JPH0812653A - Carboxylic oxime ester derivative and microbicidal agent for agricultural and horticultural purposes - Google Patents

Abstract

PURPOSE:To obtain a novel compound which is useful as a microbicidal agent for agricultural and horticultural purposes, particularly for controlling rice blast disease without chemical damage to useful crop plants. CONSTITUTION:This compound is expressed by formula I [Q is formula II or the like (R<1> is H, a 1-4C alkyl; R<2> is H, a halogen; R<3> is H, a halogen, nitro); R<4>, R<5> are H, a 1-6C alkyl, phenyl], for example, 0-(1,3-dimethyl-pyrazol-5- ylcarbonyl)pinacolone oxime. The compound of formula I is obtained by reaction of a compound of formula III with a compound of the formula: Q-COL (L is an eliminating group) in a solvent such as dichloromethane in the presence of a base such as pyridine at 0-50 deg.C. It is effective for controlling Diaporth citri, grape downy mildew, tomato late blight, peanut leaf spot and beet brown spot.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel carboxylic acid oxime ester derivative and an agricultural / horticultural fungicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art JP-A-3-120255, JP-A-4-145081, and JP-A-58-24566.
The publication describes that certain pyrazolecarboxylic acid oxime ester derivatives have herbicidal activity. Further, JP-A-3-145478 discloses that certain thiolcarboxylic acid oxime ester derivatives have herbicidal activity.

US Pat. Nos. 4,581,060 and 4,548,756 also describe that certain heterocyclic carboxylic acid oxime ester derivatives have a phytotoxicity-reducing action and a plant-regulating action. Nothing is disclosed with respect to bactericidal activity.

Furthermore, JP-A-61-267543 and JP-A-6-87812 describe that certain heterocyclic carboxylic acid oxime ester derivatives have bactericidal activity. However, nothing is described about the pyrazolecarboxylic acid oxime ester derivative and the thiazolecarboxylic acid oxime ester derivative.

[0005]

The existing agricultural and horticultural fungicides are not satisfactory in terms of the emergence of resistant bacteria and environmental safety, and their efficacy and residual efficacy.
There is a demand for the development of a more effective agricultural and horticultural fungicide against plant diseases.

[0006]

In view of such circumstances, the present inventors have conducted various studies in order to develop a compound having excellent bactericidal activity, and as a result, have shown that the carvone represented by the following formula [1] is used. The present inventors have found that the acid oxime ester derivative is safe for crops and has excellent bactericidal activity, and completed the present invention.

That is, the present invention uses the formula [1]:

[0008]

[Chemical 6]

[In the above formula, Q is

[0010]

[Chemical 7]

Or

[0012]

Embedded image

And R¹Is a hydrogen atom, C₁~ C_FourA
Rukiru group, C₂~ C_FourAlkenyl group, C₂~ C _FourArchi
Nyl group, unsubstituted phenyl group or substituted phenyl group (
The substituent is a halogen atom, C₁~ C_FourAlkyl group or
C₁~ C_FourAn alkoxy group) and R² Is a hydrogen atom,
Halogen atom, C₁~ C_FourAlkyl group, C₁~ C_FourAl
Coxy group, C₁~ C_FourHaloalkyl group, C₁~ C_FourAl
Is a carbonyl group or a cyano group, R³Is water
Elemental atom, halogen atom, nitro group or C₁~ C_FourAl
A killed group, and further or R² And R³Together with C
₃~ C₆An alkylene group may be formed and R^FourAnd R
^FiveAre each independently a hydrogen atom, C₁~ C₆Alkyl
Group, C₃~ C₆Cycloalkyl group, C₁~ C_FourAlkyl
C substituted with a group₃~ C₆Cycloalkyl group, C₂~ C
₆Alkenyl group, C₂~ C₆Alkynyl group, C₂~ C_Four
Alkylthioalkyl group, unsubstituted phenyl group or substituted
Phenyl group (the substituent is a halogen atom, C₁~ C_FourA
Rukiru group or C₁~ C_FourAlkoxy group)
Or R^FourAnd R^FiveBecome together C₃~ C₈Cycloal
Form a kill group or contain oxygen or sulfur atoms
May form a heterocycle, R⁶, R⁷Is it
Independently hydrogen atom, halogen atom, C₁~ C_FourArchi
Ru radical or C₁~ C_FourIt is a haloalkyl group. ]]
Carboxylic acid oxime ester derivative and the derivative
Agro-horticultural fungicide containing as an active ingredient, especially rice
The present invention relates to a rice blast control agent.

R ¹ is preferably a C ₁ -C ₄ alkyl group, R ² is preferably a chlorine atom, a bromine atom, a cyano group or a C ₁ -C ₄ alkyl group, and R ³ is preferably a hydrogen atom. There, R ⁴ and R ⁵ are each preferably independently C ₁ -C ₄ alkyl group, R ⁶ is preferably a chlorine atom or a C ₁ -C ₄ alkyl radical, R ⁷ is preferably C ₁ ~ It is a C ₄ alkyl group.

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. Examples of the C ₁ -C ₆ alkyl group include methyl, ethyl, n- or i-propyl, n-,
Examples include s-, i- or t-butyl, pentyl and hexyl. C ₁ -C ₄ methyl as an alkyl group, ethyl, n- or i- propyl, n-, s-, i- or t- butyl.

C₁~ C_FourAs a haloalkyl group, for example
Fluoromethyl, difluoromethyl, trifluorome
Chill, chloromethyl, bromomethyl, trifluoroethyl
, Trichloroethyl, trifluoropropyl, chloro
Butyl and the like can be mentioned. C ₃~ C₈Cycloalkyl group
Are, for example, cyclopropyl, cyclobutyl, cyclo
Lopentyl, cyclohexyl, cycloheptyl, cyclo
Examples include octyl.

C ₂ -C ₆ alkenyl groups include vinyl, allyl, 3-butenyl, 1,3-butadienyl, 4
-Pentenyl, 2,4-pentadienyl, 5-hexenyl and the like can be mentioned. The C ₂ -C ₆ alkynyl group, ethynyl, propargyl, 3-butynyl, 4-pentynyl, 5-hexynyl.

The C ₁ -C ₄ alkoxy group is methoxy, ethoxy, n- or i-propoxy, n-, s.
-, I- or t-butoxy may be mentioned. Examples of the heterocycle containing an oxygen atom or a sulfur atom include tetrahydrofuran, tetrahydrothiophene, tetrahydropyran and the like.

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

The compounds of the present invention represented by the formula [1] are shown in Tables 1 and 2. However, the compound of the present invention is not limited to these. Further, the compound of the present invention has two kinds of isomers, E and Z (syn and anti), and the present invention also includes these isomers.

In the table, Ph is a phenyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group,
Pen represents a pentyl group and Hex represents a hexyl group. c
Represents cyclo, i represents iso, s represents secondary, and t represents tertiary. Table 1

[0022]

[Chemical 9]

[0023]

[Table 1] ───────────────────────────── R ² R ³ R ⁴ R ⁵ ───────── ──────────────────── CH ₃ H H H CH ₃ H H CH ₃ CH ₃ H H Et CH ₃ H H Pr CH ₃ H Hi-Pr CH ₃ H H Bu CH ₃ H H i-Bu CH ₃ H H s-Bu CH ₃ H H t-Bu CH ₃ H H Pen CH ₃ H H Hex CH ₃ H H c-Pr CH ₃ H H 1-CH _3- c-Pr CH ₃ H H c-Bu CH ₃ H H c-Pen CH ₃ H H c-Hex CH ₃ H H CH = CH ₂ CH ₃ H H CH = CHCH ₃ CH ₃ H H CH ₂ CH = CH _{2 CH 3 H H CH = C (} CH 3) 2 CH 3 H H CH 2 C (CH 3) = CH 2 CH 3 H H C≡CH CH 3 H H C≡CCH 3 ───────── ────────────────────

[0024]

[Table 2] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── _{────────────────────────── CH 3 H H CH 2 C≡CH} CH 3 H H CH 2 C≡CCH 3 CH 3 H H CH ₂ CH ₂ C ≡ CH CH ₃ H H Ph CH ₃ H H 4-Cl-Ph CH ₃ H H 4-CH ₃ -Ph CH ₃ H H 4-OCH ₃ -Ph CH ₃ H -C (CH ₃ ) _{2 - (CH 2) 2 - CH} 3 H - (CH 2) 3 - CH 3 H - (CH 2) 4 - CH 3 H - (CH 2) 5 - CH 3 H - (CH 2) 6 - CH 3 H -(CH ₂ ) ₇ -CH ₃ H CH ₃ CH ₃ CH ₃ H CH ₃ Et CH ₃ H CH ₃ Pr CH ₃ H CH ₃ i-Pr CH ₃ H CH ₃ Bu CH ₃ H CH ₃ i-Bu CH ₃ H CH ₃ s-Bu CH ₃ H CH ₃ t-Bu CH ₃ H CH ₃ Pen ──────────────────────────────

[0025]

[Table 3] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ H CH ₃ Hex CH ₃ H CH ₃ c-Pr CH ₃ H CH ₃ 1-CH _3- c-Pr CH ₃ H CH ₃ c-Bu CH ₃ H CH ₃ c-Pen CH ₃ H CH ₃ c-Hex CH ₃ H CH ₃ CH = CH ₂ CH ₃ H CH ₃ CH = CHCH ₃ CH ₃ H CH _{3 CH 2 CH = CH 2 CH 3} H CH 3 CH = C (CH 3) 2 CH 3 H CH 3 CH 2 C (CH 3) = CH 2 CH 3 H CH 3 C≡CH CH 3 H CH 3 C≡CCH ₃ CH ₃ H -CH ₂ S- (CH ₂ ) ₂ -CH ₃ H -CH (CH ₃ ) O- (CH ₂ ) ₂ -CH ₃ H CH ₃ CH (SCH ₃ ) CH ₃ CH ₃ H CH ₃ Ph CH ₃ H CH ₃ 4-CH ₃ -Ph CH ₃ H CH ₃ 4-Cl-Ph CH ₃ H CH ₃ 4-OCH ₃ -Ph CH ₃ H Et Et CH ₃ H Et Pr ───────── ─────────────────────

[0026]

[Table 4] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ H Et i-Pr CH ₃ H Et Bu CH ₃ H Et i-Bu CH ₃ H Et s -Bu CH ₃ H Et t-Bu CH ₃ H Et Pen CH ₃ H Et Hex CH ₃ H Et c-Pr CH ₃ H Et 1-CH ₃ -c-Pr CH ₃ H Et c-Bu CH ₃ H Et c -Pen CH ₃ H Et c-Hex CH ₃ H Et CH = CH ₂ CH ₃ H Et CH = CHCH ₃ CH ₃ H Et CH ₂ CH = CH ₂ CH ₃ H Et CH = C (CH ₃ ) ₂ CH ₃ H Et CH ₂ C (CH ₃ ) = CH ₂ CH ₃ H Et C ≡ CH CH ₃ H Et C ≡ CCH ₃ CH ₃ H Et CH ₂ C ≡ CH CH ₃ H Et CH ₂ C ≡ CCH ₃ CH ₃ H Et CH ₂ CH ₂ C ≡ CH ──────────────────────────────

[0027]

[Table 5] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ H Et Ph CH ₃ H Et 4-CH ₃ -Ph CH ₃ H Et 4-Cl-Ph CH ₃ H Et 4-OCH ₃ -Ph CH ₃ H Pr Pr CH ₃ H Pr i-Pr CH ₃ H Pr Bu CH ₃ H Pr i-Bu CH ₃ H Pr s-Bu CH ₃ H Pr t-Bu CH ₃ H Pr c-Pr CH ₃ H Pr c-Hex CH ₃ H Pr CH = CH ₂ CH ₃ H Pr CH ₂ CH = CH ₂ CH ₃ HPr CH = C (CH ₃ ) ₂ CH ₃ HPr CH ₂ C≡ CH CH ₃ H Pr Ph CH ₃ H Pr 4-CH ₃ -Ph CH ₃ H Pr 4-Cl-Ph CH ₃ H Pr 4-OCH ₃ -Ph CH ₃ H c-Pr i-Pr CH ₃ H c-Pr Bu ─────────────────────────────

[0028]

[Table 6] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ H c-Pr t-Bu CH ₃ H c-Pr c-Pr CH ₃ H c-Pr c-Hex CH ₃ H c-Pr CH = CH ₂ CH ₃ H c-Pr CH ₂ CH = CH ₂ CH ₃ H c-Pr CH = C (CH ₃ ) ₂ CH ₃ H c-Pr CH ₂ C≡CH CH ₃ H c-Pr Ph CH ₃ H c-Pr 4-CH ₃ -Ph CH ₃ H c-Pr 4-Cl-Ph CH ₃ H c-Pr 4-CH ₃ -Ph CH ₃ H c-Pr 4- Cl-Ph CH ₃ H c-Hex i-Pr CH ₃ H c-Hex t-Bu CH ₃ H c-Hex c-Hex CH ₃ H c-Hex CH = CH ₂ CH ₃ H c-Hex CH = C ( CH ₃ ) ₂ CH ₃ H c-Hex Ph CH ₃ H c-Hex 4-Cl-Ph CH ₃ H CH = CH ₂ CH = CH ₂ CH ₃ H CH = CH ₂ Ph CH ₃ H CH = CH ₂ 4- Cl-Ph ──────────────────────────────

[0029]

[Table 7] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ H Ph Ph CH ₃ H Ph 4-Cl-Ph Et H CH ₃ CH ₃ Et H CH ₃ Et Et H CH ₃ t-Bu Et H CH ₃ c-Pr Et H CH ₃ CH = CH ₂ Et H CH ₃ CH = C (CH ₃ ) ₂ Et H CH ₃ 4-Cl-Ph Et H-(CH ₂ ) ₂ -Et H-(CH ₂ ) ₄ -Et H-(CH ₂ ) ₅ -Pr H CH ₃ CH ₃ Pr H CH ₃ Et Pr H CH ₃ t-Bu Pr H CH ₃ c-Pr Pr H CH ₃ CH = CH ₂ Pr H CH ₃ CH = C (CH ₃ ) ₂ Pr H CH ₃ 4-Cl-Ph Pr H-(CH ₂ ) ₂ -Pr H-(CH ₂ ) ₄ -Pr H-(CH ₂ ) ₅ -─────────────────────────────

[0030]

[Table 8] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── i-Pr H CH ₃ CH ₃ i-Pr H CH ₃ Et i-Pr H CH ₃ t-Bu i-Pr H CH ₃ c-Pr i-Pr H CH ₃ CH = CH ₂ i-Pr H CH ₃ CH = C (CH ₃ ) ₂ i-Pr H CH ₃ 4-Cl-Ph i-Pr H-( CH ₂ ) ₂ -i-Pr H-(CH ₂ ) ₄ -i-Pr H-(CH ₂ ) ₅ -t-Bu H CH ₃ CH ₃ t-Bu H CH ₃ Et t-Bu H CH ₃ t- But-Bu H CH ₃ c-Pr t-Bu H CH ₃ CH = CH ₂ t-Bu H CH ₃ CH = C (CH ₃ ) ₂ t-Bu H CH ₃ 4-Cl-Ph t-Bu H- (CH ₂ ) ₂ -t-Bu H-(CH ₂ ) ₄ -t-Bu H-(CH ₂ ) ₅ -CF ₃ H CH ₃ CH ₃ CF ₃ H CH ₃ Et ────────── ────────────────────

[0031]

[Table 9] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CF ₃ H CH ₃ t-Bu CF ₃ H CH ₃ c-Pr CF ₃ H CH ₃ CH = CH ₂ CF ₃ H CH ₃ CH = C (CH ₃ ) ₂ CF ₃ H CH ₃ 4-Cl-Ph CF ₃ H-(CH ₂ ) ₂ -CF ₃ H-(CH ₂ ) ₄ -CF ₃ H-(CH ₂ ) ₅ -H H CH ₃ CH ₃ H H CH ₃ Et H H CH ₃ t-Bu H H CH ₃ c-Pr H H CH ₃ CH = CH ₂ H H CH ₃ CH = C (CH ₃ ) ₂ H H CH ₃ 4-Cl-Ph H H-(CH ₂ ) ₂ -H H-(CH ₂ ) ₄ -H H-(CH ₂ ) ₅ -Cl H H H Cl H H CH ₃ Cl H H Et Cl H H Pr ─────────────────────────────

[0032]

[Table 10] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl H H i-Pr Cl H H Bu Cl H H i-Bu Cl H H s-Bu Cl H H t-Bu Cl H H Pen Cl H H Hex Cl H H c-Pr Cl H H 1-CH ₃ -c-Pr Cl H H c-Bu Cl H H c-Pen Cl H H c-Hex Cl H H CH = CH ₂ Cl H H CH = CHCH ₃ Cl H H CH ₂ CH = CH ₂ Cl H H CH = C (CH ₃ ) ₂ Cl H H CH ₂ C (CH ₃ ) = CH ₂ Cl H H C ≡ CH Cl H H C ≡ CCH ₃ Cl H H CH ₂ C ≡ CH Cl H H CH ₂ C ≡ CCH ₃ Cl H H Ph ──────────────────────── ───────

[0033]

[Table 11] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl H H 2,6-Cl ₂ -Ph Cl H H 4-Cl-Ph Cl H H 4- CH ₃ -Ph Cl H H 4-OCH ₃ -Ph Cl H -C (CH ₃ ) _2- (CH ₂ ) ₂ -Cl H-(CH ₂ ) ₃ -Cl H-(CH ₂ ) ₄ -Cl H- _{(CH 2) 5 - Cl H} - (CH 2) 6 - Cl H - (CH 2) 7 - Cl H CH 3 CH 3 Cl H CH 3 Et Cl H CH 3 Pr Cl H CH 3 i-Pr Cl H CH ₃ Bu Cl H CH ₃ i-Bu Cl H CH ₃ s-Bu Cl H CH ₃ t-Bu Cl H CH ₃ Pen Cl H CH ₃ Hex Cl H CH ₃ c-Pr Cl H CH ₃ 1-CH ₃ -c -Pr ─────────────────────────────

[0034]

[Table 12] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl H CH ₃ c-Bu Cl H CH ₃ c-Pen Cl H CH ₃ c-Hex Cl H CH ₃ CH = CH ₂ Cl H CH ₃ CH = CHCH ₃ Cl H CH ₃ CH ₂ CH = CH ₂ Cl H CH ₃ CH = C (CH ₃ ) ₂ Cl H CH ₃ CH ₂ C (CH ₃ ) = CH ₂ Cl _{H CH 3 C≡CH Cl H CH 3} C≡CCH 3 Cl H CH 3 CH 2 C≡CH Cl H CH 3 CH 2 C≡CCH 3 Cl H CH 3 CH 2 CH 2 C≡CH Cl H CH 3 Ph Cl H CH ₃ 4-CH ₃ -Ph Cl H CH ₃ 4-Cl-Ph Cl H CH ₃ 4-OCH ₃ -Ph Cl H Et Et Cl H Et Pr Cl H Et i-Pr Cl H Et Bu Cl H Et i -Bu ─────────────────────────────

[0035]

[Table 13] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl H Et s-Bu Cl H Et t-Bu Cl H Et Pen Cl H Et Hex Cl H Et c -Pr Cl H Et 1-CH ₃ -c-Pr Cl H Et c-Bu Cl H Et c-Pen Cl H Et c-Hex Cl H Et CH = CH ₂ Cl H Et CH = CHCH ₃ Cl H Et CH ₂ CH = CH ₂ Cl H Et CH = C (CH ₃ ) ₂ Cl H Et CH ₂ C (CH ₃ ) = CH ₂ Cl H Et C≡CH Cl H Et C≡C CH ₃ Cl H Et CH ₂ C≡CH Cl H Et CH ₂ C ≡ CCH ₃ Cl H Et CH ₂ CH ₂ C ≡ CH Cl H Et Ph Cl H Et 4-CH ₃ -Ph Cl H Et 4-Cl-Ph ──────────── ──────────────────

[0036]

[Table 14] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl H Et 4-OCH ₃ -Ph Cl H Pr Pr Cl H Pr i-Pr Cl H Pr Bu Cl H Pr i-Bu Cl H Pr s-Bu Cl H Pr t-Bu Cl H Pr c-Pr Cl H Pr c-Hex Cl H Pr CH = CH ₂ Cl H Pr CH ₂ CH = CH ₂ Cl H Pr CH = C (CH ₃ ) ₂ Cl H Pr CH ₂ C ≡ CH Cl H Pr Ph Cl H Pr 4-CH ₃ -Ph Cl H Pr 4-Cl-Ph Cl H Pr 4-OCH ₃ -Ph Cl H c-Pr i -Pr Cl H c-Pr Bu Cl H c-Pr t-Bu Cl H c-Pr c-Pr Cl H c-Pr c-Hex ────────────────── ───────────

[0037]

[Table 15] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl H c-Pr CH = CH ₂ Cl H c-Pr CH ₂ CH = CH ₂ Cl H c- Pr CH = C (CH ₃ ) ₂ Cl H c-Pr CH ₂ C ≡ CH Cl H c-Pr Ph Cl H c-Pr 4-CH ₃ -Ph Cl H c-Pr 4-Cl-Ph Cl H c- Pr 4-CH ₃ -Ph Cl H c-Pr 4-Cl-Ph Cl H c-Hex i-Pr Cl H c-Hex t-Bu Cl H c-Hex c-Hex Cl H c-Hex CH = CH ₂ Cl H c-Hex CH = C (CH ₃ ) ₂ Cl H c-Hex Ph Cl H c-Hex 4-Cl-Ph Cl H CH = CH ₂ CH = CH ₂ Cl H CH = CH ₂ Ph Cl H CH = CH ₂ 4-Cl-Ph Cl H Ph Ph Cl H Ph 4-Cl-Ph Cl H t-Bu 4-Cl-Ph ────────────────────── ────────

[0038]

[Table 16] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ F H Et CH ₃ F H t-Bu CH ₃ F H c-Pen CH ₃ F CH ₃ CH ₃ CH ₃ F CH ₃ Et CH ₃ F CH ₃ Pr CH ₃ F CH ₃ i-Pr CH ₃ F CH ₃ t-Bu CH ₃ F CH ₃ Pen CH ₃ F CH ₃ Hex CH ₃ F CH ₃ c-Pr CH ₃ F CH ₃ 1-CH ₃ -c-Pr CH ₃ F CH ₃ CH = CH ₂ CH ₃ F CH ₃ CH = C (CH ₃ ) ₂ CH ₃ F CH ₃ CH ₂ CH = CH ₂ CH ₃ F CH ₃ CH ₂ C ≡ CH CH ₃ F CH ₃ CH = CHCH ₃ CH ₃ F CH ₃ 4-Cl-Ph CH ₃ F-(CH ₂ ) ₂ -CH ₃ F-(CH ₂ ) ₃ -CH ₃ F-( CH ₂ ) ₄ -CH ₃ F-(CH ₂ ) ₅ -──────────────────────────────

[0039]

[Table 17] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ F Et Et CH ₃ F Et Pr CH ₃ F Et i-Pr CH ₃ F Et t-Bu CH ₃ F Et c-Pr CH ₃ F Et 1-CH ₃ -c-Pr CH ₃ F Et CH = CH ₂ CH ₃ F Et CH = C (CH ₃ ) ₂ CH ₃ F Et CH ₂ CH = CH ₂ CH ₃ F Et CH ₂ C ≡ CH CH ₃ F Et 4-Cl-Ph CH ₃ F Pr Pr CH ₃ F Pr i-Pr CH ₃ F Pr t-Bu CH ₃ F Pr c-Pr CH ₃ F Pr 1-CH ₃ -c-Pr CH ₃ F Pr CH = CH ₂ CH ₃ F Pr 4-Cl-Ph CH ₃ F i-Pr i-Pr CH ₃ F i-Pr t-Bu CH ₃ F i-Pr c-Pr CH ₃ F i-Pr CH = CH ₂ ──────────────────────────────

[0040]

[Table 18] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ F i-Pr 4-Cl-Ph CH ₃ F c-Pr t-Bu CH ₃ F c -Pr c-Pr CH ₃ F c-Pr CH = CH ₂ CH ₃ F c-Pr 4-Cl-Ph CH ₃ F CH = CH ₂ CH = CH ₂ CH ₃ F CH = CH ₂ Ph CH ₃ F CH = CH ₂ 4-Cl-Ph CH ₃ F Ph Ph CH ₃ F Ph 4-Cl-Ph CH ₃ Cl H CH ₃ CH ₃ Cl H Et CH ₃ Cl H t-Bu CH ₃ Cl H c-Pen CH ₃ Cl CH ₃ CH ₃ CH ₃ Cl CH ₃ Et CH ₃ Cl CH ₃ Pr CH ₃ Cl CH ₃ i-Pr CH ₃ Cl CH ₃ t-Bu CH ₃ Cl CH ₃ Pen CH ₃ Cl CH ₃ Hex CH ₃ Cl CH ₃ c- Pr ─────────────────────────────

[0041]

[Table 19] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ Cl CH ₃ 1-CH ₃ -c-Pr CH ₃ Cl CH ₃ CH = CH ₂ CH ₃ Cl CH ₃ CH = C (CH ₃ ) ₂ CH ₃ Cl CH ₃ CH ₂ CH = CH ₂ CH ₃ Cl CH ₃ CH ₂ C ≡ CH CH ₃ Cl CH ₃ CH = CHCH ₃ CH ₃ Cl CH ₃ 4-Cl- Ph CH ₃ Cl-(CH ₂ ) ₂ -CH ₃ Cl-(CH ₂ ) ₃ -CH ₃ Cl-(CH ₂ ) ₄ -CH ₃ Cl-(CH ₂ ) ₅ -CH ₃ Cl Et Et CH ₃ Cl Et Pr CH ₃ Cl Et i-Pr CH ₃ Cl Et t-Bu CH ₃ Cl Et c-Pr CH ₃ Cl Et 1-CH ₃ -c-Pr CH ₃ Cl Et CH = CH ₂ CH ₃ Cl Et CH = C ( CH ₃ ) ₂ CH ₃ Cl Et CH ₂ CH = CH ₂ CH ₃ Cl Et CH ₂ C ≡ CH CH ₃ Cl Et 4-Cl-Ph ─────────────────── ───────────

[0042]

[Table 20] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ Cl Pr Pr CH ₃ Cl Pr i-Pr CH ₃ Cl Pr t-Bu CH ₃ Cl Pr c -Pr CH ₃ Cl Pr 1-CH ₃ -c-Pr CH ₃ Cl Pr CH = CH ₂ CH ₃ Cl Pr 4-Cl-Ph CH ₃ Cl i-Pr i-Pr CH ₃ Cl i-Pr t-Bu CH ₃ Cl i-Pr c-Pr CH ₃ Cl i-Pr CH = CH ₂ CH ₃ Cl i-Pr 4-Cl-Ph CH ₃ Cl c-Pr t-Bu CH ₃ Cl c-Pr c-Pr CH ₃ Cl c-Pr CH = CH ₂ CH ₃ Cl c-Pr 4-Cl-Ph CH ₃ Cl CH = CH ₂ CH = CH ₂ CH ₃ Cl CH = CH ₂ Ph CH ₃ Cl CH = CH ₂ 4-Cl-Ph CH ₃ NO ₂ CH ₃ t-Bu-(CH ₂ ) ₃ -CH ₃ t-Bu Et F CH ₃ CH ₃ ───────────────────────── ─────

[0043]

[Table 21] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Et F CH ₃ Et Et F CH ₃ t-Bu Et F CH ₃ c-Pr Et F CH ₃ CH = CH ₂ Et F CH ₃ CH = C (CH ₃ ) ₂ Et F CH ₃ 4-Cl-Ph Et F-(CH ₂ ) ₂ -Et F-(CH ₂ ) ₄ -Et F-(CH ₂ ) ₅ -Pr F CH ₃ CH ₃ Pr F CH ₃ Et Pr F CH ₃ t-Bu Pr F CH ₃ c-Pr Pr F CH ₃ CH = CH ₂ Pr F CH ₃ CH = C (CH ₃ ) ₂ Pr F CH ₃ 4-Cl-Ph Pr F-(CH ₂ ) ₂ -Pr F-(CH ₂ ) ₄ -Pr F-(CH ₂ ) ₅ -i-Pr F CH ₃ CH ₃ i-Pr F CH ₃ Et i-Pr F CH ₃ t-Bu ─────────────────────────────

[0044]

[Table 22] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── i-Pr F CH ₃ c-Pr i-Pr F CH ₃ CH = CH ₂ i-Pr F CH ₃ CH = C (CH ₃ ) ₂ i-Pr F CH ₃ 4-Cl-Ph i-Pr F-(CH ₂ ) ₂ -i-Pr F-(CH ₂ ) ₄ -i-Pr F-(CH ₂ ) ₅ -t-Bu F CH ₃ CH ₃ t-Bu F CH ₃ Et t-Bu F CH ₃ t-Bu t-Bu F CH ₃ c-Pr t-Bu F CH ₃ CH = CH ₂ t-Bu F CH ₃ CH = C (CH ₃ ) ₂ t-Bu F CH ₃ 4-Cl-Ph t-Bu F-(CH ₂ ) ₂ -t-Bu F-(CH ₂ ) ₄ -t-Bu F-(CH ₂ ) ₅ -CF ₃ F CH ₃ CH ₃ CF ₃ F CH ₃ Et CF ₃ F CH ₃ t-Bu CF ₃ F CH ₃ c-Pr CF ₃ F CH ₃ CH = CH ₂ ──────── ─────────────────────

[0045]

[Table 23] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CF ₃ F CH ₃ CH = C (CH ₃ ) ₂ CF ₃ F CH ₃ 4-Cl-Ph CF ₃ F-(CH ₂ ) ₂ -CF ₃ F-(CH ₂ ) ₄ -CF ₃ F-(CH ₂ ) ₅ -Et Cl CH ₃ CH ₃ Et Cl CH ₃ Et Et Cl CH ₃ t-Bu Et Cl CH ₃ c-Pr Et Cl CH ₃ CH = CH ₂ Et Cl CH ₃ CH = C (CH ₃ ) ₂ Et Cl CH ₃ 4-Cl-Ph Et Cl-(CH ₂ ) ₂ -Et Cl-(CH ₂ ) ₄ -Et Cl-(CH ₂ ) ₅ -Pr Cl CH ₃ CH ₃ Pr Cl CH ₃ Et Pr Cl CH ₃ t-Bu Pr Cl CH ₃ c-Pr Pr Cl CH ₃ CH = CH ₂ Pr Cl CH ₃ CH = C (CH ₃ ) ₂ Pr Cl CH ₃ 4-Cl-Ph ─────────────────────────────

[0046]

[Table 24] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Pr Cl-(CH ₂ ) ₂ -Pr Cl-(CH ₂ ) ₄ -Pr Cl-(CH ₂ ) ₅ -i-Pr Cl CH ₃ CH ₃ i-Pr Cl CH ₃ Et i-Pr Cl CH ₃ t-Bu i-Pr Cl CH ₃ c-Pr i-Pr Cl CH ₃ CH = CH ₂ i-Pr Cl CH ₃ CH = C (CH ₃ ) ₂ i-Pr Cl CH ₃ 4-Cl-Ph i-Pr Cl-(CH ₂ ) ₂ -i-Pr Cl-(CH ₂ ) ₄ -i-Pr Cl-(CH ₂ ) ₅ -t-Bu Cl CH ₃ CH ₃ t-Bu Cl CH ₃ Et t-Bu Cl CH ₃ t-Bu t-Bu Cl CH ₃ c-Pr t-Bu Cl CH ₃ CH = CH ₂ t-Bu Cl CH ₃ CH = C (CH ₃ ) ₂ t-Bu Cl CH ₃ 4-Cl-Ph t-Bu Cl-(CH ₂ ) ₂ -t-Bu Cl-(CH ₂ ) ₄ -─────── ───────────────────────

[0047]

[Table 25] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── t-Bu Cl-(CH ₂ ) ₅ -CF ₃ Cl CH ₃ CH ₃ CF ₃ Cl CH ₃ Et CF ₃ Cl CH ₃ t-Bu CF ₃ Cl CH ₃ c-Pr CF ₃ Cl CH ₃ CH = CH ₂ CF ₃ Cl CH ₃ CH = C (CH ₃ ) ₂ CF ₃ Cl CH ₃ 4-Cl-Ph CF ₃ Cl-(CH ₂ ) ₂ -CF ₃ Cl-(CH ₂ ) ₄ -CF ₃ Cl-(CH ₂ ) ₅ -Cl F H CH ₃ Cl F H Et Cl F H t-Bu Cl F H c-Pen Cl F CH ₃ CH ₃ Cl F CH ₃ Et Cl F CH ₃ Pr Cl F CH ₃ i-Pr Cl F F CH ₃ t-Bu Cl F CH ₃ Pen Cl F CH ₃ Hex ──────────── ──────────────────

[0048]

[Table 26] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl F CH ₃ c-Pr Cl F CH ₃ 1-CH ₃ -c-Pr Cl F CH ₃ CH = CH ₂ Cl F CH ₃ CH = C (CH ₃ ) ₂ Cl F CH ₃ CH ₂ CH = CH ₂ Cl F CH ₃ CH ₂ C ≡ CH Cl F CH ₃ CH = CHCH ₃ Cl F CH ₃ 4-Cl- Ph Cl F-(CH ₂ ) ₂ -Cl F-(CH ₂ ) ₃ -Cl F-(CH ₂ ) ₄ -Cl F-(CH ₂ ) ₅ -Cl F Et Et Cl F Et Pr Cl F Et i- Pr Cl F Et t-Bu Cl F Et c-Pr Cl F Et 1-CH ₃ -c-Pr Cl F Et CH = CH ₂ Cl F Et CH = C (CH ₃ ) ₂ Cl F Et CH ₂ CH = CH ₂ Cl F Et CH ₂ C ≡ CH ──────────────────────────────

[0049]

[Table 27] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl F Et 4-Cl-Ph Cl F Pr Pr Cl Cl F Pr i-Pr Cl F Pr t-Bu Cl F Pr c-Pr Cl F Pr 1-CH ₃ -c-Pr Cl F Pr CH = CH ₂ Cl F Pr 4-Cl-Ph Cl F i-Pr i-Pr Cl F i-Pr t-Bu Cl F i-Pr c-Pr Cl F i-Pr CH = CH ₂ Cl F i-Pr 4-Cl-Ph Cl F c-Pr t-Bu Cl F c-Pr c-Pr Cl F c-Pr CH = CH ₂ Cl F c-Pr 4-Cl-Ph Cl F CH = CH ₂ CH = CH ₂ Cl F CH = CH ₂ Ph Cl F CH = CH ₂ 4-Cl-Ph Cl F Ph Ph Cl Cl F Ph 4-Cl-Ph ─────────────────────────────

[0050]

[Table 28] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl Cl H CH ₃ Cl Cl H Et Cl Cl H t-Bu Cl Cl H c-Pen Cl Cl CH ₃ CH ₃ Cl Cl CH ₃ Et Cl Cl CH ₃ Pr Cl Cl CH ₃ i-Pr Cl Cl CH ₃ t-Bu Cl Cl CH ₃ Pen Cl Cl CH ₃ Hex Cl Cl CH ₃ c-Pr Cl Cl CH ₃ 1- CH ₃ -c-Pr Cl Cl CH ₃ CH = CH ₂ Cl Cl CH ₃ CH = C (CH ₃ ) ₂ Cl Cl CH ₃ CH ₂ CH = CH ₂ Cl Cl CH ₃ CH ₂ C ≡ CH Cl Cl CH ₃ CH = CHCH ₃ Cl Cl CH ₃ 4-Cl-Ph Cl Cl-(CH ₂ ) ₂ -Cl Cl-(CH ₂ ) ₃ -Cl Cl-(CH ₂ ) ₄ -──────────── ──────────────────

[0051]

[Table 29] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl Cl-(CH ₂ ) ₅ -Cl Cl Et Et Cl Cl Et Pr Cl Cl Et i-Pr Cl Cl Et t-Bu Cl Cl Et c-Pr Cl Cl Et 1-CH ₃ -c-Pr Cl Cl Et CH = CH ₂ Cl Cl Et CH = C (CH ₃ ) ₂ Cl Cl Et CH ₂ CH = CH ₂ Cl Cl Et CH ₂ C ≡ CH Cl Cl Et 4-Cl-Ph Cl Cl Pr Pr Cl Cl Pr i-Pr Cl Cl Pr t-Bu Cl Cl Pr c-Pr Cl Cl Pr 1-CH ₃ -c-Pr Cl Cl Pr CH = CH ₂ Cl Cl Pr 4-Cl-Ph Cl Cl i-Pr i-Pr Cl Cl i-Pr t-Bu Cl Cl i-Pr c-Pr ────────────── ────────────────

[0052]

[Table 30] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Cl Cl i-Pr CH = CH ₂ Cl Cl i-Pr 4-Cl-Ph Cl Cl c-Pr t-Bu Cl Cl c-Pr c-Pr Cl Cl c-Pr CH = CH ₂ Cl Cl c-Pr 4-Cl-Ph Cl Cl CH = CH ₂ CH = CH ₂ Cl Cl CH = CH ₂ Ph Cl Cl CH = CH ₂ 4-Cl-Ph Cl Cl Ph Ph Cl Cl Ph 4-Cl-Ph CH ₃ Br CH ₃ CH ₃ CH ₃ Br CH ₃ Et CH ₃ Br CH ₃ t-Bu CH ₃ Br CH ₃ c-Pr CH ₃ Br CH ₃ CH = CH ₂ CH ₃ Br CH ₃ CH = C (CH ₃ ) ₂ CH ₃ Br CH ₃ 4-Cl-Ph CH ₃ Br-(CH ₂ ) ₂ -CH ₃ Br-(CH ₂ ) ₄ -CH ₃ Br-(CH ₂ ) ₅ -CH ₃ I CH ₃ CH ₃ ──────────────────────────────

[0053]

[Table 31] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── CH ₃ I CH ₃ Et CH ₃ I CH ₃ t-Bu CH ₃ I CH ₃ c-Pr CH _{3 I CH 3 CH = CH 2 CH} 3 I CH 3 CH = C (CH 3) 2 CH 3 I CH 3 4-Cl-Ph CH 3 I - (CH 2) 2 - CH 3 I - (CH 2) 4 - CH ₃ I-(CH ₂ ) ₅ -Et Br CH ₃ CH ₃ Et Br CH ₃ Et Et Br CH ₃ t-Bu Et Br CH ₃ c-Pr Et Br CH ₃ CH = CH ₂ Et Br CH ₃ CH = C (CH ₃ ) ₂ Et Br CH ₃ 4-Cl-Ph Et Br-(CH ₂ ) ₂ -Et Br-(CH ₂ ) ₄ -Et Br-(CH ₂ ) ₅ -Et I CH ₃ CH ₃ Et I CH ₃ Et Et I CH ₃ t-Bu ──────────────────────────────

[0054]

[Table 32] Table 1 (continued) ───────────────────────────── R ² R ³ R ⁴ R ⁵ ─── ────────────────────────── Et I CH ₃ c-Pr Et I CH ₃ CH = CH ₂ Et I CH ₃ CH = C (CH ₃ ) ₂ Et I CH ₃ 4-Cl-Ph Et I-(CH ₂ ) ₄ -Et I-(CH ₂ ) ₅ -CN H CH ₃ Et CN H CH ₃ Pr CN H CH ₃ c-Pr CN H CH ₃ 1-CH ₃ -c-Pr CN H CH ₃ t-Bu COOCH ₃ H CH ₃ Et COOCH ₃ H CH ₃ Pr COOCH ₃ H CH ₃ c-Pr COOCH ₃ H CH ₃ 1-CH ₃ -c-Pr COOCH ₃ H CH ₃ t-Bu OCH ₃ H CH ₃ Et OCH ₃ H CH ₃ Pr OCH ₃ H CH ₃ c-Pr OCH ₃ H CH ₃ 1-CH ₃ -c-Pr OCH ₃ H CH ₃ t-Bu ── ──────────────────────────── Table 2

[0055]

[Chemical 10]

[0056]

[Table 33] ──────────────────────── R ⁷ R ⁴ R ⁵ ──────────────── ──────── CH ₃ H H CH ₃ H CH ₃ CH ₃ H Et CH ₃ H Pr CH ₃ H i-Pr CH ₃ H Bu CH ₃ H i-Bu CH ₃ H s-Bu CH ₃ H t-Bu CH ₃ H Pen CH ₃ H Hex CH ₃ H c-Pr CH ₃ H 1-CH ₃ -c-Pr CH ₃ H c-Bu CH ₃ H c-Pen CH ₃ H c-Hex CH ₃ H CH = CH ₂ CH ₃ H CH = CHCH ₃ CH ₃ H CH ₂ CH = CH ₂ CH ₃ H CH = C (CH ₃ ) ₂ CH ₃ H CH ₂ C (CH ₃ ) = CH ₂ CH ₃ H C ≡CH CH ₃ H C ≡ CCH ₃ ────────────────────────

[0057]

[Table 34] Table 2 (continued) ──────────────────────── R ⁷ R ⁴ R ⁵ ─────────── ────────────── CH ₃ H CH ₂ C ≡ CH CH ₃ H CH ₂ C ≡ CCH ₃ CH ₃ H CH ₂ CH ₂ C ≡ CH CH ₃ H Ph CH ₃ H 4- Cl-Ph CH ₃ H 4-CH ₃ -Ph CH ₃ H 4-OCH ₃ -Ph CH ₃ -C (CH ₃ ) _2- (CH ₂ ) ₂ -CH _3- (CH ₂ ) ₃ -CH _3- ( CH ₂ ) ₄ -CH _3- (CH ₂ ) ₅ -CH _3- (CH ₂ ) ₆ -CH _3- (CH ₂ ) ₇ -CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ Et CH ₃ CH ₃ Pr CH ₃ CH ₃ i-Pr CH ₃ CH ₃ Bu CH ₃ CH ₃ i-Bu CH ₃ CH ₃ s-Bu CH ₃ CH ₃ t-Bu CH ₃ CH ₃ Pen ─────────────── ──────────

[0058]

[Table 35] Table 2 (continued) ──────────────────────── R ⁷ R ⁴ R ⁵ ─────────── ────────────── CH ₃ CH ₃ Hex CH ₃ CH ₃ c-Pr CH ₃ CH ₃ 1-CH ₃ -c-Pr CH ₃ CH ₃ c-Bu CH ₃ CH ₃ c -Pen CH ₃ CH ₃ c-Hex CH ₃ CH ₃ CH = CH ₂ CH ₃ CH ₃ CH = CHCH ₃ CH ₃ CH ₃ CH ₂ CH = CH ₂ CH ₃ CH ₃ CH = C (CH ₃ ) ₂ CH ₃ CH _{3 CH 2 C (CH 3)} = CH 2 CH 3 CH 3 C≡CH CH 3 CH 3 C≡CCH 3 CH 3 CH 3 CH 2 C≡CH CH 3 CH 3 CH 2 C≡CCH 3 CH 3 CH 3 CH (SCH ₃ ) CH ₃ CH ₃ CH ₃ Ph CH ₃ CH ₃ 4-CH ₃ -Ph CH ₃ CH ₃ 4-Cl-Ph CH ₃ CH ₃ 4-OCH ₃ -Ph CH ₃ Et Et CH ₃ Et Pr ── ──────────────────────

[0059]

[Table 36] Table 2 (continued) ──────────────────────── R ⁷ R ⁴ R ⁵ ─────────── ────────────── CH ₃ Et i-Pr CH ₃ Et Bu CH ₃ Et i-Bu CH ₃ Et s-Bu CH ₃ Et t-Bu CH ₃ Et Pen CH ₃ Et Hex CH ₃ Et c-Pr CH ₃ Et 1-CH ₃ -c-Pr CH ₃ Et c-Bu CH ₃ Et c-Pen CH ₃ Et c-Hex CH ₃ Et CH = CH ₂ CH ₃ Et CH = CHCH ₃ CH _{3 Et CH 2 CH = CH 2} CH 3 Et CH = C (CH 3) 2 CH 3 Et CH 2 C (CH 3) = CH 2 CH 3 Et C≡CH CH 3 Et C≡CCH 3 CH 3 Et CH 2 _{C≡CH CH 3 Et CH 2 C≡CCH 3} CH 3 Et CH 2 CH 2 C≡CH ────────────────────────

[0060]

[Table 37] Table 2 (continued) ──────────────────────── R ⁷ R ⁴ R ⁵ ─────────── ────────────── CH ₃ Et Ph CH ₃ Et 4-CH ₃ -Ph CH ₃ Et 4-Cl-Ph CH ₃ Et 4-OCH ₃ -Ph CH ₃ Pr Pr CH ₃ Pr i-Pr CH ₃ Pr Bu CH ₃ Pr i-Bu CH ₃ Pr s-Bu CH ₃ Pr t-Bu CH ₃ Pr c-Pr CH ₃ Pr c-Hex CH ₃ Pr CH = CH ₂ CH ₃ Pr CH ₂ CH = CH ₂ CH ₃ Pr CH = C (CH ₃ ) ₂ CH ₃ Pr CH ₂ C ≡ CH CH ₃ Pr Ph CH ₃ Pr 4-CH ₃ -Ph CH ₃ Pr 4-Cl-Ph CH ₃ Pr 4-OCH ₃ -Ph CH ₃ c-Pr i-Pr CH ₃ c-Pr Bu ────────────────────────

[0061]

[Table 38] Table 2 (continued) ──────────────────────── R ⁷ R ⁴ R ⁵ ─────────── ────────────── CH ₃ c-Pr t-Bu CH ₃ c-Pr c-Pr CH ₃ c-Pr c-Hex CH ₃ c-Pr CH = CH ₂ CH ₃ c -Pr CH ₂ CH = CH ₂ CH ₃ c-Pr CH = C (CH ₃ ) ₂ CH ₃ c-Pr CH ₂ C ≡CH CH ₃ c-Pr Ph CH ₃ c-Pr 4-CH ₃ -Ph CH ₃ c-Pr 4-Cl-Ph CH ₃ c-Pr 4-CH ₃ -Ph CH ₃ c-Pr 4-Cl-Ph CH ₃ c-Hex i-Pr CH ₃ c-Hex t-Bu CH ₃ c-Hex c-Hex CH ₃ c-Hex CH = CH ₂ CH ₃ c-Hex CH = C (CH ₃ ) ₂ CH ₃ c-Hex Ph CH ₃ c-Hex 4-Cl-Ph CH ₃ CH = CH ₂ CH = CH ₂ CH ₃ CH = CH ₂ Ph CH ₃ CH = CH ₂ 4-Cl-Ph ────────────────────────

[0062]

[Table 39] Table 2 (continued) ──────────────────────── R ⁷ R ⁴ R ⁵ ─────────── ────────────── CH ₃ Ph Ph CH ₃ Ph 4-Cl-Ph Et CH ₃ CH ₃ Et CH ₃ Et Et CH ₃ t-Bu Et CH ₃ c-Pr Et CH ₃ CH = CH ₂ Et CH ₃ CH = C (CH ₃ ) ₂ Et CH ₃ 4-Cl-Ph Et-(CH ₂ ) ₂ -Et-(CH ₂ ) ₄ -Et-(CH ₂ ) ₅ -Pr CH ₃ CH ₃ Pr CH ₃ Et Pr CH ₃ t-Bu Pr CH ₃ c-Pr Pr CH ₃ CH = CH ₂ Pr CH ₃ CH = C (CH ₃ ) ₂ Pr CH ₃ 4-Cl-Ph Pr-(CH ₂ ) ₂ -Pr-(CH ₂ ) ₄ -Pr-(CH ₂ ) ₅ -────────────────────────

[0063]

[Table 40] Table 2 (continued) ───────────────────────── R ⁷ R ⁴ R ⁵ ────────── ──────────────── i-Pr CH ₃ CH ₃ i-Pr CH ₃ Et i-Pr CH ₃ t-Bu i-Pr CH ₃ c-Pr i-Pr CH ₃ CH = CH ₂ i-Pr CH ₃ CH = C (CH ₃ ) ₂ i-Pr CH ₃ 4-Cl-Ph i-Pr-(CH ₂ ) ₂ -i-Pr-(CH ₂ ) ₄ -i-Pr -(CH ₂ ) ₅ -t-Bu CH ₃ CH ₃ t-Bu CH ₃ Et t-Bu CH ₃ t-Bu t-Bu CH ₃ c-Pr t-Bu CH ₃ CH = CH ₂ t-Bu CH ₃ CH = C (CH ₃ ) ₂ t-Bu CH ₃ 4-Cl-Ph t-Bu-(CH ₂ ) ₂ -t-Bu-(CH ₂ ) ₄ -t-Bu-(CH ₂ ) ₅ -CF ₃ CH ₃ CH ₃ CF ₃ CH ₃ Et ──────────────────────────

[0064]

[Table 41] Table 2 (continued) ───────────────────────── R ⁷ R ⁴ R ⁵ ────────── ──────────────── CF ₃ CH ₃ t-Bu CF ₃ CH ₃ c-Pr CF ₃ CH ₃ CH = CH ₂ CF ₃ CH ₃ CH = C (CH ₃ ) ₂ CF ₃ CH ₃ 4-Cl-Ph CF _3- (CH ₂ ) ₂ -CF _3- (CH ₂ ) ₄ -CF _3- (CH ₂ ) ₅ -H CH ₃ CH ₃ H CH ₃ Et H CH ₃ t- Bu H CH ₃ c-Pr H CH ₃ CH = CH ₂ H CH ₃ CH = C (CH ₃ ) ₂ H CH ₃ 4-Cl-Ph H-(CH ₂ ) ₂ -H-(CH ₂ ) ₄ -H -(CH ₂ ) ₅ -──────────────────────────

Next, a method for producing the compound of the present invention will be described below. Formula [2]:

[0066]

[Chemical 11]

[In the formula, R ⁴ and R ⁵ have the same meanings as described above. ] The compound represented by these, and a formula [3]:

[0068]

[Chemical 12]

[In the formula, Q has the same meaning as described above, and L represents a leaving group such as a halogen atom. ] The compound of the present invention can be produced by reacting with a compound represented by

In this production method, the reaction can be carried out using a suitable inert solvent. Examples of the solvent include hydrocarbons such as toluene, xylene and chlorobenzene, halogenated hydrocarbons such as dichloromethane, dichloroethane and chloroform, ethers such as diisopropyl ether and dioxane, esters such as ethyl acetate, nitriles such as acetonitrile. Examples thereof include 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. The amount of the reagent used in the reaction is in the range of 1 to 3 equivalents relative to 1 equivalent of the compound represented by formula [2].

In the above reaction, the reaction temperature can be set arbitrarily, but usually 0 to 50 ° C. or the reflux temperature of the solvent is preferable. After completion of the reaction, the target product can be obtained by performing a usual post-treatment.

Next, the plant diseases to be controlled by the compound of the present invention include rice blast (Pyricularia oryzae).
, Sesame leaf blight (Cochliobolus miyabeanus), blight (R
hizoctonia solani), powdery mildew of wheat (Erysiphe
graminis f.sp.hordei, f.sp.tritici), leaf spot (P
yrenophora graminea), net blotch (Pyrenophora teres)
, Fusarium head blight (Gibberella zeae), Rust (Puccinia st
riiformis, P.graminis, P.recondita, P.hordei), snow rot (Typhula sp., Micronectriella nivais), bare smut
(Ustilago tritici, U.nuda), Eye spot (Pseudocer
cosporella herpotrichoides), cloud disease (Rhynchospori
um secalis), leaf blight (Septoria tritici), wilt (Le
ptosphaeria nodorum),

Citrus black spot (Diapor the citri), scab (Elsinoe fawcetti), fruit rot (Penicillium)
digitatum, P.italicum), monili disease of apple (Scler
otinia mali), rot (Valsa mali), powdery mildew
(Podosphaera leucotricha), leaf spot (Alternaria)
mali), scab (Venturia inaequalis), pear scab (Venturia nashicola), black spot (Alternaria Kikuch)
iana), red scab (Gymnosporangium haraeanum), peach scab (Sclerotinia cinerea), scab (Cladosporiu)
m carpophilum), Phomopsis rot (Phomopsis sp.)
,

Downy mildew of grapes (Plasmopara viticola),
Black rot (Elsinoe ampelina), late rot (Glomerella c
ingulata), powdery mildew (Uncinula necator), rust
(Phakopsora ampelopsidis), oyster anthracnose (Gloeospor
ium kaki), leaf fall disease (Cercospora kaki, Mycosphaerell
a nawae), and downy mildew of the cucumber (Pseudoperenospora cubens
is), anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), vine blight (Mycosphaere)
lla melonis),

Tomato plague (Phytophthora infestans)
, Leaf spot (Alternaria solani), Leaf mold (Cladospori)
um fulvam), eggplant brown leaf spot (Phomopsis vexans), powdery mildew (Erysiphe cichoracoarum), cruciferous vegetable black spot (Alternaria japonica), white spot (Cerocospore)
lla brassicae), green onion rust (Puccinia allii), soybean purpura (Cercospora kikuchii), black spot (Elsino)
e glycines), black spot (Diaporthe phaseololum), anthracnose of kidney beans (Colletotrichum lindemuthianum),

Peanut black spot disease (Mycosphaerella per
sonatum), brown spot (Cercospora arachidicola), powdery mildew of pea (Erysiphe pisi), summer epidemic of potato
(Alternaria solani), powdery mildew of strawberry (Sphaeroth
eca humuli), tea leaf blast (Exobasidium reticula)
tum), white scab (Elsinoe leucospila), tobacco red scab
(Alternaria longipes), powdery mildew (Erysiphe cichor
acearum), anthracnose (Colletotrichum tabacum),

Brown spot of sugar beet (Cercospora beticol
a), rose scab (Diplocarpon rosae), powdery mildew
(Sphaerotheca pannosa), brown spot of chrysanthemum (Septoria chr
ysanthemiindici), white rust (Puccinia horiana), gray mold of various crops (Botrytis cinerea), and sclerotinia sclerotiorum of various crops.

When the compound of the present invention is used as an agricultural and horticultural germicide, it is generally a suitable carrier, for example, a solid carrier such as clay, talc, bentonant or diatomaceous earth, or water, alcohols (methanol, ethanol, etc.), fragrance. Group hydrocarbons (benzene, toluene, xylene, etc.),
It can be applied by mixing with a liquid carrier such as chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate etc.), acid amides (dimethylformamide etc.), and if desired, an emulsifier, a dispersant, a suspending agent, etc. Add turbidity agents, penetrants, spreading agents, stabilizers, etc. to prepare liquids, emulsions, wettable powders, powders, granules,
It can be put to practical use in any dosage form such as a flowable agent.

When the compound of the present invention is applied as a fungicide for agriculture and horticulture, foliar application, soil treatment,
Seed disinfection and the like can be mentioned, but it is also effective in general methods generally used by those skilled in the art. In addition, other types of herbicides, various insecticides, bactericides, and the like when necessary in formulation or spraying,
You may mix and apply with a plant growth regulator, a synergist, etc. The application 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 fungicides containing the compound of the present invention as an active ingredient are shown, but the invention is not limited thereto. In addition, in the following formulation examples, "part" means part by weight.

[0082]

[Table 42] Formulation Example 1 Emulsion Compound of the present invention -------- 20 parts Xylene -------- 55 parts Cyclohexanone ------- 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.

[0083]

[Table 43] Formulation Example 2 Wettable powder Compound of the present invention -------- 25 parts Diclite PFP -------- 66 parts (mixture of kaolinite and sericite; Siklite Industry Co., Ltd. ) Trade name) Solpol 5039 ------- 4 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Carplex # 80 ------- 3 parts (White carbon: Yoshino Shiono Pharmaceutical Co., Ltd. Trade 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.

[0084]

[Table 44] Formulation Example 3 Powder Compound of the present invention ------- 3 parts Carplex # 80 ------- 0.5 part (White carbon: Shionogi Pharmaceutical Co., Ltd. trade name) Clay- ----- 95 parts Diisopropyl phosphate ------- 1.5 parts The above is uniformly mixed and pulverized into a powder. Before use, spray the above powder so that the amount of active ingredient is 0.005 to 50 kg per hectare.

[0085]

[Table 45] Formulation Example 4 Granules Compound of the present invention ------- 5 parts Bentonite ------- 54 parts Talc ------- 40 parts Calcium lignin sulfonate ----- --1 part or more are uniformly mixed and pulverized, a small amount of water is added and mixed by stirring, 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.

[0086]

[Table 46] Formulation example 5 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 parts (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 contents of the present invention will be specifically described with reference to examples, but the present invention should not be limited to these.

[0088]

【Example】

 [Example 1] Inventive compound No. 1-1 synthesis

[0089]

[Chemical 13]

Pinacolone oxime 0.7 g (6.09 m
mol), triethylamine 0.74 g (7.30 mm)
ol) was dissolved in 30 ml of dichloromethane and cooled to 5 ° C under ice cooling.
Then, 1.06 g (6.70 mmol) of 1,3-dimethylpyrazole-5-carbonyl chloride was added dropwise. Next, a catalytic amount of 4-dimethylaminopyridine was added, the temperature was raised to room temperature, and the mixture was stirred for 15 minutes. 50 ml of dichloromethane and 40 ml of water were added to the reaction mixture for liquid separation, and the dichloromethane layer was dried over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure. The obtained residue is purified by silica gel column chromatography (solvent chloroform), the obtained crystals are washed with n-hexane and collected by filtration to obtain the desired O- (1,3-dimethylpyrazole-5- 0.9 g of (ylcarbonyl) pinacolone oxime was obtained as colorless crystals.

Melting point 63-64 ° C Yield 55% Next, Table 3 shows the compounds produced according to these methods. Table 3

[0092]

Embedded image

[0093]

[Table 47] ─────────────────────────────────── No. R ¹ R ² R ³ R ⁴ R ⁵ Melting point (℃) ─────────────────────────────────── 1-1 CH ₃ CH ₃ H CH ₃ t-Bu 63-64 1-2 CH ₃ CH ₃ H CH ₃ CH ₃ oily 1-3 CH ₃ CH ₃ H CH ₃ 1-CH ₃ -c-Pr oily 1-4 CH ₃ CH ₃ H CH ₃ i- Pr oily 1-5 CH ₃ CH ₃ Cl CH ₃ t-Bu 154-155 1-6 CH ₃ Et Cl CH ₃ t-Bu 68-70 1-7 CH ₃ CH ₃ H CH ₃ CH (SCH ₃ ) CH ₃ oil _{1-8 CH 3 CH 3 H -CH 2} S- (CH 2) 2 - oil _{1-9 CH 3 CH 3 H Et i} -Pr oil _{1-10 CH 3 CH 3 H -CH (} CH 3) O- _{(CH 2) 2 - 88-90 1-11} CH 3 CH 3 H CH 3 n-Pr oil _{1-12 CH 3 CH 3 H CH 3} n-Bu oil _{1-13 CH 3 H H CH 3 t} -Bu 46 -48.5 1-14 CH ₃ CH ₃ H -C (CH ₃ ) _2- (CH _{2) 2 - 45-47 1-15 CH 3} CH 3 H CH 3 Et oil _{1-16 CH 3 CH 3 H - (} CH 2) 4 - oil _{1-17 CH 3 CH 3 H CH 3} i-Bu oil 1 -18 CH ₃ Et H CH ₃ t-Bu Oil 1-19 CH ₃ t-Bu H CH ₃ t-Bu 62-65 1-20 CH _3- (CH ₂ ) ₃ -CH ₃ t-Bu 122-123 1 -21 CH ₃ CH ₃ NO ₂ CH ₃ t-Bu oil 1-22 CH ₃ CH ₃ H Et 4-Cl-Ph 88-90 1-23 CH ₃ CH ₃ H Et Et oil ────────── ────────────────────────────

[0094]

[Table 48] Table 4 (continued) ──────────────────────────────────── No. R ¹ R ² R ³ R ⁴ R ⁵ Melting point (℃) ─────────────────────────────────── 1-24 Et CH ₃ H CH ₃ t-Bu oil 1-25 CH ₃ Cl H CH ₃ t-Bu 79-80 1-26 CH ₃ Cl H CH ₃ CH ₃ 58-60 1-27 CH ₃ Cl H CH ₃ Et oil 1 -28 CH ₃ Cl H CH ₃ i-Pr oily 1-29 CH ₃ Cl H CH ₃ s-Bu oily 1-30 CH ₃ Cl H CH ₃ 1-CH ₃ -c-Pr oily 1-31 CH ₃ Cl H _{-C (CH 3) 2 - (} CH 2) 2 - 87-89 1-32 CH 3 Cl H Et Et oil _{1-33 CH 3 Cl H CH 3 4} -Cl-Ph 120-122 1-34 CH 3 Cl H H 2,6-Cl ₂ -Ph 160-161 1-35 CH ₃ Cl H t-Bu Ph 81-82 1-36 Et Cl H CH ₃ t-Bu Oily 1-37 CH ₃ CN H CH ₃ t- Bu 106-107.5 1-38 CH ₃ OCH ₃ H CH ₃ t-Bu 59-67 1-39 CH ₃ COOCH ₃ H CH ₃ t-Bu 56-59 ────────────────── ─────────────────

Example 2 Compound of the present invention No. 2-1
Synthesis of

[0096]

[Chemical 15]

1.48 g (12.8 g) of pinacolone oxime
mmol), 1.50 g of triethylamine (14.8 m)
mol) in 30 ml of dichloromethane and under ice cooling 5
2.51 g (12.8 mmol) of 2-chloro-4-methylthiazole-5-carbonyl chloride was added dropwise at ° C. Then a catalytic amount of 4-dimethylaminopyridine was added,
The temperature was raised to room temperature as it was and stirred for 2 hours. After the reaction,
Dichloromethane and water were added for extraction, the dichloromethane layer was dried over anhydrous sodium sulfate, and the solvent was evaporated. The obtained crude product was subjected to silica gel column chromatography (solvent,
Chloroform), and the obtained crystals are washed with n-hexane to obtain the desired O- (2-chloro-4-methylthiazol-5-ylcarbonyl) pinacolone oxime.
42 g was obtained as white crystals.

Melting point 67-68.5 ° C. Yield 68.8% Next, Table 4 shows compounds produced according to these methods. Table 4

[0099]

Embedded image

[0100]

[Table 49] ──────────────────────────────────── No. R ⁶ R ⁷ R ⁴ R ⁵ Melting point (℃) ──────────────────────────────────── 2-1 Cl CH ₃ CH ₃ t- Bu 67-68.5 2-2 Cl CH ₃ CH ₃ CH ₃ 59-61 2-3 Cl CH ₃ CH ₃ i-Pr Oily 2-4 Cl CH ₃ CH ₃ 1-CH ₃ -c-Pr 60-61 2- 5 Cl CH _3- (CH ₂ ) ₄ -Oil 2-6 Cl CH ₃ CH ₃ i-Bu Oil 2-7 Cl CH ₃ Et Et Oil 2-8 Cl CH ₃ CH ₃ CH (SCH ₃ ) CH ₃ Oil 2 -9 CH ₃ CH ₃ CH ₃ t-Bu 112-114 2-10 CH ₃ Et CH ₃ t-Bu 72-73 2-11 Et CH ₃ CH ₃ t-Bu 90-91.5 2-12 Cl Et CH ₃ t -Bu oil 2-13 CH ₃ CF ₃ CH ₃ t-Bu 122-123 ───────────────────────────────── ──── For use of, specifically described in the following Test Examples.

However, the present invention is not limited to these.

Test Example 1 Water surface application activity test against rice blast 1.5: Planted in 1/20000 ares beaker pot
For rice at the leaf stage, the compound emulsion of the present invention was diluted with water to 500
The pot is irrigated with 10 ml of the drug solution prepared in ppm.
Two weeks later, the treated rice is spray-inoculated with a conidial suspension of blast fungus. Relative humidity 95-100%, approx. 24 ° C
After infecting the rice with the fungus for 24 hours, the rice was left in a greenhouse, and after about 1 week, the degree of disease was examined in 6 levels of 0 to 5.

(Survey Criteria) Rao's index Index of severity 0 No disease 1 Number of lesions 1-5 2 Number of lesions 6-20 3 Number of lesions 21-40 4 Number of lesions 41-70 5 Number of lesions 71 or more

(Test Results) The following compounds showed a morbidity index of 1. The compound of the present invention No.1-1, No.1-2, No.1-4, No.1-6, No.1
-12, No.1-13, No.1-20, No.1-25, No.1-26, No.1
-27, No.1-28, No.1-29, No.1-30, No.1-32, No.1
-36, No.1-37, No.1-38, No.1-39, No.2-1, No.2-
2, No.2-3, No.2-4, No.2-5, No.2-6, No.2-9, No.2-13
,

[0105]

INDUSTRIAL APPLICABILITY These compounds of the present invention are novel compounds, exhibit excellent bactericidal action for agricultural and horticultural use, and have no phytotoxicity against useful crops, and are therefore useful as agricultural and horticultural bactericidal agents.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C07D 231/16 231/54 277/56 413/12 231 417/12 231 (72) Inventor Yasumi Yusha 1 722, Tsuboi-cho, Funabashi, Chiba, Central Research Laboratory, Nissan Chemical Industry Co., Ltd. (72) Inventor, Junichi Watanabe 1, 722, Tsuboi-cho, Funabashi, Chiba Prefecture, Central Research Laboratory, Nissan Chemical Industries, Ltd. (72) Inventor Yasuyuki Nakajima 1 722, Tsuboi-cho, Funabashi, Chiba Prefecture, Central Research Laboratory, Nissan Chemical Industry Co., Ltd. (72) Inventor Hiroshi Oyaku 1470, Shiraoka, Shiraoka Town, Minami Saitama District, Saitama Prefecture Nissan Chemical Industry Co., Ltd. Person Shigeru Sasabe 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Inside Institute for Biological Science, Nissan Kagaku Kogyo Co., Ltd. (72) Masanori Nishioka, Shiraoka-cho, Minami-Saitama-gun, Saitama Shiraoka 1470 Nissan Chemical Industry Co., Ltd. Biological Sciences in the Institute (72) inventor hometown Takashi Saitama Prefecture Minami-Saitama District Shiraoka-cho Oaza Shiraoka 1470 Nissan Chemical Industry Co., Ltd. Biological Sciences in the Institute

Claims (9)

[Claims] 1. A formula [1]:A carboxylic acid oxime ester derivative represented by: 〔the above
In the formula, Q isOr [Chemical 3]And R¹Is a hydrogen atom, C₁~ C_FourAlkyl group, C
₂~ C_FourAlkenyl group, C₂~ C _FourAlkynyl group, free
A substituted phenyl group or a substituted phenyl group (wherein the substituent is a halo
Gen atom, C₁~ C_FourAlkyl group or C₁~ C_FourA
Rucoxy group) and R² Is a hydrogen atom, halogen atom
Child, C₁~ C_FourAlkyl group, C₁~ C_FourAn alkoxy group,
C₁~ C_FourHaloalkyl group, C₁~ C_FourArcoxical
A carbonyl group or a cyano group, R³Is a hydrogen atom,
Rogen atom, nitro group or C₁~ C_FourIs an alkyl group
Or further or R² And R³Together with C₃~ C₆A
A alkylene group may be formed and R^FourAnd R^FiveIs it
Independently, hydrogen atom and C₁~ C₆Alkyl group, C₃~
C₆Cycloalkyl group, C₁~ C_FourSubstituted with an alkyl group
C₃~ C₆Cycloalkyl group, C₂~ C₆Archeni
Group, C₂~ C₆Alkynyl group, C₂~ C_FourAlkylchi
O alkyl group, unsubstituted phenyl group or substituted phenyl group
(The substituent is a halogen atom, C₁~ C_FourAlkyl groups
It is C₁~ C_FourAn alkoxy group) and further or R
^FourAnd R^FiveBecome together C₃~ C₈Form a cycloalkyl group
Or heterocycles containing oxygen or sulfur atoms
May form a clou, R⁶, R⁷Each independently
Hydrogen atom, halogen atom, C₁~ C_FourAlkyl group or
C₁~ C_FourIt is a haloalkyl group. ] 2. Q is The pyrazolecarboxylic acid oxime ester derivative according to claim 1, which is 3. R ¹ is a C ₁ -C ₄ alkyl group,
R ² is a chlorine atom, a bromine atom, a cyano group or C _{1 to} C
The pyrazolecarboxylic acid oxime ester derivative according to claim 2, wherein the pyrazolecarboxylic acid oxime ester is a _4- alkyl group, R ³ is a hydrogen atom, and R ⁴ and R ⁵ are each independently a C ₁ -C ₄ alkyl group. 4. R ¹ is a methyl group, R ² is a chlorine atom, a bromine atom or a methyl group, R ³ is a hydrogen atom, R ⁴ is a methyl group, and R ⁵ is The pyrazolecarboxylic acid oxime ester derivative according to claim 3, which is a t-butyl group. 5. Q is The thiazolecarboxylic acid oxime ester derivative according to claim 1. 6. R ⁶ is a chlorine atom or a C ₁ -C ₄ alkyl group, R ⁷ is a C ₁ -C ₄ alkyl group,
The thiazolecarboxylic acid oxime ester derivative according to claim ^{5, wherein} R ⁴ and R ⁵ are each independently a C _{1 to} C ₄ alkyl group. 7. The thiazolecarboxylic acid according to claim 6, wherein R ⁶ is a chlorine atom, R ⁷ is a methyl group, R ⁴ is a methyl group, and R ⁵ is a t-butyl group. Oxime ester derivative. 8. A fungicide for agricultural and horticultural use, which contains one or more of the carboxylic acid oxime ester derivatives according to claim 1 as an active ingredient. 9. A rice blast control agent containing, as an active ingredient, one or more of the carboxylic acid oxime ester derivatives according to claim 1.