TW520273B - Fungicidal mixtures based on tris (oxime ether) derivatives and resistance inducers - Google Patents

Abstract

Fungicidal mixtures, comprising as active components (a) phenyl acetic acid derivatives of the formula I, in which the substituents and the index are each as defined in the description, and salts thereof, and (b) at least one compound of the formulae II to III in a synergistically effective amount.

Description

520273 V. Description of the invention (1 The present invention is for controlling the killing of harmful fungi) a) Phenylacetic acid derivatives and bacteria mixtures of formula I, including R3 R, crN '(R2) m (I) 〇 Ministry of Economic Affairs wisdom Printed by the Consumer Cooperative of the Property Bureau, where the substituents and parameters have the following definitions: X is NOCH3, CH0CH3, CHCH3; Y is 0, NR; R, R are hydrogen and Ci-C4, respectively; R2 is cyano , Nitro, trifluoromethyl, halogen, alkyl and alkoxy; m is 0, 1 or 2, where r 2 may be different if m is 2; R3 is hydrogen, cyano, CVC4 alkyl, CrC4 halofluorenyl, C3-C6 cycloalkyl; R4, R6 are each hydrogen, CrCw alkyl, C3-C6 cycloalkyl, c2_C1 () fluorenyl, C2-C10 block, alkylcarbonyl, c2_c1G 晞 carbonyl , C3-C1Q alkynylcarbonyl or (^-(: ... alkanefluorenyl) groups, where these groups may be partially or completely halogenated or may be carried to two of the following groups ... Amine group, carboxyl group, amine carbonyl group, amine thiocarbonyl group, gluconic acid, c 1 _ C 'pit group' Crcm 'Cl-C6, pit group' Ci_C6 group succinyl group, Cl-c6 group oxy group, Cl_d tiger Oxygen, Cl_C6 oxocarbonyl, -4-

Five Description of the invention (2) C 1-C 6 alkylthio group, C i-c 6 alkylamino group C 1-C 6 alkylamino group

Di-C 1-C 6 amine amine group, ci-c 6 amine amine thiocarbonyl group, di-CVC6 alkylamine thiocarbonyl group, C2-C6 fluorenyl group, c2_C6 alkenyloxy group, C3-C 6 cycloalkyl group, c 3 c 6 cycloalkoxy, heterocyclyl, heterocyclyl, fluorenyl, benzyloxy, aryl, aryloxy, arylthio, heteroaryl, heteroaryloxy and heteroarylthio, where The cyclic group of this part may be partially or completely self-chemical or may carry one to three of the following groups: cyano, nitro, hydroxy, fluorenyl, amine, carboxyl, aminecarbonyl, aminethiocarbonyl, halide, Ci-C6 alkyl, CrCd alkyl, C6 C6 alkylsulfonyl, sulfinylsulfenyl, c3-c6 cycloalkyl, C6 C6 alkoxy, Cl-C6 alkyloxy, C i-C 6 alkoxycarbonyl, C 1 _ C 6 alkylthio, ci-c 6 alkylamino, mono-Ci-C6-: fe amino, Ci-C6 ammonium carbonyl, di-Ci-Ce amine carbonyl, C i-C 6 alkylamine thiocarbonyl, di-C!-C 6 alkylamine thiocarbonyl, C2-C6 fluorenyl, C2-C6 alkoxy, henyl, henyloxy, aryl, aryloxy, aryl Thio, heteroaryl, heteroaryloxy, heteroarylthio, or C (= NOR7) -An-R8; square, square, aryl, aryl, heteroaryl, heteroaryl, or hetero Sulfonyl groups, where these groups may be partially or completely self-chemical or may carry one to three of the following groups: cyano, nitro, hydroxy, thiol, amine, alkyl, aminocarbonyl, aminethiocarbonyl, halogen, ci-C 6 alkyl, C 1-c 6 -alkynyl, Ci-Ce alkylcarbonyl, CrC6 alkylsulfonyl, K6 alkylsulfinyl, C3-C6 cyclyl, Ci-CJ oxygenation, Ci -C ^ halohaloxy, ci-C 6 alkoxycarbonyl, C i-C 6 alkylthio, ci-C 6 alkylamino, di-C 1-C 6 -pit amino, C 1-C 6 Fe amine peptyl, di-ci · C 6 amine coagulation basic paper size applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 520273 A7 _ B7 5. Description of the invention (3), CrCs alkylamine sulfur Carbonyl, di-cvc6 alkylamine thiocarbonyl, c2-C6 fluorenyl, C 2-c 6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, heteroaryl, heteroaryloxy or C ( = N〇R7) -An-R8 ·, R5 is hydrogen,

Cj-Cg xyl, C2_C6 fluorenyl, C2-C6 alkynyl, where the hydrocarbon groups of these groups may be partially or completely fluorinated or may carry one to three of the following groups: cyano, nitro, hydroxyl, fluorenyl, amine Group, carboxyl group, amine carbonyl group, amine thiocarbonyl group, halogen, c 1 -C 6 alkylcarbonyl group, di_ci _ c 6 alkylamine carbonyl group, CVC6 alkylamine thiol group, di-CVC6 alkylamine thiocarbonyl group, (^ -(^ Alkylsulfonyl, C6C6 alkylsulfinyl, Ci-C ^ alkoxy, Crq haloalkoxy, C6 C6alkoxycarbonyl, C!-C6 alkylthio, ci- c 6 alkylamino, di-CrC6-fluorenylamino, c2-c6 # oxy, (: 3-06 cycloalkyl, C 3-C 6 cycloalkoxy, heterocyclyl, heterocyclooxy, aromatic Aryl, aryloxy, aryl-CVC4 alkoxy, arylthio, aryl-Ci-C4-alkylthio, heteroaryl, heteroaryloxy, heteroarylalkoxy, heteroarylthio, Heteroaryl-C 1 -C 4 sulfanyl, in which the ring group may be partially or completely drawn and / or may carry one to three of the following groups: cyano, nitro, hydroxyl, thiol, amine Alkyl, carboxyl, amine carbonyl, amine thiocarbonyl, C, c6 alkyl, C, c6 haloalkyl, Ci-Cs alkylsulfonyl, Ci-C ^ Group, c 3-C 6 cycloalkyl group, ci-C 6 alkoxy group, C!-C 6 halooxy group, C 1-C 6 fe oxycarbonyl group, C i-C 6 thio group, C i- C 6 fluorenylamino, di-C! -C 6 -alkylamino, ci-C 6 alkylamine carbonyl, di_C! -C 6 alkylamino, ci-C 6 amine thiocarbonyl, di-ci -C 6 amine thiocarbonyl, C2-C6 fluorenyl, C2-C6 fluorenyl, benzyl, octyloxy, aryl, this paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (Please read the precautions on the back --- f to fill out this page) Order the print of 520273 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the description of the invention (4) Aryloxy, arylthio, heteroaryl, heteroaryloxy Group, heteroarylthio group and C (= NOR7) -An.R8; c3-c6% jfe group, C3.C6 cycloalkenyl group, heterocyclic group, aryl group, heteroaryl group, among which the cyclic group may be partially or completely Toothed or may carry-to three of the following groups: cyano, nitro, hydroxyl, mercapto, amine, carboxyl, amine carbonyl, amine, radical, sulfonium, Ci_c6 alkyl, radical, alkylsulfonyl, Ci-C6 alkylsulfinyl fluorenyl, c3_c6 cycloalkyl, alkoxy, cvcw fluorenyl, Ci-C6: i Thio group, CrC6 alkylamino group, di-C6-alkylamino group, υ6 alkylamine carbon group, di-Crh alkylamine carbonyl group, Ci-C6 alkylamine thiocarbonyl group, di-alkylamine f carbonyl group, c2_c6 alkenyl group, c2_c6 alkenyloxy, fluorenyl, fluorenyloxy, aryl, aryloxy, heteroaryl, and heteroaryloxy; wherein A is oxygen, sulfur, or nitrogen and wherein nitrogen bears hydrogen or Ci_C6 alkyl; η is 0 Or 1; R7 is hydrogen alkyl and R8 is hydrogen or c 丨 -c 6 hydrazine, and its salt, and b) at least one fungicide is selected from the group consisting of formulae 11 to 11] [Vinckicide ° VSNck α > ^ --- (Please read the notes on the back and fill out this page) Order ·· Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (II)

520273

och2ch = ch2. (Please read the note on the back first? ΐ ΐ) The subject of the present invention is to provide a fungicidal mixture, which has a good activity that exceeds the activity of the ingredients in the mixture, especially against rice fungi. We found that The subject matter can be achieved by applying the mixture requested in item i of the patent scope. The compounds of the formula I are known per se and are described in the literature (WO 97/15552). The fungicides of the formulae II to III are also known See also in the literature. In addition, they may be sold commercially as # · ΙΙ · ΕΡ 313,512 according to the trade names described in the following paragraphs, and the common name is suggested: acibenz〇iar (trade name: Bion®, from Novartis) HI: Common name: pirobabenazole (commercial name: ryzamate < g), from Meij i S eika) Due to the C = C and C = N double bonds of compound I, compound 1 can be obtained as an E / z isomer. It is obtained as a mixture, which can be separated into individual compounds in a conventional manner, such as crystallization or chromatography. If a mixture of isomers is synthesized, separation is usually not required, because in some cases the isomers can be converted into each other during formulation or application (such as exposure, acid or base). Similar transformation effects can also occur after application. For example, when treating plants, this paper is applicable to _Α4 size ⑽ x 297.) Installed --- f fill in this page) Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperative 520273 V. Invention Note (6) The employee cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs print or print harmful pests or control animal pests. From the perspective of c = x double bond, compound-type isomers have the -0Ch3 or _Ch3 group as the main configuration relative to -C02R1). From the point of view of -C (R3) = NOCH2_ double bond, the ‘compound… 嗔 -isomer system has better activity (the main configuration is the R3 group relative to the —OCHr group). In the initial definition of Compound I, the collective terms used often represent the following substituents: Element I: fluorine, gas, bromine, and iodine; alkyl: straight or branched chain of 1 to 4, 6, or 10 carbon atoms Alkyl, such as CrCr alkyl, such as methyl, ethyl, propyl, methyl ethyl, butyl, 1-methylpropyl, 2-methylpropyl, Methyl, pentyl, methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 · ethylpropyl, hexyl, dimethylpropyl, 2 • dimethylpropyl, p-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-fluorenylpentyl, 1, dimethyldimethylbutyl, 1,2-dimethylbutyl Methyl, -dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, ethylbutyl, 2-ethylbutyl , 15l, 2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and ethyl-2-methylpropyl; halogen: fe group: 1 to 6 carbon atoms of the above straight or branched chain alkyl groups, wherein these groups-some or all of the hydrogen atoms can be replaced by the above _ atoms, such as ci_Cr self-burning , Such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethyl, difluorofluoromethyl, chlorodifluoromethyl, trifluoromethyl Base, 2-chloroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-gas-2,2-difluoroethyl 、 2,2-Digas-2 -Fluoroethyl-9- This paper is suitable for Chinese National Standard (CNS) A4 (210 X 297 mm). (Please read the notes on the back first and fill in this page) Binding · 520273 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4-hexenyl, 5-hexenyl, 3-methyl-1-pentenyl, 2-methyl-2-pentenyl, 1- Methyl-3-pentenyl, 4-methyl-3-pentenyl, 3-methyl-4-pentenyl 4-methyl-1 -pentenyl 3-methyl-2 -pentyl Fluorenyl 2-methyl-3 -pentenyl 1 -methyl-4-pentenyl 4-methyl-4-pentenyl A7 B7 V. Description of the invention (methyl, 2,2,2-trichloroethyl And pentafluoroethyl; cycloalkyl: monocyclic alkyl with 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; alkenyl: unsaturated straight or branched chain and With 2 to 6 or 10 carbon atoms and Hydrocarbyl groups having a double bond at any position, such as C2-C6-alkenyl such as vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 丨 butenyl, 2.butenyl, 3-butyridinyl, 1-methyl-propenyl, 2-methyl-propenyl, ^ methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-i-butenyl, 2-fluorenyl-butenyl, 3-methyl-1-butenyl, 1 -Methyl-2-butenyl, 2-methyl-2-butynyl, 3-methyl-2-butanyl, 1-methyl-3-butanyl, 2-methyl-3-butynyl Group, 3-methyl-3-butenyl, i, fluorene-dimethyl · 2-propenyl, 12-dimethyl-1-propenyl, 1,2-dimethyl-1-propenyl , 丨 ethylpropenyl, 1-ethyl-2_propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-methyl-1-pentenyl, 2- Methyl-1-pentamidine 1 -methyl-2 -pentene 4-methyl-2-pentane · 3-methyl-3-pentyl 2-methyl-4 -pentyl 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 ,; Ι, 3_dimethyl_1_butenyl, 1,3-dimethyl_2_butenyl, 1,3-dimethyl_3_butenyl, 2,2-difluorenyl -3-butenyl, 2,3-dimethyl-1-butenyl, 2,3_dimethyl 10- (Please read the note on the back first? Matters refill this page}

520273 Α7 ---- B7 V. Description of the invention (8) group-2_butylfluorenyl, 2,3-dimethyl · 3-butenyl, 3,3-dimethyl- 丨 -butylfluorenyl ^ -dimethyl-2- -Butenyl ~ ethylethyl "-butenyl ~ ethylethyl-butylamino, 1-ethyl-3_butenyl, 2-ethyl-1_butenyl, 2-ethyl-2-butynyl, 2 · Ethyl-3 · butenyl, -trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, ethyl-2-fluorenyl j · propenyl and 丨 _ Ethyl-2-methyl-2-propanyl; decanyl: a straight or branched hydrocarbon group having 2 to 10 carbon atoms and a triple bond at any position, such as a C2-C6-alkynyl group such as ethynyl , 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentyl, 3-pentynyl, 4-pentynyl, 4-methyl _2-Butyl, ^ methyl-3-butynyl, 2-methyl-3-butynyl, 丨,! -Dimethyl-2-propynyl, 丨 -ethyl_2_propane Alkynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, fluorenyl-2_pentyl, 1-methyl-3_pentynyl, 丨 _methyl _4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentyl Alkynyl, 4-fluorenyl-2-pentyl, 1,1-dimethyl · 2-butynyl, υ-dimethyl-3 -butynyl, 1,2-dimethyl-3-butene Alkynyl, 2,2-dimethyl-3-butynyl, ethyl · 2 · butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, and 1- Ethyl-1-methyl-2 -propanyl; heterocyclyl or heterocyclooxy, heterothio and heterocyclic amino: 3 to 6 members, saturated or unsaturated mono- or polycyclic heterocyclic A ring containing 1 to 3 heteroatoms selected from oxygen, nitrogen, and sulfur and via an oxygen atom (heterocyclicoxy), or via a sulfur atom (heterocyclicthio) or via a nitrogen atom (heterocyclicamino) Directly bonded to the main chain such as 2-tetrahydrofuranyl'oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydropyrimyl, 3-tetrahydrophenyl, 2-pyrrolidinyl, 3- Pyrrolidinyl, 3 · isorazolidinyl, -11-This paper size is based on China⑱i? Bi7A4 specification (210 x 297 public love) (Please read the notes on the back first ^ --- --- πFill this page ) Order · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy V-· 70225 A7 _B7 V. Description of the invention (9) -Iso-p-sulphonyl, 4-iso-sigma sitting group, 5--iso-sawadian, 3--r-bital, 4--rho-base, 5-r-bital, 2 -4 sigma, 4-17 stubium, 5-4 sintered base, 2-p sedral base, 4-p sedral base, 5-p sedral base, 2-microphone Dysprosyl, 4-imidodolide, 1,2,4-amidazolidin-3-yl, 1,2,4-humidazolidin-5-yl, 1,2,4-pyrimidazolidine -3-yl, 1,2,4 -pyrazadiazin-5-yl, 1,2,4-trituridine-3-yl, 1,3,4-humidazolidin-2-yl, 1,3,4-pyrimidazolidin-2-yl, 1,3,4-trituridine-2 -yl, 2,3-dihydroan-2-an, 2,3 -dihydroanan -3-yl, 2,3-dihydrop-furan-4-yl, 2,3-dihydroanil-5-yl, 2,5-dihydroanil-2-yl, 2,5-di Sulfan-3-yl, 2,3-dihydrop-phenphen-2 · yl, 2,3 -dimo-p-phenphen-3 -yl '2,3 -dimo-p-phenphen-4 -yl' 2,3--wind p-phene-5 -yl '2,5 -dimur p-phenphen-2 -yl' 2,5 -di-mothorphine-3 -yl '2,3-diazepine p ratio ^ — 2-radical '2, 3-. — Wind ip than ming ^-3-radical' 2, 3 — — rat ^ ratio ^ each -4-radical '2, 3-two wind? Than each p--5 -yl '2,5 -diazepine p-bilo-2 -yl' 1,5--nitrogen? Bilo-3 -yl, 2,3-dihydroisoxazol-2-yl, 2,3-dihydroisozazol-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-dihydroisopyrazol-3-yl, 2,5-dihydroisopyrazol-4-yl, 2,5-dihydroisopyrazol-5-yl, 2, 3 -Dihydroisopyrazole-3 -yl, 2,3-dihydroisopyrazole-4-yl, 2,3-dihydroisopyrazole-5-yl, 4,5-dihydroisopyrazole-3 -Radical, 4,5 -dihydroisopyridyl-4-yl, 4,5-dihydroisopyridyl-5-yl, 2,5-dihydroisopyrazole-3 -yl, 2,5 -Dihydroisopyrazole-4-yl, 2,5-dihydroisopyrazole-5-yl, 2,3-dihydroindazol-3-yl, 2,3-dihydrohumidazol-4-yl , 2,3-Dihydrohumidazole-5 -yl, 4,5-dihydrohumidazole-3 -yl, 4,5 -dihydrooxazole-4 -yl, -12- This paper is applicable to the national standard of 5ft (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back ^ Install --- π fill out this page) · Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs 52〇273 A7 B7 V. Description of the invention (10 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4丄 Dihydrooxazole-5 · yl, 2,5_dihydroisopyrazole · 3 · yl, 2 5 dihydroisopyrazol-5-yl, 2,5-dihydroisopyrrol-5-yl, 2 2,3-dichlorothiazol 2.3-dihydroxazol-4-yl, 2,3_dihydroxazol-5-yl, dihydroxazol-2-yl, 4,5-dihydrooxazole-4- Base, 4,5_dihydrooxazole_5_yl, 2 5_dihydrooxazol-2-yl, 2,5-dihydrooxazole_4yl, 2,5_dihydrooxazole; Radical, 2.3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3, dihydrooxazol-5-yl '4,5-dihydropyrazol-2-yl, 4,5_dihydropyrazol-4-yl, 4 5_dihydropyrazol-5-yl, 2,5-dihydropyrazol-2-yl, 2,5_dihydrooxazolyl, 2.5- Dihydrooxazole_5_yl, 2,3_dihydroimidazol · 2-yl, 2, fluorenyldihydroimidazole_4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydro Imidazolyl, 4 5_dihydroimidazol-4-yl, 4,5_dihydroimidazol-5-yl, 2,5_dihydroimidazolyl, 2.5-dihydroimidazol-4-yl, 2,5-di Hydroimidazol-5-yl, 2-morpholinyl,% morpholinyl, 2-hexahydropyridyl, 3-hexahydropyridyl, 4-hexahydropyridyl, 3.tetrahydropyridyl, 4-tetrahydropyridyl Hydrogenyl, 2-tetrahydropyrimidinyl, 4 • tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrimidinyl,丨, 3,5 _ Tetrachlorodicultivated 2-based, 1,2,4 -tetrahydrotrigenated -3 -based, 1,3-dihydrogenated p-based,] [3 -dipyrim-2-yl, 2-tetrahydropiperanyl, 1,3-dioxolane-2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-pyrimidin-2-yl, 413 ， 1_benzopyrimidin · 2-yl '1,1_dioxo_2,3,4,5_tetrahydropyrimidine · 2-yl, benzoxen-3-yl, 2Η-1,4 -Benzophenanthryn-3-yl, i, 3_diaphthrin_2_yl, and 1,3-diPsed-2-yl, aryl or aryloxy, arylthio, arylcarbonyl and Aromatic fluorenyl: aromatic monocyclic or polyepoxy, which is directly or via an oxygen atom (_〇_) (aryloxy) or a sulfur atom (_ 8-) (arylthio), via a carbonyl group (-〇 〇-) (arylcarbonyl), via sulfonyl group (-5〇2- -13- this paper? Long-length standard applies to China National Standard (CNS) A4 specifications (210 X 297 public love) (Please read the notes on the back first ^ Install-f fill in this page) Order v 520273

V. Description of the invention (η) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy) or (Fang Xingyi) Bonded to the main chain, for example, «, M and phenanthrene, or this milk based, phenanthrene And the corresponding carbonyl silk base; heteroaryl or heteroaryloxy, heteroarylthio, heteroarylcarbonyl and heteroarylfluorenyl. 10,000-cyclic or polycyclic radicals which may contain in addition to carbocyclic members — To four nitrogen atoms or containing-to three nitrogen atoms and _ one oxygen or sulfur atom or one oxygen or sulfur atom 'and directly or via an oxygen source (_〇 ·) (heteroaryloxy) Or via a sulfur atom (-s-) (heteroarylthio) 'via a carbonyl i (_c〇 _) (heteroarylcarbonyl) or via a sulfonyl group (-S〇2-) (heteroarylsulfonyl), etc. Those bonded to the main chain; for example: -3 five-membered heteroaryl group having one to two nitrogen atoms: 5-membered heteroaryl ring group, in addition to carbon atoms, may contain 1 to 3 nitrogen atoms as ring members such as eight Pyrrolyl, 3-pyrrolidyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, i, 2, 4-triazol-3-yl and ι, 3,4-triazol-2-yl;-1 to 4 gas atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom Or a 5-membered heteroaryl group with 1 oxygen or sulfur atom; a heteroaryl group with a 5-membered ring, in addition to carbon atoms, may contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom Or 1 oxygen or sulfur atom as a ring member, such as 2-octyl, 3-octyl, 2-r selphenyl, 3-p selphenyl, 2-ρ ratio p each group, 3-p ratio p-bases, 3-iso4-tauyl, 4-iso-meta-tyl, 5-iso-tautomethyl, 3--iso-p-plug. Sitting base, 4-isop Sawakey, 5-isosoul turkey, 3 · p ratio Junki, 4-p ratio. Seki, 5-p than Junki, 2-4 Junki, 4-Saki Junki, 5-p 唆, 2-p Saikou, 4-Soul Junki, 5-p Sesalki, 2-imidyl, 4-imidazolyl, 1,2,4-4 dituryl-3 -yl, 1,2,4-p dituryl-5 -yl, 1,2,4-oroxadiazole -3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, -14- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) equipment — (please read the notes on the back to fill out this page) Order v 520273 A7 B7 V. Description of the invention (l2 1,3,4-present diazole · 2-based, ι, 3,4-port Said π sitting -2 radical, 1,3,4- = upper 2-radical;, Diazole-containing 1 to 3 nitrogen atoms or 1 nitrogen atom and / or 1 oxygen or sulfur atom # Longci 5-membered heteroaryl: a heteroaryl group with a 5-membered ring, except for the carbon atom $ = may contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom as a ring member, and Two adjacent carbocyclic members or one nitrogen and one adjacent carbocyclic member can be bridged by Ding-1,3-Diwo-1,4 -diyl; clothing-bonded via nitrogen and containing 1 to 4 nitrogens 5_membered heteroaryl or bonded via nitrogen and containing 1 to 3 nitrogen atoms Benzene fused 5 _membered heteroaryl · · heteroaryl with 5-membered ring, in addition to carbon atoms may contain 丨 4 nitrogen atoms or ^ 3 nitrogen atoms as ring members, and two adjacent carbon Ring members or 丨 nitrogen and 丨 adjacent carbocyclic members can be D-two hoof], [two base bridge, these rings are linked to the main chain via one of the ring members;-containing 1 to 3 or 1 Or a 6-membered heteroaryl group with 4 nitrogen atoms: a heteroaryl group with a 6-membered ring, in addition to carbon atoms, may contain 43 or 4 to 4 nitrogen atoms as ring members, such as 2-pyridyl, 3 _Pyridyl, 4-pyridyl,% Dalyl, 4-tarphinyl, 2-fluorenyl, 4-fluorenyl, 5_, silk, 2-webuyl, 1,3,5-trihu-2-yl,丨 '2,4 · Sangen_3 • radical and 丨, ^, ^ tetragen-3-radical; • Phenylhydrazone fused with 1 to 4 nitrogen atoms 6_member heteroaryl: 6_member heteroaryl "Cycloyl radicals, two of which are adjacent to the carbocyclic member can be butyl-diphenylene, i.e. diphenylene, diphenylene, diisocyanate, and oxazoline, as well as corresponding oxygen, sulfur, Talking about bases or continuous bases. Heteroarylamino ·· Aromatic-cyclic or polycyclic radicals, except for carbon fluorene to 15- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 public love) _

I Page Order 520273

5. Description of the invention (I3) Four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom, and are directly bonded to the main chain. The term "partially or fully halogenated" means that some or all of the hydrogen atoms in the group may be replaced by the same or different as described above. As for its biological activity ', a compound of formula j is preferred, wherein m is 0. Likewise, preferred are compounds of formula I, wherein R i is methyl. In addition, 'I is a compound I in which R3 is hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or Cf3. In addition, preferred is compound I, in which R3 is methyl. In addition, preferred is compound I, in which R3 is cyano. In addition, preferred is compound VII, in which R3 is cyclopropyl. In addition, the preferred ones are compounds! , Where r3 is CF3. In addition, preferred is compound I, wherein R5 is hydrogen, cyclopropyl, methyl, ethyl, isopropyl, unsubstituted or substituted aryl, or heteroaryl. In addition, preferred is compound I, in which r 5 is methyl. In addition, preferred is compound ί, in which R5 is ethyl. In addition, preferred is compound ί, in which R5 is isopropyl. In addition, preferred is compound ί, in which R5 is cyclopropyl. In addition, preferred is compound I, in which R5 is C F 3. In addition, preferred is compound I, in which R5 is an unsubstituted or substituted aryl or heteroaryl. In addition, preferred is compound I, in which R5 is an unsubstituted or substituted pyridyl, pyrimidinyl, pyrimidinyl, damatyl, or trisylphenyl. In addition, the preferred compound is compound I, in which R5 is unsubstituted or substituted. • 16- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm).

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Order V Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 520273 A7 B7

V. Description of the invention (U-Uranyl, p-secenyl or pyrrolyl. = Outer 'is the preferred compound z, where r5 is unsubstituted or substituted ° Earth, 嗔 Junyl, isodecyl, iso Fluorenyl, fluorenyl, or yell. Sorry. Outer 'more perylene compounds!' Where r5 is unsubstituted or substituted ^ monool, pyrimidazolyl, or triazolyl. = External 'is a better compound BU is a phenyl group, which is unsubstituted or bears-or two of the following groups: nitro, cyano, hydroxyl, amine, amine carbonyl, thiocarbonyl, autogen, C, -C4, Ci_c4 ^ Carbonyl, Ci_c4 oxonite, C, -C4_alkoxy, Ci_c4 amine, di_C_4 amine, CVC4 alkylsulfonyl, Ci_C4 alkoxycarbonyl, Ci-q make amine carbonyl or di_ C1-C4 alkylamine carbonyl. In addition, preferred compounds are ί, wherein R4 is hydrogen, C | _c6 alkyl, f2-C6 fluorenyl, cvc: 6 alkynyl, allyl, aralkyl, heteroaralkyl , Aryloxyalkyl, heteroaryloxyalkyl, aryl, or heteroaryl. In addition, the preferred compound is Compound I, in which R4 is Ci_C6 alkyl. In addition, the preferred compound I is disclosed in W 0 9 7/1 5 5 5: 2. The mixture contained in the present invention The compounds have good activity against a wide range of phytopathogenic fungi, especially from the classes Ascomycetes, Deuteromycetes, Thinomycetes, and Basidiomycetes. They are useful for controlling various crops such as cotton, vegetables (such as cucumbers, beans) , Fanzhuang, potato, and gourd) 'Barley, grass, oats, bananas, coffee, corn, fruits, rice, corn, rye, soybeans, grapes, wheat' Ornamental plants, sugar cane and many seeds of various fungi are particularly important It is especially suitable for the control of the following plant pathogenic fungi: Cereal powdery mildew -17- This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) Cooperative printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative, 520273 A7 B7 V. Description of the invention (is) (Erysiphe gram inis), Erysiphe cichoracearum and Sphaerotheca fuliginea, Apple Podsphaera leucotricha, Unc inula ne cat or Grape stalk, Grain stalk Pucciniaspecies species, Rhizoctonia species of cotton, rice and grassland, Ustilago species of cereals and sugarcane, Venturia inaequalis (scab) of apples , Helminthosporium species of cereals, Septoria nodorum of wheat, strawberries, vegetables, decorative plants and grapes Botrytis cinerea (Gray mold), groundnut tail of groundnut Cercospora arachidicola, Pseudocercosporella herpotrichoides of wheat and barley, Pyriculairia oryzae, Phytophthora infestans of potato and tomato, and Plasmopara viticola), Pseudoperonospora species of hops and courgettes, Alternaria species of vegetables and fruits, Mycosphaerella species and Fusarium and verticilla Spore (Vertici 11 ium) species. Compound 11 is commercially available as an anti-bioassay (i.e., the active ingredient for immunity against disease attack), that is, II has no direct fungicidal activity, but it has bacteriostatic resistance against the harmfulness of treated plants. Compounds used as fungicides] [Z is commercially available. When preparing the mixture, it is best to use pure active ingredients 丨 and J 丨 to J J J and against --- (Please read the note on the back first and fill in this page) I-1,-order -18-

520273 A7

«Bacteria and pests, active ingredients of nematodes or growth regulators or other fertilizers for human injury or other compounds! Mixed with at least one compound or applied separately and has the ability to fight a wide range of phytopathogenic fungi, Ascomycetes, Deuteromycetes, Phycomycetes, and Basidiomycetes: This is applicable for its comprehensive effects The killing effect of leaves and soil action = Xingbi Temple on red crops such as cotton, vegetables (such as cucumber, potato, gourd), barley, grass, oats, fragrant rice, corn, two fruits, rice, Leymus, soybeans, grapes 'wheat, ornamentals', sugar cane, and many fungi on a variety of seeds are particularly important. It is especially suitable for the control of the following plant pathogenic fungi: Cereal powdery mildew (^ SiPhe), Erysiphe cichoracearum and Sphaerotheca fuliginea, Pod Sphaera leucotricha of apple, Uncinula necator of grape, Pucciniaspecies species of cereals, Rhizoctonia of cotton, rice and grassland species), Ustilago species of cereals and sugarcane, Venturia inaequalis (scabies), Helminthosporium species of cereals, Gramineae of wheat Spores (Septoria nodorum), strawberries, vegetables, decorative plants and grapes Botrytis cinerea (Gray mildew), Cercospora arachidicola, Pseudocercosporella herpotrichoides of wheat and barley '' Oryzae indica-19- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back first and fill in This page) is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by 520273 A7. 5. Description of the invention (丨 7) (Pyricularia 〇ryzae) 'Phytophthofa infestans of potato and tomato, grape uniaxial sign of grape growth (Plasmopara viticola), hopseed and courgery pseUdoperonsporasCies species, AlternarU sPecieS species of vegetables and fruits, Mycosphaerella species And Fusarium and Vertici 11 ium species. The mixture of the present invention is particularly suitable for controlling Lectobacillus oryzae. The compound and the mixture of at least one compound 11 to 111 may be applied together or separately simultaneously or sequentially, and when applied separately, the order usually does not have any effect on the control results. Depending on the type of effect required, the application rate of the mixture according to the invention (especially agricultural crops) is from 0.001 to 8 kg / ha, preferably from 0-1 to 5 kg / ha, especially from 0.5 to 3.0. Kg / ha. The application rate of the compound I is from 0.01 to 25 kg / ha, preferably from 0.05 to 2.5 kg / ha, especially from 0.01 to 10 kg / ha. Correspondingly, in the examples of compounds π to In, the application rate is from 0.001 to 5 kg / A are, preferably from 0.05 to 2 kg / ha, especially from 0.001 to}. 0 kg / Ha. Y treats the seeds, and the application rate of the mixture is usually from 0.01 to U 0 g of A kg of seeds, preferably from 0.01 to 100 g / kg, especially from 0 to π g / kg. If you want to control phytopathogenic harmful fungi, the compound ζ and at least one π to III can be applied separately or together, either before seeding, plant or plant sowing or -20- This paper size applies to X 297 mm) (please Read the note on the back first? ^ 11Fill this page)

Order V 520273 A7

520273

V. Description of the invention (I9, tributylphenyl polyglycol ether, alkaryl polyether alcohol, isotridecanol, moon dagger: alcohol / ethylene oxide condensate, ethoxylated sesame sesame oil, polyoxyethylene ;: Ethers: Polypropane alkyl ethers, lauryl alcohol polyglycol ether acetates, sorbitol esters, lignosulphuric acid waste liquid or methyl cellulose. Powders, substances for distribution and powders can be borrowed Mix or grind characters] and at least one compound or compound! And at least one compound II to III mixture, prepared with a solid carrier. Granules (such as coated particles, infiltrated particles or homogeneous particles) are generally It is prepared by combining the active ingredient (or active ingredients) on a solid support. The material or solid support is, for example, mineral soil such as silica, silica, silicate, talc, kaolin, limestone, lime, chalk, red basalt, Loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, abrasive synthetic materials and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and products of plant origin such as cereal flour, bark flour, wood flour And nutshell powder, fiber Powder or other solid carrier. This formulation usually includes any one of compound I and at least one compound from 0.1 to 95% by weight, preferably 0.5 to 90% by weight 0 / 〇] [丨 到 丨 i 丨 or compound i Mixture with at least one of 11 to 111. The active ingredient uses purity from 90% to 100% 'k good 95% to 100% (determined by n MR spectrum or η PLC). The corresponding formulation can kill An effective amount of a mixture of fungi or a fungicidal effective amount of compound I and at least one compound 丨 to nj compounds (in the case of separate application, treatment of harmful fungi, their habitats, or plants, seeds, soils to control fungi , Area, material or space are free from infringement. Application can be performed before and after being infected by harmful fungi. 22- This paper size applies to China National Standard (CNS) A4 (21〇X 297 public love) (Please read the back Attention '; --install --- > fill out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 520273

Examples of such preparations including active ingredients are: I. A solution containing 90 parts by weight of the active ingredient and 10 parts by weight of N-methylpyrrolidine; this solution is preferably used as a microdrop. II, containing 20 weight Parts of active ingredient, 80 parts by weight of dimethyl, 10 parts by weight of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid N-monoethanolamine, adduct, 5 parts by weight of dodecylbenzene A mixture of calcium sulfonate, 5 parts by weight of 40 mol ethylene oxide and 1 mol of castor oil adduct; a fine dispersion of this solution in water to obtain a dispersion; 'ΠΙ. Contains 20 parts by weight of active ingredients , 40 parts by weight of cyclohexanone, 3 () parts by weight of isobutanol, 20 parts by weight of an adduct of 40 mol ethylene oxide and 1 mol castor oil; an aqueous dispersion containing IV by weight of an active ingredient , 25 parts by weight of cyclohexanol, 65 parts by weight of mineral oil fractions with a boiling point of 210 to 280 ° C, and 10 parts by weight of 400 moles of ethylene oxide and 1 mole of castor oil Aqueous dispersion; V. 80 parts by weight of active ingredient, 3 parts by weight of diisobutylnaphthalene-1-sulfonic acid sodium salt, 10 parts by weight obtained from sulfite ground in a hammer mill A mixture of liquid sodium lignosulphate and 7 parts by weight of crushed silica gel; a finely distributed mixture of this mixture in water to obtain a spray mixture; VI. An intimate mixture of 3 parts by weight of active ingredient and 97 parts by weight of fine-grained kaolin; this dust includes 3 weight. Active ingredients; VII. A tight mixture of 30 weight active ingredients, 92 weight parts of crushed silicone and 8 weight parts of paraffin oil sprayed onto the surface of this silicone; this formulation imparts good adhesion to the active ingredients; VIII_40 weight parts of active ingredients, 10 parts by weight of phenolsulfonic acid / urea / formaldehyde condensation-23- (Please read the notes on the back first ^ Fill in this page to fill in this page)

Order V Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy

This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297 Public Love 520273 A7 B7 V. Description of the invention (23)) Table 1: Examples of active ingredient concentrations in ppm Untreated control group efficacy% 1C (100% disease) 0 2C compound Γ 2.0 20 0.5 0 3C compound II 2.0 0 0.5 0 4C compound III 2.0 0 0.5 0 Table 2: Examples Mixtures of the present invention (concentration in ppm) Calculate efficacy by observing efficacy * 5 2 ppm Γ + 2 ppm II 40 20 6 0.5 ppm Γ + 0.5 ppm II 20 0 7 2 ppm Γ + 2 ppm III 50 20 8 0.5 ppm Γ + 0.5 ppm III 25 0 *) Calculated using Kirby formula. (Please read the note on the back first and fill in this page) --Installation I. Order Ϊ. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The experimental results show that the observed power of all mixed ratios is more efficient than that calculated using the Kirby formula. -26- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

520273 Patent Application No. 088104664 it〗 lj Patent Application Amendment (November 91) — Patent Application Scope 1. A fungicidal mixture comprising a synergistically effective amount of the following ingredients as the active ingredient a) benzene of formula Γ Acetic acid derivative And its salt (Γ) and b) at least one compound of formulae (II) to (III) UI) Order (III) 0CHoCH = CK 2 .According to the fungicidal mixture of item 1 of the scope of the patent application, it is adjusted to two paper sizes to apply Chinese National Standard (CNS) A4 specifications (210 X 297 mm). One part includes the compound (Γ) in a solid or liquid carrier, and the other part includes at least one compound (11) to (III) in a solid or liquid carrier. I. A method for controlling harmful fungi, including treating the fungus with a fungicidal mixture according to any one of the items in the scope of patents No. 1 and No. 2 of the Chinese patent, its habitat, or materials, plants, Seed, soil, area or space, wherein compound (1,) and at least one compound (i) to (III) can be applied simultaneously, together or separately or sequentially. 4. The method according to item 3 of the patent application, in which harmful fungi and habitats, or materials, plants, and species that want to prevent fungi from being invaded; soil, area, or open space, use 0.005 to jin The compound (J 丨) is treated in the root benefit range item 1 per hectare. May 5. The method according to item 3 of the patent, in which harmful fungi, or materials, plants, and species that want to prevent fungi from being invaded; 2: area or space, using 0.01L kg / ha of roots At least one compound (11) to (1 treatment in range i). &Quot;