TW548078B - Fungicidal mixtures based on tris(oxime ether) derivatives and other strobilurins - Google Patents

Abstract

Fungicidal mixtures, comprising as active components (a) phenylacetic 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 compounds of the formulae II to V, in a synergistically effective amount.

Description

548078 5. Description of the invention (1) The present invention is a fungicidal mixture for controlling harmful fungi, including a) phenylacetic acid derivatives of formula I

(R2) m (manufactured) wherein the substituents and parameters have the following definitions: X ^ noch3, choch3, chch3;

Y is 0, NR R1, R are hydrogen and CfQ alkyl, respectively; R2 is cyano, nitro, trifluoromethyl, halogen, Cf C4 alkyl, and Ci-Q Λ alkoxy; m is 0, 1 or 2, where m is 2 then the R2 group may be different; R3 is hydrogen, cyano, Ci-C4 alkyl, Ci-C4_xyl, C3-C6 cycloxyl; R4, R6 are each hydrogen , Lu

CfC1 () courtyard, C3-C6 cyclohexyl, CfCio dilute radical, C2-C1 () fast radical, Hyundaiyl, C2-C1Q alkenyl, C3- (31 () alkynyl or Ci-C1Q ^ Permethrin, where these groups may be partially or fully i-lated or may carry one to three of the following groups: cyano, succinyl, warpyl, thiol, amine, wei, amine, amine, Benzene, Ci-C6 alkyl group, C ^ -alkyl group, c ^ -06 pyrolite group, m%

548078 V. Description of the invention (2)-C6 alkanesulfenyl, Ci-C6 alkoxy, Q-Cs haloalkoxy, Cl-c6 alkoxy supporting group, (^-() 6sulfanyl, C丨 -C6 amine group, amine group 06, C 丨 -C6 amine group, bis-Ci-C6 amine group, C!-C6 amine thio group, bis-Ci-Cs amine group Jiki, C2-C6 dilute, C2-C6 alkenyl, C3-C6 cycloalkyl, 'c3-c6 cycloalkoxy, heterocyclyl, heterocyclooxy, f-based, penoxy, aromatic> ; Aryl, aryloxy, arylthio, heteroaryl, heteroaryloxy, and heteroarylthio, in which the ring group may be partially or fully halogenated or may carry one to three of the following groups: cyano , Nitro, hydroxy, mercapto, amine, carboxyl, amine carbonyl, amine thiol, halogen, Ci-Ce radical, C ^ -C6 halogen radical sulphur yellow base, Lu Ci-C6 alkylsulfinyl Group, heteroarylthio or C (= N0R7) -An-R8; aryl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroarylcarbonyl or heteroarylsulfonyl, these groups may be partially or completely Halogenated or may carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amine, carboxyl, amine carbonyl, amine thiol, halogen, Ci- C6 base, Ci-C6 iii base, Cj-C6 base, Citrine base, C! -06 courtyard subacid, C3-06 ring courtyard, courtyard oxygen, 1-C6 tooth oxygen Group, q-C6 oxoyl group,-C6 thiol group, C6 amine group, di-C! -C6 amine group, Ci-Cs amine group, di-Cf C6 alkylamine carbonyl group, Cf c6 Alkylamine thiocarbonyl, di-q-c6 alkylamine thiocarbonyl, c2-c6 alkenyl, c2-c6 alkenyloxy, f-based, 1oxy, aryl, aryloxy, heteroarylluyl, heteroaryloxy Or C (= N0R7) -An-R8; R5 is hydrogen, C6 alkyl, Ci-C6 alkenyl, C2-C6 alkynyl, in which the nicotinyl group may be partially or completely dented or may carry one to Three of the following groups: cyano, nitro, hydroxy, thiol, amine, carboxyl, aminecarbonyl, aminethiocarbonyl, halogen

548078 V. Description of the invention (3)-Element, alkylamine carbonyl, di-q-C6 alkylamine carbonyl, CfQ alkylamine thiocarbonyl, di-Ci-C6: amine thiosulfanyl, C 丨 -C6 institute continued S blue Base, sulfonyl acid, CfCg alkoxy, Ci-C6 halooxy, CfCs oxywei, Ci-C6 thio, Ci-C6 amine, di-Ci-C6 amine, C2-C6 dilute oxygen, C3-C6-cycloalkyl, c3-c6 cycloalkoxy, heterocyclyl, heterocyclooxy, aryl, aryloxy. Radical, aryl-c "c4 alkoxy, Arylthio; aryl-(^-(: 4 alkylthioamino, heteroaryl, heteroaryloxy, heteroaryl-CfG alkoxy, heteroarylthio, heteroaryl-c ^ -q alkane Thio, the cyclic group of which part may be partially or completely halogenated and / or may carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, Φ amino, cyclyl, amine, Amine Thioyl, 〇 丨 -C6 alkyl, C ^ -C6 halosulfan, Ci-C6 pyroxanthate, C6 subcontinuous SS * group, 03-() 6 cycloalkyl, Ci-C6 alkane Oxy, Ci-C6 alkoxy, Cf c6 alkoxycarbonyl, alkylthio, amine, di-C! -C6 amine, Ci-C6 amine, bis-Cf C6 amine Base, Ci-C6 amine thiothioate, -C!-C6 amido, C2-C6 alkenyl, c2-c6 alkenyl, mesyl, benzyl, aryl, aryloxy, arylthio, heteroaryl, heteroaryloxy Group, heteroarylthio group and C (= N0R7) -An-R8; c3-c6 cycloalkyl group, c3-c6 cycloalkenyl group, heterocyclic group, aryl group, heteroaryl group, among which the cyclic group may be partially or completely ii or may carry one to three of the following groups: cyano, nitro, hydroxy, thiol, amine, carboxyl, amine carbonyl, amine thiocarbonyl, cyanogen, Ct-C6 alkyl, Ci-Cgiii alkyl , C6 sintered Si «-based, Ci-C6 sulphured 8¾-based, C3-C6 ring-based radical, Hyunoxy, C6 halo-substituted oxygen, C!-C6 alkoxy-based radical, q-C6 thio-based radical, Ci-C6 amine group, di-q-C6 amine group, Cf C6 amine group, di-C: -C6 amine group, CfCg amine group, di-C ^ -C6 amine group Peep group, C2 ~ * C6 dilute group, C2 ~~ C6 oxy group,

Page 10 548078

548078

(V)

Alas, only the factory in May Koji Temple can now apply for a patent scope. The compounds of the formula I are known per se and are described in the literature (WO 9/15 5 5 2). The wide fungus ^ η t v is also known and described in the literature. In addition, they can be obtained commercially as required under the trade names described in the following brackets: II Common name .azoxystrobin (trade name: Amistar®, from

Zeneca); ΠΙ · Ε-Α-253,313, common name: kresoxim-methyl (trade name: Brio®, from BASF); IV: EP 398,692, suggested common name: metominosi: robin (development code SSF-126, from Shionogi) ; V: EP 398,692, CAS RN 162535-21-9, SSF 129,

Page 12 548078 V. Description of the invention (6)-

Development product of Shi on〇gi Co., Ltd. Due to the C = C- and C = N-double bonds of compound I, compound I can be obtained as a mixture of E / Z isomers, which can be separated into individual compounds in a conventional manner (such as crystallization or chromatography). -If a mixture of isomers is obtained by synthesis, usually no separation is required, because in some cases the isomers can be converted into each other during formulation or application (such as exposure, acid or base). Similar transformations can also occur after application, such as in the treatment of plants, or harmful fungi or animal pests to be controlled. From the view of the 0 × double bond, the E-type isomer of compound I has better activity (mainly in the form of -0CH3 or -CH3 relative to -CC ^ R1). From the point of view of -C (R3) = N 0 C H2-double bond, the cis isomer of compound I has better activity (mainly in the R3 group relative to the _ 0 C Η 2-group). In the definition of compound I at the beginning, collective terms used often represent the following substituents: halogen: fluorine, chlorine, bromine, and iodine; 'alkyl: a straight or branched chain of 1 to 4, 6, or 10 carbon atoms Alkyl, such as CfCe-alkyl, such as fluorenyl, ethyl, propyl, 1-fluorenylethyl, butyl, 1-fluorenylpropyl, 2-fluorenylpropyl, 1,1-difluorenyl Ethyl, pentyl, 1-fluorenylbutyl, 2-fluorenylbutyl, 3-methylbutyl, 2,2-difluorenylpropyl, 1-4 ^ ethylpropyl, hexyl, 1 , 1-Difluorenylpropyl, 1,2-difluorenylpropyl, 1-fluorenylpentyl, 2-methylpentyl, 3-fluorenylpentyl, 4-fluorenylpentyl, 1,1 -Difluorenylbutyl, 1,2-difluorenylbutyl, 1,3-difluorenylbutyl, 2,2-difluorenylbutyl, 2,3-difluorenylbutyl, 3, 3 -Difluorenylbutyl, 1-ethylbutyryl, 2-ethylbutyl, 1,1,2-difluorenylpropyl, 1,2,2-trimethylpropyl

Page 13 548078 5. Description of the invention (7) group, 1-ethyl-1-fluorenylpropyl and 1-ethyl-2-methylpropyl, haloalkyl: 1 to 6 carbon atoms as described above Chain or branched alkyl groups, in which some or all of the hydrogen atoms of these groups may be substituted by the above-mentioned tooth atoms, such as Ci-Cf haloalkyl groups, such as chloromethyl, dichlorofluorenyl, trifluorofluorenyl, fluorenyl, Difluorofluorenyl, trifluorofluorenyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluorofluorenyl, 1-fluoroethyl, chloroethyl, 2,2-difluoroethyl, 2,2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-digas-2-fluoroethyl, 2,2,2-tri Chloroethyl and pentafluoroethyl; Cycloalkyl: monocyclic alkyl with 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; Alkenyl: unsaturated straight chain or A branched hydrocarbon group having 2 to 6 or 10 carbon atoms and a double bond at any position, such as C2-C6-alkenyl such as vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl , 1-butenyl, 2-butenyl, 3-butenyl, 1-fluorenyl-1-propenyl, 2-fluorenyl-1-propenyl, methyl-2-propanyl Alkenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-fluorenyl-1-butenyl, 2- Fluorenyl-1-butenyl, 3-fluorenyl-1-butenyl, 1-fluorenyl-2 -butenyl, 2-fluorenyl-2 -butenyl, 3-methyl-2 -butenyl Alkenyl, 1-fluorenyl-3-butenyl, 2-methyl-3-butenyl, 3-fluorenyl-3-butenyl, 1,1-difluorenyl-2-propenyl, 1 , 2-Dimethyl-1-propenyl, 1,2-Difluorenyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, I-hexane Diyl, 2-hexyl, 3-hexyl, 4-hexyl, 5-hexyl, 1-fluorenyl-1-pentenyl, 2-fluorenyl-1-pentenyl, 3 -Fluorenyl-1-pentenyl, 4-methyl-1-pentenyl, 1-fluorenyl-2-pentenyl, 2-fluorenyl-2-pentenyl, 3-fluorenyl-2- Dilute

Page 14 548078 V. Description of the invention (8) " group, 4-fluorenyl-2 -pentenyl, 1-methyl-3 -pentenyl, 2-fluorenyl-3 -pentenyl, 3- Methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-fluorenyl-4-pentenyl, 3-fluorenyl-4-pentyl Alkenyl, 4-fluorenyl-4 -pentenyl, 1,1-difluorenyl-2 -butenyl, 1,1-difluorenyl-3 -butenyl, 1,2-difluorenyl -1-butenyl, 1,2-difluorenyl-2 -butenyl, 1,2-, difluorenyl-butenyl, 1,3-difluorenyl-1-butenyl, 1, 3 -Difluorenyl-2 -butenyl, 1,3-difluorenyl-3 -butenyl, 2,2-difluorenyl-3 -butenyl, 2,3_dimethyl_1_butyl Diluted group, 2,3-Dimethyl-2-butanyl group, 2,3-Difluorenyl-3- butanyl group, 3,3-Difluorenyl-1-butanyl group, 3,3-di Fluorenyl-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-trisynyl-2-propenyl, ethyl-1-fluorenyl- 2-propenyl, 1-ethylmethyl-1-propenyl, and 1-ethyl-2-fluorenyl-2-propenyl Group, 'alkynyl: a straight or branched chain hydrocarbon group having 2 to 10 carbon atoms and a triple bond at any position, such as c2-C6-fastyl such as ethynyl, 1-propynyl, 2 -Propyl, 1-Butyl, 2-Butyl, 3-Butyl, 1-fluorenyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentyl , 4-pentynyl, 1-fluorenyl-2 -butynyl, 1-fluorenyl-3 -butynyl, 2-fluorenyl-3 -butynyl, ru 3-fluorenyl-1-butan Alkynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propanyl, 1-hexyl, 2-hexyl, 3-hexyl, 4-hexyl , 5-hexynyl, 1-fluorenyl-2 -pentynyl, 1-fluorenyl-3 -pentynyl, 1-fluorenyl-4-pentynyl, 2-fluorenyl-3 -pentynyl , 2-fluorenyl-4-pentynyl, 3-fluorenyl-1-pentynyl, 3-fluorenyl-4-pentynyl, 4-fluorenyl-1-pentynyl, 4-fluorenyl

Page 15 548078 V. Description of the invention (9) 2-Pentynyl, 1,1-Difluorenyl-2-butynyl, 1,1-Difluorenyl-3-butadiyl, 1, 2 Dimethyl-3-butadiyl, 2,2-dimethyl-3 -butynyl, 3,3-difluorenyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3 -butynyl and 1-ethyl-1-fluorenyl-2-propynyl;-heterocyclyl or heterocyclooxy, heterocyclic Thio and heterocyclic amino: 3 to 6 members, saturated or partially unsaturated mono- or polycyclic heterocyclic rings, which contain 1 to 3 heteroatoms selected from oxygen, nitrogen, and sulfur and pass through oxygen Atom (heterocyclooxy), or directly bonded to the main chain via a sulfur atom (heterocyclicthio) or via a nitrogen atom (heterocyclicamino) such as 2-tetraazapyranyl 'ethylene oxide' 3 -Tetraazapyranyl '2-tetraazetyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isomorphazolyl, 4-isomorphazolyl , 5-Isopyrazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl sigma, 3 -la. Stilbene, 4-stilbyl, 5-lava sigma base, 2-mosal sigma radix, 4-ming sigma stilbyl, 5-moss stilbyl, 2-thiazole σ-based, 5-thioσ-fluorenyl, 2-imidazolyl, 4-oramizoridinyl, 1,2,4-pyridadiazol-3-yl, 1,2,4-morphadiazole Pyridin-5-yl, 1,2,4-thiadiazolidine-3-yl, 1,2,4-diazolidin-5-yl, 1,2,4-triazol-3-yl , 1,3,4-morphazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2, 3 -di Hydrofuran-2-yl, 2, 3 -dihydrofuran-3 -yl '2,3-dihydrofuran-4 -yl'2,3 -dihydrofuran-5 -yl'xin 2, 5 -Dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 2,3-dihydrothiophene-2 -yl, 2, 3 -dihydrothiophene-3 -yl, 2, 3 -di Hydrothiophene-4-yl, 2,3-dihydrothiophene-5-yl, 2, 5-dihydrothiophene-2-yl, 2, 5-dihydrothiophene-3-yl, 2,3-dihydro ρ each -2-yl, 2,3-dihydro D bilo_3 -yl, 2,3 -dihydropyridine each with 4-one radical, and 2,3-dihydrodipyridyl each with -5 -yl , 2, 5 —Dihydro ports are each 2- 2 groups,

Page 16 548078 V. Description of the Invention (2) 2,5 -dihydropyrrole-3 -yl'2, 3 -dihydroisozozole-3 -yl, 2, 3 -dihydroisomorphazole-4 -yl , 2, 3-dihydroisomorphazol-5-yl, 4, 5-dihydroisomorphazol-3-yl, 4,5-dihydroisomorphazol-4-yl, 4,5-dihydroiso Morphant-5-yl, 2,5-dihydroisothiazol-3-yl, 2, 5-dihydroisothiazol-4-yl, 2, 5-dihydroisothiazol-5-yl, 2, 3-dihydroisopyrazole-3-yl, 2,3-dihydroisopyrazole-4-yl, 2,3-dihydroisopyrazole-5-yl, 4,5-dihydroisopyrazole -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-dihydromorphazole-3 -yl, 2,3-dihydroimidazol-4-yl , 2,3 -dihydro ·? Σ sitting 5-group, 4,5 -diazepine-3-group, 4,5 -diazepine-4 -yl, 4,5 -dihydromorphazole -5 -yl, 2, 5-dihydromorphazole-3 -yl, 2, 5-dihydromorphazole-4 -yl, 2, 5 -dihydromorphazole-5 -yl, 2, 3 -dihydro Thiazole-2 -yl, 2,3-dihydrothiazole-4 -yl, 2, 3 -dihydrothiazole-5 -yl, 4, 5 -dihydrothiazole-2-, , 4, 5-dihydromorphazole-4 -yl, 4, 5-dihydromorphazole-5 -yl, 2, 5-dihydrothiazole-2 -yl, 2, 5-dihydrothiazole 4-based, 2,5-dihydrothiazole-5 -yl, '2,3-diazamiso-2 -yl, 2,3-dihydromiso-4 -yl, 2,3--diazine Taste Mizuki-5 -yl, 4,5-dihydroimidino-2-yl, 4,5-dihydroimidino-4-yl, 4,5-dihydroimidazol-5-yl, 2,5 -Dihydroimido ° -2-yl, 2,5-dihydroimidino-4-yl, 2, 5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2- Hexahydropyridyl, 3-hexahydropyridyl, 4-hexahydropyridyl, 3-tetrahydropyridyl, 4-tetrahydropyridyl, 2-tetrahydropyrimidyl, 4-tetrahydropyrimidyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyridyl, 1,3,5-tetrachlorotriwell-2 -yl, 1,2,4-tetrahydrotriazol-3 -yl, 1,3 -di Nitroxan-2-yl, 1,3-di pupil-2-yl, 2-tetrahydrofuranyl, 1,3-dioxolane-2-yl, 3, 4, 5, 6-tetrahydropyridine-2 -

Page 17 548078 V. Description of the invention (π) radical, 4Η-1,3-thiagen-2-yl, 4Η-3, benzobenzothi-2-yl, 1,1-dioxo-2,3 , 4,5-tetrahydrothien-2-yl, 2Η-1,4-benzothiagen-3-yl, 2Η-1,4-benzomorpho-3-yl, 1,3-dihydro Well-2-group and 1,3-di-2-group; _ aryl or aryloxy, arylene, aryl, and aromatic acid groups: aromatic monocyclic ν or polycyclic hydrogen group, which directly Or via an oxygen atom (-0-) (aryloxy) or a sulfur atom (-S-) (arylthio), via a number group (-C0-) (arylene), via a sulphuryl group (-so2-) Or (arylsulfonyl) bonded to the main chain, for example, phenyl, phenyl, and phenanthryl 'or phenoxy', naphthyl and phenanthryloxy with the corresponding aryl and sulfonyl, heteroaryl Or heteroaryloxy, heteroarylthio, heteroarylamino, heteroarylcarbonyl and heteroarylsulfonyl: aromatic monocyclic or polycyclic radicals, which may contain one to four nitrogen atoms or One to three nitrogen atoms and one oxygen or sulfur atom or containing one oxygen or sulfur atom, and directly or via an oxygen atom (-0-) (heteroaryloxy) or via a sulfur atom (-S-) (hetero Arylthio), bonded to the main chain via carbonyl '(-C 0-) (heteroarylcarbonyl) or via sulfonyl (-S 02-) (heteroarylsulfonyl); for example-containing Five-membered heteroaryl group of one to three nitrogen atoms: 5-membered heteroaryl ring group, which may contain 1 to 3 nitrogen atoms as ring members in addition to carbon atoms, such as 2-pyrrolidinyl, 3-pyridyl, 3 -D [i 嗤, 4-pharyngeal, 5-crocodile, 2-miso, 4-kou mikou, 1,2, 4-trisalino-3, and 1, 3, 4 -A trimethyl group;-a 5-membered heteroaryl group containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or 1 oxygen or sulfur atom: a 5-aryl heteroaryl group, In addition to carbon atoms, it can contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom

Page 18 548078 5. Description of the invention (12) or 1 oxygen or sulfur atom is a ring member, such as 2-pyranyl, 3-pyranyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isomorphazolyl, 4-isomorphazolyl, 5-isomorphazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-oxazolyl, 2-morphazolyl, .4-morphazolyl, 5-morphazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazole , 4-imidazolyl, 1,2,4-morphadiazol-3-yl, 1,2,4-morphadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1 1,2,4-thiadiazol-5-yl, 1,2,4-triamidine-3 -yl, 1,3,4-pyrazine disalyl-2 -yl, 1,3,4-Hitomi -2 -yl, 1,3,4-triazole-2 -yl;--benzo-fused 5-membered containing 1 to 3 nitrogen atoms or 1 nitrogen atom and / or 1 oxygen or sulfur atom Heteroaryl: a heteroaryl group with a 5-membered ring, which may contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom as a ring member in addition to carbon atoms, and two of which are adjacent carbocyclic rings Or 1 nitrogen and 1 adjacent carbon ring member can be, Ding-1, 3-Dilute-1 4-Diyl bridge, ·-5-membered heteroaryl via nitrogen bonding and containing 1 to 4 nitrogen atoms or benzo-fused 5-membered heteroaromatic via nitrogen bonding and containing 1 to 3 nitrogen atoms Base: A heteroaryl group with a 5-membered ring. In addition to carbon atoms, it may contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms as ring members, and two adjacent carbon ring members or 1 nitrogen and 1 adjacent carbon. The ring members can be bridged by but-1,3-diene-1,4-diyl, these rings are linked to the main chain via one of the nitrogen ring members;-containing 1 to 3 or 1 or 4 nitrogens 6-membered heteroaryl: a heteroaryl with 6-membered ring, which can contain 1 to 3 or 1 to 4 nitrogen atoms as ring members in addition to carbon atoms, such as 2-pharyngeyl, 3-roleyl , 4-Hydroxybenzyl, 3—Oxyl, 4—Oxyl-based, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 2-pyrimidyl, 1, 3, 5-

Page 19 548078 V. Description of the invention (13) Sangen-2-Ji, 1,2, 4-Sangen-3-Ji and 1,2, 4, 5-Sigen-3-Ji;-Including 1 to Benzo with 4 nitrogen atoms is slightly 6-membered heteroaryl: 6-membered heteroaryl ring group, in which two adjacent carbocyclic members can be bridged by butane-1,3-diene-1,4-diyl group such as D Kui command, Yi D Kui Lin, Zou Wa Lin, and D_ °, and corresponding oxygen, sulfur, Weiji or Xiang donkey. Heteroarylamino: an aromatic monocyclic or polycyclic group, which may contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom in addition to the carbon ring member, and is directly bonded to the host Those on the chain. The term π partially or fully halogenated means that some or all of the hydrogen atoms in the group may be replaced by the same or different halogen atoms as described above. With regard to its biological activity, compounds of formula I are preferred, where m is 0. Likewise, preferred are compounds of formula I, wherein R1 is fluorenyl. Furthermore, preferred is compound I, wherein 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 I, in which R3 is cyclopropyl. In addition, preferred is compound I, in which R3 is C F 3. 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 R5 is a fluorenyl group. In addition, preferred is compound I, in which R5 is ethyl. In addition, preferred is compound I, in which R5 is isopropyl. _ Further, preferred is compound I, in which R5 is cyclopropyl.

I imim

T (li p. 20 548078

Substitution or Selection V. Description of the Invention (14) In addition, the preferred compound is compound I, of which R5 is CF3. In addition, preferred is compound I, in which R5 is unaryl or heteroaryl. 'In addition' is more preferably compound I pyridyl, pyrimidinyl, pyrenyl, and further more preferably is compound I furyl, thienyl, or pyrrolyl. Among them, R5 is unsubstituted or substituted. Wherein R5 is unsubstituted or substituted by the dwellings of the parent family, 丄, 丄, Indian wood is substituted or taken as thiazolyl, isomorphazolyl, isothiazolyl, pyrrolyl, or pyrazole. Σ Sitting Kiki. ^^ Preferred compound 1, wherein R5 is unsubstituted or substituted carbazolyl, thiadiazolyl or triazolyl. The preferred compound is compound I, in which R5 is phenyl, which is unsubstituted 1 > one to two of the following groups: nitro, cyano, hydroxyl, amine, amine carbonyl, and carbonyl. , Tooth element, Cl-C4 alkyl group, Cl- * alkyl group, Ci-c4 alkoxydisulfide 4 ^ alkoxy group, CrQ alkylamino group, di-c "C4 alkylamino group, CrC4 two-two-one soil Cl ~ C4 alkoxycarbonyl, ci-Q alkylamine carbonyl or di-Ci-Q alkylamine alkyl 0 = two, preferably compound I, wherein R4 is hydrogen, Ci-c6 alkyl, · 6 rare earth alkynyl, Allyl, aryl, heteroaryl, aryloxy, aryloxy, heteroaryl, heteroaryloxyalkyl, aryl, or heteroaryl. In addition, ^ is preferably a compound, wherein R4 is Ci-C6 alkyl. In addition, Chevrogate Compound I is disclosed in WO 9 7/15, 5, 5 2.. Compound I contained in the mixture of Mu Gong gg 丄 ^ ^ has a wide range of plant pathogens

苐 Page 21 548078 V. Description of the invention (15) Sexual fungi, especially from Ascomycetes, Deuteromycetes, Pleurotus and Basidiomycetes, have good activity. They control various crops such as cotton, vegetables (such as cucumbers, beans, tomatoes, potatoes, and gourds), barley, grass, oats, bananas, coffee, corn, fruits, rice, corn, rye, soybeans, grapes, wheat, Ornamental plants, sugar cane, and many fungi on a variety of seeds are particularly important. It is particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis of cereals, Erysiphe cichoracearum and Sphaerotheca f ul i gi nea, II. Podsphaera leucotricha, Unc i nu 1 a necat or grape vine, Pucciniaspecies species, Rhizoctonia species of cotton, rice and grass ) Species, Ustilago species of cereals and sugarcane, Venturia inaequalis (sore disease) 'Helminthosporium species' species of apple, wheat needles Septoria nodorum, Botrytis cinerea (Botrytis cinerea), Botrytis cinerea (Gray mildew), Cercospora arachidic ο 1 a), wheat and barley (Pseudocercosporel la herpotrichoides), Pyricularia or y zae, Phy tophthor a inf estans, Grapes of Plasmopara viticola (P 1 a s m ◦ p a r a v i 11 c ο 1 a), hops and cucumber of false downy mildew (Pseudoperonospora species) ^, vegetables & f if t # before each

548078 5. Description of the invention (16)-Alternaria species, Mycosphaerella species, Fusarium and Verticillium species. Compounds I I -V as fungicides are commercially available. When preparing the mixture, it is preferred to use pure active ingredients 1 and 111 and other active ingredients or other fertilizers that are resistant to harmful fungi and pests such as insects, mites or nematodes or growth regulators or other fertilizers. Compound I and at least one compound II — The mixture of V can be applied simultaneously, successively, or separately and has significant activity against a wide range of phytopathogenic fungi, especially from the Ascomycetes, Deuteromycetes, Leuconomycetes, and Basidiomycetes. Some are comprehensive and therefore suitable as leaf and soil fungicides. They control various crops such as cotton, vegetables (e.g. cucumbers, legumes, fans, potatoes and gourds), barley, grass, oats, bananas, coffee, corn, fruits, rice, corn, rye, soybeans, grapes, Triticum aestivum, ornamentals, sweetness, and many fungi on a variety of seeds are particularly important. It is especially suitable for the prevention and treatment of the following phytopathogenic fungi: Erysiphe graminis' (Erysiphe cichoracearum and Sphaerotheca fuliginea), white apple P. dosphaera leucotricha, Grape shells of grapes (Uncinu 1 anecat 〇r), Pucciniaspecies species of cereals, Puccinia species of cotton, rice and grass ( Rhizoctonia species), cereals and sugarcane Ustilago species, 'Venturia inaequal is (disease)', a long snail (Helininthosporiuin)

Page 23 548078

548078 5. Description of the invention (18) _ For seed treatment, the application rate of the mixture is per kilogram of seed, preferably 0.01 to 100 g / eight kilograms to 250 grams per kilogram. Λ jin, especially from 0.01 to 50 g / if you want to control plant pathogenic harmful fungi, work 1 to 7 separately or together, you can use 3 objects 1 and at least-before or after the soil, or Plants are germinated and planted according to the invention. The fungal mixture is prepared according to the invention: ". The powder and suspension liquid or formulated into a highly concentrated aqueous solution, dispersion, emulsion, oil dispersion are suspended or granular, and sprayed by spraying. , Word ^ uncle, things for dissemination ▲ The state of use varies according to the intended purpose Spear, dusting, dispersing or watering application. The distribution of the highlighting mixture is fine and uniform. For example, it is necessary to ensure as far as possible the preparation system of this formulation According to the known party, if necessary, use emulsifiers and ingredients ;: thinner == agent and / or carrier and as a diluent; ^ dilute the active ingredients, if water-suitable auxiliary agent & too μ Λ / , He / cereal as auxiliary solvent. For this purpose-family (such as gas stupid); two oils. Such as = such as diphenylbenzene, chlorinated aromatics (such as cyclohexyl), Tian Er), alcohol award ( (Such as methyl alcohol, butanol), ketones such as ground H2N2 3 T amine, methyl methyl with amine) and water; containing synthetic ore Materials (such as fine collars, clay, talc, chalk) and grinding I anionic emulsification, f Γ 、,, acid salts); emulsifiers such as non-ionic and acid esters) and ethylene oxide fatty alcohol ethers, alkanes Sulfonates and aromatics are suitable such as lignosulfite waste liquid and methyl cellulose. Butyl dibasic acids are aromatic acids such as wood-, pan-, zero- and di-acid. They are salts, alkaline earth metals Salts and ammonium salts, fatty acids, alkanes 548078 V. Description of the invention (19) Alkali metal salts, alkaline earth metal salts and ammonium salts of alkyl and alkarylsulfonic acids, alkyl lauryl ethers and fatty alcohol sulfates, and sulfated ten Hex-, hepta-, and stearyl alcohol salts, or fatty alcohol glycol ether salts, sulfonated and its derivatives and condensates of acetaldehyde, or condensates of sulfonic acid and phenol and acetaldehyde , Polyoxyethylene octylphenol ether, ethoxy isooctyl-, octyl or nonyl-phenol, alkylphenol polydi-ol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohol , Isotridecyl alcohol, fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetic acid Esters, sorbitol esters, lignosulfite waste liquid or fluorenyl cellulose. | Powders, substances for dispersal and dusts can be mixed or ground together to compound I and at least one compound II to V, or compound I and at least one compound Mixtures II to V are prepared with solid carriers. Granules (such as coated granules, infiltrated granules, or homogeneous granules) are generally prepared by combining active ingredients (or active ingredients) on a solid carrier. Fillers or solids The carrier is, for example, mineral soils such as silica, silica gel, silicate, -talc, southern territories, limestone, lime, white ridge, red basalt, loess, clay, dolomite, stone diatomaceous earth, sulfuric acid, magnesium sulfate , Oxidation ball, grinding synthetic materials and fertilizers such as sulfuric acid, basic acid, ammonium phosphonate, urea, and products of plant origin such as cereal flour, bark powder, wood powder and nut shell powder, cellulose powder or other solid carriers. This formulation usually comprises any one of compound I and at least one compound I to V or a mixture of compound I and at least one I to V from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight. The active ingredient is used from 90% to 100% purity, which is better than 95% to 100% (determined by NMR spectrum or HPLC).

Page 26 548078 5. Description of the invention (20) The corresponding formulation can be a fungicidal effective amount of the mixture or a fungicidal effective amount of the compound I and at least one compound II to V (in the case of separate application, the harmful fungi and their habitats are treated). , Or plants, seeds, soil, areas, materials or spaces to be controlled for fungi to be protected from damage.. Application can be carried out before or after infection with harmful fungi. Examples of such preparations including active ingredients are: ”I. Contains 90 parts by weight of active Ingredients and a solution of 10 parts by weight of N-fluorenylpyrrolidone; this solution is preferably used as a microdrop; II. Contains 20 parts by weight of the active ingredient, 80 parts by weight of dimethyl, and 10 to 10 parts by weight of 8 to 10 Addition of Molar ethylene oxide with 1 Molar oleic acid N-monoethanolamine, 5 parts by weight of calcium dodecylbenzenesulfonate, 5 parts by weight of 40 moles of ethylene oxide and 1 mole A mixture of adducts of ricinus castor oil; a fine dispersion of this solution in water to obtain a dispersion; III. Contains 20 parts by weight of active ingredient, 40 parts by weight of cyclohexane, 30 parts by weight ~ isobutanol, 20 parts by weight The addition of 40 moles of ethylene oxide and 1 mole of castor oil _ Aqueous dispersion of the product; I V. Contains 20 parts by weight of active ingredient, 25 parts by weight of cyclohexanol, 65 parts by weight of boiling point 2 1 to 2 8 0 ° C of mineral oil fractions and 10 parts by weight Aqueous dispersion of 40 moles of ethylene oxide and 1 mole of castor oil adduct; $ V, ground in a hammer mill containing 80 parts by weight of active ingredient and 3 parts by weight of diisobutyl- 1-A mixture of sodium sulfonate, 10 parts by weight of sodium acid salt of lignin derived from sulfite waste liquid and 7 parts by weight of crushed stone gum; a spray mixture is obtained by finely distributing the mixture in water; VI. 3 Intimate mixing of 9 parts by weight of active ingredients and 9 parts by weight of fine-grained kaolin ·

Page 27 548078 V. Invention V (22) ^ ~ ^ --- 2 2 (1 6 7)] Determine the expected efficiency of the active ingredient mixture and compare it with the observed efficiency. Untreated, expressed as% of untreated control group

Kirby formula: E 2 X + y-xy / iQQ E ^ Expected efficiency expressed as% of active ingredient A and B in a concentration of a and b in the control group T χ When active ingredient A in concentration a is used Efficiency at the time y Efficiency when using the active ingredient B at concentration b Example 1: Activity (protection) against rice scar fungus Spray potted rice seedlings with an aqueous formulation of active ingredients "Tai Nong 6 7" So far, the preparation was prepared from a stock solution containing 10% active ingredient, 63% cyclohexanone and 2 7% emulsifier. The next day, the plant was inoculated with an aqueous spore suspension of Magnaporthe grisea. The test plants were placed in a greenhouse at 2 2-2 4. (: and 9 5-9 9% relative humidity in a greenhouse for 6 days. Then the progress of leaf infection was visually observed. The visual measurement of the percentage of infected leaf area was used to measure the untreated control The percentage indicates conversion to efficiency. The efficiency of 0 indicates the same degree of disease as the untreated control group. The efficiency of 100 means 0% of the disease. Using the Colby formula (Colby, SR · " Calculating synergistic and antagonistic responses of herbicide combinations ", Weeds , 15, 2nd 0- 22 pages, 1 9 6 7) Determine the expected efficiency of the active ingredient composition and compare it with the observed efficiency. The compound I used is the following ingredient a):

Page 29

Claims (1)

548078 Case No. 88104665 6. Scope of patent application-M: Amendment Shaving1. A crop protection mixture, which includes emperor synergies and responsibilities; as active ingredient, '+ a) phenylacetic acid derivative of formula I (I) where the substituents and parameters have the following definitions: — X is NOCH3, CHOCH3, CHCH3; Y is 0, NR R1, R are hydrogen and alkyl, respectively; R2 is cyano, nitro, trifluoromethyl, Halogen, Ci-C4 alkyl, and Ci-C4 alkoxy; m is 0, 1, or 2, where in is 2, the R2 group may be different; R3 to R6 are each a d-alkyl group, and a salt thereof , And b) at least one compound of formula II and formula III O: \ 57 \ 57739-920102.ptc Page 34 548078 Case No. 88104665 Month Amendment CH3〇2C > ^ 〇Me (III) 2. The fungicidal mixture according to item 1 of the scope of the patent application is adjusted in two parts, one part of which is a compound of formula I in a solid or liquid carrier, and the other part of which is included in a solid or liquid carrier. At least one compound of formula II and formula III in a liquid carrier. 3. A method for controlling harmful fungi comprising a synergistically effective amount of a) phenylacetic acid derivative of formula I (I) O: \ 57 \ 57739-920102.ptc Page 35 548078 O: \ 57 \ 57739-920102.ptc Page 36 548078 _Case No. 88104665_ Year Month_ Amendment VI. Application for a patent to deal with fungi, their habitats, or materials, plants, and seeds that want to prevent fungi from being invaded , Soil, area or space, wherein the compound of formula I and at least one compound of formula II and III can be applied simultaneously, together or separately or sequentially. 4. The method according to item 3 of the scope of patent application, in which harmful fungi, their habitats, or materials, plants, seeds, soil, areas or space systems that want to prevent and control fungi from infestation, use 0.05 to 1 kg. / Ha treatment of compounds of formula I. 5. The method according to item 3 of the scope of patent application, in which harmful fungi, their habitats, or materials, plants, seeds, soil, areas or space systems that want to control fungi from their infestation use 0.01 to 1 kg / Hectares are treated with at least one compound of formula II and III. O: \ 57 \ 57739-920102.ptc Page 37