CH Me Me 7-8 CH ₂ Ph Me Me 7-9 OMe Me Me 7-10 OEt Me Me 7-11 OCH ₂ CH = CH ₂ Me Me 7-12 OCH ₂ Ph Me Me 7-13 H Et Et 7-14 Me Et Et 7-15 Et Et Et 7-16 n-Pr Et Et 7-17 cyc-Pr Et Et 7-18 CH ₂ CH = CH ₂ Et Et 7-19 CH ₂ C ≡ CH Et Et 7-20 CH ₂ Ph Et Et 7- 21 OMe Et Et 7-22 OEt Et Et 7-23 OCH ₂ CH = CH ₂ Et Et ────────────────────────────── ──────

[0069]

[Table 18] Table 7 (continued) ─────────────────────────────────── Compound No. R ¹⁷ R ¹⁸ R ¹⁹ ─────────────────────────────────── 7-24 OCH ₂ Ph Et Et 7 _{-25 H - (CH 2) 4} - 7-26 Me - (CH 2) 4 - 7-27 Et - (CH 2) 4 - 7-28 n-Pr - (CH 2) 4 - 7-29 cyc- _{Pr - (CH 2) 4 -} 7-30 CH 2 CH = CH 2 - (CH 2) 4 - 7-31 CH 2 C≡CH - (CH 2) 4 - 7-32 CH 2 Ph - (CH 2) _{4 - 7-33 OMe - (CH 2} ) 4 - 7-34 OEt - (CH 2) 4 - 7-35 OCH 2 CH = CH 2 - (CH 2) 4 - 7-36 OCH 2 Ph - (CH 2 _{) 4 - 7-37 Me - (CH} 2) 5 - 7-38 Et - (CH 2) 5 - 7-39 cyc-Pr - (CH 2) 5 - 7-40 CH 2 CH = CH 2 - (CH _{2) 5 - 7-41 CH 2 C≡CH} - (CH 2) 5 - 7-42 CH 2 Ph - (CH 2) 5 - 7-43 OMe - (CH 2) 5 - 7-44 OEt - (CH _{2) 5 - 7-45 OCH 2 CH} = CH 2 - (CH 2) 5 - ────────────────────────────── ───── Table 8

[0070]

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[0071]

[Table 19] ─────────────────────────────────── Compound No. WR ²⁰ ─────────────────────────────────── 8-1 OH 8-2 O Me 8- 3 O Et 8-4 O n-Pr 8-5 O CH ₂ Ph 8-6 O CH ₂ Ph (4-t-Bu) 8-7 SH 8-8 S Me 8-9 S Et 8-10 S n-Pr 8-11 S CH ₂ Ph 8-12 S CH ₂ Ph (4-t-Bu) ─────────────────────────── ───────── Table 9

[0072]

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[0073]

[Table 20] ─────────────────────────────────── Compound No. R ²¹ R ²² R ²³ R ²⁴ ─────────────────────────────────── 9-1 H H Me Me 9-2 Me H Me Me 9-3 Me Me Me Me 9-4 H H Me Et 9-5 Me H Me Et 9-6 H H Et Et 9-7 Me H Et Et 9-8 H H n-Pr _{n-Pr 9-9 H H CH 2} CH = CH 2 CH 2 CH = CH 2 9-10 H H - (CH 2) 4 - 9-11 H H - (CH 2) 5 - 9-12 H H - _{(CH 2) 6 - 9-13 H} H Me Ph 9-14 H H Me CH 2 Ph ──────────────────────────── ────── Table 10

[0074]

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[0075]

[Table 21] ─────────────────────────────────── Compound No. TR ²⁵ ─────────────────────────────────── 10-1 T1 H 10-2 T1 Me 10- 3 T1 Et 10-4 T1 n-Pr 10-5 T1 t-Bu 10-6 T1 CH ₂ Ph 10-7 T2 H 10-8 T2 Me 10-9 T2 Et 10-10 T2 n-Pr 10-11 T2 t-Bu 10-12 T2 CH ₂ Ph 10-13 T3 H 10-14 T3 Me 10-15 T3 Et 10-16 T3 n-Pr 10-17 T3 t-Bu 10-18 T3 CH ₂ Ph 10-19 T4 H 10-20 T4 Me 10-21 T4 Et 10-22 T4 n-Pr 10-23 T4 t-Bu ─────────────────────────── ──────────

[0076]

[Table 22] Table 10 (continued) ──────────────────────────────────── Compound No. TR ²⁵ ─────────────────────────────────── 10-24 T4 CH ₂ Ph 10-25 T5 H 10-26 T5 Me 10-27 T5 Et 10-28 T5 n-Pr 10-29 T5 t-Bu 10-30 T5 CH ₂ Ph 10-31 T6 H 10-32 T6 Me 10-33 T6 Et 10-34 T6 n-Pr 10-35 T6 t-Bu 10-36 T6 CH ₂ Ph 10-37 T7 H 10-38 T7 Me 10-39 T7 Et 10-40 T7 n-Pr 10-41 T7 t-Bu 10-42 T7 CH ₂ Ph 10-43 T8 H 10-44 T8 Me 10-45 T8 Et ───────────────────────────────── ─── In Table 10 above, T1 to T8 represent the following structures.

[0077]

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Next, a method for producing the compound of the present invention will be described below. Synthesis of compound represented by general formula [1] (Production method 1)

[0079]

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(X, R ¹ and R ² have the same meanings as described above) (Production method 2)

[0081]

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(X, R ¹ , R ⁴ and R ⁵ have the same meanings as described above.) In (Production Method 1), the journal of heterocyclic chemistry (J. Heterocycle) is used.
c Chem. ), 22: 1621 (1985), and Chemical Abstracts (Chemical Ab).
Structs 58, 3408 (1963); Chemical Abstracts (Chemical Abst)
(racts) 61, 8298 (1964).

The synthesis method of the general formula [1] according to (Production method 1) will be described. The desired product [1] can be synthesized by converting 2-halogeno-4-alkyl-5-thiazolecarboxylic acid into a carboxylic acid halide [3] and then synthesizing it with various alcohols and amines according to a conventional method.

In the step of halogenating a carboxylic acid, thionyl halide, phosphorus halide, phosgene and the like can be added directly, but usually in an inert solvent such as chloroform, benzene and toluene at 0 to 120 ° C. or in a solvent. It is better to carry out at the reflux temperature. The step of condensation to the desired product [1] can be carried out in a suitable inert solvent. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene and chlorobenzene, halogenated hydrocarbons such as chloroform and dichloroethane, ethers such as diisopropyl ether and dioxane, nitriles such as acetonitrile, dimethyl sulfoxide and dimethylformamide. And other polar solvents. If necessary, an organic base (pyridine, triethylamine, etc.) or an inorganic base (potassium carbonate, sodium hydride, etc.) may be added. The reaction temperature is usually preferably 0 to 50 ° C.

In (Production Method 2), the 5-thiazoleamide compound [1a] is reacted with phosphorus pentadisulfide or Lawesson's reagent in an inert solvent to synthesize the desired thioamide compound [1b]. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform and dichloroethane, and the reaction temperature can be from room temperature to the boiling point of the solvent. The reflux temperature of the solvent is preferable.

Next, as a plant disease to be controlled by the compound of the present invention, rice blast (Pyricularia) is used.
a oryzae), sesame leaf blight (Cochliobo)
lus miyabeanus), blight (Rhizo)
Ctonia solani),

Powdery mildew of wheat (Brysiphe
graminis f. sp. hordei, f. s
p. tritici), leaf spot disease (Pyrenophor)
a graminea), net blotch (Pyrenopho)
ra teres), Fusarium head blight (Gibberella)
zeae), rust disease (Puccinia strii)
formis, P .; graminis. P. recon
data, P.P. hordei), snow rot (Typhul)
a sp. , Micronectorella niv
ais), naked smut (Ustilago tritic)
i, U. nuda), eye spot (Pseudoce)
rcosporella herpotrichoid
es), cloud disease (Rhynchosporium se)
calis), leaf blight (Septoria triti)
ci), wilt disease (Leptosphaeria nod)
orum),

Citrus black spot disease (Diaportthe)
citri), scab (Elsinoe fauce)
tti), fruit rot (Penicillium di)
Gitatum, P.G. italicum), monili disease of apple (Sclerotinia mali), rot (Valsa mali), powdery mildew (Podo)
sphaera leucotricha), leaf spot disease (Alternaria mali), scab (Ve)
nturia inaequalis),

Pear scab (Venturia nas)
hicola), Black spot (Alternaria Ki)
kuchiana), red scab (Gymnosporan)
gium haraaenum), peach scab (Sc)
lerotinia cinerea), scab (Cl
adosporium carpophilum), Phomopsis rot (Phomopsis sp.),

Downy mildew of Plasmopara
viticola), black scab (Elsinoe am)
pelina), late rot (Glomerella ci)
ngulata), powdery mildew (Uncinula n)
ecator), rust (Phakopsora am)
pelopsis), anthracnose of oyster (Gloeos)
pork kaki), leaf scab (Corcospo)
ra kaki, Mycosphaerella na
wae), downy mildew of cucurbits (Pscudopereno)
spora cubensis),

Anthracnose (Colletotrichum)
lagenarium), powdery mildew (Sphaero)
theca fuliginea), vine blight (Myc)
osphaerella melonis, Phytophthora infestan of tomato
s), ring spot disease (Alternaria solan)
i), leaf mold (Cladosporiumulva)
m),

Brown rot of eggplant (Phomopsis ve)
xans), powdery mildew (Erysiphe cich)
oracoarum), black spot of cruciferous vegetables (Al
ternaria japonica), vitiligo disease (Ce
rocosporella brassicae), rust onion (Puccinia allii),

Soybean Purpura (Cercospora)
kikuchii), black scab (Elsinoe gl)
ycinees), Black spot disease (Diaporthe pha)
seaolum), anthracnose of green beans
otrichum Iindemuthianum),
Peanut black spot disease (Mycosphaerella)
personatum), brown spot (Cercospor)
a arachidicola), powdery mildew of pea (Brysiphe pisi),

Summer blight of potato (Alternari)
a solani), powdery mildew of strawberry (Sphae)
rotheca humuli), rice blast (E)
xobasidium reticulatum, white scab (Blsinoe leucospila), tobacco red scab (Alternaria longipede)
s), powdery mildew (Brysiphe cichora)
cearum), anthracnose (Colletotrichu)
m tabacum),

Brown spot of sugar beet (Cercospora)
beticola), scab of rose (Diploca)
rpon rosae), powdery mildew (Sphaero)
theca pannosa, brown spot of chrysanthemum (Sep)
toria chrysanthemiindic
i), White rust (Puccinia horian)
a), Botrytis c. of various crops
inerea), sclerot disease of various crops (Sclerot)
inia sclerotiorum) and the like.

When the compound of the present invention is used as an agricultural and horticultural germicide, it is generally a suitable carrier, for example, solid carrier such as clay, talc, bentonant, diatomaceous earth or water, alcohols (methanol, ethanol, etc.), and aroma. Mixed with liquid carriers such as group hydrocarbons (benzene, toluene, methylnaphthalene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetates), acid amides (dimethylformamide, etc.) Any agent such as a liquid agent, an emulsion, a wettable powder, a powder agent, a granule agent, a flowable agent, etc. can be applied, if desired, by adding an emulsifier, a dispersant, a suspension agent, a penetrant, a spreading agent, a stabilizer and the like. The mold can be put to practical use.

When the compound of the present invention is applied as a fungicide for agricultural and horticultural use, foliar application, soil treatment,
Seed disinfection and the like can be mentioned, but it is also effective in general methods generally used by those skilled in the art. In addition, various herbicides, various insecticides, bactericides, etc. at the time of formulation or spraying as needed.
You may mix and apply with a plant growth regulator, a synergist, etc. The application amount of the compound of the present invention varies depending on the application scene, application time, application method, target disease, cultivated crop, etc., but generally 0.005 to 50 k per hectare as an active ingredient amount.
g is appropriate. Next, formulation examples of bactericides containing the compound of the present invention as an active ingredient will be shown, but the formulations are not limited thereto. In addition, in the following formulation examples, "part" means part by weight.

Formulation Example 1 Emulsion Compound of the present invention 20 parts Methylnaphthalene 55 parts Cyclohexanone 20 parts Sorpol 2680 5 parts (Nonionic surfactant and anionic surfactant Mixture: trade name of Toho Kagaku Kogyo Co., Ltd. The above is uniformly mixed to form an emulsion. At the time of use, the above emulsion is diluted 50 to 20000 times and sprayed so that the amount of active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 2 Wettable powder Compound of the present invention: 25 parts Di-crite PEP: 66 parts (mixture of kaolinite and sericite: trade name of Di-crite Industry Co., Ltd.) Solpol 5039 4 parts (anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Carplex # 80 ……… 3 parts (White carbon: Shionogi Seiyaku Co., Ltd. trade name) Calcium lignin sulfonate ……… 2 parts or more Are uniformly mixed and pulverized to obtain a wettable powder. Upon use, the wettable powder is diluted 50 to 20000 times and sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 3 Powder Compound of the present invention: 3 parts Carplex # 80: 0.5 part (White carbon: Shionogi Pharmaceutical Co., Ltd. trade name) Clay: 95 parts Diisopropyl phosphate …… 1.5 parts or more are uniformly mixed and pulverized into a powder. At the time of use, the amount of the active ingredient is 0.005 to 5 per hectare.
Sprinkle so that it weighs 0 kg.

Formulation Example 4 Granules Compound of the present invention: 5 parts Bentonite: 30 parts Talc: 64 parts Calcium lignin sulfonate: 1 part The above ingredients are uniformly mixed and ground, and a small amount of water is added. Stir to mix, granulate with an extrusion-type granulator, and dry to obtain granules. At the time of use, the amount of the active ingredient of the above-mentioned granules is 0.
Spray so that the amount becomes 005 to 50 kg.

Formulation Example 5 Flowable agent Compound of the present invention 25 parts Solpol 3353 5 parts (Nonionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Lunox 1000C ... 0.5 parts ( Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name Zansan gum (natural polymer) …… 0.2 parts Sodium benzoate …… 0.4 parts propylene glycol …… 10 parts water …… 58 .9 parts The above components except the active ingredient (the compound of the present invention) are uniformly dissolved, and then the compound of the present invention is added and well stirred, followed by wet grinding with a sand mill to obtain a flowable agent. At the time of use, the flowable agent is diluted 50 to 20000 times so that the amount of active ingredient is 0.005 to 50k per hectare.
Disperse so that it becomes g.

[0103]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the contents of the present invention will be specifically described by way of examples, but the present invention should not be limited to these. In addition, compound No. Are compound Nos. Shown in Tables 1 to 10. Represents

Example 1 2-Chloro-4-methyl-5-thiazolecarboxylic acid 2
-Phenylpropyl ester [Compound of the present invention No. 1-
Synthesis of 24 (a)] 0.75 g of 2-chloro-4-methyl-5-thiazolecarboxylic acid chloride was dissolved in 30 ml of chloroform. 2-phenylpropyl alcohol 0.4 to this solution
8 g were added. Under ice cooling, triethylamine 0.4 there
2 g was added dropwise, then 4-dimethylaminopyridine was added in a catalytic amount, and the mixture was stirred at room temperature for 16 hours. The reaction solution was
After washing with 0 ml, the chloroform layer was dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the liquid residue was purified by silica gel column chromatography (solvent: chloroform) to give compound N of the present invention.
o. 1.03 g of 1-24 (a) was obtained as a colorless liquid.
(N _D ^20.5 1.5647)

Example 2 N- (2-chloro-4-methylthiazole-5-carbonyl)-(L) -phenylalanine methyl ester [Compound No. of the present invention] Synthesis of 3-17 (a)] 1.29 g of 2-chloro-4-methyl-5-thiazolecarboxylic acid chloride was dissolved in 50 ml of chloroform. To this solution was added 1.29 g of (L) -phenylalanine methyl ester hydrochloride. Under ice cooling, 1.47 g of triethylamine was added dropwise thereto, then 4-dimethylaminopyridine was added in a catalytic amount, and the mixture was stirred at room temperature for 48 hours. The reaction solution was washed with 200 ml of water and the chloroform layer was dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure,
The crystals of the residue were washed with n-hexane to give the compound of the present invention No. 3-17 (a) as colorless crystals
86 g was obtained. (Melting point 97 to 98 ° C.) Next, Table 11 shows physical properties and the like of the compound of the general formula [1] produced according to these methods. No. in the table. Are compound Nos. Shown in Tables 1 to 3. Represents

[0106]

[Table 23] Table 11 ────────────────────────────────── Compound No. Physical property values ────────────────────────────────── 1-18 (a) n _D ^20.6 1.56884 1- 19 (a) n _D ^20.8 1.5614 1-22 (a) n _D ^20.7 1.5709 1-24 (a) n _D ^20.5 1.5647 1-28 (a) n _D ^19.5 1.5938 1-29 ( a) n _D ^19.5 1.5931 3-2 (a) n _D ^17.7 1.5477 3-10 (a) viscous substance 3-14 (a) viscous substance 3-17 (a) mp 91-92 ° C 3- 23 (a) mp 64-65 ° C. 3-37 (a) n _D ^20.1 1.5335 7-3 (a) n _D ^19.5 1.5352 7-10 (a) mp 70-72 ° C. 9-12 (a) n _D ^19.5 1.5552 10-14 (a) n _D ^19.6 1.5489 ──────────────────────────────────

The usefulness of the compound of the present invention will be specifically described in the following test examples. However, it is not limited only to these. Test Example 1 Cucumber downy mildew control effect test A 1.5-leaf stage cucumber (cultivar: Sagamihanjiro) grown in a pot with a diameter of 7 cm was sprayed with a chemical solution prepared by diluting the compound emulsion of the present invention with water to 500 ppm. 20 ml was sprayed per pot using a gun. The day after spraying, cucumber downy mildew (Pseudoperonospora cuben)
A spore suspension of sis) (2 × 10 ⁵ cells / ml) was sprayed, and placed in an inoculation box at a temperature of 25 ° C. and a humidity of 95% or more overnight. Then, put it in a greenhouse, measure the ratio of the lesion area formed 7 days after inoculation to the inoculated leaves, according to the following formula,
The control value was calculated.

Control value = [1- (treatment area lesion area ratio / non-treatment area lesion area rate) × 100 As a result, the following compounds showed a control value of 100. Compound No. 1-18 of the present invention ( a), No. 1-22
(A), No. 1-24 (a)

Test Example 2 Rice blast control test (water surface application) To a 1.5 leaf stage rice planted in a beaker pot of 120,000 are, the compound emulsion of the present invention was diluted with water to 500 ppm.
The pot is irrigated with 10 ml of the drug solution prepared in 1. Two weeks later, the treated rice is spray-inoculated with a conidial suspension of blast fungus. After infecting rice with the bacteria for 24 hours at a relative humidity of 95 to 100% in a drug at 24 ° C., the rice was left in a greenhouse, and after about 1 week, the degree of disease was examined in 6 stages of 0 to 5.

[0110] As a result, the following compounds showed a morbidity index 1. Inventive Compound No. 1-24 (a), No. 1-18 (a),
No. 1-17 (a), No. 3-23 (a)

[0111]

INDUSTRIAL APPLICABILITY These present compounds show an excellent activity for controlling agricultural and horticultural diseases and have no phytotoxicity against useful crops, and are therefore useful as agricultural and horticultural fungicides.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 417/06 211 211 C07D 417/06 211 (72) Inventor Toshiaki Takeyama 722 Tsuboi-cho, Funabashi, Chiba Prefecture 1 Nissan Chemical Industry Co., Ltd. Central Research Institute (72) Inventor Junichi Watanabe 722 Tsuboi-cho, Funabashi City, Chiba Prefecture 1 Nissan Chemical Industry Co., Ltd. Central Research Laboratories (72) Inventor Hiroshi Oyaku Shiraoka, Minami Saitama District, Saitama Prefecture Shiraoka 1470 Nissan Kagaku Kogyo Co., Ltd.Bioscience Research Institute (72) Inventor Masanori Nishioka Shiraoka, Shiraoka-cho, Minami Saitama-gun, Saitama 1470 Nissan Kagaku Kogyo Co., Ltd. Bioscience Research (72) Inventor Takashi Furusato 1470 Shiraoka Nissan Biochemical Research Institute

Claims (4)

[Claims] 1. A general formula [1]:[In the above formula, X represents a halogen atom, W represents an oxygen atom or a sulfur atom, R¹Is C₁~ C_FourRepresents an alkyl group or halogen atom
And then R^TwoIs -OR^ThreeGroup, -N (R^Four) (R^Five) Group, -N
(R⁶)-[C (R⁷) (R⁸)]_n-CO_TwoR⁹Base,
−N (R^Ten) -N (R¹¹) (R¹²) Group, -N (R ¹³)
(OR¹⁴) Group, -N (R^Fifteen) SO_TwoR¹⁶Group, N (R¹⁷)
SO_TwoN (R¹⁸) (R¹⁹) Group, -SR²⁰Group, -OC (R
^{twenty one}) (R^{twenty two}) CON (R^{twenty three}) (R^{twenty four}) Group or the following formula:Represents a group represented by^ThreeIs C_Three~ C₈Cycloalkyl group, substituted aryl
Group, substituted benzyl group, optionally substituted aryl C
_Two~ C_FourAlkyl group, optionally substituted aryl C
_Two~ C_FourAlkenyl group, optionally substituted hetero group
Reel C₁~ C_FourAlkyl group or may be substituted
Heterocyclyl C₁~ C_FourRepresents an alkyl group, R^FourIs a hydrogen atom or C₁~ C_FourRepresents an alkyl group, R^FiveIs optionally substituted heteroaryl C₁~ C_Four
Alkyl group, optionally substituted heterocyclyl C
₁~ C_FourAlkyl group, optionally substituted aryl C
_Two~ C_FourAlkenyl group, C₁~ C_FourAlkylcarbonyl
Group, optionally substituted arylcarbonyl group, C₁
~ C_FourAlkoxycarbonyl group or substituted
Good aryl C₁~ C_FourRepresents an alkoxycarbonyl group
And then R⁶Is a hydrogen atom, C₁~ C_FourAlkyl group, formyl group,
C₁~ C_FourAlkylcarbonyl group, which may be substituted
Arylcarbonyl group, C₁~ C_FourAlkoxycarbo
Nyl group or optionally substituted aryl C₁~ C_Four
Represents an alkoxycarbonyl group, R⁷And R⁸Are each independently a hydrogen atom, C₁~ C
₆Alkyl groups (these are R⁷, R⁸Ring together
May form an alkyl group), may be substituted
Aryl group, optionally substituted aryl C₁~ C_Four
Alkyl group or C₁~ C_TwoAlkylthio C₁~ C_FourA
Represents a alkyl group, n represents 1, 2, or 3, R⁹Is a hydrogen atom, C₁~ C_FourAlkyl group or substituted
Optionally aryl C₁~ C_FourRepresents an alkyl group, R^TenIs a hydrogen atom, C₁~ C_FourAlkyl group, C_Two~ C_FourA
Lucenyl group, optionally substituted aryl group, substituted
Optionally aryl C₁~ C_FourAlkyl group, C₁~
C_FourAlkylcarbonyl group, C₁~ C_FourAlkoxycal
Bonyl group or optionally substituted aryl C₁~ C
_FourRepresents an alkoxycarbonyl group, R¹¹And R¹²Are each independently a hydrogen atom, C₁~ C
₆Alkyl groups (these are R¹¹, R¹²Ring together
May form an alkyl group), may be substituted
Aryl group, optionally substituted aryl C₁~ C_Four
Alkyl group, formyl group, C₁~ C_FourAlkyl carboni
Group, optionally substituted arylcarbonyl group, C
₁~ C_FourAlkoxycarbonyl group or substituted
Moyo Aryl C₁~ C_FourRepresents an alkoxycarbonyl group
And then R¹³And R¹⁴Are each independently a hydrogen atom, C₁~
C₆Alkyl groups (these are R¹³, R¹⁴Together, ring
A linear alkyl group may be formed), C_Two~ C_FourAlkene
Group, C_Two~ C_FourAlkynyl group, optionally substituted
Aryl group, optionally substituted aryl C₁~ C_Four
Alkyl group, formyl group, C₁~ C_FourAlkyl carboni
Group, optionally substituted arylcarbonyl group, C
₁~ C_FourAlkoxycarbonyl group or substituted
Moyo Aryl C₁~ C_FourRepresents an alkoxycarbonyl group
And then R^FifteenIs a hydrogen atom, C₁~ C_FourAlkyl group, C_Two~ C_FourA
Lucenyl group, C_Two~ C _FourAlkynyl group, C_Three~ C₈Shiku
Alkyl group, optionally substituted aryl C₁~ C
_FourAlkyl group, C₁~ C_FourAlkoxy group, C_Two~ C_FourA
Lucenyloxy group, C_Two~ C_FourAlkynyloxy group
Is an optionally substituted aryl C₁~ C_FourAlkylio
Represents a xy group, R¹⁶Is C₁~ C_FourAlkyl group or may be substituted
Represents an aryl group, R¹⁷Is C₁~ C_FourAlkyl group, C_Three~ C₈Cycloalkyl
Group, C_Two~ C_FourAlkenyl group, C_Two~ C_FourAlkynyl
Group, optionally substituted aryl C₁~ C_FourAlkyl
Group, C₁~ C_FourAlkoxy group, C_Two~ C_FourAlkenylo
Xy group, C_Two~ C_FourAlkynyloxy group or substituted
Optionally aryl C₁~ C_FourShow alkyloxy group
And then R¹⁸And R¹⁹Is independently C₁~ C₆Alkyl
Groups (these are R¹⁸, R ¹⁹Together, a cyclic alkyl group
May be formed), R²⁰Is a hydrogen atom, C₁~ C_FourAlkyl group or substituted
Optionally aryl C₁~ C_ThreeRepresents an alkyl group, R^{twenty one}And R^{twenty two}Are each independently a hydrogen atom or C₁
~ C_FourRepresents an alkyl group, R^{twenty three}And R^{twenty four}Are each independently a hydrogen atom, C₁~ C
₆Alkyl groups (these are R^{twenty three}, R^{twenty four}Together
An alkyl group may be formed), C_Two~ C_FourAlkenyl
Group, an optionally substituted aryl group,
Moyo Aryl C ₁~ C_FourRepresents an alkyl group, R^{twenty five}Is a hydrogen atom, C₁~ C_FourAlkyl group or substituted
Optionally aryl C₁~ C_FourRepresents an alkyl group, R²⁶Is a hydrogen atom or C₁~ C_FourRepresents an alkyl group, m represents 2, 3 to 5, and the expression "substituted aryl group" means a substituent on the aryl ring.
A cyano group or C₁~ C_FourRepresenting an alkoxy group, the expression "substituted benzyl group" means a halogen atom, cyano
Group, nitro group, C₁~ C _FourAlkyl group or C₁~ C_Four
Represents a benzyl group substituted by an alkoxy group, and the expression "which may be substituted" means, in addition to a hydrogen atom,
As a substituent, a halogen atom, a cyano group, a nitro group, C₁
~ C_FourAlkyl group or C₁~ C_FourTable of alkoxy groups
However, the expression "aryl" refers to aromatic substances such as benzene and naphthalene.
Group of compounds, the expression "heteroaryl" refers to pyridine, furan, thio
It represents a 5-membered or 6-membered aromatic heterocycle such as phen, and the expression "heterocyclyl" means piperidine, morpholine.
Amine, tetrahydrofuran, tetrahydrothiophene, etc.
It represents a 5-membered ring and a 6-membered non-aromatic heterocycle. ]
Thiazole carboxylic acid derivative. 2. A plant disease controlling agent containing as an active ingredient one or more of the thiazolecarboxylic acid derivative according to claim 1. 3. In the general formula [1] according to claim 1,
R ³ is a C _{4 to} C ₈ alkyl group, a C _{4 to} C ₈ haloalkyl group, a C _{2 to} C ₄ alkenyl group, a C _{2 to} C ₄ alkynyl group, a benzyl group or an aryl group (halogen, lower alkyl, trifluoromethyl and Optionally substituted by a nitro group), or R ⁴ and R ⁵ are each independently a hydrogen atom or an optionally substituted aryl C ₁ -C ₄ alkyl group. A plant disease control agent containing one or more as an active ingredient. 4. A rice blast control agent which comprises, as an active ingredient, one or more of the thiazolecarboxylic acid derivatives according to claim 1 or 3.