JPH08208621A - Agent for controlling plant disease - Google Patents

Abstract

PURPOSE: To obtain a plant disease-controlling agent containing a pyrazoline derivative as an active ingredient. CONSTITUTION: The plant disease-controlling agent contains a compound of formula I (R<1> to R<4> are H, halogen, akyl, etc.; R<5> is H, F, alkoxy, etc.; R<6> , R<7> are each hydrocarbon; R<8> , R<9> are each H, alkyl, etc.; but R<1> to R<5> are not simultaneously H) as an active ingredient. The compound of formula I is obtained by reacting a pyrazoline compound of formula II with a compound of formula: R<6> X, R<66> OSO2 CH3 or R<66> 2 SO4 (R<66> is primary or secondary alkyl; X is halogen) in the presence of an acid-releasing agent (e.g. sodium hydride) in a solvent (e.g. THF) at 30-120 deg.C. The plant disease-controlling agent is effective for controlling diseases such as Botrytis cinerea, Erysiphe cichoracearum, Sclerotinia sclerotiorum, Pyricularia oryzae, Septoria tritici, Venturia inaequalis, Gleoeosporium tabacum, Puccinia striiformis, and Cercospora arachidicola. The application amount of the plant disease-controlling agent is 0.001-100g/arm, and the application concentration is 0.0001-1%.

Description

Detailed Description of the Invention

[0001]

OBJECT OF THE INVENTION The present invention relates to a plant disease control agent.

The present inventors have earnestly studied to develop an excellent plant disease control agent, and as a result, have shown the following general formula:
It was found that the pyrazoline derivative represented by the formula (3), especially the pyrazoline derivative represented by the following general formula (6) has an excellent controlling effect against plant diseases, and the present invention has been completed. That is, the present invention is represented by the general formula

Embedded image [In the formula, R ^{1 to} R ⁴ are a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, a cyano group, a nitro group, or a substituted group. Represents a phenyl group which may be substituted or a phenoxy group which may be substituted, and R ⁵ represents a hydrogen atom, a fluorine atom or an alkoxy group, or two adjacent R ^{1 to} R ⁵ are bonded at the terminal. , A group represented by CH = CH-CH = CH, a methylenedioxy group optionally substituted with a halogen atom, or an alkylene optionally containing one oxygen atom and optionally substituted with an alkyl group. Represents a group, R ⁶ and R ⁷ are the same or different,
Represents an optionally substituted hydrocarbon group, R ⁸ and R ⁹ are the same or different and represent a hydrogen atom or an alkyl group, or R ⁸ and R ⁹ are bonded at the terminal to represent an alkylene group. . However, R ^{1 to} R ⁵ are not all hydrogen atoms at the same time. ] The plant disease controlling agent characterized by containing the pyrazoline derivative shown by these as an active ingredient, and General formula 6

[Chemical 6] [In the formula, R ¹¹ is a halogen atom, an alkyl group, a haloalkyl group, an alkoxy 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 represents an optionally substituted phenoxy group, R
^{21 to} R ⁴¹ are hydrogen atom, halogen atom, alkyl group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, haloalkylthio group, cyano group, optionally substituted phenyl group, or optionally substituted. Represents a phenoxy group, R ⁵¹ represents a hydrogen atom, a fluorine atom or an alkoxy group, R ⁶ and R ⁷ represent the same or different hydrocarbon groups which may be substituted, and R ⁸ and R ⁹ represent The same or different, each represents a hydrogen atom or an alkyl group, or R ⁸ and R ⁹ are bonded to each other at the terminals to represent an alkylene group. ] The pyrazoline derivative shown by these is provided.

Furthermore, the present invention provides a compound represented by the general formula 7 as a useful intermediate in the production of the pyrazoline derivative represented by the general formula 5.

[Chemical 7] [In the formula, R ^{1 to} R ⁴ are a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, a cyano group, a nitro group, or a substituted group. Represents a phenyl group which may be substituted or a phenoxy group which may be substituted, and R ⁵ represents a hydrogen atom, a fluorine atom or an alkoxy group, or two adjacent R ^{1 to} R ⁵ are bonded at the terminal. , A group represented by CH = CH-CH = CH, a methylenedioxy group optionally substituted with a halogen atom, or an alkylene optionally containing one oxygen atom and optionally substituted with an alkyl group. Represents a group, and R ⁷¹ represents an optionally substituted hydrocarbon group having 3 to 17 carbon atoms. However, R ^{1 to} R ⁵ are not all hydrogen atoms at the same time. ] The pyrazoline compound shown by these is also provided. As an embodiment of the pyrazoline compound, a compound represented by the general formula:

Embedded image [In the formula, R ¹¹ is a halogen atom, an alkyl group, a haloalkyl group, an alkoxy 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 represents an optionally substituted phenoxy group, R
^{21 to} R ⁴¹ are hydrogen atom, halogen atom, alkyl group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, haloalkylthio group, cyano group, optionally substituted phenyl group, or optionally substituted. Represents a phenoxy group, R ⁵¹ represents a hydrogen atom, a fluorine atom or an alkoxy group, and R ⁷¹ represents an optionally substituted hydrocarbon group having 3 to 17 carbon atoms. ] The pyrazoline compound shown by these is mentioned.

The compound represented by the general formula 5 can exist in various tautomeric structures represented by the following formula 9 when R ⁸ and / or R ⁹ is a hydrogen atom. It includes all possible tautomers.

[Chemical 9] [In the formula, W represents R ⁸ or R ⁹ . ]

Derivation of pyrazoline of the general formulas 5 and 6
And pyrazoline compounds of general formulas 7 and 8
Where R¹~ R^FourOr R¹¹~ R⁴¹Indicated by
Rogen atoms include fluorine, chlorine, and bromine
Child, iodine atom, etc.
Chain or branched C₁~ C_FiveAlkyl group (for example,
For example, methyl group, ethyl group, n-propyl group, isopropyl group
Group, tert-butyl group, etc.), haloalkyl group
Are the same or different 1 to 11 halogens
Atom-substituted linear or branched C₁~ C_Five
Alkyl groups (eg trifluoromethyl group, tetraf
Luoroethyl group, heptafluoropropyl group, etc.)
The alkoxy group may be straight-chain or branched.
C₁~ C_FiveAlkoxy group (for example, a methoxy group, an
Toxy group, n-propyloxy group, isopropyloxy
Groups, etc., and examples of the alkoxyalkoxy group include
Linear or branched (C₁~ C₃) Alkoxy
(C₁~ C₃) Alkoxy groups (eg methoxymethoxy)
And the same haloalkoxy group.
Or substituted with 1 to 11 different halogen atoms
Straight or branched C₁~ C_FiveAlkoxy group
(For example, trifluoromethoxy group, difluoromethoxy group
Si group, tetrafluoroethoxy group, etc.)
The thio group is a linear or branched C₁~
C_FiveAlkylthio groups (eg, methylthio group, ethyl
Thio group, etc.), and the haloalkylthio group includes
Substituted with the same or different 1 to 11 halogen atoms
Straight-chain or branched C₁~ C_FiveThe alkyl
Examples include thio groups (eg, trifluoromethylthio group)
And the optionally substituted phenyl groups are the same
1 to 5 may be substituted with different substituents.
A phenyl group, which may be substituted
Si group, 1 to 5 substituents with the same or different substituents
Phenoxy group, which may be substituted,
Optionally a phenyl group and an optionally substituted phenyl group
Examples of the substituent in the noxyl group include halogen atom.
Child (fluorine atom, chlorine atom, bromine atom, iodine atom
Etc.), C₁~ C_FiveAlkyl groups (for example, methyl group,
Cyl group), C₁~ C_FiveAn alkoxy group of
Xy group, ethoxy group, etc.), C ₁~ C_FiveAlkylthio group of
(Eg, methylthio group, ethylthio group, etc.), C₁~ C
_FiveA haloalkyl group, preferably C₁~ C₂The halo archi
Group (eg trifluoromethyl group), C₁~ C_Fiveof
A haloalkoxy group, preferably C₁~ C₂The halo arcoki
Si group (eg trifluoromethoxy group, difluorometh
Xyl group), C ₁~ C_FiveA haloalkylthio group of
Is C₁~ C₂Haloalkylthio groups (eg trifluoro
And a cyano group, and R^FiveIndicated by
The alkoxy group to be used may be straight-chain or branched-chain.
C₁~ C_FiveAlkoxy group (for example, a methoxy group, an
Toxy group, n-propyloxy group, isopropyloxy
Group etc.). Pyrazoline derivative of the general formula
And a pyrazoline compound of the general formula¹
~ R^FiveMay be substituted with a halogen atom represented by
Examples of the methylenedioxy group include methylenedioxy
Group, difluoromethylenedioxy group, oxygen source
May include an alkyl group (eg, methyl group, etc.)
C₁~ C_FourAn alkyl group) optionally substituted with
A xylene group (eg C₂~ C₆As an alkylene group),
For example, trimethylene group, tetramethylene group, OCH₂CH₂
Group represented by, OCH₂CH (CH₃) Is a group such as
Can be The pyrazoline derivatives of the general formulas 5 and 6
In terms of plant disease control efficacy, R¹~ R^FourOr R¹¹
~ R⁴¹The preferred substituents of are halogen atoms
(Especially chlorine atom, bromine atom), alkyl group (especially methyl
Group), and from the viewpoint of gray mold control efficacy, R¹~
R^FourOr R¹¹~ R⁴¹The second position is a preferred substitution position of
And 2nd and 6th place are listed, and from the viewpoint of powdery mildew control efficacy
R¹~ R^Four3-position and 2-position are preferable substitution positions of
can give.

Pyrazoline derivatives represented by the general formulas 5 and 6
At R⁶And R⁷, As well as the general formula
In the pyrazoline compounds of Chemical formulas 7 and 8⁷¹Indicated by
As the optionally substituted hydrocarbon group, a straight-chain
Or branched chain C₁~ C_TenAn alkyl group of (for example,
Ethyl group, propyl group, isopropyl group, butyl group, a
Sobutyl group, sec-butyl group, 2-methylbutyl group, 2
-Ethylpropyl group, tert-butyl group, etc.), linear
C-branched C₂~ C_TenAlkenyl groups (eg 1
-Methyl-2-propenyl group), straight-chain or branched
Chain C₂~ C_TenAn alkynyl group (eg, 1-methyl
-2-propynyl group), the same or different 1-2
Linear or branched chain substituted with one halogen atom
Shape C₁~ C_TenAlkyl group, same or different 1 to
Linear or branched, substituted with 19 halogen atoms
Chain C₂~ C_TenAlkenyl groups, identical or different
Linear or substituted with 1 to 17 halogen atoms
Is a branched C₂~ C_TenAn alkynyl group of C₁~ C_FiveA
Lucoxy (straight or branched) C₁~ C_FiveAl
Kill group (eg, methoxymethyl group, 1-methoxyethyl group
Group), C₁~ C_FiveAlkylthio (straight chain or
C)₁~ C_FiveAlkyl groups (eg methylthio
Methyl group, 1-methylthioethyl group, etc.), the same or
C substituted with 1 to 11 different halogens₁~ C_Five
1 to 11 having the same or different alkoxy groups
Linear or branched C substituted with 1 halogen
₁~ C_FiveAlkyl groups of 1 to 11 which are the same or different
C substituted with 1 halogen₁~ C_FiveAlkylthio group of
1 to 11 halogens having the same or different
A linear or branched C substituted with₁~ C_FiveA
A straight or branched chain substituted with an alkyl group or a cyano group
Shape C₁~ C_FiveAn alkyl group of (for example, 1-cyanoethyl
Group), C₁~ C_FiveSubstituted with an alkoxycarbonyl group
Straight-chain or branched C ₁~ C_FiveAlkyl group of
(For example, 1- (methoxycarbonyl) ethyl group etc.),
It may be substituted with a halogen atom and contains an unsaturated bond.
I don't mind, C₃~ C ₈A cycloalkyl group of (for example,
Cyclohexyl group, cyclopentyl group) 1 to 5 substituted with the same or different substituents
Optionally substituted phenyl group [as a substituent, for example,
Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine
Elementary atom), C₁~ C_FiveAlkyl groups of (eg, methyl
Group, ethyl group, etc.), C₁~ C_FiveAlkoxy group (for example,
For example, methoxy group, ethoxy group, etc.), C₁~ C_FiveThe archi
Ruthio group (eg, methylthio group, ethylthio group, etc.),
C₁~ C_FiveA haloalkyl group, preferably C₁~ C₂Ha
Low alkyl group (eg trifluoromethyl group), C₁
~ C_FiveA haloalkoxy group, preferably C₁~ C₂The halo
Alkoxy group (eg trifluoromethoxy group, diflu
Oromethoxy group, etc.), C₁~ C_FiveHaloalkylthio group
Preferably C₁~ C₂Haloalkylthio groups of
And a cyano group, etc.
It ], 1 to 5 substituents which may be the same or different
C which may be substituted₇~ C₁₇Aralkyl groups of (eg
For example, benzyl group, α-methylbenzyl group, α, α-di
Methylbenzyl group, etc.) [As a substituent, for example, halo
Gen atom (fluorine atom, chlorine atom, bromine atom, iodine source)
Child etc.), C₁~ C_FiveAn alkyl group (for example, a methyl group,
Ethyl group), C₁~ C_FiveAlkoxy group (for example,
Toxy group, ethoxy group, etc.), C₁~ C_FiveAlkylthio
Group (eg, methylthio group, ethylthio group, etc.), C₁~
C_FiveA haloalkyl group, preferably C₁~ C₂The halo al
Kill group (eg trifluoromethyl group etc.), C₁~ C_Five
A haloalkoxy group, preferably C₁~ C₂The halo arco
Xy group (eg trifluoromethoxy group, difluorome
Toxy group), C₁~ C_FivePreferred haloalkylthio groups
Kuha C₁~ C₂Haloalkylthio groups of
And an cyano group. 〕But
can give. However, here, in the general formulas 7 and 8,
In compounds, R⁷¹May be replaced as indicated by
The hydrocarbon group has 3 to 17 total carbon atoms.

In the pyrazoline derivatives represented by the general formulas 5 and 6, the alkyl group represented by R ⁸ and R ⁹ is a C ₁ -C ₅ alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group). , Butyl group, isobutyl group, sec-butyl group, etc.), and the alkylene group formed by combining R ⁸ and R ⁹ at the terminal is C _2-
Examples thereof include C ₅ alkylene groups (eg, tetramethylene group, pentamethylene group, ethylene group, etc.). General formula
In the pyrazoline derivatives of Chemical formulas 5 and 6, from the viewpoint of plant disease control efficacy, one preferable embodiment of R ⁶ and R ⁷ is:
A straight-chain or branched C ₃ -C ₁₀ alkyl group, especially a secondary one (wherein secondary means 1 branch at the α-position of the N atom).
Number is say what) C ₃ -C say that the α- position of N atoms branches there are two and the alkyl group or tertiary (wherein tertiary ₁₀₎ alkyl C ₃ -C ₁₀ , R ⁶ ,
Another preferred embodiment of R ^{7 is} a secondary C _{3 to} C ₁₀ alkynyl group or a tertiary C _{3 to} C ₁₀ alkynyl group, and as a particularly preferred embodiment of R ⁶ and R ⁷ , tert-
Butyl group, isopropyl group, 1-methylbutyl group, sec
A butyl group and a 1-ethyl-2-propynyl group, and R ⁸ and R ⁹ are preferred as one embodiment of R ⁸ and R ^9.
Are hydrogen atoms or C ₁ -C ₅ alkyl groups (for example, methyl group, ethyl group), and particularly, both are hydrogen atoms.

Next, a method for producing the pyrazoline derivative represented by the general formula 5 will be described. Of the pyrazoline derivatives of the general formula 5, those in which R ⁶ and R ⁷ are optionally substituted tertiary alkyl groups and R ⁸ and R ⁹ are both hydrogen atoms are represented by the general formula

[Chemical 10] [In the formula, R ^{1 to} R ⁵ have the same meanings as defined in the general formula 5 above. ] And a phenylacetonitrile compound represented by the formula:

[Chemical 11] [In the formula, R ⁶¹ and R ⁷² are the same or different and each represents an optionally substituted tertiary alkyl group. ] And the diaziridinone derivative represented by
In the presence of ~ 2.0 equivalents of base, usually at -78 ° C to 50 ° C,
It can be usually produced by reacting for 0.5 to 24 hours. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether, nitriles such as acetonitrile and isobutyronitrile, and N, N. Examples include acid amides such as dimethylformamide and N, N-dimethylacetamide, sulfur compounds such as dimethyl sulfoxide, and mixtures thereof. Examples of the base include inorganic bases such as sodium hydride and organic bases such as lithium diisopropylamide. After completion of the reaction, if necessary, after neutralization with a dilute acid such as dilute hydrochloric acid, a usual treatment such as extraction with an organic solvent and concentration is performed, and if necessary, further purification by chromatography, recrystallization, etc. The compound can be isolated. A commercially available phenylacetonitrile compound represented by the general formula 10 is used as a raw material compound for producing the pyrazoline derivative of the general formula 5, or Beilstein 9,441 and Shin Jikken Kagaku Koza (Maruzen Co., Ltd.) Volume 14 [III] Page 1434 (1985
Year) and the like. The diaziridinone derivative represented by the general formula 11 is Th
It can be produced according to the method described in e Journal of Organic Chemistry 34 , 2254 (1969).

Among the pyrazoline derivatives of general formula 5,
Those in which R ⁸ and R ⁹ are hydrogen atoms have the general formula 1
Two

[Chemical 12] [In the formula, R ^{1 to} R ⁵ and R ⁷ have the same meanings as defined in the general formula 5 above. ] The pyrazoline compound shown by this, and the general formula of 1.0-5.0 equivalent normally with respect to it.
Chemical 13

Embedded image R ⁶ X, R ⁶⁶ OSO ₂ CH ₃ or R ⁶⁶ ₂ SO ₄ [wherein, R ⁶ has the same meaning as defined in the above general formula 5, R ⁶⁶ is a primary or secondary alkyl group. Represents a group, X is a halogen atom (eg, chlorine atom, bromine atom,
Represents an iodine atom). ] In the presence of a deoxidizing agent, usually in a solvent, usually 1.0 to 10.0 equivalents
Usually, it can be manufactured by reacting at 30 ° C to 120 ° C for usually 1 hour to 30 hours. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone and cyclohexanone. , Alcohols such as methanol, ethanol, isopropanol, t-butanol and diethylene glycol, nitriles such as acetonitrile, acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide, sulfur such as dimethyl sulfoxide and sulfolane A compound, or a mixture thereof is included. Examples of the deoxidizing agent include pyridine,
Examples thereof include organic bases such as triethylamine, and inorganic bases such as sodium carbonate, potassium carbonate and sodium hydride. After completion of the reaction, usual post-treatments such as extraction with an organic solvent and concentration are carried out, and if necessary, further purification is carried out by chromatography, recrystallization and the like, whereby the desired compound can be isolated. The pyrazoline derivative of the general formula 5 can also be produced according to the method described in JP-A No. 1-160968.

Of the pyrazoline derivatives of the general formula 5, R
⁸ as R ⁹ is not hydrogen atom at the same, of the pyrazoline derivatives of the general formula of 5, as R ^8, R ⁹ are both hydrogen atoms, whereas the normal 1.0 to 4.0 equivalents of formula (I), in [II], or [III] R ⁸⁸ -X (I) R ⁸⁸ ₂ SO ₄ [II] X-R ⁹⁹ -X (III) [wherein, R ⁸⁸ represents an alkyl group, R ⁹⁹ represents an alkylene group, and X represents a chlorine atom, a bromine atom or an iodine atom. ] In the presence of a compound, which is usually 3 to 5 equivalents of a base, and usually 0.1 to 1.0 equivalents of a phase transfer catalyst, in a solvent, usually at 20 ° C to 100 ° C, usually 1 to 7
It can be produced by reacting for 2 hours. Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane and chlorobenzene, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and ethylene glycol. Ethers such as dimethyl ether, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and isobutyronitrile, acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide, water, etc. A mixture can be given. Examples of the base used include inorganic bases such as sodium hydroxide, potassium hydroxide and potassium carbonate. Examples of the phase transfer catalyst used include quaternary ammonium salts such as tetra-n-butylammonium bromide, tetra-n-butylammonium chloride and benzyltriethylammonium chloride. After completion of the reaction, usual post-treatments such as extraction with an organic solvent and concentration are carried out, and if necessary, further purification is carried out by chromatography, recrystallization and the like, whereby the desired compound can be isolated.

Next, specific examples of the pyrazoline derivative represented by the general formula 5 are shown in chemical formulas 14 to 41. In the following "Me", a methyl "Et" is ethyl, "nPr" Ya "Pr" a is n- propyl, "Ph" a phenyl, the "HC ₂ F _4" is HCF ₂
CF ₂ is shown respectively.

Embedded image General formula [In the chemical formula 14, the substituents of R ^{1 to} R ⁴ are those shown in Table 1 to Table 15. ]

[0011]

[Table 1]

[Table 2]

[0012]

[Table 3]

[0013]

[Table 4]

[Table 5]

[0014]

[Table 6]

[0015]

[Table 7]

[0016]

[Table 8]

[0017]

[Table 9]

[Table 10]

[0018]

[Table 11]

[0019]

[Table 12]

[0020]

[Table 13]

[0021]

[Table 14]

[0022]

[Table 15]

[0023]

Embedded image General formula [In Chemical Formula 15, the substituents of R ^{1 to} R ⁴ represent those shown in Tables 16 and 17, and R ⁵ represents a fluorine atom, a methoxy group or an ethoxy group. ]

[0024]

[Table 16]

[Table 17]

[0025]

Embedded image General formula

[0026]

[Chemical 17] A compound represented by the formula [in the formulas 16 and 17, R ¹ to
The substituents for R ⁴ are those shown in Tables 18 and 19. ]

[0027]

[Table 18]

[0028]

[Table 19]

[0029]

Embedded image

[0030]

[Chemical 19] In the compound [Formula 18 and Formula 19 as shown in, R ⁵
Represents a fluorine atom, a methoxy group or an ethoxy group. ]

[0031]

Embedded image General formula

[Chemical 21]

[0032]

[Chemical formula 22]

[Chemical formula 23]

[0033]

[Chemical formula 24] [Compounds 20 to 24, R ^{1 to} R ⁴
The substituents of are as shown in Table 20. ]

[0034]

[Table 20]

[0035]

[Chemical 25]

[Chemical formula 26]

[0036]

[Chemical 27]

[Chemical 28]

[0037]

[Chemical 29]

Embedded image A compound represented by the formula [in the formulas 25 to 30, R ^{1 to} R ⁴
The substituents of are as shown in Table 21, and R ⁵ is a fluorine atom, a methoxy group or an ethoxy group. ]

[0038]

[Table 21]

[0039]

[Chemical 31]

Embedded image

[0040]

[Chemical 33]

Embedded image

[0041]

Embedded image

Embedded image

[0042]

Embedded image

[Chemical 38]

[0043]

[Chemical Formula 39]

[Chemical 40]

[0044]

Embedded image A compound represented by the formula [in the formulas 31 to 41, R ^{1 to} R ⁴
The substituents of are as described in Table 22 and Table 23. ]

[0045]

[Table 22]

[Table 23]

The pyrazoline compound represented by the general formula (12), which is a starting compound for producing the pyrazoline derivative of the general formula (5), is

Embedded image [In the formula, R ^{1 to} R ⁵ have the same meanings as defined in the general formula 5, and R ⁸ represents an alkyl group (for example, a C _{1 to} C ₄ alkyl group such as a methyl group or an ethyl group). ] The phenyl cyanoacetic acid ester compound of

Embedded image R ⁷ NHNH ₂ wherein, R ⁷ has the same meaning as defined in the formula of 5. ], And usually at 40 to 100 ° C. for 1 hour to 1
It can be produced by reacting for 0 hours.
In the reaction, a solvent is not always necessary, but the reaction can be performed in a solvent, and examples of the solvent that can be used include alcohols such as methanol and ethanol.
After completion of the reaction, usual post-treatments such as extraction with an organic solvent and concentration are carried out, and if necessary, further purification is carried out by chromatography, recrystallization and the like, whereby the desired compound can be isolated. The phenyl cyanoacetic acid ester compound represented by the general formula 42 is available in Chem. Lett. P. 193 (1983),
It can be produced according to the method described in J. Org. Chem. 58 , 7606 (1993) and JP-A No. 1-160968.

Next, specific examples of the pyrazoline compound represented by the general formula 12 are shown in the chemical formulas 44 to 47.

Embedded image General formula [In the chemical formula 44, the substituents of R ^{1 to} R ⁴ are the same as those shown in Tables 1 to 15]. ]

Embedded image General formula Embedded image [in Chemical Formula 45, the substituents of R ^{1 to} R ⁴ are the same as those shown in Tables 18 and 19 above. ]

Embedded image General formula [In the chemical formula 46, the substituents of R ^{1 to} R ⁴ represent the compounds shown in Table 16 and Table 17,
R ⁵ represents a fluorine atom, a methoxy group or an ethoxy group. ]

[Chemical 47] [Wherein R ⁵ represents a fluorine atom, a methoxy group or an ethoxy group]. ]

As a plant disease in which the pyrazoline derivative of the general formula 5 is effective, rice blast (Pyriculari)
a oryzae), sesame leaf blight (Cochliobolus miyabeanus)
, Rhizoctonia solani, powdery mildew of wheat (Erysiphe graminis f. Sp. Hordei, f. Sp. Tritic
i), Fusarium head blight (Gibberella zeae), Rust (Puccinia s)
triiformis, P. graminis, P. recondita, P. hordei)
, Snow rot (Typhula sp., Micronectriella nivalis),
Naked smut (Ustilago tritici, U. nuda), eye spot
(Pseudocercosporella herpotrichoides), cloud disease (Rh
ynchosporium secalis), leaf blight (Septoria tritici)
, Wilt disease (Leptosphaeria nodorum), net leaf spot (Pyren
ophora teres), citrus black spot (Diaporthe citr)
i), scab (Elsinoe fawcetti), fruit rot (Peni
cillium digitatum, P. italicum), monili disease of apple (Sclerotinia mali, Monilinia mali), rot
(Valsa mali), powdery mildew (Podosphaera leucotrich
a), leaf spot disease (Alternaria mali), scab (Venturia)
inaequalis), pear scab (Venturia nashicola),
Black spot (Alternaria kikuchiana), scab (Gymnospora)
ngium haraeanum), sclerotinia (Sclerotinia fructigena)
, Monilia disease (Monilinia fructigena), Peach scab (Sclerotinia cinerea, Monilinia fructicola)
, Scab (Cladosporium carpophilum), Phomopsis rot (Phomopsis sp.), Black scab of grape (Elsinoe)
ampelina), late rot (Glomerella cingulate), powdery mildew (Uncinula nacator), rust (Phakopsora ampel)
opsidis), oyster anthracnose (Gloeosporium kaki), deciduous tree
(Cercospora kaki, Mycosphaerella nawae), Anthracnose (Colletotrichum lagenarium), powdery mildew (Sp
haerotheca fuliginea), vine blight (Mycosphaerella me
lonis), tomato ring spot (Alternaria solani), leaf mold (Cladosporium fulvum), eggplant brown leaf spot (Phomopsis)
vexans), powdery mildew (Erysiphe cichoracearum),
Black spot (Alternaria japonica), white spot (Cercosporella brassicae), and rust onion (Puccin) of cruciferous vegetables
ia allii), soybean purpura (Cercospora kikuchii),
Black scab (Elsinoe glycines), Black spot (Diapor the ph
aseolorum var. sajae), anthracnose of the kidney bean (Colletot
richum lindemuthianum), peanut black sickness (Mycosp
haerella personnatum), brown spot (Cercospora arachid)
icola), powdery mildew of pea (Erysiphe pisi), summer blight of potato (Alternaria solani), powdery mildew of strawberry (Sphaerotheca humuli), rice blast of tea (Exobas)
idium reticulatum), white scab (Elsinoe leucospila),
Tobacco scab (Alternaria longipes), powdery mildew
(Erysiphe cichoracearum), anthracnose (Colletotrichum t
abacum), brown leaf spot of sugar beet (Cercospora beticola),
Rose scab (Diplocarpon rosae), powdery mildew (Spha
erotheca pannosa), brown spot of chrysanthemum (Septoria chrysant)
hemi-indici), white rust (Puccinia horiana), gray mold of various crops (Botrytis cinerea), Botrytis disease of various crops (Botrytis spp.), sclerotinia sclerotiorum of various crops, etc. Can be mentioned.

When the pyrazoline derivative represented by the general formula 5 is used as an active ingredient of a plant disease controlling agent, it may be used as it is without adding any other ingredients, but it is usually a solid carrier, a liquid carrier or an interface. Used as an emulsion, wettable powder, suspension, granule, powder, liquid or the like by mixing with an active agent and other auxiliary agents for formulation. In these formulations, the pyrazoline derivative as an active ingredient is usually contained in a weight ratio of 0.1 to 99.
%, Preferably 1 to 80%. Examples of the solid carrier include kaolin clay, attapulgite clay, bentonite, acid clay, phyllophyllite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, fine powder or particles of synthetic hydrous silicon oxide, and the like. As the liquid carrier, aromatic hydrocarbons such as xylene and methylnaphthalene, isopropanol, ethylene glycol,
Alcohols such as cellosolve, acetone, cyclohexanone, ketones such as isophorone, soybean oil, vegetable oils such as cottonseed oil, dimethyl sulfoxide, acetonitonil, water and the like, and as a surfactant used for emulsification, dispersion, wet extension, etc. , Alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates,
Anionic surfactants such as polyoxyethylene alkylaryl ether phosphate salt, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester And nonionic surfactants. Examples of the auxiliary agent for formulation include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like. These formulations are used as they are or after diluted with water for foliage spraying, seed treatment, or powdered, granulated and mixed in soil, or applied in various forms such as soil application. . In addition, when used in combination with other plant disease controlling agents, it can be expected to enhance the controlling effect. Further, it can be used in combination with an insecticide, an acaricide, a nematicide, a herbicide, a plant growth regulator, a fertilizer or a soil conditioner. Other plant control agents that can be mixed include, for example, propiconazole, triadimenol, prochloraz, penconazole, tebuconazole, flucirazole, diniconazole, bromuconazole, epoxyconazole, difenoconazole, cyproconazole, metconazole, triflumizole. , Tetraconazole, microbutanyl, fenbuconazole, hexaconazole, fluquinconazole, RPA400727, azole fungicides such as bitertanol, imazalil and flutriafol, cyclic amines such as fenpropimorph, tridemorph and fenpropidine Bactericidal compounds, carbendazim, benomyl, thiabendazole, benzimidazole bactericidal compounds such as thiophanate methyl, procymidone, cyprodinil, pirime Nil, dietofencarb, thiuram, fluazinam, mancozeb, iprodione, vinclozolin, chlorothalonil, captan, mepanipyrim, fenpiclonil, fludioxonil, diclofluanide, folpet, methyl methoxyimino-α- (o-tolyloxy) -o-tolylacetate (BAS490F). ), Methyl (E)-{2-
[6- (2-Cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate (IC
IA5504), N-methyl-α-methoxyimino-2
-[(2,5-Dimethylphenoxy) methyl] phenylacetamide and the like. The pyrazoline derivative represented by the general formula 5 can be used as an active ingredient of a plant disease controlling agent for paddy fields, fields, orchards, tea fields, meadows, lawns and the like. When the pyrazoline derivative represented by the general formula 5 is used as an active ingredient of a plant disease controlling agent, its application amount is usually 0.001 g to 100 g per 1 are, preferably
0.01g to 10g, when the emulsion, wettable powder, suspension, liquid, etc. are diluted with water and applied, the application concentration is 0.0001%
-1%, preferably 0.001% -0.1%. Granules, powders, etc. are applied as they are without any dilution. When the seeds are used after treatment, the application rate is usually 0.001 g to 100 g, preferably 1 to 100 g, preferably 1 g of seeds,
0.01g-10g can be used.

[0050]

EXAMPLES The present invention will be described in more detail below with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. First, a production example of the pyrazoline derivative represented by the general formula 5 will be shown. Production Example 1 Sodium hydride (60% oil dispersion) 5
To a suspension of 60 mg in 10 ml of tetrahydrofuran, 1.5 g of 2-chlorophenylacetonitrile under ice cooling.
Was added dropwise to a solution of 10 ml of tetrahydrofuran. After stirring under ice cooling for 1 hour, a solution prepared by dissolving 1.7 g of N, N'-ditert-butyldiaziridinone in 10 ml of tetrahydrofuran was added dropwise. After the dropping, 5 at room temperature
Stirred for hours. Then, 14 ml of IN hydrochloric acid was added under ice cooling, and the mixture was extracted with diethyl ether. After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure,
The residue was subjected to column chromatography to give compound 3 500
to obtain mg. Production Example 2 1-tert-butyl-4- (2-chlorophenyl) -5-
Amino-pyrazolin-3-one 1.3 g, 2-iodopropane 1.3 g, potassium carbonate 1.6 g and ethanol 20
The ml mixture was heated to reflux for 10 hours. The solvent was evaporated under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was subjected to column chromatography,
400 mg of compound 20 was obtained. Production Example 3 1,2-di (tert-butyl) -4- (3-bromophenyl) -5-amino-pyrazolin-3-one (Compound 6)
550 mg, tetra-n-butylammonium bromide 75 mg,
Dimethylsulfate 190mg, 45% sodium hydroxide solution
A mixture of 0.45 ml and 1.5 ml of dichloromethane was stirred at 25 ° C for 40 hours. After completion of the reaction, 10 ml each of water and dichloromethane were added for liquid separation, the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography to obtain 310 mg of compound 77 and 180 mg of compound 78 was obtained. Production Example 4 Sodium hydride (60% oil dispersion) 1
To 60 mg toluene 30 ml and 1-tert-butyl-4-
(2,6-Dichlorophenyl) -5-amino-pyrazolin-3-one (1.00 g) was added, and the mixture was heated at 100 ° C for 2 hours. To this was added 550 mg of isopropyl methanesulfonate, and the mixture was further heated at 100 ° C. for 3 hours. After the reaction was completed, water was added and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was subjected to column chromatography to give compound 28 355 mg.
I got Production Example 5 1-tert-butyl-4- (3-chlorophenyl) -5-
Amino-pyrazolin-3-one 1.3 g, 2-iodobutane 1.8 g, potassium carbonate 2.1 g and ethanol 20 ml.
The mixture was heated to reflux for 10 hours. The solvent was evaporated under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was subjected to column chromatography to give the compound 59450 mg. Production Example 6 1-tert-butyl-4- (2-methylphenyl) -5-
Amino-pyrazolin-3-one 1.23 g, 2-iodobutane 1.84 g, potassium carbonate 2.1 g and ethanol 20 ml
The mixture was heated to reflux for 10 hours. The solvent was evaporated under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was subjected to column chromatography to give the compound 33250 mg.

Examples of the pyrazoline derivative represented by the general formula:
Compound number and physical property value (melting point or ¹H-NMR data)
Both are shown in Tables 24 to 28 (pyrazoli represented by the general formula 5).
It is shown in the definition of the substituent of the derivative. ) And shown in Table 29
You.

[Table 24]

[Table 25]

[0052]

[Table 26]

[Table 27]

[0053]

[Table 28]

¹ H-NMR (CDCl ₃ / TMS) δ (ppm) * 1: 7.6 to 7.2 (m, 8H), 4.35 to 4.1 (m, 3H), 2.4 (s, 3)
H), 1.2 (d, 6H) * 2: 7.55 to 7.24 (m, 8H), 4.33 to 4.22 (m, 3H), 1.17
(d, 6H) * 3: 7.45 to 7.19 (m, 4H), 4.32 (s, 2H), 3.49 (m, 1
H), 1.86 (m, 2H), 1.43 to 1.17 (m, 14H), 0.93 (t, 3H) * 4: 7.51 to 7.15 (m, 4H), 4.66 (s, 2H), 3.48 (m, 1
H), 1.92 to 1.16 (m, 16H), 0.90 (t, 3H) * 5: 7.58 to 7.22 (m, 9H), 4.26 (s, 2H), 3.59 (q, 2
H), 1.08 (t, 3H) * 6: 7.20 to 6.81 (m, 3H), 4.15 (s, 2H), 3.74 (s, 3
H), 3.6 (m, 1H), 1.40 to 1.33 (m, 15H) * 7: 7.28 to 7.05 (m, 4H), 4.21 (s, 2H), 3.37 (m, 1
H), 2.51 (q, 2H), 2.03 to 1.83 (m, 2H), 1.41 to 0.90
(m, 18H) * 8: 7.28 to 7.11 (m, 4H), 4.21 (s, 2H), 3.5 (m, 1
H), 2.28 (s, 3H), 2.0 to 0.87 (m, 19H) * 9: 7.28 to 6.99 (m, 4H), 4.43 (s, 2H), 3.6 (m, 1
H), 2.8 ~ 2.6 (m, 2H), 2.17 (s, 3H), 1.95 (t, 1H),
1.46 ~ 1.10 (m, 12H) * 10: 7.1 ~ 7.0 (m, 3H), 4.13 (s, 2H), 3.48 (m, 1H)
, 2.19 (s, 3H), 2.18 (s, 3H), 1.93 (m, 2H), 1.42
(s, 9H), 1.35 (d, 3H), 0.94 (q, 3H) * 11: 7.07 (d, 2H), 6.97 (m, 1H), 4.15 (s, 2H), 3.
35 (m, 1H), 2.28 (s, 3H), 2.14 (s, 3H), 1.90 (m, 2
H), 1.40 (s, 9H), 1.26 (d, 3H), 0.92 (q, 3H) * 12: 7.45 to 7.20 (m, 9H), 3.72 (s, 2H), 3.55 (m, 1
H), 1.36 (d, 6H), 1.20 (s, 9H) * 13: 6.70 (s, 2H), 4.62 (s, 2H), 3.86 (s, 6H), 3.
82 (s, 3H), 3.62 (m, 1H), 1.40 (s, 9H), 1.36 (d, 6
H) * 14: 7.4 to 7.0 (m, 4H), 4.12 (s, 2H), 3.35 (m, 1H)
, 3.05 (m, 1H), 1.85 (m, 2H), 1.40 (s, 9H), 1.25
(m, 6H), 1.11 (d, 3H), 0.93 (q, 3H) * 15: 7.26 to 7.05 (m, 4H), 3.95 to 2.6 (m, 4H), 1.26
(s, 9H), 1.24 to 1.22 (m, 12H), 1.01 (t, 3H) * 16: 7.3 to 7.2 (m, 4H), 4.4 to 4.3 (m, 1H), 3.17 to 3.
07 (m, 2H), 1.31 (s, 9H), 1.30 (s, 9H), 1.15 (t, 3
H) * 17: 7.33 to 6.98 (m, 9H), 4.61 (s, 2H), 3.35 (m, 1
H), 1.9 (m, 2H), 1.38 (s, 9H), 1.28 (d, 2H), 0.90
(t, 3H) * 18: 7.55 to 7.22 (m, 8H), 4.21 (s, 2H), 4.05 to 3.97
(m, 1H), 1.88 to 0.78 (m, 8H) * 19: 7.4 to 7.0 (m, 3H), 4.3 (s, 2H), 2.2 (s, 3H), 1.
4 (s, 9H) * 20: 7.45 to 7.1 (m, 2H), 4.2 (s, 2H), 3.71 to 3.60 (m,
1H), 1.45 to 1.39 (m, 15H) In Tables 24 to 28 above, tBu represents a tert-butyl group,
iPr is an isopropyl group, Ph is a phenyl group, sBu is s
ec-butyl group, nPr is n-propyl group, Et is ethyl group, 1-EtPr is 1-ethylpropyl group, c-Hex is cyclohexyl group, c-Pent is cyclopentyl group, Propy
Represents a 2-propynyl group, and Butyn represents a 3-butynyl group.

[Table 29] ¹ H-NMR (CDCl ₃ / TMS) δ (ppm) * 21: 7.15 to 7.1 (m, 2H), 1.38 (s, 9H), 7.05 to 6.95
(m, 1H), 1.37 (d, 6H), 4.34 (s, 2H), 3.62 (m, 1H)
, 2.93 (t, 2H), 2.85 (t, 2H), 2.04 (t, 2H) * 22: 7.15 ~ 6.90 (m, 3H), 4.2 (s, 2H), 3.6 (m, 1H),
3.0 to 2.7 (m, 4H), 1.85 to 1.70 (m, 4H), 1.39 (s, 9H)
, 1.29 (d, 6H)

Next, production examples of the pyrazoline compound represented by the general formula 12 will be shown. Example of Preparation of Intermediate To 3.1 g of tert-butylhydrazine hydrochloride was added 4.8 g of 28% sodium methylate methanol solution, and the mixture was stirred at room temperature for 3 hours.
Stir for 0 minutes. After filtering off the precipitated salt by suction filtration,
Ethyl 2-chlorophenylcyanoacetate (5.6 g) was added to the filtrate, and the mixture was heated under reflux for 2 hours. After distilling off the solvent, the residue was washed with diethyl ether, and 1-tert-butyl-4- (2
4 g of -chlorophenyl) -5-amino-pyrazolin-3-one were obtained.

Some of the examples of the pyrazoline compound represented by the general formula 12 are shown in Tables 30 and 31 together with ¹ H-NMR data. (Indicated by the definition of the substituent of the pyrazoline compound represented by the general formula 12)

[Table 30]

[Table 31] In Tables 30 and 31, tBu represents a tert-butyl group, iPr represents an isopropyl group, and Ph represents a phenyl group.

Formulation examples are shown below. The compounds are shown in Table 24.
~ Shown by the compound number in Table 29. Moreover, a part represents a weight part. Formulation Example 1 50 parts of compounds 1-109, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain each wettable powder. Formulation Example 2 10 parts of Compounds 1 to 109, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 parts of xylene are mixed well to obtain each emulsion. Formulation Example 3 2 parts of compounds 1 to 109, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay were well pulverized and mixed, and water was added and kneaded well, and then granulated. Dry to obtain each granule. Formulation Example 4 25 parts of compounds 1 to 109, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed, wet-milled until the particle size of the active ingredient is 5 microns or less, and each suspension agent is prepared. To get Formulation Example 5 10 parts of compounds 1 to 109, 1 part of polyoxyethylene styryl phenyl ether and 89 parts of water are mixed to obtain respective liquid preparations.

Next, Test Examples will show that the pyrazoline derivative represented by the general formula 5 is useful as an active ingredient of a plant disease controlling agent. The pyrazoline derivatives are shown in Tables 24 to 29.
The compound number is shown. As for the bactericidal effect, the disease state of the test plant at the time of the investigation, that is, the flora of leaves, stems, etc., and the extent of lesions were visually observed, and the disease severity was determined by the lesion area ratio. Test Example 1 Cucumber gray mold control test (preventive effect) 90 ml plastic pots were filled with sandy loam and cucumber
(Sagamihanjiro) was sown and cultivated in a greenhouse for 10 days. Compounds 1, 3, 5, 13, 1 formulated according to Formulation Example 4
4, 17, 20, 22, 24, 25, 26, 27, 2
8, 29, 31, 33, 34, 35, 37, 40, 4
1, 54, 58, 63, 65, 68, 70, 71, 7
Each of 2, 79, 80, 96, 99, 102 and 105
A 500 ppm water suspension was sprayed on the foliage so that the cotyledons spread sufficiently on the leaf surface of the cucumber seedling. After air-drying the chemical,
The PDA medium containing mycelium of Botrytis cinerea was inoculated on the cotyledon surface of the cucumber seedlings, kept at 15 ° C. in the dark and humid for 4 days, and the degree of disease onset was investigated. As a result, the untreated group had a disease severity of 100%, but the groups treated with the above compounds all had a disease severity of less than 10%. Test Example 2 Wheat Powdery Mildew Control Test (Therapeutic Effect) 90 ml plastic pot filled with sandy loam soil, wheat
(Norin 73) was sown and cultivated in a greenhouse for 10 days.
The wheat seedlings developed on the second leaf were sprinkled and inoculated with spores of wheat powdery mildew (Erysiphe graminis f. Sp. Tritici). Compounds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 1 which were grown in a growth chamber at 15 ° C. for 2 days after inoculation and were prepared according to Preparation Example 2
4, 15, 16, 18, 21, 23, 25, 29, 3
0, 32, 33, 43, 49, 53, 55, 59, 6
6, 73, 77, 78, 81, 85, 86, 89, 9
A 500 ppm aqueous solution of each of 0, 91, 92, 95, 96, 98, 101 and 102 was foliage-sprayed so that it was sufficiently attached to the leaf surface of the wheat seedling. After spraying, the plants were grown in a growth chamber at 15 ° C for 10 days, and the degree of disease was investigated. As a result, the untreated group had a disease severity of 100%, but the groups treated with the above compounds all had a disease severity of less than 10%. Test Example 3 Wheat powdery mildew control test (permeation transfer effect) 90 ml plastic pot filled with sandy loam
(Norin 73) was sown and cultivated in a greenhouse for 10 days.
Compounds 1, 2, 3, 4, 5, prepared according to Formulation Example 4,
6, 7, 8, 9, 10, 12, 13, 14, 15, 1
6, 18, 20, 21, 22, 23, 25, 28, 2
9, 30, 31, 32, 33, 34, 35, 37, 4
1, 43, 46, 52, 53, 55, 57, 59, 6
0, 65, 66, 67, 68, 69, 70, 71, 7
2, 73, 74, 76, 79, 80, 81, 85, 8
6, 96, 98, 100, 101, 102, 104, 105 and
Each of the 106 water suspensions contained 2.5 active ingredients per pot.
The seedlings of the wheat seedlings in which the second leaf was developed to have mg were irrigated. After treatment in a greenhouse at 24 ° C for 5 days, wheat powdery mildew (Erysiphe graminis f. Sp. Tritic
The spores of i) were sprinkled and inoculated on the wheat seedlings. After inoculation, it was kept in a broth chamber at 15 ° C for 10 days, and the degree of disease onset was investigated. As a result, the untreated group had a disease severity of 100%, but the groups treated with the above compounds all had a disease severity of less than 10%. Test Example 4 Stem rot control test for kidney bean (preventive effect) Sand loamy soil was filled in a 130 ml plastic pot,
(Long quail green beans) were sown and cultivated in a greenhouse for 14 days. Compounds 1, 3, 5, 1 prepared according to Formulation Example 1
3, 14, 17, 20, 22, 24, 25, 26, 2
7, 28, 29, 31, 33, 34, 35, 37, 4
1, 54, 58, 63, 65, 68, 70, 71, 7
Each of 2, 79, 80, 96, 99, 102 and 105
A 500 ppm aqueous suspension was sprayed on the foliage so that the primary leaves were sufficiently attached to the leaf surface of the kidney bean seedlings. Sclerotinia (Sclerotinia) cultivated in PDA medium after air drying
Sclerotiorum) fungal discs were inoculated on the leaves.
After being kept at 24 ° C. and high humidity for 4 days, the degree of disease onset was investigated.
As a result, the untreated group had a disease severity of 70%, but the groups treated with the above-mentioned compounds all had a disease severity of less than 5%. Test Example 5 Wheat Powdery Mildew Control Test (Seed Treatment Effect) Compounds 2, 3, 4, 5, 6 prepared according to Formulation Example 4
7, 8, 9, 10, 12, 14, 15, 16, 18, 2
1, 22, 23, 25, 29, 30, 32, 333, 4
3, 49, 53, 55, 59, 66, 73, 77, 7
8, 79, 81, 85, 86, 89, 90, 91, 9
Each of 2, 96, 101 and 102 was spray-treated on wheat (Norin 73) seeds using a seed dresser so that the amount of active ingredient was 400 g per 100 kg of seeds. Then, a 130 ml plastic pot was filled with sandy loam soil, and the treated seeds were sown and cultivated in a greenhouse for 20 days. The wheat seedlings developed on the fourth leaf were inoculated by sprinkling with spores of wheat powdery mildew (Erysiphe graminis f. Sp. Tritici). After inoculation, it was kept in a broth chamber at 15 ° C for 10 days, and the degree of disease onset was investigated. As a result, the untreated group had a disease severity of 100%, but the groups treated with the above compounds all had a disease severity of less than 10%.

[0059]

EFFECT OF THE INVENTION The pyrazoline derivative represented by the general formula 5 shows an excellent controlling effect against plant diseases.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Norio Kimura 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Yoshitaka Takano 4-2-1 Takashi, Takarazuka-shi, Hyogo No. Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Makoto Fujimura 4-2-1 Takashi Takarazuka-shi Hyogo Prefecture Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Yuko Yamazaki 4-2-1 Takashi Takarazuka-shi, Hyogo No. Sumitomo Chemical Industry Co., Ltd.

Claims (13)

[Claims] 1. A compound represented by the general formula: [In the formula, R ^{1 to} R ⁴ are a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, a cyano group, a nitro group, or a substituted group. Represents a phenyl group which may be substituted or a phenoxy group which may be substituted, and R ⁵ represents a hydrogen atom, a fluorine atom or an alkoxy group, or two adjacent R ^{1 to} R ⁵ are bonded at the terminal. , A group represented by CH = CH-CH = CH, a methylenedioxy group optionally substituted with a halogen atom, or an alkylene optionally containing one oxygen atom and optionally substituted with an alkyl group. Represents a group, R ⁶ and R ⁷ are the same or different,
Represents an optionally substituted hydrocarbon group, R ⁸ and R ⁹ are the same or different and represent a hydrogen atom or an alkyl group, or R ⁸ and R ⁹ are bonded at the terminal to form an alkylene group. Represent. However, R ^{1 to} R ⁵ are not all hydrogen atoms at the same time. ] The plant disease control agent containing the pyrazoline derivative shown by these as an active ingredient. 2. R¹~ R^FourIs a hydrogen atom, a halogen atom,
C₁~ C_FiveAlkyl group of C₁~ C _FiveThe haloalkyl
Group, C₁~ C_FiveAn alkoxy group of (C₁~ C₃) Arco
Kishi (C₁~ C₃) Alkoxy group, C₁~ C_FiveHalo a
Lucoxy group, C₁~ C_FiveAlkylthio group of C₁~ C_Five
Haloalkylthio group, cyano group, nitro group, phenyl
A group (the phenyl group is a halogen atom, C₁~ C_FiveThe archi
Group, C₁~ C_FiveAlkoxy group of C₁~ C_FiveThe archi
Ruthio group, C₁~ C_FiveHaloalkyl group, C₁~ C_Fiveof
Haloalkoxy group, C₁~ C_FiveThe haloalkylthio group
Or optionally substituted with a cyano group), or pheno
An oxy group (the phenoxy group is a halogen atom, C₁~ C_Fiveof
Alkyl group, C₁~ C_FiveAlkoxy group of C₁~ C_Fiveof
Alkylthio group, C₁~ C_FiveHaloalkyl group, C₁~
C_FiveHaloalkoxy group, C₁~ C _FiveThe haloalkyl
O group or cyano group may be substituted),
R^FiveIs hydrogen atom, fluorine atom or C₁~ C_FiveArco
A xy group or R¹~ R^FiveAdjacent to
Two are linked at the ends and are represented by CH = CH-CH = CH
Group, methylene optionally substituted with a halogen atom
Dioxy group, trimethylene group, tetramethylene group, OCH
₂CH₂Groups represented by or OCH₂ CH (CH₃)
Group, R⁶And R⁷Are the same or different, and C₁~ C_Tenof
Alkyl group, C₂~ C _TenAlkenyl group of C₂~ C_Tenof
Alkynyl group, same or different 1 to 21 halo
C substituted with a gen atom₁~ C_TenAlkyl groups of the same
Substituted with 1 to 19 different halogen atoms
C₂~ C_TenAlkenyl groups of the same or different 1 to
C substituted with 17 halogen atoms₂~ C_TenThe archi
Nyl group, C₁~ C_FiveAlkoxy C₁~ C_FiveAn alkyl group,
C₁~ C_FiveAlkylthio C₁~ C _FiveAlkyl group, same as
Or C substituted with 1 to 11 different halogens₁
~ C_FiveIdentical or different 1 having an alkoxy group
~ C substituted with 11 halogens₁~ C_FiveThe alkyl
Group, substituted with 1 to 11 halogens which are the same or different
C₁~ C_FiveHaving the same alkylthio group,
Or C substituted with 1 to 11 different halogens₁~
C_FiveC substituted with an alkyl group or cyano group ₁~ C_Fiveof
C₁~ C_FiveAlkyl group of C₁~ C_FiveThe alkoxycar
C substituted with a bonyl group₁~ C_FiveAlkyl group of C₃~
C₈A cycloalkyl group of (wherein the cycloalkyl group is a halogen
Substituted with a hydrogen atom, or may contain an unsaturated bond
Good), phenyl group (the phenyl group is a halogen atom, C
₁~ C_FiveAlkyl group of C₁~ C_FiveAlkoxy group of C
₁~ C_FiveAlkylthio group of C₁~ C_FiveThe haloalkyl
Group, C₁~ C_FiveHaloalkoxy group, C₁~ C_FiveThe halo
May be substituted with an alkylthio group or a cyano group
I) or C₇~ C₁₇Aralkyl group of (the aralkyl
Group is a halogen atom, C₁~ C_FiveAlkyl group of C₁~ C
_FiveAlkoxy group of C₁~ C_FiveAlkylthio group of C₁
~ C_FiveHaloalkyl group, C₁~ C_FiveThe haloalkoxy
Group, C₁~ C_FiveA haloalkylthio group or a cyano group of
Optionally substituted), and R⁸And R⁹But the same
One or different, hydrogen atom or C ₁~ C_FiveThe archi
R group or R⁸And R⁹Are joined at the ends
A tetramethylene group, a pentamethylene group or an ethylene
The plant disease controlling agent according to claim 1, which is a quinone group. 3. R ⁶ and R ⁷ are the same or different,
The pyrazoline derivative represented by the general formula 1 according to claim 1, which is a tert-butyl group, an isopropyl group, a 1-methylbutyl group or a sec-butyl group. 4. A general formula: ## STR2 ##[In the formula, R¹¹Is a halogen atom, alkyl group, haloalkoxy
Group, alkoxy group, haloalkoxy group, alkylthio
Group, haloalkylthio group, cyano group, even if substituted
Good phenyl group or optionally substituted phenoxy
Represents a Si group, R ^{twenty one}~ R⁴¹Is a hydrogen atom, a halogen atom,
Alkyl group, haloalkyl group, alkoxy group, alkoxy group
Cyalkoxy group, haloalkoxy group, alkylthio group,
Haloalkylthio group, cyano group, nitro group, substituted
An optionally substituted phenyl group or an optionally substituted phenyl group
Represents an enoxy group, R⁵¹Is a hydrogen atom, a fluorine atom or
Represents an alkoxy group, R⁶And R⁷Are the same or
Are different and represent an optionally substituted hydrocarbon group.
Then R⁸And R⁹Are the same or different and are hydrogen atoms
Or represents an alkyl group, or R⁸And R⁹But
It is bonded at the terminal to represent an alkylene group. ] Indicated by
Lazoline derivative. 5. R¹¹Is a halogen atom, C₁~ C_FiveAl
Kill group, C₁~ C_FiveHaloalkyl group, C₁~ C_FiveA
Lucoxy group, (C₁~ C₃) Alkoxy (C₁~ C₃)
Alkoxy group, C₁~ C_FiveHaloalkoxy group, C₁~
C_FiveAlkylthio group of C₁~ C_FiveThe haloalkylthio
Group, cyano group, nitro group, phenyl group, (the phenyl group
Is a halogen atom, C₁~ C_FiveAlkyl group of C₁~ C_Five
Alkoxy group of C₁~ C_FiveAlkylthio group of C₁~
C_FiveHaloalkyl group, C₁~ C_FiveThe haloalkoxy
Group, C₁~ C_FiveA haloalkylthio group or a cyano group of
Optionally substituted), or a phenoxy group (wherein
Noxy group is a halogen atom, C₁~ C_FiveAlkyl group of C
₁~ C_FiveAlkoxy group of C₁~ C_FiveAlkylthio
Group, C₁~ C _FiveHaloalkyl group, C₁~ C_FiveHalo a
Lucoxy group, C₁~ C_FiveHaloalkylthio group or
Optionally substituted with an ano group), R^{twenty one}~ R⁴¹Is a hydrogen atom, halogen atom, C₁~ C_Fiveof
Alkyl group, C₁~ C _FiveHaloalkyl group, C₁~ C_Five
Alkoxy group of C₁~ C_FiveHaloalkoxy group, C₁
~ C_FiveAlkylthio group of C₁~ C_FiveThe haloalkyl
O group, cyano group, phenyl group (the phenyl group is a halogen
Atom, C₁~ C_FiveAlkyl group of C₁~ C_FiveThe Archoki
Shi group, C₁~ C_FiveAlkylthio group of C₁~ C_FiveThe halo
Alkyl group, C₁~ C_FiveHaloalkoxy group, C₁~ C
_FiveSubstituted with a haloalkylthio group or a cyano group of
Or a phenoxy group (the phenoxy group is
Rogen atom, C₁~ C_FiveAlkyl group of C₁~ C_FiveA
Lucoxy group, C₁~ C_FiveAlkylthio group of C₁~ C_Five
Haloalkyl group, C₁~ C_FiveHaloalkoxy group, C
₁~ C_FiveSubstituted with a haloalkylthio group or a cyano group of
R), and R⁵¹Is a hydrogen atom or a fluorine atom
Or C₁~ C_FiveAn alkoxy group of R,⁶And R⁷Are the same or different, and C₁~ C_Tenof
Alkyl group, C₂~ C _TenAlkenyl group of C₂~ C_Tenof
Alkynyl group, same or different 1 to 21 halo
C substituted with a gen atom₁~ C_TenAlkyl groups of the same
Substituted with 1 to 19 different halogen atoms
C₂~ C_TenAlkenyl groups of the same or different 1 to
C substituted with 17 halogen atoms₂~ C_TenThe archi
Nyl group, C₁~ C_FiveAlkoxy C₁~ C_FiveAn alkyl group,
C₁~ C_FiveAlkylthio C₁~ C _FiveAlkyl group, same as
Or C substituted with 1 to 11 different halogens₁
~ C_FiveIdentical or different 1 having an alkoxy group
~ C substituted with 11 halogens₁~ C_FiveThe alkyl
Group, substituted with 1 to 11 halogens which are the same or different
C₁~ C_FiveHaving the same alkylthio group,
Or C substituted with 1 to 11 different halogens₁~
C_FiveC substituted with an alkyl group or cyano group ₁~ C_Fiveof
Alkyl group, C₁~ C_FiveAt the alkoxycarbonyl group of
Converted C₁~ C_FiveAlkyl group of ,, C₃~ C₈Shiku
Alkyl group (wherein the cycloalkyl group is a halogen atom)
Substituted, may contain unsaturated bonds),
Phenyl group (the phenyl group is a halogen atom, C₁~ C_Fiveof
Alkyl group, C₁~ C_FiveAlkoxy group of C₁~ C_Fiveof
Alkylthio group, C₁~ C_FiveHaloalkyl group, C₁~
C_FiveHaloalkoxy group, C₁~ C_FiveThe haloalkyl
O group or cyano group), or
C₇~ C₁₇Aralkyl group of (wherein the aralkyl group is a halogen
Atom, C₁~ C_FiveAlkyl group of C₁~ C_FiveThe Archoki
Shi group, C₁~ C_FiveAlkylthio group of C₁~ C_FiveThe halo
Alkyl group, C₁~ C_FiveHaloalkoxy group, C₁~ C
_FiveSubstituted with a haloalkylthio group or a cyano group of
R)⁸And R⁹Are the same or different
Becomes, hydrogen atom or C₁~ C_FiveIs an alkyl group of
Or R⁸And R⁹Are bonded at the ends,
Is a ethylene group, a pentamethylene group, or a ethylene group,
The pyrazoline derivative according to claim 4. 6. R ^{31 to} R ⁵¹ are all hydrogen atoms, and R ^31
21, the 6-position, a hydrogen atom, a halogen atom, an alkyl group of C ₁ -C _5, a haloalkyl group of _{C 1 ~C 5, C 1 ~C} 5
Alkoxy group, C ₁ -C ₅ haloalkoxy group, C ₁
To C ₅ alkylthio group, C _{1 to} C ₅ haloalkylthio group, cyano group, phenyl group (the phenyl group is a halogen atom, C _{1 to} C ₅ alkyl group, C _{1 to} C ₅ alkoxy group, C ₁ To C ₅ alkylthio group, C _{1 to} C ₅ haloalkyl group, C _{1 to} C ₅ haloalkoxy group, C _{1 to} C
₅ may be substituted with a haloalkylthio group or a cyano group), or a phenoxy group (the phenoxy group is a halogen atom, a C ₁ -C ₅ alkyl group, a C ₁ -C ₅ alkoxy group, C ₁ -C ₅ alkylthio groups, C ₁ -C ₅
Haloalkyl group, C ₁ -C ₅ haloalkoxy group, C
_1- C ₅ haloalkylthio group or cyano group), which is a pyrazoline derivative according to claim 5. 7. A plant disease controlling agent comprising the pyrazoline derivative according to claim 3, 4, 5 or 6 as an active ingredient. 8. The general formula: embedded image [In the formula, R ^{1 to} R ⁴ are a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, a cyano group, a nitro group, or a substituted group. Represents a phenyl group which may be substituted or a phenoxy group which may be substituted, and R ⁵ represents a hydrogen atom, a fluorine atom or an alkoxy group, or two adjacent R ^{1 to} R ⁵ are bonded at the terminal. , A group represented by CH = CH-CH = CH, a methylenedioxy group optionally substituted with a halogen atom, or an alkylene optionally containing one oxygen atom and optionally substituted with an alkyl group. Represents a group, and R ⁷¹ represents an optionally substituted hydrocarbon group having 3 to 17 carbon atoms. However, R ^{1 to} R ⁵ are not all hydrogen atoms at the same time. ] The pyrazoline compound shown by these. 9. R¹~ R^FourIs a hydrogen atom, a halogen atom,
C₁~ C_FiveAlkyl group of C₁~ C _FiveThe haloalkyl
Group, C₁~ C_FiveAn alkoxy group of (C₁~ C₃) Arco
Kishi (C₁~ C₃) Alkoxy group, C₁~ C_FiveHalo a
Lucoxy group, C₁~ C_FiveAlkylthio group of C₁~ C_Five
Haloalkylthio group, cyano group, nitro group, phenyl
A group (the phenyl group is a halogen atom, C₁~ C_FiveThe archi
Group, C₁~ C_FiveAlkoxy group of C₁~ C_FiveThe archi
Ruthio group, C₁~ C_FiveHaloalkyl group, C₁~ C_Fiveof
Haloalkoxy group, C₁~ C_FiveThe haloalkylthio group
Or optionally substituted with a cyano group), or pheno
An oxy group (the phenoxy group is a halogen atom, C₁~ C_Fiveof
Alkyl group, C₁~ C_FiveAlkoxy group of C₁~ C_Fiveof
Alkylthio group, C₁~ C_FiveHaloalkyl group, C₁~
C_FiveHaloalkoxy group, C₁~ C _FiveThe haloalkyl
O group or cyano group may be substituted),
R^FiveIs hydrogen atom, fluorine atom or C₁~ C_FiveArco
A xy group or R¹~ R^FiveAdjacent to
Two are linked at the ends and are represented by CH = CH-CH = CH
Group, methylene optionally substituted with a halogen atom
Dioxy group, trimethylene group, tetramethylene group, OCH
₂CH₂Groups represented by or OCH₂ CH (CH₃)
Group, R⁷¹But C₃~ C_TenAlkyl group of C₃~ C_TenArche
Nyl group, C₃~ C_TenAlkynyl groups of the same or different
C substituted with 1 to 21 halogen atoms ₃~ C_Ten
Alkyl groups, the same or different 1 to 19 halo
C substituted with a gen atom₃~ C_TenAlkenyl groups of the same
Or substituted with 1 to 17 different halogen atoms
C₃~ C_TenAn alkynyl group of C₁~ C_FiveAlkoxy C
₂~ C_FiveAlkyl group, C₁~ C_FiveAlkylthio C₂~ C
_FiveAlkyl group, same or different 1 to 11 halo
C substituted with gen₁~ C_FiveHaving an alkoxy group,
Substituted with 1 or 1 to 11 different halogens
C₂~ C_FiveAlkyl groups of 1 to 1 which are the same or different
C substituted with one halogen₁~ C_FiveAlkylthio
1 to 11 halogens having the same or different groups
C replaced by₂~ C_FiveThe alkyl group and cyano group of
Converted C₂~ C_FiveAlkyl group of C₁~ C _FiveArco
C substituted with an oxycarbonyl group₂~ C_FiveThe alkyl
Group, C₃~ C₈A cycloalkyl group of (the cycloalkyl
The group may be substituted with a halogen atom and may be an unsaturated bond.
May be included), a phenyl group (the phenyl group is a halogen
Atom, C₁~ C_FiveAlkyl group of C₁~ C_FiveArco
Xy group, C₁~ C_FiveAlkylthio group of C₁~ C_FiveHa
Lower alkyl group, C₁~ C_FiveHaloalkoxy group, C₁~
C _FiveSubstituted with a haloalkylthio group or a cyano group of
Or C₇~ C₁₇Aralkyl group of
The aralkyl group is a halogen atom, C₁~ C_FiveAn alkyl group of
C₁~ C_FiveAlkoxy group of C₁~ C_FiveAlkylthio
Group, C₁~ C_FiveHaloalkyl group, C₁~ C_FiveHalo a
Lucoxy group, C₁~ C_FiveHaloalkylthio group or
And optionally substituted with an ano group).
The listed pyrazoline compounds. 10. The pyrazoline compound according to claim 8, wherein R ⁷¹ is a tert-butyl group, an isopropyl group, a 1-methylbutyl group, or a sec-butyl group. 11. A general formula: embedded image [In the formula, R ¹¹ is a halogen atom, an alkyl group, a haloalkyl group, an alkoxy 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 represents an optionally substituted phenoxy group, R
^{21 to} R ⁴¹ are hydrogen atom, halogen atom, alkyl group, haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, haloalkylthio group, cyano group, optionally substituted phenyl group, or optionally substituted. Represents a phenoxy group, R ⁵¹ represents a hydrogen atom, a fluorine atom or an alkoxy group, and R ⁷¹ represents an optionally substituted hydrocarbon group having 3 to 17 carbon atoms. ] The pyrazoline compound shown by these. 12. R¹¹Is a halogen atom, C₁~ C_FiveA
Rukiru group, C₁~ C_FiveHaloalkyl group, C₁~ C_Fiveof
An alkoxy group, (C₁~ C₃) Alkoxy (C₁~
C₃) Alkoxy group, C₁~ C_FiveA haloalkoxy group of
C₁~ C_FiveAlkylthio group of C₁~ C_FiveThe halo archi
Ruthio group, cyano group, nitro group, phenyl group (the phenyl group
Group is a halogen atom, C₁~ C_FiveAlkyl group of C₁~
C_FiveAlkoxy group of C₁~ C_FiveAlkylthio group of C
₁~ C_FiveHaloalkyl group, C₁~ C_FiveThe halo arcoki
Shi group, C₁~ C_FiveHaloalkylthio group or cyano group
Optionally substituted with) or a phenoxy group (wherein
The enoxy group is a halogen atom, C₁~ C_FiveAn alkyl group of
C₁~ C_FiveAlkoxy group of C₁~ C_FiveAlkylthio
Group, C₁~ C_FiveHaloalkyl group, C₁~ C_FiveHalo a
Lucoxy group, C₁~ C_FiveHaloalkylthio group or
Optionally substituted with an ano group), R^{twenty one}~ R⁴¹Is a hydrogen atom, halogen atom, C₁~ C_Fiveof
Alkyl group, C₁~ C _FiveHaloalkyl group, C₁~ C_Five
Alkoxy group of C₁~ C_FiveHaloalkoxy group, C₁
~ C_FiveAlkylthio group of C₁~ C_FiveThe haloalkyl
O group, cyano group, phenyl group (the phenyl group is a halogen
Atom, C₁~ C_FiveAlkyl group of C₁~ C_FiveThe Archoki
Shi group, C₁~ C_FiveAlkylthio group of C₁~ C_FiveThe halo
Alkyl group, C₁~ C_FiveHaloalkoxy group, C₁~ C
_FiveSubstituted with a haloalkylthio group or a cyano group of
Or a phenoxy group (the phenoxy group is
Rogen atom, C₁~ C_FiveAlkyl group of C₁~ C_FiveA
Lucoxy group, C₁~ C_FiveAlkylthio group of C₁~ C_Five
Haloalkyl group, C₁~ C_FiveHaloalkoxy group, C
₁~ C_FiveSubstituted with a haloalkylthio group or a cyano group of
R), and R⁵¹Is a hydrogen atom or a fluorine atom
Or C₁~ C_FiveAn alkoxy group of R,⁷¹But C₃~ C_TenAlkyl group of C₃~ C_TenArche
Nyl group, C₃~ C_TenAlkynyl groups of the same or different
C substituted with 1 to 21 halogen atoms ₃~ C_Ten
Alkyl groups, the same or different 1 to 19 halo
C substituted with a gen atom₃~ C_TenAlkenyl groups of the same
Or substituted with 1 to 17 different halogen atoms
C₃~ C_TenAn alkynyl group of C₁~ C_FiveAlkoxy C
₂~ C_FiveAlkyl group, C₁~ C_FiveAlkylthio C₂~ C
_FiveAlkyl group, same or different 1 to 11 halo
C substituted with gen₁~ C_FiveHaving an alkoxy group,
Substituted with 1 or 1 to 11 different halogens
C₂~ C_FiveAlkyl groups of 1 to 1 which are the same or different
C substituted with one halogen₁~ C_FiveAlkylthio
1 to 11 halogens having the same or different groups
C replaced by₂~ C_FiveThe alkyl group and cyano group of
Converted C₂~ C_FiveAlkyl group of C₁~ C _FiveArco
C substituted with an oxycarbonyl group₂~ C_FiveThe alkyl
Group, C₃~ C₈A cycloalkyl group of (the cycloalkyl
The group may be substituted with a halogen atom and may be an unsaturated bond.
May be included), a phenyl group (the phenyl group is a halogen
Atom, C₁~ C_FiveAlkyl group of C₁~ C_FiveArco
Xy group, C₁~ C_FiveAlkylthio group of C₁~ C_FiveHa
Lower alkyl group, C₁~ C_FiveHaloalkoxy group, C₁~
C _FiveSubstituted with a haloalkylthio group or a cyano group of
Or C₇~ C₁₇Aralkyl group of
The aralkyl group is a halogen atom, C₁~ C_FiveAn alkyl group of
C₁~ C_FiveAlkoxy group of C₁~ C_FiveAlkylthio
Group, C₁~ C_FiveHaloalkyl group, C₁~ C_FiveHalo a
Lucoxy group, C₁~ C_FiveHaloalkylthio group or
Optionally substituted with an ano group),
The pyrazoline compound described. 13. R ^{31 to} R ⁵¹ are all hydrogen atoms,
R ²¹ is a 6-position hydrogen atom, a halogen atom, C _{1 to} C ₅
Alkyl group, C ₁ -C ₅ haloalkyl group, C ₁ -C
₅ alkoxy groups, C ₁ -C ₅ haloalkoxy groups, C
_{1 to} C ₅ alkylthio group, C _{1 to} C ₅ haloalkylthio group, cyano group, phenyl group (the phenyl group is a halogen atom, C _{1 to} C ₅ alkyl group, C _{1 to} C ₅ alkoxy group, C alkylthio group ₁ -C _5, a haloalkyl group of C ₁ -C _5, a haloalkoxy group C _{1 ~C 5,} C ₁ ~
It may be substituted with a C ₅ haloalkylthio group or a cyano group, or a phenoxy group (the phenoxy group is a halogen atom, a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ alkoxy group, C ₁ to C ₅ alkylthio group, C ₁ -C
₅ haloalkyl groups, C ₁ -C ₅ haloalkoxy groups,
A pyrazoline compound according to claim 12, which may be substituted with a C _{1 to} C ₅ haloalkylthio group or a cyano group.