JPH07224041A - Pyrazolylacetic acid derivative and agricultural and horticultural fungicide comprising the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as an agricultural and horticultural fungicide having excellent controlling effects on pathogenic fungi of various plants. CONSTITUTION:A compound of formula I (A is hydroxy, a 1-6C alkoxy, etc.; B is a single bond, CH2O, etc.; R<1> is H, a halogen, etc.; R<2> is H or a 1-4C alkyl; R<3> is H, an aryl, etc.; Y is O, CHOCH3, etc.; in the case in which B is CE C, A is not methoxy) such as methyl 2-[3-ethyl-4-methyl-4-{(alpha-methyl-3- trifluoromethylbenzylidene)aminooxymethyl}pyrazol-5-yl]-2-methoxyimino acetate. The compound, for example, is obtained by halomethylating a compound of formula II (R<6> is CH3 or CH5), reacting the resultant compound with a corresponding hydroxy derivative to give a compound of formula III, then reacting dimethyl sulfoxide and successively reacting the reaction product with a halogenating agent and an alcohol.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel pyrazolyl acetic acid derivative, and an agricultural and horticultural fungicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, it is known that certain pyrazolylacetic acid derivatives have biological activity such as bactericidal effect. For example, European Patent Application Publication No. 433899 discloses the following compounds:

[Chemical 2] European Patent Application Publication No. 483851 describes the following compounds.

[Chemical 3] However, under these circumstances, these compounds are not always sufficient as agricultural and horticultural fungicides.

[0003]

Means for Solving the Problems The present inventors have focused their attention on pyrazolyl acetic acid derivatives and, as a result of extensive studies, have found that pyrazolyl acetic acid derivatives having a specific structure have excellent bactericidal activity and can be applied to plants. On the other hand, they have found that they have extremely excellent permeability, and have completed the present invention.

That is, the gist of the present invention resides in a pyrazolyl acetic acid derivative represented by the following general formula (I) and an agricultural and horticultural fungicide containing the same as an active ingredient.

[Chemical 4](In the above general formula, A is a hydroxy group, C₁~ C₆The al
Represents a coxy group or a methylamino group, B is a single bond,-
CH₂O-, -CH₂ON = C (R^Four)-, -CH₂S
-, -CH₂SO-, -CH₂SO₂-, -CO-,-
CH = NO- (CR^FourR^Five)_n -, -C≡C-, -CH
= CH- or -CH₂CH₂Represents −, and n is 0 or
Represents 1, R¹Is a hydrogen atom, a halogen atom or C₁~
C_FourRepresents an alkyl group of R,²Is a hydrogen atom or C₁
~ C_FourRepresents an alkyl group of R,³Is a hydrogen atom, substituted
May be C₁~ C₈Substituted with an alkyl group
Good C₂~ C₈Alkenyl group, which may be substituted
I C₂~ C₈An alkynyl group, optionally substituted C
₃~ C₇A cycloalkyl group, which may be substituted
Represents a reel group or an optionally substituted heterocyclic group.
And R^FourIs a hydrogen atom, C ₁~ C_FourAlkyl group of C₁~
C_FourAlkoxy group of C₁~ C_FourAlkylthio group of
Represents a cyano group, R^FiveIs a hydrogen atom or C₁~ C_Fourof
Represents an alkyl group, Y is an oxygen atom, CHOCH₃, CH
CH₃, CHC₂H_Five, CHSCH₃Or NOCH₃
When B is —C≡C—, A is a methoxy group.
Absent)

The present invention will be described in detail below. The pyrazolyl acetic acid derivative of the present invention is represented by the above general formula (I). In the above general formula (I), A represents a hydroxy group; a C ₁ -C ₆ alkoxy group such as a methoxy group, an ethoxy group, an iso-propoxy group, and an n-butoxy group; or a methylamino group. Preferred as A is a hydroxy group,
A methoxy group or a methylamino group.

B is a single bond, --CH ₂ O--, --CH ₂ ON
^{= C (R 4) -,} - CH 2 S -, - CH 2 SO -, - C
_{H 2 SO 2 -, - CO} -, - CH = NO- (CR
⁴ R ⁵ ) _n- , -C≡C-, -CH = CH- or -C
H ₂ CH ₂ —, n represents 0 or 1, and B represents —
When C≡C-, A is not a methoxy group. Preferred as among these B _{is, -CH 2 O -, - CH} 2 O
^{N = C (R 4) -} , - CH 2 S -, - CO -, - CH =
_{^{NO- (CR 4 R 5) n}} - or -CH = CH-.

R ¹ is a hydrogen atom; a fluorine atom, a chlorine atom,
Halogen atom such as bromine atom; or methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-
It represents a C ₁ -C ₄ alkyl group such as a butyl group. Of these, preferred as R ¹ is a methyl group or an ethyl group. R ² is hydrogen atom; or methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-
It represents a C ₁ -C ₄ alkyl group such as a butyl group. Of these, a methyl group is preferable as R ² .

R ³ is a hydrogen atom; methyl group, ethyl group, n-
C ₁ -C ₈ alkyl groups such as propyl group, iso-propyl group, n-butyl group, sec-butyl group, n-pentyl group; C ₂ -C such as vinyl group, propenyl group, butenyl group, hexenyl group ₈ alkenyl group; C ₂ -C ₈ alkynyl group such as ethynyl group, butynyl group or pentynyl group; C ₃ -C ₇ cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclohexyl group; phenyl group, naphthyl group Or an optionally substituted aryl group; or a substitution of pyridyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group, furyl group, thienyl group, morpholinyl group, benzodioxanyl group, benzofuranyl group, etc. Represents an optionally substituted heterocyclic group. The above alkyl group, alkenyl group, alkynyl group and cycloalkyl group are each a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; or a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group. Groups, sec-butyl groups, and other C ₁ -C ₄ alkyl groups may be optionally substituted. The above aryl group and heterocyclic group include halogen atoms such as fluorine atom, chlorine atom, and bromine atom; methyl group, ethyl group, n-propyl group,
C ₁ such as iso-propyl group, n-butyl group, sec-butyl group
To C ₄ alkyl group; C _{1 to} C ₄ haloalkyl group such as trifluoromethyl group, difluoromethyl group, trichloromethyl group or dichlorodifluoroethyl group; substituted with halogen atom or C _{3 to} C ₆ cycloalkyl group Optionally substituted C ₁ -C ₆ alkoxy groups such as methoxy group, ethoxy group, iso-propoxy group, n-butoxy group;
Alternatively, it may be substituted with a C ₁ -C ₆ alkylthio group such as a methylthio group, an ethylthio group, an iso-propylthio group, and an n-butylthio group. Of these, preferred as R ³ is a hydrogen atom or an optionally substituted aryl group.

R ⁴ is a hydrogen atom; methyl group, ethyl group, n-
Propyl, iso- propyl, n- butyl group, an alkyl group of C ₁ -C _4, such as sec- butyl group; methoxy group, ethoxy group, iso- propoxy group, C ₁ -C such n- butoxy
₄ alkoxy groups; methylthio group, ethylthio group, iso-
It represents a C ₁ -C ₄ alkylthio group such as a propylthio group or an n-butylthio group; or a cyano group. R of these
Preferred as ⁴ are a methyl group and an ethyl group.

R ⁵ is hydrogen atom; or methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-
It represents a C ₁ -C ₄ alkyl group such as a butyl group. Of these, preferred as R ⁵ is a hydrogen atom. Y
Is an oxygen atom, CHOCH ₃ , CHCH ₃ , CHC
₂ H ₅ , CHSCH ₃ or NOCH ₃ , of which preferred as Y is an oxygen atom, CHOCH
₃ or NOCH ₃ . The compounds of the present invention are all novel compounds and are produced, for example, according to the following reaction formula (1).

[0011]

[Chemical 5] (In the above formula, B, R ¹ , R ² and R ³ are as defined in the above general formula (I), and Z is CH ₂ C
1, CH ₂ Br, CH ₂ OH or CHO, R ⁶
Represents a methyl group or an ethyl group, R ⁷ represents a hydrogen atom or a methylthio group, and D represents a methoxy group, a methyl group, an ethyl group or a methylthio group)

The methoxyiminoacetic acid amide derivative represented by the general formula (Ic) is obtained by converting the α-ketoester derivative represented by the general formula (Ia) into O-methylhydroxyl in an inert solvent such as methanol. It is obtained by reacting an amine hydrochloride and the resulting methoxyiminoacetic acid ester derivative represented by the general formula (Ib) with methylamine in the presence of alcohols such as methanol or water. The methoxyacrylic acid derivative represented by the general formula (Id) is α represented by the general formula (Ia).
-Ketoester derivatives such as sodium hydride, sodium methylate, n-butyllithium or potassium-tert-
In the presence of a base such as butyrate, an inert solvent (for example,
It can be obtained by reacting the corresponding phospholane (Wittig reaction) in diethyl ether, tetrahydrofuran, dimethylformamide or dimethylsulfoxide).

The α-ketoester derivative (Ia), which is an important intermediate in this reaction, is obtained by adding the corresponding pyrazolylcarboxylic acid derivative (IV) to dimethylsulfoxide or methyl methylsulfinylmethyl in the presence of a base.
Reaction of sulfide with β-keto sulfoxide (V) thus obtained and reaction with halogenating agent (Synthesis 41 (1982)
Reference), and then reacting with an alcohol such as methanol in the presence of a base (Pummerer reaction).

When B represents --CH ₂ O--, --CH ₂ ON = C (R ⁴ )-or --CH ₂ S-- in the pyrazolylcarboxylic acid derivative (IV), it is represented by the corresponding general formula (III). The resulting halomethyl derivative or hydroxymethyl derivative can be obtained by reacting the corresponding hydroxy derivative or mercapto derivative with a base (potassium carbonate or sodium hydride). The thioether derivative can be further oxidized with a peroxide such as metachloroperbenzoic acid to obtain a pyrazolylcarboxylic acid derivative (IV) in which B is represented by —CH ₂ SO— or —CH ₂ SO ₂ —.

Of the pyrazolylcarboxylic acid derivative (IV)
B is -CH = NO- (CR^FourR^Five) _n-Indicates phase
The aldehyde derivative represented by the corresponding general formula (III),
O-substituted or unsubstituted in an inert solvent such as alcohol
It can be obtained by reacting hydroxyamine
Wear. In the pyrazolylcarboxylic acid derivative (IV), B is
When CH = CH- is shown, it is represented by the corresponding general formula (III).
Aldehyde derivatives, sodium hydride, Natri
Ummethylate, n-butyllithium or potassium-t
In the presence of a base such as ert-butyrate, an inert solvent (eg
For example, diethyl ether, tetrahydrofuran, dimethyl
Formamide or dimethyl sulfoxide)
Of the corresponding phosphorane (Wittig reaction)
It can be obtained by The obtained compound is Pd / C
By the presence of a catalyst such as, and hydrogenation, B-
CH₂CH ₂A pyrazolylcarboxylic acid derivative represented by
(IV) can be obtained.

The corresponding pyrazolylcarboxylic acid derivative represented by the general formula (III) can be obtained by subjecting the pyrazolylcarboxylic acid derivative represented by the general formula (II) to halomethylation or formylation by Friedel-Crafts reaction. it can. Α, an important intermediate in this reaction
-The ketoester derivative (Ia) can also be produced by the following reaction formula.

[0017]

[Chemical 6] (In the formula, B, R ¹ , R ² , R ³ and R ⁶ are as defined in the general formula (I) and the reaction formula) The α-keto ester derivative (Ia) corresponds to The pyrazolylcarboxylic acid chloride derivative (VI) is reacted with a cyanating agent such as sodium cyanide, potassium cyanide, or copper cyanide (see Tet. Lett. 26 2275 (1974)), and the resulting acyl cyanide is treated under acidic conditions with methanol or the like. React with alcohol (Angew. Chem 94 1 (1
982) or Tet. Lett. 21 3539 (1980)).

The methoxyiminoacetic acid derivatives represented by the above general formulas (Ib) and (Ic) have isomers due to the methoxyimino moiety. All of them can be converted into the E-form by treating with an acid such as hydrochloric acid, sulfuric acid or methanesulfonic acid in an alcohol solvent such as methanol or ethanol. Further, the methoxyacrylate derivative represented by the general formula (Id) has an isomer due to the acrylate moiety. All of them can be converted to the E form by treating with a base such as potassium carbonate or sodium methylate in an alcohol solvent such as methanol or ethanol, or in dimethylformamide, dimethylsulfoxide or water. .

The compounds of the present invention thus obtained are all novel and have excellent bactericidal activity. Particularly, since it has an excellent control effect against pathogenic bacteria of various plants, it is useful as a fungicide for agriculture and horticulture. For example, rice blast (Pyricularia orizae); rice blight (Rhizoc)
tonia solani); powdery mildew of wheat (Erysiphe gramini)
s); Various rust diseases of barley (Puccinia recondita); Gray mold disease of vegetables and fruit trees (Botrytis cinerea); Not only high activity against epidemics of various crops (Phytophthora infestance), but also residual effect It is useful as a fungicide for agricultural and horticultural use because it has a long period of time and has excellent permeability to plants.

When the compound of the present invention is used as a fungicide for agricultural and horticultural use, this compound may be used as it is, but in order to effectively disperse the active ingredient in the application scene,
It is preferable to add an auxiliary agent according to a conventional method and use it in the form of emulsion, wettable powder, powder, granule and the like. When the agricultural or horticultural fungicide of the present invention is applied, when it is used in the form of an emulsion, the compound of the present invention is usually 10 to 80 parts, preferably 10 parts.
~ 70 parts, the solvent is usually 10-90 parts, preferably 20-
80 parts and a surfactant are usually 3 to 20 parts, preferably 5 to
A mixture of 15 parts in an appropriate ratio is used as a raw material, and when used, it is diluted with water to a predetermined concentration and applied by a method such as spraying. When used in the form of a wettable powder, the compound of the present invention is usually 5 to 80 parts, preferably 10 to 70 parts, and the extender is usually 10 to 90 parts, preferably 20 to 8 parts.
0 part and a surfactant are usually 1 to 20 parts, preferably 3 to 1
5 parts are mixed at an appropriate ratio, and the mixture is diluted with water or the like to a predetermined concentration and used as in the case of the emulsion.

When used in the form of powder, the compound of the present invention is usually 0.1 to 10 parts, preferably 1 to 5 parts, and a bulking agent such as kaolin, bentonite and talc is usually 90 to 9 parts.
A uniform mixture of 9.9 parts, preferably 95 to 99 parts, is used. The fungicide for agricultural and horticultural use of the present invention can also be used as a mixture with other active ingredients that do not inhibit the fungicidal effect of the present active ingredient, for example, fungicides, insecticides, acaricides and the like. The agricultural and horticultural fungicide of the present invention can be suitably applied to both foliar application and water surface application. In the case of foliage application, the effective content is usually 10 to 1 in the form of emulsion or wettable powder.
It may be diluted with water to contain 000 ppm, and 10 to 500 liters may be applied per 10 ares.

[0022]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Synthesis Example 1 Methyl 2- [3-ethyl-1-methyl-4-{(α-
Synthesis of methyl-3-trifluoromethylbenzylidene) aminooxymethyl} pyrazol-5-yl] -2-methoxyiminoacetate (Compound No. 71 in Table 1 below)
And 72)

5-ethoxycarbonyl-3-ethyl-1
-Methylpyrazole 25 g (137 mmol), phosphoric acid 18 ml, concentrated hydrochloric acid 45 ml, and acetic acid 90 ml were added to a mixture of paraformaldehyde 9.6 g (320 mmo).
1) was added, and the mixture was stirred at 100 ° C. for 2 hours. After cooling the reaction mixture, 300 ml of ethyl acetate was added, and the mixture was washed successively with water, saturated aqueous sodium hydrogen carbonate, water, and saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (SiO ₂ 200 g, hexane / ethyl acetate = 9/1, 6/1) to give 4-chloromethyl-5-ethoxycarbonyl which is an important intermediate. -3-Ethyl-1-methylpyrazole (13.4
6 g, yield 44.2%) was obtained. The physical properties of the obtained compound are as follows.

¹ H-NMR δ (ppm): 1.29 (3H, t), 1.43
(3H, t), 2.69 (2H, q), 4.11 (3H, s), 4.41 (3H, s), 4.75 (3
H, s) ¹³ C-NMR δ (ppm): 13.7, 14.1, 19.4, 36.0, 39.
9, 61.3, 119.4, 130.7, 152.5, 159.7

60% sodium hydride 0.40 (10 m
mol) in a DMF 10 ml suspension under ice-cooling m-trifluoromethylacetophenone oxime 2.0 g (10 m
mol) was added and the mixture was stirred for 1 hour, then, 2.3 g (10 mmol) of 4-chloromethyl-5-ethoxycarbonyl-3-ethyl-1-methylpyrazole was added, and the mixture was added at room temperature to 22
Stir for hours. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent, the residue was subjected to silica gel column chromatography (SiO ₂ 60 g, hexane /
Ethyl acetate = 15/1, 10/1) and purified by 5-
Ethoxycarbonyl-3-ethyl-1-methyl-4-
{(Α-Methyl-3-trifluoromethylbenzylidene) aminooxymethyl} pyrazole (3.30 g, yield 83.1%) was obtained. The physical properties of the obtained compound are as follows. ¹ H-NMR δ (ppm): 1.27 (3H, t), 1.39 (3H, t), 2.20
(3H, s), 2.75 (2H, q), 4.12 (3H, s), 4.39 (2H, q), 5.34 (2
H, s), 7.48 (1H, dd), 7.60 (1H, d), 7.80 (1H, d), 7.92 (1
H, s) ¹³ C-NMR δ (ppm): 160.3

In a nitrogen stream, 60% sodium hydride
To a suspension of 66 g (16.6 mmol) in 7 ml of THF, methylmethylsulfinylmethyl sulfide (FAMS) was added.
A solution of 1.03 g (8.3 mmol) of O) in 2 ml of THF was added, and the mixture was stirred at room temperature for 2 hours, and then 5-ethoxycarbonyl-3-ethyl-1-methyl-4-{(α-methyl-
3.0 g (7.56 mmol) of 3-trifluoromethylbenzylidene) aminooxymethyl} pyrazole was added, and the mixture was stirred at room temperature for 22 hours. 0.2m of water in the reaction mixture
1, acetic acid 0.95 ml, and toluene 20 ml were sequentially added, and the mixture was stirred at room temperature for 1 hour, filtered, the solvent was distilled off from the filtrate, and the residue was subjected to silica gel column chromatography (SiO ₂ 50 g, hexane / ethyl acetate = 1. / 1,1
/ 3), 3-ethyl-1-methyl-5-
(Α-Methylthio-α-methylsulfinyl) acetyl-4-{(α-methyl-3-trifluoromethylbenzylidene) aminooxymethyl} pyrazole (1.96
g, yield 54.5%).

Then, the obtained 3-ethyl-1-methyl-5- (α-methylthio-α-methylsulfinyl) acetyl-4-{(α-methyl-3-trifluoromethylbenzylidene) aminooxymethyl} pyrazole 1.9
5 g (4.10 mmol), pyridine 1.0 ml (1
2.3 mmol), and to a mixture of 20 ml of methanol, 1.10 g (8.2 mm) of N-chlorosuccinimide.
was added and the mixture was stirred at room temperature for 2 hours. 0.2 ml of water and 0.87 g of anhydrous sodium carbonate in the reaction mixture
(8.2 mmol) was added, and the mixture was further stirred for 2 hours. Toluene 40 ml was added to the reaction mixture and filtered, the solvent was distilled off from the filtrate, and the residue was subjected to silica gel column chromatography (SiO ₂ 50 g, hexane / ethyl acetate = 15 /
1,8 / 1) and methyl [3-ethyl-1-
Methyl-4-{(α-methyl-3-trifluoromethylbenzylidene) aminooxymethyl} pyrazole-5
Il] glyoxylate (1.04 g, yield 40%) was obtained. The physical properties of the obtained compound are as follows. ¹ H-NMR δ (ppm): 1.28 (3H, t), 2.18 (3H, s), 2.73
(2H, q), 3.87 (3H, s), 4.10 (3H, s), 5.18 (2H, s), 7.49 (1
H, dd), 7.61 (1H, d), 7.79 (1H, d), 7.89 (1H, s) ¹³ C-NMR δ (ppm): 163.0, 177.3

Then, the obtained methyl [3-ethyl-1-
Methyl-4-{(α-methyl-3-trifluoromethylbenzylidene) aminooxymethyl} pyrazole-5
Il] glyoxylate 0.67 g (1.63 mmo
l), 0.25 g of methoxyamine hydrochloride (2.91 mm)
ol), pyridine 0.3 ml (3.64 mmol), acetic acid 1 ml, and methanol 10 ml were stirred at room temperature for 3 days. To the reaction mixture was added 80 ml of toluene, washed with water and saturated saline, and dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography (SiO ₂ 50 g, hexane / ethyl acetate = 10/1, 5/1, 1/1),
E form (0.33 g, yield 46.0%) and Z form (0.13 g, yield 18.1%) of the title compound were obtained.

Synthesis Example 2 N-methyl-2- [1,3-dimethyl-4-{(α-methyl-3-trifluoromethylbenzylidene) aminooxymethyl} pyrazol-5-yl] -2-methoxyiminoamine Synthesis of Cetamide (Synthesis of Compound No. 95 in Table 1) Methyl 2- [1,3-dimethyl-4-{(α-methyl-3-trifluoromethylbenzylidene) aminooxymethyl} pyrazol-5-yl] 2-Methoxyiminoacetate (0.53 g) in 4 ml of 5 ml of methanol
5 ml of 0% methylamine / methanol solution was added, and the mixture was stirred at room temperature overnight. After completion of the reaction, the solvent was distilled off and the residue was recrystallized (ethyl acetate / hexane = 1/9) to obtain 0.55 g of the title compound in a quantitative yield. The compounds in Table 1 were synthesized in the same manner except that the starting materials were changed.

[0030]

[Table 1] Table 1 ──────────────────────────────────── No. R ¹ R ² Y A BR ³ isomer ──────────────────────────────────── 1 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ OHE 2 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ OHZ 3 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ OHE 4 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2-CH ₃ -Phenyl E 5 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2-CH ₃ -Phenyl Z 6 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 2-CH ₃ -Phenyl E 7 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2,5- (CH ₃ ) ₂ -Phenyl E 8 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2,5- (CH ₃ ) ₂ -Phenyl Z 9 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 2,5- (CH ₃ ) ₂ -Phenyl E 10 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2,5- (CH ₃ ) ₂ -Phenyl E 11 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2,5- (CH ₃ ) _2- Phenyl Z 12 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 2,5- (CH ₃ ) _2- Phenyl E 13 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2,4-Cl ₂ -Phenyl E 14 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 2,4-Cl ₂ -Phenyl E 15 CH ₃ CH ₃ NOCH ₃ O CH ₃ CH ₂ O 2,5-Cl ₂ -Phenyl E 16 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2,5-Cl ₂ -Phenyl Z 17 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 2,5 -Cl ₂ -Phenyl E 18 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2-CH ₃ , 4-OCH ₃ -Phenyl E 19 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 2-CH ₃ , 4, OCH ₃ -Phenyl E 20 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2-CH ₃ , 4-OC ₃ H ₇ (iso) -Phenyl E 21 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 2-CH ₃ , 4-OC ₃ H ₇ (iso) -Phenyl E 22 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2-CH ₃ , 4-OCH ₂ CCH-Phenyl E 23 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 2 -CH ₃ , 4-OCH ₂ CCH-Phenyl E ────────────────────────────────────

[0031]

[Table 2] (Continued Table 1) ──────────────────────────────────── No. R ¹ R ² Y A BR ³ isomer ──────────────────────────────────── 24 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 3-SC ₂ H ₅ -Phenyl E 25 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 3-SC ₂ H ₅ -Phenyl E 26 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 3- SC ₃ H ₇ (iso) -Phenyl E 27 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 3-SC ₃ H ₇ (iso) -Phenyl E 28 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 3-CF ₃ -Phenyl E 29 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 3-CF ₃ -Phenyl E 30 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 4-CF ₃ -Phenyl E 31 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 4-CF ₃ -Phenyl E 32 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 3-OCF ₃ -Phenyl E 33 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 3-OCF ₃ -Phenyl E 34 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 4-OCF ₃ -Phenyl E 35 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 4-OCF ₃ -Phenyl E 36 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O Tetrahydropyran- 2-yl E 37 CH ₃ CH ₃ NO CH ₃ OCH ₃ CH ₂ O Tetrahydropyran-2-yl Z 38 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O CH ₃ E 39 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O CH ₃ Z 40 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O CCl ₃ E 41 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ OHE 42 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ OHE 43 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2,4- (CH ₃ ) ₂ -Phenyl E 44 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 2,4- (CH ₃ ) ₂ -Phenyl E 45 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2,5- (CH ₃ ) ₂ -Phenyl E ─────────────────────────────────────

[0032]

[Table 3] (continued from Table 1) ──────────────────────────────────── No. R ¹ R ² Y A BR ³ isomer ──────────────────────────────────── 46 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 2,5- (CH ₃ ) _2- Phenyl E 47 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 2-naphthyl E 48 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 4-CF ₃ -Phenyl E 49 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 5-CF ₃ -pyridin-2-yl E 50 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ O 3-Cl-5-CF ₃ -Pyridin-2 -yl E 51 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ O 3-Cl-5-CF ₃ -Pyridin-2-yl E 52 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ OHE 53 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 2,5- (CH ₃ ) 2-Phenyl E 54 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 2,4- (CH ₃ ) 2-Phenyl E 55 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 2,4-Cl ₂ -Phenyl E 56 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 2,5-Cl ₂ -Phenyl E 57 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 2-CH ₃ , 4, OCH ₃ -Phenyl E 58 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 2-CH ₃ , 5-OCHF ₂ -Phenyl E 5 9 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 2-Cl, 5-OCHF ₂ -Phenyl E 60 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 3-CF ₃ -Phenyl E 61 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 4-CF ₃ -Phenyl E 62 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 3-OCF ₃ -Phenyl E 63 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 4-OCF ₃ -Phenyl E 64 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ S 2,5- (CH ₃ ) _2- Phenyl E 65 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ S 2-naphthyl E 66 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ S 4-CF ₃ -Phenyl E 67 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ S 5-CF ₃ -pyridin-2-yl E ──────────────────── ─────────────────

[0033]

[Table 4] (Continued Table 1) ──────────────────────────────────── No. R ¹ R ² Y A BR ³ isomer ──────────────────────────────────── 68 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ S 3-Cl-5-CF ₃ -Pyridin-2-yl E 69 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ S 3-Cl-5-CF ₃ -Pyridin-2-yl E 70 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ O 3-SC ₂ H ₅ -Phenyl E 71 C ₂ H ₅ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-CF ₃ -Phenyl E 72 C ₂ H ₅ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-CF ₃ -Phenyl Z 73 C ₂ H ₅ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-CF ₃ -Phenyl E 74 C ₂ H ₅ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-OCF ₃ -Phenyl E 75 C ₂ H ₅ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 4-OCF ₃ -Phenyl E 76 C ₂ H ₅ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-OCHF ₂ -Phenyl E 77 C ₂ H ₅ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 3-OCHF ₂ -Phenyl E 78 C ₂ H ₅ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-Cl-Phenyl E 79 C ₂ H ₅ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-Cl-Phenyl Z 80 C ₂ H ₅ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 4-Cl-Phenyl E 81 C ₂ H ₅ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-CH ₃ -Phenyl E 82 C ₂ H ₅ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-CH ₃ -Phenyl Z 83 C ₂ H ₅ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 3-CH ₃ -Phenyl E 84 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-Cl-Phenyl E 85 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-Cl-Phenyl Z 86 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 4-Cl-Phenyl E 87 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-Cl-Phenyl E 88 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-Cl-Phenyl Z 89 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 3-Cl-Phenyl E ───── ───────────────────────────────

[0034]

[Table 5] (Continued Table 1) ──────────────────────────────────── No. R ¹ R ² Y A BR ³ isomer ──────────────────────────────────── 90 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-CF ₃ -Phenyl E 91 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-CF ₃ -Phenyl E 92 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 4-CF ₃ -Phenyl E 93 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-CF ₃ -Phenyl E 94 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-CF ₃ -Phenyl E 95 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 3-CF ₃ -Phenyl E 96 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3- OCF ₃ -Phenyl E 97 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-OCF ₃ -Phenyl E 98 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-OCHF ₂ -Phenyl E 99 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) Phenyl E 100 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-OCF ₃ -Phenyl E 101 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-OCF ₃ -Phen yl E 102 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-OCHF ₂ -Phenyl E 103 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-OCHF ₂ -Phenyl E 104 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-CH ₃ -Phenyl E 105 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-Cl-Phenyl E 106 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-CF ₃ -Phenyl E 107 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-Br-Phenyl E 108 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-SCH ₃ -Phenyl E 109 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-OCH ₃ -Phenyl E 110 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-CF ₃ -Phenyl E 111 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-Cl-Phenyl E ───────────────────── ───────────────

[0035]

[Table 6] (Continued Table 1) ──────────────────────────────────── No. R ¹ R ² Y A BR ³ isomer ──────────────────────────────────── 112 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-CH ₃ -Phenyl E 113 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-Br-Phenyl E 114 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-OCH ₃ -Phenyl E 115 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3,4-CF ₃ -Phenyl E 116 CH ₃ CH ₃ CHOCH ₃ OCH ₃ CH ₂ ONC ( CH ₃ ) Phenyl E 117 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-CF ₃ -Phenyl E 118 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 3-CF ₃ -Phenyl E 119 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4-CF ₃ -Phenyl E 120 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 4-CF ₃ -Phenyl E 121 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 3-OCF ₃ -Phenyl E 122 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 3-OCHF ₂ -Phenyl E 123 CH ₃ CH ₃ NOCH ₃ OCH ₃ CH ₂ ONC (CH ₃ ) 4 -OCF ₃ -Phenyl E 124 CH ₃ CH ₃ NOCH ₃ NHCH ₃ CH ₂ ONC (CH ₃ ) 3-OCF ₃ -Phenyl E 125 CH ₃ CH ₃ NOCH ₃ NHCH ₃ C≡C 3-CF ₃ -Phenyl E 126 CH _{3 CH 3 NOCH 3 NHCH 3 C≡C} 4-CF 3 -Phenyl E 127 CH 3 CH 3 NOCH 3 NHCH 3 C≡C 4-CF 3 -Phenyl E 128 CH 3 CH 3 NOCH 3 NHCH 3 C≡C 3- _{OCF 3 -Phenyl E 129 CH 3 CH} 3 NOCH 3 NHCH 3 C≡C 3-OCF 3 -Phenyl E 130 CH 3 CH 3 NOCH 3 NHCH 3 C≡C 4-OCF 3 -Phenyl E 131 CH 3 CH 3 NOCH 3 NHCH ₃ C ≡ C 3-OCF ₃ -Phenyl E ────────────────────────────────────

¹ H-NMR (CDCl
_The analytical values according to ₃ ) were as follows.

Compound No. 1; 2.05 (1H, t), 2.30 (3H,
s), 3.64 (3H, s), 3.93 (3H, s), 4.15 (3H, s), 4.34 (2H, d) Compound No. 2; 2.17 (1H, t), 2.28 (3H, s), 3.84 (3H,
s), 3.92 (3H, s), 4.07 (3H, s), 4.43 (2H, d) Compound No. 4; 2.15 (3H, s), 2.31 (3H, s), 3.67 (3H,
s), 3.80 (3H, s), 4.06 (3H, s), 4.80 (2H, s), 6.78-6.88
(2H, m), 7.10-7.16 (2H, m) Compound No. 5; 2.17 (3H, s), 2.28 (3H, s), 3.65 (3H,
s), 3.92 (3H, s), 4.02 (3H, s), 4.83 (2H, s), 6.82-6.93
(2H, m), 7.10-7.20 (2H, m)

Compound No. 6; 2.13 (3H, s), 2.28 (3H,
s), 2.82 (3H, d), 3.65 (3H, s), 3.93 (3H, s), 4.78 (2H,
s), 6.8-6.9 (3H, m), 7.05-7.15 (2H, m) Compound No. 7; 2.10 (3H, s), 2.31 (6H, s), 3.67 (3H,
s), 3.81 (3H, s), 4.08 (3H, s), 4.78 (2H, s), 6.63 (1H,
s), 6.67 (1H, d), 6.98 (1H, d) Compound No. 8; 2.12 (3H, s), 2.27 (3H, s), 2.33 (3H,
s), 3.66 (3H, s), 3.92 (3H, s), 4.03 (3H, s), 4.81 (2H,
s), 6.68 (1H, d), 6.72 (1H, s), 7.00 (1H, d) Compound No. 9; 2.09 (3H, s), 2.28 (6H, s), 2.83 (3H,
d), 3.365 (3H, s), 3.94 (3H, s), 4.77 (2H, s), 6.63 (1H,
d), 6.65 (1H, s), 6.90 (1H, br), 6.95 (1H, d)

Compound No. 10; 2.12 (3H, s), 2.24 (3H,
s), 2.30 (3H, s), 3.66 (3H, s), 3.81 (3H, s), 4.07 (3H,
s), 4.76 (2H, s), 6.69 (1H, d), 6.91 (1H, d), 6.93 (1H, s) Compound No. 11; 2.04 (3H, s), 2.14 (3H, s), 2.26 (3H,
s), 3.67 (3H, s), 3.91 (3H, s), 4.03 (3H, s), 4.79 (2H,
s), 6.79 (1H, d), 6.94 (2H, m) Compound No. 15; 2.32 (3H, s), 3.66 (3H, s), 3.87 (3H,
s), 4.09 (3H, s), 4.87 (2H, s), 6.86 (1H, s), 6.87 (1H,
d), 7.25 (1H, d)

Compound No. 16; 2.30 (3H, s), 3.76 (3H,
s), 3.88 (3H, s), 4.05 (3H, s), 4.93 (2H, s), 6.88 (1H,
d), 7.01 (1H, s), 7.27 (1H, d) Compound No. 17; 2.31 (3H, s), 2.89 (3H, d), 3.67 (3H,
s), 4.00 (3H, s), 4.88 (2H, s), 6.77 (1H, br), 6.87 (1H,
d), 6.88 (1H, s), 7.24 (1H, d) Compound No. 30; 2.30 (3H, s), 3.66 (3H, s), 3.84 (3H,
s), 4.05 (3H, s), 4.86 (2H, s), 6.93 (2H, d), 7.52 (2H,
d) Compound No. 36; 1.4-1.9 (6H, m), 2.26 (3H, s), 3.49 (1
H, m), 3.65 (3H, s), 3.80 (1H, m), 3.89 (3H, s), 4.12 (3H,
s), 4.22,4.26,4.51,4.55 (2H, ABq), 4.55 (1H, dd) Compound No. 37; 1.4-1.9 (6H, m), 2.27 (3H, s), 3.52 (1
H, m), 3.87 (3H, s), 3.88 (3H, s), 3.89 (1H, m), 4.05 (3H,
s), 4.30,4.34,4.55,4.59 (2H, ABq), 4.58 (1H, dd)

Compound No. 38; 2.25 (3H, s), 3.28 (3H,
s), 3.87 (3H, s), 3.89 (3H, s), 4.05 (3H, s), 4.24 (2H, s) Compound No. 39; 2.25 (3H, s), 3.23 (3H, s), 3.65 (3H,
s), 3.89 (3H, s), 4.12 (3H, s), 4.20 (2H, s) Compound No. 40; 2.24 (3H, s), 3.66 (3H, s), 3.92 (3H,
s), 4.17 (3H, s) Compound No. 47 ； 2.22 (3H, s), 3.60 (3H, s), 3.79 (3H,
s), 3.94 (2H, s), 3.98 (3H, s), 7.1-7.3 (3H, m), 7.7-7.8
(4H, m) Compound No. 48; 2.22 (3H, s), 3.62 (3H, s), 3.87 (3H,
s), 3.91 (2H, s), 4.07 (3H, s), 7.30 (2H, d), 7.48 (2H, d)

Compound No. 49; 2.29 (3H, s), 3.61 (3H,
s), 3.89 (3H, s), 4.07 (3H, s), 4.20 (2H, s), 7.19 (1H,
d), 7.63 (1H, d), 8.63 (1H, s) Compound No. 50; 2.31 (3H, s), 3.62 (3H, s), 3.90 (3H,
s), 4.08 (3H, s), 4.19 (2H, s), 7.71 (1H, d), 8.55 (1H, d) Compound No. 71; 1.30 (3H, t), 2.18 (3H, s), 2.72 (2H,
q), 3.66 (3H, s), 3.82 (3H, s), 4.02 (3H, s), 5.01 (2H,
s), 7.47 (1H, dd), 7.59 (1H, d), 7.79 (1H, d), 7.89 (1H,
s)

Compound No. 72 ； 1.27 (3H, t), 2.20 (3H, t
s), 2.73 (2H, q), 3.84 (3H, s), 3.92 (3H, s), 4.05 (3H,
s), 5.08 (2H, s), 7.47 (1H, dd), 7.59 (1H, d), 7.82 (1H,
d), 7.93 (1H, s) Compound No. 78; 1.29 (3H, t), 2.13 (3H, s), 2.71 (2H,
q), 3.66 (3H, s), 3.81 (3H, s), 4.04 (3H, s), 4.97 (3H,
s), 7.32 (2H, d), 7.54 (2H, d) Compound No. 79; 1.26 (3H, t), 2.15 (3H, s), 2.71 (2H,
q), 3.82 (3H, s), 3.92 (3H, s), 4.05 (3H, s), 5.03 (3H,
s), 7.32 (2H, d), 7.58 (2H, d) Compound No. 80 ； 1.28 (3H, t), 2.12 (3H, s), 2.71 (2H,
q), 2.85 (3H, d), 3.66 (3H, s), 3.95 (3H, s), 4.97 (2H,
s), 6.75 (1H, br), 7.31 (2H, d), 7.53 (2H, d)

Compound No. 81; 1.29 (3H, t), 2.14 (3H,
s), 2.37 (3H, s), 2.72 (2H, q), 3.66 (3H, s), 3.80 (3H,
s), 4.04 (3H, s), 4.98 (2H, s), 7.16 (1H, d), 7.23 (1H, d
d), 7.37 (1H, d), 7.43 (1H, s) Compound No. 82; 1.27 (3H, t), 2.17 (3H, s), 2.37 (3H,
s), 2.72 (2H, q), 3.82 (3H, s), 3.92 (3H, s), 4.05 (3H,
s), 5.04 (2H, s), 7.16 (1H, d), 7.24 (1H, dd), 7.42 (1H,
d), 7.47 (1H, s)

Compound No. 83; 1.28 (3H, t), 2.13 (3H,
s), 2.35 (3H, s), 2.71 (2H, q), 2.81 (3H, d), 3.66 (3H,
s), 3.93 (3H, s), 4.97 (2H, s), 6.75 (1H, br), 7.13 (1H,
d), 7.21 (1H, dd), 7.35 (1H, d), 7.39 (1H, s) Compound No. 84 ； 2.13 (3H, s), 2.31 (3H, s), 3.65 (3H,
s), 3.81 (3H, s), 4.04 (3H, s), 4.96 (2H, s), 7.32 (2H,
d), 7.55 (2H, d) Compound No. 85; 2.15 (3H, s), 2.32 (3H, s), 3.84 (3H,
s), 3.91 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 7.32 (2H,
d), 7.57 (2H, d) Compound No. 86; 2.12 (3H, s), 2.31 (3H, s), 2.86 (3H,
d), 3.65 (3H, s), 3.95 (3H, s), 4.96 (2H, s), 6.82 (1H, b
r), 7.30 (2H, d), 7.53 (2H, d)

Compound No. 87; 2.13 (3H, s), 2.32 (3H,
s), 3.65 (3H, s), 3.84 (3H, s), 4.04 (3H, s), 4.98 (2H,
s), 7.24-7.35 (2H, m), 7.48 (1H, d), 7.61 (1H, s) Compound No. 88; 2.16 (3H, s), 2.32 (3H, s), 3.84 (3H,
s), 3.91 (3H, s), 4.06 (3H, s), 5.04 (2H, s), 7.23-7.36
(2H, m), 7.50 (1H, d), 7.64 (1H, s) Compound No. 89; 2.12 (3H, s), 2.31 (3H, s), 2.88 (3H,
d), 3.64 (3H, s), 3.89 (3H, s), 4.99 (2H, s), 6.95 (1H, b
r), 7.22-7.35 (2H, m), 7.43 (1H, d), 7.64 (1H, s) Compound No. 90; 2.17 (3H, s), 2.32 (3H, s), 3.65 (3H,
s), 3.81 (3H, s), 4.04 (3H, s), 5.00 (2H, s), 7.61 (2H,
d), 7.72 (2H, d)

Compound No. 91; 2.19 (3H, s), 2.33 (3H,
s), 3.84 (3H, s), 3.91 (3H, s), 4.06 (3H, s), 5.07 (2H,
s), 7.60 (2H, d), 7.75 (2H, d) Compound No. 92; 2.17 (3H, s), 2.32 (3H, s), 2.87 (3H,
d), 3.66 (3H, s), 3.95 (3H, s), 5.00 (2H, s), 6.84 (1H, b
r), 7.59 (2H, d), 7.71 (2H, d) Compound No. 93; 2.18 (3H, s), 2.33 (3H, s), 3.65 (3H,
s), 3.83 (3H, s), 4.03 (3H, s), 5.00 (2H, s), 7.47 (1H, d
d), 7.59 (1H, d), 7.79 (1H, d), 7.89 (1H, s) Compound No. 94; 2.18 (3H, s), 2.31 (3H, s), 3.82 (3H,
s), 3.89 (3H, s), 4.03 (3H, s), 5.05 (2H, s), 7.44 (1H, d
d), 7.56 (1H, d), 7.79 (1H, d), 7.90 (1H, s) Compound No. 94; 2.17 (3H, s), 2.33 (3H, s), 2.88 (3H,
d), 3.65 (3H, s), 3.88 (3H, s), 5.01 (2H, s), 6.87 (1H, b
r), 7.47 (1H, dd), 7.58 (1H, d), 7.76 (1H, d), 7.91 (1H,
s)

Formulation Example 1 Compound No. shown in Table 1 20 parts of compound 2 and 7 of diatomaceous earth
5 parts and 5 parts of a surfactant containing alkylbenzene sulfonic acid as a main component were uniformly pulverized and mixed to obtain a wettable powder. Formulation Example 2 Compound No. shown in Table 1. 30 parts of the compound of 3 and "Solpol" 3005X (trademark of Toho Chemical Industry Co., Ltd., a mixture of a nonionic surfactant and an anionic surfactant) 15
Parts, xylene 25 parts, and dimethylformamide 30 parts were mixed and dissolved to obtain an emulsion. Next, the usefulness of the compound of the present invention as a fungicide for agricultural and horticultural use will be clarified by listing test examples.

Test Example 1 Wheat Powdery Mildew Control Effect Test A wettable powder prepared in the same manner as in Formulation Example 1 was added to water in 1-2 leaf stage wheat (variety: Norin 61) grown in a pot with a diameter of 6 cm. 10ml per pot after diluting to the specified concentration
The foliage was sprayed at the ratio of. After air-drying with a chemical solution, a spore suspension obtained from wheat leaves infected with wheat powdery mildew (Erysiphe graminis) was spray-inoculated and then left in a greenhouse for 7 to 10 days.

[Equation 1] For evaluation, the diseased area ratio of each leaf was evaluated, and the control value was calculated by the following formula. Control value (%) = {(average diseased area ratio of untreated plot)-
(Average area ratio of treated area) × 100 / (average diseased area ratio of untreated area) As a result, the compounds showing an effect of 98% or more at the active ingredient concentration of 200 ppm are the compound No. 1 in Table 1. 4-1
1, 16-22, 28-35, 47-51, 56-9
It was 8,100-125.

Test Example 2 Wheat Leaf Rust Control Efficacy Test A wettable powder prepared in the same manner as in Test Example 1 was prescribed with water in 1-2 leaf stage wheat (variety: Norin 61) grown in pots having a diameter of 6 cm. 10ml per pot, diluted to the concentration
The foliage was sprayed at the ratio of. After air-drying with a chemical solution, a spore suspension obtained by grinding wheat leaves infected with wheat leaf rust (Puccinia recondita) was spray-inoculated and then placed in a humid chamber at 22 ° C for 15 minutes.
After being kept for a time, it was left on a water tank in a greenhouse for 7 days.

[Equation 2] For evaluation, the diseased area ratio of each leaf was evaluated and the control value was calculated by the following formula. Control value (%) = {(average diseased area ratio of untreated plot)-
(Average area ratio of treated area) × 100 / (average diseased area ratio of untreated area) As a result, the compounds showing an effect of 98% or more at the active ingredient concentration of 200 ppm are the compound No. 1 in Table 1. 4-1
1, 16-22, 28-35, 47-51, 56-9
It was 8,100-125.

[0051]

The compounds of the present invention are all novel compounds and have excellent bactericidal activity. Particularly, since it has an excellent control effect against pathogenic bacteria of various plants, it is useful as a fungicide for agriculture and horticulture.

Claims (2)

[Claims] 1. A pyrazolyl vinegar represented by the following general formula (I):
Acid derivative. [Chemical 1](In the above general formula, A is a hydroxy group, C₁~ C₆The al
Represents a coxy group or a methylamino group, B is a single bond,-
CH₂O-, -CH₂ON = C (R^Four)-, -CH₂S
-, -CH₂SO-, -CH₂SO₂-, -CO-,-
CH = NO- (CR^FourR^Five)_n -, -C≡C-, -CH
= CH- or -CH₂CH₂Represents −, and n is 0 or
Represents 1, R¹Is a hydrogen atom, a halogen atom or C₁~
C_FourRepresents an alkyl group of R,²Is a hydrogen atom or C₁
~ C_FourRepresents an alkyl group of R,³Is a hydrogen atom, substituted
May be C₁~ C₈Substituted with an alkyl group
Good C₂~ C₈Alkenyl group, which may be substituted
I C₂~ C₈An alkynyl group, optionally substituted C
₃~ C₇A cycloalkyl group, which may be substituted
Represents a reel group or an optionally substituted heterocyclic group.
And R^FourIs a hydrogen atom, C ₁~ C_FourAlkyl group of C₁~
C_FourAlkoxy group of C₁~ C_FourAlkylthio group of
Represents a cyano group, R^FiveIs a hydrogen atom or C₁~ C_Fourof
Represents an alkyl group, Y is an oxygen atom, CHOCH₃, CH
CH₃, CHC₂H_Five, CHSCH₃Or NOCH₃
When B is —C≡C—, A is a methoxy group.
Absent) 2. A fungicide for agriculture and horticulture, which comprises the pyrazolyl acetic acid derivative according to claim 1 as an active ingredient.