JPH09176125A - 5-pyrazolecarboxylic acid amide derivative and plant blight controlling agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound exhibiting excellent plant blight controlling action and useful as an active component of agricultural and horticultural fungicide. SOLUTION: The objective compound is expressed by the formula I (X is a halogen; W is O or S; R<1> is a 1-4C alkyl; R<2> and R<3> are each H, a 1-10C alkyl, a 2-6C alkenyl, etc.), e.g. N-(3-chloro-1-methyl-5-pyrazolecarbonyl) isobutyramide. The compound of the formula I can be produced by reacting a carboxylic acid halide of the formula II with an amine of the formula III in a solvent (e.g. chloroform) at 0-120 deg.C. The compound of the formula I is especially effective for the control of rice blast and is also effective for controlling powdery mildew of wheat, melanose of orange, brown rot of peach, rust of Welsh onion, powdery mildew of strawberry, etc. The application amount of the compound of the formula I is about 0.005-50kg per 1ha.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel 5-pyrazolecarboxylic acid amide derivative, and a plant disease controlling agent, particularly a rice blast controlling agent, containing the 5-pyrazolecarboxylic acid amide derivative as an active ingredient.

[0002]

2. Description of the Related Art Certain types of 5-pyrazolecarboxylic acid amide derivatives are disclosed in JP-A-52-87168, JP-A-63-119463, JP-A-63-135364,
JP-A-2-157266, JP-A-2-250869, patents for sterilizing agents, JP-A-3-223256, and JP-A-3-
It is known in the insecticide patent of 63262.

Further, in Japanese Patent Laid-Open No. 1-121263, the following formula:

[0004]

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Compounds having bactericidal activity have been disclosed. JP-A-1-199963 discloses the following formula:

[0006]

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Compounds having bactericidal activity have been disclosed. JP-A-3-17063 discloses the following formula:

[0008]

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Compounds having the bactericidal activity shown by are disclosed. JP-A-3-236368 discloses the following formula:

[0010]

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Compounds having bactericidal activity are disclosed: However, the 5-pyrazolecarboxylic acid amide derivative of the present invention and its plant disease controlling activity are not disclosed in the above publication.

[0012]

The existing fungicides for agricultural and horticultural use are not satisfactory in view of problems such as increase in resistant bacteria, environmental safety, their efficacy and residual efficacy. Therefore, there is a demand for the development of a more inexpensive and useful control agent against plant diseases.

[0013]

In view of such circumstances, the present inventors have conducted various studies to develop an excellent fungicide, and as a result, a novel 5-pyrazolecarboxylic acid amide derivative has been proved to be a plant disease control agent. As a result, they have found that they have a remarkable controlling activity, and have reached the present invention. That is, the present invention provides formula (1):

[0014]

[Chemical 6]

[In the above formula, X represents a halogen atom, and R
¹ represents a C ₁ -C ₄ alkyl group, W represents an oxygen atom or a sulfur atom,

R ² and R ³ are each independently a hydrogen atom,
C ₁ -C ₁₀ alkyl group, C ₂ -C ₆ alkenyl group, C ₂
To C ₁₀ alkynyl group, C _{3 to} C ₁₀ cycloalkyl group, optionally substituted aryl C _{2 to} C ₄ alkenyl group,
^{- [C (R 4) (} R 5)] p -R 6 group, -CO- (O) _m
^{- [C (R 4) (} R 5)] p -R 7 groups, -S (O) _n -R
^{7 group, -CON (R 8) (R} 9) ^{group, -N (R 8) (R} 9)
^{Group, -N = C (R 10)} (R 11) group, the ¹² group -OR, in some cases, become together R ² and R ^3, C ₂ ~C ₁₀ cyclic alkylene or oxygen, sulfur or nitrogen may form a C ₂ -C ₆ cyclic alkylene containing atoms, in some cases, C ₁ -C ₆ alkyl group on the ring, C ₁ -C ₄ alkoxycarbonyl group may be substituted.

P is 0 or an integer of 1 to 8, and m is 0.
Or 1 represents, n represents 0, 1 or 2,

R^FourAnd R^FiveAre each independently a hydrogen atom,
Halogen atom, C₁~ C₆Alkyl group, C_Two~ C₆Al
Kenyl group, C_Two~ C₆Alkynyl group, C₁~ C₆Haloa
Alkyl group, C_Two~ C₆Haloalkenyl group, C_Two~ C₆Ha
Loalkynyl group, C_Three~ C₆Cycloalkyl group, C₁~
C₆Alkoxy group, C₁~ C₆Haloalkoxy group, substituted
Optionally substituted aryl group, optionally substituted aryl group
Teloaryl group, optionally substituted benzyl group, C
₁~ C_FourAlkylcarbonyl group, C₁~ C₆Alkoxy
Carbonyl group, hydroxycarbonyl group, C₁~ C_FourA
Rukiruthio C₁~ C_FourAlkyl group, C₁~ C_FourAlkyl
Sulfinyl C₁~ C_FourAlkyl group, C ₁~ C_FourArchi
Lesulfonyl C₁~ C_FourAlkyl group or C₁~ C_FourA
Lucyloxy C₁~ C_FourRepresents an alkyl group, and in some cases
For R^FourAnd R^FiveAre together C_Three~ C₆Cycloal
A kill group may be formed.

R⁶Is hydrogen atom, halogen atom, C₁~ C
_TenAlkyl group, C_Two~ C_TenAlkenyl group, C_Two~ C_TenA
Rukinyl group, C₁~ C_TenHaloalkyl group, C_Two~ C_TenHa
Alkenyl group, C_Two~ C_TenHaloalkynyl group, C_Three~
C_TenCycloalkyl group, C₁~ C_TenAlkoxy group, C₁
~ C₆Haloalkoxy group, C_Two~ C₆Haloalkenylo
Xy group, C_Two~ C₆Haloalkynyloxy group, C_Three~ C
₆Cycloalkyloxy group, optionally substituted ant
Group, optionally substituted heteroaryl group, substituted
Optionally substituted heterocyclyl groups, substituted
Optionally aryloxy group, optionally substituted hetero
Aryloxy group, hydroxyl group, C₁~ C ₆Alkyl carb
Nyloxy group, optionally substituted arylcarbonyl
Luoxy group, -S (O)_n-R¹³Group, C₁~ C₆Arco
Xycarbonyl group, hydroxycarbonyl group, -CON
(R¹⁴) (R^Fifteen) Group or -N (R¹⁴) (R^Fifteen) Represents a group,

R⁷Is a hydrogen atom, C₁~ C₆Alkyl group,
C_Two~ C₆Alkenyl group, C_Two~ C ₆Alkynyl group, C
₁~ C₆Haloalkyl group, -N (R¹⁴) (R^Fifteen) Group, substituted
Optionally substituted aryl group, optionally substituted aryl group
Or an optionally substituted heteroaryl group
Represents

R⁸And R⁹Are each independently a hydrogen atom,
C₁~ C_TenAlkyl group, C_Two~ C_TenAlkenyl group, C_Two
~ C_TenAlkynyl group, C_Three~ C_TenCycloalkyl group, C
₁~ C_TenHaloalkyl group, C_Two~ C_TenHaloalkenyl
Group, C_Two~ C_TenHaloalkynyl group, which may be substituted
Aryl group, optionally substituted benzyl group, substituted
Optionally substituted heteroaryl group, C₁~ C₆Archi
Lecarbonyl group, C₁~ C₆Haloalkylcarbonyl
Group, optionally substituted arylcarbonyl group, substituted
Optionally substituted heteroarylcarbonyl group, C₁~
C₆Represents an alkoxycarbonyl group or a formyl group,
In some cases, R⁸And R⁹Are together C_Three~ C_Ten
Cyclic alkylene, or oxygen, sulfur or nitrogen atom
Including C_Two~ C ₆It may form a cyclic alkylene.

R ¹⁰ and R ¹¹ are each independently a hydrogen atom,
C ₁ -C ₆ alkyl groups, C ₁ -C ₆ haloalkyl groups, C
_{3 to} C _{8 represents a} cycloalkyl group or an optionally substituted aryl group,

R¹²Is a hydrogen atom, C₁~ C_TenAlkyl
Group, C_Two~ C_TenAlkenyl group, C_Two~ C_TenAlkynyl
Group, C₁~ C_TenHaloalkyl group, C_Two~ C_TenHalo arche
Nyl group, C_Three~ C_TenCycloalkyl group, substituted
Optionally benzyl group, optionally substituted aryl C
_Two~ C_FourAlkyl group, optionally substituted aryl C_Two
~ C_FourAlkenyl group, optionally substituted aryl
Group, C₁~ C₆Alkoxy C₁~ C₆Alkyl group, C₁
~ C₆ Dialkylamino C₁~ C₆ Alkyl group, C ₁~
C₆ Alkylthio C₁~ C₆ Alkyl group, C₁~ C₆A
Lucoxycarbonyl C₁~ C₆Alkyl group, substituted
Phenyloxy C₁~ C₆Alkyl group, tri
Is a methylsilylethyl group,

R ¹³ is a C ₁ -C ₆ alkyl group, C ₁ -C ₆
Represents a haloalkyl group or an aryl group which may be substituted, and R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, C ₁
To C ₆ alkyl group, C _{2 to} C ₆ alkenyl group, C _{2 to} C
_{6 represents an} alkynyl group, an optionally substituted aryl group, an optionally substituted benzyl group or an optionally substituted heteroaryl group, and in some cases, R ¹⁴ and R ¹⁵ are taken together to form C ₃ ~C ₈ may form a cyclic alkylene.

The expression "optionally substituted" means hydrogen.
In addition to atoms, as a substituent, halogen atom, cyano group, nit
B group, C₁~ C_FourAlkyl group, C₁~ C_FourAlkoxy
Group, C ₁~ C_FourHaloalkyl group, C₁~ C_FourHalo alco
Xy group, aryl group, aryloxy group, benzyloxy
Si group, C_Three~ C₆Cycloalkyl group, C₁~ C_FourArco
Xycarbonyl group, C₁~ C_FourAlkylthio group, C₁~
C_FourHaloalkylthio group, C₁~ C_FourAlkylsulfi
Nyl group, C₁~ C_FourAlkylsulfonyl group, styryl
Group, amino group, C₁~ C_FourAlkoxycarbonylamino
Group, C₁~ C_FourAlkoxycarbonyloxy group, amino
Represents a carbonyl group or a hydroxycarbonyl group,

The expression "aryl" means aromatic compounds of benzene and naphthalene, and "heteroaryl".
The expression of means a 5-membered ring, a 6-membered ring or an aromatic heterocyclic compound having a condensed ring thereof or an aromatic heterocyclic compound condensed with a benzene ring, and the expression “heterocyclyl” means a 3-membered ring. To 6-membered non-aromatic heterocyclic compounds. ] The present invention relates to a novel 5-pyrazolecarboxylic acid amide derivative and a plant disease controlling agent containing the derivative as an active ingredient.

In the compound of the general formula (1), the halogen atom of X is a fluorine atom, a chlorine atom, a bromine atom,
An iodine atom is mentioned, but a chlorine atom or a bromine atom is particularly preferable, and the C ₁ -C ₄ alkyl group for R ¹ is
A methyl group, an ethyl group, an n-propyl group or an i-propyl group can be mentioned, but a methyl group is particularly preferable, and W represents an oxygen atom or a sulfur atom, and an oxygen atom is preferable.

R ² is a hydrogen atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, an optionally substituted benzyl group, a formyl group, a C ₁ -C ₆ alkylcarbonyl group, or a substituted group. Optionally arylcarbonyl group, optionally substituted heteroarylcarbonyl group or C
_{1 to} C ₆ alkoxycarbonyl group and the like can be mentioned, but especially hydrogen atom, methyl group, ethyl group, propyl group, i-
Propyl group, n-, i- or s-butyl group, methoxy group, ethoxy group, benzyl group, acetyl group, propionyl group, optionally substituted benzoyl group, optionally substituted pyrazole carbonyl group, substituted And optionally a thiazolecarbonyl group or a methoxycarbonyl group is preferable.

R^ThreeIs not particularly limited, but
And R^ThreeIs-[C (R^Four) (R^Five)] _P-R⁶Group, -S
(O)_n-R⁷Group, -N (R⁸) (R⁹) Group or -OR
¹²And R is^Four, R^FiveIs hydrogen atom, methyl group, i-type
Ropyl group, methylthioethyl group, methylsulfonylethyl
R group or benzyl group, R⁶May be replaced
An aryl group, an optionally substituted heteroaryl group,
An optionally substituted heterocyclyl group, C₁~ C₆A
Lucoxy group, hydroxyl group or C₁~ C₆Alkoxycarbo
A nyl group, p is 0 to 2, R⁷Is C₁~ C
₆Alkyl group, -N (R¹⁴) (R^Fifteen) Group or substituted
An aryl group which may be present, n is 0 to 2,
Particularly, n is preferably 2. R⁸, R⁹Is a hydrogen atom, C₁~
C_TenAlkyl group, optionally substituted aryl group,
An optionally substituted heteroaryl group or C₁~ C
₆An alkylcarbonyl group, optionally R⁸
And R ⁹Are together C_Three~ C_TenForming a cyclic alkylene
May be R¹²Is C ₁~ C_TenAlkyl group, C_Two
~ C_TenAlkenyl group, C_Two~ C_TenHaloalkenyl group, placement
Optionally substituted benzyl group or optionally substituted
A good phenylethyl group, R¹⁴, R^FifteenIs C₁~ C
_FourAlkyl groups are preferred.

The definitions of the substituents and the like of R ² and R ^{3 have} the following meanings. Halogen atom means fluorine, chlorine, bromine and iodine, and is a C ₁ -C ₄ alkyl group, C ₁
To C ₆ alkyl group and C _{1 to} C ₁₀ alkyl group include, for example, methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl, pentyl,
Hexyl, heptyl, nonyl, octyl and the like can be mentioned. Examples of the C ₁ -C ₆ alkylcarbonyl group include acetyl, propionyl and the like.

Aryl groups include phenyl and naphthyl. Examples of the heteroaryl group include furan, thiophene, pyrazole, thiazole, imidazole, pyridine, pyrimidine, triazine, benzofuran, indole and the like. Examples of the C ₁ -C ₆ alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propylcarbonyl, i-propylcarbonyl, n-butylcarbonyl and the like. C ₂
As the -C ₁₀ alkenyl group, vinyl, propenyl, butenyl, hexenyl and the like can be mentioned. The C ₂ -C ₁₀ haloalkenyl group, 1-chloro-1-propenyl, 1
-Bromo-1-propenyl. The C ₃ -C ₈ cycloalkyl group, cyclopropyl, cycloheptyl, cyclohexyl, and the like.

Examples of the heterocyclyl group include oxirane, oxetane, tetrahydrofuran, dioxolane, tetrahydropyran, dioxane, tetrahydrothiophene, pyrrolidine, piperidine, piperazine, morpholine and thiomorpholine.

The compound of 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 3. However, the compound of the present invention is not limited to these. In the table, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Pen is a pentyl group, Hex is a hexyl group, n is normal, i is iso, and s is s. Represents a secondary, c represents cyclo, t represents tertiary, and Ph represents a phenyl group.

Table 1

[0036]

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[0037]

[Table 1] ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-1 OH-H 1-2 OH-2 -Cl 1-3 OH-3-Cl 1-4 OH-4-Cl 1-5 OH-2-Me 1-6 OH-3-Me 1-7 OH-4-Me 1-8 _{O H - 2-CF 3 1-9} O H - 4-CF 3 1-10 O H - 2-C00H 1-11 O H - 2-COOMe 1-12 O H - 4-F 1-13 O H - 4-Br 1-14 OH − 4-Et 1-15 OH − 4-n-Pr 1-16 OH − 4-i-Pr 1-17 OH − 4-CN 1-18 OH − 4 -COOMe 1-19 OH − 4-COOEt 1-20 OH − 4-CONHMe 1-21 OH − 4-CONHEt 1-22 OH − 4-CON (Me) ₂ 1-23 OH − 4- OMe ─────────────────────────────────

[0038]

[Table 2] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-24 OH − 4-OEt 1-25 OH − 4-OCHF ₂ 1-26 OH − 4-OCF ₃ 1-27 OH − 2,4-Cl ₂ 1-28 OH − 2,6-Cl ₂ 1-29 OH − 2,4-Me _{2 1-30 O H - 2,6-Me} 2 1-31 O H - 2,4-F 2 1-32 O H - 2,6-F 2 1-33 O H - 3,4- (OMe) ₂ 1-34 OH CH ₂ H 1-35 OH CH ₂ 2-Cl 1-36 OH CH ₂ 3-Cl 1-37 OH CH ₂ 4-Cl 1-38 OH CH ₂ 2-Me 1 -39 OH CH ₂ 3-Me 1-40 OH CH ₂ 4-Me 1-41 OH CH ₂ 2-CF ₃ 1-42 OH CH ₂ 4-CF ₃ 1-43 OH CH ₂ 4- F 1-44 OH CH ₂ 4-Br 1-45 OH CH ₂ 4-Et ────────────────────────────── ───

[0039]

[Table 3] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-46 OH CH ₂ 4-n-Pr 1- 47 OH CH ₂ 4-i-Pr 1-48 OH CH ₂ 4-CN 1-49 OH CH ₂ 4-COOMe 1-50 OH CH ₂ 4-COOEt 1-51 OH CH ₂ 4-CONHMe 1-52 OH CH ₂ 4-CON (Me) ₂ 1-53 OH CH ₂ 4-OMe 1-54 OH CH ₂ 4-OEt 1-55 OH CH ₂ 4-OCHF ₂ 1-56 OH CH ₂ 4-OCF ₃ 1-57 OH CH ₂ 2,4-Cl ₂ 1-58 OH CH ₂ 2,4-F ₂ 1-59 OH CH ₂ 3,4- (OMe) ₂ 1-60 OH CH (Me) H 1-61 OH CH (Me) 2-Cl 1-62 OH CH (Me) 3-Cl 1-63 OH CH (Me) 4-Cl 1-64 OH CH ( Me) 2-Me 1-65 OH CH (Me) 3-Me 1-66 OH CH (Me) 4-Me 1-67 OH CH (Me) 2-CF ₃ ───────── ────────────────────────

[0040]

[Table 4] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-68 OH CH (Me) 4-CF ₃ 1 -69 OH CH (Me) 4-F 1-70 OH CH (Me) 4-Br 1-71 OH CH (Me) 4-Et 1-72 OH CH (Me) 4-n-Pr 1 -73 OH CH (Me) 4-i-Pr 1-74 OH CH (Me) 4-CN 1-75 OH CH (Me) 4-OMe 1-76 OH CH (Me) 4-OEt 1 -77 OH CH (Me) 4-OCHF ₂ 1-78 OH CH (Me) 4-OCF ₃ 1-79 OH CH (Me) 2,4-Cl ₂ 1-80 OH CH (Me) 2 , 4-F ₂ 1-81 OH CH (Me) 3,4- (OMe) ₂ 1-82 OH C (Me) ₂ H 1-83 OH C (Me) ₂ 2-Cl 1-84 O H C (Me) ₂ 3-Cl 1-85 OH C (Me) ₂ 4-Cl 1-86 OH C (Me) ₂ 2-Me 1-87 OH C (Me) ₂ 3-Me 1- 88 OH C (Me) ₂ 4-Me 1-89 OH C (Me) ₂ 2-CF ₃ ────────────────────────── ───────

[0041]

[Table 5] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-90 OH C (Me) ₂ 4-CF ₃ 1-91 OH C (Me) ₂ 4-F 1-92 OH C (Me) ₂ 4-Br 1-93 OH C (Me) ₂ 4-Et 1-94 OH C (Me) ₂ 4 -n-Pr 1-95 OH C (Me) ₂ 4-i-Pr 1-96 OH C (Me) ₂ 4-CN 1-97 OH C (Me) ₂ 4-OMe 1-98 OH C (Me) ₂ 4-OEt 1-99 OH C (Me) ₂ 4-OCHF ₂ 1-100 OH C (Me) ₂ 4-OCF ₃ 1-101 OH C (Me) ₂ 2,4- Cl ₂ 1-102 OH C (Me) ₂ 2,4-F ₂ 1-103 OH C (Me) ₂ 3,4- (OMe) ₂ 1-104 OH CH ₂ CH ₂ H 1-105 O H CH ₂ CH ₂ 2-Cl 1-106 OH CH ₂ CH ₂ 3-Cl 1-107 OH CH ₂ CH ₂ 4-Cl 1-108 OH CH ₂ CH ₂ 2-Me 1-109 OH CH ₂ CH ₂ 3-Me 1-110 OH CH ₂ CH ₂ 4-Me 1-111 OH CH ₂ CH ₂ 2-CF ₃ ─────────────────── ─────────────

[0042]

[Table 6] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-112 OH CH ₂ CH ₂ 4-CF ₃ 1 -113 OH CH ₂ CH ₂ 4-F 1-114 OH CH ₂ CH ₂ 4-Br 1-115 OH CH ₂ CH ₂ 4-Et 1-116 OH CH ₂ CH ₂ 4-n-Pr 1 -117 OH CH ₂ CH ₂ 4-i-Pr 1-118 OH CH ₂ CH ₂ 4-CN 1-119 OH CH ₂ CH ₂ 4-COOMe 1-120 OH CH ₂ CH ₂ 4-COOEt 1 -121 OH CH ₂ CH ₂ 4-CONHMe 1-122 OH CH ₂ CH ₂ 4-CON (Me) ₂ 1-123 OH CH ₂ CH ₂ 4-OMe 1-124 OH CH ₂ CH ₂ 4- OEt 1-125 OH CH ₂ CH ₂ 4-OCHF ₂ 1-126 OH CH ₂ CH ₂ 4-OCF ₃ 1-127 OH CH ₂ CH ₂ 2,4-Cl ₂ 1-128 OH CH ₂ CH _{2 2,4-F 2 1-129 O H} CH 2 CH 2 3,4- (OMe) 2 1-130 O H CH 2 CH 2 O H 1-131 O H CH 2 CH 2 O 2-Cl 1- 132 OH CH ₂ CH ₂ O 3-Cl 1-134 OH CH ₂ CH ₂ O 4-Cl ─────────────────────────── ──────

[0043]

[Table 7] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-135 OH CH ₂ CH ₂ O 2-Me 1 -136 OH CH ₂ CH ₂ O 3-Me 1-137 OH CH ₂ CH ₂ O 4-Me 1-138 OH CH ₂ CH ₂ O 2-CF ₃ 1-139 OH CH ₂ CH ₂ O 4 -CF ₃ 1-140 OH CH ₂ CH ₂ O 4-F 1-141 OH CH ₂ CH ₂ O 4-Br 1-142 OH CH ₂ CH ₂ O 4-Et 1-143 OH CH ₂ CH ₂ O 4-n-Pr 1-144 OH CH ₂ CH ₂ O 4-i-Pr 1-145 OH CH ₂ CH ₂ O 4-CN 1-146 OH CH ₂ CH ₂ O 4-OMe 1- 147 OH CH ₂ CH ₂ O 4-OEt 1-148 OH CH ₂ CH ₂ O 4-OCHF ₂ 1-149 OH CH ₂ CH ₂ O 4-OCF ₃ 1-150 OH CH ₂ CH ₂ O 2 , 4-Cl ₂ 1-151 OH CH ₂ CH ₂ O 2,4-F ₂ 1-152 OH CH ₂ CH ₂ O 3,4- (OMe) ₂ 1-153 OH CH ₂ CH ₂ O 2 -Me-4-Cl 1-154 OH CH ₂ CH ₂ O 2-Cl-4-Me 1-155 OH (CH ₂ ) ₃ H 1-156 OH (CH ₂ ) ₃ 2-Cl ─── ─────────────────────────────

[0044]

[Table 8] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-157 OH (CH ₂ ) ₃ 3-Cl 1 -158 OH (CH ₂ ) ₃ 4-Cl 1-159 OH (CH ₂ ) ₃ 2-Me 1-160 OH (CH ₂ ) ₃ 3-Me 1-161 OH (CH ₂ ) ₃ 4- Me 1-162 OH (CH ₂ ) ₃ 2-CF ₃ 1-163 OH (CH ₂ ) ₃ 4-CF ₃ 1-164 OH (CH ₂ ) ₃ 4-F 1-165 OH (CH ₂ ) ₃ 4-Br 1-166 OH (CH ₂ ) ₃ 4-Et 1-167 OH (CH ₂ ) ₃ 4-n-Pr 1-168 OH (CH ₂ ) ₃ 4-i-Pr 1- 169 OH (CH ₂ ) ₃ 4-CN 1-170 OH (CH ₂ ) ₃ 4-OMe 1-171 OH (CH ₂ ) ₃ 4-OEt 1-172 OH NH H 1-173 OH NH 4-Cl 1-174 OH NH 4-F 1-175 OH NH 4-Me 1-176 OH NH 4-Et 1-177 OH NH 4-i-Pr 1-178 OH NH 4-OMe ────────────────────────────────

[0045]

[Table 9] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-179 OH NH 4-OEt 1-180 OH NH 2-Me-4-Cl 1-181 OH NH 2-Cl-4-Me 1-182 OH N (Me) H 1-183 OH N (Me) 4-Cl 1-184 OH N ( Me) 4-F 1-185 OH N (Me) 4-Me 1-186 OH N (Me) 4-Et 1-187 OH N (Me) 4-i-Pr 1-189 OH N ( Me) 4-OMe 1-190 OH N (Me) 4-OEt 1-191 OH N (Me) 2-Me-4-Cl 1-192 OH N (Me) 2-Cl-4-Me 1 -193 OH N (Ph) H 1-194 OH N (Ph) 4-Cl 1-195 OH N (Ph) 4-F 1-196 OH N (Ph) 4-Me 1-197 OH N (Ph) 4-Et 1-198 OH N (Ph) 4-i-Pr 1-199 OH N (Ph) 4-OMe 1-200 OH N (Ph) 4-OEt 1-201 OH N (Ph) 2-Me-4-Cl ────────────────────────────────

[0046]

[Table 10] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-202 OH N (Ph) 2-Cl-4 -Me 1-203 OH CONH H 1-204 OH CONH 4-Cl 1-205 OH CONH 4-F 1-206 OH CONH 4-Me 1-207 OH CONH 4-Et 1-208 OH CONH 4-i-Pr 1-209 OH CONH 4-OMe 1-210 OH CONH 4-OEt 1-211 OH CONH 2-Me-4-Cl 1-212 OH CONH 2-Cl-4-Me 1-213 OH NHCO H 1-214 OH NHCO 4-Cl 1-215 OH NHCO 4-F 1-216 OH NHCO 4-Me 1-217 OH NHCO 4-Et 1-218 OH NHCO 4 -i-Pr 1-219 OH NHCO 4-OMe 1-220 OH NHCO 4-OEt 1-221 OH NHCO 2-Me-4-Cl 1-222 OH NHCO 2-Cl-4-Me 1- 223 OH CH (Me) CH (OH) H ────────────────────────────────

[0047]

[Table 11] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-224 OH CH (Me) CH (OH) 4 -Cl 1-225 OH CH (Me) CH (OH) 4-F 1-226 OH CH (Me) CH (OH) 4-Me 1-227 OH CH (Me) CH (OH) 4-Et 1-228 OH CH (Me) CH (OH) 4-i-Pr 1-229 OH CH (Me) CH (OH) 4-OMe 1-230 OH CH (Me) CH (OH) 4-OEt 1-231 OH CH (Me) CH (OH) 2-Me-4-Cl 1-232 OH CH (Me) CH (OH) 2-Cl-4-Me 1-234 OH CH = CH H 1 -235 OH CH = CH 4-Cl 1-236 OH CH = CH 4-F 1-237 OH CH = CH 4-Me 1-238 OH CH = CH 4-Et 1-239 OH CH = CH 4-i-Pr 1-240 OH CH = CH 4-OMe 1-241 OH CH = CH 4-OEt 1-242 OH CH = CH 2-Me-4-Cl 1-243 OH CH = CH 2-Cl-4-Me 1-244 OH CH ₂ CH = CH H 1-245 OH CH ₂ CH = CH 4-Cl 1-246 OH CH ₂ CH = CH 4-F ───── ────────────────────────────

[0048]

[Table 12] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-247 OH CH ₂ CH = CH 4-Me 1 -248 OH CH ₂ CH = CH 4-Et 1-249 OH CH ₂ CH = CH 4-i-Pr 1-250 OH CH ₂ CH = CH 4-OMe 1-251 OH CH ₂ CH = CH 4-OEt 1-252 OH CH ₂ CH = CH 2-Me-4-Cl 1-253 OH CH ₂ CH = CH 2-Cl-4-Me 1-254 OH SO ₂ H 1-255 OH SO ₂ 4-Cl 1-256 OH SO ₂ 4-F 1-257 OH SO ₂ 4-Me 1-258 OH SO ₂ 4-Et 1-259 OH SO ₂ 4-i-Pr 1-260 OH SO ₂ 4-OMe 1-261 OH SO ₂ 4-OEt 1-262 OH SO ₂ 2-Me-4-Cl 1-263 OH SO ₂ 2-Cl-4-Me 1-264 OH SO ₂ 3-Cl-4-Me 1-265 O Me − H 1-266 O Me − 4-Cl 1-267 O Me − 4-F 1-268 O Me − 4-Me ──────── ─────────────────────────

[0049]

[Table 13] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-269 O Me − 4-Et 1-270 O Me − 4-i-Pr 1-271 O Me − 4-OMe 1-272 O Me − 4-OEt 1-273 O Me − 4-CN 1-274 O Me − 2-Me-4-Cl 1-275 O Me − 2-Cl-4-Me 1-276 O COMe − H 1-277 O COMe − 4-Cl 1-278 O COMe − 4-F 1-279 O COMe − 4-Me 1-280 O COMe − 4 -Et 1-281 O COMe − 4-i-Pr 1-282 O COMe − 4-OMe 1-283 O COMe − 4-OEt 1-284 O COMe − 2-Me-4-Cl 1-285 O COMe − 2-Cl-4-Me 1-286 O COPh − H 1-287 O COPh − 4-Cl 1-288 O COPh − 4-F 1-289 O COPh − 4-Me 1-290 O COPh − 4-Et ────────────────────────────────

[0050]

[Table 14] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-291 O COPh − 4-i-Pr 1-292 O COPh − 4-OMe 1-293 O COPh − 4-OEt 1-294 O COPh − 2-Me-4-Cl 1-295 O COPh − 2-Cl-4-Me 1-296 O COOMe − H 1- 297 O COOMe − 4-Cl 1-298 O COOMe − 4-F 1-299 O COOMe − 4-Me 1-300 O COOMe − 4-Et 1-301 O COOMe − 4-i-Pr 1-302 O COOMe − 4-OMe 1-303 O COOMe − 4-OEt 1-304 O COOMe − 2-Me-4-Cl 1-305 O COOMe − 2-Cl-4-Me 1-306 O CHO − H 1-307 O CHO-4-Cl 1-308 O CHO-4-F 1-309 O CHO-4-Me 1-310 O CHO-4-Et 1-311 O CHO-4-i-Pr 1-312 O CHO-4 -OMe ─────────────────────────────────

[0051]

[Table 15] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-313 O CHO − 4-OEt 1-314 O CHO − 2-Me-4-Cl 1-315 O CHO − 2-Cl-4-Me 1-316 O Me CH ₂ H 1-317 O Me CH ₂ 4-Cl 1-318 O Me CH ₂ 4-F 1 -319 O Me CH ₂ 4-Me 1-320 O Me CH ₂ 4-Et 1-321 O Me CH ₂ 4-i-Pr 1-322 O Me CH ₂ 4-OMe 1-323 O Me CH ₂ 4- OEt 1-324 O Me CH ₂ 2-Me-4-Cl 1-325 O Me CH ₂ 2-Cl-4-Me 1-326 O COMe CH ₂ H 1-327 O COMe CH ₂ 4-Cl 1-328 O COMe CH ₂ 4-F 1-329 O COMe CH ₂ 4-Me 1-330 O COMe CH ₂ 4-Et 1-331 O COMe CH ₂ 4-i-Pr 1-332 O COMe CH ₂ 4-OMe 1 -333 O COMe CH ₂ 4-OEt 1-334 O COMe CH ₂ 2-Me-4-Cl ──────────────────────────── ─────

[0052]

[Table 16] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-335 O COMe CH ₂ 2-Cl-4-Me 1-336 O SO ₂ Me CH ₂ H 1-337 O SO ₂ Me CH ₂ 4-Cl 1-338 O SO ₂ Me CH ₂ 4-F 1-339 O SO ₂ Me CH ₂ 4-Me 1-340 O SO ₂ Me CH ₂ 4-Et 1-341 O SO ₂ Me CH ₂ 4-i-Pr 1-342 O SO ₂ Me CH ₂ 4-OMe 1-343 O SO ₂ Me CH ₂ 4-OEt 1-344 O SO ₂ Me CH ₂ 2-Me-4-Cl 1-345 O SO ₂ Me CH ₂ 2-Cl-4-Me 1-346 O Me CH ₂ CH ₂ H 1-347 O Me CH ₂ CH ₂ 4-Cl 1-348 O Me CH ₂ CH ₂ 4-F 1-349 O Me CH ₂ CH ₂ 4-Me 1-350 O Me CH ₂ CH ₂ 4-Et 1-351 O Me CH ₂ CH ₂ 4-i-Pr 1-352 O Me CH ₂ CH ₂ 4-OMe 1-353 O Me CH ₂ CH ₂ 4-OEt 1-354 O Me CH ₂ CH ₂ 2-Me-4-Cl 1-355 O Me CH ₂ CH ₂ 2 -Cl-4-Me 1-356 O COMe CH ₂ CH ₂ H ─────────────────────────────────

[0053]

[Table 17] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-357 O COMe CH ₂ CH ₂ 4-Cl 1- 358 O COMe CH ₂ CH ₂ 4-F 1-359 O COMe CH ₂ CH ₂ 4-Me 1-360 O COMe CH ₂ CH ₂ 4-Et 1-361 O COMe CH ₂ CH ₂ 4-i-Pr 1- 362 O COMe CH ₂ CH ₂ 4-OMe 1-363 O COMe CH ₂ CH ₂ 4-OEt 1-364 O COMe CH ₂ CH ₂ 2-Me-4-Cl 1-365 O COMe CH ₂ CH ₂ 2-Cl -4-Me 1-366 O SO ₂ Me CH ₂ CH ₂ H 1-367 O SO ₂ Me CH ₂ CH ₂ 4-Cl 1-368 O SO ₂ Me CH ₂ CH ₂ 4-F 1-369 O SO ₂ Me CH ₂ CH ₂ 4-Me 1-370 O SO ₂ Me CH ₂ CH ₂ 4-Et 1-371 O SO ₂ Me CH ₂ CH ₂ 4-i-Pr 1-372 O SO ₂ Me CH ₂ CH ₂ 4 -OMe 1-373 O SO ₂ Me CH ₂ CH ₂ 4-OEt 1-374 O SO ₂ Me CH ₂ CH ₂ 2-Me-4-Cl 1-375 O SO ₂ Me CH ₂ CH ₂ 2-Cl-4 -Me 1-376 SH-H 1-377 SH--4-Cl 1-378 SH-4-F ──────────────────────── ─────────

[0054]

[Table 18] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-379 SH − 4-Me 1-380 SH − 4-Et 1-381 SH − 4-i-Pr 1-382 SH − 4-OMe 1-383 SH − 4-OEt 1-384 SH − 4-OEt 1-385 SH − 2- Me-4-Cl 1-386 SH--2-Cl-4-Me 1-387 SH CH ₂ H 1-388 SH H CH ₂ 4-Cl 1-390 SH CH ₂ 4-F 1-391 S H CH ₂ 4-Me 1-392 SH CH ₂ 4-Et 1-393 SH CH ₂ 4-i-Pr 1-394 SH CH ₂ 4-OMe 1-395 SH CH ₂ 4-OEt 1- 396 SH CH ₂ 2-Me-4-Cl 1-397 SH CH ₂ 2-Cl-4-Me 1-398 SH CH ₂ CH ₂ H 1-399 SH CH ₂ CH ₂ 4-Cl 1- 400 SH CH ₂ CH ₂ 4-F 1-401 SH CH ₂ CH ₂ 4-Me ───────────────────────────── ────

[0055]

[Table 19] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-402 SH CH ₂ CH ₂ 4-Et 1- 403 SH CH ₂ CH ₂ 4-i-Pr 1-404 SH CH ₂ CH ₂ 4-OMe 1-405 SH CH ₂ CH ₂ 4-OEt 1-406 SH CH ₂ CH ₂ 2-Me-4 -Cl 1-407 SH CH ₂ CH ₂ 2-Cl-4-Me 1-408 S Me-H 1-409 S Me-4-Cl 1-410 S Me-4-F 1-411 S Me-4 -Me 1-412 S Me − 4-Et 1-413 S Me − 4-i-Pr 1-414 S Me − 4-OMe 1-415 S Me − 4-OEt 1-416 S Me − 2-Me- 4-Cl 1-417 S Me − 2-Cl-4-Me 1-418 S Me CH ₂ H 1-419 S Me CH ₂ 4-Cl 1-420 S Me CH ₂ 4-F 1-421 S Me CH ₂ 4-Me 1-422 S Me CH ₂ 4-Et 1-423 S Me CH ₂ 4-i-Pr ───────────────────────── ────────

[0056]

[Table 20] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-424 S Me CH ₂ 4-OMe 1-425 S Me CH ₂ 4-OEt 1-426 S Me CH ₂ 2-Me-4-Cl 1-427 S Me CH ₂ 2-Cl-4-Me 1-428 S Me CH ₂ CH ₂ H 1-429 S Me CH ₂ CH ₂ 4-Cl 1-430 S Me CH ₂ CH ₂ 4-F 1-431 S Me CH ₂ CH ₂ 4-Me 1-432 S Me CH ₂ CH ₂ 4-Et 1-433 S Me CH ₂ CH ₂ 4-i-Pr 1-434 S Me CH ₂ CH ₂ 4-OMe 1-435 S Me CH ₂ CH ₂ 4-OEt 1-436 S Me CH ₂ CH ₂ 2-Me-4-Cl 1-437 S Me CH ₂ CH ₂ 2-Cl-4-Me 1-438 S H NH H 1-439 S H NH 4-Cl 1-440 S H NH 4-F 1-441 S H NH 4-Me 1-442 S H NH 4-Et 1-443 S H NH 4-i-Pr 1-444 S H NH 4-OMe 1-445 S H NH 4-OEt ───────────────── ────────────────

[0057]

[Table 21] Table 1 (continued) ──────────────────────────────── Compound No. W A B D ──────────────────────────────── 1-446 SH NH 2-Me-4-Cl 1 -447 SH H 2-Cl-4-Me 1-448 OH-2- (OCH ₂ Ph (2-Me)) ───────────────────── ──────────── Table 2

[0058]

Embedded image

[0059]

[Table 22] ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-1 OH-H 2-2 OH-Me 2-3 OH-Et 2-4 OH-n-Pr 2-5 OH-i-Pr 2-6 OH-c-Pr 2-7 OH-n-Bu 2-8 OH-i -Bu 2-9 OH-s-Bu 2-10 OH-t-Bu 2-11 OH-n-Pen 2-12 OH-c-Pen 2-13 OH-CH ₂ CH (Me) Et 2-14 OH-n-Hex 2-15 OH-CH ₂ CH ₂ CHMe ₂ 2-16 OH- [3-OH-c-Hex] 2-17 OH- [4-OH-c- Hex] 2-18 OH- [4-t-Bu-c-Hex] 2-19 OH-CH ₂ CH = CH ₂ 2-20 OH-CH ₂ CH = CHCl 2-22 OH-CH ₂ C≡CH 2-23 OH-C (Me) ₂ C≡CH 2-24 OH-CH ₂ CH ₂ Cl ─────────────────────── ──────────

[0060]

[Table 23] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-25 OH-CH ₂ CH ₂ F 2-26 OH-CH ₂ CF ₃ 2-27 O Me-H 2-28 O Me-Me 2-29 O Me-Et 2-30 O Me-n-Pr 2-31 O Me-i-Pr 2-32 O Me − c-Pr 2-33 O Me − n-Bu 2-34 O Me − i-Bu 2-35 O Me − s-Bu 2-36 O Me − t-Bu 2-37 O Me − n-Pen 2-38 O Me − c-Pen 2-39 O Me − CH ₂ CH (Me) Et 2-40 O Me − n-Hex 2-41 O Me − c-Hex 2-42 O Me − CH ₂ CH = CH ₂ 2-43 O Me-CH ₂ CH = CHCl 2-44 O Me-CH ₂ C ≡ CH 2-45 O Me-C (Me) ₂ C ≡ CH 2-46 O Me-CH ₂ CH ₂ Cl ─ ───────────────────────────────

[0061]

[Table 24] Table 1 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-47 O Me − CH ₂ CH ₂ F 2-48 O Et-n-Bu 2-49 O COMe-H 2-50 O COMe-Me 2-51 O COMe-Et 2-52 O COMe-n-Pr 2-53 O COMe-i-Pr 2-54 O COMe − C-Pr 2-55 O COMe − n-Bu 2-56 O COMe − i-Bu 2-57 O COMe − s-Bu 2-58 O COMe − t-Bu 2-59 O COMe − n-Pen 2 -60 O COMe − c-Pen 2-61 O COMe − CH ₂ CH (Me) Et 2-62 O COMe − n-Hex 2-63 O COMe − c-Hex 2-64 O COMe − CH ₂ CH = CH ₂ 2-65 O COMe-CH ₂ CH = CHCl 2-66 O COMe-CH ₂ C≡CH 2-67 O COMe-C (Me) ₂ C≡CH 2-68 O COMe-CH ₂ CH ₂ Cl ── ──────────────────────────────

[0062]

[Table 25] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-69 O COMe − CH ₂ CH ₂ F 2-70 O COMe-CH ₂ CF ₃ 2-71 O COPh-H 2-72 O COPh-Me 2-73 O COPh-Et 2-74 O COPh-n-Pr 2-75 O COPh-i-Pr 2-76 O COPh-c-Pr 2-77 O COPh-n-Bu 2-78 O COPh-i-Bu 2-79 O COPh-s-Bu 2-80 O COPh-t-Bu 2-81 O COPh-n-Pen 2-82 O COPh-c-Pen 2-83 O COPh-CH ₂ CH (Me) Et 2-84 O COPh-n-Hex 2-85 O COPh-c-Hex 2-86 O COPh-CH ₂ CH = CH ₂ 2-87 O COPh-CH ₂ CH = CHCl 2-88 O COPh-CH ₂ C≡CH 2-89 O COPh-C (Me) ₂ C≡CH 2-90 O COPh-CH ₂ CH ₂ Cl ─ ───────────────────────────────

[0063]

[Table 26] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-91 O COPh − CH ₂ CH ₂ F 2-92 O COPh-CH ₂ CF ₃ 2-93 OSO ₂ Me-H 2-94 OSO ₂ Me-Me 2-95 OSO ₂ Me-Et 2-96 OSO ₂ Me-n-Pr 2-97 OSO ₂ Me − i-Pr 2-98 OSO ₂ Me − c-Pr 2-99 OSO ₂ Me − n-Bu 2-100 OSO ₂ Me − i-Bu 2-101 OSO ₂ Me − s-Bu 2-102 OSO ₂ Me − t-Bu 2-103 OSO ₂ Me − n-Pen 2-104 OSO ₂ Me − c-Pen 2-105 OSO ₂ Me − CH ₂ CH (Me) Et 2- 106 OSO ₂ Me-n-Hex 2-107 OSO ₂ Me-c-Hex 2-108 OSO ₂ Me-CH ₂ CH = CH ₂ 2-109 OSO ₂ Me-CH ₂ CH = CHCl 2-110 OSO ₂ Me − CH ₂ C ≡ CH 2-111 OSO ₂ Me − (Me) ₂ C ≡ CH 2-112 OSO ₂ Me − CH ₂ CH ₂ Cl ───────────── ─────────────────────

[0064]

[Table 27] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-113 OSO ₂ Me − CH ₂ CH ₂ F 2 -114 O SO ₂ Me-CH ₂ CF ₃ 2-115 OH-NH ₂ 2-116 OH-NHMe 2-117 OH-NHEt 2-118 OH-NH-n-Pr 2-119 OH- NH-i-Pr 2-120 OH-NH-n-Bu 2-121 OH-NH-t-Bu 2-122 OH-NHCH ₂ CH = CH ₂ 2-123 OH-NHCH ₂ Ph 2- 124 OH-N (Me) ₂ 2-125 OH-N (CH ₂ Ph) ₂ 2-126 O Me-NH ₂ 2-127 O Et-NH ₂ 2-128 On-Pr-NH ₂ 2- 129 O i-Pr-NH ₂ 2-130 On-Bu-NH ₂ 2-131 O CH ₂ CH = CH ₂ -NH ₂ 2-132 O Me NH COMe 2-134 O Et NH COMe 2-135 On -Pr NH COMe ────────────────────────────────

[0065]

[Table 28] Table 2 (continued) ──────────────────────────────── Compound No. W A E G ──────────────────────────────── 2-136 O i-Pr NH COMe 2-137 On -Bu NH COMe 2-138 O CH ₂ CH = CH ₂ NH COMe 2-139 O Me NH COPh 2-140 O Et NH COPh 2-141 On-Pr NH COPh 2-142 O i-Pr NH COPh 2- 143 On-Bu NH COPh 2-144 O CH ₂ CH = CH ₂ NH COPh 2-145 OH-Y1 2-146 OH-Y2 2-147 OH-Y3 2-148 OH-OH 2-149 OH-OMe 2-150 OH-OEt 2-151 OH-On-Pr 2-152 OH-Oi-Pr 2-153 OH-On-Bu 2-154 OH-Ot-Bu 2-155 OH-OCH ₂ CH = CH ₂ 2-156 OH-OCH ₂ CH = CHCl 2-157 OH-OCH ₂ Ph ────────────────────── ───────────

[0066]

[Table 29] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-158 OH-OCH ₂ (4-Cl-Ph ) 2-159 OH-OCH ₂ (4-Me-Ph) 2-160 OH-OCH ₂ CH ₂ Ph 2-161 OH-OCH ₂ CH ₂ (4-Cl-Ph) 2-162 OH- OCH ₂ CH ₂ (4-Me-Ph) 2-163 OH-OCH ₂ CH = CHPh 2-164 OH-OCH ₂ COOMe 2-165 OH-OCH ₂ COOEt 2-166 OH-OCH ₂ CH ₂ SiMe ₃ 2-167 O Me − OH 2-168 O Me − OMe 2-169 O Me − OEt 2-170 O Me − OCH ₂ Ph 2-171 O Me − OCH ₂ CH ₂ Ph 2-172 O COMe − OMe 2-173 O COMe − OEt 2-174 O COMe − On-Pr 2-175 O COMe − Oi-Pr 2-176 O COMe − On-Bu 2-177 O COMe − Ot-Bu 2-178 O COMe − OCH ₂ CH = CH ₂ 2-179 O COMe − OCH ₂ CH = CHCl ─────────────────────────────────

[0067]

[Table 30] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-180 O COMe − OCH ₂ Ph 2-181 O COMe -OCH ₂ (4-Cl-Ph) 2-182 O COMe -OCH ₂ (4-Me-Ph) 2-183 O COMe -OCH ₂ CH ₂ Ph 2-184 O COMe -OCH ₂ CH ₂ (4-Cl -Ph) 2-185 O COMe − OCH ₂ CH ₂ (4-Me-Ph) 2-186 O COMe − OCH ₂ CH = CHPh 2-187 O COMe − OCH ₂ COOMe 2-189 O COMe − OCH ₂ COOEt 2 -190 OH-SO ₂ Me 2-191 OH-SO ₂ Et 2-192 OH-SO ₂ n-Pr 2-193 OH-SO ₂ CH ₂ Ph 2-194 OH-SO ₂ NMe ₂ 2 _{-195 O H - SO 2 NEt 2} 2-196 O H - SO 2 NHMe 2-197 O H - SO 2 NHEt 2-198 O H - SO 2 NH-n-Pr 2-199 O H - SO 2 NH- i-Pr 2-200 OH-CHO 2-201 OH-COMe 2-202 OH-COEt ─────────────────────────── ──────

[0068]

[Table 31] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-203 OH-CO-n-Pr 2-204 OH-CO-i-Pr 2-205 OH-CO-n-Bu 2-206 OH-COCH ₂ Ph 2-207 OH NH CHO 2-208 OH NH COMe 2-209 OH NH COEt 2 -210 OH NH CO-n-Pr 2-211 OH NH CO-i-Pr 2-212 OH NH CO-n-Bu 2-213 OH NH COCH ₂ Ph 2-214 OH NH SO ₂ Me 2-215 OH NH SO ₂ Et 2-216 OH NH SO ₂ -n-Pr 2-217 OH NH SO ₂ CH ₂ Ph 2-218 OH NH SO ₂ NMe ₂ 2-219 OH NH SO ₂ NEt ₂ 2-220 OH NH SO ₂ NHMe 2-221 OH NH SO ₂ NHEt 2-222 OH NH SO ₂ NHPr 2-223 OH NH SO ₂ NH-i-Pr 2-224 OH NH CONMe ₂ ────────────────────────────────

[0069]

[Table 32] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-225 OH NH COOMe 2-226 OH NH COOEt 2-227 OH NH COO-n-Pr 2-228 OH NH COO-i-Pr 2-229 OH NH COO-n-Bu 2-230 OH NH COO-i-Bu 2-231 OH NH COO-t-Bu 2-232 OH NH COOCH ₂ Ph 2-234 OH NH COOPh 2-235 OH CH ₂ COOH 2-236 OH CH ₂ COOMe 2-237 OH CH ₂ COOEt 2-238 OH CH ₂ COO-n-Pr 2-239 OH CH ₂ COO-i-Pr 2-240 OH CH ₂ COO-n-Bu 2-241 OH CH ₂ COO-i-Bu 2-242 OH CH ₂ COO-t-Bu 2-243 O H CH 2 COOCH 2 Ph 2-244 O H CH 2 COOPh 2-245 O H CH (Me) COOH 2-246 O H CH (Me) COOMe 2-247 O H CH ( Me) COOEt ────────────────────────────────

[0070]

[Table 33] Table 2 (continued) ──────────────────────────────── Compound No. W A E G ──────────────────────────────── 2-248 OH CH (Me) COO-n-Pr 2-249 OH CH (Me) COO-i-Pr 2-250 OH CH (Me) COO-n-Bu 2-251 OH CH (Me) COO-i-Bu 2-252 OH CH (Me ) COO-t-Bu 2-253 OH CH (Me) COOCH ₂ Ph 2-254 OH CH (Me) COOPh 2-255 OH C (Me) ₂ COOH 2-256 OH C (Me) ₂ COOMe 2-257 OH C (Me) ₂ COOEt 2-258 OH C (Me) ₂ COO-n-Pr 2-259 OH C (Me) ₂ COO-i-Pr 2-260 OH C (Me) ₂ COO-n-Bu 2-261 OH C (Me) ₂ COO-i-Bu 2-262 OH C (Me) ₂ COO-t-Bu 2-263 OH C (Me) ₂ COOCH ₂ Ph 2 -264 OH C (Me) ₂ COOPh 2-265 OH CH (i-Pr) _L COOH 2-266 OH CH (i-Pr) _L COOMe 2-267 OH CH (i-Pr) _L COOEt 2 -268 OH CH (i-Pr) _L COO-n-Pr 2-269 OH CH (i-Pr) _L COO-i-Pr ────────────────── ───────────────

[0071]

[Table 34] Table 2 (continued) ──────────────────────────────── Compound No. WA EG ──────────────────────────────── 2-270 OH CH (i-Pr) _L COO- n-Bu 2-271 OH CH (i-Pr) _L COO-i-Bu 2-272 OH CH (i-Pr) _L COO-t-Bu 2-273 OH CH (i-Pr) _L COOCH ₂ Ph 2-274 OH CH (i-Pr) _L COOPh 2-275 OH CH (Ph) COOH 2-276 OH CH (Ph) COOMe 2-277 OH CH (Ph) COOEt 2-278 OH CH (Ph) COO-n-Pr 2-279 OH CH (Ph) COO-i-Pr 2-280 OH CH (Ph) COO-n-Bu 2-281 OH CH (Ph) COO-i- Bu 2-282 OH CH (Ph) COO-t-Bu 2-283 OH CH (Ph) COOCH ₂ Ph 2-284 OH CH (Ph) COOPh 2-285 OH CH (CH ₂ Ph) _L COOH 2-286 OH CH (CH ₂ Ph) _L COOMe 2-287 OH CH (CH ₂ Ph) _L COOEt 2-288 OH CH (CH ₂ Ph) _L COO-n-Pr 2-289 OH CH ( CH ₂ Ph) _L COO-i-Pr 2-290 OH CH (CH ₂ Ph) _L COO-n-Bu 2-291 OH CH (CH ₂ Ph) _L COO-i-Bu ────── ──────────────────────────

[0072]

[Table 35] Table 2 (continued) ──────────────────────────────── Compound No. W A E G ──────────────────────────────── 2-292 OH CH (CH ₂ Ph) _L COO- t-Bu 2-293 O H CH ( CH 2 Ph) L COOCH 2 Ph 2-294 O H CH (CH 2 Ph) L COOPh 2-295 O H CH [CH 2 (4-F-Ph)] COOMe 2 -296 OH CH [CH ₂ (4-F-Ph)] COOEt 2-297 OH CH [CH ₂ (2-F-Ph)] COOH 2-298 OH CH [CH ₂ (2-F-Ph) )] COOMe 2-299 OH CH [CH ₂ (2-F-Ph)] COOEt 2-300 OH CH [CH ₂ (2-F-Ph)] COO-n-Pr 2-301 OH CH [ CH ₂ (4-Cl-Ph)] COOMe 2-302 OH CH [CH ₂ (4-Cl-Ph)] COOEt 2-303 OH CH [CH ₂ (4-Cl-Ph)] COO-n- Pr 2-304 OH CH (CH ₂ CH ₂ SMe) _L COOH 2-305 OH CH (CH ₂ CH ₂ SMe) _L COOMe 2-306 OH CH (CH ₂ CH ₂ SMe) _L COOEt 2-307 O H CH (CH ₂ CH ₂ SMe) _L COO-n-Pr 2-308 OH CH (CH ₂ CH ₂ SMe) _L COO-i-Pr 2-309 OH CH (CH ₂ CH ₂ SMe) _L COO- n-Bu 2-310 OH CH (CH ₂ CH ₂ SMe) _L COO-i-Bu 2-311 OH CH (CH ₂ CH ₂ SMe) _L COO-t-Bu 2-312 OH CH (CH _{2 CH 2 SMe) L COOCH 2 Ph} 2-313 O H CH (CH 2 CH 2 SMe) L COOPh ── ─────────────────────────────

[0073]

[Table 36] Table 2 (continued) ──────────────────────────────── Compound No. W A E G ──────────────────────────────── 2-314 OH CH (CH ₂ CONH ₂ ) _L COOH 2-315 OH CH (CH ₂ CONH ₂ ) _L COOMe 2-316 OH CH (CH ₂ CONH ₂ ) _L COOEt 2-317 OH CH (CH ₂ CH ₂ CONH ₂ ) _L COOH 2-318 OH CH (CH ₂ CH ₂ CONH ₂ ) _L COOMe 2-319 OH CH (CH ₂ CH ₂ CONH ₂ ) _L COOEt 2-320 OH C (Me) (i-Pr) COOH 2-321 OH C (Me) (i-Pr) COOMe 2-322 OH C (Me) (i-Pr) COOEt 2-323 OH C (Me) (i-Pr) COO-n-Pr 2-324 OH C (Me) ( i-Pr) COO-i-Pr 2-325 OH C (Me) (i-Pr) COO-n-Bu 2-326 OH C (Me) (i-Pr) COO-i-Bu 2-327 O H C (Me) (i -Pr) COO-t-Bu 2-328 O H C (Me) (i-Pr) COOCH 2 Ph 2-329 O H C (Me) (i-Pr) COOPh 2- 330 OH CH (i-Bu) _L COOH 2-331 OH CH (i-Bu) _L COOMe 2-332 OH CH (i-Bu) _L COOEt 2-333 OH CH (i-Bu) _L COO -n-Pr 2-334 OH CH (OH) CCl ₃ 2-335 OH CH (OMe) CCl ₃ ───────────────────────── ────────

[0074]

[Table 37] Table 2 (continued) ──────────────────────────────── Compound No. W A E G ──────────────────────────────── 2-3336 OH C (Me) ₂ CH ₂ OH 2 -337 OH C (Me) ₂ CH ₂ OCOMe 2-338 OH C (Me) ₂ CH ₂ OCOPh 2-339 OH CH ₂ CH ₂ NMe ₂ 2-340 OH CH ₂ CH ₂ NEt ₂ 2-341 OH CH ₂ CH ₂ N (CH ₂ Ph) ₂ 2-342 OH CH ₂ CH ₂ Y1 2-343 OH CH ₂ CH ₂ Y2 2-344 OH CH ₂ CH ₂ Y3 2-345 OH CH _{2 CH 2 Y4 2-346 S H - H} 2-347 S H - Me 2-348 S H - Et 2-349 S H - n-Pr 2-350 S H - i-Pr 2-351 S H - c- Pr 2-352 SH-n-Bu 2-353 SH-i-Bu 2-354 SH-s-Bu 2-355 SH-t-Bu 2-356 SH-n-Pen 2-357 S H-c-Pen ────────────────────────────────

[0075]

[Table 38] Table 2 (continued) ──────────────────────────────── Compound No. W A E G ──────────────────────────────── 2-358 SH-CH ₂ CH (Me) Et 2 -359 SH-n-Hex 2-360 SH-c-Hex 2-361 OH CO NH ₂ 2-362 OH CO NHMe 2-363 OH CO NHEt 2-364 OH CO NH-n-Pr 2-365 OH CO NH-n-Bu 2-366 OH CO NH-t-Bu 2-367 OH CO N (Me) ₂ 2-368 OH CO N (Et) ₂ 2-369 OH CH ₂ CH ₂ COOH 2-370 OH CH ₂ CH ₂ COOMe 2-371 OH CH ₂ CH ₂ COOEt 2-372 OH CH ₂ CH ₂ COO-n-Pr 2-373 OH CH ₂ CONH CH ₂ COOH 2 -374 OH CH ₂ CONH CH ₂ COOMe 2-375 OH CH ₂ CONH CH ₂ COOEt 2-376 OH CH ₂ CONH CH ₂ COO-n-Pr 2-377 O Me − SO ₂ NH ₂ 2-378 O Me − SO ₂ NHMe 2-379 O Me − SO ₂ NHEt ─────────────────────────────────

[0076]

[Table 39] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-380 O Me − SO ₂ NH-n-Pr 2 -381 O Me − SO ₂ N (Me) ₂ 2-382 O Me − SO ₂ N (Et) ₂ 2-383 O Et − SO ₂ NH ₂ 2-384 O Et − SO ₂ NHMe 2-385 O Et − SO ₂ NHEt 2-386 O Et − SO ₂ NH-n-Pr 2-387 O Et − SO ₂ N (Me) ₂ 2-388 O Et − SO ₂ N (Et) ₂ 2-389 O Me CH ₂ COOH 2-390 O Me CH ₂ COOMe 2-391 O Me CH ₂ COOEt 2-392 O Me CH ₂ COO-n-Pr 2-393 O Me CH (Me) COOH 2-394 O Me CH (Me) COOMe 2- 395 O Me CH (Me) COOEt 2-396 O Me CH (Me) COO-n-Pr 2-397 O Me C (Me) ₂ COOH 2-398 O Me C (Me) ₂ COOMe 2-399 O Me C (Me) ₂ COOEt 2-400 O Me C (Me) ₂ COO-n-Pr 2-401 O Me CH (i-Pr) COOH ─────────────────── ──────────────

[0077]

[Table 40] Table 2 (continued) ──────────────────────────────── Compound No. W A E G ──────────────────────────────── 2-402 O Me CH (i-Pr) COOMe 2- 403 O Me CH (i-Pr) COOEt 2-404 O Me CH (i-Pr) COO-n-Pr 2-405 O Me CH (CH ₂ Ph) COOH 2-406 O Me CH (CH ₂ Ph) COOMe 2-407 O Me CH (CH ₂ Ph) COOEt 2-408 O Me CH (CH ₂ Ph) COO-n-Pr 2-409 O Me CH (CH ₂ CH ₂ SMe) COOH 2-410 O Me CH (CH ₂ CH ₂ SMe) COOMe 2-411 O Me CH (CH ₂ CH ₂ SMe) COOEt 2-412 O Me CH (CH ₂ CH ₂ SMe) COO-n-Pr 2-413 OH CH (Me) _D COOMe 2 -414 OH CH (Me) _D COOEt 2-415 OH CH (Me) _L COOMe 2-416 OH CH (Me) _L COOEt 2-417 OH CH (i-Pr) COOH 2-418 OH CH (i-Pr) COOMe 2-419 OH CH (i-Pr) COOEt 2-420 OH CH (i-Pr) COO-n-Pr 2-421 OH CH (CH ₂ Ph) COOH 2-422 O H CH (CH ₂ Ph) COOMe 2-423 OH CH (CH ₂ Ph) COOEt ─────────────────────────────── ──

[0078]

[Table 41] Table 2 (continued) ──────────────────────────────── Compound No. W A E G ──────────────────────────────── 2-424 OH CH (CH ₂ Ph) COO-n -Pr 2-425 OH CH (CH ₂ CH ₂ SMe) COOH 2-426 OH CH (CH ₂ CH ₂ SMe) COOMe 2-427 OH CH (CH ₂ CH ₂ SMe) COOEt 2-428 OH CH (CH ₂ CH ₂ SMe) COO-n-Pr 2-429 OH CH ₂ Z1 2-430 OH CH ₂ Z2 2-431 O CH ₂ Ph CH ₂ COOMe 2-432 O CH ₂ Ph CH ₂ COOEt 2- 433 O CH ₂ Ph CH (Me) COOMe 2-434 O CH ₂ Ph CH (Me) COOEt 2-435 O CH ₂ Ph CH ₂ CH ₂ COOMe 2-436 O CH ₂ Ph CH ₂ CH ₂ COOEt 2-437 O H CH (Me) CH ₂ COOMe 2-438 OH CH (Me) CH ₂ COOEt 2-439 O CH ₂ Ph CH (Me) CH ₂ COOMe 2-440 O CH ₂ Ph CH (Me) CH ₂ COOEt 2- 441 O Me NHCO Z3 2-442 O Me NHCO Z4 2-443 O Me NHCO Z5 2-444 O i-Pr NHCO Z3 2-445 O OMe-SON (Me) ₂ ──────────── ─────────────────────

[0079]

[Table 42] Table 2 (continued) ──────────────────────────────── Compound No. W A E G ──────────────────────────────── 2-446 O OEt − SON (Me) ₂ 2-447 OOCH ₂ Ph-SON (Me) ₂ 2-448 OH-Oi-Bu 2-449 OH-Os-Bu 2-450 OH-On-Pen 2-451 OH-OCH ₂ CH ₂ CHMe ₂ 2 -452 OH-OCH ₂ CH ₂ OPh 2-453 OH-OCH ₂ CH (Me) OPh 2-454 OH-OCH (Me) CH ₂ OPh 2-455 OH CH ₂ CH ₂ OMe 2-456 O H CH ₂ CH ₂ OEt 2-457 OH CH ₂ CH ₂ On-Pr 2-458 OH CH ₂ CH ₂ CH ₂ OMe 2-459 OH CH ₂ CH ₂ CH ₂ OEt 2-460 OH CH ₂ CH ₂ CH ₂ On-Pr 2-461 OH-c-Hex 2-462 OH-nC ₇ H ₁₅ 2-463 OH-nC ₈ H ₁₇ 2-464 OH-nC ₉ H ₁₉ 2-465 OH C (Me) ₂ COCHCl ₂ 2-466 OH C (Me) ₂ COCHBr ₂ 2-467 OH CH ₂ CH ₂ NH-c-Pen ────────────────── ───────────────

[0080]

[Table 43] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-468 OH (CH ₂ ) ₃ NH-c- Hex 2-469 O H over _{O (CH 2) 3 OPh 2-470} O H over On-Hex 2-471 O H over OnC ₇ H ₁₅ 2-472 O H over OnC ₈ H ₁₇ 2-473 O H over ONC ₉ H ₁₉ 2-474 OH-OnC ₁₀ H ₂₁ 2-475 OH-OCH (Me) Ph 2-476 OH-OCH ₂ CH (Me) Ph 2-477 OH-OCH (Me) COOMe 2- 478 OH-OCH (Me) COOEt 2-479 OH-OC (Me) ₂ COOMe 2-480 OH-OC (Me) ₂ COOEt 2-481 OH-OCH ₂ C (Me) = CH ₂ 2- 482 O H over _{OCH 2 CH = CH-Me 2-483} O H over OCH ₂ C≡CH 2-484 O H over OCH ₂ C≡C-Me 2-485 O H over nC ₁₀ H ₂₁ 2-486 O Hー CH ₂ CH (Et) (CH ₂ ) ₃ Me 2-487 OH ー (CH ₂ ) ₃ OEt 2-488 OH ー (CH ₂ ) ₃ NEt ₂ 2-489 OH ー (CH ₂ ) ₃ OCH ₂ CH (Et) (CH ₂ ) ₃ Me ─────────────────────────────────

[0081]

[Table 44] Table 2 (continued) ──────────────────────────────── Compound No. WAEG ──────────────────────────────── 2-490 OH ー (CH ₂ ) ₃ -Y3 2 -491 OH CH ₂ CH ₂ OH 2-492 OH CH (Me) CH ₂ OH 2-493 OH CH ₂ CH (Me) OH 2-494 OH CH (Et) CH ₂ OH 2-495 OH CH (CH ₂ Ph) CH ₂ OH 2-496 OH CH (CH ₂ CH ₂ SMe) CH ₂ OH 2-497 OH CH (CH ₂ OH) COOMe 2-498 O CH ₂ Ph CH (CH ₂ Ph) COOMe 2-499 OH CH (CH ₂ CH ₂ SO ₂ Me) COOMe 2-500 OH CH (CH ₂ CH ₂ SO ₂ Me) COOEt 2-501 OH CH (CH ₂ CH ₂ SO ₂ Me) COO- n-Pr 2-502 OH CH (CH ₂ CH ₂ SO ₂ Me) COO-t-Bu ──────────────────────────── ───── In Table 2 above, D or L represents a series of configurations of compounds. In Table 2 above, Y1 to Y4 and Z1 to Z5 represent the following structures.

[0082]

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Table 3

[0084]

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[0085]

[Table 45] ───────────────────── Compound No. W Q ───────────────────── 3-1 O Y1 3-2 O Y2 3-3 O Y3 3-4 O Y4 3-5 O Y5 3- 6 O Y6 3-7 O Y7 3-8 O Y8 3-9 O Y9 3-10 O Y10 3-11 O Y11 3-12 O Y12 3-13 O Y13 3-14 O Y14 3-15 O Y15 3- 16 O Y16 3-17 O Y17 3-18 O Y18 3-19 O Y19 3-20 O Y20 3-21 O Y21 3-22 O Y22 3-23 O Y23 ──────────── ─────────

[0086]

[Table 46] Table 3 (continued) ───────────────────── Compound No. W Q ───────────────────── 3-24 O Y24 3-25 O Y25 3-26 O Y26 3-27 O Y27 3-28 O Y28 3- 29 O Y29 3-30 O Y30 3-31 O Y31 3-32 O Y32 3-33 O Y33 3-34 O Y34 3-35 O Y35 3-36 O Y36 3-37 O Y37 3-38 O Y38 3- 39 O Y39 3-40 O Y40 3-41 O Y41 3-42 O Y42 3-43 O Y43 3-44 O Y44 3-45 O Y45 ───────────────── ────

[0087]

[Table 47] Table 3 (continued) ───────────────────── Compound No. W Q ───────────────────── 3-46 O Y46 3-47 O Y47 3-48 O Y48 ──────────── ─────────

In Table 3 above, Y1 to Y48 represent the following structures.

[0089]

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[0090]

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[0091]

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[0092]

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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)

[0094]

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(X, R ¹ , R ² and R ³ have the same meanings as described above.) (Production method 2)

[0096]

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(X, R ¹ , R ² and R ³ have the same meanings as described above.) (Production method 3)

[0098]

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(X, R ¹ , R ² and R ³ have the same meanings as described above.) (Production method 4)

[0100]

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(X, R ¹ , R ² and R ³ have the same meanings as described above, and L represents a leaving group such as a halogen atom.) In (Production Method 1), 3-amino-1-alkylpyrazole ( By diazotizing 2) according to a conventional method and adding a copper halide, 3-halogeno-1-alkylpyrazole (3) can be synthesized.

The diazotization step is usually carried out in a mineral acid such as hydrochloric acid or sulfuric acid in the range of -10 ° C to room temperature, preferably 0 to 10 ° C. In the reaction with a copper halide, it is possible to add it directly to the diazonium solution, but it is usually desirable to suspend the copper salt in an inert solvent such as chloroform and then add the diazonium solution. Reaction is 0-10
It is preferably carried out at 0 ° C. or the reflux temperature of the solvent.

Next, BuLi (butyl lithium) and LDA
5-Pyrazolecarboxylic acid (4) can be synthesized by lithiating the 5-position using a lithium compound such as (lithium diisopropylamide) and reacting with carbon dioxide gas. The lithiation and the subsequent carboxylic acid introduction step are usually carried out in an inert solvent such as diethyl ether or tetrahydrofuran,
In the range of −120 ° C. to room temperature, preferably −80 ° C. to 0
It is good to carry out at ° C. After completion of the reaction, a carboxylic acid is obtained by performing a usual post treatment.

The 5-pyrazolecarboxylic acid (4) is converted into a carboxylic acid halide (5) by a conventional method and then reacted with various amines (6) to synthesize the desired product (1a). In the step of halogenating a carboxylic acid, thionyl halide, phosphorus halide, phosgene, etc. can be added directly, but usually in an inert solvent such as chloroform, benzene, toluene or the like, 0 to 120 ° C. or the reflux temperature of the solvent. Good to do in.

The amidation step can be carried out in a suitable inert solvent. As the solvent, for example, toluene, xylene, aromatic hydrocarbons such as chlorobenzene, chloroform, halogenated hydrocarbons such as dichloroethane, diisopropyl ether, ethers such as dioxane, nitriles such as acetonitrile, dimethyl sulfoxide,
Examples include polar solvents such as dimethylformamide. 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 0 to
50 ° C. is preferred. In (Production Method 2), the 5-pyrazolecarboxylic acid amide compound (1a) is allowed to react 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 room temperature to the boiling point of the solvent, preferably The reflux temperature of the solvent is good. In (Production Method 3), 3-halogeno-1
-Alkylpyrazole (3) was lithiated at the 5-position using a lithium compound such as LDA (lithium diisopropylamide) and reacted with ethyl chloroformate or diethyl carbonate to give ethyl 5-pyrazolecarboxylic acid ester (7). Can be synthesized.

The steps of lithiation and subsequent introduction of an ethyl ester group are usually carried out in an inert solvent such as diethyl ether or tetrahydrofuran at a temperature of -120 ° C to room temperature, preferably -80 ° C to 0 ° C. . After the reaction is complete,
Ethyl ester is obtained by performing a usual post-treatment. 5-Pyrazolecarboxylic acid ethyl ester (7)
The target compound (1a) can be synthesized by reacting with the various amines (6).

The amidation step can be carried out in a suitable inert solvent. As the solvent, for example, toluene, xylene, aromatic hydrocarbons such as chlorobenzene, chloroform, halogenated hydrocarbons such as dichloroethane, diisopropyl ether, ethers such as dioxane, nitriles such as acetonitrile, dimethyl sulfoxide,
Examples include polar solvents such as dimethylformamide. If necessary, an organic base (pyridine, triethylamine, etc.) or an inorganic base (potassium carbonate, sodium hydride, etc.) may be added.

The reaction temperature is preferably 0 to 120 ° C. or the reflux temperature of the solvent. In (Production Method 4), 5-pyrazolecarboxylic acid chloride (5) or 5-pyrazolecarboxylic acid amide (9) synthesized from 5-pyrazolecarboxylic acid ethyl ester (7) was added to
The target compound (1a) can be synthesized by reacting with various reagents having a leaving group such as halogen. The reaction with various reagents 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.

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 (Erysiphe)
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.G. recon
data, P.P. hordei), snow rot (Typhla)
sp. , Micronectorella niva
is), naked smut (Ustilago tritic)
i, U. nuda), eye spot (Pseudoce)
rcosporella herpotrichoid
es), cloud disease (Rhyncosporium sec)
alis), leaf blight (Septoria tritic)
i), blight (Leptosphaeria nodo)
rum),

Citrus black spot disease (Diaportthe)
citri), scab (Elsinoe fauce)
tti), fruit rot (Penicillium di)
gitarum, P.G. italicum), apple monili disease (Sclerotinia mail), rot (Valsa mali), powdery mildew (Podo)
sphaera leucotricha), leaf spot disease (Alternaria mali), scab (Ve)
nurtia inaqualis, pear scab (Venturia nashicola), black spot (Alternaria kikuchiana), red scab (Gymnosporangium haraen)
um),

Peach scab (Sclerotinia)
cinerea), scab (Cladosporium)
carpophilum), Phomopsis rot (P
homopsis sp. ), Downy mildew of grape (Pla
Smopara viticola), black scab (El)
sinoe ampelina), late rot (Glome
rella ingulata), powdery mildew (Un
Cinula necator), rust (Phako)
psora ampelopsidis), oyster anthracnose (Glocosporium kaki), leaf scab (Cercospora kaki, Mycospha)
erella nowa), downy mildew of smelt (Pse)
udoperenospora cubensis),

Anthracnose (Coletotrichum)
lagenarium), powdery mildew (Sphaero)
theca fuliginea), vine blight (Myc)
osphaerella melonis, Phytophthora infestan of tomato
s), ring spot disease (Alternaria solan)
i), leaf mold (Cladosporium fulvu)
m), brown leaf spot of aubergine (Phomopsis vexan)
s), powdery mildew (Erysiphe cichora)
Coarum), black spot of cruciferous vegetables (Alter)
naria japonica), White spot (Ceroc)
osporella brassicae),

Rust disease of leeks (Puccinia all)
ii), soybean purpura (Cercospora ki)
kuchii), black scab (Elsinoe glyc)
ines), Black spot (Diaportthe phase)
anthracnose (Colletot)
richum lindemuthianum), peanut black astringent disease (Mycosphaerella pe)
rsonatum), brown spot (Cercospora)
arachidicola), powdery mildew of pea (Erysiphe pisi), summer blight of potato (Alternaria solani),

Powdery mildew of strawberry (Sphaeroth
eca humuli), rice blast of tea (Exoba)
sidium reticulatum), white scab (E
lsinoe leucospila), tobacco scab (Alternaria longipes), powdery mildew (Erysiphe cichoracearu)
m), anthracnose (Coletotrichum tab)
acum), 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.), 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, and if desired, an emulsifier, a dispersant, a suspension agent, a penetrant, a spreading agent, a stabilizer and the like are added. The mold can be put to practical use.

When the compound of the present invention is used 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, other types of herbicides, various insecticides, bactericides, and the like when necessary in formulation or spraying,
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 the bactericide containing the compound of the present invention as an active ingredient are shown, but the invention is 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 interface Mixture with activator: trade name of Toho Chemical Industry Co., Ltd. The above is uniformly mixed to obtain 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 Diklite PEP ………… 66 parts (mixture of kaolinite and sericite: trade name of Sieglite Co., Ltd.) Solpol 5039 … 4 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. product name) Carplex # 80 ………… 3 parts (White carbon: Shionogi Pharmaceutical Co., Ltd. product name) Calcium lignin sulfonate …… 2 parts The above is 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 Phosphorus Diisopropyl acid ……………… 1.5 parts The above is uniformly mixed and pulverized to give 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 Lignin sulfonate Calcium: 1 part The above components are uniformly mixed and ground to obtain a small amount of water. Is added and mixed by stirring, granulated by an extrusion granulator, and dried 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: trade name of Toho Chemical Industry Co., Ltd.) Zansan gum (natural polymer) …… 0.2 parts Sodium benzoate ………… 0.4 parts Propylene glycol ………… 10 Part Water: 58.9 parts The above components except the active ingredient (the compound of the present invention) are uniformly dissolved, then the compound of the present invention is added, and the mixture is stirred well and wet-ground in 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.

[0125]

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.

Example 1 N- (p-methoxyphenylethyl) -3-chloro-1
-Methyl-5-pyrazolecarboxylic acid amide [the compound of the present invention No. Synthesis of 1-123 (a)] 0.5 g of 3-chloro-1-methyl-5-pyrazolecarboxylic acid chloride was dissolved in 30 ml of chloroform.
P-Methoxyphenylethylamine 0.46 was added to this solution.
g was added. Under ice cooling, 0.34 of triethylamine
g was added, and the mixture was stirred at room temperature for 1 hour. 100m water for reaction
After washing with 1, the chloroform layer was dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the crystals of the residue were washed with n-hexane to give the compound N of the present invention.
o. 0.8 g of 1-123 (a) was obtained as colorless crystals. (Melting point 129 to 130 ° C)

Example 2 N- (3-chloro-1-methylpyrazole-5-carbonyl)-(L) -phenylalanine methyl ester [Compound No. of the present invention] 2-286 (a)] Synthesis 1.0 g of 3-chloro-1-methyl-5-pyrazolecarboxylic acid chloride was dissolved in 30 ml of chloroform.
Furthermore, 1.33 g of (L) -phenylalanine methyl ester hydrochloride was added. Triethylamine 1.2 under ice cooling
4 g was added, and the mixture was stirred at room temperature for 18 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 remaining crystals were washed with n-hexane to give the compound No. 1 of the present invention. 1.38 g of colorless crystals of 2-286 (a) was obtained. (Melting point 100-102 ° C)

Example 3 N- (3-chloro-1-methylpyrazole-5-carbonyl) -1-aminopyrrolidine [Compound of the present invention No. 2
Synthesis of −145 (a)] 0.69 g of 1-aminopyrrolidine hydrochloride was dissolved in 20 ml of chloroform and cooled with ice. Triethylamine (1.24 g) was added dropwise thereto, followed by dropwise addition of 3-chloro-1-methyl-5-pyrazolecarboxylic acid chloride (1.0 g), and the mixture was stirred at room temperature for 4 days. 20 ml of water was added, the chloroform layer was separated, and the aqueous layer was diluted with 20 ml of chloroform to 2 times.
It was extracted twice, and the chloroform layers were combined and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, the residue was purified by silica gel chromatography (chloroform), and the compound No. 2-145 (a) colorless crystals 0.78
g was obtained. (Melting point 196.5 to 197.5 ° C)

Example 4 O-Ethyl-N- (3-chloro-1-methylpyrazole-5-carbonyl) -hydroxylamine [Compound No. of the present invention. 2-150 (a)] Synthesis of 3-chloro-1-methyl-5-pyrazolecarboxylic acid chloride (0.66 g), O-ethylhydroxylamine hydrochloride (0.72 g) and chloroform (40 ml) in a mixed solution under ice cooling under triethylamine 1 0.5 g was added dropwise. After stirring at room temperature for one day, 20 ml of water was added, the chloroform layer was separated, the aqueous layer was extracted twice with 10 ml of chloroform, and the chloroform layers were combined and dried over anhydrous sodium sulfate.
After filtration, the solvent was distilled off under reduced pressure, the residue was purified by silica gel chromatography (ethyl acetate / n-hexane = 1/3), and the compound No. 2-150 (a) colorless crystals 0.2
g was obtained. (Melting point 69-72 ° C.) [Example 5] on-hexyl-N- (3-chloro-1-methylpyrazole-5-carbonyl) -hydroxylamine [invention compound No. 2-470 (a)] Synthesis Hydroxylamine hydrochloride 0.7 g was dissolved in water 5 ml, and chloroform 20 ml was added. A solution prepared by dissolving 2.21 g of anhydrous potassium carbonate in 5 ml of water was added dropwise with stirring under ice cooling. Then 3-chloro-1-methyl-5
-A solution of 1.43 g of pyrazolecarboxylic acid chloride dissolved in 4 ml of chloroform was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 2 hours as it was. Then, 10 ml of chloroform and 10 ml of water were added, the chloroform layer was separated, the aqueous layer was extracted once with 20 ml of chloroform, the chloroform layers were combined, washed with 20 ml of water, and then dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure,
1.25 g of N- (3-chloro-1-methylpyrazole-5-carbonyl) -hydroxylamine were obtained.

Next, the above compound was dissolved in 50 ml of ethanol, and a solution prepared by dissolving 0.4 g of potassium hydroxide in 2 ml of water was added under ice cooling. Then 1.18 g of n-hexyl bromide was added. Further anhydrous sodium carbonate 0.9
A solution prepared by dissolving 2 g in 2 ml of water was added, and the mixture was heated under reflux for 1 hour. After cooling, the solvent was distilled off under reduced pressure, 20 ml of water was added to the residue, and the mixture was made acidic with 10% hydrochloric acid. The released oily substance was extracted 3 times with 30 ml of chloroform, and the chloroform layer was
The combined solution was washed with 40 ml of water and then dried over anhydrous sodium sulfate. After filtration, the solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (chloroform) to give a pale yellow oily substance. This was crystallized when it was chilled with ice. After washing with n-hexane while cooling with ice, the crystals were collected by filtration. Inventive Compound No. 2-4
1 g of 70 (a) was obtained as colorless crystals. (Melting point 39-
43 ° C.) [Example 6] Nn-octyl-3-chloro-1-methyl-5-pyrazolecarboxylic acid amide [the compound of the present invention No. 2-46
Synthesis of 3 (a)] 2.83 g of 3-chloro-1-methyl-5-pyrazolecarboxylic acid ethyl ester was dissolved in 30 ml of ethanol. To this solution was added 2.9 g of n-octylamine.
Then, the mixture was heated under reflux for 6 hours. After allowing the reaction solution to cool, the solvent was distilled off under reduced pressure, and 80 ml of chloroform was added to the residue. The chloroform solution was washed 3 times with 30 ml of 10% hydrochloric acid and then twice with 30 ml of water. The chloroform layer was dried over anhydrous sodium sulfate, filtered, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (chloroform). 2-463
3.2 g of (a) was obtained as a colorless oil. (N _D
^22.0 1.5074)

[Reference Example] Synthesis of 3-chloro-1-methyl-5-pyrazolecarboxylic acid chloride 65 g of 3-amino-1-methylpyrazole was added to 55 g of concentrated hydrochloric acid.
Dissolve in 0 ml. 62 g of sodium nitrite was added to 120 ml of water while maintaining a temperature of 0 to 5 ° C under ice cooling.
Was added dropwise. After completion of dropping, stirring was further continued at this temperature for 1 hour. The diazonium solution was added dropwise to a solution prepared by suspending 70 g of cuprous chloride in 500 ml of chloroform. On the way, 20 g of cuprous chloride was added twice.
After the dropping is completed, the reaction is allowed to proceed at 50 ° C. for 5 hours, then at room temperature for
Stir for 5 hours. The solution was filtered through Celite and neutralized by adding sodium carbonate. The chloroform layer was separated, the aqueous layer was further extracted twice with 300 ml of chloroform, and the combined chloroform solution was washed with saturated saline and then dried over anhydrous sodium sulfate. The solvent was concentrated under reduced pressure and distilled under reduced pressure to obtain 52 g of 3-chloro-1-methylpyrazole as a yellow oily substance. (Boiling point: 88-93
C./35 mmHg) Next, 45 g of this compound was added to 100 m of tetrahydrofuran.
It was dissolved in 1. After cooling to −78 ° C., 250 ml of n-butyllithium (1.6M hexane solution) was added dropwise.

After completion of dropping, the mixture was stirred at -78 ° C for 1.5 hours. Carbon dioxide was blown into this solution for about 20 minutes, and then the temperature was raised to room temperature. To this solution was added 150 ml of water, and then 150 ml of 2N hydrochloric acid to adjust the pH to 2
Was adjusted. It was extracted twice with 300 ml of ethyl acetate and dried over anhydrous sodium sulfate. After filtration and concentration under reduced pressure, the obtained crystals were washed with n-hexane and then dried to obtain 52.4 g of naked-color crystals of 3-chloro-1-methyl-5-pyrazolecarboxylic acid. (Melting point 160-163 ° C) 50 g of the carboxylic acid was suspended in 100 ml of benzene, 75 ml of thionyl chloride was added dropwise, and the mixture was heated under reflux for 3 hours. After cooling, the solvent was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain 52 g of the target 3-chloro-1-methyl-5-pyrazolecarboxylic acid chloride. (Boiling point: 78-80
C./2 mmHg) Next, Table 4 shows the 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

Table 4

[0134]

[Table 48] Table 4 (1) Table 4 (2) ─────────────────────────────── Compound No. Physical property value Compound No. Physical property value ─────────────── ──────────────── 1-1 (a) mp 120-121 ℃ 1-35 (a ) mp 119-120 ℃ 1-2 (a) mp 139-140.5 ℃ 1-36 (a) mp 97-98 ℃ 1-3 (a) mp 140-141.5 ℃ 1-37 (a) Oil 1-4 (a) mp 188-189 ℃ 1-38 (a) mp 125-126 ℃ 1-5 (a) mp 158-159 ℃ 1-40 (a) mp 75-77 ℃ 1-6 (a) mp 117- 118 ℃ 1-43 (a) mp 96-97 ℃ 1-7 (a) mp 158-159 ℃ 1-53 (a) mp 89-90 ℃ 1-8 (a) mp 163-164 ℃ 1-57 ( a) mp 112-114 ℃ 1-10 (a) mp 227-237 ℃ 1-60 (a) mp 116-117 ℃ 1-11 (a) mp 175-176 ℃ 1-63 (a) mp 159-162 ℃ 1-13 (a) mp 194-195 ℃ 1-82 (a) mp 147-148 ℃ 1-14 (a) mp 153-154 ℃ 1-104 (a) mp 84-86 ℃ 1-16 (a ) mp 109.5-110.5 ℃ 1-107 (a) mp 103-105 ℃ 1-17 (a) mp 212-214 ℃ 1-123 (a) mp 129-130 ℃ 1-19 (a) mp 196-197 ℃ 1-129 (a) Sticky 1-23 (a) mp 168-170 ℃ 1-172 (a) Sticky 1-24 (a) mp 109-110 ℃ 1-182 (a) mp 115-116 ℃ 1-27 ( a) mp 156-157 ℃ 1-193 (a) mp 185-186 ℃ 1-28 (a) mp 174.5-175.5 ℃ 1-172 (a) Sticky butterfly 1-29 (a) mp 140-141.5 ℃ 1 -182 (a) mp 115-116 ℃ 1-30 (a) mp 162.5-163.5 ℃ 1-193 (a) mp 185-186 ℃ ─────────────── ─── ─────────────

[0135]

[Table 49] Table 4 (3) Table 4 (4) ────────────────────────────── Compound No. Physical property value Compound No. Physical property value ─────────────── ─────────────── 1-203 (a) mp 123-124 ℃ 2-1 (a) mp 117-178 ℃ 1-213 (a) mp 225-226 ℃ 2-2 (a) mp 123-124 ℃ 1-223 (a) mp 156-157 ℃ 2-5 (a) mp 76-77 ℃ 1 -254 (a) mp 199-201 ℃ 2-7 (a) mp 42-44 ℃ 1-265 (a) Oil 2-8 (a) n _D ^19.6 1.5282 1-448 (a) mp 88-90 ℃ 2-10 (a) mp 104-106 ℃ ─────────────── 2-13 (a) n _D ^19.6 1.5169 2-14 (a) n _D ^20.8 1.5144 2-15 ( a) n _D ^20.1 1.5148 2-16 (a) mp 108-109.5 ° C 2-17 (a) mp 138.5-140 ° C 2-18 (a) Oil 2-23 (a) mp 113-115 ° C 2-24 (a) mp 92-94 ℃ 2-25 (a) mp 99-101 ℃ 2-26 (a) mp 117-118 ℃ 2-28 (a) mp 33-34 ℃ 2-48 (a) Oil 2 -115 (a) mp 161-161.5 ℃ 2-121 (a) mp 121-122 ℃ ──────────────────

[0136]

[Table 50] Table 4 (5) Table 4 (6) ──────────────── ───────────────── Compound No. Physical property value Compound No. Physical property value ──────────────── ───────────────── 2-123 (a) n _D ^19.3 1.5802 2-190 ( a) mp 158-162 ℃ 2-124 (a) mp 86-88 ℃ 2-207 (a) mp 86-87 ℃ 2-125 (a) mp 132-133 ℃ 2-208 (a) mp 152-153 ℃ 2-126 (a) n _D ^21.5 1.5410 2-226 (a) mp 128-130 ℃ 2-129 (a) n _D ^20.0 1.5270 2-231 (a) mp 156-157 ℃ 2-131 (a) n _D ^20.0 1.5508 2-235 (a) mp 209-211 ℃ 2-145 (a) mp 196.5-197.5 ℃ 2-236 (a) Oil 2-146 (a) mp 206-207 ℃ 2-242 (a) Oil 2-147 (a) mp 177-178 ℃ 2-243 (a) mp 91-92 ℃ 2-148 (a) mp 151-153 ℃ 2-246 (a) mp 101-103 ℃ 2-149 ( a) mp 82-86 ℃ 2-256 (a) mp 71-74 ℃ 2-150 (a) mp 69-72 ℃ 2-258 (a) mp 86-87.5 ℃ 2-152 (a) mp 52-54 ℃ 2-260 (a) mp 98-99 ℃ 2-154 (a) mp 131-132 ℃ 2-265 (a) mp 145-148 ℃ 2-155 (a) mp 68-70 ℃ 2-266 (a ) n _D ^20.6 1.5101 2-157 (a) mp 93-95 ℃ 2-276 (a) mp 93-94 ℃ 2-158 (a) mp 75-76 ℃ 2-286 (a) mp 100- 102 ° C 2-166 (a) Oily substance 2-287 (a) Viscous substance 2-168 (a) Oily substance 2-288 (a) Viscous substance 2-190 (a) mp 158-162 ° C 2-290 (a) n _D ^20.7 1.5380 ──────────────── ─────────────────

[0137]

[Table 51] Table 4 (7) Table 4 (8) ──────────────── ─────────────────── Compound No. Physical property value Compound No. Physical property value ──────────────── ────────────────── 2-295 (a) mp 96-98 ℃ 2- 366 (a) mp 215-216 ℃ 2-297 (a) mp 113-115 ℃ 2-370 (a) n _D ^20.5 1.5236 2-301 (a) mp 122-123 ℃ 2-374 (a) mp 135- 137 ℃ 2-305 (a) Oil 2-387 (a) n _D ^19.6 1.5146 2-306 (a) mp 38-40 ℃ 2-391 (a) n _D ^19.5 1.5084 2-307 (a) n _D ^20.6 1.5286 2-398 (a) mp 69-70 ℃ 2-308 (a) n _D ^20.7 1.5152 2-422 (a) mp 67-69 ℃ 2-309 (a) n _D ^20.9 1.5249 2-429 (a) mp 49-51 ℃ 2-314 (a) mp 165-167 ℃ 2-432 (a) Oily substance 2-317 (a) mp 185-187 ℃ 2-436 (a) n _D ^21.4 1.5447 2-318 (a) mp 144-146 ℃ 2-438 (a) Oily matter 2-321 (a) mp107-108 ℃ 2-441 (a) mp 189-191 ℃ 2-331 (a) Viscous material 2-444 (a) Viscosity Butterflies 2-332 (a) mp 67-69 ℃ 2-446 (a) mp 60-63 ℃ 2-333 (a) mp 54-56 ℃ 2-150 (g) n _D ^19.8 1.5401 2-334 (a ) mp 167-168 ℃ 2-422 (g) mp 96-97 ℃ 2-335 (a) mp 123-125 ℃ 2-156 (a) mp 55-58 ℃ 2-33 6 (a) mp 93-95 ℃ 2-11 (a) n _D ^22.0 1.5160 2-337 (a) n _D ^20.5 1.5074 2-153 (a) mp 66-68 ℃ 2-340 (a) Oil 2- 151 (a) mp 61-62 ℃ ──────────────── ───────────────────

[0138]

[Table 52] Table 4 (9) Table 4 (10) ────────────────────────────────── Compound No. Physical property value Compound No. Physical property value ──────────────── ───────────────── 2-286 (g) mp 96-97 ℃ 2-481 (a) n _D ^21.5 1.5364 2-437 (a) Oil 2-485 (a) n _D ^21.9 1.5042 2-448 (a) mp 41-43 ° C 2-486 (a) n _D ^22.0 1.5103 2-449 ( a) mp 87-89 ℃ 2-491 (a) mp 110-112 ℃ 2-450 (a) mp 30-32 ℃ 2-492 (a) Oil 2-452 (a) mp 78-83 ℃ 2- 494 (a) mp 107-109 ℃ 2-456 (a) Oil 2-495 (a) mp 101-104 ℃ 2-461 (a) mp 142-143 ℃ 2-496 (a) mp 119-120 ℃ 2-462 (a) n _D ^22.0 1.5102 2-497 (a) mp 124-125 ℃ 2-463 (a) n _D ^22.0 1.5074 2-498 (a) Sticky butterfly 2-464 (a) n _D ^22.1 1.5058 ───────────────── 2-466 (a) mp108-110 ℃ 2-468 (a) n _D ^20.1 1.5316 2-469 (a) n _D ^22.3 1.5597 2-470 (a) mp 39-43 ℃ 2-471 (a) Sticky material 2-472 (a) n _D ^21.2 1.4990 2-473 (a) n _D ^22.0 1.4920 2-474 (a) n _D ^19.1 1.5033 2-475 (a) n _D ^22.1 1.5594 ──────────────────

[0139]

[Table 53] Table 4 (11) Table 4 (12) ─────────────────────────────── Compound No. Physical property value Compound No. Physical property value ─────────────── ──────────────── 3-2 (a) mp 101-102 ℃ 3-44 (a) ) Sticky material 3-3 (a) Oily material 3-45 (a) Sticky material 3-7 (a) mp 128-130 ℃ 3-46 (a) mp 88-91 ℃ 3-8 (a) mp 136-138 ℃ 3-47 (a) Sticky material 3-10 (a) mp 125-126 ℃ 3-48 (a) Sticky material 3-12 (a) mp 145-146 ℃ ────── ────────── 3-13 (a) mp 161-163 ℃ 3-15 (a) mp 164-167 ℃ 3-17 (a) mp 143-144 ℃ 3-18 (a) mp 163-165 ℃ 3-22 (a) mp 206-207 ℃ 3-23 (a) mp 124-125 ℃ 3-24 (a) mp 117-118 ℃ 3-25 (a) mp 96-99 ℃ 3- 30 (a) n _D ^19.4 1.5294 3-31 (a) n _D ^20.1 1.5301 3-35 (a) n _D ^20.1 1.5270 3-38 (a) n _D ^19.4 1.5241 3-41 (a) n _D ^20.1 1.5382 ── ──────────────

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 drug 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 cubens)
is) spore suspension (2 × 10 ⁵ cells / ml),
It was placed in an inoculation box at a temperature of 25 ° C. and a humidity of 95% or more for one day.
Then, it was placed in a greenhouse and the ratio of the lesion area formed 7 days after inoculation to the inoculated leaves was measured, and the control value was calculated according to the following formula.

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.

Inventive Compound No. 2-121 (a), No. Two
-235 (a), No. 2-243 (a), No. 2-287 (a), N
o. 2-306 (a), No. 2-307 (a), No. 2-308
(a), No. 2-331 (a), No. 2-333 (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 the rice with the fungus in a relative humidity of 95 to 100% at about 24 ° C. for 24 hours, the rice was left in a greenhouse, and after about one week, the degree of disease was examined in 6 stages of 0 to 5. (Survey Criteria) Disease Index Degree of disease 0 No disease 1 Number of lesions 1-5 2 Number of lesions 6-20 3 Number of lesions 21-40 4 Number of lesions 41-70 5 Number of lesions 71 or more As a result, the following The compound showed a morbidity index of 1.

Inventive Compound No. 1-4 (a), No. 1
-5 (a), No. 1-6 (a), No. 1-7 (a), N
o. 1-8 (a), No. 1-10 (a), No. 1-11 (a)
, No. 1-14 (a), No. 1-17 (a), No. 1-1
9 (a), No. 1-23 (a), No. 1-24 (a), No.
1-28 (a), No. 1-35 (a), No. 1-36 (a), N
o. 1-37 (a), No. 1-38 (a), No. 1-39 (a)
, No. 1-40 (a), No. 1-43 (a), No. 1-5
3 (a), No. 1-57 (a), No. 1-60 (a), No.
1-63 (a), No. 1-82 (a), No. 1-104 (a), N
o. 1-107 (a), No. 1-123 (a), No. 1-129
(a), No. 1-172 (a), No. 1-182 (a), No. 1
-203 (a), No. 1-213 (a), No. 1-254 (a), N
o. 1-265 (a), No. 2-1 (a), No. 2-2 (a)
, No. 2-5 (a), No. 2-7 (a), No. 2-
8 (a), No. 2-13 (a), No. 2-14 (a), No.
2-15 (a), No. 2-23 (a), No. 2-24 (a), N
o. 2-25 (a), No. 2-26 (a), No. 2-121
(a), No. 2-123 (a), No. 2-124 (a), No. 2
-125 (a), No. 2-126 (a), No. 2-131 (a), N
o. 2-145 (a), No. 2-146 (a), No. 2-147
(a), No. 2-148 (a), No. 2-149 (a), No. 2
-150 (a), No. 2-152 (a), No. 2-154 (a), N
o. 2-155 (a), No. 2-157 (a), No. 2-158
(a), No. 2-168 (a), No. 2-190 (a), No. 2
-207 (a), No. 2-208 (a), No. 2-226 (a), N
o. 2-231 (a), No. 2-236 (a), No. 2-242
(a), No. 2-243 (a), No. 2-246 (a), No. 2
-258 (a), No. 2-260 (a), No. 2-265 (a), N
o. 2-266 (a), No. 2-276 (a), No. 2-286
(a), No. 2-287 (a), No. 2-288 (a), No. 2
-290 (a), No. 2-295 (a), No. 2-297 (a), N
o. 2-301 (a), No. 2-305 (a), No. 2-306
(a), No. 2-307 (a), No. 2-308 (a), No. 2
-314 (a), No. 2-317 (a), No. 2-318 (a), N
o. 2-321 (a), No. 2-331 (a), No. 2-332
(a), No. 2-334 (a), No. 2-335 (a), No. 2
-336 (a), No. 2-370 (a), No. 2-374 (a), N
o. 2-387 (a), No. 2-422 (a), No. 2-429
(a), No. 2-436 (a), No. 2-437 (a), No. 2
-440 (a), No. 2-443 (a), No. 2-445 (a), N
o. 2-150 (g), No. 2-422 (g), No. 3-3 (a)
, No. 3-7 (a), No. 3-10 (a), No. 3-1
3 (a), No. 3-15 (a), No. 3-30 (a), No.
3-31 (a), No. 3-35 (a), No. 3-38 (a), N
o. 3-46 (a), No. 2-286 (g), No. 2-437
(a), No. 2-463 (a), No. 2-11 (a), No. 2
-470 (a), No. 2-448 (a), No. 2-449 (a), N
o. 2-484 (a), No. 2-464 (a), No. 2-462
(a), No. 2-489 (a), No. 2-469 (a), No. 2
-472 (a), No. 2-473 (a), No. 2-471 (a), N
o. 2-156 (a), No. 2-450 (a), No. 2-474 (a)

[0145]

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 A01N 43/824 A01N 43/84 101 43/84 101 C07D 401/12 231 C07D 401/12 231 403 / 06 203 403/06 203 203 207 207 209 209 403/12 231 403/12 231 405/12 231 405/12 231 409/12 231 409/12 231 413/06 231 413/06 231 413/12 231 413/12 231 417/12 231 417/12 231 A01N 43/82 101C (72) Inventor Toshiaki Takeyama 722 Tsuboi-cho, Funabashi-shi, Chiba 1 Nissan Chemical Industry Co., Ltd. Central Research Laboratory (72) Inventor Takamasa Kikuchi Tsuboi, Funabashi-shi, Chiba 722, Machi 1 Central Research Laboratory, Nissan Chemical Industries, Ltd. (72) Inventor, Junichi Watanabe 722, Tsuboi-cho, Funabashi, Chiba Prefecture Industrial Chemistry Co., Ltd. Central Research Institute (72) Inventor Hiroshi Oyaku 1470 Shiraoka, Shiraoka-cho, Minami Saitama-gun, Saitama Nissan Chemical Industry Co., Ltd.Biological Research Institute (72) Masanori Nishioka Shiraoka, Shirooka-cho, Minami-Saitama-gun, Saitama 1470 Nissan Kagaku Kogyo Co., Ltd.Biological Sciences Research Institute (72) Inventor Takashi Furusato Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama 1470 Nissan Kagaku Kogyo Co., Ltd.

Claims (20)

[Claims] 1. A compound of the general formula (1)[In the above formula, X is a halogen atom, R¹Is C₁~ C_FourAn alkyl group, W is an oxygen atom or a sulfur atom, R^TwoAnd R^ThreeAre each independently a hydrogen atom, C₁~
C_TenAlkyl group, C_Two~ C₆Alkenyl group, C_Two~ C_Ten
Alkynyl group, C_Three~ C_TenCycloalkyl group, substituted
Optionally aryl C_Two~ C_FourAlkenyl group,-[C
(R^Four) (R^Five)]_p-R⁶Group, -CO- (O)_m-[C
(R^Four) (R^Five)]_p-R⁷Group, -S (O)_n-R⁷Group,
-CON (R⁸) (R⁹) Group, -N (R⁸) (R⁹) Group,-
N = C (R^Ten) (R¹¹) Group or -OR¹²If and if
Depending on R^TwoAnd R^ThreeTogether with C_Two~ C_Tenring
Forming a linear alkylene or oxygen, sulfur or nitrogen atom
C containing_Two~ C₆Forms a cyclic alkylene, and optionally
Is C on the ring₁~ C₆Alkyl group or C₁~ C_FourAl
It may be substituted with a cooxycarbonyl group, p is 0 or an integer of 1 to 8, m is 0 or 1, n is 0, 1 or 2, and R^FourAnd R^FiveAre each independently a hydrogen atom, a halogen
Atom, C₁~ C₆Alkyl group, C_Two~ C₆Alkenyl
Group, C_Two~ C₆Alkynyl group, C₁~ C₆Haloalkyl
Group, C_Two~ C₆Haloalkenyl group, C_Two~ C₆Haloal
Quinyl group, C_Three~ C₆Cycloalkyl group, C₁~ C₆A
Lucoxy group, C₁~ C₆Haloalkoxy group, substituted
Optionally substituted aryl group, optionally substituted hetero group
Reel group, optionally substituted benzyl group, C₁~ C
_FourAlkylcarbonyl group, C₁~ C₆Alkoxycarbo
Nyl group, hydroxycarbonyl group, C₁~ C_FourAlkyl
Thio C₁~ C_FourAlkyl group, C₁~ C_FourAlkylsulf
Inil C₁~ C_FourAlkyl group, C₁~ C_FourAlkylsul
Honil C₁~ C_FourAlkyl group or C₁~ C_FourAlkyl
Oxy C₁~ C_FourAn alkyl group, and in some cases,
R^FourAnd R^FiveTogether with C_Three~ C₆Cycloalkyl
May form a group, R⁶Is a hydrogen atom, a halogen atom, C₁~ C_TenAlkyl
Group, C_Two~ C_TenAlkenyl group, C_Two~ C_TenAlkynyl
Group, C₁~ C_TenHaloalkyl group, C_Two~ C_TenHalo arche
Nyl group, C_Two~ C_TenHaloalkynyl group, C_Three~ C_TenShiku
Lower alkyl group, C ₁~ C_TenAlkoxy group, C₁~ C₆
Haloalkoxy group, C_Two~ C₆Haloalkenyloxy
Group, C_Two~ C₆Haloalkynyloxy group, C_Three~ C₆Shi
Chloroalkyloxy group, optionally substituted aryl
Group, optionally substituted heteroaryl group, substituted
Optionally substituted heterocyclyl group, optionally substituted
Aryloxy group, optionally substituted heteroari
Group, hydroxyl group, C₁~ C₆Alkylcarbonyl
Oxy group, optionally substituted arylcarbonyl group
Xy group, -S (O)_n-R¹³Group, C₁~ C₆Alkoxy
Carbonyl group, hydroxycarbonyl group, -CON (R
¹⁴) (R^Fifteen) Group or -N (R¹⁴) (R^Fifteen) Group, R
⁷Is a hydrogen atom, C₁~ C₆Alkyl group, C_Two~ C₆A
Lucenyl group, C_Two~ C₆Alkynyl group, C₁~ C₆Halo
Alkyl group, -N (R¹⁴) (R^Fifteen) Group, even if substituted
Good aryl group, optionally substituted benzyl group,
Is an optionally substituted heteroaryl group, R⁸And R⁹Are each independently a hydrogen atom, C₁~
C_TenAlkyl group, C_Two~ C_TenAlkenyl group, C_Two~ C_Ten
Alkynyl group, C_Three~ C_TenCycloalkyl group, C₁~ C
_TenHaloalkyl group, C_Two~ C_TenHaloalkenyl group, C_Two
~ C_TenHaloalkynyl group, optionally substituted aryl
Group, optionally substituted benzyl group, substituted
Optionally a heteroaryl group, C₁~ C₆Alkyl carb
Nyl group, C₁~ C₆Haloalkylcarbonyl group, substituted
Optionally substituted arylcarbonyl group, substituted
Good heteroarylcarbonyl group, C₁~ C₆Arco
A oxycarbonyl group or a formyl group, and in some cases
For R⁸And R⁹Together with C_Three~ C_TenRing Al
Forms xylene or contains oxygen, sulfur or nitrogen atoms
C_Two~ C₆R may form a cyclic alkylene, R^TenAnd R¹¹Are each independently a hydrogen atom, C₁~
C₆Alkyl group, C₁~ C₆Haloalkyl group, C_Three~ C
₈Cycloalkyl group or optionally substituted aryl
R¹²Is a hydrogen atom, C₁~ C_TenAlkyl group, C_Two~ C_Ten
Alkenyl group, C_Two~ C_TenAlkynyl group, C₁~ C_TenHa
Lower alkyl group, C_Two~ C_TenHaloalkenyl group, C_Three~ C
_TenCycloalkyl group, optionally substituted benzyl
Group, optionally substituted aryl C_Two~ C_FourAlkyl
Group, optionally substituted aryl C_Two~ C_FourAlkenyl
Group, optionally substituted aryl group, C₁~ C₆Al
Coxy C₁~ C₆Alkyl group, C₁~ C₆ Dialkylur
Mino C₁~ C₆ Alkyl group, C ₁~ C₆ Alkylthio C
₁~ C₆ Alkyl group, C₁~ C₆Alkoxycarbonyl
C₁~ C₆Alkyl group, optionally substituted phenyl
Oxy C₁~ C₆Alkyl group, trimethylsilylethyl
Group, R¹³Is C₁~ C₆Alkyl group, C₁~ C₆Haloalk
R group or an optionally substituted aryl group, R¹⁴And R^FifteenAre each independently a hydrogen atom, C₁~
C₆Alkyl group, C_Two~ C₆Alkenyl group, C_Two~ C₆
Alkynyl group, optionally substituted aryl group, substituted
Optionally substituted benzyl group or optionally substituted
A heteroaryl group, optionally R¹⁴And R
^FifteenTogether with C_Three~ C₈Forming a cyclic alkylene
And the expression "optionally substituted" means hydrogen source
In addition to the halogen atom, cyano group, nitro
Group, C₁~ C_FourAlkyl group, C₁~ C_FourAn alkoxy group,
C₁~ C_FourHaloalkyl group, C₁~ C_FourHaloalkoxy
Group, aryl group, aryloxy group, benzyloxy
Group, C_Three~ C₆Cycloalkyl group, C₁~ C_FourAlkoki
Cicarbonyl group, C₁~ C_FourAlkylthio group, C₁~ C
_FourHaloalkylthio group, C₁~ C_FourAlkylsulfini
Group, C₁~ C_FourAlkylsulfonyl group, styryl group,
Amino group, C₁~ C_FourAn alkoxycarbonylamino group,
C₁~ C_FourAlkoxycarbonyloxy group, aminocal
The term “aryl” means a carbonyl group or a hydroxycarbonyl group, and the expression “aryl” means benzene and naphthalene.
An aromatic compound is meant, and the expression "heteroaryl" means a 5-membered ring, a 6-membered ring or
These fused-ring aromatic heterocyclic compounds or benzene rings
An aromatic heterocyclic compound fused with, and the expression "heterocyclyl" means
A non-aromatic heterocyclic compound is meant. ] Represented by 5
Pyrazolecarboxylic acid amide derivative. 2. X is a chlorine atom or a bromine atom,
The 5-pyrazolecarboxylic acid amide derivative according to claim 1, wherein R ¹ is a methyl group, and W is an oxygen atom or a sulfur atom. 3. X is a chlorine atom or a bromine atom,
R¹Is a methyl group, W is an oxygen atom, R^Two
Is a hydrogen atom, C₁~ C_TenAlkyl group, C₁~ C_TenAl
Coxy group, optionally substituted benzyl group, formyl
Group, C₁~ C ₆Alkylcarbonyl group, substituted
Optionally substituted arylcarbonyl group, optionally substituted arylcarbonyl group
Teloarylcarbonyl group or C₁~ C₆Alkoxy
A 5-pyrazolecar according to claim 1, which is a carbonyl group.
Bonamide derivative. 4. X is a chlorine atom or a bromine atom,
R¹Is a methyl group, W is an oxygen atom, R^Two
Is a hydrogen atom, C₁~ C_TenAlkyl group, C₁~ C_TenAl
Coxy group, optionally substituted benzyl group, formyl
Group, C₁~ C ₆Alkylcarbonyl group, substituted
Optionally substituted arylcarbonyl group, optionally substituted arylcarbonyl group
Teloarylcarbonyl group or C₁~ C₆Alkoxy
A carbonyl group, R^Three,-[C (R^Four)
(R^Five)]_p-R⁶Group, -S (O)_n-R⁷Group, -N
(R⁸) (R⁹) Group or -OR¹²And R is^TwoAnd R
^ThreeBut together C_Two~ C_TenForming a cyclic alkylene,
C on the ring₁~ C₆Alkyl group or C₁~ C_FourA
The lucoxycarbonyl group may be substituted,
The listed 5-pyrazolecarboxylic acid amide derivatives. 5. A chlorine atom, R ¹ is a methyl group, W is an oxygen atom, R ² is a hydrogen atom,
A C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group or a benzyl group, R ³ represents a C ₁ -C ₁₀ alkyl group,
[C (R ⁴ ) (R ⁵ )] _p —R ⁶ group, R ⁴ and R
⁵ is a hydrogen atom, a C ₁ -C ₄ alkyl group or a benzyl group, and R ⁶ is an optionally substituted phenyl group, an optionally substituted heteroaryl group, or an optionally substituted heterocyclyl. 5. The 5-pyrazolecarboxylic acid amide derivative according to claim 1, wherein the 5-pyrazolecarboxylic acid amide derivative is a group and p is 0, 1 or 2. 6. X is a chlorine atom, R ¹ is a methyl group, W is an oxygen atom, R ² is a hydrogen atom,
C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group or a benzyl group, R ^{3 is, - [C (R 4)} (R 5)]
a _p -R ⁶ group, R ^4, R ⁵ is a hydrogen atom, C ₁ -C ₄
Alkyl group, benzyl group, C ₁ -C ₄ alkylthio C ₁
To C ₄ alkyl group, C _{1 to} C ₄ alkylsulfonyl C ₁
To C ₄ alkyl group, R ⁶ is a C _{1 to} C ₆ alkoxy group, a hydroxyl group or a C _{1 to} C ₆ alkoxycarbonyl group, and p is 0, 1 or 2.
Pyrazolecarboxylic acid amide derivative. 7. X is a chlorine atom and R¹But methyl
A group, W is an oxygen atom, R^TwoBut the hydrogen atom,
C₁~ C_TenAlkyl group, C₁~ C_TenAn alkoxy group or
A benzyl group, R^ThreeBut S (O)_n-R⁷Group, -N
(R⁸) (R ⁹) Group or -OR¹²And R is⁷But,
C₁~ C₆Alkyl group, optionally substituted phenyl group
Or -N (R¹⁴) (R^Fifteen) Group, R¹⁴, R^FifteenIs C
₁~ C_FourAn alkyl group, n is 2, R⁸And R⁹Are each independently a hydrogen atom or
Optionally substituted phenyl group, optionally substituted benzene group
Dil group, optionally substituted heteroaryl group, C₁
~ C₆An alkylcarbonyl group, which may be substituted
Nzoyl group or C₁~ C₆With an alkoxycarbonyl group
Yes, in some cases R⁸And R⁹Together with C
_Three~ C_TenR may form a cyclic alkylene, R¹²Is a hydrogen atom, C₁~ C_TenAlkyl group, C_Two~ C_Ten
Alkenyl group, C_Two~ C_TenHaloalkenyl group, C₁~ C
_FourAlkoxycarbonyl C₁~ C_FourAlkyl group, substituted
Optionally substituted phenyl group, optionally substituted benzene group
A dil group or an optionally substituted phenylethyl group
A 5-pyrazolecarboxylic acid amide derivative according to claim 1.
conductor. 8. X is a chlorine atom, R ¹ is a methyl group, W is an oxygen atom, and R ² and R ³ are taken together to form a C ₂ -C ₁₀ cyclic alkylene. And optionally a C ₁ -C ₆ alkyl group or C ₁
The 5-pyrazolecarboxylic acid amide derivative according to claim 1, which may be substituted with a C ₄ alkoxycarbonyl group. 9. X is a chlorine atom, R ₁ is a methyl group, W is an oxygen atom, R ² is a hydrogen atom, and R is
The 5-pyrazolecarboxylic acid amide derivative according to claim _{1, wherein} ³ is a C ₁ -C ₁₀ alkyl group. 10. X is a chlorine atom, R ₁ is a methyl group, W is an oxygen atom, R ² is a hydrogen atom,
The 5-pyrazolecarboxylic acid amide derivative according to claim 1, wherein R ³ is a C _{1 to} C ₁₀ alkoxy group or a C _{2 to} C ₁₀ alkenyloxy group. 11. X is a chlorine atom, R ₁ is a methyl group, W is an oxygen atom, R ² is a hydrogen atom or an optionally substituted benzyl group, and R ³ is-[C
(R ⁴ ) (R ⁵ )] _p —R ⁶ group, and P is 1 or 2
R ⁴ is a hydrogen atom, a methyl group or an ethyl group, R ⁵ is a hydrogen atom, a methyl group, an i-propyl group, a benzyl group or a methylthioethyl group, and R ⁶ is a methoxycarbonyl group or an ethoxycarbonyl group. A 5-pyrazolecarboxylic acid amide derivative according to claim 1, which is a propyloxycarbonyl group or a t-butoxycarbonyl group. 12. X is a chlorine atom, R ¹ is a methyl group, W is an oxygen atom, and R ² is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an allyl group or a t-butyl group. And R ³ is a —N (R ⁸ ) (R ⁹ ) group, and R ⁸
Is a hydrogen atom, methyl group, ethyl group, isopropyl group, allyl group, t-butyl group, formyl group, acetyl group, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, and R ⁹ is a hydrogen atom, methyl A 5-pyrazolecarboxylic acid amide derivative according to claim 1, which is a group, and R ⁸ and R ⁹ may be combined to form a C ₄ cyclic alkylene. 13. X is a chlorine atom, R ¹ is a methyl group, W is an oxygen atom, and R ² is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a cyclopropyl group, a methoxy group, ethoxy. A 5-pyrazolecarboxylic acid amide derivative according to claim 1, wherein R ³ is a group, R ³ is a S (O) _n —R ⁷ group, n is 2, and R ⁷ is a methyl group or a dimethylamino group. 14. X is a chlorine atom, R ¹ is a methyl group, W is an oxygen atom, R ² and R ³ together are a C ₄ cyclic alkylene, and C ₁ to The 5-pyrazolecarboxylic acid amide derivative according to claim 1, which is substituted with a C ₄ alkoxycarbonyl group. 15. The 5-pyrazolecarboxylic acid amide derivative according to claim 1, which is selected from the following (1) to (7). (1) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) isobutyramide (2) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -n-hexylamide (3) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -n-octylamide (4) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -n-decanylamide (5) N- (3- Chloro-1-methyl-5-pyrazolecarbonyl) -tetrahydrofurfurylamide (6) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -4-methylanilide (7) N-dimethylsulfamoyl -N-ethyl-3-
Chloro-1-methyl-5-pyrazolecarboxylic acid amide 16. The 5-pyrazolecarboxylic acid amide derivative according to claim 1, which is selected from the following (1) to (15): (1) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -glycine methyl ester (2) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -alanine methyl ester (3) N -(3-Chloro-1-methyl-5-pyrazolecarbonyl) -valine methyl ester (4) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -phenylalanine methyl ester (5) N- (3- Chloro-1-methyl-5-pyrazolecarbonyl) -phenylalanine ethyl ester (6) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -methionine methyl ester (7) N- (3-chloro-1- Methyl-5-pyrazolecarbonyl) -methionine ethyl ester (8) N- (3-chloro-1-methyl-5-pyrazole carbonyl ) -Methionine-n-propyl ester (9) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -methionine-t-butyl ester (10) N- (3-chloro-1-methyl-5) -Pyrazolecarbonyl) -proline methyl ester (11) N-benzyl-N- (3-chloro-1-methyl-
5-Pyrazolecarbonyl) -β-alanine ethyl ester (12) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -β-methylalanine methyl ester (13) N- (3-chloro-1-methyl -5-pyrazolecarbonyl) -2,2-dimethylethanolamide (14) N- (3-bromo-1-methyl-5-pyrazolecarbonyl) -phenylalanine methyl ester (15) N- (3-chloro-1-methyl -5-Pyrazolecarbonyl) -dimethylglycine methyl ester 17. The 5-pyrazolecarboxylic acid amide derivative according to claim 1, which is selected from the following (1) to (20). (1) O-methyl-N- (3-chloro-1-methyl-5
-Pyrazolecarbonyl) -hydroxylamine (2) O-ethyl-N- (3-chloro-1-methyl-5)
-Pyrazolecarbonyl) -hydroxylamine (3) O-n-propyl-N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (4) O-i-propyl-N- (3-chloro -1-Methyl-5-pyrazolecarbonyl) -hydroxylamine (5) O-n-butyl-N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (6) O-s-butyl- N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (7) O-i-butyl-N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (8) O-t-butyl-N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (9) O-allyl-N- (3-chloro-1- Methyl-5
-Pyrazolecarbonyl) -hydroxylamine (10) O-methallyl-N- (3-chloro-1-methyl-
5-Pyrazolecarbonyl) -hydroxylamine (11) O-n-pentyl-N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (12) On-hexyl-N- (3- Chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (13) O-n-heptyl-N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (14) O-n-octyl -N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (15) On-nonyl-N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (16) ) On-decanyl-N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -hydroxylamine (17) O-ethyl-N- (3 Chloro-1-methyl-5
-Pyrazolecarbonyl) -N-dimethylsulfamoyl-hydroxylamine (18) O-benzyl-N- (3-chloro-1-methyl-
5-Pyrazolecarbonyl) -hydroxylamine (19) O-ethyl-N- (3-bromo-1-methyl-5)
-Pyrazolecarbonyl) -hydroxylamine (20) O-methyl-N- (3-chloro-1-methyl-5)
-Pyrazolecarbonyl) -N-methyl-hydroxylamine 18. The 5-pyrazolecarboxylic acid amide derivative according to claim 1, which is selected from the following (1) to (16): (1) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N-methylhydrazine (2) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N-ethylhydrazine (3 ) N- (3-Chloro-1-methyl-5-pyrazolecarbonyl) -N-i-propylhydrazine (4) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N-allylhydrazine (5 ) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -Nt-butylhydrazine (6) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N'-methylhydrazine ( 7) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N'-ethylhydrazine (8) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N'-i-p Ropyrhydrazine (9) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N'-allylhydrazine (10) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N ' -T-Butylhydrazine (11) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -1-aminopyrrolidine (12) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N ′ -Formylhydrazine (13) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N′-acetylhydrazine (14) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N ′ -Methoxycarbonylhydrazine (15) N- (3-chloro-1-methyl-5-pyrazolecarbonyl) -N′-ethoxycarbonylhydrazine (16) N- (3-chloro Ro-1-methyl-5-pyrazolecarbonyl) -N′-t-butoxycarbonylhydrazine 19. Claims 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
A plant disease controlling agent, which comprises, as an active ingredient, one or more of the 5-pyrazolecarboxylic acid amide derivatives according to 17 or 18. 20. The plant disease controlling agent according to claim 19, wherein the plant disease is rice blast.