JPH0665237A - Substituted pyrazole derivative and germicide for agriculture and horticulture - Google Patents

Abstract

PURPOSE:To provide a novel compound useful as a germicide for agriculture and horticulture. CONSTITUTION:A compound of formula I [R<1> is halogen, (halo)alkyl, alkoxy, alkylthio; R<2> is (halo)alkyl; X is -N(R<3>)-, -CO-, -C(R<4>)(R<5>)-; Y is -O-,-S(O)-; (n) is 0-2; R<3> is H, alkanoyl, etc.; R<4>, R<5> are H, halogen, alkoxy, etc.; A is (substituted)phenyl; B is (substituted)heterocyclic group], e.g. 2-pyridyl-(4-(4- chlorophenylthio)-1,3-dimethyl-5-pyrazolyl)methanol. The compound of formula I is obtained by reacting a substituted pyrazole of formula II (X is -N(R<3>)-) with a heterocyclic compound of formula: L-B (L is a releasing group such as halogen), if necessary, in the presence of a base in a solvent. The compound of formula I is useful for plant diseases such as gray mold, rice sheath blight, melon downy mildew, and the melanose, powdery mildew, bitter rot and epidemic of citruses.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel pyrazole derivative and an agricultural / horticultural fungicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Various bactericides have been developed so far, but they are not always satisfactory because of their efficacy and appearance of resistant bacteria. Also, JP-A 1-125379, EP
-459333A1 and JP-A-3-141276 describe that certain pyrazole derivatives have bactericidal activity.

[0003]

The compounds described in the above publications are not satisfactory in terms of potency, residual efficacy, phytotoxicity, etc., and are more useful for plant and garden diseases. Development of a bactericide is desired.

[0004]

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

[0005]

[Chemical 2]

[In the above formula, R ¹ represents a halogen atom, an alkyl group, an alkoxy group, an alkylthio group or a haloalkyl group, R ² represents an alkyl group or a haloalkyl group, and X represents —N (R ³ ). -, -CO- or ^{-C (R 4) (R 5} ) - represents, R ³ represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a -COR ⁶ or -SO ₂ R ⁷ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group or —OR ⁸ , and R ⁸ is a hydrogen atom, an alkyl group, a haloalkyl group or an alkenyl group. , An alkynyl group,
Alkoxyalkyl group, cyanoalkyl group, alkylcarbonylalkyl group, alkoxycarbonylalkyl group, unsubstituted or substituted phenylalkyl group, -COR ⁶ or -SO ₂ R ⁷ represents, R ⁶ is a hydrogen atom, an alkyl group Represents a haloalkyl group, an unsubstituted or substituted phenyl group, an unsubstituted or substituted phenylalkyl group, an alkoxy group or -N (R ⁹ ) (R ¹⁰ ),
R ⁷ represents an alkyl group, a haloalkyl group, an unsubstituted or substituted phenyl group or —N (R ⁹ ) (R ¹⁰ ), and R ⁹
And R ¹⁰ each independently represent a hydrogen atom, an alkyl group or an unsubstituted or substituted phenyl group,
Y represents an oxygen atom, -S-, -SO-, or -SO ₂ - represents, A
Represents an unsubstituted or substituted phenyl group,
B represents an unsubstituted or substituted heterocyclic group.
Provided that R ¹ is an alkyl group, X is —N (R ³ ) —, and B is
The case of an unsubstituted 2-pyridyl group, an unsubstituted 2-pyrimidyl group or an unsubstituted 2-pyrazyl group is excluded. ] It is related with the substituted pyrazole derivative represented by these, or its salt, and the agricultural and horticultural germicide containing this derivative as an active ingredient.

In the present invention, the substituents in the above formula have the following meanings. The halogen atom means fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine. The number of carbon atoms of the alkyl of the alkyl group, the alkoxy group and the alkylthio group means 1 to 6, for example, methyl, ethyl, n- or i-propyl, n-,
s-, i- or t-butyl, pentyl, hexyl,
Methoxy, ethoxy, n- or i-propoxy, n
-, S-, i- or t-butoxy, pentoxy, hexoxy, methylthio, ethylthio, n- or i-
Examples include propylthio, n-, s-, i- or t-butylthio. Preferably, methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, s-, i- or t-butoxy. Is mentioned.

The number of carbon atoms of the alkyl of the haloalkyl group is 1 to
6 means, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, trifluoroethyl, trichloroethyl, trifluoropropyl and the like. The phenyl group having a substituent has 1 to 5 substituents, and the types of the substituents may be the same or different. Examples of the substituent include a phenyl group substituted with a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkylthio group, a nitro group, a cyano group and the like. However, n in the above definition is normal, i is iso, s is secondary,
t represents tertiary.

The above-mentioned heterocyclic ring represented by B is a 5- or 6-membered heterocyclic ring containing one or more nitrogen atoms or a condensed heterocyclic ring containing one or more nitrogen atoms, such as pyridine, pyrimidine, Examples thereof include pyridazine, pyrazine, triazine, pyrrole, pyrazole, imidazole, thiazole and oxazole. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group and the like.

The substituent for R ¹ is preferably a lower alkyl group or a halogen atom, more preferably a halogen atom. The substituent of R ² preferably represents an alkyl group. Y preferably represents a -S-, X is preferably -N (R ³⁾ - represents, R ³ preferably represents a hydrogen atom or -CHO. A is preferably a halogen atom,
Represents a phenyl group having at least one substituent selected from an alkyl group and a haloalkyl group, and B is preferably a pyridyl group having an unsubstituted or halogen atom as a substituent, or a pyrimidyl group having an unsubstituted or substituent halogen atom. Represents

The compounds of the present invention represented by the formula [1] are shown in Table 1. However, the compound of the present invention is not limited to these. Compound No. is referred to in the description below. In the tables, Ph represents a phenyl group, i represents iso, t represents tertiary, Et represents ethyl group, and Pr represents propyl group.

Table 1

[0013]

[Chemical 3]

In the compound represented by

[0015]

[Table 1] ────────────────────────────── Compound No. R ¹ R ² X Y W _n B ──── ────────────────────────── 1 Cl CH ₃ NH S 4-Cl B1 2 Cl CH ₃ NH S 2,4-Cl ₂ B1 3 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B1 4 Cl CH ₃ NCHO S 4-Cl B1 5 Cl CH ₃ NH S 4-CH ₃ B1 6 Cl CH ₃ NH S 2,4-Cl ₂ B1 7 Cl CH ₃ NH S 2,3-Cl ₂ B1 8 CH ₃ O CH ₃ NH S 4-Cl B1 9 CH ₃ O CH ₃ NH S 3-Cl, 4-CH ₃ B1 10 CH ₃ O CH ₃ NH S 2, 4-Cl ₂ B1 11 CH ₃ O CH ₃ NH S 2-F, 4-CH ₃ B1 12 CH ₃ O CH ₃ NH S 3-F, 4-CH ₃ B1 13 CH ₃ O CH ₃ NCHO S 2,4 -Cl ₂ B1 14 CH ₃ O CH ₃ NCHO S 3-Cl, 4-CH ₃ B1 15 CH ₃ S CH ₃ NH S 4-Cl B1 16 CH ₃ S CH ₃ NH S 3,4-Cl ₂ B1 17 CH ₃ S CH ₃ NH S 2,4-Cl ₂ B1 18 CH ₃ S CH ₃ NH S 3-Cl, 4-CH ₃ B1 19 CH ₃ S CH ₃ NH S 2-Cl, 4-CH ₃ B1 20 CH ₃ S CH ₃ NH S 3-F, 4-CH ₃ B1 21 C l CH ₃ NH S 4-Cl B2 22 Cl CH ₃ NH S 2,4-Cl ₂ B2 23 Cl CH ₃ NCH ₃ S 4-Cl B1 ────────────────── ─────────────

[0016]

[Table 2] Table 1 (continued) ────────────────────────────── Compound No. R ¹ R ² X Y W _n B ────────────────────────────── 24 Cl CH ₃ NCH ₃ S 2,4-Cl ₂ B1 25 Cl CH ₃ NCH ₃ S 3-Cl, 4-CH ₃ B1 26 Cl CH ₃ NEt S 4-Cl B1 27 Cl CH ₃ Ni-Pr S 4-CH ₃ B1 28 Cl Et NH S 2,4-Cl ₂ B1 29 Cl i -Pr NH S 2,4-Cl ₂ B1 30 Cl CHF ₂ NH S 4-Cl B1 31 Cl CHF ₂ NH S 3-Cl, 4-CH ₃ B1 32 Cl CF ₃ NH S 2,4-Cl ₂ B1 33 Cl CF ₃ NH S 2-F, 4-CH ₃ B1 34 Cl CH ₃ NSO ₂ CH ₃ S 3-F, 4-CH ₃ B1 35 Cl CH ₃ NSO ₂ CH ₃ S 2,4-Cl ₂ B1 36 Cl CH ₃ NSO ₂ CH ₃ S 3-Cl, 4-CH ₃ B1 37 Cl CH ₃ NCH ₃ S 3-Cl, 4-CH ₃ B2 38 Cl CH ₃ NEt S 4-Cl B2 39 Cl CH ₃ Ni-Pr S 4-CH ₃ B2 40 Cl Et NH S 2,4-Cl ₂ B2 41 Cl i-Pr NH S 2,4-Cl ₂ B2 42 Cl CHF ₂ NH S 4-Cl B2 43 Cl CHF ₂ N H S 3-Cl, 4-CH ₃ B2 44 Cl CF ₃ NH S 2,4-Cl ₂ B2 45 Cl CF ₃ NH S 2-F, 4-CH ₃ B2 ───────────── ─────────────────

[0017]

[Table 3] Table 1 (continued) ────────────────────────────── Compound No. R ¹ R ² X Y W _n B ────────────────────────────── 46 Cl CH ₃ NSO ₂ CH ₃ S 3-F, 4-CH ₃ B2 47 Cl CH ₃ NH S 4-Cl B3 48 Cl CH ₃ NH S 2,4-Cl ₂ B3 49 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B4 50 Cl CH ₃ NH S 4-Cl B4 51 Cl CH ₃ NH S 4-CH ₃ B5 52 Cl CH ₃ NH S 2,4-Cl ₂ B5 53 Cl CH ₃ NH S 2,4-Cl ₂ B6 54 Cl CH ₃ NH S 4-Cl B6 55 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B7 56 Cl CH ₃ NH S 2,4-Cl ₂ B7 57 Cl CH ₃ NH S 2-F, 4-CH ₃ B8 58 Cl CH ₃ NH S 3-F, 4- CH ₃ B9 59 Cl CH ₃ NH S 2,4-Cl ₂ B10 60 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B11 61 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B12 62 Cl CH ₃ NH S 4-Cl B13 63 Cl CH ₃ NH S 4-CH ₃ B14 64 Cl CH ₃ NH S 2,4-Cl ₂ B15 65 Cl CH ₃ NH S 2,4-Cl ₂ B16 66 Cl CH ₃ NH S 4-Cl B16 67 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B17 ──────────────────────────────

[0018]

[Table 4] Table 1 (continued) ────────────────────────────── Compound No. R ¹ R ² X Y W _n B ────────────────────────────── 68 Cl CH ₃ NH S 2,4-Cl ₂ B17 69 Cl CH ₃ NH S 2-F, 4-CH ₃ B18 70 Cl CH ₃ NH S 3-F, 4-CH ₃ B18 71 CH ₃ CH ₃ CH ₂ S 4-Cl B1 72 CH ₃ CH ₃ CH ₂ S 2,4-Cl ₂ B1 73 CH ₃ CH ₃ CH ₂ S 2-Cl, 4-CH ₃ B1 74 CH ₃ CH ₃ CH ₂ S 2-F, 4-CH ₃ B1 75 CH ₃ CH ₃ CH (OH) S 4-Cl B1 76 CH ₃ CH ₃ CH (OH) S 2,4-Cl ₂ B1 77 CH ₃ CH ₃ CH (OH) S 2-Cl, 4-CH ₃ B1 78 CH ₃ CH ₃ CH (OH) S 3-Cl, 4-CH ₃ B1 79 CH ₃ CH ₃ CH (OH) S 2-F, 4-CH ₃ B1 80 CH ₃ CH ₃ CH (OH) S 3-F, 4-CH ₃ B1 81 CH ₃ CH ₃ CH ( OCH ₃ ) S 4-Cl B1 82 CH ₃ CH ₃ CH (OCH ₃ ) S 2,4-Cl ₂ B1 83 CH ₃ CH ₃ CH (OCOCH ₃ ) S 4-Cl B1 84 CH ₃ CH ₃ CH (OCOCH ₃ ) S 2,4-Cl ₂ B1 85 CH ₃ CH ₃ CH (OCOCH ₃ ) S 2-Cl, 4-CH ₃ B1 86 CH ₃ CH ₃ CH (OCOCH ₃ ) S 2-F, 4-CH ₃ B1 87 CH ₃ CH ₃ CH (F) S 4-Cl B1 88 CH ₃ CH ₃ CH (F) S 2,4-Cl ₂ B1 89 CH ₃ CH ₃ CH (Cl) S 4-Cl B1 ────────────────────────── ────

[0019]

[Table 5] Table 1 (continued) ────────────────────────────── Compound No. R ¹ R ² X Y W _n B ────────────────────────────── 90 CH ₃ CH ₃ CH (Cl) S 2,4-Cl ₂ B1 91 CH ₃ CH ₃ C = OS 4-Cl B1 92 CH ₃ CH ₃ C = OS 2,4-Cl ₂ B1 93 CH ₃ CH ₃ C = OS 2-Cl, 4-CH ₃ B1 94 CH ₃ CH ₃ C = OS 2-F, 4-CH ₃ B1 95 CH ₃ CH ₃ CH ₂ S 4-Cl B2 96 CH ₃ CH ₃ CH ₂ S 2,4-Cl ₂ B2 97 CH ₃ CH ₃ CH ₂ S 2-Cl, 4 -CH ₃ B2 98 CH ₃ CH ₃ CH ₂ S 2-F, 4-CH ₃ B2 99 CH ₃ CH ₃ CH (OH) S 4-Cl B2 100 CH ₃ CH ₃ CH (OH) S 2,4-Cl ₂ B2 101 CH ₃ CH ₃ CH (OH) S 2-Cl, 4-CH ₃ B2 102 CH ₃ CH ₃ CH (OH) S 3-Cl, 4-CH ₃ B2 103 CH ₃ CH ₃ CH (OH) S 2-F, 4-CH ₃ B2 104 CH ₃ CH ₃ CH (OH) S 3-F, 4-CH ₃ B2 105 CH ₃ CH ₃ CH (OCH ₃ ) S 4-Cl B2 106 CH ₃ CH ₃ CH ( OCH ₃ ) S 2,4-Cl ₂ B2 107 CH ₃ CH ₃ CH (OCOCH ₃ ) S 4-Cl B2 108 CH ₃ CH ₃ CH (OCOCH ₃ ) S 2,4-Cl ₂ B2 109 CH ₃ CH ₃ CH (OCOCH ₃ ) S 2-Cl, 4-CH ₃ B2 110 CH ₃ CH ₃ CH (OCOCH ₃ ) S 2-F, 4-CH ₃ B2 111 CH ₃ CH ₃ CH (F) S 4-Cl B2 ──────────────── ─────────────

[0020]

[Table 6] Table 1 (continued) ────────────────────────────── Compound No. R ¹ R ² X Y W _n B ────────────────────────────── 112 CH ₃ CH ₃ CH (F) S 2,4-Cl ₂ B2 113 CH ₃ CH ₃ CH (Cl) S 4-Cl B2 114 CH ₃ CH ₃ CH (Cl) S 2,4-Cl ₂ B2 115 CH ₃ CH ₃ C = OS 4-Cl B2 116 CH ₃ CH ₃ C = OS 2,4-Cl ₂ B2 117 CH ₃ CH ₃ C = OS 2-Cl, 4-CH ₃ B2 118 CH ₃ CH ₃ C = OS 2-F, 4-CH ₃ B2 119 CH ₃ CH ₃ C (CH ₃ ) (OH) S 4-Cl B2 120 CH ₃ CH ₃ C (CH ₃ ) (OH) S 2,4-Cl ₂ B2 121 CH ₃ CH ₃ C (CH ₃ ) (OCOCH ₃ ) S 4-Cl B2 122 CH ₃ CH ₃ C (CH ₃ ) (OCOCH ₃ ) S 2,4-Cl ₂ B2 123 CH ₃ CH ₃ C (CH ₃ ) (F) S 4-Cl B2 124 CH ₃ CH ₃ C (CH ₃ ) ( F) S 2,4-Cl ₂ B2 125 CH ₃ CH ₃ C (Et) (OH) S 4-Cl B2 126 CH ₃ CH ₃ C (Et) (OH) S 2,4-Cl ₂ B2 127 CH ₃ CH ₃ C (i-Pr) (OH) S 4-Cl B2 128 CH ₃ CH ₃ C (i-Pr) (OH) S 2,4-Cl ₂ B2 129 CH ₃ CH ₃ C (i-Pr) (OH) S 2-Cl, 4-CH ₃ B2 130 CH ₃ CH ₃ C (i-Pr) (OH) S 2-F, 4-CH ₃ B2 131 CH ₃ CH ₃ CH (CH ₃ ) S 4-Cl B2 132 CH ₃ CH ₃ CH (CH ₃ ) S 2,4- Cl ₂ B2 133 CH ₃ CH ₃ CH (CH ₃ ) S 2-Cl, 4-CH ₃ B2 ──────────────────────────── ──

[0021]

[Table 7] Table 1 (continued) ─────────────────────────────── Compound No. R ¹ R ² X Y W _n B ─────────────────────────────── 134 CH ₃ CH ₃ CH (CH ₃ ) S 2-F, 4 -CH ₃ B2 135 Cl CH ₃ CH ₂ S 4-Cl B2 136 Cl CH ₃ CH ₂ S 2,4-Cl ₂ B2 137 Cl CH ₃ CH ₂ S 2-Cl, 4-CH ₃ B2 138 Cl CH ₃ CH ₂ S 2-F, 4-CH ₃ B2 139 CH ₃ O CH ₃ CH ₂ S 4-Cl B2 140 CH ₃ O CH ₃ CH ₂ S 2,4-Cl ₂ B2 141 CH ₃ O CH ₃ CH ₂ S 2 -Cl, 4-CH ₃ B2 142 CH ₃ O CH ₃ CH ₂ S 2-F, 4-CH ₃ B2 143 CH ₃ CH ₃ NH S 4-Cl B19 144 CH ₃ CH ₃ NH S 2-Cl B19 145 CH ₃ CH ₃ NH S 2,4-Cl ₂ B19 146 CH ₃ CH ₃ NH S 3-Cl, 4-CH ₃ B19 147 CH ₃ CH ₃ NH S 2-Cl, 4-CH ₃ B19 148 CH ₃ CH ₃ NH O 4-Cl B20 149 CH ₃ CH ₃ NH S 2-Cl B20 150 CH ₃ CH ₃ NH S 2,4-Cl ₂ B20 151 CH ₃ CH ₃ NH S 3-Cl, 4-CH ₃ B20 152 CH ₃ CH ₃ NH S 2-Cl, 4-CH ₃ B20 153 CH ₃ CH ₃ NCHO S 4-Cl B19 154 CH ₃ CH ₃ NCHO S 2-Cl B19 155 CH ₃ CH ₃ NCHO S 2,4-Cl ₂ B19 ──────────────────────────────

[0022]

[Table 8] Table 1 (continued) ─────────────────────────────── Compound No. R ¹ R ² X Y W _n B ─────────────────────────────── 156 CH ₃ CH ₃ NCHO S 3-Cl, 4-CH ₃ B19 157 CH ₃ CH ₃ NCHO S 2-Cl, 4-CH ₃ B19 158 CH ₃ C ₂ H ₅ NH S 4-Cl B19 159 CH ₃ C ₂ H ₅ NH S 2-Cl B19 160 CH ₃ C ₂ H ₅ NH S 2,4-Cl ₂ B19 161 CH ₃ C ₂ H ₅ NH S 3-Cl, 4-CH ₃ B19 162 CH ₃ C ₂ H ₅ NH S 2-Cl, 4-CH ₃ B19 163 CH ₃ C ₂ H ₅ NH S 2-F, 4-CH ₃ B19 164 CH ₃ C ₂ H ₅ NH S 3-F, 4-CH ₃ B19 165 CF ₃ CH ₃ NH S 2,4-Cl ₂ B19 166 CF ₃ CH ₃ NH S 2,4-Cl ₂ B20 167 Cl CH ₃ NH S 3,4-Cl ₂ B1 168 Cl CH ₃ NH S 3-F, 4-CH ₃ B1 169 Cl CH ₃ NH S 3-Cl, 4-F B1 170 Cl CH ₃ NH S 3-F, 4-OCH ₃ B1 171 Cl CH ₃ NH S 3-Cl, 4-OCH ₃ B1 172 Cl CH ₃ NH S 2-Cl, 4-CH ₃ B1 173 Cl CH ₃ NH S 2-F, 4-Br B1 174 Cl CH ₃ NH S 2-F, 4-Cl B1 175 Cl CH ₃ NH S 2-F, 4-CH ₃ B1 176 Cl CH ₃ NH S 2,3 , 4-Cl ₃ B1 177 Cl CH ₃ NH S 4-CH ₃ B2 ──────────────────────────────

[0023]

[Table 9] Table 1 (continued) ─────────────────────────────── Compound No. R ¹ R ² X Y W _n B ─────────────────────────────── 178 Cl CH ₃ NH S 3,4-Cl ₂ B2 179 Cl CH ₃ NH S 2-Cl-4-CH ₃ B2 180 Cl CH ₃ NH S 3-Cl-4-CH ₃ B2 181 Cl CH ₃ NH S 2-F, 4-Cl B2 182 Cl CH ₃ NH S 2-F , 4-CH ₃ B2 183 Cl CH ₃ NH S 3-F, 4-CH ₃ B2 184 Cl CH ₃ NH S 3-CH ₃ , 4-CH ₃ B2 185 Cl CH ₃ NH S 2-F, 5-CH ₃ B2 186 Cl CH ₃ NH S 3-Cl-4-F B2 187 Cl CH ₃ NCHO S 4-CH ₃ B1 188 Cl CH ₃ NCHO S 3,4-Cl ₂ B1 189 Cl CH ₃ NCHO S 3-F, 4-CH ₃ B1 190 Cl CH ₃ NCHO S 2,3,4-Cl ₃ B1 191 Cl CH ₃ NCHO S 3-F, 4-CH ₃ B2 192 Cl CH ₃ NH S 2-Cl B19 193 Cl CH ₃ NH S 4-Cl B19 194 Cl CH ₃ NH SO 4-CH ₃ B19 195 Cl CH ₃ NH SO ₂ 4-CF ₃ B19 196 Cl CH ₃ NH S 4-OCH ₃ B19 197 Cl CH ₃ NH S 2,4-Cl ₂ B19 198 Cl CH ₃ NH S 2-Cl, 4-CH ₃ B19 199 Cl CH ₃ NH S 3-Cl, 4- CH ₃ B19 ──────────────────────────────

[0024]

[Table 10] Table 1 (continued) ─────────────────────────────── Compound No. R ¹ R ² X Y W _n B ─────────────────────────────── 200 Cl CH ₃ NH S 2-F, 4-Cl B19 201 Cl CH ₃ NH S 2-F, 4-CH ₃ B19 202 Cl CH ₃ NH S 2,3,4-Cl ₃ B19 203 Cl CH ₃ NCHO SH B19 204 Cl CH ₃ NCHO S 2-Cl B19 205 Cl CH ₃ NCHO S 4-Cl B19 206 Cl CH ₃ NCHO S 4-CH ₃ B19 207 Cl CH ₃ NCHO S 4-CF ₃ B19 208 Cl CH ₃ NCHO S 4-OCH ₃ B19 209 Cl CH ₃ NCHO S 2,4-Cl ₂ B19 210 Cl CH ₃ NCHO S 2-Cl, 4-CH ₃ B19 211 Cl CH ₃ NCHO S 3-Cl, 4-CH ₃ B19 212 Cl CH ₃ NCHO S 2-F, 4-Cl B19 213 Cl CH ₃ NCHO S 2-F, 4-CH ₃ B19 214 Cl CH ₃ NCHO S 2,3,4-Cl ₃ B19 215 Cl CH ₃ NH SH B20 216 Cl CH ₃ NH S 2-Cl B20 217 Cl CH ₃ NH S 4- _{Cl B20 218 Cl CH 3 NH S} 4-CH 3 B20 21 _{Cl CH 3 NH S 4-CF} 3 B20 220 Cl CH 3 NH S 4-OCH 3 B20 221 Cl CH 3 NH S 2,4-Cl 2 B20 ──────────────── ─────────────

[0025]

[Table 11] Table 1 (continued) ─────────────────────────────── Compound No. R ¹ R ² X Y W _n B ─────────────────────────────── 222 Cl CH ₃ NH S 2-Cl, 4-CH ₃ B20 223 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B20 224 Cl CH ₃ NH S 2-F, 4-Cl B20 225 Cl CH ₃ NH S 2-F, 4-CH ₃ B20 226 Cl CH ₃ NH S 2 , 3,4-Cl ₃ B20 227 Cl CH ₃ NCHO SH B20 228 Cl CH ₃ NCHO S 2-Cl B20 229 Cl CH ₃ NCHO S 4-Cl B20 230 Cl CH ₃ NCHO S 4-CH ₃ B20 231 Cl CH ₃ NCHO S 4-CF ₃ B20 232 Cl CH ₃ NCHO S 4-OCH ₃ B20 233 Cl CH ₃ NCHO S 2,4-Cl ₂ B20 234 Cl CH ₃ NCHO S 2-Cl, 4-CH ₃ B20 235 Cl CH ₃ NCHO S 3-Cl, 4-CH ₃ B20 236 Cl CH ₃ NCHO S 2-F, 4-Cl B20 237 Cl CH ₃ NCHO S 2-F, 4-CH ₃ B20 238 Cl CH ₃ NCHO S 2,3, _{4-Cl 3 B20 239 Br CH} 3 NH SH B19 240 Br CH 3 NH S 2-Cl _{19 241 Br CH 3 NH S 2,4} -Cl 2 B19 242 Br CH 3 NH S 3-Cl, 4-CH 3 B19 243 Br CH 3 NH S 3-F, 4-CH 3 B19 ────── ───────────────────────

[0026]

[Table 12] Table 1 (continued) ─────────────────────────────── Compound No. R ¹ R ² X Y W _n B ─────────────────────────────── 244 Br CH ₃ NH S 2,3,4-Cl ₃ B19 245 Br CH ₃ NCHO S 4-Cl B19 246 Br CH ₃ NCHO S 2,4-Cl ₂ B19 247 Br CH ₃ NH S 2,4-Cl ₂ B20 248 Br CH ₃ NH S 3-Cl, 4-CH ₃ B20 249 Br CH ₃ NH S 3-Cl, 4-CH ₃ B21 250 Br CH ₃ NH S 3-F, 4-CH ₃ B21 251 Br CH ₃ NH S 4-Cl B22 252 Br CH ₃ NH S 2,4- Cl ₂ B22 253 Br CH ₃ NH S 2,4-Cl ₂ B23 254 Br CH ₃ NH S 3-F, 4-CH ₃ B23 255 Br CH ₃ NH S 2,4-Cl ₂ B24 256 Br CH ₃ NH S 3-Cl, 4-CH ₃ B24 257 Br CH ₃ NH S 3-F, 4-CH ₃ B25 258 Br CH ₃ NH S 2,3,4-Cl ₃ B25 259 Br CH ₃ NH S 2,4-Cl ₂ B26 260 F CH ₃ NH S 2,4-Cl ₂ B19 261 F CH ₃ NH S 3-Cl, 4-CH ₃ B20 262 F CH ₃ NH S 3-Cl, 4 -CH ₃ B21 263 CH ₃ CH ₃ NH S 2,4-Cl ₂ B21 264 CH ₃ CH ₃ NH S 3-Cl, 4-CH ₃ B21 265 CH ₃ CH ₃ NH S 3-F, 4-CH ₃ B21 ─────────────────────────────

[0027]

[Table 13] Table 1 (continued) ─────────────────────────────── Compound No. R ¹ R ² X Y W _n B ─────────────────────────────── 266 CH ₃ CH ₃ NH S 2-F, 4-CH ₃ B21 267 CH ₃ CH ₃ NH S 2-Cl, 4-CH ₃ B21 268 Cl CH ₃ NH S 2,4-Cl ₂ B21 269 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B21 270 CH ₃ CH ₃ NH S 4-Cl B22 271 CH ₃ CH ₃ NH S 2,4-Cl ₂ B22 272 CH ₃ CH ₃ NH S 3-Cl, 4-CH ₃ B22 273 Cl CH ₃ NH S 2,4-Cl ₂ B22 274 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B22 275 CH ₃ CH ₃ NH S 2,4-Cl ₂ B23 276 CH ₃ CH ₃ NH S 3-Cl, 4-CH ₃ B23 277 CH ₃ CH ₃ NH S 2-F, 4-Cl B23 278 CH ₃ CH ₃ NH S 3-F, 4-CH ₃ B23 279 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B23 280 CH ₃ CH ₃ NH S 2,4- Cl ₂ B24 281 CH ₃ CH ₃ NH S 3-Cl, 4-CH ₃ B24 282 Cl CH ₃ NH S 2,4-Cl ₂ B24 283 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B2 4 284 CH ₃ CH ₃ NH S 2,4-Cl ₂ B25 285 Cl CH ₃ NH S 3-Cl, 4-CH ₃ B25 286 CH ₃ CH ₃ NH S 2,4-Cl ₂ B26 ────── ───────────────────────── In the above table, B1-B26 represent the following chemical structures.

[0028]

[Chemical 4]

[0029]

[Chemical 5]

[0030]

[Chemical 6]

[0031]

[Chemical 7]

Next, a method for producing the compound of the present invention is shown in a reaction scheme and explained below.

Reaction scheme (Production method 1)

[0034]

[Chemical 8]

(Production method 2)

[0036]

[Chemical 9]

(Production method 3)

[0038]

[Chemical 10]

(Production method 4)

[0040]

[Chemical 11]

(Production Method 1) Formula [2]:

[0042]

[Chemical 12]

[In the formula, R ¹ , R ² , Y and A have the same meanings as described above, and X represents -N (R ³ )-. And a substituted pyrazole represented by the formula [3]: LB [3] [In the formula, L represents a leaving group such as a halogen atom, and B represents the same meaning as described above. ] The compound of the present invention can be produced by reacting with a heterocycle represented by At this time, when X in the formula [2] is —NCOR ⁴ or —NSO ₂ R ^5, it is hydrolyzed in the post-treatment and the like, and the product X is
Sometimes it can be obtained in NH.

In the above reaction, a solvent is not always necessary, but examples of the solvent used include hydrocarbons such as toluene, xylene and chlorobenzene, halogenated hydrocarbons such as dichloroethane, diisopropyl ether and dioxane. And ethers such as ethyl acetate, nitriles such as acetonitrile, and polar solvents such as dimethylsulfoxide and dimethylformamide. If necessary, an organic base (pyridine, triethylamine, etc.) or an inorganic base (potassium carbonate, sodium hydride, etc.) may be added.

If necessary, a copper salt or a copper complex may be added as a catalyst. The amount of reagent used in the above reaction is
The heterocycle represented by the formula [3] is in the range of 1 to 5 equivalents relative to 1 equivalent of the substituted pyrazole represented by the formula [2]. In the above reaction, the reaction temperature can be arbitrarily set, but usually room temperature to 200 ° C. or the reflux temperature of the solvent is preferable. After completion of the reaction, the desired product can be obtained by performing usual post-treatment.

(Production Method 2) (a) Formula [4]:

[0047]

[Chemical 13]

[In the formula, R ¹ and R ² have the same meanings as described above, and X represents -N (R ³ )-. ] The pyrazole represented by the formula [3] and the heterocycle represented by the formula [3] are reacted with a suitable solvent and a base as necessary to obtain the formula [7]:

[0049]

[Chemical 14]

[In the formula, R ¹ , R ² , X and B have the same meanings as described above. ] Is manufactured. At this time, X in the formula [4] is -N
When it is COR ⁴ or —NSO ₂ R ⁵ , it may be hydrolyzed in a post-treatment or the like to give X in the formula [7] as —NH. Examples of the solvent used in the above reaction include hydrocarbons such as toluene, xylene and chlorobenzene, halogenated hydrocarbons such as dichloroethane, ethers such as diisopropyl ether and dioxane, and esters such as ethyl acetate. , Nitriles such as acetonitrile,
Examples include polar solvents such as dimethyl sulfoxide and dimethylformamide.

Examples of the base used include potassium carbonate, sodium hydride and the like. Moreover, you may add a copper salt, a copper complex, etc. as a catalyst as needed. In the above reaction, the reaction temperature can be arbitrarily set, but usually, room temperature to 200 ° C. or the reflux temperature of the solvent is preferable.

(B) Formula [5]:

[0053]

[Chemical 15]

[In the formula, R ¹ and R ² have the same meanings as described above,
L represents a leaving group such as a halogen atom. And a pyrazole represented by the formula [6]: HX-B [6] [In the formula, B represents the same meaning as described above, and X represents -N (R ³ )-. ] The heterocycle represented by the formula [7]: by reacting with a suitable solvent and a base, if necessary.

[0055]

[Chemical 16]

[In the formula, R ¹ , R ² , X and B have the same meanings as described above. ] Is manufactured. At this time, X in the formula [6] is -N
When it is COR ⁴ or —NSO ₂ R ⁵ , it may be hydrolyzed in a post-treatment or the like to obtain X in the formula [7] by —NH 2. Examples of the solvent used in the above reaction include hydrocarbons such as toluene, xylene and chlorobenzene, halogenated hydrocarbons such as dichloroethane, ethers such as diisopropyl ether and dioxane, and esters such as ethyl acetate. , Nitriles such as acetonitrile,
Examples include polar solvents such as dimethyl sulfoxide and dimethylformamide.

Examples of the base used include potassium carbonate, sodium hydride and the like. Moreover, you may add a copper salt, a copper complex, etc. as a catalyst as needed. In the above reaction, the reaction temperature can be arbitrarily set, but is usually room temperature to
200 ° C. or solvent reflux temperature is preferred.

The pyrazole represented by the formula [7] obtained in the following (a) or (b) and the formula [8]: AYL [8] [wherein A represents the same meaning as described above] , Y has the same meaning as described above except for an oxygen atom, and L represents a leaving group such as a halogen atom. ] The compound of the present invention can be produced by reacting the compound shown by the above with a suitable solvent and a base if necessary.

Examples of the solvent used in the above reaction include hydrocarbons such as toluene, xylene and chlorobenzene, halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride, diisopropyl ether and dioxane. Examples thereof include ethers, esters such as ethyl acetate, nitriles such as acetonitrile, and polar solvents such as dimethyl sulfoxide and dimethylformamide.

The base used is pyridine,
Examples include triethylamine and potassium carbonate. In the above reaction, the reaction temperature can be arbitrarily set, but is usually 0 ° C to
100 ° C. is preferred. (Production method 3) When X = N−R ³ , R ³ ≠ H

[9]:

[0061]

[Chemical 17]

[In the formula, R ¹ , R ² , Y, A and B have the same meanings as described above. ] And the formula [1
0]: R ³ -L [10] [wherein R ³ has the same meaning as described above except for a hydrogen atom, and L 3
Represents a leaving group such as a halogen atom. ] The compound of the present invention can be produced by reacting the compound shown by the above with a suitable solvent and a base if necessary.

Examples of the solvent used in the above reaction include hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride, diisopropyl ether, tetrahydrofuran and dioxane. Examples thereof include ethers, esters such as ethyl acetate, nitriles such as acetonitrile, and polar solvents such as dimethyl sulfoxide and dimethylformamide.

As the base used, pyridine,
Examples thereof include organic bases such as triethylamine and inorganic bases such as potassium carbonate and sodium hydride. In the above reaction, the reaction temperature can be arbitrarily set, but it is usually 0 ° C to 100 ° C.
Is preferred.

(Production Method 4) When X = CH (R ⁴ ) Formula [12]:

[0066]

[Chemical 18]

[In the formula, R ¹ , R ² , Y, A, B and R ₄ have the same meanings as described above. ] The compound of formula [13]: is reacted by using a suitable reducing agent.

[0068]

[Chemical 19]

[In the formula, R ¹ , R ² , Y, A, B and R ₄ have the same meanings as described above. ] The compound of the present invention represented by Examples of the reducing agent used in the above reaction include phosphorus compounds such as P ₂ I ₄ .

[0070]

EXAMPLES Next, specific production examples will be shown.

[Production Example 1] (Synthesis of compound No. 99 of the present invention) Synthesis of 2-pyridyl- (1,3-dimethyl-5-pyrazolyl) methanol 300 ml of dry tetrahydrofuran solution in which 5.5 g of 2-bromopyridine was dissolved Was cooled to -78 ° C and n-
Butyllithium hexane solution (15W / W%) 5.45
g was slowly added dropwise, and the mixture was stirred for 30 minutes. Then 1,
4.2 g of 3-dimethyl-5-formylpyrazole-7
It was slowly added dropwise at 8 ° C. Then, the temperature was slowly raised to room temperature and the mixture was stirred for 15 hours.

The solution was neutralized by adding 2N hydrochloric acid, and the mixture was extracted 3 times with 150 ml of ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solution; chloroform) to give 2-pyridyl- (1,
5.2 g of 3-dimethyl-5-pyrazolyl) methanol were obtained as a brown oil.

Inventive Compound No. Synthesis of 99 2-pyridyl- (1,3-dimethyl-5-pyrazolyl)
60 ml of a dry chloroform solution containing 3 g of methanol
At room temperature, 3.4 g of 4-chlorophenylsulfenyl chloride was added dropwise thereto, and the mixture was stirred for 12 hours. After the solvent was distilled off, 50 ml of ethyl acetate and 50 ml of 10% aqueous sodium hydrogen carbonate solution were added, and the mixture was stirred for 30 minutes. After separating the organic layer, the aqueous layer was extracted three times with 50 ml of ethyl acetate.
The combined organic layers were dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solution; chloroform) to give 2-
Pyridyl- (4- (4-chlorophenylthio) -1,3
1.2 g of -dimethyl-5-pyrazolyl) methanol was obtained as white crystals. Melting point 90.0-91.0 ° C

Production Example 2 (Compound No. 115 of the present invention)
Synthesis of compound of the present invention obtained in Production Example 1 99 1.2 g
Was dissolved in 50 ml of dry dichloromethane, 1.5 g of manganese dioxide was added at room temperature, and the mixture was stirred for 2 hours. The inorganic material was filtered off through Celite, the solvent was evaporated under reduced pressure, and the residue was crystallized from diisopropyl ether to give 2-pyridyl- (4- (4-chlorophenylthio) -1,3-dimethyl-5-pyrazolyl) ketone. 1.0 g was obtained as white crystals. Melting point 111.0-113.0 ° C

[Production Example 3] (Synthesis of Compound No. 95 of the Present Invention) A benzene solution 1 containing 0.5 g of diphosphorus tetraiodide under a nitrogen stream.
0 ml was heated to reflux for 10 minutes. The compound of the present invention No. obtained in Production Example 1 was added to this solution. 30 ml of a benzene solution in which 99 (1.2 g) was dissolved was added dropwise, and the mixture was heated under reflux for 16 hours. After cooling with air, 5 ml of 10% aqueous sodium hydrogen sulfite solution was added, and the mixture was stirred at room temperature for 1 hour.

This solution was extracted 3 times with 50 ml of ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solution; chloroform) to give 4-
(4-chlorophenylthio) -1,3-dimethyl-5-
0.34 g of (2-pyridylmethyl) pyrazole was obtained.
Melting point 80.0-82.0 ° C

Production Example 4 (Synthesis of Compound No. 22 of the Present Invention) 3-Chloro-1-methyl-4-nitro-5- (2-
Synthesis of pyridylamino) pyrazole Suspended N, N with 4.6 g (55%) of sodium hydride
-In 100 ml of dimethylformamide, under ice cooling, N- (2
A mixed solution of 11.4 g of -pyridyl) formamide and 20 ml of N, N-dimethylformamide was added dropwise, and the mixture was stirred at room temperature for about 1 hour. Next, 3,5-dichloro-1-methyl-
A solution prepared by dissolving 17.5 g of 4-nitropyrazole in 20 ml of N, N-dimethylformamide was added dropwise under ice cooling, and then the mixture was heated with stirring at 60 ° C. for 8 hours. After cooling, N, N-dimethylformamide was distilled off under reduced pressure and extracted with chloroform. The organic layer was washed with an aqueous sodium carbonate solution, subsequently washed with water and then dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, the remaining crystals were washed with isopropyl ether, filtered and dried to give the desired 3-chloro-1.
14.2 g of -methyl-4-nitro-5- (2-pyridylamino) pyrazole were obtained. Melting point 127.0-129.
0 ° C

Synthesis of 4-amino-3-chloro-1-methyl-5- (2-pyridylamino) pyrazole 3-chloro-1-methyl-4-nitro-5- (2-pyridylamino) pyrazole 7 g and ethanol 50 ml It was added to a mixed solution of 50 ml of concentrated hydrochloric acid and dissolved. At room temperature, a mixed solution of 31 g of stannous chloride dihydrate and 70 ml of ethanol was added dropwise thereto, and the mixture was stirred at 80 ° C. for 7 hours. After cooling, the reaction solution was poured into ice water, and a 20% aqueous sodium hydroxide solution was added to make the solution alkaline. It was extracted with ethyl acetate, washed with water, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain 5.0 g of the target 4-amino-3-chloro-1-methyl-5- (2-pyridylamino) pyrazole as crystals. Melting point 151.0-153.
0 ° C

3-chloro-1-methyl-5- (2-
Synthesis of pyridylamino) pyrazole 1.5 g of 4-amino-3-chloro-1-methyl-5- (2-pyridylamino) pyrazole was added to a mixed solution of 50 ml of ethanol and 5 ml of concentrated sulfuric acid, and the mixture was heated under reflux. 1.1 g of sodium nitrite was added little by little to this solution. At this time, generation of nitrogen gas was observed. After the addition of sodium nitrite was completed, the mixture was heated under reflux for 30 minutes. After cooling, 20% aqueous sodium hydroxide solution was added to make the mixture alkaline, followed by extraction with chloroform. The organic layer was washed with water and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure. The residue is purified by silica gel column chromatography (developing solution; chloroform-ethyl acetate) to give 3-chloro-
1.1 g of 1-methyl-5- (2-pyridylamino) pyrazole was obtained. Melting point 105.0-106.0 ° C

Inventive Compound No. Synthesis of 22 3-chloro-1-methyl-5- (2-pyridylamino)
1.05 g of pyrazole was dissolved in 30 ml of anhydrous chloroform. 1.3 g of 2,4-dichlorophenylsulfenyl chloride was added dropwise to this solution, and the mixture was stirred at room temperature for 3 hours. After adding a sodium carbonate aqueous solution, the mixture was extracted with chloroform, the organic layer was washed with water, and then dried over anhydrous sodium sulfate. After filtration, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solution; chloroform) to give 3-chloro-4- (2,4-dichlorophenylthio) -1-methyl-5- (. 1.42 g of 2-pyridylamino) pyrazole was obtained. Melting point 147.0-1
48.0 ° C

[Production Example 5] (Inventive compound No. 16)
Synthesis of 8-) Synthesis of 5-amino-3-chloro-1-methyl-4-methoxycarbonylpyrazole 100 g of 3,5-dichloro-1-methyl-4-methoxycarbonylpyrazole was added to anhydrous dimethyl sulfoxide 35.
It was dissolved in 0 ml, subsequently 37.3 g of sodium azide was added, and the mixture was stirred at 60 ° C. for 3 days. The reaction solution was poured into 800 ml of ice water, and the separated crystals were filtered and washed with water. By drying the crystals, 5-azido-3-chloro-1-
About 65% of methyl-4-methoxycarbonylpyrazole
81.5 g of inclusions were obtained. To this mixture, 400 ml of anhydrous methanol and 1.5 g of piperidine were added, and ice water was added to about 1
Cooled to 5 ° C. Hydrogen sulfide gas was blown therein for about 1 hour. Subsequently, nitrogen gas was blown for about 15 minutes to remove excess hydrogen sulfide gas. The protruding sulfur was removed by filtration, and the solvent was distilled off under reduced pressure. 150 ml of chloroform on the residue
And 50 ml of saturated aqueous sodium carbonate solution were added, and the mixture was stirred for 30 minutes. After extraction with chloroform, washing with water, and drying with anhydrous sodium sulfate. After filtration and evaporation of the solvent, the residue was purified by silica gel column chromatography (developing solution; chloroform-ethanol) to give 5 as pale yellow crystals.
47.1 g (yield 52%) of -amino-3-chloro-1-methyl-4-methoxycarbonylpyrazole was obtained. Melting point 104.0-105.0 ° C

Synthesis of 5-amino-3-chloro-1-methylpyrazole 5-amino-3-chloro-1-methyl-4-methoxycarbonylpyrazole 55.5 g was added to sodium hydroxide 3
1.4 g of the solution was added to a mixed aqueous solution of 200 ml of methanol and 250 ml of water, and the mixture was heated under reflux for 3 hours. After cooling
The solvent was distilled off under reduced pressure. Add 300 ml of water and add hydrochloric acid (31
%) To acidify to pH 2. The separated crystals were filtered, washed with water and dried to obtain about 50 g of white crystals of (5-amino-3-chloro-1-methyl-4-pyrazolyl) carboxylic acid.

Next, 100 ml of hydrochloric acid (31%) and 50 ml of water
The above crystals were added little by little while the mixed aqueous solution of was heated and stirred at 80 ° C. (Evolution of carbon dioxide was observed.) After the addition of crystals was completed, stirring was further carried out at 80 ° C. for 3 hours. Then, under reduced pressure, about half of the water was distilled off, and then an aqueous potassium hydroxide solution was added to make the solution alkaline to a pH of about 11. Further, 300 ml of acetonitrile was added to a portion where water was completely distilled off under reduced pressure, followed by drying with anhydrous sodium sulfate and anhydrous potassium carbonate. After filtration, acetonitrile was distilled off under reduced pressure to obtain 35 g of 5-amino-3-chloro-1-methylpyrazole as white crystals (yield 91%).
Was obtained. Melting point 84.0-85.0 ° C

3-chloro-1-methyl-5- (2-
Synthesis of pyrimidylamino) pyrazole 5-amino-3-chloro-1-methylpyrazole 52 g
27.3 g of formic acid was added, followed by dropwise addition of 50.4 g of acetic anhydride. It was stirred at room temperature for 2 days. The solvent was distilled off under reduced pressure. Chloroform (160 ml) was added and the mixture was dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off to give N- (3-chloro-1-methyl-5-pyrazolyl).
About 68 g of formamide was obtained. This was used in the next reaction without purification. Sodium hydride (55% oily)
21 g of suspended N, N-dimethylformamide 400
A mixture of 68 g of the above N- (3-chloro-1-methyl-5-pyrazolyl) formamide and 120 ml of N, N-dimethylformamide was added dropwise to the ml solution under ice cooling. After stirring at room temperature for 4 hours, 2-chloropyrimidine 49.
9 g was added. Then, the mixture was stirred at room temperature for 2 hours and at 120 ° C. for 15 hours. After cooling, the solvent was distilled off under reduced pressure, 200 ml of chloroform and 200 ml of water were added, and the mixture was stirred at room temperature for 2 hours. It was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain a brown crystalline substance. After 100 ml of ethanol and 100 ml of diethyl ether were added thereto and stirred, the crystals were filtered, washed with ethanol and dried to give 43 g of 3-chloro-1-methyl-5- (2-pyrimidylamino) pyrazole (yield 52 %) Obtained. Melting point 146.
0-148.0 ° C

3-chloro-4- (3-fluoro-4)
-Methylphenylthio) -1-methyl-5- (2-pyrimidylamino) pyrazole (present compound No.
Synthesis of 168) 16.6 g of 3-chloro-1-methyl-5- (2-pyrimidylamino) pyrazole was added to 150 ml of anhydrous chloroform.
And was cooled to about 10 ° C. with ice water. There, 3-
A mixed solution of 16.1 g of fluoro-4-methylphenylsulfenyl chloride and 10 ml of chloroform was added dropwise. After the completion, the mixture was stirred at room temperature for 6 hours. 50 ml of saturated sodium carbonate aqueous solution was added, and the mixture was further stirred for 30 minutes. It was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After filtration, chloroform was distilled off under reduced pressure to obtain crystals. 50 ml of diethyl ether and 50 ml of ethanol were added thereto, and the mixture was stirred, then the crystals were separated by filtration and washed with ethanol. The crystals were dried to give 3-chloro-4- (3-fluoro-4-methylphenylthio) -1-methyl-5- (2-pyrimidylamino) as light gray crystals.
21.5 g (yield 77%) of pyrazole was obtained. Melting point 178.0-179.0 ° C

Production Example 6 N- (3-chloro-4- (3-fluoro-4-methylphenylthio) -1-methyl-5-pyrazolyl) -N-
Synthesis of (2-pyrimidyl) formamide (Synthesis of compound No. 189 of the present invention) 3-chloro-4- (3-fluoro-4-methylphenylthio) -1-methyl-5- (2-pyrimidylamino) pyrazole 25. 0 g, formic acid 13.5 g and acetic anhydride 3
0.4 g was added, and the mixture was stirred at room temperature for 14 hours. After distilling off the solvent of the homogenized reaction solution under reduced pressure, chloroform 100
ml and 100 ml of water were added and stirred for 1 hour. The chloroform layer was extracted, washed with water, and dried over anhydrous sodium sulfate. After filtration, chloroform was distilled off under reduced pressure, 2 ml of diisopropyl ether was added to precipitate crystals, and the crystals were washed with 40 ml of normal hexane and filtered. Normal n-hexane 4
It was washed with a mixed solution of 0 ml and 7 ml of diisopropyl ether. By drying this, N- (3
23.9 g (yield 88%) of -chloro-4- (3-fluoro-4-methylphenylthio) -1-methyl-5-pyrazolyl) -N- (2-pyrimidyl) formamide were obtained. Melting point 91.0-92.0 ° C

[Production Example 7] (Compound No. 278 of the present invention)
Synthesis of 1,3-dimethyl-5- (6-fluoro-2-pyridylamino) pyrazole To a solution of 1.5 g of suspended sodium hydride (55% oily) in N, N-dimethylformamide was added N. −
(1,3-Dimethyl-5-pyrazolyl) formamide 4
A mixed solution of g and 15 ml of N, N-dimethylformamide was added dropwise under cooling. After completion of dropping, the mixture was stirred at room temperature for 4 hours. 3.2 g of 2,6-difluoropyridine was added, and the mixture was stirred at room temperature for 18 hours and at 130 ° C. for 3 hours. After cooling, the solvent was distilled off under reduced pressure, the residue was extracted with chloroform, washed with water,
It was dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solution; chloroform) to give 3.6 g of 1,3-dimethyl-5- (6-fluoro-2-pyridylamino) pyrazole. Yield 65%) was obtained. Melting point 11
2.0-113.0 ° C

1,3-dimethyl-4- (3-fluoro-4-methylphenylthio) -5- (6-fluoro-
Synthesis of 2-pyridylamino) pyrazole (Synthesis of compound No. 278 of the present invention) 0.6 g of 1,3-dimethyl-5- (6-fluoro-2-pyridylamino) pyrazole was added to 30 ml of anhydrous chloroform.
Was dissolved in the solution, 0.61 g of 3-fluoro-4-methylphenylsulfenyl chloride was added, and the mixture was stirred at room temperature for 12 hours. 10 ml of saturated sodium carbonate aqueous solution was added and stirred for 30 minutes. It was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After filtration, the solvent was evaporated under reduced pressure, and the remaining crystals were washed with diisopropyl ether to give 1,3-dimethyl-4- (3-fluoro-4-methylphenylthio) -5- (6-fluoro- 0.72 g (yield 71%) of 2-pyridylamino) pyrazole was obtained. Melting point 96.0-98.0 ° C

[Production Example 8] (Synthesis of Compound No. 9 of the Invention) Synthesis of 5-amino-3-methoxy-1-methylpyrazole 5-Amino-3-methoxy-1-methyl-4-methoxycarbonylpyrazole 10 0.5 g was added to an aqueous solution of 150 ml of methanol and 150 ml of water in which 6.1 g of sodium hydroxide was dissolved, and the mixture was heated and refluxed for 3 hours. After cooling
The solvent was distilled off under reduced pressure, and hydrochloric acid was added to make the solution acidic with pH 2 under ice cooling. After completely distilling off the water under reduced pressure, ethanol 1
50 ml was added and dried over anhydrous sodium sulfate. After filtration, the ethanol was distilled off, leaving a pale yellow oil.
Add 100 ml of xylene and 0.5 g of copper powder and heat to reflux 1
It went for 8 hours. After the copper powder was removed by filtration and xylene was distilled off under reduced pressure, 100 ml of acetonitrile was added and the mixture was dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain 6.67 g (yield 92%) of 5-amino-3-methoxy-1-methylpyrazole.

3-methoxy-1-methyl-5- (2
Synthesis of 5-pyrimidylamino) pyrazole 5-amino-3-methoxy-1-methylpyrazole 6.
To 67 g, add 6.6 g of formic acid, followed by 1 part of acetic anhydride.
6.2 g was added dropwise, and the mixture was stirred at room temperature for 3 days. The solvent was distilled off under reduced pressure, 100 ml of chloroform was added, and the mixture was dried over anhydrous sodium sulfate. After filtration and concentration under reduced pressure, N- (3
9.7 g of crude product of -methoxy-1-methyl-5-pyrazolyl) formamide was obtained. The next reaction was carried out without purification. Sodium hydride (55% oil) 3.
N, N-dimethylformamide 150 in which 3 g was suspended
A mixed solution of 9.7 g of N- (3-methoxy-1-methyl-5-pyrazolyl) formamide and 50 ml of N, N-dimethylformamide was added dropwise to ml, and the mixture was stirred at room temperature for 4 hours. Then add 7.9 g of 2-chloropyrimidine,
The mixture was stirred at 100 ° C for 18 hours. After cooling, the residue concentrated under reduced pressure was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solution; chloroform) to give 3-methoxy-1 as an oily substance.
2.6 g (24% yield) of -methyl-5- (2-pyrimidylamino) pyrazole were obtained.

Synthesis of 4- (3-chloro-4-methylphenylthio) -3-methoxy-1-methyl-5- (2-pyrimidylamino) pyrazole (Compound No. of the present invention)
Synthesis of 9) 0.7 g of 3-methoxy-1-methyl-5- (2-pyrimidylamino) pyrazole was dissolved in 30 ml of anhydrous chloroform, 0.65 g of 3-chloro-4-methylphenylsulfenyl chloride was added, and the mixture was stirred at room temperature. Stir for 18 hours.
A saturated aqueous sodium carbonate solution was added, and the mixture was stirred at room temperature for 30 minutes, extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solution; chloroform) to give 4- (3-chloro-4-methylphenylthio) -3-methoxy-1-methyl-5. -(2-
0.57 g of pyrimidylamino) pyrazole (yield 51
%) Obtained. Melting point 148.0 to 150.0 ° C. Table 2 shows the physical properties of the compounds produced according to these methods.

Table 2

[0093]

[Table 14] ────────────────────────────── Compound ¹ H-NMR No. Physical property δ (ppm, CDCl ₃ ) , Reference material TMS ────────────────────────────── 1 mp 168.0 to 169.0 ℃ 2 mp 175.0 to 176.0 ℃ 3 mp 162.0 to 163.0 ℃ 4 mp 91.0-93.0 ℃ 5 mp 184.0-185.0 ℃ 6 mp 172.0-174.0 ℃ 7 mp 179.0-181.0 ℃ 9 mp 148.0-150.0 ℃ 10 mp 209.0-210.0 ℃ 11 mp 137.0-138.0 ℃ 12 mp 153.0-155.0 ℃ 15 mp 209.0 to 212.0 ℃ 16 mp 168.0 to 170.0 ℃ 17 mp 92.0 to 95.0 ℃ 18 mp 136.0 to 138.0 ℃ 19 mp 120.0 to 124.0 ℃ 20 mp 177.0 to 180.0 ℃ 21 mp 157.0 to 159.0 ℃ 22 mp 147.0 to 148.0 ℃ 95 mp 80.0 to 82.0 ℃ 96 mp 88.0 to 89.0 ℃ ───────────────────────────────

[0094]

[Table 15] Table 2 (continued) ────────────────────────────── Compound ¹ H-NMR No. Physical property δ (ppm, CDCl ₃ ), reference material TMS ────────────────────────────── 99 mp 90.0 to 91.0 ℃ 100 mp 142.0 to 145.0 ℃ 104 Resin 2.20 (s, 6H), 3.55 (s, 3H), 5.10 (bs, 1H), 6.05 (s, 1H), 6.50 ~ 7.60 (m, 6H), 8.40 (d, 1H, J = 5Hz) 105 Oil 2.17 (s, 3H), 3.30 (s, 3H), 3.68 (s, 3H), 5.68 (s, 1H), 6.80 ~ 7.70 (m, 7H), 8.30 ~ 8.50 (m, 1H) 107 oil 2.10 (s, 3H), 2.25 (s, 3H), 4.05 (s, 3H), 6.80-8.70 (m, 9H) 111 oil 2.19 (s, 3H), 3.77 (s, 3H), 6.67 (d, 1H, J = 45Hz) 6.90 to 7.70 (m, 7H), 8.51 (d, 1H, J = 5Hz) 115 mp 111.0 to 113.0 ° C 119 oil 2.03 (s, 3H), 2.16 (s, 3H) , 3.69 (s, 3H), 6.00 (bs, 1H), 6.80 ~ 8.51 (m, 8H) 127 Resinous 0.50 (d, 3H, J = 7Hz), 1.00 (d, 3H, J = 7Hz), 2.02 ( s, 3H), 3.21 to 3.65 (m, 1H), 3.87 (s, 3H), 6.00 (bs, 3H), 6.61 to 8.35 (m, 8H) 131 oil 1.71 (d, 3H, J = 7Hz), 2.17 (s, 3H), 3.73 (s, 3H), 4.69 (q, 1H, J = 7Hz), 6.70 ~ 7.60 (m, 7Hz), 8.30 ~ 8.50 (m , 1H) ───────────────────────────────

[0095]

[Table 16] Table 2 (continued) ────────────────────────────── Compound ¹ H-NMR No. Physical Properties δ (ppm, CDCl ₃ ), reference material TMS ────────────────────────────── 145 mp 218.0-220.0 ℃ 155 mp 121.0- 122.0 ℃ 167 mp 174.0 to 175.0 ℃ 168 mp 178.0 to 179.0 ℃ 169 mp 157.0 to 159.0 ℃ 170 mp 156.0 to 157.0 ℃ 171 mp 159.0 to 160.0 ℃ 172 mp 184.0 to 186.0 ℃ 173 mp 179.0 to 180.0 ℃ 174 mp 186.0 to 187.0 175 mp 172.0 to 173.0 ° C 176 mp 172.0 to 174.0 ° C 177 mp 154.0 to 155.0 ° C 178 mp 136.0 to 139.0 ° C 179 mp 167.0 to 168.0 ° C 180 mp 144.0 to 145.0 ° C 181 mp 132.0 to 133.0 ° C 182 mp 144.0 to 145.0 ° C 132.0-133.0 ℃ 184 mp 149.0-150.0 ℃ 185 mp 143.0-144.0 ℃ ─────────────────── ─────────────

[0096]

[Table 17] Table 2 (continued) ─────────────────────────────── Compound ¹ H-NMR No. Physical Properties δ (ppm, CDCl ₃ ), reference material TMS ─────────────────────────────── 186 mp 140.0-141.0 ℃ 187 mp 90.0 to 91.0 ° C. 188 oil 189 mp 91.0 to 92.0 ° C. 190 resinous 191 oil 263 mp 153.0 to 154.0 ° C. 264 mp 117.0 to 119.0 ° C. 265 mp 108.0 to 110.0 ° C. 266 mp 116.0 to 118.0 ° C. 270 oily substance 271 mp 183.0 to 184.0 ℃ 275 mp 172.0 to 174.0 ℃ 276 mp 104.0 to 106.0 ℃ 277 mp 142.0 to 144.0 ℃ 278 mp 96.0 to 98.0 ℃ ──────────────────────── In using the compound of the present invention as an agricultural and horticultural fungicide, generally, a suitable carrier such as clay, talc, vent is used. Solid carriers such as Nantes and diatomaceous earth or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate) Etc.), acid amides (dimethylformamide, etc.) and the like can be mixed and applied with a liquid carrier, and if desired, an emulsifier, a dispersant, a suspending agent, a penetrant, a spreading agent, a stabilizer, etc. are added, It can be put into practical use in any dosage form such as a liquid preparation, an oil preparation, an emulsion, a wettable powder, a powder preparation, a granule preparation and a flowable preparation.

If necessary, other herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like may be mixed and applied during preparation or spraying. The application dose of the compound of the present invention varies depending on the application scene, application time, application method, target disease, cultivated crop and the like, but generally, an effective amount of about 0.005 to 50 kg per hectare is suitable. Next, formulation examples of bactericides containing the compound of the present invention as an active ingredient will be shown, but the formulations are not limited thereto. In addition, in the following formulation examples, "part" means part by weight.

Formulation Example 1 Emulsion Compound of the present invention -------- 20 parts Xylene -------- 55 parts N, N-Dimethylformamide ------- 20 parts Solpol 2680- -------- 5 parts (mixture of nonionic surfactant and anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) The above components are uniformly mixed to form an emulsion. For use, the 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 Diclite PFP -------- 66 parts (mixture of kaolinite and sericite; Siglite Industrial Co., Ltd.) Product name: Solpol 5039 ------- 4 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. product name) Carplex # 80 ------- 3 parts (White carbon: Shionogi & Co. Brand name Calcium lignin sulfonate ------- 2 parts or more are uniformly mixed and pulverized to obtain a wettable powder. Before use, dilute the wettable powder 50 to 20000 times and spray it so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 3 Oil agent Compound of the present invention --- 10 parts Methylcellosolve -------- 90 parts The above ingredients are uniformly mixed to obtain an oil agent. At the time of use, the above oil agent is sprinkled so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 4 Powder Compound of the present invention ------- 3.0 parts Carplex # 80 ------- 0.5 part (white carbon: Shionogi Pharmaceutical Co., Ltd. trade name) Clay --- ---- 95 parts Diisopropyl phosphate ------- 1.5 parts The above is mixed and pulverized uniformly to give a powder. Before use, spray the above powder so that the amount of active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 5 Granules Compound of the present invention ------- 5 parts Bentonite ------- 54 parts Talc ------- 40 parts Calcium lignin sulfonate --- -1 part or more is uniformly mixed and pulverized, a small amount of water is added, and the mixture is stirred and mixed, granulated by an extrusion granulator, and dried to obtain granules. When using the above granules, the amount of active ingredient is 0.0 per hectare.
Sprinkle so that it becomes 05 to 50 kg.

Formulation Example 6 Flowable agent Compound of the present invention ------- 25 parts Solpol 3353 ------- 10 parts (Nonionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Lunox 1000C ------- 0.5 part (anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) 1% xanthan gum aqueous solution ------- 20 parts (natural polymer) water ------ -44.5 parts The above components except the active ingredient (the compound of the present invention) are uniformly dissolved, and then the compound of the present invention is added and well stirred, followed by wet grinding with a sand mill to obtain a flowable agent. Before use, dilute the flowable agent 50 to 20000 times and spray so that the amount of active ingredient is 0.005 to 50 kg per hectare.

Next, the plant diseases targeted by the compounds of the present invention include rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus miyabeanus), and blight (Rhizoc).
tonia solani), powdery mildew of wheat (Erysiphe gram)
inis f.sp.hordei, f.sp.tritici), leaf spot disease (Pyrenoph
ora graminea), net blotch (Pyrenophora teres), red mold (Gibberella zeae), rust (Puccinia striiformi)
s, P.graminis, P.recondita, P.hordei), snow rot (Typh
ula sp., Micronectriella nivais), bare smut (Ustilag
o tritici, U.nuda), eye spot (Pseudocercosporell
a herpotrichoides), cloud disease (Rhynchosporium secali
s), leaf blight (Septoria tritici), blight (Leptosphaeri)
a nodorum),

Citrus black spot (Diapor the citri), scab (Elsinoe fawcetti), fruit rot (Penicillium)
digitatum, P.italicum), monili disease of apple (Scler
otiniamali), rot (Valsa mali), powdery mildew (P
odosphaera leucotricha), leaf spot disease (Alternaria ma
li), scab (Venturia inaequalis), pear scab
(Venturia nashicola), Black spot (Alternaria Kikuchia)
na), red scab (Gymnosporangium haraeanum), peach scab (Sclerotinia cinerea), scab (Cladosporium ca)
rpophilum), Phomopsis rot (Phomopsis sp.), downy mildew of grapes (Plasmopara viticola), black rot (Elsi
noe ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora amp)
elopsidis), oyster anthracnose (Gloeosporium kaki), leaf scab (Cercospora kaki, Mycosphaerella nawae),

Downy mildew (Pseudoperenospora cuben) of cucumber
sis), anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), vine blight (Mycosphaere)
lla melonis), a tomato plague (Phytophthora infesta)
ns), ring spot (Alternaria solani), leaf mold (Cladosp)
orium fulvam), brown leaf spot of eggplant (Phomopsis vexans),
Powdery mildew (Erysiphe cichoracoarum), Black spot (Alternaria japonica), White spot (Cerocospor) of cruciferous vegetables
ella brassicae), green onion rust (Puccinia allii), soybean purpura (Cercospora kikuchii), black spot (Elsi)
noe glycines), scab (Diaporthe phaseololum), kidney anthracnose (Colletotrichum lindemuthianum), peanut black astringent (Mycosphaerella personatum), brown spot (Cercospora arachidicola), and pea powdery mildew.
(Erysiphe pisi),

Summer blight of potato (Alternaria solan
i), strawberry powdery mildew (Sphaerothecahumuli), tea net blast (Exobasidium reticulatum), white scab (Elsin
oe leucospila), tobacco scab (Alternaria longipe)
s), powdery mildew (Erysiphe cichoracearum), anthracnose
(Colletotrichum tabacum), brown leaf spot of sugar beet (Cerco
spora beticola), rose scab (Diplocarpon rosae)
, Powdery mildew (Sphaerotheca pannosa), brown spot of chrysanthemum
(Septoria chrysanthemiindici), White rust (Puccinia
horiana), gray mold of various crops (Botrytis cinere
a), sclerotinia sclerotiorum, etc. The usefulness of the compound of the present invention will be specifically described in the following test examples. However, it is not limited to these.

Test Example 1 Gray mold control effect test A 1 to 2 leaf stage cucumber (cultivar: Sagamihanjiro) grown in a pot with a diameter of 7 cm was diluted with water to give 5
The chemical solution adjusted to 00 ppm was sprayed with 20 ml per pot using a spray gun. The next day, the leaves were cut from the cucumber sprayed with the drug solution and placed in a vat lined with water soaked paper. Add to this the Botrytis ciner
ea) spore suspension (1.0% glucose, 2.5% yeast extract, 150 × 40 / field) was spray-inoculated. After inoculation, the vat was covered with vinyl and placed in a thermostatic chamber at a temperature of 18 ° C. for 5 days. The diameter of the lesion formed was measured, and the control value was calculated according to the following formula. Control value = [1- (treatment group lesion diameter (mm) / untreated group lesion diameter (mm))] × 100 As a result, the following compounds showed a control value of 100. Inventive compound No1, No2, No3, No4, No
6, No9, No11, No12, No21, No22, No9
5, No96, No111, No131, No167, No168, No169
, No170, No171, No172, No173, No174, No175
, No176, No177, No178, No180, No181, No182
, No183, No185, No186, No188, No189, No190
, No191, No263, No264, No265, No266, No276
, No277, No278

Test Example 2 Rice Stripe Blight Control Effect Test 3 to 4 leaf stage rice cultivated in a pot with a diameter of 5 cm (variety:
Nihonbare), the compound emulsion of the present invention was diluted with water to 500 pp
Immediately after 5 ml of the stock solution was irrigated with the drug solution prepared to m, 15 ml per pot was sprayed in the same pot. Three days after the treatment, rice grain contaminated with Rhizoctonia solani was placed at the base of the strain and inoculated. Then, the pot was placed in an inoculation box having a temperature of 28 ° C. and a humidity of 95% or more, and the height of the lesion formed 5 days after the inoculation above the ground pole was measured, and the control value was calculated according to the following formula. Control value = [1- (highly treated lesions / highly untreated lesions)] x
100 As a result, the following compounds showed a control value of 100. Inventive compound No1, No2, No3, No6, No
7, No9, No11, No12, No17, No21, No2
2, No95, No96, No99, No100, No104, No105
, No111, No115, No167, No168, No169, No170
, No171, No172, No173, No174, No175, No176
, No178, No179, No180, No181, No182, No183
, No184, No185, No186, No187, No189, No190
, No191, No263, No275, No276, No277, No278

[0110]

The compound of the present invention is a novel compound,
It has an excellent bactericidal action for agricultural and horticultural use, and has no phytotoxicity against useful crops.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location A01N 43/707 8930-4H 43/78 D 8930-4H C07D 401/06 8829-4C 401/12 231 8829-4C 403/06 8829-4C 417/06 9051-4C 417/12 231 9051-4C (72) Inventor Hiroshi Hirohara 1 722, Tsuboicho, Funabashi, Chiba Prefecture Nissan Chemical Industry Co., Ltd. Central Research Laboratory (72) Invention Takeshi Mita 1 722, Tsuboi-cho, Funabashi, Chiba Prefecture, Central Research Laboratory, Nissan Chemical Industries, Ltd. (72) Inventor, Hideo Suzuki 1, 722, Tsuboi-cho, Funabashi City, Chiba Prefecture, Central Research Laboratory, Nissan Chemical Industries, Ltd. (72) Inventor, Furusato Takashi 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Prefectural Institute of Biological Sciences, Nissan Chemical Industry Co., Ltd. NISSAN CHEMICAL INDUSTRIES, LTD.Biological Sciences Research Institute (72) Inventor Masato Nakayama 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama NISSAN CHEMICAL INDUSTRIES, LTD. 1470 NISSAN CHEMICAL INDUSTRIAL CO., LTD.Biological Sciences Research Institute (72) Inventor Ryutaro Toyota Shiraoka, Shirooka-cho, Minami Saitama-gun, Saitama 1470 NISSAN CHEMICAL INDUSTRIES CO., LTD. 1470 Nissan Chemical Industries, Ltd.

Claims (8)

[Claims] 1. A formula [1]: [In the above formula, R ¹ represents a halogen atom, an alkyl group, an alkoxy group, an alkylthio group or a haloalkyl group,
R ² represents an alkyl group or a haloalkyl group, and X is
-N (R ³ )-, -CO- or -C (R ⁴ ) (R ⁵ )-represents, R ³ represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, -COR ⁶ or- Represents SO ₂ R ⁷ , R ⁴ and R
⁵ independently represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group or -OR ⁸ , and R ⁸ represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, or an alkoxy group. Alkyl group, cyanoalkyl group, alkylcarbonylalkyl group, alkoxycarbonylalkyl group, unsubstituted or substituted phenylalkyl group, -COR ⁶ or
Represents -SO ₂ R ⁷ , R ⁶ represents a hydrogen atom, an alkyl group, a haloalkyl group, an unsubstituted or substituted phenyl group, an unsubstituted or substituted phenylalkyl group, an alkoxy group or -N (R ⁹ ) (R ¹⁰ ), R ⁷ represents an alkyl group, a haloalkyl group, an unsubstituted or substituted phenyl group or —N (R ⁹ ) (R ¹⁰ ), and R ⁹ and R ¹⁰ represent
Each independently represents a hydrogen atom, an alkyl group or an unsubstituted or substituted phenyl group, Y represents an oxygen atom, —S—, —SO—, or —SO ₂ —, and A is unsubstituted or substituted. Represents a phenyl group having a group, and B represents an unsubstituted or substituted heterocyclic group having a substituent. However, R ¹ is
In the alkyl group, X is —N (R ³ ) — and B is an unsubstituted 2-
Except for a pyridyl group, an unsubstituted 2-pyrimidyl group or an unsubstituted 2-pyrazyl group. ] The substituted pyrazole derivative represented by these, or its salt. 2. The substituted pyrazole derivative according to claim 1, wherein A is a phenyl group having at least one substituent selected from a halogen atom, an alkyl group and a haloalkyl group. 3. The substituted pyrazole derivative according to claim 2, wherein X is —N (R ³ ) —. 4. The substituted pyrazole derivative according to claim 3, wherein Y is —S—. 5. The substituted pyrazole derivative according to claim 4, wherein R ¹ is a lower alkyl group or a halogen atom, and R ² is a lower alkyl group. 6. The substituted pyrazole derivative according to claim 5, wherein B is an unsubstituted or substituted pyridyl group or an unsubstituted or substituted pyrimidyl group. 7. The substituted pyrazole derivative according to claim 6, wherein R ¹ is a halogen atom. 8. A fungicide for agricultural and horticultural use containing one or more of the substituted pyrazole derivatives according to claim 1 as active ingredients.