JP2002507551A - Fungicide mixture based on tris (oxime ether) derivative and insecticide - Google Patents

Abstract

(57) [Summary] As an active ingredient, a) Formula I: Wherein the substituents and indices are as defined in the specification, respectively, and a salt thereof, and b) Formulas II to XI: Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image A mixture for protecting cultivated plants, comprising a synergistic effect amount of at least one compound represented by the formula:

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to: a) Formula I:

[0002]

Embedded image[However, X is NOCH_Three, CHOCH_Three, CHCH_ThreeY represents O, NR; R¹, R are each independently of one another hydrogen or C₁~ C_FourR represents alkyl;^TwoIs cyano, nitro, trifluoromethyl, halogen, C₁~ C_FourAlkyl or C₁~ C_FourM represents 0, 1 or 2, and when m is 2, a group R^TwoMay be different from each other; R^ThreeIs hydrogen, cyano, C₁~ C_FourAlkyl, C₁~ C_FourHaloalkyl, C_Three~ C₆R represents cycloalkyl;^Four, R⁶Are independently of each other hydrogen, C₁~ C_TenAlkyl, C_Three~ C₆Cycloalkyl, C_Two~ C_TenAlkenyl, C_Two~ C_TenAlkynyl, C₁~ C_TenAlkylcarbonyl, C_Two~ C_TenAlkenylcarboni
Le, C_Three~ C_TenAlkynylcarbonyl or C₁~ C_TenAlkylsulfonyl ｛these
May be partially or completely halogenated, or may have from 1 to 3
Groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, amino
Nocarbonyl, aminothiocarbonyl, halogen, C₁~ C₆Alkyl, C₁~ C₆ Haloalkyl, C₁~ C₆Alkylsulfonyl, C₁~ C₆Alkylsulfoxyl,
C₁~ C₆Alkoxy, C₁~ C₆Haloalkoxy, C₁~ C₆Alkoxycarbonyl
, C₁~ C₆Alkylthio, C₁~ C₆Alkylamino, di-C₁~ C₆Alkylam
No, C₁~ C₆Alkylaminocarbonyl, di-C₁~ C₆Alkylaminocarboni
Le, C₁~ C₆Alkylaminothiocarbonyl, di-C₁~ C₆Alkylaminothio
Carbonyl, C_Two~ C₆Alkenyl, C_Two~ C₆Alkenyloxy, C_Three~ C₆Cyclo
Alkyl, C_Three~ C₆Cycloalkyloxy, heterocyclyl, heterocyclyl
Xy, benzyl, benzyloxy, aryl, aryloxy, arylthio,
Heteroaryl, heteroaryloxy and heteroarylthio (their cyclic
Groups may be partially or completely halogenated, or 1-3
The following groups of: cyano, nitro, hydroxyl, mercapto, amino, carboxy
, Aminocarbonyl, aminothiocarbonyl, halogen, C₁~ C₆Alkyl,
C₁~ C₆Haloalkyl, C₁~ C₆Alkylsulfonyl, C₁~ C₆Alkylsulfo
Kisil, C_Three~ C₆Cycloalkyl, C₁~ C₆Alkoxy, C₁~ C₆Haloalkoki
Si, C₁~ C₆Alkyloxycarbonyl, C₁~ C₆Alkylthio, C₁~ C₆Al
Killamino, di-C₁~ C₆Alkylamino, C₁~ C₆Alkylaminocarbonyl
, Di-C₁~ C₆Alkylaminocarbonyl, C₁~ C₆Alkylaminothiocarbo
Nil, di-C₁~ C₆Alkylaminothiocarbonyl, C_Two~ C₆Alkenyl, C_Two ~ C₆Alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, heteroaryl, heteroaryloxy, heteroarylthio
E or C (= NOR⁷) -A_n-R⁸Aryl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroaryl,
Loarylcarbonyl or heteroarylsulfonyl. These groups are partially
Or even completely halogenated, or 1-3 of the following groups: cyano, d
Toro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl,
Aminothiocarbonyl, halogen, C₁~ C₆Alkyl, C₁~ C₆Haloalkyl,
C₁~ C₆Alkylcarbonyl, C₁~ C₆Alkylsulfonyl, C₁~ C₆Alkyl
Sulfoxyl, C_Three~ C₆Cycloalkyl, C₁~ C₆Alkoxy, C₁~ C₆Haloa
Lucoxy, C₁~ C₆Alkyloxycarbonyl, C₁~ C₆Alkylthio, C₁~ C₆Alkylamino, di-C₁~ C₆Alkylamino, C₁~ C₆Alkylaminocarbonyl, di-C₁~ C₆Alkylaminocarbonyl, C₁~ C₆Alkylaminothi
Ocarbonyl, di-C₁~ C₆Alkylaminothiocarbonyl, C_Two~ C₆Alkene
Le, C_Two~ C₆Alkenyloxy, benzyl, benzyloxy, aryl, aryl
Ruoxy, heteroaryl, heteroaryloxy or C (= NOR⁷) -A_n-R⁸Represents｝ which may have: R^FiveIs hydrogen, C₁~ C₆Alkyl, C_Two~ C₆Alkenyl, C_Two~ C₆Alkynyl—the charcoal of these groups
The hydride group can be partially or completely halogenated, or 1-3
The following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl
, Aminocarbonyl, aminothiocarbonyl, halogen, C₁~ C₆Alkylam
Nocarbonyl, di-C₁~ C₆Alkylaminocarbonyl, C₁~ C₆Alkylam
Notthiocarbonyl, di-C₁~ C₆Alkylaminothiocarbonyl, C₁~ C₆Al
Killsulfonyl, C₁~ C₆Alkylsulfoxyl, C₁~ C₆Alkoxy, C₁~ C₆Haloalkoxy, C₁~ C₆Alkoxycarbonyl, C₁~ C₆Alkylthio, C₁~ C₆Alkylamino, di-C₁~ C₆Alkylamino, C_Two~ C₆Alkenylo
Kissi, C_Three~ C₆Cycloalkyl, C_Three~ C₆Cycloalkyloxy, heterocyclyl
, Heterocyclyloxy, aryl, aryloxy, aryl-C₁~ C_FourA
Lucoxy, arylthio, aryl-C₁~ C_FourAlkylthio, heteroaryl,
Heteroaryloxy, heteroaryl-C₁~ C_FourAlkoxy, heteroaryl
Thio, heteroaryl-C₁~ C_FourAlkylthio (for these cyclic groups,
Even if partially or completely halogenated and / or from 1 to 3
: Cyano, nitro, hydroxyl, mercapto, amino, carboxyl, amino
Carbonyl, aminothiocarbonyl, C₁~ C₆Alkyl, C₁~ C₆Haloalkyl
, C₁~ C₆Alkylsulfonyl, C₁~ C₆Alkylsulfoxyl, C_Three~ C₆Shiku
Lower alkyl, C₁~ C₆Alkoxy, C₁~ C₆Haloalkoxy, C₁~ C₆Alkoki
Cicarbonyl, C₁~ C₆Alkylthio, C₁~ C₆Alkylamino, di-C₁~ C₆ Alkylamino, C₁~ C₆Alkylaminocarbonyl, di-C₁~ C₆Alkyria
Minocarbonyl, C₁~ C₆Alkylaminothiocarbonyl, di-C₁~ C₆Archi
Ruaminothiocarbonyl, C_Two~ C₆Alkenyl, C_Two~ C₆Alkenyloxy,
Benzyl, benzyloxy, aryl, aryloxy, arylthio, heteroa
Reel, heteroaryloxy, heteroarylthio and C (= NOR⁷) -A_n -R⁸May be included). C_Three~ C₆Cycloalkyl, C_Three~ C₆Cycloalkenyl, heterocyclyl, ant
These heterocyclic groups are partially or completely halogenated
Or one to three of the following groups: cyano, nitro, hydroxyl, mel
Capto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, ha
Rogen, C₁~ C₆Alkyl, C₁~ C₆Haloalkyl, C₁~ C₆Alkylsulfoni
Le, C₁~ C₆Alkylsulfoxyl, C_Three~ C₆Cycloalkyl, C₁~ C₆Arco
Kissi, C₁~ C₆Haloalkoxy, C₁~ C₆Alkoxycarbonyl, C₁~ C₆Al
Kircio, C₁~ C₆Alkylamino, di-C₁~ C₆Alkylamino, C₁~ C₆A
Alkylaminocarbonyl, di-C₁~ C₆Alkylaminocarbonyl, C₁~ C₆A
Alkylaminothiocarbonyl, di-C₁~ C₆Alkylaminothiocarbonyl, C _Two ~ C₆Alkenyl, C_Two~ C₆Alkenyloxy, benzyl, benzyloxy, a
Having reel, aryloxy, heteroaryl and heteroaryloxy.
A represents oxygen, sulfur, or hydrogen or C₁~ C₆Represents nitrogen containing alkyl
N represents 0 or 1; R⁷Is hydrogen or C₁~ C₆Represents alkyl; and R⁸Is hydrogen or C₁~ C₆A phenylacetic acid derivative represented by the formula: and salts thereof, and b) Formulas II to XI:

[0003]

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Embedded image A mixture for controlling harmful fungi and insects, comprising at least one insecticide selected from the group consisting of:

[0004] The object of the present invention is to provide a mixture which on the one hand exhibits a good bactericidal action, alone against fungal diseases of rice, above the action of the individual components of the mixture, and on the other hand a good insecticidal action. Is to do. In climatic regions where rice is grown, harmful insects are usually also present, so it is preferable to combine fungicidal and insecticidal activities.

The present inventors have found that the object of the invention is achieved by the mixture of claim 1.

The compounds of the formula I and their preparation are known per se and are described in the literature (WO
97/15552).

Insecticides of the formulas II to XI are also known and disclosed in the literature. In addition, they are commercially available under the trade names in brackets below: II: EP-A 192 060, generic name: imidacloprid (
Product name: Admire (registered trademark) (Admire ^R ), Gauco (registered trademark) (Gaucho ^R )
Bayer (Bayer) Ltd.); III: Generic name: Asetoamipirido: manufactured (acetamiprid) (trade name Mosupiran (TM) (Mospilan ^R), Nippon Soda Co.); IV: RAS RN 120738-89-8, common name : Nitenpyran (nite
npyram) (trade name: Best Garde (registered trademark) (Bestgard ^R), Takeda Chemical
V. Colliot et al., Proc. Br. Conf. Dis. 1 , (1992), 29, Generic name: fipronil (trade name: Legend (registered trademark) (Regent ^R ), Ron) VI: US Pat. No. 3,474,170, US Pat. No. 3,474,171 and DE-C1493646.
A generic name: carbofuran (trade name: Krater (registered trademark) (Cu
raterr ^R), Bayer (Bayer) Ltd .; Furadan (R) (Furadanr ^R), manufactured by F MC); VII:.. .. Proc Br Crop Prot Conf 2 (1979), 557, common name: carbosulfan (Carbosulfan) (trade name: Marshall (registered trademark) (Marshall ^R ), FMC)
Made by the company); VIII:.... FR-A2489329; Proc Int Congr Plant Prot 10th edition, 2 (1983), 360, common name: benfuracarb (benfuracarb) (trade name: on-call (registered trademark) (Oncol ^R) , Otsuka Co., Furakon (TM) (Furacon ^R), Siapa Chem companies made); IX:. CAS RN 111988-49-9 , common name: thiacloprid (th
iacloprid) (a product of Bayer); X: Proc. of the 1998 Brigton Conference "Pests and Diseases", Volume 1,
27-36 (MTI446, manufactured by Mitsui); XI: Proc. Of the 1998 Brigton Conference "Pests and Diseases", Volume 1
, Pages 27-36 (CGA293343, manufactured by Novartis):

Due to the C ＝ C and C ＝ N double bonds of compound I, the preparation of compound I
/ Z isomer mixture is obtained. This mixture can be separated into the individual compounds by customary methods, for example by crystallization or chromatography.

However, if the synthesis results in a mixture of isomers, the individual isomers will interconvert during preparation for use or during use (eg, under the action of light, acid or base). Separation is generally not necessary, as it may be obtained. For example, when treating plants, it is also possible for a similar conversion to take place after application, in the treated plants or in the harmful fungi or animals to be controlled.

Regarding the C ＝ X double bond, the E isomer is preferred from the viewpoint of the action of compound I (−
CO ₂ configurations based on -OCH ₃ or -CH ₃ group regarding R ^1).

For the —C (R ³ ) ＝ NOCH ₂ — double bond, the cis isomer is preferred in view of the action of compound I (configuration based on the group R ³ for the —OCH ₂ group).

In the definition of compounds I mentioned at the outset, the following common terms were used, which generally represent the following groups: halogen: fluorine, chlorine, bromine and iodine; alkyl: 1-4, 1- A linear or branched hydrocarbon group having 6 or 1 to 10 carbon atoms, for example the following C ₁ -C ₆ alkyl, namely methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl Propyl, 2-methylpropyl,
1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3
-Methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,
1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl ;

Haloalkyl: a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups may be replaced by halogen atoms as described above. Examples of such haloalkyl include, for example, the following C ₁ -C ₂ haloalkyl: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl,
Dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-
Fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,
2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl; cycloalkyl: a monocyclic alkyl group having 3 to 6 carbon ring members, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; alkenyl Is a linear or branched alkenyl group having a double bond at any position and having 2 to 6 or 2 to 10 carbon atoms, and examples of such alkenyl include the following C ₂ to C ₆ alkenyl, i.e. ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl -2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2
-Butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl -1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl , 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3 -Methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3
-Pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2
-Methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1 -Butenyl, 1,2-dimethyl-2-butenyl, 1,2
-Dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-
Butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3
-Dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2
-Butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1
-Propenyl and 1-ethyl-2-methyl-2-propenyl;

Alkynyl: a straight chain having a triple bond at any position and having 2 to 10 carbon atoms
A chain or branched alkynyl group, examples of which are: _Two ~ C₆Alkynyl, ie ethynyl, 2-propynyl, 2-butynyl, 3-butynyl
1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pen
Tinyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-
3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl
2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-
Methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pen
Tinyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl
4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-bu
Tinyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,
2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3
-Butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-pro
Pinyl;

Heterocyclyl or heterocyclyloxy, heterocyclylthio and heterocyclylamino: having 1 to 3 heteroatoms selected from oxygen, nitrogen and sulfur atoms and directly or via an oxygen atom (heterocyclyloxy), or a sulfur atom A 3- to 6-membered saturated or partially unsaturated monocyclic or polycyclic heterocyclyl (heterocycle) bonded to the skeleton via (heterocyclylthio) or via a nitrogen atom (heterocyclylamino), for example, 2-tetrahydrofuranyl , Oxiranyl,
3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-
Isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl,
4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-
Pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5
-Thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4
-Oxadiazolidine-3-yl, 1,2,4-oxadiazolidine-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidine-
5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidine-2-yl, 1,3,4-thiadiazolidine-2-yl, 1,3,4- Triazolidine-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,3-dihydrofur-4-yl, 2,3-dihydrofura-5
-Yl, 2,5-dihydrofur-2-yl, 2,5-dihydrofur-3-yl,
2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,
3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl, 2,5-
Dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl , 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl, 2,3- Dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-
Dihydroisoxazol-5-yl, 2,5-dihydroisothiazole-3-
Yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydroisopyrazol-3-yl, 2,3-dihydroisopyrazol-4-yl, 2,3-dihydroisopyrazol-5-yl,
4,5-dihydroisopyrazol-3-yl, 4,5-dihydroisopyrazol-4-yl, 4,5-dihydroisopyrazol-5-yl, 2,5-dihydroisopyrazol-3-yl, 2, 5-dihydroisopyrazol-4-yl, 2,5
-Dihydroisopyrazol-5-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrooxazole-3 -Yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-3-yl, 2,5-dihydrooxazol-4-yl, 2,
5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5
Yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazole-
4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2, 3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5
-Dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazole-
2-yl, 2,5-dihydroimidazol-4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl,
3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1
, 3,5-Tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl, 2-tetrahydropyrani 1,3-dioxolan-2-yl, 3
, 4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazine-2
-Yl, 4H-3,1-benzothiazin-2-yl, 1,1-dioxo-2,3
, 4,5-Tetrahydrothien-2-yl, 2H-1,4-benzothiazine-3
-Yl, 2H-1,4-benzoxazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl;

Aryl or aryloxy, arylthio, arylcarbonyl and arylsulfonyl: directly or through an oxygen atom (—O—) (aryloxy), through a sulfur atom (—S—) (arylthio), a carbonyl group ( —A— or an aromatic monocyclic or polycyclic group bonded to the (arylsulfonyl) skeleton through a sulfonyl group (—SO ₂ —), such as phenyl, naphthyl and phenanthrenyl or phenyloxy. , Naphthyloxy and phenanthrenyloxy, and the corresponding carbonyl and sulfonyl groups; heteroaryl or heteroaryloxy, heteroarylthio, heteroarylcarbonyl and heteroarylsulfonyl: in addition to the carbon ring members, 1 to 4
Or one to three nitrogen atoms and one oxygen or sulfur atom, or one oxygen or sulfur atom, and directly or
-Heteroaryloxy) through a -O-) or (heteroarylthio) through a sulfur atom (-S-), (heteroarylcarbonyl) or a sulfonyl group (- An aromatic monocyclic or polycyclic group bonded to the (heteroarylsulfonyl) skeleton via SO ₂ —), for example a 5-membered heteroaryl containing 1 to 3 nitrogen atoms: in addition to carbon atoms, 5-membered heteroaryl group optionally containing 1 to 3 nitrogen atoms, for example 2-
Pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl,
2-imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl and 1,3,4-triazol-2-yl;

5-membered heteroaryl containing 1-4 nitrogen atoms or 1-3 nitrogen atoms and one sulfur or oxygen atom, or one oxygen or sulfur atom: In addition, a 5-membered ring which may further contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur atom or oxygen atom, or 1 oxygen atom or sulfur atom as a ring member Heteroaryl groups such as 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl,
-Isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl , 5-thiazolyl, 2-imidazolyl, 4-imidazolyl,
1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazole-5
-Yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazole-2 -Yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl; 1 to 3 nitrogen atoms or 1 nitrogen atom and / or 1 oxygen atom or sulfur 5-membered benzofused heteroaryl containing atoms: in addition to carbon atoms, as ring members, 1-
Containing four nitrogen atoms, or one to three nitrogen atoms and one sulfur or oxygen atom, or one oxygen atom, or one sulfur atom and two adjacent carbon ring members or one 5-membered heteroaryl group in which one nitrogen atom and one adjacent carbon ring member may be bridged by a buta-1,3-diene-1,4-diyl group; linked via nitrogen, and 5-membered heteroaryl containing 1-4 nitrogen atoms,
Alternatively, a 5-membered benzofused heteroaryl bonded via nitrogen and containing 1 to 3 nitrogen atoms: containing 1 to 4 and 1 to 3 nitrogen atoms as ring members in addition to carbon atoms, respectively Two adjacent carbon ring members or one nitrogen atom and one adjacent carbon ring member may be bridged by a buta-1,3-diene-1,4-diyl group, A 5-membered heteroaryl group linked to the skeleton through one of the nitrogen ring members;

6-membered heteroaryl containing 1 to 3 and 1 to 4 nitrogen atoms, respectively: in addition to carbon atoms, 1 to 3 nitrogen atoms and 1 to 4 nitrogen atoms as ring members 6-membered heteroaryl groups, each having 2-pyridinyl, 3-pyridinyl, 4
-Pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-
Pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazine-
2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl; 6-membered benzo-fused heteroaryl containing 1-4 nitrogen atoms: 2 6-membered heteroaryl groups in which adjacent carbon ring members may be bridged by buta-1,3-diene-1,4-diyl groups, such as quinoline, isoquinoline, quinazoline and quinoxaline, and the corresponding oxy groups , Thio, carbonyl or sulfonyl groups.

Heteroarylamino: Apart from carbon ring members, further contains 1 to 4 nitrogen atoms, or 1 to 3 nitrogen atoms and one oxygen or sulfur atom, and forms a skeleton via a nitrogen atom. An aromatic monocyclic or polycyclic group to be bonded;

The expression “partially or completely halogenated” means that some or all of the hydrogen atoms of the radical so characterized are replaced by the same or different halogen atoms as defined above. Means that you can.

From the standpoint of biological action, preference is given to compounds of the formula I in which m is 0.

Likewise, preference is given to compounds of the formula I in which R ¹ represents methyl.

In addition, compounds I in which R ³ represents hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF ₃ are preferred.

Furthermore, preference is given to compounds of the formula I in which R ³ represents methyl.

In addition, a compound I in which R ³ represents cyano is preferred.

Furthermore, compounds I in which R ³ represents cyclopropyl are preferred.

Furthermore, compounds I in which R ³ represents CF ₃ are preferred.

Furthermore, compounds I in which R ⁵ represents hydrogen, cyclopropyl, methyl, ethyl, isopropyl, unsubstituted or substituted aryl or heteroaryl are preferred.

Furthermore, compounds I in which R ⁵ represents methyl are preferred.

Furthermore, compounds I in which R ⁵ represents ethyl are preferred.

Furthermore, compounds I in which R ⁵ represents isopropyl are preferred.

Furthermore, compounds I in which R ⁵ represents cyclopropyl are preferred.

Furthermore, compounds I in which R ⁵ represents CF ₃ are preferred.

Furthermore, compounds I in which R ⁵ represents unsubstituted or substituted aryl or heteroaryl are preferred.

Furthermore, compounds I in which R ⁵ represents unsubstituted or substituted pyridyl, pyrimidyl, pyrazinyl, pyridazinyl or triazinyl are preferred.

Furthermore, compounds I in which R ⁵ represents unsubstituted or substituted furyl, thienyl or pyrrolyl are preferred.

Furthermore, compounds I in which R ⁵ represents unsubstituted or substituted oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl or imidazolyl are preferred.

Furthermore, compounds I in which R ⁵ represents unsubstituted or substituted oxadiazolyl, thiadiazolyl or triazolyl are preferred.

Further, R ⁵ is one or two of the following groups: nitro, cyano, hydroxyl, amino, aminocarbonyl, aminothiocarbonyl, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylamino, di -C ₁ -C ₄ alkylamino, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkoxycarbonyl, Preference is given to compounds I which represent phenyl optionally having C ₁ -C ₄ alkylaminocarbonyl or di-C ₁ -C ₄ alkylaminocarbonyl.

Further, when R ⁴ is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, allyl, arylalkyl, heteroarylalkyl, aryloxyalkyl, heteroaryloxyalkyl, Compounds I representing aryl or heteroaryl are preferred.

Furthermore, compounds I in which R ⁴ represents C ₁ -C ₆ alkyl are preferred.

Furthermore, compounds I disclosed in WO 97/15552 are preferred.

The compounds I contained in the mixtures according to the invention have a remarkable effect on a wide range of phytopathogenic fungi, in particular on ascomycetes, incomplete fungi, alga and carrier fungi.

They can be of various cultivated plants, such as cotton, vegetables (eg cucumber, beans, tomatoes, potatoes and cucumber), barley, turf, oats, bananas, coffee, corn, fruits, rice, rye, soy, grapes Of wheat, decorative plants, sugarcane and their seeds are of particular importance.

The novel mixtures are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis, a cereal crop, and Erysiphe cichoraaceae, a Cucurbitaceae family.
arum) and Sphaerotheca fulginea (Sphaerotheca ful)
ignea), Apple Podsphaera leuco tricha (Podsphaera leuco)
tricha), Grape Uncinula necator, Cereals Puccinia species, Cotton, Rice and Shiva Rhizoctonia species, Cereals and Sugarcane Ustilago ostraia, Ustilago ostraia, Ustilago gustria, Ustilago gustria ostigora, Ustilago o. (Venturia inaequalis
Rot), cereals and rice Helminthosporium
) Seeds, wheat Septoria nodorum, strawberries, vegetables, ornamental plants and grape Botrytis kinerea (Botryt)
is cinerea, gray mold), peanut cercospora arachidikola (Cercospora ara)
chdicola), Pseudokercosporella herpotrichoides of wheat and barley (Pse
udocercosporella herpotrichoides, Pyricularia oriza on rice and turf
e) Potato and tomato phytopitra infestation (Phytopht)
hora infestans), Plasmopara viticola of grape (Plasmopara viticola)
), Pseudoperonospora of hops and cucumber
ra) species, Alternaria species of vegetables and fruits, Mycosphaerella species of bananas, and Fusarium and Verticillium
ium) species.

The compounds represented by the formulas II to XI are used for controlling pests such as insects, arachnids and nematodes. They may be used in the protection of crops and in the control of pests in the areas of hygiene, stockpiling and veterinary medicine. In particular, they are suitable for controlling the following pests: Lepidoptera pests include, for example, Agrotis ypsilon, Agrotis segetum, Alabama argilaraea
acea), Anticarcia gemataris (Anticarsia gemma)
talis), Argyresthia conjugera (Argyresthia co.)
njugella), Autographa gamma
a), Bupalus pinialius, Cacoesia murinanas, Capua reticulana, Chematobia burmata
imatobia brumata), Choristoneura fumiferana (Ch
oristoneura fumiferana, Choristoneura occidentalis, Cirphis ununcuncta, Cyrdia pomonella, Denia d'Oro d'Mendro, Denia d'Omondo
rolimus pini), Diaphania nitidaris (Diaphani)
a nitridaris), Diatra Air Grandiosera (Diatr)
aea grandiosella, Ealias insulana, Erasmopalpas lignoseras (Elasmopa)
lpus lignocellus, Oipoesilia ampiguera (Eu)
poecilia ambiguella), Evetria buliana (Eve
tria bouliana, Fertia subterranea (Feltia)
subterranea), Galeria melonera (Galleria mel)
lonella), Graphorita fune
brana), Graholita moresta, (Grapholita molest)
a), Heliothis armigera, Heliotis virescens, Heliothis zea, Helluandalis (Hello)
la undalis, Hibernia defoliaria (Hibernia d)
efoliaria), Hyphantria cunea
nea), Hyponomeuta marineras
lplus), Keiferia lycopersicera (Keifferia lyco)
persicella), Lambdina fisseriaria (Lambdina f)
iscellaria) and Laphygma exigua (Laphygma exi)
gua), Leucoptera coffee
la), Leucoptera sitella
, Lithocolletis blanc
cardella), Lobesia botrana
, Loxostege sticticalis
alis), Lymantria dispar
, Rimantoria-Monacha (Lymantria monacha), Rionechia-Kurerukera (Lyonetia clerkella), Marakosoma-Noisutoria (Malacosoma neustria), Mamesutora-Burashikae (Mamestra brassicae), Orugyia-Pusoidotsugata (Orgyia pseudotsugata), Osutorinia-Nubirarisu (Ostrinia nubilalis), Panorisu・ Flame (Panol)
is Flammea), Pectinophora gossypiera (Pectinop)
hora gossypiella), Peridroma sausia (Peridro)
ma saucia), Phalera buscept
hala), Phthorimaea op.
erculella), Phylocunitis citrela (Phyllocnit)
is citrella), Pieris brassica (Pieris brass)
icae), Platypena scabra
, Plutella xylostella,
Pseudoplusia include
ns), Phyacionia furstrana
ana), Scrobipalpula absolta
soluta), Cittroga cerelera
lla), Sparganothis pil
leriana), Spodoptera frugiperda (Spodoptera fr)
ugiperda), Spodoptera litraris (Spodoptera li)
totoralis), Spodoptera litura
ura), Thaumatopoea piiocampa (Thaumatopoea pi)
tycampa), Tritrix viridana (Tortrix virid)
ana), Trichoplusia ni, and Zeiraphera canadensis.

As the Coleoptera, for example, Agrilas sinuatus (A
grilus sinuatus, Agriotes lineaetus (Agriot)
es lineatus), Agriotes obscurus, Amphimaras Solstitialis (Amphi)
mallus solstitialis, Anisandra dispar (A
nisandrus dispar, Anthonymus grandis (Anth)
onomus grandis), Anthonomus pomolum (Anthonom)
us pomorum), Atomaria lin (Atomaria lin)
earis), Blastfagus piniperda (Blastophagus p.
iniperda), Blitophaga undata
ata), Bruchus rufimanus,
Bruchus pisorum, Bruchus lentis, Bruchus betulae, Cassida nebulosa (Casida nebula)
osa), Cerotoma trifurcata
), Chute Lynch assimilias (Ceuthorhynchus a)
ssimilis), Shootleenkas Napi (Ceuthorrhynch)
us napi), Chaetocnema tibiaryl (Chaetocnema)
tibialis), Conoderas vespertinas (Conoderus v
espertinus), Cryoceris asparagus
asparagi), Diabrotica Longicoronis (Diabrotic)
a longicornis), Diabrotica 12-Punctata (Dia)
brotica 12-puncta), Diabrotica virgifera, Epilashna varivestis, Epitrix hiltipenus epsilon entrepreneurs, Epitrix hirnitsino stipulation.
Hylobius abietis, Hypera bruneipennis, Hypera postica, Ips Tipographas (Ips)
typographhus, Lema bilineat
a), Lema melanopus, Leptinotarsa
Desemlineata (Leptinotarsa decemlineata), Limonius californicus (Limonius californicus)
, Lisorhoptrus oryzophilus
ophilus), Melanotus communis
nis), Meligethes aeneus,
Melonlona hippocastani
), Melolonta melonlonta
, Olema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon achaleta pyreta phyla cochalia phaedon cochalia phaedon cochlea, Phaedon cochalia
, Phyllophaga sp., Phylopertha Horticola, Phyllotreta nemorum, Phyllotreta nemorum
Stylorata (Phyllotreta striolata), Popilia
Japonica (Popillia japonica), Sithona linetas (S
itona lineatus, Sitophilus granaria (Sitophi)
rus granaria).

As Diptera, Aedes aegypti
egypti), Aedes vexans, Anastrepha ludens, Anopheles maculipenis, Ceratitis acrisya crisapati, ceratitis acrisica crisapita crispia crisapita crisapita crisapita crisapita crisapita crispia crispia crisapita crispia crispia crispia crispia crispia crispia crispia crispia crispia crispia crispia crispa crispia crispia crispia crispia crispia crispia crispia crispia crispia crispia crispia cami Chrysomya hominivorax, Chrysomya macellalia, Contarinia sorchikola, Condylonia anthropofaga (Cordylopia rep.) pipiens), Dakasu-Kyukyurubitae (Dacus cucurbitae), Dakasu-Oreare (Dacus
oleae), Dasineura brassica
ae), Fannia canicularis
, Gasterophilus internalis (Gasterophilus i)
ntestinalis), Glossina morcitans (Glossina mo)
rsitans), Haematobia irritance
tans), Haplodiprosis questris, Hylemia platura
tura), Hypoderma lineata,
Liriomyza sativae, Liriomiza
Trifoly (Lilliomiza trifolii), Lucilia caprina, Lucilia cuprina (Lucilia)
cuprina), Lucilia sericata
Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Ostras
trus ovis, Oscinella frit
t), Pegomya hysociami, Phorbia antiqua, Phorbia brassicae, Phorbia brassicae (P)
horbia coarcata), Lagoletis cerasi (Rhagole)
tis cerasi), Lagoletis pomonera (Rhagoletis)
pomonella), Tabanas bovinus (Tabanus bovinus)
), Tipula oleracea, and Tipula paludosa.

As the order Thysanoptera, for example, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tricentiella, Frankliniella
, Siltthrips citri, Trips oryzae, Thrips palmi (Th
rips palmi), Trips tabaci
Belongs.

As Hymenoptera, for example, Asaria rosae (Ath)
alia rosae), Atta cephalotes (Atta cephalotes)
s), Atta sexdens, Ata texana (
Atta texana), Hoplocampa minuta (Hoplocampam)
inuta), Hoplocampa testudinea (Hoplocampate)
studinea), Monomorium pharaonis (Monomorium p.
haraonis), Solenopsis gem
inata), Solenopsis invic
ta) belongs.

As Heteroptera, for example, Acrosternum hilare, Brissas leucopteras (
Blissus leucopterus, Siltpertis notatas (C
yrtopeltis notatus, Disdelkas singlatas (D
ysdercus singulatus, Dysdercus intermedius, Eurygaster integricepts, Eustistus impictives
ntris), Leptoglossus philopes (Leptoglossus)
phyllopus), Lygus lineolais (Lygus lineola)
ris), Lygus platensis, Nezara viridula, Piezma Kadrata (P
esma quadrata), Solubea Insularis (Solubea)
insulinis), Tianta perditol (Thyanta per)
ditor).

[0052] Homoptera include, for example, Acyrthosiphon onobrysis, Adelges laricis, Aphidra nasturti (Ap
Hidula nasturtii), Aphis fabae (Aphis fa)
bae), Aphis pomi, Aphis sambushi (A
phis sambuci, Brachycudas Cardi
audus cardui, Brevicorine Brassicaea (Brevicor)
yne brassicae), Cerrosifa gossypi (Cerosip)
ha gossipii), Dreyfusia Nordmannyanae (Dreyf
usia nordmannianae, Dreyfusia Piscea (Drey
fusia piceae), Dysaphis r.
adicola), Disauracoltum soudsolani (Dysaulacor)
thum pseudosolani), Empoasca Fabae (Empo)
asca fabae), Macrosiphum
avenae), Macrosiphum euphorbia (Macrosiphum e)
uphorbiae), Macrosiphon r.
osae), Megoura viciae, Methoporophium dirhodum, Myzodes persicae, Myzaspa lasiva sicacy
lugens), Pemphigus balsalius (Pemphigus b)
ursarius), Perkinsiel
a saccharicida), Phorodon Humley
humuli), Psylla mali, Psylla piri, Roperomies ascaronicas (Rhopal)
omyzus ascalonicus, Roperocihum maidis (Rh)
opalosiphum maidis), Sapphaphi mara (Sappaph
is mala), Sapphaphis mali, Sizafis graminum, Schizoneura lanuginosa, Triairolodes vapoleario driosa
rum) and Viteus vitifoli belong.

For example, Caroptermes flavicoris (Casoptera)
lotteres flavicollis), Leukothermis flavipes (
Leucotermes flavipes, Reticulitermes lucifugus, and Termes natalensis.

The Orthoptera includes, for example, Achet domestica (Achet)
a domestica), Blatta orientalis (Blatta ori)
entalis), Blattella germana
nica), Forficula auricularia (Forficula au)
ricularia), Glylotalpa Grylotalpa
pa grilllotalpa), Locusta migratoria (Locusta)
migratoria, Melanoplus vibitatas (Melanoplus)
bivittatus), Melanoplus Femur-Rubram (Melanop)
rus femurrubrum), Melanoplus Mexicana (Melan)
opus mexicanus, Melanoplus Sanguineapes (Mela)
noplus sanguinipes, Melanoplus spletas (Mel
annoplus spretus), Nomadarix septemfasciata (
Nomadacris septemfasciata), Periplaneta Americana (Periplaneta americana), Shisutoserusa-Americana (Schistocerca americana), Shisutoserusa-Santuario de la Peregrina (Schistocerca peregrina), Sutauronotasu-Marokkanasu (Stauronotus maroccanus), Takishinesu-Ashinamorasu (Tachycines asynamorus) belongs.

Acarina, such as Amblyma americana
omma americanum), Amblyomma bariegatam (Ambl)
yomma variegatum, Argus persicas (Argas p)
ericus), Bophylus annulatus (Boophilus ann)
ulatus), Boophilus decoloratus (Boophilus deco)
loratus), Boophilus microplus (Boophilus mic)
roplus), Brevipalpus phoenicis
hoenicis), Bryobia praeosa (Bryobia prae)
tiosa), Dermasenthol Silvalam (Dermacentor si)
lvarum), Eotetranychus carpini, Eriophes sheeldni (Eriphys shel)
doni), Hyalomma truncatum
m), Ixodes ricinus, Ixodes ricinus
Rubicandus (Ixodes rubicundus), Ornithodorus moubata (Onithodorus moubata), Otobius megnini (
Otobius megnini, Parateranicus pirosas (Parat)
eranychus pirosus, Dharmanisas galinae (Derm)
anyssus gallinae), Filocaputorta Olaybora (Phy
loccaptruta oleivora), Polyphagotarsonemus latus (Polyphagotarsonemus latus), Psoroptes.
Obis (Psoroptes ovis), Lipicephalus appendiculatus (Rhipicephalus appendiculatus), Lipisphalus evertsea (Rhipipephalus evertsi),
Sarcoptes scabiei, Tetranychus cinnabarinus
, Tetranychus kanzawai,
Tetranychus pacificus
, Tetranychus terarius,
Tetranychus urticae belongs.

As nematodes, for example, rootworm nematodes, for example, meloidogine
oidogyne hapla), meloidogine incognita (Meloi
dogyne incognita), meloidogine Javanica (Melo)
idogyne javanica).

The cyst-forming nematodes include, for example, Globodera lostiensis (Globode)
ra rotochiensis), Heterodera avenae (Heterod)
era avenae), Heterodera gricines
lycines), heterodera shirt tee (Heterodera sch)
atii), Heterodera trifol
ii) Stem and leaf nematodes include, for example, Veronolymes longi caudatus (Be
lonolaimus longicaudatus, Ditylenchus destructor, Ditylencus destructor
Ditylenchus dipsaci, Heliocotilencus multicintus
tus), Longidolas elongatus (Longidoras elonga)
tus), Radophorus similis
, Rotylencus robustus,
Trichodrus primitivu
s), Tyrencholynchus c
laytoni), Tylenchorincus dobius
hus dubius, Pratilenkas negrektus
chus neighbors, Pratilenkas penetrance (Prat)
Yellenus penetrans, Pratilencus curvitatas, and Pratilenchus goodyi.

Under the conditions of the application area, the application rate of the active ingredient for controlling pests is usually 0.01 to 2.0 kg per hectare (0.01 km ² ), and 0.02 to 1 kg. . 0 kg is preferred.

It is particularly preferred that the mixtures according to the invention can be used for controlling plant diseases and harmful insects in rice.

The compound I and at least one of the compounds II to XI can be applied simultaneously, jointly or separately, or continuously, and the order of application when applied separately generally controls. The outcome is not affected.

Depending on the nature of the desired effect, the application rates with the mixtures according to the invention are, in particular in crops, from 0.01 to 8 kg per hectare, preferably from 0.1 to 5 kg, especially from 0.5 to 5 kg. ~ 3.0 kg is desirable.

The application rates of compound I are from 0.01 to 2.5 kg per hectare,
It is preferably from 0.5 to 2.5 kg, particularly preferably from 0.1 to 1.0 kg.

When treating seed, the application rate of the mixture is generally 0.001 kg of seed.
1 to 250 g, preferably 0.01 to 100 g, particularly preferably 0.01 to 50 g.

When controlling harmful fungi that are pathogenic to plants, they can be sprayed or sprayed on seeds, plants or soil separately or together before or after sowing or before or after germination. Is applied with compound I and compounds II to XI or at least one mixture of compound I and compounds II to XI.

The mixtures according to the invention can, for example, be in the form of solutions, powders, suspensions which can be directly sprayed on,
Alternatively, it can be prepared in the form of concentrated aqueous, oily or other suspensions, dispersions, emulsions, oily dispersions, pastes, dusts, dusts or granules, and can be sprayed, misted or dusted It can be applied by spraying or pouring. The form of use is determined based on the purpose of use. In each case, it should be ensured that the distribution of the mixture according to the invention is as fine and uniform as possible.

The preparations are obtained in a known manner, for example by extending the active ingredient with solvents and / or carriers, if necessary using emulsifiers and dispersants. If water is used as the diluent, another organic solvent can be used as an auxiliary solvent. Auxiliaries for this include: solvents such as aromatics (eg, xylene), chlorinated aromatics (eg, chlorobenzene), paraffins (eg, petroleum fractions), alcohols (eg, , Methanol, butanol), ketones (eg, cyclohexanone), amines (
E.g. ethanolamine, dimethylformamide) and water; carriers such as natural rock powder (e.g. kaolin, clayey soil, talc, chalk), synthetic rock powder (e.g. highly dispersible silica gel, silicate); emulsifiers, e.g. Nonionic and anionic emulsifiers (eg, polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates), and dispersants, such as lignin sulfite waste liquors and methylcellulose, are relevant.

Examples of the surfactant include the following. Aromatic sulfonic acids (eg, lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, dibutylnaphthalenesulfonic acid), and alkali metal salts, alkaline earth metal salts and ammonium salts of fatty acids, alkyl sulfonates, alkyl aryl sulfonates , Alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, and salts of sulfated hexadecanol, heptadecanol and octadecanol, or salts of fatty alcohol glycol ethers, sulfonated naphthalene and its derivatives and formaldehyde. Condensation products, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated-isooctylpheno Octylphenol or nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohol, isotridecyl alcohol, fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxy Propylene, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin-sulfite waste liquor or methylcellulose.

The powder, dusting and dusting agent comprises at least one of the compound I and the compounds II to XI
It can be prepared by mixing or milling together a species, or a mixture of at least one compound I and compounds II to XI, with a solid carrier material. Granules (eg, coated granules, impregnated granules, and homogeneous granules) can generally be prepared by binding the active ingredient to a solid carrier.

The filler or solid carrier may be, for example, a mineral earth (eg, silica, silica, silica gel, silicate, talc, kaolin, limestone, lime, chalk, bolus, calcareous yellow clay,
Clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic resin), fertilizers (eg, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea), vegetable products (eg, cereal flour, bark, wood and Walnut flour), cellulose powder or other solid carrier material.

In general, the preparations comprise from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of one of the compounds I and at least one of the compounds II to XI, or of the compounds I and II to XI At least one mixture of At this time, the active ingredient has a purity of 90.
-100%, especially 95-100% (according to NMR or HPLC spectrum).

[0071] At least one compound, mixture or corresponding preparation of compound I and compounds II to XI may be used as a harmful fungus, in its habitat, or in plants, seeds, soil,
Regions, materials or spaces, the bactericidal effect of the mixture, or if applied separately,
It is applied by treatment with at least one fungicidally effective amount of compound I and compounds II to XI.

The application can be carried out before or after infection with the harmful fungi.

Examples of preparations containing the active ingredient are shown below: A solution comprising 90 parts by weight of active ingredient and 10 parts by weight of N-methylpyrrolidone, preferably used in the form of microdroplets; II. 20 parts by weight of active ingredient, 80 parts by weight of xylene, 10 parts by weight of ethylene oxide of oleic acid N-monoethanolamide (1 mol) (8 to 10 mol)
A mixture consisting of the adduct, 5 parts by weight of a calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of an adduct of castor oil (1 mol) with ethylene oxide (40 mol);
This solution is finely dispersed in water to obtain a dispersion; III. 20 parts by weight of active ingredient, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol and 20 parts by weight of castor oil (1 mol) ethylene oxide (
40 mol) aqueous dispersion consisting of the adduct; IV. 20 parts by weight of active ingredient, 25 parts by weight of cyclohexanol, 65 parts by weight of mineral oil fraction (boiling point: 210-280 ° C.) and 10 parts by weight of castor oil (1 mol)
An aqueous dispersion comprising an ethylene oxide (40 mol) adduct of 80 parts by weight of the active ingredient, 3 parts by weight of sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of sodium salt of ligninsulfonic acid (obtained from waste sulfite) and 7 parts by weight of finely divided silica gel, A mixture which is ground in a hammer mill; by finely dispersing this mixture in water,
A spray mixture is obtained; VI. A homogeneous mixture (blend) consisting of 3 parts by weight of active ingredient and 97 parts by weight of finely divided kaolin; this dust contains 3% by weight of active ingredient; VII. A homogeneous mixture of 30 parts by weight of active ingredient, 92 parts by weight of finely divided silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel; a preparation having good adhesion to the active ingredient VIII. 40 parts by weight of active ingredient, 10 parts by weight of sodium salt of phenolsulfonic acid / urea / formaldehyde condensate, stable aqueous dispersion consisting of 2 parts by weight of silica gel and 48 parts by weight of water; this dispersion is further diluted IX. 20 parts by weight of active ingredient, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of sodium salt of phenolsulfonic acid / urea / formaldehyde condensate and 88 parts by weight A stable oily dispersion composed of paraffinic mineral oil.

The synergy of the mixtures according to the invention was demonstrated by the following experiments: The active ingredients were separately separated as emulsions at a concentration of 10% by weight in a mixture consisting of 63% by weight of cyclohexanone and 27% by weight of an emulsifier. Or together and diluted accordingly with water to obtain the desired concentration.

Evaluation was performed by measuring the damaged leaf surface in%. This percentage was converted to potency. The efficacy ( W ) is determined by the following Abbot equation.

Abbott's formula: W = (1−α) · 100 / β In the above formula, α is the damage (%) of the treated plant by fungi, and β is the damage of the untreated (control) plant by fungi (%) ) And.

A potency of 0 indicates that the treated plant suffered the same damage as the untreated plant,
Efficacy 100 indicates that the treated plants were not damaged at all.

Depending on the mixture of active ingredients, the expected potency is determined by the Colby formula [RS Colby
, Weeds 15 , pp. 20-22 (1967)] and compared to the actually observed potency.

Colby's formula: E = x + y−x · y / 100 where E is the expectation expressed as a percentage of the untreated control when using a mixture of active ingredients A and B at concentrations a and b. X is the potency (%) expressed as% of the untreated control when the active ingredient A is used at the concentration a, and y is the potency when the active ingredient B is used at the concentration b. , Potency (%) relative to untreated control, respectively.

[Use Example 1] Effect on Pyricularia oryzae (Protection) Potato-planted rice seedling (Tai-Nong 67 equivalent) leaves 10% active ingredient, 63% cyclohexanone and 27% An aqueous preparation of the active ingredient prepared from the stock solution comprising the emulsifier was sprayed until the solution drip. The next day, the plants were sprayed with an aqueous spore suspension of P. oryzae. The test plants were then stored in a climatized chamber at 22-24 ° C. and relative humidity (95-99%) for 6 days. The growth rate of the fungi on the leaves was visually evaluated.

The value measured visually for the percentage of damaged leaf surface (%) was converted to potency as% of untreated control. A potency of 0 indicates the same damage as the untreated control and a potency of 100 indicates 0% damage. The expected efficacy of the combined active ingredients was determined by the Colby formula (Colby, SR "Calculating synergistic
and antagonistic responses of herbicide combinations ", Weeds, 15, 20-22
P., 1967) and compared to the efficacy actually observed.

The following compounds I ′ were used as component a):

[0083]

Embedded image

The experimental results are shown in Tables 1 and 2 below:

[0085]

[Table 1]

[Table 2] ^* Calculated by Colby's formula

The experimental results show that the potency actually observed at all mixing ratios is higher than the potency previously calculated by Colby's equation.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 47/40 A01N 47/40 Z 51/00 51/00 (81) Designated country EP (AT, BE, CH) , CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ) , TM), AL, AU, BG, BR, BY, CA, CN, CZ, GE, HU, ID, IL, IN, JP, KR, KZ, LT, LV, MK, MX, NO, NZ, PL , RO, RU, SG, SI, SK, TR, UA, US, ZA (72) Inventor Sauter, Hubert Germany, D-68167, Mannheim, Nekar Promenade, 20 ( 72) Inventor Ammerman, Eberhardt Germany, D-64646, Hepenheim, Von-Gagern-Strasse, 2 (72) Inventor Lorenz, Giesera Germany, D-67434, Neustadt, Erlenweg, 13 (72) Inventor Stratman , Siegfried Germany, D-67117, Limburger Hof, Donersbergstrasse, 9F term (reference) 4H011 AA01 BA01 BA06 BB06 BB09 BB10 BB11 BB13 BC01 BC03 BC05 BC06 BC07 BC09 BC14 BC18 BC19 BC20 BC22 DA02 DA13 DA14 DA15 DA16 DC10 DD03 DE15 DH10 [Continued from summary] Embedded image Embedded image Embedded image Embedded image Embedded image A mixture for protecting cultivated plants, comprising at least one compound represented by the formula (1) in a synergistic effect amount.

Claims (4)

[Claims] 1. As active ingredients: a) Formula I:[However, X is NOCH_Three, CHOCH_Three, CHCH_ThreeY represents O, NR; R¹, R are each independently of one another hydrogen or C₁~ C_FourR represents alkyl;^TwoIs cyano, nitro, trifluoromethyl, halogen, C₁~ C_FourAlkyl or C₁~ C_FourM represents 0, 1 or 2, and when m is 2, a group R^TwoMay be different from each other; R^ThreeIs hydrogen, cyano, C₁~ C_FourAlkyl, C₁~ C_FourHaloalkyl, C_Three~ C₆R represents cycloalkyl;^Four, R⁶Are independently of each other hydrogen, C₁~ C_TenAlkyl, C_Three~ C₆Cycloalkyl, C_Two~ C_TenAlkenyl, C_Two~ C_TenAlkynyl, C₁~ C_TenAlkylcarbonyl, C_Two~ C_TenAlkenylcarboni
Le, C_Three~ C_TenAlkynylcarbonyl or C₁~ C_TenAlkylsulfonyl ｛these
May be partially or completely halogenated, or may have from 1 to 3
Groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, amino
Nocarbonyl, aminothiocarbonyl, halogen, C₁~ C₆Alkyl, C₁~ C₆ Haloalkyl, C₁~ C₆Alkylsulfonyl, C₁~ C₆Alkylsulfoxyl,
C₁~ C₆Alkoxy, C₁~ C₆Haloalkoxy, C₁~ C₆Alkoxycarbonyl
, C₁~ C₆Alkylthio, C₁~ C₆Alkylamino, di-C₁~ C₆Alkylam
No, C₁~ C₆Alkylaminocarbonyl, di-C₁~ C₆Alkylaminocarboni
Le, C₁~ C₆Alkylaminothiocarbonyl, di-C₁~ C₆Alkylaminothio
Carbonyl, C_Two~ C₆Alkenyl, C_Two~ C₆Alkenyloxy, C_Three~ C₆Cyclo
Alkyl, C_Three~ C₆Cycloalkyloxy, heterocyclyl, heterocyclyl
Xy, benzyl, benzyloxy, aryl, aryloxy, arylthio,
Heteroaryl, heteroaryloxy and heteroarylthio (their cyclic
Groups may be partially or completely halogenated, or 1-3
The following groups of: cyano, nitro, hydroxyl, mercapto, amino, carboxy
, Aminocarbonyl, aminothiocarbonyl, halogen, C₁~ C₆Alkyl,
C₁~ C₆Haloalkyl, C₁~ C₆Alkylsulfonyl, C₁~ C₆Alkylsulfo
Kisil, C_Three~ C₆Cycloalkyl, C₁~ C₆Alkoxy, C₁~ C₆Haloalkoki
Si, C₁~ C₆Alkyloxycarbonyl, C₁~ C₆Alkylthio, C₁~ C₆Al
Killamino, di-C₁~ C₆Alkylamino, C₁~ C₆Alkylaminocarbonyl
, Di-C₁~ C₆Alkylaminocarbonyl, C₁~ C₆Alkylaminothiocarbo
Nil, di-C₁~ C₆Alkylaminothiocarbonyl, C_Two~ C₆Alkenyl, C_Two ~ C₆Alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, heteroaryl, heteroaryloxy, heteroarylthio
E or C (= NOR⁷) -A_n-R⁸Aryl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroaryl,
Loarylcarbonyl or heteroarylsulfonyl. These groups are partially
Or even completely halogenated, or 1-3 of the following groups: cyano, d
Toro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl,
Aminothiocarbonyl, halogen, C₁~ C₆Alkyl, C₁~ C₆Haloalkyl,
C₁~ C₆Alkylcarbonyl, C₁~ C₆Alkylsulfonyl, C₁~ C₆Alkyl
Sulfoxyl, C_Three~ C₆Cycloalkyl, C₁~ C₆Alkoxy, C₁~ C₆Haloa
Lucoxy, C₁~ C₆Alkyloxycarbonyl, C₁~ C₆Alkylthio, C₁~ C₆Alkylamino, di-C₁~ C₆Alkylamino, C₁~ C₆Alkylaminocarbonyl, di-C₁~ C₆Alkylaminocarbonyl, C₁~ C₆Alkylaminothi
Ocarbonyl, di-C₁~ C₆Alkylaminothiocarbonyl, C_Two~ C₆Alkene
Le, C_Two~ C₆Alkenyloxy, benzyl, benzyloxy, aryl, aryl
Ruoxy, heteroaryl, heteroaryloxy or C (= NOR⁷) -A_n-R⁸Represents｝ which may have: R^FiveIs hydrogen, C₁~ C₆Alkyl, C_Two~ C₆Alkenyl, C_Two~ C₆Alkynyl—the charcoal of these groups
The hydride group can be partially or completely halogenated, or 1-3
The following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl
, Aminocarbonyl, aminothiocarbonyl, halogen, C₁~ C₆Alkylam
Nocarbonyl, di-C₁~ C₆Alkylaminocarbonyl, C₁~ C₆Alkylam
Notthiocarbonyl, di-C₁~ C₆Alkylaminothiocarbonyl, C₁~ C₆Al
Killsulfonyl, C₁~ C₆Alkylsulfoxyl, C₁~ C₆Alkoxy, C₁~ C₆Haloalkoxy, C₁~ C₆Alkoxycarbonyl, C₁~ C₆Alkylthio, C₁~ C₆Alkylamino, di-C₁~ C₆Alkylamino, C_Two~ C₆Alkenylo
Kissi, C_Three~ C₆Cycloalkyl, C_Three~ C₆Cycloalkyloxy, heterocyclyl
, Heterocyclyloxy, aryl, aryloxy, aryl-C₁~ C_FourA
Lucoxy, arylthio, aryl-C₁~ C_FourAlkylthio, heteroaryl,
Heteroaryloxy, heteroaryl-C₁~ C_FourAlkoxy, heteroaryl
Thio, heteroaryl-C₁~ C_FourAlkylthio (for these cyclic groups,
Even if partially or completely halogenated and / or from 1 to 3
: Cyano, nitro, hydroxyl, mercapto, amino, carboxyl, amino
Carbonyl, aminothiocarbonyl, C₁~ C₆Alkyl, C₁~ C₆Haloalkyl
, C₁~ C₆Alkylsulfonyl, C₁~ C₆Alkylsulfoxyl, C_Three~ C₆Shiku
Lower alkyl, C₁~ C₆Alkoxy, C₁~ C₆Haloalkoxy, C₁~ C₆Alkoki
Cicarbonyl, C₁~ C₆Alkylthio, C₁~ C₆Alkylamino, di-C₁~ C₆ Alkylamino, C₁~ C₆Alkylaminocarbonyl, di-C₁~ C₆Alkyria
Minocarbonyl, C₁~ C₆Alkylaminothiocarbonyl, di-C₁~ C₆Archi
Ruaminothiocarbonyl, C_Two~ C₆Alkenyl, C_Two~ C₆Alkenyloxy,
Benzyl, benzyloxy, aryl, aryloxy, arylthio, heteroa
Reel, heteroaryloxy, heteroarylthio and C (= NOR⁷) -A_n -R⁸May be included). C_Three~ C₆Cycloalkyl, C_Three~ C₆Cycloalkenyl, heterocyclyl, ant
These heterocyclic groups are partially or completely halogenated
Or one to three of the following groups: cyano, nitro, hydroxyl, mel
Capto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, ha
Rogen, C₁~ C₆Alkyl, C₁~ C₆Haloalkyl, C₁~ C₆Alkylsulfoni
Le, C₁~ C₆Alkylsulfoxyl, C_Three~ C₆Cycloalkyl, C₁~ C₆Arco
Kissi, C₁~ C₆Haloalkoxy, C₁~ C₆Alkoxycarbonyl, C₁~ C₆Al
Kircio, C₁~ C₆Alkylamino, di-C₁~ C₆Alkylamino, C₁~ C₆A
Alkylaminocarbonyl, di-C₁~ C₆Alkylaminocarbonyl, C₁~ C₆A
Alkylaminothiocarbonyl, di-C₁~ C₆Alkylaminothiocarbonyl, C _Two ~ C₆Alkenyl, C_Two~ C₆Alkenyloxy, benzyl, benzyloxy, a
Having reel, aryloxy, heteroaryl and heteroaryloxy.
A represents oxygen, sulfur, or hydrogen or C₁~ C₆Represents nitrogen containing alkyl
N represents 0 or 1; R⁷Is hydrogen or C₁~ C₆Represents alkyl; and R⁸Is hydrogen or C₁~ C₆A phenylacetic acid derivative represented by the formula: and salts thereof, and b) Formulas II to XI: Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded imageA mixture for protecting cultivated plants, comprising a synergistic effect amount of at least one compound represented by the formula: 2. One part comprising Compound I in a solid or liquid carrier and the other part comprising at least one of Compounds II to XI in a solid or liquid carrier.
A fungicide mixture according to claim 1, consisting of two parts. 3. Use of the fungicide composition according to claim 1 or 2 to produce harmful fungi,
A method for controlling harmful fungi treating the material, plant, seed, soil, area or space to be protected from the habitat or fungal infection, comprising applying compound I and at least one of compounds II to XI , Simultaneously, together, separately or sequentially. 4. The compound I according to claim 1, wherein the amount of the compound I is 0.005 per hectare.
4. The method of claim 3, wherein ~ 1 kg is used to treat the harmful fungus, its habitat, or the plant, seed, soil, area, material or space to be protected therefrom.