|Title of Invention||
A FUNGICIDAL MIXTURE
|Abstract||Disclosed is a process for producing zeaxanthin and ß-cryptoxanthin which comprises cultivating a recombinant microorganism which is expressing a ß-carotene hydroxylase gene and belonging to the genus Xanthophyllomyces (Phaffia) in an aqueous nutrient medium under aerobic conditions, and isolating the resulted carotenoids from the cells of said recombinant microorganism or from the cultured broth. C C C C C|
Moreover, the invention relates to methods for controlling harmful fungi using mixtures of the compounds I and/or Ila-f and III and the use of the compounds I and/or Ila-f and III for preparing such mixtures.
The compounds of the formula I, their preparation and their action against harmful fungi are known from the literature (WO-A 96/01256 and 96/01258).
The formula I represents in particular carbamates in which the combination of the substituents corresponds to one row of the following table:
The compounds of the formulae Ila-f, their preparation and their action against harmful fungi are likewise known from the literature.
The formula Ilf represents in particular compounds in which the combination of the variables X, Y and Z corresponds to one row of the table below:
Particular preference is given to the compounds 1.12, 1.23, 1.32 and 1.38. Particular preference is given to mixtures which comprise the compound 1.32 (common name: Pyraclostrobin). In another embodiment of the mixtures according to the invention, preference is given to the compound of the formula Ila.
The compound of the formula III (common name: dithianon) and processes for its preparation are described in GB-A 857 383.
It is an object of the present invention to provide mixtures which have improved activity against harmful fungi combined with a reduced total amount of active compounds applied (synergistic mixtures), with a view to reducing the application rates and improving the activity spectrum of the known compounds.
We have found that this object is achieved by the mixtures defined at the outset. Moreover, we have found that applying the compounds I and/or Ila-f and III simultaneously, i.e. together or separately, or applying the compounds I and/or Ila-f and III in succession provides better control of harmful fungi than is possible with the individual compounds alone.
In relation to the C=CH or C=N double bonds, the compounds of the formulae Ila-f can be present in the E or the Z configuration (in relation to the carboxylic acid function). Accordingly, they can be used in the mixture according to the invention either as pure E or Z isomers or as E/Z isomer mixtures. The E/Z isomer mixture or the Z isomer is preferably used, the Z isomer being particularly preferred.
The C=N double bond of the oxime ether group in the side chain of the compound lie can exist as pure E or Z isomers or as an E/Z isomer mixture. The compounds Ila-f can be used in the mixtures according to the invention either as isomer mixtures or as pure isomers.
Owing to their basic character, the compounds I, and Ila-f 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, carbonic acid, sulfuric acid, phosphoric acid and nitric acid.
Suitable organic acids are, for example, formic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, 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 with 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two sulfo groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic
radicals, such as phenyl and naphthyl, which carry one or two phosphoric acid radicals), it being possible for the alkyl or aryl radicals to carry further substituents, eg. p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.
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 subgroup, in particular chromium, manganese, iron, cobalt, nickel, copper and zinc, and others. Particular preference is given to the metal ions of the elements of the subgroups of the fourth period. The metals can be present in the various valencies which they can assume.
When preparing the mixtures, it is preferred to employ the pure active compounds I and/or Ila-f and III, with which further active compounds against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers can be admixed as required.
The mixtures of the compounds I and/or Ila-f and III, or the simultaneous, joint or separate use of the compounds I and/or Ila-f and III, have outstanding action against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically and are therefore also suitable for use as foliar and soil-acting fungicides.
They are especially important for controlling a large number of fungi in a variety of crop plants, such as cotton, vegetable species (for example cucumbers, beans and cucurbits), barley, grass, oats, coffee, maize, fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator 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 grapevines, Cercospora arachidicola in groundnuts,
Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Pseudoperonospora species in cucurbits and hops, Plasmopara viticola in grapevines, Alternaria species in vegetables and fruit and Fusarium and Verticillium species.
Furthermore, they can be used in the protection of materials (e.g. in the protection of wood), for example against Paecilomyces variotii.
The compounds I and/or Ila-f and III 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 control results.
The compounds I and/or Ila-f and III are usually applied in a weight ratio of from 10:1 to 1:100, preferably from 1:1 to 1:20, in particular from 1:1 to 1:10 (I and/or Ila-f : III).
Depending on the nature of the desired effect, the application rates of the mixtures according to the invention are, for the compounds I and/or Ila-f from 5 to 500 g/ha, preferably from 50 to 500 g/ha, in particular from 50 to 200 g/ha.
Correspondingly, the application rates of the compound III are usually from 5 to 2000 g/ha, preferably from 10 to 1000 g/ha, in particular from 50 to 750 g/ha.
For seed treatment, the application rates of the mixture are generally from 0.001 to 100 g/kg of seed, preferably 0.01 to 50 g/kg, in particular 0.01 to 10 g/kg.
If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and/or Ila-f and III or of the mixtures of the compounds I and/or Ila-f and III is effected by spraying or dusting the seeds, the plants or the soils before or after sowing, or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention, or the compounds I and/or Ila-f and III, 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, 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 ensure as fine and uniform a distribution as possible of the mixture according to the invention.
The formulations are prepared in a manner known per se, eg. by I adding solvents and/or carriers. It is usual to admix inert additives, such as emulsifiers or dispersants, with the formulations.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acids, 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, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose.
Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds I and/or Ila-f and III or the mixture of the compounds I and/or Ila-f and III with a solid carrier.
Granules (eg. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active compound, or active compounds, to a solid carrier.
Fillers or solid carriers are, for example, mineral earths, such as silica gel, silicic acids, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, 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.
The formulations generally comprise from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of one of the compounds I and/or Ila-f and III or of the mixture of the compounds I and/or Ila-f and III. The active compounds are employed in a purity of
from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum or HPLC).
The compounds I and/or Ila-f and III, the mixtures or the corresponding formulations are applied by treating the harmful fungi, the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally effective amount of the mixture, or of the compounds I and/or Ila-f and III in the case of separate applications. Application can be effected before or after infection by the harmful fungi.
The fungicidal activity of the compound and of the mixtures can be demonstrated by the following experiments:
The active compounds are prepared separately or together as a 10% strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkyl phenols) and 10% by weight of Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) and diluted with water to the desired concentration.
Evaluation is carried out by determining the infected leaf areas in percent. These percentages are converted into efficacies. The expected efficacies of the active compound mixtures are determined using Colby's formula [R.S. Colby, Weeds 15., 20-22 (1967)] and compared with the observed efficacies.
E = x + y -x-y/100
E expected efficacy, expressed in % of the untreated control,
when using the mixture of the active compounds A and B at the concentrations a and b
x efficacy, expressed in % of the untreated control, when using active compound A at a concentration of a
y efficacy, expressed in % of the untreated control, when using active compound B at a concentration of b
The efficacy (E) is calculated as follows using Abbot's formula:
E = (1 - cc/p)*100
a corresponds to the fungal infection of the treated plants in % and
P corresponds to the fungal infection of the untreated (control) plants in %
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.
Use Example 1 - activity against apple scab (Venturia inaequalis on apple trees)
During a summer season, the leaves of outdoor apple trees of the cultivar "Golden Delicious" were sprayed to runoff point eight times at intervals of 10 to 16 days using an aqueous suspension which had been prepared from a stock solution comprising 10% of active compound, 85% of cyclohexanone and 5% of emulsifier or mixtures of active compounds in the ratios given below. Owing to the natural infection pressure, the leaves were periodically infected by airborne spores or by wetting with aqueous spore suspensions of Venturia inaequalis. The climatic conditions supported the development of the foliar scab to such an extent that at the time of evaluation towards the end of the season virtually all leaves were infected with scab. The infection was determined visually in %.
The values determined visually for the percentage of infected leaf areas were converted into efficacies in % of the untreated control. An efficacy of 0 means the same degree of infection as in the untreated control, an efficacy of 100 means 0% infection. The expected efficacies of the active compound combinations were [lacuna] using Colby's formula (Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, 15., pp. 20-22, 1967).
The expected efficacies of the active compound combinations were determined using Colby's formula (Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, 15, pp. 2 0-22, 1967) and compared with the observed efficacies. ! Table 3: Comparative tests
* using Colby's formula
Use example 2 - activity against peronospora of vines caused by Plasmopara viticola
Leaves of potted vines of the cultivar "Muller-Thurgau" were sprayed to runoff point with an aqueous preparation of active compound which had been prepared from a stock solution comprising 10% of active compound, 85% of cyclohexanone and 5% of emulsifier. The next day, the undersides of the leaves were inoculated with an aqueous zoospore suspension of Plasmopara viticola. The vines were then initially placed in a water-vapor-saturated chamber at 24°C for 48 hours and then in a greenhouse at 20-30°C for 5 days. After this period of time, the plants were again placed in a moist chamber for 16 hours to promote sporangiophore eruption. The extent to which the infection had developed on the undersides of the leaves was then determined visually.
The values determined visually for the percentage of infected leaf area were converted into efficacies in percent of the untreated control as described above. The expected efficacies of the active compound combinations were determined using Colby's formula and compared with the observed efficacies.
The test results show that in all cases the observed efficacy is higher than the efficacy calculated beforehand using Colby's formula.
1. A fungicidal mixture, comprising A) at least one active strobilurin compound selected from al) carbamates of the formula I
in which T is OH or N, n is 0, 1 or 2 and R is halogen, Ci-C4-alkyl or Ci-C4-haloalkyl,
where the radicals R may be different if n is 2,
a2) the phenyl acetic acid derivatives of the formulae Ha to lie
T T ll TTJ*
3. The fungicidal mixture as claimed in claim 1, comprising the compound of the formula Ha.
4. 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 a compound of the formula I and/or Ila-f as claimed in claim 1 and the compound of the formula III as claimed in claim 1.
5. The method as claimed in claim 4, which comprises treating the harmful fungi, their
habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them
with from 5 to 500 g/ha of at least one compound I and/or Ila-f as claimed in claim 1.
6. The method as claimed in claim 4, which comprises treating the harmful fungi, their
habitat, or the plants, seeds, soils, areas, materials or spaces to be kept free from them
with from 5 to 2000 g/ha of the compound III as claimed in claim 1.
|Indian Patent Application Number||750/CHENP/2004|
|PG Journal Number||15/2008|
|Date of Filing||08-Apr-2004|
|Name of Patentee||BASF AKTIENGESELLSCHAFT|
|Applicant Address||D-67056 Ludwigshafen|
|PCT International Classification Number||A01N 43/32|
|PCT International Application Number||PCT/EP02/09835|
|PCT International Filing date||2002-09-03|