TW423958B - Fungicidal mixtures - Google Patents

Abstract

A fungicidal mixture comprising (a) an oxime ether of the formula I, where the substituents have the following meaning: X is amino (NH); Y is N; Z is oxygen or sulfur; R' is C1-C6-alkyl; and (b) a dithiocarbamate (II) selected from the group consisting of -manganese ethylenebis(dithiocarbamate) (zinc complex) (IIa), -manganese ethylenebis(dithiocarbamate) (IIb), -zinc ammoniate ethylenebis(dithiocarbamate) (IIc) and -zinc ethylenebis(dithiocarbamate) (IId) or (c) 1-(2-cyano-2-methoxyiminoacethyl)-3-ethylurea (III) H3CCH2-NHCONH-C(CN)=NOCH3 (III) in a synergistically active amount.

Description

4 2 3 9 5 8 A7 B7

1 ΟΠ3 j. 2-R · YOCH3 V. Description of the invention (1 The present invention relates to a fungicidal mixture, including a synergistically active amount a) Rib ether of formula I: ch3 NOCH, gh3x ^. I 0) where substituted Has the following meanings: X is oxygen or amine (NH); 'Y is CH or N; Z is oxygen, sulfur, amine (NH) or Ci_4 alkylamino (NC, _4 alkyl); R is C | — 4 secondary, C 1 · 6 卣, alkynyl, C 3-6 alkynyl, dilute group, 〇3.6 block, C3-6 haloalkynyl, C3.6 alkynyl, (: 3-6 Cycloalkyl methyl groups may be partially or fully aerated and / or may be hydrogenated with one to three of the following groups and / or benzyl groups may be provided with one to three of the following groups: cyano, C | _4 alkyl, Cb4 haloalkyl, (V4 alkoxy, C4 haloalkoxy, and C! _4 thio group; ^ and b) a dithiocarbamate selected from the group consisting of: "" Ethylbis (dithioaminoformate) manganese (zinc complex) (IIa), -Ethylbis (dithioaminoformate) manganese (lib), Ethylbis (dithio) Amine amino acid) zinc ammonium (lie) and -ethylenyl bis (dithiocarbamate) zinc (lid), and / or c) 1- (2-amino-2) -Ethyloxy group of methoxyimine) -3 -Ethyl legs (III): H3CCH2-NHCONH-C (CN) = NOCH3 (III) This paper size applies to China National Standard (CNS) A4 (210X 297 Mm)-installed ---- · --ordered ------ salty (please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 423958 Α7 Β7 Central of the Ministry of Economic Affairs Printed by the Zhunzhou Bureau Shellfish Consumer Cooperative Co., Ltd. V. Description of the Invention (2) Furthermore, the present invention relates to a method for controlling ¥ 丨 bacteria using a mixture of a compound 丨 and [〖and / or〗 〖, and related compounds jj j And the use for preparing such a mixture. The compound of formula I, its preparation method and its effect against harmful pinworms have been disclosed in the literature (WO-A 95 / 21,153, WO-A 95 / 21,154, DE 195 28 651.0). Dithioaminogallate II, its preparation method and its anti-harmful fungi function have also been revealed (Ila: common name: zinc manganese napu (mancozeb), US-A 3,379,610; lib: common name: manabi napu (maneb ), US-A 2,504,404; lie: previous common name: metiram, US-A 3,248,400; IId: common name: zinc naim (2 丨 1 ^), -US-A 2,457,674). Compound III, its preparation method, and its antibacterial effect on tadpoles have also been revealed (us_A 3,957,847; common name: simoxanin ((^ 111〇 ^^ 1 ^ 1)). 0 An object of the present invention is to provide an improved anti-harm 眞Bactericidal mixtures, which reduce the total amount of active ingredient combinations (synergistic mixtures) applied, can reduce the application rate and improve the bacterial spectrum of known compound effects. It has been found that this purpose can be achieved by the previously defined mixtures. In addition, it has also been found that compound I, π & / or III, or sequential application of compounds I, II, and III can be used to obtain better control of harmful fungi than when individual compounds are used. The present invention relates to Mixtures of compounds I and π or I and] [u and mixtures including compound I, compound 11 and compound π 丨. Formula 1 especially represents a B ether in which X is oxygen and Υ or CH or amine and Υ is The oxime ether of Ν ^ Furthermore, it is preferably a compound in which ζ is oxygen. (Please read the notes on the back before filling this page.) 23 95 〇A7 B7 V. Description of the invention (the same Preferably, the compound I in which R1 is a tombstone or a fluorenyl group is used according to its use in the synergistic mixture of the present invention. 'The best compounds are listed in the following table: Table 1 wherein each compound ZR' is equivalent to Table A —The compound of formula IA

(IA) Table 2 wherein each compound Z R ′ is equivalent to the compound of the formula IB in Table A—Column CHa 1 Table A. CH30

〇BJ Indian Consumer Code of the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, ZRr 1.1 t O-CH2CH2CH3 /1.2 〇-CH (CH3) 2 1.3 0-CH2CH2CH2CH3 t 1.4 〇-CH (CH3) CH2CH3 1,5 0 ~ CH2CH (CH3) 2 1.6 〇-c (ch3) 3 1: 7 SC (CH3) 3 1.8 0 ™ CHiCH3) CH2CH2CH3, 1,9 0-CB2C (CH3) 3 1.10 〇-CH2C (Cl) -CCl2 1,11 o -ch2ch = ch-ci (· trans) 1.12 Q-CH2C (CH3) = CH2 1.13 o-ch2- (cyclopropylbenzene 1.14 o-ch2-c6h5 1.15 '0 ~ CH2- [4 ~ F-C6H4] 1 , 16 0'CEi2CH3 1.17 0-CH (CH2CH3) 2

J --- „------ install ----.-- order ----- brigade (please read the precautions on the back before filling out this page) __I This paper size applies to Chinese national standards (CNS> M specifications (210X297 male thin) 423958 A7 B7 V. Description of the invention (4) Where there is a double bond with 〇Υ, the compound of formula I may have several acid functional groups. According to this configuration (about

m is one of the two isomers or E / Z (please read the notes on the back before filling out this page-the mixture of isomers is used for Bensamin, θ into a poor moon shape * s It is better to use E / Z isomers or E isomers, and E isomers are particularly preferred. Chemical compounds! The C = N double bond in the side chain can be pure. Or 2 isomers = or the main E / Z isomer mixture state. Compounds! It can be used in the mixture of the present invention as a mixture of isomers or as a pure isomer. From the point of view of its use, a particularly good compound ί It is the cis-group pair ZR |) in which the fluorene end group of the side chain is. 3 Due to its experimental properties, compounds can form adducts or salts with inorganic or organic acids or metals. Inorganic acids (examples are hydrogen from acids such as hydrofluoric acid, hydrogen acid, hydrogen brook acid and chloroiodic acid, sulfuric acid 'phosphoric acid, and nitric acid. The Central Samples Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, Printing Applicable: Organic acids of tritium are for example Formic acid, carbonic acid and alkanoic acid, such as acetic acid 'trifluoroacetic acid' triacetic acid and propionic acid, also glycolic acid, thiocyanic acid 'propanolic acid' succinic acid citric acid, benzoic acid, cinnamic acid, oxalic acid. Acids (sulfonic acids having linear or branched alkyl groups of 1 to 20 carbon atoms), aromatic sulfonic acids or aryl disulfonic acids (aralkyl groups having one or two sulfonic groups such as phenyl and Fluorenyl), alkylphosphonic acid (phosphonic acid of linear or branched alkyl group containing 1 to 20 carbon atoms), arylphosphonic acid or arylbisphosphonic acid (aromatic acid having one or two phosphonic acid groups attached thereto) Groups, such as phenyl and fluorenyl), may have substituents for alkyl and aryl groups, such as p-toluene acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzene Formic acid, 2_ethoxybenzoic acid, etc. Suitable metal ions are (especially) elements of the second main group, especially the Chinese national standard (CN S) Α4 size (210X297 cm) Duo Packing A7 B7, Shellfish Consumer Cooperation, Central Standards Bureau, Ministry of Economic Affairs 5. Description of the invention (5) Magnesium, the third and fourth main group elements, especially aluminum, tin and lead, Metal elements of the one to eight subgroups, especially mm zinc and other elements of the fourth cycle subgroup. Metals can exhibit various valences that can be assumed. When preparing this mixture, it is preferred to use pure The active ingredient is called Chuan: if necessary, it can also be mixed with other active ingredients that are resistant to harmful maggots or other pests (such as insects, mites and nematodes), or weeding or growth-regulating active ingredients or fertilizers. Mixtures of compounds I, 11 and I π Compounds I, 11 and 111 are used simultaneously or separately to distinguish their activity against a broad range of phytopathogenic Pseudomonas, especially Ascomycetes, Deuteromycetes, and medicinal bacteria (Phyeomycetes) and Basidiomycetes. Some of them are organized and therefore can be used as fungicides on leaves and soil. This mixture is used in various crops such as cotton, vegetable species ( Such as courgettes, soybeans and gourds), barley, grassland, oak, coffee, corn, fruit trees, rice, rye, soybeans, grape vines, wheat, decorative plants, sugarcane and various seeds are particularly important for controlling large numbers of fungi. Particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (mildew) in cereals, Erysiphe cichoracearum in gourds and Sphaerotheca fuliginea , Podsphaera leucotricha in apples, Puccinia in genus Puccinia, Rhizoctonia in cotton, rice and hemp, in shells and sugarcane Ustilago, Venturia inaequalis in apple This paper size is applicable to China National Standard (CNS > A4 size (210X297 mm) ---- „----- -• Install ------- Order ------- i ^ {Please read the notes on the back before filling out this page) 423958 A7 B7 V. Description of Invention (6) (scab) Helminthosporium (Helminthosporium) eptoria nodorum), Botrytis cinerea (Botrytis cinerea) in strawberry 'vegetable' decorative plants and grapes, Cercospora arachidicola in groundnut, and pseudocosporium in wheat and barley ( Pseudocercosporella herpotrichoides), Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Pseudoperonospora in gourds and hops, among grapes Plasmopara viticola, Alternaria, Fusarium and Verticillium in vegetables and fruits. Furthermore, it can be used to protect substances (such as wood) against Paecilomyces variotii ° Compounds II and / or III can be applied simultaneously or separately or sequentially. When applied separately, the order of application is usually The control measurement results have no effect. The ratio of the amount of compound I to 11 is generally 200: 1 to 1: 1: 1, preferably 100: 1 to 1: 1, especially 50: 1 to 5: 1 (11: 1) by weight . The dosage ratio of printed compounds I to III in the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is generally 10: 1 to 1: 1, preferably 5: 1 to 0 _ 2: 1, especially 3: 1 to 1: 3 (111: 1) weight ratio. The application rate of the mixture of the present invention depends on the nature of the desired effect. In the case of Compound I, it is usually from 0.005 to 0.5 kg / area, preferably from 0.001 to 0.5 kg / area, especially. . 〇〗 to 0.3 kg / area. The application rate of Compound II is usually from 0.1 to 10 kg / acre, preferably 0. This paper size is applicable to the national standard (CNS) A4 secret (210 X 297 male thin). Printing 423958 A7 --------, ____________ B7 Five 'invention description (7) ~ to 5 kg / area, especially 1 to 4 kg / area. The application rate of Compound III is generally from 0.05 to 0.8 kg / area, preferably from 0.01 to 0.5 kg / area ', especially from 0.05 to 0.3 kg / area. For seed treatment, the application rate of the mixture is usually from 0.001 to 100 g / kg of seed, preferably from 0.01 to 50 g / kg of seed, especially from 0.01 to 10 g / kg of seed. If it is desired to control plant pathogenic harmful fungi, before or after planting, or before or after plant germination, spray or spread compound 4III or compounds I, π and 111 mixture.

The fungicidal synergistic mixture of the present invention, or Compound I can be formulated into, for example, ready-to-spray solutions, powders and suspended liquids or highly concentrated aqueous' oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, Powders, spreading materials or granules, and applied by spraying, atomizing, dusting, spreading or pouring. The state of use depends on the intended purpose; in any case, it is preferred to use the D formulation in as fine and uniform a distribution as possible of the mixture of the invention, which can be prepared according to methods known per se, such as adding a solvent and / or a carrier. Generally, inert additives such as emulsifiers or dispersants are mixed in the formulation. Suitable surfactants are aromatic continuous acids such as the alkali metal salts, alkaline earth metal salts and ammonium salts of wood-, di-, ten-, and dibutylphosphonium-sulfonic acids and fatty acids, alkyl and alkylarylsulfonic acids. Salts 'alkyl lauryl sulfonium and fatty alcohol sulfonates, and sulfated cetyl alcohol' heptadecyl and stearyl alcohol salts, or fatty alcohol diol mystery salts, sulfonated naphthalene and its derivatives Condensate with formaldehyde, 荇 or the condensate of tea acid and aging · and the condensate of phytoethene, polyoxyethylated octyl, ethoxylated isooctyl_ -10- This paper is from Shicaiguan family materials ((: Just 44 Secrets (2 offering 297 mm) a '-1.1 — ^ ------ install ------, order ----- ^-soul (please read the precautions on the back first) (Fill in this page again.) Seal of Consumers' Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs 423 958 A7 _______B7 V. Description of the Invention (8), Octyl- or Nonyl-phenol, Alkylphenol Polyglycol Ether, Tributylbenzene Polyglycol ether, alkylaryl polyether alcohol, isotridecanol, fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropyl alkyl ether, lauryl alcohol Polyglycol ether acetate, sorbitol ester, lignosulfite Acid salt waste liquid or methyl cellulose. Powder materials and powders for spreading can be prepared by compound [, π and / or], or a mixture of compounds I, II and III with a solid carrier or-grinding Granules (such as coated granules, infusion granules, or uniform granules) are generally prepared by incorporating the active ingredients into a solid carrier. Fillers or solid solid carriers are, for example, minerals such as sandstone, dream gum, oxalate, talc , Kaolin, limestone, lime 'chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, abrasive composites, and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea And plant-derived products such as cereal flour, bark flour, wood flour and core-shell flour, cellulose powder, or other solid carriers. Formulations usually include from 0.1 to 95% by weight, preferably 0.5 to 90% by weight. Compounds I, II and / or III, or mixtures of compounds I, II & II. The active ingredient uses a purity from 90% to 100%, preferably 95% to 100% (based on NMR or HPLC spectra). Compound I ' II and / or I π, or mixed , Or the corresponding formulation, is a mixture of bactericidal active amounts, or compounds I, Π, and / or III, which are bactericidal active amounts when used separately, to treat harmful bacillus or plants, seeds, soil, areas, Material or space to keep it free of fungi. Harmful paper ^^: Shicai Guanjia Network L (⑽ 丨 Α4 · (2! () ≫ < 297 public race) ---- ^- ----- Meal -------. Order ------ ^ (Please read the precautions on the back before filling out this page) Printed by APC Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs, A7 _____87 ___ 5 2. Description of the invention (9) Pleurotus can be applied before and after infection. Examples of the synergistic effect of the mixture of the present invention against harmful bacillus bacteria The bactericidal effect of compounds and mixtures is demonstrated by the following experiments: The active ingredients are formulated separately or together to contain 70% by weight of cyclohexanone and 20% by weight of Nekanil® LN AP6, wetting agent with emulsifying and dispersing effect (mainly ethoxylated alkylphenol) and weight. A mixture of AEmulphor® EL (Emulan® EL, an ethoxylated fatty alcohol-based emulsifier), and diluted with water to the required concentration. Estimated by determining the percentage of infected leaf area. These percentages are converted into the degree of action, using the Colby, s formula [RS, Colby, Weeds IX, 20-22 (1967)] to determine the expected degree of action of the active ingredient mixture and to compare with the observed degree of action. Kirby formula: e = x ten y + z X y. Z / 100 E Expected degree of activity, when using a mixture of active ingredients A 'B and C in concentrations a, b, and c,% of untreated control Indicates that the degree of action x is the degree of action of y when the active ingredient A in the concentration a is used and the untreated control group, and the degree of action is 2 when the concentration of the active ingredient b in the concentration b is used and the untreated control group. The concentration of the active ingredient C in the concentration c and the untreated control group indicates' ", and the efficiency (E) is calculated using the following Abbot's formula: E = (1-) 10 0 //? Α relative to the treated plant % Infected with Pseudomonas spp., And-^ ------, install -------. Order ------ Wei (please read the precautions on the back before filling this page)- 12-

423958 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ¾ A7 B7 V. Description of the invention (10) The effect of the point (10) relative to the infection of P. infestans in the untreated plant (control group) 〇 The degree of infection indicates that the treated plant ’s infection is equivalent to Infection degree of untreated control plants: A degree of action of 100 indicates that the treated plants are uninfected. Examples 1 -1 4 Anti-Plasmopara viticola activity Multiple " Milller ^ Thurgau " The leaves are sprayed with an aqueous active compound preparation, consisting of 10% active compound, 63%. /. It is made of cyclohexanone and 27% emulsifier as raw material solution, spraying-until dripping. In order to evaluate the long term of the substance, the spray coating film was dried and the plants were left in the greenhouse for 7 days. The leaves were then inoculated only with an aqueous suspension of the zoospores of the genus Uniaxially grapes, and the vines were placed in a chamber saturated with water vapour at a temperature of 24. (: Let stand for 48 hours, and then put it in a greenhouse of 20-30 Ό for 5 days. Then the plants are placed in a high-humidity room for 16 hours to stimulate the fungus spores = Then visually evaluate the infection of the underside of the leaves Table 3. · Example concentration of activated cereal active compounds in carcass fluid (ppm) Degree of action of the treated control group%: IV control group (99% 〇 (untreated) infection 2V A = Table 1A1 25 74 ， No. 1.2 10 5 0 0 3V Table 1A 5------- ， No. 1.4 / 4 4V Π Group Napu 100 η 50, η 25 \ J 0 5V Hc = iL Dehu 100 74 50 — --48 -13- This paper uses Chinese National Standard (CNS) A4 (210X297 mm) ----- Ml It-I— II I--11-'Order --u-ll · — I Brigade (Please read the notes on the back before filling out this page) 423958 A7

7 B V. Description of the invention (11) Table 4: Example printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs of the Consumers 'Cooperative Cooperative Society' Concentration of active compound in spray solution (ppm) Observed degree of action Calculated action degree η: 6 10A + 100 lib, 100 0 ΐ 7 5A + 50 lib 100 0 3 10A + 50 lib 92 0 9 5Λ + 25 lib 92 0 10 25A + 25 lib 95 74 11 10A r + 100 lie 100 74 12 10A ten 50 lie 100 48 13 ^ 5B + 50 lib .92 74 1Λ 5B 4 50 lie 95 86 ν * Calculated by Kirby method This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) (Please read the note on the back first Please fill out this page again) /! 9 ^ ° 5 〇'42395b A7 B7 V. Description of the invention (丨 2) Example 15-33 Various activities against Phytophthora infe stans in Fanzhuang "GroBe Fleischtomate ) 'S potted prism leaf spraying aqueous suspension, which is prepared from a raw material solution containing 10% active compound '63% cyclohexanone and 27% emulsifier, spraying until dripping, clear. The next day, The leaves were infected with an aqueous suspension of zoospores of the pathogenic Phytophthora infestans. The plants were then placed at 16-18 ° C In a steam-saturated room, 6 days later, tomato blight developed in infected untreated control plants to a level where the percentage of infection can be visually assessed. (Please read the precautions on the back before filling out this page) Economic I Central Standard Bureau Cooperative Consumer Co-operative Printing Table 5: Example Active Compound Concentration of Active Compounds in Spray Solution (PPm) Degree of Action of Untreated Control Group 15V Control Group (99% 0 (Untreated) Infection 16V Β = Table 1A, 20 '88 No. 1.2 ", 1 0 0 5 0 17V Table 1A, 100 74 No. 1.4! 20 1 Π 65 XU 5 65 0 18V Π b = Manganese 100 50 0 〇 25 0 19V nc = Avoid rotten 500 93 This paper size applies to China National Standard (CNS) M specifications (210X297 mm) 8593 24

7 7 AB V. Description of the invention (〖3) Table 6: Concentration of active compounds in the spraying solution of Du Yinyu, an example of shellfish consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs (ppnj observed effect, calculated by the degree of action 1) (- ) 20 10Λ + 100 lib 100 0 21 5A + 50 lib 100, 0 22 20A + 100 lib 100 \ 86 23 10A + 50 lib 77 0 24 5A-+ 25 lib 77 0 25 5A + 50 lib 100 93 26 10A + 50 lie 100 93 27 10B f + 100 lib 100 65 28 5B +, 50 lib 100 0 29 2 OB + 100 lib 100 65 30 10B + 50 lib 100 65 '31 5B + 25 lib 77 0 32 100B + 100 lib 100 β 74 33 5B + 50 lie 100 93 • 16- --7--....... I—1 ”ί---s I k I n (Please read the notes on the back before filling this page) .1 The paper size applies to the Chinese National Standard (CNS) M specification (210X297 mm) 4 3 9 5 8 A7 B7 V. Description of the invention (14 Example 3 4 _ 4 0 Various curative activities against phytohormones) Batch of Uer-Thurgan "potted grape vine leaves were inoculated with an aqueous suspension of the spores of the fungal spores of the grape mold, and the vine was then placed in a steaming room at 22-24X for 48 hours, then Remove from the chamber, and spray with an active compound aqueous formulation until it dries. The formulation is prepared from a raw material solution of 10% active compound, 63% cyclohexanone, and 27% emulsifier. ° Spray After the coating film was dried, the plants were cultivated in a 20-3 ° C greenhouse for 5 days, and the plants were placed in a high-humidity climatic chamber-left for 16 hours to stimulate the fungus spore formation. Then, the degree of infection on the underside of the leaves was visually evaluated (Please read the precautions on the back before filling out this page) Printed by the Ministry of Economic Affairs, Standards Bureau, Consumer Cooperatives, Table 7 Example of the active compound active compound in the spray liquid (ppm) ^ Ice rent% 34V control group (un-treated) (99% infection) ---------------------- 0 35V Table 1A 25 ------ ---------- 19 0, No. 1.2 12.5 36V B = Table 1A, No. 1,4 12.5 · 0 37V ΙΙΙ = ΦPrivate Zero 25 "90 / 12.5 60 i this -17-2 IQX297 public director 423958 A7 B7 V. Description of the invention (15 Table 8: Example 38 '_____ 1' Active compound at-* Greaves peak. Concentration (ppm) --- "-Observation of the degree of action to calculate the _ degree 〇 · *) 25A + 25 III 100 92 39 12,5A + 80, 60 12.5 III 40 12.5B 80 60 12.5 III \ * Calculated by Kirby method. The results of the examples prove that the observed effects are higher than the effects calculated by the Kirby formula at all mixing ratios. IV. —Equipment ^ ^ Order --- Brigade (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs -18 Private paper standards are subject to the Chinese solid standard (CNS > A4 specifications (210X297)

Claims (1)

S 8 8 8 ABCD 8¾. Patent Application Fanyuan 1. A fungicidal mixture, including synergistically active amounts: a) Ether of formula I: ch3 N〇CH3 ZR '(I) The policy of the male workers' consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, where the substituents have the following meanings: X is amine (NH); Y is N; Z is oxygen or sulfur; alkyl; and b) Dithiocarbamates from: • Ethylbis (dithiocarbamate) manganese (zinc complex) (IIa), -Ethylbis (dithiocarbamate) ) Manganese (lib), ethylene bis (dithiocarbamate) zinc ammonium complex (VII) and-ethylene bis (dithiocarbamate) zinc (IId), or c) 1- (2-cyano-2-methoxyimine ethylamido) -3-ethylurea (III): H3CCH2-NHCONH-C (CN) = NOCH3 (III) 〇 2. According to the scope of patent application The fungicidal mixture of item 1 comprising ethylene dibis (dithiocarbamate) manganese (zinc complex) (IIa). 3. The fungicidal mixture according to item 1 of the patent application, including manganese (zinc complex) (IIb) of bis (dithioaminoformate). 4. According to the fungicidal mixture of item 1 of the scope of the patent application, including secondary ethyl bis ------------- (please read "Note on the back side ^ > before filling out this page) Paper size applies to China National Standards (CNS) A4 scale (2 丨 〇 X 2M mm) 423958 A8 B8 C8 DS Printed by the Central Standards Bureau of the Ministry of Economic Affairs and the Industrial Cooperative Cooperative. 6. Scope of Patent Application (Dithioamino Formate) Zinc Sulfate (IIC) ^ 5. The fungicidal mixture according to item 1 of the scope of patent application, including ethylene Zinc bis (dithiocarbamate) (11 d). 6. The fungicidal mixture according to item 1 of the scope of the patent application, including compound u or compound II »7. The fungicidal mixture according to claim 1 of the patent application, wherein the weight ratio of compound u to compound I is 2 0 0 : 1 to 0.1: 1 8. — A method for controlling harmful fungi, comprising treating harmful fungi with a compound of formula I according to item ^ of the scope of the patent application and a compound of formula n or formula III according to item 1 of the scope of the patent application 'Its environment, or treated plants, soil' areas, materials or spaces to keep them fungus-free; wherein the compound of formula I is an oxime ether of the formula: ch3 n〇ch3 z ~ η. '(丨). Wherein the substituent has The following meanings: X is amine (NH); Y is N; Z is oxygen or sulfur; IV is Cu alkyl; the compound of formula II is a dithiocarbamate selected from the group consisting of: Bis (dithiocarbamate) manganese (zinc complex) (IIa), -ethylene bis (dithiocarbamate) manganese (lib), -2- n ^ i -tf-1 in I r [) ^ (Please read the precautions on the back before filling in this page> i Paper Λ New Choi Guan Family Materials (CNS) (2ωχ 297 male thin) 423 95 8 as Β8 C8 DS 6. Scope of patent application-Ethyl bis (dithioaminocarboxylic acid) zinc amino complex (π) and-Ethyl bis (dithioaminocarboxylic acid) Zinc (lid) The compound of formula III is 1- (2-cyano-2-methoxyimine of ethylamidine) -3-ethylurea or H3CCH2-NHCONH-C (CN) = NOCH3. 9. According to the application The method according to item 8 of the patent includes the use of Compound I from 0.005 to 0.5 kg / public enemy. 10. The method according to item 8 of the patent application includes the use of Compound II from 0 "to 10 kg / are. -1 J. I ^^ 1 0---. U ^^^ 1 ^^^ 1 ^^^ 1 an HI — ^ i》 ai (please read the precautions on the back before writing this page) Printed by the Bureau ’s Consumer Cooperatives ^ This paper is a Chinese standard (CNS) M specification (210X297 mm) No. 86105284 patent + Chinese specification page, please order Ml. 4. Abstract of Chinese invention (name of invention) k hi Yuexin Correction Supplement I A fungicidal mixture comprising a synergistically active amount of a) fatty ether of formula I: (f) where the substituents have the following meanings: X is amine (NH); Y is N; Z is oxygen or sulfur; R 'is Cu alkyl; and (Please read the weeping matters on the back before filling in each page襕) Abstract of the invention in English (Name of the invention: FUNGICIDAL MIXTURES A fungicidal mixture comprising a) an oxime ether of the formula I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs x where the formulas have the following meaning: {〇is amino (NH); Y is N; Z is oxygen or sulfur; R 'is Ci-Cs-alkvl; and -2-This paper applies the Chinese National Standard (CNS) A4 specification (2) χ 297 mm 4 2 3 yb 〇 86105284 IV. Abstract of Chinese invention < Name of preparation b) Dithioamino formate selected from the following groups:-ethyl bis ( Dithioaminocarboxylic acid) (Zinc complex) (IIa) '-Ethylbis (dithioamino T acid) Photo (11b)'-Ethylbis (dithioamino acid) ) Zinc gas complex (Π) and-ethylene bis (dithiocarbamate) zinc (11 d) 'or c) 1- (2-cyano-2-methoxyimine) of the formula Ethyl) -3-ethylurea (Η1): h3cch2-nhconh-C (cn) = noch3 (ηι) ° (Please read the notes on the back before filling in the columns on this page) ---- * — J Order I -r English Abstract of Invention (Name of the invention: Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs b) a dithiocarbamate (II) selected from the group consisting of -manganese ethylenebis (dithiocarbamate) (zinc complex) (Ha),- m anganese ethylenebis (dithiocarbamate) -zinc ainmoniate ethylenebis (dithiocarbamate) (lie) and -2inc ethylenebis (dithiocarbamate) (lid) 〇rc) 1 ~ (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (工 工 I) H3CCH2- NHCONH'C (CN) = NOCH3 (III) in a synergistically active amount. -2b-This paper size is applicable to the national standard (CNS) M specification (210 X 297 cm) Line I S 8 8 8 ABCD 8¾. Patent Application Fanyuan 1. A fungicidal mixture, including synergistically active amounts: a) Ether of formula I: ch3 N〇CH3 ZR '(I) The policy of the male workers' consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, where the substituents have the following meanings: X is amine (NH); Y is N; Z is oxygen or sulfur; alkyl; and b) Dithiocarbamates from: • Ethylbis (dithiocarbamate) manganese (zinc complex) (IIa), -Ethylbis (dithiocarbamate) ) Manganese (lib), ethylene bis (dithiocarbamate) zinc ammonium complex (VII) and-ethylene bis (dithiocarbamate) zinc (IId), or c) 1- (2-cyano-2-methoxyimine ethylamido) -3-ethylurea (III): H3CCH2-NHCONH-C (CN) = NOCH3 (III) 〇 2. According to the scope of patent application The fungicidal mixture of item 1 comprising ethylene dibis (dithiocarbamate) manganese (zinc complex) (IIa). 3. The fungicidal mixture according to item 1 of the patent application, including manganese (zinc complex) (IIb) of bis (dithioaminoformate). 4. According to the fungicidal mixture of item 1 of the scope of the patent application, including secondary ethyl bis ------------- (please read "Note on the back side ^ > before filling out this page) Paper size applies to China National Standards (CNS) A4 scale (2 丨 〇 X 2M mm)