ZA200005439B

ZA200005439B - Pyrazolinone derivatives.

Info

Publication number: ZA200005439B
Application number: ZA200005439A
Authority: ZA
Inventors: Masaya Hashizume; Norio Kimura; Noboru Yamamoto
Original assignee: Sumitomo Chemical Co
Priority date: 1998-04-23
Filing date: 2000-10-05
Publication date: 2002-06-14

Description

¥ : : -~ © E4586 p 1 145/27

DESCRIPTION

PYRAZOLINONE DERIVATIVES

. oo Technical Field

The present invention relates to the pyrazolinone derivatives, their uses and intermediate products.

Background Art

The present invention aims at providing the compounds having an excellent plant disease controlling agent.

Detailed Description of the Invention

As a result of extensive studies on the subject matter, the present inventors found that the pyrazolinone derivatives represented by the following formula [1] have an excellent controlling effect against plant diseases, and attained the present invention on the basis of this finding.

The present invention provides the pyrazolinone derivatives (hereinafter referred to as the present compounds) represented by the formula [I]:

an0skd? 00%" a ¢ h

I 2 0

R3 R'o RS of — \ \ Nar X

RY R2 NH;Y [wherein R!, R?, R®, R! and R® may be identical or different and represent independently an hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, a cyano group, a nitro group, an optionally substituted phenyl group or an optionally substituted phenoxyl group, or adjacent two of R!, R?, R® R? and R® are combined : at the ends to represent a group of the formula CH=CH- : CH=CH, a methylenedioxy group which may be substituted with a halogen atom, or an alkylene group which may contain one oxygen atom and may be substituted with an alkyl group;

R® represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted phenyl group, or an optionally substituted alicyclic hydrocarbon group;

X represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted phenyl group, an optionally substituted alkoxy

2 3 group, an optionally substituted alkenyloxy group, an optionally substituted alkynyloxy group, an optionally substituted phenoxyl group, an optionally substituted alkylthio group, an optionally substituted alkenylthio group, an optionally substituted alkynylthio group, an optionally substituted phenylthio group, or an optionally substituted alicyclic hydrocarbon group; and

Y represents an oxygen atom or a sulfur atom] and the plant disease controlling agents containing the present compound as an active ingredient.

The present invention further provides the pyrazolinone compounds represented by the following formula [II] which are useful as the intermediates for the preparation of the present compounds (these pyrazolinone compounds being hereinafter referred to as intermediates

A):

R31 R"o RS a6 .

NH

RY p21 NH; [wherein RY, R?!, R3®, R*" and R°! may be identical or different and represent independently a hydrogen atom, a : halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, a cyano group, a nitro group, an optionally substituted phenyl group or an optionally substituted

IS 4 phenoxyl group; or adjacent two of RY, R?*, R*, R* and R’! are combined at the ends to represent a group of the formula

CH=CH-CH=CH, a methylenedioxy group which may be substituted with a halogen atom, or an alkylene group which may contain one oxygen atom and may be substituted with an alkyl group; and

R® represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted phenyl group or an optionally substituted alicyclic hydrocarbon group] and the pyrazolinone compounds represented by the formula [III] which are also useful as the intermediates for the preparation of the present compounds (these pyrazolinone compounds being hereinafter referred to as intermediates B):

R32 Rg hd

R%2 R22 NH; vy? [wherein RY?, R%*?, R*, R*? and R’® may be identical or different and represent independently a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio

: © 20005439 + S group, a cyano group, a nitro group, an optionally substituted phenyl group or an optionally substituted phenoxyl group, or adjacent two of RY, Rr?, R3, R* and R® are combined at the ends and represent a group of the formula

CH=CH~-CH=CH, a methylenedioxy group which may be substituted with a halogen atom, or an alkylene group which may contain one oxygen atom and may be substituted with an alkyl group;

X! represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted phenyl group, an optionally substituted alkoxy group, an optionally substituted alkenyloxy group, an optionally substituted alkynyloxy group, an optionally substituted phenoxyl group, an optionally substituted alkylthio group, an optionally substituted alkenylthio : group, an optionally substituted alkynylthio group, an optionally substituted phenylthio group, or an optionally substituted alicyclic hydrocarbon group; and

Y? represents an oxygen atom or a sulfur atom].

Modes for Carrying out the Invention

In the present invention, the halogen atoms represented by R!, R?, rR}, R*, R°, R'Y, R?, R®, R%, R’, R!?,

R??, R32, R% and R°? in the formulae [I] to [III] include fluorine, chlorine, bromine and iodine.

The alkyl groups include C1-C5 alkyl groups such

The haloalkyl groups include C1-C5 haloalkyl groups such as trifluoromethyl, tetrafluoroethyl and heptafluoropropyl.

The alkoxy groups include Cl1-C5 alkoxy groups such as methoxy, ethoxy, normal propyloxy, isopropyloxy, n-butoxy and n-pentyloxy.

The alkoxyalkyl groups include Cl-C3 alkoxy Cl-

C3 alkyl groups such as methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl and ethoxypropyl.

The alkoxyalkoxy groups include Cl1-C3 alkoxy Cl-

C3 alkoxy groups such as methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy and ethoxypropoxy.

The haloalkoxy groups include C1-C5 haloalkoxy groups such as trifluoromethoxy, difluoromethoxy and tetrafluoroethoxy.

The alkylthio groups include C1l-C5 alkylthio groups such as methylthio, ethylthio, n-propylthio, n- butylthio and n-pentylthio.

The haloalkylthio groups include C1-C5 haloalkylthio groups such as trifluoromethylthio.

The optionally substituted phenyl and phenoxyl groups include those which may be substituted with at least one group selected from halogen atoms, C1-C5 alkyl groups, Cl-C5 alkoxy groups, Cl-C5 alkylthio groups, Cl-C5 haloalkyl groups, C1-C5 haloalkoxy groups, C1-C5 sk haloalkylthio groups and cyano groups. : Examples of the above-mentioned substituents are shown below: oo

Halogen atoms: fluorine, chlorine, bromine and 5S iodine;

Co C1-C5 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl and n-pentyl; © C1-C5 alkoxy groups: methoxy and ethoxy;

Cl-C5 alkylthio groups: methylthio and ethylthio;

Cl-C5 haloalkyl groups, preferably Cl-C2 haloalkyl groups: trifluoromethyl; oo

Cl-C5 haloalkoxy groups, preferably Cl-C2 > haloalkoxy groups: trifluoromethoxy and difluoromethoxy;

Cl-C5 haloalkylthio groups, preferably Cl-C2 : haloalkylthio groups: trifluoromethylthio; and

Cyano groups. .

Referring to the above R's, adjacent two of R! to : rR’, R™ to R*, and R® to R* may be combined at the ends to form a methylenedioxy group which may be substituted with : a halogen atom, such as difluoromethylenedioxy, or an - alkylene group (such as Cl1-C6 alkylene group) which may contain an oxygen atom and may be substituted with an alkyl group (e.g. Cl-C4 alkyl group), such as trimethylene, © 25 tetramethylene, a group of the formula OCH,CH, or a group of the formula OCH,CH (CH3) .

In the present compounds in view of the controlling effect against plant diseases, it is desirable - CORRECTED SHEET 2002 -04- 18

I” 8 that 1 to 3 substituents selected from R' to R® is a halogen atom (especially chlorine), a haloalkyl group (especially trifluoromethyl) or an alkyl group (especially methyl), and the remainder of the substituents are a hydrogen atom. In view of the efficacy against Botrytis cinerea, it is desirable that R3, R? and R®> are a hydrogen atom.

Examples of the optionally substituted alkyl groups represented by R® and R®! in the present invention include the following:

Cl-Cl1l0 alkyl groups such as ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 1- methylbutyl and l-ethylpropyl;

C1-C10 haloalkyl groups such as l-methyl-2,2,2- trifluoroethyl and l-methyl-3-chloropropyl;

Cl-C5 alkoxy Cl1-C5 alkyl groups such as 2- methoxyethyl;

Cl-C5 alkylthio C1-C5 alkyl groups such as 2- methylthioethyl;

C1l-C5 haloalkoxy Cl1-C5 alkyl groups such as 1- methyl-(2,2,2-trifluoroethoxy) ethyl;

Cl-C5 haloalkoxy Cl1-C5 haloalkyl groups;

Cl-C5 haloalkylthio Cl1-C5 alkyl groups such as l-methyl-(2,2,2-trifluoroethylthio)ethyl;

Cl-C5 haloalkylthio Cl1-C5 haloalkyl groups;

Cyano C1-C5 alkyl groups such as l-cyanoethyl;

Cyano C1-C5 haloalkyl groups such as l-cyano- 2,2,2-trifluorocethyl;

Cl-C5 alkoxycarbonyl C1-C5 alkyl groups such as 1- (methoxycarbonyl) ethyl; and

Cl-C5 alkyl groups substituted with a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, such as 1-cyclopropyethyl.

Examples of the optionally substituted alkenyl groups represented by R® and R®' include:

C3-C10 alkenyl groups such as l-methyl-2- propenyl; and

C3-C10 haloalkenyl groups.

Examples of the optionally substituted alkynyl groups include:

C3-C10 alkynyl groups such as l-methyl-2- propynyl, and C3-Cl0 haloalkynyl groups.

Examples of the optionally substituted alicyclic hydrocarbon groups include:

C3-C8 alicyclic hydrocarbon groups; : C3-C8 alicyclic hydrocarbon groups which may be substituted with a halogen atom and may contain unsaturated bonds, such as cyclopentyl and cyclohexyl; and

Phenyl groups and C7-Cl7 aralkyl groups which may be substituted with at least one group selected from halogen atoms, Cl1-C5 alkyl groups, Cl-C5 alkoxyl groups,

C1-C5 alkylthio groups, Cl-C5 haloalkyl groups, Cl1-C5 : haloalkoxyl groups and C1-C5 haloalkylthio groups and cyano group, such as benzyl, a-methylbenzyl and «, a- dimethylbenzyl.

Examples of the optionally substituted alkyl groups represented by X or X' in the present invention include:

Cl-C10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, 2- methylbutyl, isopentyl and tertiary butyl;

C1-C10 haloalkyl groups such as trifluoromethyl, tetrafluoroethyl, 2-chloroethyl, 3-chloropropyl and 4- chlorcbutyl;

Cl-C5 alkoxy C1~C5 alkyl groups such as methoxymethyl and 2-methoxyethyl;

Cl-C5 alkylthio C1-C5 alkyl groups such as methylthiomethyl and 2-methylthioethyl;

C1-C5 haloalkoxy Cl-C5 alkyl groups such as 2,2,2-trifluoroethoxymethyl;

Cl1-C5 haloalkoxy C1-C5 haloalkyl groups:

Cl1-C5 haloalkylthio C1-C5 alkyl groups such as 2,2,2-trifluorocethylthiomethyl;

Cl-C5 haloalkylthio C1-C5 haloalkyl groups;

Cyano C1-C5 alkyl groups such as cyanomethyl, 1- cyanoethyl and 2-cyanoethyl;

Cyano Cl-C5 haloalkyl groups; and

Cl-C5 alkoxycarbonyl C1-C5 alkyl groups such as 1- (methoxycarbonyl) ethyl.

Examples of the optionally substituted aralkyl groups include C7-Cl7 aralkyl groups which may be substituted with at least one group selected from halogen atoms, Cl1-C5 alkyl groups, C1l-C5 alkoxyl groups, C1-C5 alkylthio groups, Cl-C5 haloalkyl groups, Cl-C5 haloalkoxyl groups, Cl1-C5 haloalkylthio groups and cyano groups, such as benzyl, a-methylbenzyl and a, a- dimethylbenzyl; and

Cl-C5 alkyl groups substituted with a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, such as cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl.

Examples of the optionally substituted alkenyl groups include C2-C10 alkenyl groups such as vinyl, 1- propenyl, Z2-propenyl, l-butenyl, 2-~-butenyl and 3-butenyl; and

C2-Cl10 haloalkenyl groups such as 3,3,3- trifluoropropenyl, and 1,1,2,3,3-pentafluoro-2-propenyl.

Examples of the optionally substituted alkynyl groups include C2-C1l0 alkynyl groups such as ethynyl, propalgyl, 2-butynyl and 3-butynyl; and C2-Cl0 haloalkynyl groups such as 3,3,3-tetrafluoropropynyl.

Examples of the optionally substituted alkoxyl groups include C1-Cl0 alkoxyl groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, isobutoxy, 2-methylbutoxy and isopentyloxy;

Cl1-C10 haloalkoxyl groups such as trifluoroethoxy, tetrafluoroethoxy, pentafluoroethoxy, tetrafluoropropoxy, 2-chloroetoxy, 3-chloropropoxy and 4- chlorobutoxy;

Cil~-C5 alkoxy Cl-C5 alkoxyl groups such as 2-

- | 12 methoxyethoxy; oo

Cl1-C5 alkylthio C1-C5 alkoxyl groups such as 2- methylthioethoxy;

Cl-C5 haloalkoxy Cl-C5 alkoxyl groups such as 2.2. 2-trifluoroethoxymethoxy;

N C1-C5 haloalkoxy C1-C5 haloalkoxyl groups;

Cl-C5 haloalkylthio C1-C5 alkoxyl groups such as : 2,2,2-trifluoroethylthiomethoxy; ~~ Cl-C5 haloalkylthio C1-C5 haloalkoxyl groups; | Cyano Cl-C5 alkoxyl groups such as 2- cyvanoethoxy; : | : : Cl-C5 alkoxycarbonyl Cl-C5 alkoxyl groups such as 2-{(methoxycarbonyl) ethoxyl; : Cl-C5 alkoxyl groups substituted with a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, such as cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy and cyclohexylmethoxy.

Examples of the optionally substituted oo alkenyloxy groups include C2-C10 alkenyloxy groups such as 2-propenyloxy, 2-butenyloxy and 3-butenyloxy; and : c2-C10 haloalkenyloxy groups such as 2,3,3- : trifluoro-2-propenyloxy, 4,4,4-trifluoro-2-butenyloxy, 2,3-difluoro-2-butenyloxy, and 2,4,4,4-tetrafluoro-2- butenyloxy.

Examples of the optionally substituted ~ alkynyloxy groups include C2-Cl0 alkynyloxy groups such as 2-propynyloxy, 2-butynyloxy and 3-butynyloxy; and

CORRECTED SHEET 2002 -04- 18

C2-C10 haloalkynyloxy groups such as 4-chloro-2- butynyloxy.

Examples of the optionally substituted alkylthio groups include C1-C10 alkylthio groups such as methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, isobutylthio, 2-methylbutylthio and isopentylthio;

Cl1-C10 haloalkylthio groups such as trifluoroethylthio, tetrafluoroethylthio, . pentafluorcethylthio, tetrafluoropropylthio, 2- chloroethylthio, 3-chloropropylthio, and 4- chlorobutylthio;

Cl-C5 alkoxy Cl-C5 alkylthio groups such as 2- methoxyethylthio:

Cl-C5 alkylthio Cl1-C5 alkylthio groups such as 2-methylthioethylthio;

Cl-C5 haloalkoxy C1-C5 alkylthio groups such as 2,2,2-tetrafluorocethoxymethylthio; :

Cl-C5 haloalkoxy C1-C5 haloalkylthio groups; : Cl-C5 haloalkylthio C1-C5 alkylthio groups such as 2,2,2-tetrafluorcethylthiomethylthio:

C1-C5 haloalkylthio C1-C5 haloalkylthio groups;

Cyano C1-C5 alkylthio groups such as 2- cyanoethylthio;

Cl-C5 alkoxycarbonyl C1-C5 alkylthio groups such as 2-(methoxycarbonyl)ethylthio;

Cl-C5 alkylthio groups substituted with a C3-CS8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, such as a 14 cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, (1- cyclopentenyl)methylthio, and (l-cyclohexenyl)methylthio.

Examples of the optionally substituted alkenylthio groups include C2-Cl10 alkenylthio groups such as 2-propenylthio, 2-butenylthio and 3-butenylthio;

C2-C10 haloalkenylthio groups such as 2,3, 3- tetrafluoro-2-propenylthio, 4,4,4-tetrafluoro-2- butenylthio, 2,3-difluoro-2-butenylthio and 2,4,4,4- tetrafluoro-2-butenylthio.

Examples of the optionally substituted alkynylthio groups include C2-C1l0 alkynylthio groups such as 2-propynylthio, 2-butenylthio and 3-butenylthio; and

C2-C10 haloalkynylthio groups.

Examples of the optionally substituted alicyclic hydrocarbon groups include C3-C8 alicyclic hydrocarbon groups which may be substituted with a halogen atom and may contain unsaturated bonds, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, l-cyclopentenyl, 2- cyclopentenyl, 3-cyclopentenyl, 1,3-cyclopentadienyl, 2,4- cyclopentadienyl, l-cyclohexenyl, 2-cyclohexenyl and 3- cyclohexenyl.

Examples of the optionally substituted phenyl groups, phenoxyl groups, C7-Cl7 aralkyloxy groups, C7-Cl7 aralkylthio groups and phenylthio groups include the phenyl groups, phenoxyl groups, C7-Cl7 aralkyl groups (such as benzyl, a-methylbenzyl and a, a -dimethylbenzyl),

C7-C17 aralkyloxy groups and C7-Cl7 aralkylthio groups

2 15 (such as benzylthio) which may be substituted with at least one group selected from halogen atoms, C1-C5 alkyl groups, Cl-C5 alkoxyl groups, Cl-C5 alkylthio groups, Cl-

C5 haloalkyl groups, Cl1-C5 haloalkoxyl groups, Cl-C5 haloalkylthio groups and cyano group.

Examples of the substituents include: halogen atoms such as fluorine, chlorine, bromine and iodine;

Cl-C5 alkyl groups such as methyl, ethyl, n- propyl, i-propyl, n-butyl and n-pentyl;

Cl-C5 alkoxyl groups such as methoxy and ethoxy;

Cl-C5 alkylthio groups such as methylthio and . ethylthio;

Cl1-C5 haloalkyl groups, preferably Cl-C2 haloalkyl groups such as trifluoromethyl;

Cl1-C5 haloalkoxyl groups, preferably C1-C2 haloalkoxyl groups such as trifluoromethoxy and : difluoromethoxy;

C1l-C5 haloalkylthio groups, preferably C1-C2 haloalkylthio groups such as trifluoromethylthio; and : cyano groups.

In the present compounds in view of their efficacy for plant diseases, preferred examples of the substituents represented by X are Cl1-C5 alkyl groups, Cl-

C5 haloalkoxyl groups, C2-C5 alkenyloxy groups, C2-C5 haloalkenyloxy groups, C2-C5 alkynyloxy groups, C2-C5 haloalkynyloxy groups, C1-C5 alkylthio groups, C1-C5 haloalkylthio groups, C2-C5 alkenylthio groups, C2-C5

@& eS) 16 haloalkenylthio groups, C2-C5 alkynylthio groups and C2-C5 haloalkynylthio groups.

The present compounds can exist in the form of various tautomeric structures represented by the following formula [VII], and all of these tautomers are embraced within the concept of the present compounds.

RY R'q Re R® R'Q ge aS: —_— pane \ NX ———F No _X

RY R2 NHyY RY R2 I

R3 R' oH RE

N’ ==

R* R2 NH Y

Further, the present compounds may take the form of stereoisomers originating in the presence of double bonds and asymmetric carbon atoms, and these stereoisomers and their mixtures are also comprehended in the present compounds.

The intermediate A can exist in the form of various tautomeric structures represented by the following formula [VIII], and all of these tautomers are included in the intermediate A of the present invention.

a 2 17 31 31 1

RY R'h Re R* R'bH gS? R3 Rp RO

R51 Nest FN a RS N

N\ NH NH ~~ ZN 41 521 NH

R41 r2' NH; R41 R21 nn RY R 2 3 Rh RE R' R'bH Re!

N’ N 51 \ - 51 /

The intermediate A may take the form of stereoisomers originating in the presence of double bonds and asymmetric carbon atoms, and these stereoisomers and their mixtures also fall within the ambit of the present compound. : The intermediate B can exist in the form of various tautomeric structures represented by the following formula [IX], and all of these tautomers are comprehended in the intermediate B of the present invention. 32

RZ RD R*? RH R* R'QH 52 NH 52 =N — R52 NH = Ll med Lh = a a.

R42 R% NH,Y' R42 R22 NH Y! R42 R22 NH Y! 32 R'D R32 ROH — R52 NH a Ro2 =N

Y, Y,

a 2 18

Further, in the intermediate B, there may exist the stereoisomers originating in the presence of double bonds and asymmetric carbon atoms, and these stereoisomers and their mixtures are also embraced in the concept of intermediate B according to the present invention.

The present compounds can be produced from the following processes. (Process 1)

An alkaline metal salt of an intermediate A is reacted with a compound represented by the formula (X]:

Y

AN

V4 X [wherein X and Y are as defined previously, and 2 represents a halogen atom (such as chlorine atom or bromine atom)] in an organic solvent.

The reaction is carried out at a temperature in the range of usually 80 to 140°C for a period of usually 0.1 to 5 hours, using a compound of the formula [X] usually in a ratio of 1 to 3 moles, preferably 1.1 to 2 moles to one mole of an alkaline metal salt of an intermediate A.

As the organic solvent in the above reaction, : aromatic hydrocarbons such as toluene, xylene and : chlorobenzene, ethers such as diethyl ether, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, diisopropyl ether and dimethoxyethane, dimethylformamide, and mixtures thereof a

N 19 can be used. 1,4-dioxane or dimethoxyethane is preferably used. :

After the completion of the reaction, the reaction solution is poured into water and subjected to the ordinary after-treatments such as extraction with an organic solvent and concentration to give the present compound. The obtained compound can be purified by suitable means such as washing with an organic solvent, recrystallization and column chromatography.

An alkaline metal salt of an intermediate A can be produced by reacting an intermediate A with sodium hydroxide, anhydrous lithium hydroxide or a lithium hydroxide monohydrate under an azeotropic dehydrating condition, or by reacting an intermediate A with sodium hydride or lithium hydride.

In case of reacting an intermediate A with sodium hydroxide, anhydrous lithium hydroxide or a lithium hydroxide monohydrate under an azeotropic dehydrating condition, the reaction is carried out usually at 80 to 140°C for usually 0.5 to 12 hours by supplying usually 1 to 5 moles, preferably 1.1 to 2 moles of sodium hydroxide, anhydrous lithium hydroxide or a lithium hydroxide monohydrate to one mole of an intermediate A, using, for example, an aromatic hydrocarbon such as toluene, xylene or chlorobenzene as the reaction solvent.

In case of reacting an intermediate A with sodium hydride or lithium hydride, the reaction is conducted usually at 60 to 120°C for a period of usually 1

N 20 to 12 hours by supplying 1 to 2 moles of sodium hydride or lithium hydride to one mole of an intermediate A, using, for example, an aromatic hydrocarbon such as toluene,

Xylene or chlorobenzene, an ether such as diethyl ether, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, diisopropyl ether or dimethoxyethane, or dimethylformamide, preferably 1,4-dioxane or dimethoxyethane as the reaction solvent.

After the completion of the reaction, the solvent in the reaction solution is distilled off under reduced pressure to form an alkaline metal salt of an intermediate A.

The compounds represented by the formula [X] can : be produced, for instance, according to the methods described in Org. Syn. 1, 147; J. Am. Chem. Soc. 73, 3796 (1951); J. Am. Chem. Soc. 81, 714 (1959); Angew. Chem. Int.

Ed. Engl., 26, 894 (1987); and Synthesis, 760 (1986).

The intermediates A can be produced by acting an acid catalyst to the pyrazolinone derivatives represented by the formula [XI]:

R31 Ro RE

N’ rR L N

R41 R? \¥h [wherein R!?, R?', R?, R*!, R’! and R® are as defined previously].

The reaction is carried out usually at a temperature in the range of 80 to 120°C for a period of usually 1 to 12 hours by supplying usually 0.1 mole to an excess amount of an acid to one mole of a pyrazolinone derivative of the formula [XI]. 5 As the acid in the above reaction, there can be used, for example, mineral acids such as hydrochloric acid and sulfuric acid in the form of an aqueous solution.

As the solvent, the above-mentioned acids, alcohols such as methanol and ethanol, their mixtures, etc., can be used.

After the completion of the reaction, the reaction solution may be neutralized with a basic aqueous solution such as a sodium hydroxide solution or a sodium hydrogencarbonate solution, then concentrated and washed with water to produce an intermediate A. The obtained compound can be purified by suitable means such as washing with an organic solvent, recrystallization, column chromatography, etc.

The pyrazolinone derivatives represented by the formula [XI] can be produced according to the method described in JP-A-8-208621. (Process 2)

An alkaline metal salt of an intermediate B is reacted with a compound represented by the formula [XII]:

R®-L [wherein R® is as defined above, and L represents a chlorine atom, a bromine atom, an iodine atom, a C1-Cl0 alkanesulfonyloxy group or an optionally substituted

3 22 benzenesulfonyloxy group] in an organic solvent.

The reaction is carried out usually at a temperature in the range of 60 to 150°C, preferably 80° to 120°C for a period of usually 0.1 to 12 hours by supplying usually 1 to 5 moles, preferably 1 to 2.5 moles of a compound of the formula [XI] to one mole of an alkaline metal salt of an intermediate B.

The organic solvents usable for the above reaction include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, aliphatic hydrocarbons such as normal hexane and normal heptane, ethers such as tetrahydrofuran, 1,4-dioxane and tetrahydropyran, and their mixtures.

After the completion of the reaction, the reaction solution is poured into acidic water and then subjected to the ordinary after-treatments such as extraction with an organic solvent, concentration, etc., to produce the present compound. The obtained compound can be purified by suitable means such as washing with an organic solvent, recrystallization, column chromatography, etc.

An alkaline metal salt of an intermediate B can be produced by reacting an intermediate B with sodium hydroxide, anhydrous lithium hydroxide or a lithium hydroxide monohydrate under an azeotropic dehydrating condition, or by reacting an intermediate B with sodium hydride or lithium hydride.

In case of reacting an intermediate B with

3 23 sodium hydroxide, anhydrous lithium hydroxide or a lithium hydroxide monohydrate under an azeotropic dehydrating condition, the reaction is carried out usually at 80 to 140°C for usually 0.5 to 12 hours by supplying usually 1 to 5 moles, preferably 1.1 to 2 moles of sodium hydroxide, anhydrous lithium hydroxide or a lithium hydroxide monohydrate to one mole of an intermediate B using, for instance, an aromatic hydrocarbon such as toluene, xylene or chlorobenzene as the reaction solvent.

In case of reacting an intermediate B with sodium hydride or lithium hydride, the reaction is carried out usually at 60 to 120°C for usually 1 to 12 hours by supplying 1 to 2 moles of sodium hydride or lithium hydride to one mole of an intermediate B, using an aromatic hydrocarbon such as toluene, xylene or chlorobenzene, an ether such as diethyl ether, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, diisopropyl ether or dimethoxyethane, dimethylformamide or the like, preferably 1,4-dioxane or dimethoxyethane as the reaction solvent. | The intermediates B can be produced, for example, by the following processes. {Preparation process 1 of the intermediate}

A pyrazolinone compound represented by the formula [V']:

R32 R20 \~NH - R¥ R22 NH»

4 24 [wherein R'?, R%*?, R%?, R* and R°’ are as defined above] is reacted with a compound represented by the formula [XIII]: 71 x! h! [wherein X' and Y! are as defined above, and Z' represents a halogen atom (such as chlorine atom or bromine atom)] in an organic solvent in the presence of a base.

The reaction is carried out usually at a temperature in the range of 0 to 100°C, preferably 10 to 50°C, for a period of usually 1 to 12 hours by supplying usually 0.8 to 1.2 mole, preferably 1 to 1.1 mole of a compound of the formula [XIII] to one mole of a pyrazolinone compound of the formula {(V’]. A base is used in a ratio of usually 1 to 5 moles, preferably 1 to 1.5 mole.

As the base, there can be used inorganic bases, for example, alkaline metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, alkaline metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate and calcium carbonate, and alkaline metal bicarbonates such as: sodium bicarbonate and potassium bicarbonate, and organic bases such as pyridine, N,N-dimethylpyridine and triethylamine.

In case of using an inorganic base, it may be applied as i. 25 an aqueous soclution.

As the solvent, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, aliphatic hydrocarbons such as normal hexane and normal heptane, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran, 1,4-dioxane and tetrahydropyran, and their mixtures can be used.

Water may be allowed to co-exist with an organic solvent, in which case water and the organic solvent may stay 10° homogeneous or heterogeneous.

After the completion of the reaction, the reaction solution is poured into acidic water and subjected to the ordinary after-treatments such as extraction with an organic solvent, concentration of the organic layer, etc., to obtain an intermediate B. The obtained compound may be purified by suitable means such as washing with an organic solvent, recrystallization, column chromatography, etc.

The pyrazolinone derivatives represented by the formula [V’] can be produced, for example, according to the method described in J. Chem. Soc. Chem. Commum., 23, 1755-1757 (1993).

The compounds represented by the formula [XIII] ~ can be produced according to the methods described in Org.

Syn. 1, 147; J. Am. Chem. Soc. 73, 3796 (1951); J. Am.

Chem. Soc., 81, 714 (1959); Angew. Chem. Int. Ed. Engl., 26, 984 (1987); Synthesis, 760 (1986), etc. {Preparation process 2 of the intermediate}

A pyrazolinone compound represented by the formula (V’] is reacted with a compound represented by the formula [XIV]: 2°-G [wherein G represents a Cl-C5 trialkylsilyl group such as trimethylsilyl, treithylsilyl, dimethylethylsilyl, dimethylisopropyl or tert-butyldimethylsilyl, and z? represents a halogen atom such as chlorine, bromine or iodine] in an organic solvent in the presence of a base, then further reacted with a compound represented by the formula [XIII], and subjected to the after-treatments in acidic water.

The reaction is carried out usually at a temperature in the range of 0 to 100°C, preferably 0 to 30°C for a period of usually 1 to 12 hours by supplying usually 1 to 1.5 mole, preferably 1 to 1.2 mole of a compound of the formula [XIV] and a compound of the formula [XIII] to one mole of a pyrazolinone compound of the formula [V’]. The ratio of the base used in the reaction is usually 2 to 10 moles, preferably 2 to 5 moles.

As the base, organic bases such as pyridine and triethylamine can be used.

a a 27

After the completion of the reaction, the reaction solution is poured into acidic water, or if necessary the reaction solution is filtered to remove the precipitate and the filtrate is poured into acidic water, then stirred under reflux for 0.5 to 5 hours, preferably 0.5 to 2 hours, extracted with an organic solvent, and subjected to the after-treatments such as concentration of the organic layer to give a pyrazolinone compound of the formula [VI]. The obtained compound can be purified by suitable means such as washing with an organic solvent, recrystallization, column chromatography, etc. (Process 3)

An intermediate B and a compound represented by the formula [XII] are reacted in an organic solvent in the presence of a base.

The reaction is carried out at a temperature in the range of usually 60 to 180°C, preferably 80 to 120°C for a period of usually 1 to 12 hours by supplying usually 1 to 5 moles, preferably 1 to. 2.5 moles of a compound of the formula [XI] to one mole of an alkaline metal salt of an intermediate B and allowing a base to exist in a ratio of usually 1 to 5 moles, preferably 1 to 2.5 moles.

As the base in the above reaction, organic bases, for example, alkaline metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, alkaline metal or alkaline earth metal carbonates such as sodium carbonate,

potassium carbonate, magnesium carbonate and calcium carbonate, alkaline metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, pyridine, N-N- dimethylpyridine, triethylamine, etc., can be used.

As the organic solvent for the above reaction, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, aliphatic hydrocarbons such as normal hexane and normal heptane, ethers such as tetrahydrofuran, 1,4-dioxane and tetrahydropyran, and their mixtures are usable.

If necessary, molecular sieves (synthetic zeolite) may be allowed to exist in the reaction system.

After the completion of the reaction, the reaction solution is poured into acidic water and subjected to the ordinary after-treatments such as extraction with an organic solvent, concentration, etc., to obtain the present compound. The obtained compound may be purified by suitable means such as washing with an organic solvent, recrystallization, column chromatography, etc.

When the present compound is used as an active ingredient of the plant diseases controlling agent, the compounds may be used as they are without adding any other components, but usually they are mixed with proper adjuvants such as solid carrier, liquid carrier, surfactant, etc., and formulated into a desired form of preparation such as emulsifiable concentrate, wettable powder, flowable, dust, granule, etc. In these formulations, the content of the present compound as an active ingredient is usually 0.1 to 99%, preferably 1 to 90% in ratio by weight.

Examples of the solid carriers usable in the formulations include fine powders or granules of kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corncob, walnut shell, urea, ammonium sulfate, synthetic hydrous silicon oxide and the like. Examples of the liquid carriers include : aromatic hydrocarbons such as xylene and methyl naphthalene, alcohols such as isopropanol, ethylene glycol and cellosolve, ketones such as acetone, cyclohexanone and isophorone, plant oils such as soybean oil and cottonseed 0il, dimethyl sulfoxide, acetonitrile and water.

Examples of the surfactants usable for the above formulations include anionic surfactants such as alkylsulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinate, polyoxyethylene alkylaryl ether phosphoric ester salts, naphthalenesulfonic acid-formalin condensate, etc., and nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene-alkylpolyoxypropene block copolymer, sorbitan fatty acid esters, etc.

Examples of the adjuvants usable for the above formulations include lignin sulfonate, alginates, polyvinyl alcohol, gum arabic, carboxymethyl cellulose (CMC), acidic isopropyl phosphate (PAP) and the like.

The present compound may be applied in folian application, soil treatment, seed disinfection and the a like, and usually any application method which one skilled in the art employs may also be used.

When the present compound is used as an active ingredient for the plant disease controlling agent, the quantity of the compound (active ingredient) to be applied is usually 0.01 to 50 g/are, preferably 0.05 to 10 g/are, though it is variable depending on the type of the plant (crop, etc.) to be treated, type of the plant disease to be controlled, degree of affection by the disease, dosing form way of application, time of application, weather conditions, etc.

In case the compound is used in the form of an emulsifiable concentrate, wettable powder, flowable etc. by diluting it with water, the concentration of the compound in such aqueous formulations should be 0.0001 to 0.5%, preferably 0.0005 to 0.2%. When the compound is used as a dust or granule, it may be applied as it is without dilution.

The present compound can be used as a controlling agent against plant diseases in the plowed fields, paddy fields, orchards, tea plantations, pastures, lawns and the like. Also, an increased germicidal effect can be expected by using the compounds in admixture with other known plant disease controlling agents. Examples of such admixable other controlling agent include azole type germicidal compounds such as Propiconazole, Triadimenol,

Prochloraz Penconazole, Tebuconazole, Flusilazole,

Diniconazole, Bromconazole, Epoxyconazole, Diphenoconazole,

3 31

Ciproconazole, Metoconaznole, Triflumizole, Tetraconazole,

Microbutanil, Fenbuconal, Hexaconazole, Fluquinconazole,

Triticonazole (RPA4007), Bitertanol, Imazalil, and

Flutriafol, cyclic amine type germicidal compounds such as

Fenpropimorph, Tridemorph and Fenpropidin, benzimidazole type germicidal compounds such as Carbendazim, Benonyl,

Tiabendazole and Thiophanate-methyl, procymidone,

Cyprodinil, Pyrimethanil, Diethofencarb, Thiuram,

Fluazinam, Mancozeb, Iprodione, Vinclozolin, Chloro- thalonil, Captan, Mapanipyrim, Fenpiclonil, Kresoxim- methyl, Fludioxonil, Dichlofluanide, Folpet, Azoxystrobin, and N-methyl-a -methoxyimino-2~[(2,5~-dimethylphenoxy) methyl] -phenylacetamide. Further, the compounds of the present invention can be used in admixture or combination with the known insecticides, miticides, nemacides, herbicides, plant growth regulators and fertilizers.

The present compound are effective for controlling a variety of plant diseases, for example, those mentioned below:

Pyricularia oryzae, Cochliobolus miyabeanus, ~ Rhizoctonia solani, Erysiphe graminis, Gibberella zeae,

Puccinia striiformis, P. graminis, P. recondita, P. hordei,

Typhula sp., Micronectriella nivalis, Ustilago tritici, U. nuda, Tilletia caries, Pseudocercosporella herpotrichoides,

Rhynchosporium secalis, Septoria tritici, Leptosphaeria nodorum, Diaporthe citri, Elsinoe fawcetti, Penicillium digitatum, P. italicum, Sclerotinia mali, Valsa mali,

Pososphaera leucotricha, Alternaria mali, Venturia

“a 32 inaeqgaulis, Venturia nashicola, V. pirina, Alternaria kikuchiana, Gymnosporangium haraeanum, Sclerotinia cinerea,

Cladosporium carpophilum, Phomopsis sp., Elsinoe ampelina,

Glomerella cingulata, Uncinula necator, Phakopsora ampelopsidis, Guignardia bidwellii, Plasmopara viticola,

Gloeosporium kaki, Cercospora kaki, Mycosphaerella nawae,

Colletotrichum lagenarium, Sphaerotheca fuliginea,

Mycosphaerella melonis, Fusarium oxysporum,

Pseudoperonospora cubensis, Phytophthora sp., Pythium sp.,

Alternaria solani, Cladosporium fulvum, Phytophthora infestans, Phomopsis vexans, Erysiphe cichoracearum,

Alternaria japonica, Cercosporella brassicae, Puccinia allii, Cercospora kikuchii, Elsinoe glycines, Diaporthe phaseolorum var. sojae, Colletotrichum lindemthianum,

Cercospora personata, Cercospora arachidicola, Erysiphe pisi, Alternaria solani, Phytophthora infestans,

Sphaerotheca humuli, Exobasidium reticulatum, Elsinoe leucospila, Alternaria longipes, Erysiphe cichoracearum,

Colletorichum tabacum, Peronospora tabacina, Phytophthora nicotianae, Cercospora beticola, Diplocarpon rosae,

Sphaerotheca pannosa, Septoria chrysanthemi indici,

Puccinia horiana, Botrytis cinerea of various farm products, and Sclerotinia sclerotiorum.

EXAMPLES

The present invention is explained in more detail in the following Production Examples, Formulation

Examples and Test Examples, but it should be understood that the scope of the present invention is not restricted to these Examples.

First, the production examples of the present compound, their intermediate A and intermediate B are described. In the following descriptions of the Examples, the compound numbers correspond to those shown in Tables 1 to 64 given below. The symbol “ (+)-"” or “(-)-"” put in front of the compound number indicates that the compound is a single body of an optically active substance or a mixture of optically active substances and has a plus (+) or minus (-) specific rotation.

For the purity assay of the obtained objective products, liquid chromatographic analysis (hereinafter referred to as LC) was conducted under the following conditions. <LC conditions>

Analyzer: low pressure gradient type (Hitachi L-6000

Series) : Column: L-column ODS (4.6 mm¢ x 150 mm; mfd. by

Kagakuhin Kensa Kyokai (Chemical Substances :

Testing Association)

Column temperature: 40°C

Detector: UV (254 nm)

Mobile phase condition: gradient method (solution A & solution B)

Time (min): 0, 10, 35, 45

Solution B conc. (%): 50, 50, 100, 100

Flow rate (ml/min): 1.0 ml/min

Claims

“ WHAT IS CLAIMED IS:

1. The pyrazolinone derivatives represented by the formula [I]: R® R'p RE of — N N\ Nar X R4 R2 NH, Y wherein R?, R?, R?, R? and R® may be identical or different and represent independently a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxyl group, an alkoxyalkyl group, an alkoxyalkoxyl group, a haloalkoxyl group, an alkylthio group, a haloalkylthio group, a cyano group, a nitro group, an optionally substituted phenyl group or an optionally substituted phenoxyl group, or adjacent two of RY, R?, R®, R! and R® are combined at the ends to represent a group of the formula CH=CH- CH=CH, a methylenedioxy group which may be substituted with a halogen atom or an alkylene group which may contain one oxygen atom and may be substituted with an alkyl group; R® represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an opticnally substituted alkynyl group, an optionally substituted phenyl group or an optionally substituted alicyclic hydrocarbon group;

X represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted phenyl group, an optionally substituted alkoxyl group, an optionally substituted alkenyloxy group, an optionally substituted alkynyloxy group, an optionally substituted phenoxyl group, an optionally substituted alkylthio group, an optionally substituted alkenylthio group, an optionally substituted alkynylthio group, an . optionally substituted phenylthio group or an optionally substituted alicyclic hydrocarbon group; and Y reprsents an oxygen atom or a sulfur atom.

2. The pyrazolinone derivatives according to Claim 1, wherein in the formula [I], RY, R?, R?, R! and R® are identical or different and represent independently a hydrogen atom, a halogen atom, a Cl1-C5 alkyl group, a Cl- C5 haloalkyl group, a C1-C5 alkoxyl group, a Cl-C3 alkoxy Cl-C3 alkyl group, a Cl1-C3 alkoxy C1-C3 alkoxyl group, a Cl-C5 haloalkoxyl group, a Cl-C5 alkylthio group, a Cl1-C5 haloalkylthio group, a cyano group, a nitro group, or a phenyl or phenoxyl group which may be substituted with at least one group selected from the group consisting of halogen atoms, C1-C5 alkyl groups, Cl- CS alkoxyl groups, Cl-C5 alkylthio groups, C1-C5 haloalkyl groups, Cl1-C5 haloalkoxyl groups, C1-C5 haloalkylthio groups and cyano groups, Or adjacent two of R!}, R?, R®} R* and R® are combined at the ends to represent a group of the formula CH=CH-

CH=CH, a methylenedioxy group which may be substituted with a halogen atom, a trimethylene group, a tetramethylene group, a group represented by the formula OCH,CH; or a group represented by the formula OCH,CH(CHs);

R® represents a Cl1-Cl1l0 alkyl group, a C3-Cl0 alkenyl group, a C3-Cl0 alkynyl group, a Cl1-Cl0 haloalkyl group, a C3-C10 haloalkenyl group, a C3-Cl0 haloalkynyl group, a Cl-C5 alkoxy C1-C5 alkyl group, a Cl-C5 alkylthio Cl-C5 alkyl group, a Cl-C5 haloalkoxy C1-C5 alkyl group, a

C1-C5 haloalkoxy C1-C5 haloalkyl group, a Cl-C5 haloalkylthio C1-C5 alkyl group, a Cl1-C5 haloalkylthio Cl- C5 haloalkyl group, a cyano Cl-C5 alkyl group, a cyano Cl- C5 haloalkyl group, a Cl1-C5 alkoxycarbonyl C1-C5 alkyl group,

i5 a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds,

a Cl-C5 alkyl group substituted with a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds,

a phenyl or C7-Cl7 aralkyl group which may be substituted with at least one group selected from the group consisting of halogen atoms, C1-C5 alkyl groups, Cl- CS alkoxyl groups, Cl-C5 alkylthio groups, C1-C5 haloalkyl groups, Cl-C5 haloalkoxyl groups, Cl1-C5 haloalkylthio groups and cyano groups;

X represents a Cl1-Cl0 alkyl group, a C2-Cl0 alkenyl group, a C2-Cl0 alkynyl group, a Cl1-Cl0 haloalkyl group, a C2-Cl10 haloalkynyl group, a C2-Cl0 haloalkenyl group, a Cl1-C5 alkoxy C1-C5 alkyl group, a Cl1-C5 alkylthio Cl-C5 alkyl group, a Cl-C5 halcalkoxy C1-C5 alkyl group, a Cl-C5 haloalkoxy Cl1-C5 haloalkyl group, a Cl-C5 haloalkylthio C1-C5 alkyl group, a Cl-C5 haloalkylthio Cl- C5 haloalkyl group, a cyano Cl1-C5 alkyl group, a cyano Cl- C5 haloalkyl group, a C1-C5 alkyl group substituted with a Cl-C5 alkoxycarbonyl group, a Cl1-C5 alkyl group substituted with a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds,

a Cl-C10 alkoxyl group, a C2-Cl0 alkenyloxy group, a C2-C10 alkynyloxy group, a Cl-C10 haloalkoxyl group, a C2-Cl0 haloalkenyloxy group, a C2-Cl1l0 haloalkynyloxy group, Cl-C5 alkoxy Cl1-C5 alkoxyl group, a Cl-C5 alkylthio C1-C5 alkoxyl group, a Cl-C5 haloalkoxy Cl-C5 alkoxyl group, a Cl-C5 halocalkoxy C1-C5 haloalkoxyl group, a Cl-C5 halocalkylthio C1-C5 alkoxyl group, a Cl1-C5 haloalkylthio C1-C5 halocalkoxyl group, a cyano C1l-C5 alkoxyl group, a Cl-C5 alkoxycarbonyl C1-C5 alkoxyl group, a Cl-C5 alkoxyl group substituted with a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, a phenyl group, C7-C1l7 aralkyl group, phenoxyl group, C7-Cl7 aralkyloxy group, phenylthio group or C7-Cl17 aralkylthio group which may be substituted with at least : one group selected from the group consisting of halogen atoms, Cl1-C5 alkyl groups, Cl-C5 alkoxyl groups, C1-C5 alkylthio groups, Cl1-C5 haloalkyl groups, Cl1-C5 haloalkoxy Cl-C5 haloalkylthio groups and cyano groups, a Cl-Cl0 alkylthio group, a C2-C1l0 alkenylthio group, a C2-Cl10 alkynylthio group, a C1-Cl0 halocalkylthio group, a C2-Cl0 haloalkynylthio group, a C2-Cl0 haloalkenylthio group, a Cl1-C5 alkoxy Cl-CS5 alkylthio group, a Cl1-C5 alkylthio C1-C5 alkylthio group, a C1-C5 haloalkoxy C1-C5 alkylthio group, a Cl1-C5 haloalkoxy C1-C5 haloalkylthio group, a Cl-C5 haloalkylthio C1-C5 alkylthio group, a Cl-C5 haloalkylthio C1-C5 haloalkylthio group, a cyano Cl-C5 alkylthio group, a Cl-C5 alkoxycarbonyl C1-C5 alkylthio group, : a Cl1-C5 alkylthio group substituted with a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, or a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds.

3. The pyrazolinone derivatives according to Claim 1 or 2, wherein in the formula [I], R!, R? R%® R? and R® are identical or different and represent independently a hydrogen atom, a halogen atom, a Cl1-C5 alkyl group, a Cl- C5 haloalkyl group or a Cl-C5 alkoxyl group, or adjacent two of RY, R?, R?} R! and R® are combined at the ends to represent a group of the formula CH=CH-CH=CH.

4. The pyrazolinone derivatives according to Claim 1, 2 or 3, wherein in the formula [I], R?, RY and R® are a hydrogen atom.

5. The pyrazolinone derivatives according to Claim 1, 2, 3 or 4, wherein in the formula [I], R! is a halogen atom or a methyl group which may be substituted with a halogen atom, and R? is a hydrogen atom, a halogen atom or a methyl group which may be substituted with a halogen atom.

6. The pyrazolinone derivatives according to Claim 1, 2, 3, 4 or 5, wherein in the formula [I], R® is a C1-C10 alkyl group, a C3-C1l0 alkenyl group, a C3-C10 alkynyl group, a Cl1-Cl0 haloalkyl group, a C3-Cl0 haloalkenyl group, a C3-Cl1l0 haloalkynyl group, a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, or a Cl1-C5 alkyl group substituted with a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds.

7. The pyrazolinone derivatives according to Claim 1, 2, 3, 4, 5 or 6, wherein in the formula [I], X is a Cl- C10 alkyl group, a C2-Cl0 alkenyl group, a C2-C1l0 alkynyl group, a Cl-C1l0 haloalkyl group, a C2-Cl0 halocalkenyl group, a C2-C10 haloalkynyl group, a phenyl group, phenoxyl group or phenylthio group which may be substituted with at least one group selected from the group consisting of halogen atoms, Cl-C5 alkyl groups, C1l-C5 alkoxyl groups, Cl-C5 alkylthio groups, Cl-C5 haloalkyl groups, C1-C5 haloalkoxyl groups, a Cl-C5 haloalkylthio groups and cyano groups,

a Cl-C10 alkoxyl group, a C2-Cl0 alkenyloxy group, a C2-Cl10 alkynyloxy group, a Cl-Cl0 haloalkoxyl group, C2-Cl10 haloalkenyloxy group, a C2-Cl0 haloalkynyloxy group, a Cl-C10 alkylthio group, a C2-Cl0 alkenylthio group, a C2-Cl1l0 alkynylthio group, a C1-Cl0 haloalkylthio group, a C2-Cl0 haloalkenylthio group or a C2-Cl0 haloalkynylthio group, or a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom or may contain unsaturated bonds.

8. The pyrazolinone derivatives according to Claim 1, 2, 3, 4, 5 or 6, wherein in the formula [I], X is a methylthio group, an ethylthio group, a propylthio group or a 2-propenylthio group.

9. The pyrazolinone derivatives according to Claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein in the formula [I], R® is an isopropyl group, a l-methylbutyl group or a sec-butyl group.

10. The pyrazolinone derivatives according to Claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein in the formula [I], Y is an oxygen atom.

11. A plant disease controlling agent characterized in that it contains a pyrazolinone derivative set forth in Claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 as an active ingredient.

12. The pyrazolinone compounds represented by the formula [II]:

R3' Rg R61 I'd a 8: NH : R41 R21 NH, wherein R!?, rR?! R*!, R* and R®! may be identical or different and represent independently a hydrogen atom, a ’ halogen atom, an alkyl group, a haloalkyl group, an alkoxyl group, an alkoxyalkyl group, an alkoxyalkoxyl group, a haloalkoxyl group, an alkylthio group, a haloalkylthio group, a cyano group, a nitro group, an optionally substituted phenyl group or an optionally substituted phenoxyl group, or adjacent two of R'Y, R?!, R3, R* and R® are combined at the ends to represent a group of the formula CH=CH-CH=CH, a methylenedioxy group which may be substituted with a halogen atom, or an alkylene group which may contain one oxygen atom and may be substituted with an alkyl group; and RS? represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group or an optionally substituted alicyclic hydrocarbon group.

13. The pyrazolinone compounds according to Claim 12, wherein in the formula [II], RY, R?', R®, R* and R*® are identical or different and represent independently a hydrogen atom, a halogen atom, a Cl1-C5 alkyl group, a Cl-

C5 haloalkyl group, a Cl1-C5 alkoxyl group, a Cl-C3 alkoxy Cl-C3 alkyl group, a Cl1-C3 alkoxy Cl1-C3 alkoxyl group, a Cl1-C5 haloalkoxyl group, a Cl-C5 alkylthio group, a C1-C5 haloalkylthio group, a cyano group, a nitro group,

a phenyl group or phenoxyl group which may be substituted with at least one group selected from the group consisting of halogen atoms, C1-C5 alkyl groups, Cl- C5 alkoxyl groups, C1-C5 alkylthio groups, C1-C5 haloalkyl groups, Cl-C5 haloalkoxyl groups, C1-C5 halecalkylthio groups and cyano groups, Or adjacent two of Rr, R?!, R3!, R* and R%! are combined at the ends to represent a group of the formula CH=CH-CH=CH, a methylenedioxy group (which may be substituted with a halogen atom), a trimethylene group, a tetramethylene group, a group represented by the formula OCH2;CH,; or a group represented by the formula OCH,CH (CH3) ; and R® is a C1-C10 alkyl group, a C3-C10 alkenyl group, a C3-C1l0 alkynyl group, a Cl-Cl0 haloalkyl group, a C3-C10 haloalkenyl group, a C3-Cl0 haloalkynyl group, a Cl-C5 alkoxy Cl1-C5 alkyl group, a Cl1-C5 alkylthio C1-C5 alkyl group, a Cl1-C5 haloalkoxy Cl- C5 alkyl group, a Cl- C5 haloalkoxy C1-C5 haloalkyl group, a Cl-C5 halecalkylthio Cl-C5 alkyl group, a Cl-C5 haloalkylthio C1-C5 haloalkyl group, a cyano Cl1-C5 alkyl group, a cyano Cl-C5 haloalkyl group, a Cl1-C5 alkoxycarbonyl C1-C5 alkyl group, a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, a Cl1-C5 alkyl group substituted with a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, or a C7-Cl7 aralkyl group which may be substituted with at least one group selected from the group consisitng of halogen atoms, C1-C5 alkyl groups, Cl1-C5 alkoxyl groups, Cl-C5 alkylthio groups, Cl-C5 haloalkyl groups, C1-C5 haloalkoxyl groups, C1-C5 haloalkylthio groups and cyano groups.

14. The pyrazolinone compounds according to Claim 12 or 13, wherein in the formula [II], R', R?}, R’', R*' and R® are identical or different and represent independently a hydrogen atom, a halogen atom, a Cl1-C5 alkyl group, a Cl- C5 haloalkyl group or a Cl-C5 alkoxyl group, or : adjacent two of R!?, R?Y, R3Y, R*! and R®! are combined at the ends to represent a group of the formula CH=CH-CH=CH.

15. The pyrazolinone compounds according to Claim 12, 13 or 14, wherein in the formula [II], R*, R*!' and R®? are a hydrogen atom.

16. The pyrazolinone compounds according to Claim 12, 13, 14 or 15, wherein in the formula [II], R'? is a halogen atom or a methyl group which may be substituted with a halogen atom, and R? is a hydrogen atom, a halogen atom or a methyl group which may be substituted with a halogen atom.

17. The pyrazolinone compounds according to Claim 12,

13, 14, 15 or 16, wherein in the formula [II], R® is an isopropyl group, a l-methylbutyl group or a sec-butyl group.

18. The pyrazolinone compounds represented by the formula [III]: R32 RQ NH 00 x A R% R22 NH; vy? wherein RY, R??, R*, R*? and R’® may be identical or different and represent independently a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxyl group, an alkoxyalkyl group, an alkoxyalkoxyl group, a haloalkoxyl group, an alkylthio group, a haloalkylthio group, a cyano group, a nitro group, an optionally substituted phenyl group or an optionally substituted phenoxyl group, or adjacent two of R'Y?, R??, R*?, R*? and R®? are combined at the ends to represent a group of the formula CH=CH-CH=CH, a methylenedioxy group which may be substituted with a halogen atom or an alkylene group which may contain one oxygen atom and may be substituted with an alkyl group; : X! represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally

¢ 140 substituted phenyl group, an optionally substituted alkoxyl group, an optionally substituted alkenyloxy group, an optionally substituted alkynyloxy group, an optionally substituted phenoxyl group, an optionally substituted alkylthio group, an optionally substituted alkenylthio group, an optionally substituted alkynylthio group, an optionally substituted phenylthio group or an optionally substituted alicyclic hydrocarbon group; and y! represents. an oxygen atom or a sulfur atom.

19. The pyrazolinone compounds according to Claim 18, wherein in the formula [III], R'?, R?, R%, R% and R* are identical or different and represent independently a hydrogen atom, a halogen atom, a C1-C5 alkyl group, a Cl- C5 haloalkyl group, a Cl1-C5 alkoxyl group, a Cl-C3 alkoxy (C1l-C3 alkyl group, a Cl-C3 alkoxy Cl1-C3 alkoxyl group, a C1-C5 haloalkoxyl group, a Cl-C5 alkylthio group, Cl-C5 haloalkylthio group, a cyano group, a nitro group or a phenyl or phenoxyl group which may be substituted with at least one group selected from the group consisting of halogen atoms, Cl1-C5 alkyl groups, Cl- C5 alkoxyl groups, C1-C5 alkylthio groups, C1-C5 haloalkyl groups, Cl-C5 haloalkoxyl groups, Cl-C5 haloalkylthio groups and cyano groups, Or adjacent two of R}?, R??, R*, R* and R* are combined at the ends to represent a group of the formula CH=CH-CH=CH, a methylenedioxy group (which may be substituted with a halogen atom), a trimethylene group, a : tetramethylene group, a group represented by the formula w . } | : 4 141 : } OCHCH; or a group represented by the formula OCH;CH(CH3); and : X' represents a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-Cl10 alkynyl group, a C1-C10 haloalkynyl group, a C2-Cl0 haloalkynyl group, a C2-Cl0 haloalkynyl ~ group, a Cl-C5 alkoxy Cl-CS5S alkyl group, a C1l-C5 alkylthio Cl-C5 alkyl group, a Cl-C5 haloalkoxy C1-C5 alkyl group, a C1-C5 haloalkoxy Cl1-C5 haloalkyl group, a C1-C5 . haloalkylthio Cl-C5 alkyl group, a Cl1-C5 haloalkylthio Cl- C5 haloalkyl group, a cyano C1-C5 alkyl group, a cyano Cl- a.

C5 haloalkyl group, a Cl-C5 alkyl group substituted with a Cl-C5 alkoxycarbonyl group, a Cl-C5 alkyl group substituted with a C3-C8 : alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, a phenyl, C7-Cl7 aralkyl, phenoxyl, C7-C17 aralkyloxy, phenylthio or C7-Cl17 aralkylthio group which may be substituted with at least one group selected from the group consisting of halogen atoms, C1-C5 alkyl groups, Cl-C5 alkoxyl groups, Cl-C5 alkylthio groups, C1-C5 ) haloalkyl groups, Cl-C5 haloalkoxyl groups, Cl1-C5 haloalkylthio groups and cyano groups, a Cl-Cl10 alkoxyl group, a C2-Cl0 alkenyloxy group, a C2-Cl0 alkynyloxy group, a C1-C10 haloalkoxyl group, a C2-Cl0 haloalkenyloxy group, a C2-C10 haloalkynyloxy group, a C1-C5 alkoxy Cl-C5 alkoxyl group, a Cl-C5 alkylthio C1-C5.alkoxyl group, a Cl-C5 haloalkoxy Cl-C5 alkoxyl group, a Cl1-C5 haloalkoxy Cl1-C5 haloalkoxyl CORRECTED SHEET 2002 -04- 18 group, a C1-C5 haloalkylthio C1-C5 alkoxyl group, a C1-C5 haloalkylthio C1-C5 haloalkoxyl group, a cyano Cl-C5 alkoxyl group, a Cl-C5 alkoxycarbonyl C1-C5 alkoxyl group, a Cl-C5 alkoxyl or Cl1-C5 alkylthio group 5 substituted with a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds, a Cl1-C10 alkylthio group, a C2-Cl0 alkenylthio group, a C2-C10 alkynylthio group, a C1-C10 haloalkylthio group, a C2-Cl0 haloalkenylthio group, a C2-Cl0 haloalkynylthio group, a Cl1-C5 alkoxy C1-C5 alkylthio group, a Cl1-C5 alkylthio C1-C5 alkylthio group, a C1-C> haloalkoxy Cl-C5 alkylthio group, a C1-C5 haloalkoxy C1-C5 : haloalkylthio group, a Cl-C5 haloalkylthio C1-C5 alkylthio group, a Cl-C5 haloalkylthio C1-C5 haloalkylthio group, a cyano Cl-C5 alkylthio group, a Cl-C5 alkoxycarbonyl C1-C5 alkylthio group or a C3-C8 alicyclic hydrocarbon group which may be substituted with a halogen atom and may contain unsaturated bonds.

20. The pyrazolinone compounds according to Claim 18 or 19, wherein in the formula [III], R'?, R??, R*?, R* and R>? are identical or different and represent independently a hydrogen atom, a halogen atom, a Cl-C5 alkyl group, a : C1-C5 haloalkyl group or a Cl-C5 alkoxyl group, or adjacent two of R'?, R??, R%?, R* and R* are combined at the ends to represent a group of the formula CH=CH-CH=CH.

21. The pyrazolinone compounds according to Claim 18, 19 or 20, wherein in.the formula [III], R*?, R*® and R* are a hydrogen atom.

22. The pyrazolinone compounds according to Claim 18, 5 19, 20 or 21, wherein in the formula [III], R'? is a halogen atom or a methyl group which may be substituted with a halogen atom, and R* is a hydrogen atom, a halogen atom or a methyl group which may be substituted with a halogen atom.

23. The pyrazolinone compounds according to Claim 18, 19, 20, 21 or 22, wherein in the formula [III], x! is a Cl- C10 alkyl group, a C2-Cl10 alkenyl group, a C2-Cl0 alkynyl group, a Cl-Cl0 haloalkyl group, a C2-Cl0 haloalkenyl group, a C2-Cl0 haloalkynyl group, a Cl-Cl0 alkoxyl group, a Cl1-Cl0 haloalkoxyl group, a C2-Cl0 alkenyloxy group, a C2-C10 haloalkenyloxy group, a C2-Cl10 alkynyloxy group, a C2-C10 haloalkynyloxy group, a phenyl, phenoxyl or phenylthio group which may be substituted with at least one group selected from the group consisting of halogen atoms, C1-C5 alkyl groups, Cl- C5 alkoxyl groups, Cl1l-C5 alkylthio groups, Cl1-C5 haloalkyl groups, Cl1-C5 haloalkoxyl groups, Cl1-C5 haloalkylthio groups and cyano groups, a Cl1-Cl1l0 alkylthio group, a C2-Cl0 alkenylthio group, a C2-Cl0 alkynylthio group, a Cl1-C1l0 halocalkylthio group, a C2-C10 haloalkenylthio group, C2-C1l0 haloalkynylthio group or a C3-C8 alicyclic hydrocarbon : group which may be substituted with a halogen atom and may

« “e 144 contain unsaturated bonds.

24. The pyrazolinone compounds according to Claim 18, 19, 20, 21, 22 or 23, wherein in the formula [III], X' is a methylthio group, an ethylthio group, a propylthio group or a 2-propenylthio group.

25. The pyrazolinone compounds according to Claim 18, 19, 20, 21, 22, 23 or 24, wherein in the formula [III], y?! is an oxygen atom.

26. A method for controlling plant diseases which comprises applying a pyrazolinone derivative of the - formula [I] set forth in Claim 1 as an active ingredient to a place where the germs of plant diseases propagate.

27. Use of the pyrazolinone derivatives of the formula [I] set forth in Claim 1 as an active ingredient of the plant disease controlling agent. i 20005434