NZ500988A

NZ500988A - Fungicidal mixture comprising a phenyl benzyl ether and (2-chlorophenyl)-(4-chlorophenyl)-(pyrimidin-5-yl)methanol

Info

Publication number: NZ500988A
Application number: NZ500988A
Authority: NZ
Inventors: Siegfried Strathmann; Klaus Schelberger; Dietrich Mappes; Gerd Stammler; Hubert Sauter; Erich Birner; Manfred Hampel; Eberhard Ammermann; Gisela Lorenz
Original assignee: Basf Ag
Priority date: 1997-05-30
Filing date: 1998-05-18
Publication date: 2001-11-30
Also published as: BR9809514A; UA63959C2; CZ426499A3; CN101253862B; JP2002500657A; CO5040025A1; IL132717A; HUP0004178A3; SK283727B6; TW394668B; PT984690E; DK0984690T3; EA199901067A1; CZ293939B6; EP0984690B1; KR100495844B1; CN1259011A; CA2290519A1; DE59807876D1; AR013925A1

Abstract

A fungicidal mixture comprising synergistic amounts of; (a) a phenyl benzyl derivative of the formula I.a or I.b; and (b) compound of formula II, (±)-(2-cholrophenyl) (4-chlorophenyl) (primidin-5-yl)methanol.

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number 500988 0050/48028 ft®® b* <T i Fungicidal mixture The present invention relates to a fungicidal mixture which comprises 10 a) a phenyl benzyl ether derivative of the formula I.a or I.b CH3 CH3 .0^ Jk .0. 15 0CHn 0CH3 CH3 |.b and 20 t>) (±) - (2-chlorophenyl) (4-chlorophenyl) (pyrxmidin-5-yl)methanol CI OH 25 V C. -J/ \ N\ _ N in a synergistically effective amount. 30 Moreover, the invention relates to methods for controlling harmful fungi using mixtures of the compounds I (I.a and I.b) and II and to the use of the compounds I and II for the preparation of such mixtures. The compounds I, their preparation and their activity against 35 harmful fungi are disclosed in the literature (EP-A 253 213, EP-A 254 426). Also disclosed is the compound II (GB-A 1,218,623 and EP-A-645084 common name: Fenarimol), its preparation and its activity against 40 harmful fungi. It is an object of the present invention to provide mixtures which have an improved activity against harmful fungi combined with a reduced total amount of active ingredients applied 45 (synergistic mixtures), with a view to reducing the application , '"6V.:ce Or hz. } :: 17^-17:71 5 y t » - |i 5 10 15 20 0050/48028 rates and. to improving' the activity spectrum of the known compounds. It is a further object of the invention to at least provide the public with a useful alternative. We have found that these objects are achieved by the mixture defined at the outset. Moreover, we have found that better control of harmful fungi is possible by applying the compound I and the compound II simultaneously, either together or separately, or by applying the compound I and the compounds II in succession than when the individual compounds are used on their own. Owing to their basic character, the compounds I and the compound II are capable of forming salts or adducts with inorganic or organic acids or with metal ions. Examples of inorganic acids are hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydriodic acid, and furthermore sulfuric acid, phosphoric acid and nitric acid. Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, 25 and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals, such as phenyl 30 and naphthyl, which carry one or two sulfo groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two phosphoric acid 35 radicals), it being possible for the alkyl or aryl radicals to carry further substituents, e.g. p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc. 40 45 Suitable metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, of the third and fourth main group, in particular aluminum, tin and lead, and of the first to eighth sub-group, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Particular preference is given to.the metal ions of' the 1 |;-r , ' j '"c..'ce or- NZ. j r «7 onoi >! j / V I /. O w1 I I 0050/48028 I o 3 elements of the sub-groups of the fourth period. The metals can exist in the various valences which they can assume. When preparing the mixtures, it is preferred to employ pure 5 active ingredients I and II, to which further active ingredients against harmful fungi of other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active ingredients or fertilizers can be admixed, if so required. 10 The mixtures of compounds I and II, or the simultaneous joint or separate use of the compounds I and II, exhibit outstanding activity against a wide range of phytopathogenic fungi, m particular from the classes of the Ascomycetes, Basidiomycetes, ^ Phycomycetes and Deuteromycetes. Some of them act systemically and can therefore be employed as foliar and soil-acting fungicides. They are especially important for controlling a large number of 20 fungi in a variety of crop plants, such as cotton, vegetable species (e.g. cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds. 25 They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) m cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator 30 in grapevines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries, vegetables, ornamentals and 35 grapevines, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in grapevines, Pseudoperonospora species in hops and cucumbers, Alternaria 40 species in vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species. 45 Furthermore, it can be used in the production of materials (e.g. in the protection of wood), for example against Paecilomyces variotii. , - !. r riCPi ITY I CrT C12 OF N Z. • \ n o r> i . * /-• U I 0050/48028 4 The compounds I and II can be applied simultaneously, either together or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures. 5 The compounds I and II are usually used in a weight ratio of 10:1 to 0.1:1, preferably 5:1 to 0.2:1, in particular 3:1 to 0.3:1. 10 Depending on the kind of effect desired, the application rates of the mixtures according to the invention are, in particular in agricultural crops, from 0.01 to 8 kg/ha, preferably 0.1 to 5 kg/ha, in particular 0.2 to 3.0 kg/ha. 15 The application rates of the compounds I are from 0.005 to 0.5 kg/ha, preferably 0.05 to 0.5 kg/ha, in particular 0.05 to 0.3 kg/ha. 20 Correspondingly, in the case of compounds II, the application rates are from 0.05 to 0.5 kg/ha, preferably 0.1 to 0.5 kg/ha, in particular 0.1 to 0.3 kg/ha. For seed treatment, the application rates of mixture are 25 generally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, in particular 0.01 to 50 g/kg. If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and II or of the mixtures of the compounds I and II is effected by spraying or dusting the seeds, the plants or the soils before or after sowing of the plants, or before or after plant emergence. 35 The fungicidal synergistic mixtures according to the invention, or the compounds I and II, can be formulated for example in the form of ready-to-spray solutions, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, 40 dusts, materials for broadcasting or granules, and applied by spraying, atomizing, dusting, broadcasting or watering. The use form depends on the intended purpose; in any case, it should guarantee as fine and uniform as possible a distribution of the mixture according to the invention. 45 5 The formulations are prepared in a manner known per se, e.g. by adding solvents and/or carriers. It is usual to admix inert additives, such as emulsifiers or dispersants, with the formulations. 5 Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, e.g. lignin-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, 15 polyoxyethylene octyl phenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohols/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or 20 polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose. Powders, materials for broadcasting and dusts can be prepared by 25 mixing or joint grinding of the compounds I or II or the mixture of the compounds I and II with a solid carrier. Granules (e.g. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active 30 ingredient, or active ingredients, to a solid carrier. Fillers or solid carriers are, for example, mineral earths, such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, 35 calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, and fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers. 40 The formulations generally comprise from 0.1 to 95% by weight, preferably 0.5 to 90 % by weight, of one of the compounds I or II or of the mixture of the compounds 3 and II. The active ingredients are employed in a purity of from 90% to 100%, 45 preferably 95% to 100% (according to NMR-spectrum-or; HPLC) . ' O,-,::CE OF NZ. i il 4 *7 i i M i| i i % j /.uji i « 0050/48028 6 The compounds I or II, or the mixtures, or the corresponding formulations, are applied by treating the harmful fungi, their habitat, or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally active amount of 5 the mixture, or of the compounds I and II in the case of separate application. Application can be effected before or after infection by the harmful fungi. 10 Use example The synergistic activity of the mixtures according to the 15 invention was demonstrated by the following experiments: The active ingredients, separately or together, were formulated as a 10% emulsion in a mixture of 63% by weight of cyclohexanone and 27% by weight of emulsifier, and diluted with water to a 20 desired concentration. Use example 1 - Activity against Puccinia recondita on wheat (wheat leaf rust) 25 Leaves of potted wheat seedlings of the variety "Friihgold" were dusted with spores of the wheat leaf rust (Puccinia recondita). Thereafter, the pots were kept in a chamber of high atmospheric humidity (90 to 95%) and 20 to 22°C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into 30 the leaf tissue. The next day, the infected plants were sprayed to runoff point with an aqueous preparation of active ingredient which had been prepared from a stock solution comprising 10% of active compound, 63% of cyclohexanone and 27% of emulsifier. After the spraycoating had dried on, the test plants were 35 cultivated for 7 days in a greenhouse at 20-22°C and 65-70% relative atmospheric humidity. Thereafter, the extent of the rust fungus development on the leaves was determined. Evaluation was carried out by determining the infected leaf 40 areas in percent. These percentages were converted into efficacies. The efficacy (E) was calculated as follows using Abbot's formula: 45 E= (1 - a)*100/p 0050/48028 7 a corresponds to the fungal infection of the treated plants in % and p corresponds to the fungal infection of the untreated (control) plants in % 5 An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected. 10 The expected efficacies of the mixtures of the active ingredients were determined using Colby's formula [R.S. Colby, Weeds 15., 20-22 (1967)] and compared with the observed efficacies. 15 Colby's formula: E = x + y - x*y/100 E expected efficacy, expressed in % of the untreated control, 2Q when using the mixture of the active ingredients A and B at the concentrations a and b x efficacy, expressed in % of the untreated control, when using active ingredient A at a concentration of a y efficacy, expressed in % of the untreated control, when 25 using active ingredient B at a concentration of b The results are shown in Tables 2 and 3 below. Table 2 Ex. Active ingredient Concentration of Efficacy in % of active ingredient the untreated in the spray control liquor in ppm 1 C Control (100% infection) 0 (untreated) 2 C la 200 20 100 20 50 0 3 C II 20 0 10 0 45 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 0050/48028 8 Table 3 5 Ex. Mixtures according to the invention Observed efficacy Calculated efficacy*);4;200 ppm la +;20 ppm II (mixture 10:1);65;20;10;5;100 ppm la +;2 0 ppm 11 (mixture 5:1);70;20;6;50 ppm la;35;0;15;10 ppm lb (mixture 5:1);*") calculated using Colby's formula The test results show that the observed efficacy in all mixing ratios is higher than the efficacy which had been calculated beforehand using Colby's formula (from Synerg 101.XLS). 25 30 35 40 45 0050/48028 J o n We claim: 1.
A fungicidal mixture, comprising 10 15 a) a phenyl benzyl ether derivative of the formula I.a or I.b and 20 25 b) (±)-(2-chlorophenyl)(4-chlorophenyl)(pyrimidin-5-yl)methanol CI CI // w OH C - V // w in a synergistically effective amount. 30 A fungicidal mixture as claimed m claim 1, wherein the weight ratio of the compounds I to the compound II is 10:1 to 0.1:1. 35 40 45
3. A method for controlling harmful fungi, which comprises treating the harmful fungi, their habitat, or the plants, seeds, soils, areas, materials or spaces to be kept free from them with synergistically effective amounts of a compound of the formula I as set forth in claim 1 and the compound of the formula II as set forth in claim 1.
4. A method as claimed in claim 3, wherein a compound I as set forth in claim 1 and the compound II as set forth in claim 1 are applied simultaneously, that is either together or separately, or in succession. , ' Or.'-.Ct Or N I. 17,!' i i::i 0050/48028 £f=> ^ b> • ■ ^ 10
5. A method as claimed in claim 3, wherein the harmful fungi, their habitat, or the plants, seeds, soils, areas, materials, or spaces to be kept free from them are treated with 0.005 to 0.5 kg/ha of a compound I as set forth in 5 claim 1. 10 15
6. A method as claimed in claim 3, wherein the harmful fungi, their habitat, or the plants, seeds, soils, areas, materials or spaces to be kept free from them are treated with 0.05 to 0.5 kg/ha of the compound II as set forth in claim 1.
7. The use of a compound I as set forth in claim 1 for preparing fungicidally effective synergistic mixtures as claimed in claim 1.
8. The use of the compound II as set forth in claim 1 for preparing fungicidally active synergistic mixtures as claimed in claim 1. 20
9. A fungicidal composition comprising a mixture as claimed m claim 1 which is conditioned in two parts, one part comprising a compound of the formula I as set forth in claim 1 in a solid or liquid carrier, and the other part comprising a compound of the 25 formula II as set forth in claim 1 in a solid or liquid carrier.
10. A fungicidal mixture as claimed in claim 1, substantially as herein described with reference to any one of the Examples, 30 excluding the comparative Example.
11. A fungicidal mixture as claimed in any one of claims 1, 2 or 9, substantially as herein described.
12. A method as claimed in claim 3, substantially as herein described with reference to any one of the Examples, excluding the comparative Example. 40
13. A method as claimed in any one of claims 3 to 6, substantially as herein described. 45
14. The use as claimed in claim 7 or claim 8, substantially as herein described. BASF Aktiengesellschaft 35 by its Attorneys BALDWIN SHELSTON WATERS </div>