WO2021104910A1 - Method to control septoria tritici resistant to c14-demethylase inhibitor fungicides - Google Patents

Method to control septoria tritici resistant to c14-demethylase inhibitor fungicides Download PDF

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WO2021104910A1
WO2021104910A1 PCT/EP2020/082205 EP2020082205W WO2021104910A1 WO 2021104910 A1 WO2021104910 A1 WO 2021104910A1 EP 2020082205 W EP2020082205 W EP 2020082205W WO 2021104910 A1 WO2021104910 A1 WO 2021104910A1
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compound
mutation
plants
septoria tritici
del460
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PCT/EP2020/082205
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French (fr)
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Dieter Strobel
Christian Harald WINTER
Andreas Koch
Markus Gewehr
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Basf Se
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Priority to EP20804553.4A priority Critical patent/EP4064840A1/en
Publication of WO2021104910A1 publication Critical patent/WO2021104910A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention relates to a method for controlling Septoria tritici (synonym Zymoseptoria tritici ) resistant to C14-demethylase (in sterol biosynthesis) inhibitor fungicides (also called DMI fungicides) on cereal plants, comprising applying to the plants, their seed or the soil a fungicid- ally effective amount of 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4,5- dihydro-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (I) or 4-[[6-[2-(2,4-difluorophenyl)-1,1- difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyri
  • resistance refers to an acquired, heritable reduction in sensitivity of a fungus to a specific anti-fungal agent (or fungicide).
  • Septoria tritici is a species of filamentous fungus, an ascomycete in the family Myco- sphaerellaceae. It is a plant pathogen causing septoria leaf blotch, which is currently the most dominant cereal disease. Control of Septoria leaf blotch is becoming more and more difficult for farmers.
  • Reason is the capability of the fungi to develop resistance to widely used powerful fun gicidal agents. For example, fungicides containing azole and strobilurine mixtures have been widely and suc cessfully used in recent years for Septoria control.
  • DM I Demethlyation inhibitor
  • DM I fungicides are acting by inhibiting the enzyme lanosterol 14a-demethylase encoded by the CYP51 gene resulting in amino acid alterations.
  • the most important mechanisms leading to reduced DMI sensitivity are based on development of new mutations or on the accumulation of mutations in the CYP51 gene.
  • the present invention comprises a method for controlling Septoria tritici that is already resistant to DMI fungicides, in particular, Septoria tritici comprising mutations in the CYP51 gene, on cereals, said method comprising applying to the plants, their seed or the soil a fungi- cidally effective amount of 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-thioxo-4,5- dihydro-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (I) or 4-[[6-[2-(2,4-difluorophenyl)-1,1- difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (II).
  • compound (II) is applied.
  • compound (I) and compound (II) can be used in form of
  • compound (I) is used as racemate.
  • compound (I) is used as (R)-enantiomer with an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, pref erably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%.
  • compound (I) is used as a pure (R)-enantiomer.
  • compound (I) is used as (S)-enantiomer with an en antiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, prefera bly at least 90%, more preferably at least 95%, yet more preferably at least 98% and most pref erably at least 99%.
  • compound (I) is used as a pure (S)- enantiomer.
  • compound (II) is used as race- mate.
  • compound (II) is used as (R)-enantiomer with an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%.
  • compound (II) is used as a pure (R)-enantiomer.
  • compound (II) is used as (S)-enantiomer with an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, pref erably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%.
  • compound (II) is used as a pure (S)-enantiomer.
  • Septoria tritici resistant to DMI fungicides in particular Septo- ria tritici comprising at least one mutation in the CYP51 gene, is controlled.
  • the mutation occurs in the amino acid positions selected from 50, 107, 134, 136,
  • the mutations are preferably selected from the alterations listed in Table 1.
  • Septoria tritici comprises at least one mutation in the CYP51 gene.
  • the mutation is in the amino acid position 50, preferably the mutation is M.1.
  • the mutation is in the amino acid position 107, prefera bly the mutation is M.2.
  • the mutation is in the amino acid position 134, prefera bly the mutation is M.3.
  • the mutation is in the amino acid position 136, prefera bly the mutation is M.4 or M5.
  • the mutation is in the amino acid position 137, prefera bly the mutation is M.6.
  • the mutation is in the amino acid position 178, prefera bly the mutation is M.7.
  • the mutation is in the amino acid position 188, prefera bly the mutation is M.8. According another specific embodiment, the mutation is in the amino acid position 208, prefera bly the mutation is M.9.
  • the mutation is in the amino acid position 259, prefera bly the mutation is M.10.
  • the mutation is in the amino acid position 284, prefera bly the mutation is M.11.
  • the mutation is in the amino acid position 303, prefera bly the mutation is M.12.
  • the mutation is in the amino acid position 311 , prefera bly the mutation is M.13.
  • the mutation is in the amino acid position 312, prefera bly the mutation is M.14.
  • the mutation is in the amino acid position 379, prefera bly the mutation is M.15.
  • the mutation is in the amino acid position 381 , prefera bly the mutation is M.16.
  • the mutation is in the amino acid position 410, prefera bly the mutation is M.17.
  • the mutation is in the amino acid position 412, prefera bly the mutation is M.18.
  • the mutation is in the amino acid position 459, prefera bly the mutation is M.19, M.20, M.21 or M.22.
  • the mutation is in the amino acid position 460, prefera bly the mutation is M.23 or M.24.
  • the mutation is in the amino acid position 461 , prefera bly the mutation is M.25, M.26, M.27, M.28, M.29 or M.30.
  • the mutation is in the amino acid position 476, prefera bly the mutation is M.31.
  • the mutation is in the amino acid position 490, prefera bly the mutation is M.32.
  • the mutation is in the amino acid position 510, prefera bly the mutation is M.33.
  • the mutation is in the amino acid position 513, prefera bly the mutation is M.34.
  • the mutation is in the amino acid position 524, prefera bly the mutation is M.35.
  • Septoria tritici comprises at least two mutations in the CYP51 gene.
  • the said two mutations occur in the positions selected from 50+107, 50+134, 50+136, 50+137, 50+178, 50+188, 50+208, 50+259, 50+284, 50+303, 50+311 , 50+312, 50+379, 50+381 , 50+410, 50+412, 50+459, 50+460, 50+461, 50+476, 50+490, 50+510, 50+513, 50+524, 107+134, 107+136, 107+137, 107+178, 107+188, 107+208, 107+259, 107+284, 107+303, 107+311, 107+312, 107+379, 107+381, 107+410, 107+412, 107+459, 107+460, 107+461, 107+476, 107+490, 107+510, 107+513, 107+524, 134+136, 134+137, 134+178, 134+178,
  • the combination A15 is particularly preferred.
  • Septoria tritici comprises at least three mutations in the CYP51 gene.
  • the said three mutations occur in the positions selected from
  • Septoria tritici comprises at least four mutations in the CYP51 gene.
  • the said four mutations occur in the positions selected from
  • Septoria tritici comprises at least five mutations in the CYP51 gene.
  • Septoria tritici comprises at least six mutations in the CYP51 gene.
  • Septoria tritici comprises at least seven mutations in the CYP51 gene.
  • Septoria tritici comprises at least eight mutations in the CYP51 gene.
  • Septoria tritici comprises at least the following mutation combinations:
  • the method comprises applying a fungicidally effective amount of com pound (I) or compound (II) to the cereal plants.
  • the method comprises applying a fungicidally effective amount of compound (I) or compound (II) to the cereal seeds.
  • cereal as used herein comprises wheat and triticale.
  • the present invention relates to a method for controlling Sep- toria tritici that is resistant to DM I fungicides on wheat or triticale, comprising applying to the plants, their seed or the soil a fungicidally effective amount of compound (I) or compound (II).
  • the method comprises applying to the wheat or triticale plants a fungicidally effective amount of compound (I) or compound (II).
  • the method comprises applying to the wheat or triticale seeds a fungicidally effective amount of compound (I) or compound (II).
  • the present invention relates to a method for controlling Sep- toria tritici that is resistant to DM I fungicides on wheat, comprising applying to the plants, their seed or the soil a fungicidally effective amount of compound (I) or compound (II).
  • the method comprises applying to the wheat plants a fungicidally effective amount of compound (I) or compound (II).
  • the method comprises applying to the wheat seeds a fungicidally effective amount of compound (I) or compound (II).
  • Application of the compound (I) or compound (II) to the plants, their seed or the soil in the method according to present invention may be carried out in spray application, in seed treat- merit, in drip and drench applications, in-furrow applications, on-seed application and overall soil incorporation, chemigation, i.e. by addition of the active ingredients to the irrigation water, and in hydroponic/mineral systems.
  • fungicidal action against Septoria tritici means a signifi cant reduction in primary infection by Septoria tritici, compared with the untreated plant, prefer ably a significant reduction (by a value of between 40-79% compared to an untreated control plant), compared with the untreated plant (100%); more preferably, the primary infection by Septoria tritici is entirely suppressed (by a value of between 80-100% compared to an untreated control plant).
  • the control is for protection of plants which have not yet been infected.
  • the above reduction in primary infection by Septoria tritici, compared with the untreated plant is of at least 40%, more preferably at least 60%, even more preferably at least 70%.
  • the above reduction of at least 40%, more preferably at least 60%, even more preferably at least 70% is achieved by using at most 200 g a.i. / 100kg seed, such as at most 150 g a.i. / 100kg seed or such as at most 140 g a.i. / 100kg seed.
  • plant propagation material is to be understood to denote all the generative parts of the plant in particular seeds
  • Plants and as well as the propagation material of said plants, which can be treated with fungi- cidally effective amount of compound (I) or compound (II) include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecti cides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by tradi tional breeding methods and/or the generation of mutants, or by recombinant procedures.
  • compounds (I) or (II) in a method according to the present invention can be ap plied (as seed treatment, spray treatment, in furrow or by any other means) also to plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agri_products.asp).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modi fications also include but are not limited to targeted post-transitional modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • compound (I) or compound (II) can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, pow- ders, pastes granules, pressings, capsules, and mixtures thereof.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound I or compound (II).
  • the formulations are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: ’’Agglomeration”, Chemical Engi neering, Dec.
  • composition types see also “Catalogue of pesticide formulation types and interna tional coding system”, Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International) are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g.
  • suspensions e. g. SC, OD, FS
  • emulsifiable concentrates e. g. EC
  • emulsions e. g. EW, EO, ES, ME
  • capsules e. g. CS, ZC
  • pastes
  • WG WG
  • SG GR
  • FG GG
  • MG MG
  • insecti cidal articles e. g. LN
  • gel formulations for the treatment of plant propagation mate rials such as seeds (e. g. GF).
  • the formulations may comprise auxiliaries which are customary in agrochemical formulations.
  • auxiliaries which are customary in agrochemical formulations.
  • the auxiliaries used depend on the particular application form and active substance, respective ly.
  • auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment formulations).
  • the formulations generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substances.
  • the active substance concentrations in the ready-to-use preparations can be varied within rela tively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1% by weight of compound (I) or compound (II).
  • Compound (I) or compound (II) may be used together with other pesticides, such as herbicides, fungicides, insecticides or bactericides. These agents can be admixed with compound (I) or compound (II) in a weight ratio of 1:100 to 100:1, preferably 1 :10 to 10:1, if appropriate immedi ately prior to use (tank mix).
  • Compound (I) or compound (II) may also be used together with fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and saf- eners. These may be used sequentially or in combination with the above-described composi tions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with the fertilizers.
  • fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and saf- eners.
  • Compound (I) or compound (II) are applied by treating the fungi or the plants, plant propagation materials (preferably seeds), materials or soil to be protected from fungal attack with a pesti- cidally effective amount of compound (I) or compound (II).
  • the application can be carried out both before and after the infection of the materials, plants or plant propagation materials (pref erably seeds) by the pests.
  • pesticidally effective amount means the amount of compound (I) or compound (II) or of compositions comprising compound (I) or or compound (II) needed to achieve an observa ble effect on growth, including the effects of necrosis, death, retardation, prevention, and re moval, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary.
  • a pesticidally effective amount will also vary accord ing to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the application rates of compound (I) or compound (II) are from 0,1 g/ha to 10000 g/ha, preferably 2 g/ha to 2500 g/ha, more preferably from 5 to 1000 g/ha, most preferably from 10 to 750 g/ha, in particular from 20 to 700 g/ha.
  • the compound (I) or compound (II) are used for the protection of the seed and the seedlings' roots and shoots, preferably the seeds as set forth above.
  • compositions comprising compound (I) or compound (II) can be applied to plant propaga tion materials, particularly seeds, diluted or undiluted.
  • the compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, prefer ably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting and soaking application methods of the propa gation material (and also in furrow treatment).
  • the compounds or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the application rates of the in ventive mixture are generally for the formulated product (which usually comprises from 10 to 750 g/l of the active(s)) .
  • the compounds were dissolved in a mixture of acetone and/or dimethylsulfoxide and the wet ting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a ratio (volume) solvent-emulsifier of 99 to 1 to give a total volume of 5 ml. Subsequently, water was added to total volume of 100 ml. This stock solution was then diluted with the described solvent- emulsifier-water mixture to the final concentration given in the table below.
  • Wettol which is based on ethoxylated alkylphenoles
  • Leaves of potted wheat seedlings were inoculated with an aqueous spore suspension of Zy moseptoria tritici. Then the plants were immediately transferred to a humid chamber at 18-22°C and a saturated relative humidity. After 4 days, the plants were sprayed to run-off with the pre viously described spray solution. The plants were allowed to air-dry and then transferred to a greenhouse chamber at 18-22°C and a relative humidity of about 70 %. After 4 weeks the se verity of fungal attack on leaves was visually assessed as % diseased leaf area.
  • Leaves of potted wheat seedlings were sprayed to run-off with the previously described spray solution.
  • the plants were allowed to air-dry and then placed in a greenhouse chamber at 19°C and a relative humidity of about 55 %.
  • Seven days later the plants were inoculated with an aqueous spore suspension of Zymoseptoria tritici. Thereafter the plants were immediately trans ferred to a humid chamber at 18-22°C and a saturated relative humidity. After 4 days the plants were placed in chamber at 18-22°C and a relative humidity of about 70 %.
  • the severity of fungal attack on leaves was visually assessed as % diseased leaf area.
  • Isolate (A) carries the following mutations in CYP 51: L50S, V136A and Y461S.
  • Isolate (B) carries the following mutations in CYP 51: L50S, V136C, S188N, A379G, 1381V, Del Y459, DelG460, S524T

Abstract

Method to control Septoria tritici resistant to C14-demethylase inhibitor fungicides The present invention relates to a method for controlling Septoria tritici comprising at least one mutation in the CYP51 gene and being resistant to C14-demethylase (in sterol biosynthesis) inhibitor fungicides (DMI fungicides) on cereal plants, comprising applying to the plants, their seed or the soil a fungicidally effective amount of 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2- hydroxy-3-(5-thioxo-4,5-dihydro-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (I) or 4-[[6-[2- (2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (II).

Description

Method to control Septoria tritici resistant to C14-demethylase inhibitor fungicides Description The present invention relates to a method for controlling Septoria tritici (synonym Zymoseptoria tritici ) resistant to C14-demethylase (in sterol biosynthesis) inhibitor fungicides (also called DMI fungicides) on cereal plants, comprising applying to the plants, their seed or the soil a fungicid- ally effective amount of 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4,5- dihydro-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (I) or 4-[[6-[2-(2,4-difluorophenyl)-1,1- difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (II).
Compound (I) has the chemical formula
Figure imgf000002_0001
Compound (II) hast he chemical formula
Figure imgf000002_0002
One task the farmer is faced with in relation to the use of pesticides is that the repeated and exclusive application of an individual pesticidal compound leads in many cases to a rapid selec- tion of harmful fungi, which have developed acquired resistance against the active compound in question. Therefore, there is a need for pest control agents that help prevent or overcome such upcoming resistance.
The term “resistance” as used herein, refers to an acquired, heritable reduction in sensitivity of a fungus to a specific anti-fungal agent (or fungicide).
Septoria tritici is a species of filamentous fungus, an ascomycete in the family Myco- sphaerellaceae. It is a plant pathogen causing septoria leaf blotch, which is currently the most dominant cereal disease. Control of Septoria leaf blotch is becoming more and more difficult for farmers. Reason is the capability of the fungi to develop resistance to widely used powerful fun gicidal agents. For example, fungicides containing azole and strobilurine mixtures have been widely and suc cessfully used in recent years for Septoria control.
Strobilurins lost their activity due to the development of the G143A resistance which is mean while widespread in most cereal growing regions in Europe (Fraaije B. A., Brunett F. J., Clark W. S., Motteram J., Lucas J. A. (2005). Resistance development to Qol inhibitors in populations of Mycosphaerella graminicola in the UK. Modern fungicides and antifungal compounds II, eds Lyr H., Russell P. E., Dehne H-W. Gisi U. Kuck K-H, 14th International Reinhardsbrunn Sympo sium, BCPC, Alton, UK, pp 63-71).
The, activity of azole fungicides eroded due to a sensitivity shift of Septoria tritici. In particular, DM I (Demethlyation inhibitor) fungicides from the class of azoles lose their activity due to the development of resistance in different plant pathogenic fungi. The loss of activity is described in various publications such as
Cools H.J., Fraaije B.A. (2013). Update on mechanisms of azole resistance in Myco sphaerella graminicola and implications for future control. Pest Management Science 69: 150-155.
- AHDB Fungicide performance update December 2017
(https://cereals.ahdb.org.uk/media/1326769/Fungicide-performance-data-2017-7-December- 2017.pdf; page 24).
Huf A., Rehfus A., Lorenz K.-H., Bryson R., Voegele R.T. and Stammler G. (2018). Proposal for a new nomenclature for CYP51 haplotypes in Zymoseptoria tritici and analysis of their distribution in Europe. Plant Pathology DOI 10.1111/ppa.12891.
DM I fungicides are acting by inhibiting the enzyme lanosterol 14a-demethylase encoded by the CYP51 gene resulting in amino acid alterations. The most important mechanisms leading to reduced DMI sensitivity are based on development of new mutations or on the accumulation of mutations in the CYP51 gene.
Surprisingly, we have found that the application of 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2- hydroxy-3-(5-thioxo-4,5-dihydro-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (I) or 4-[[6-[2- (2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (II) shows an unexpected fungicidal activity towards Septoria tritici being resistant against DMI fungicides, in particular, towards Septoria tritici comprising mutations in the CYP51 gene.
Thus, the present invention comprises a method for controlling Septoria tritici that is already resistant to DMI fungicides, in particular, Septoria tritici comprising mutations in the CYP51 gene, on cereals, said method comprising applying to the plants, their seed or the soil a fungi- cidally effective amount of 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-thioxo-4,5- dihydro-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (I) or 4-[[6-[2-(2,4-difluorophenyl)-1,1- difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (II).
4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3- pyridyljoxyjbenzonitrile and 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4,5- dihydro-1, 2, 4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile are alternative names for compound
(I)·
According to one ambodiment compound (I) is applied.
According to another embodiment, compound (II) is applied.
According to still another embodiment, a mixture of compound (I) and compound (II) is applied.
4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4,5-dihydro-1,2,4-triazol-1- yl)propyl]-3-pyridyl]oxy]benzonitrile (I) and 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3- (1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (II) both comprise chiral centers and are generally obtained in the form of racemates. The R- and S-enantiomers of compound (I) and compound (II) can be separated and isolated in pure form with methods known by the skilled person, e.g. by using chiral HPLC.
Therefore, in the method according to the present invention, compound (I) and compound (II), can be used in form of
- a racemic mixture of the of the (R)-enantiomer and the (S)-enantiomer;
- a mixture with any other proportions of the (R)-enantiomer and the (S)-enantiomer;
- pure (R)-enantiomer or
- pure (S)-enantiomer.
According one specific embodiment of the present invention, compound (I) is used as racemate. According to one another specific embodiment, compound (I) is used as (R)-enantiomer with an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, pref erably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%. According to a particular embodiment, compound (I) is used as a pure (R)-enantiomer.
According to another specific embodiment, compound (I) is used as (S)-enantiomer with an en antiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, prefera bly at least 90%, more preferably at least 95%, yet more preferably at least 98% and most pref erably at least 99%. According to a particular embodiment, compound (I) is used as a pure (S)- enantiomer.
According one specific embodiment of the present invention, compound (II) is used as race- mate.
According to one another specific embodiment, compound (II) is used as (R)-enantiomer with an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%. According to a particular embodiment, compound (II) is used as a pure (R)-enantiomer.
According to another specific embodiment, compound (II) is used as (S)-enantiomer with an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, pref erably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%. According to a particular embodiment, compound (II) is used as a pure (S)-enantiomer.
According to the present invention Septoria tritici resistant to DMI fungicides, in particular Septo- ria tritici comprising at least one mutation in the CYP51 gene, is controlled.
Preferably, the mutation occurs in the amino acid positions selected from 50, 107, 134, 136,
137, 178, 188, 208, 259, 284, 303, 311, 312, 379, 381, 410, 412, 459, 460, 461, 476, 490, 510, 513, 524; more preferably in the positions 50, 134, 136, 188, 379, 381, 459, 460, 461, 513, 524, most preferably in the positions more preferably in the positions 50, 136, 381, 459, 460, 461, 524.
The mutations are preferably selected from the alterations listed in Table 1.
Table 1:
Figure imgf000005_0004
Figure imgf000005_0001
Figure imgf000005_0002
Figure imgf000005_0003
In this table, the alterations are to be understood as follows: for examples the alteration (M.1) L50S means that Leucin in position 50 is replaced by Serin.
According to one embodiment, Septoria tritici comprises at least one mutation in the CYP51 gene.
According one specific embodiment, the mutation is in the amino acid position 50, preferably the mutation is M.1.
According another specific embodiment, the mutation is in the amino acid position 107, prefera bly the mutation is M.2.
According another specific embodiment, the mutation is in the amino acid position 134, prefera bly the mutation is M.3.
According another specific embodiment, the mutation is in the amino acid position 136, prefera bly the mutation is M.4 or M5.
According another specific embodiment, the mutation is in the amino acid position 137, prefera bly the mutation is M.6.
According another specific embodiment, the mutation is in the amino acid position 178, prefera bly the mutation is M.7.
According another specific embodiment, the mutation is in the amino acid position 188, prefera bly the mutation is M.8. According another specific embodiment, the mutation is in the amino acid position 208, prefera bly the mutation is M.9.
According another specific embodiment, the mutation is in the amino acid position 259, prefera bly the mutation is M.10.
According another specific embodiment, the mutation is in the amino acid position 284, prefera bly the mutation is M.11.
According another specific embodiment, the mutation is in the amino acid position 303, prefera bly the mutation is M.12.
According another specific embodiment, the mutation is in the amino acid position 311 , prefera bly the mutation is M.13.
According another specific embodiment, the mutation is in the amino acid position 312, prefera bly the mutation is M.14.
According another specific embodiment, the mutation is in the amino acid position 379, prefera bly the mutation is M.15.
According another specific embodiment, the mutation is in the amino acid position 381 , prefera bly the mutation is M.16.
According another specific embodiment, the mutation is in the amino acid position 410, prefera bly the mutation is M.17.
According another specific embodiment, the mutation is in the amino acid position 412, prefera bly the mutation is M.18.
According another specific embodiment, the mutation is in the amino acid position 459, prefera bly the mutation is M.19, M.20, M.21 or M.22.
According another specific embodiment, the mutation is in the amino acid position 460, prefera bly the mutation is M.23 or M.24.
According another specific embodiment, the mutation is in the amino acid position 461 , prefera bly the mutation is M.25, M.26, M.27, M.28, M.29 or M.30.
According another specific embodiment, the mutation is in the amino acid position 476, prefera bly the mutation is M.31.
According another specific embodiment, the mutation is in the amino acid position 490, prefera bly the mutation is M.32.
According another specific embodiment, the mutation is in the amino acid position 510, prefera bly the mutation is M.33.
According another specific embodiment, the mutation is in the amino acid position 513, prefera bly the mutation is M.34.
According another specific embodiment, the mutation is in the amino acid position 524, prefera bly the mutation is M.35.
According to another embodiment, Septoria tritici comprises at least two mutations in the CYP51 gene.
Preferably, the said two mutations occur in the positions selected from 50+107, 50+134, 50+136, 50+137, 50+178, 50+188, 50+208, 50+259, 50+284, 50+303, 50+311 , 50+312, 50+379, 50+381 , 50+410, 50+412, 50+459, 50+460, 50+461, 50+476, 50+490, 50+510, 50+513, 50+524, 107+134, 107+136, 107+137, 107+178, 107+188, 107+208, 107+259, 107+284, 107+303, 107+311, 107+312, 107+379, 107+381, 107+410, 107+412, 107+459, 107+460, 107+461, 107+476, 107+490, 107+510, 107+513, 107+524, 134+136, 134+137, 134+178, 134+188, 134+208, 134+259, 134+284, 134+303, 134+311, 134+312, 134+379, 134+381, 134+410, 134+412, 134+459, 134+460, 134+461, 134+476, 134+490, 134+510, 134+513, 134+524, 136+137, 136+178, 136+188, 136+208, 136+259, 136+284, 136+303, 136+311, 136+312, 136+379, 136+381, 136+410, 136+412, 136+459, 136+460, 136+461, 136+476, 136+490, 136+510, 136+513, 136+524,
137+178, 137+188, 137+208, 137+259, 137+284, 137+303, 137+311, 137+312, 137+379, 137+381, 137+410, 137+412, 137+459, 137+460, 137+461, 137+476, 137+490, 137+510, 137+513, 137+524,
178+188, 178+208, 178+259, 178+284, 178+303, 178+311, 178+312, 178+379, 178+381, 178+410, 178+412, 178+459, 178+460, 178+461, 178+476, 178+490, 178+510, 178+513, 178+524,
188+208, 188+259, 188+284, 188+303, 188+311, 188+312, 188+379, 188+381, 188+410, 188+412, 188+459, 188+460, 188+461, 188+476, 188+490, 188+510, 188+513, 188+524,
208+259, 208+284, 208+303, 208+311, 208+312, 208+379, 208+381, 208+410, 208+412, 208+459, 208+460, 208+461, 208+476, 208+490, 208+510, 208+513, 208+524, 259+284, 259+303, 259+311, 259+312, 259+379, 259+381, 259+410, 259+412, 259+459, 259+460, 259+461 , 259+476, 259+490, 259+510, 259+513, 259+524, 284+303, 284+311, 284+312, 284+379, 284+381, 284+410, 284+412, 284+459, 284+460, 284+461, 284+476, 284+490, 284+510, 284+513, 284+524, 303+311, 303+312, 303+379, 303+381, 303+410, 303+412, 303+459, 303+460, 303+461, 303+476, 303+490, 303+510, 303+513, 303+524, 311+312, 311+379, 311+381, 311+410, 311+412, 311+459, 311+460, 311+461, 311+476, 311+490, 311+510, 311+513, 311+524, 312+379, 312+381, 312+410, 312+412, 312+459, 312+460, 312+461, 312+476, 312+490, 312+510, 312+513, 312+524,
379+381, 379+410, 379+412, 379+459, 379+460, 379+461, 379+476, 379+490, 379+510, 379+513, 379+524,
381+410, 381+412, 381+459, 381+460, 381+461, 381+476, 381+490, 381+510, 381+513, 381+524,
410+412, 410+459, 410+460, 410+461, 410+476, 410+490, 410+510, 410+513, 410+524, 412+459, 412+460, 412+461, 412+476, 412+490, 412+510, 412+513, 412+524, 459+460, 459+461, 459+476, 459+490, 459+510, 459+513, 459+524, 460+461, 460+476, 460+490, 460+510, 460+513, 460+524, 461+476, 461+490, 461+510, 461+513, 461+524, 476+490, 476+510, 476+513, 476+524, 490+510, 490+513, 490+524,
510+513, 510+524,
513+524. The sign “+” is to be read as “and”, so that, for example, the mutations occuring in the positions 50+107 means that one mutation occurs in the position 50 and the second one in the position 107. Specific combinations of the two mutations in CYP51 gene of Septoria tritici are given in Table
A.
Table A
Figure imgf000008_0001
Figure imgf000008_0002
Figure imgf000008_0003
Figure imgf000009_0001
Figure imgf000009_0002
Figure imgf000009_0003
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0003
Figure imgf000011_0001
Figure imgf000011_0002
Figure imgf000011_0003
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000012_0003
Figure imgf000013_0003
Figure imgf000013_0001
Figure imgf000013_0002
The combination A15 is particularly preferred.
According to a further embodiment, Septoria tritici comprises at least three mutations in the CYP51 gene.
Preferably, the said three mutations occur in the positions selected from
50+134+136, 50+134+188, 50+134+379, 50+134+381, 50+134+459,
50+134+460, 50+134+461, 50+134+513, 50+134+524, 50+136+188,
50+136+379, 50+136+381, 50+136+459, 50+136+460, 50+136+461,
50+136+513, 50+136+524, 50+188+379, 50+188+381, 50+188+459,
50+188+460, 50+188+461, 50+188+513, 50+188+524, 50+379+381,
50+379+459, 50+379+460, 50+379+461 , 50+379+513, 50+379+524,
50+381+459, 50+381+460, 50+381+461, 50+381+513, 50+381+524,
50+459+460, 50+459+461 , 50+459+513, 50+459+524, 50+460+461 ,
50+460+513, 50+460+524, 50+461+513, 50+461+524, 50+513+524,
134+136+188, 134+136+379, 134+136+381, 134+136+459, 134+136+460,
134+136+461, 134+136+513, 134+136+524, 134+188+379, 134+188+381,
134+188+459, 134+188+460, 134+188+461, 134+188+513, 134+188+524,
134+379+381, 134+379+459, 134+379+460, 134+379+461, 134+379+513,
134+379+524, 134+381+459, 134+381+460, 134+381+461, 134+381+513,
134+381+524, 134+459+460, 134+459+461, 134+459+513, 134+459+524,
134+460+461, 134+460+513, 134+460+524, 134+461+513, 134+461+524
134+513+524,
136+188+379, 136+188+381, 136+188+459, 136+188+460, 136+188+461,
136+188+513, 136+188+524, 136+379+381, 136+379+459, 136+379+460,
136+379+461, 136+379+513, 136+379+524, 136+381+459, 136+381+460,
136+381+461, 136+381+513, 136+381+524, 136+459+460, 136+459+461,
136+459+513, 136+459+524, 136+460+461, 136+460+513, 136+460+524,
136+461+513, 136+461+524, 136+513+524,
188+379+381, 188+379+459, 188+379+460, 188+379+461, 188+379+513,
188+379+524, 188+381+459, 188+381+460, 188+381+461, 188+381+513,
188+381+524, 188+459+460, 188+459+461, 188+459+513, 188+459+524,
188+460+461, 188+460+513, 188+460+524, 188+461+513, 188+461+524, 188+513+524,
379+381+459, 379+381+460, 379+381+461, 379+381+513, 379+381+524,
379+459+460, 379+459+461 , 379+459+513, 379+459+524, 379+460+461 ,
379+460+513, 379+460+524, 379+461+513, 379+461+524, 379+513+524,
381+459+460, 381+459+461, 381+459+513, 381+459+524, 381+460+461,
381+460+513, 381+460+524, 381+461+513, 381+461+524, 381+513+524,
459+460+461 , 459+460+513, 459+460+524, 459+461+513, 459+461+524, 459+513+524,
460+461+513, 460+461+524, 460+513+524,
461+513+524.
According to a further embodiment, Septoria tritici comprises at least four mutations in the CYP51 gene.
Preferably, the said four mutations occur in the positions selected from
50+134+136+188, 50+134+136+379, 50+134+136+381, 50+134+136+459,
50+134+136+460, 50+134+136+461, 50+134+136+513, 50+134+136+524,
50+134+188+379, 50+134+188+381, 50+134+188+459, 50+134+188+460,
50+134+188+461, 50+134+188+513, 50+134+188+524, 50+134+379+381,
50+134+379+459, 50+134+379+460, 50+134+379+461, 50+134+379+513,
50+134+379+524, 50+134+381+459, 50+134+381+460, 50+134+381+461,
50+134+381+513, 50+134+381+524, 50+134+459+460, 50+134+459+461,
50+134+459+513, 50+134+459+524, 50+134+460+461, 50+134+460+513,
50+134+460+524, 50+134+461+513, 50+134+461+524, 50+134+513+524,
50+136+188+379, 50+136+188+381, 50+136+188+459, 50+136+188+460,
50+136+188+461, 50+136+188+513, 50+136+188+524, 50+136+379+381,
50+136+379+459, 50+136+379+460, 50+136+379+461, 50+136+379+513,
50+136+379+524, 50+136+381+459, 50+136+381+460, 50+136+381+461,
50+136+381+513, 50+136+381+524, 50+136+459+460, 50+136+459+461,
50+136+459+513, 50+136+459+524, 50+136+460+461, 50+136+460+513,
50+136+460+524, 50+136+461+513, 50+136+461+524, 50+136+513+524,
50+188+379+381, 50+188+379+459, 50+188+379+460, 50+188+379+461,
50+188+379+513, 50+188+379+524, 50+188+381+459, 50+188+381+460,
50+188+381+461, 50+188+381+513, 50+188+381+524, 50+188+459+460,
50+188+459+461, 50+188+459+513, 50+188+459+524, 50+188+460+461,
50+188+460+513, 50+188+460+524, 50+188+461+513, 50+188+461+524,
50+188+513+524, 50+379+381+459, 50+379+381+460, 50+379+381+461,
50+379+381+513, 50+379+381+524, 50+379+459+460, 50+379+459+461,
50+379+459+513, 50+379+459+524, 50+379+460+461, 50+379+460+513, 50+379+460+524, 50+379+461+513, 50+379+461+524, 50+379+513+524, 50+381+459+460, 50+381+459+461, 50+381+459+513, 50+381+459+524, 50+381+460+461, 50+381+460+513, 50+381+460+524, 50+381+461+513, 50+381+461+524, 50+381+513+524, 50+459+460+461, 50+459+460+513, 50+459+460+524, 50+459+461+513, 50+459+461+524, 50+459+513+524, 50+460+461+513, 50+460+461+524, 50+460+513+524, 50+461+513+524,
134+136+188+379 134+136+188+381, 134+136+188+459, 134+136+188+460
134+136+188+461 134+136+188+513, 134+136+188+524, 134+136+379+381
134+136+379+459 134+136+379+460, 134+136+379+461, 134+136+379+513
134+136+379+524 134+136+381+459, 134+136+381+460, 134+136+381+461
134+136+381+513 134+136+381+524, 134+136+459+460, 134+136+459+461
134+136+459+513 134+136+459+524, 134+136+460+461, 134+136+460+513
134+136+460+524 134+136+461+513, 134+136+461+524, 134+136+513+524
134+188+379+381 134+188+379+459, 134+188+379+460, 134+188+379+461
134+188+379+513 134+188+379+524, 134+188+381+459, 134+188+381+460
134+188+381+461 134+188+381+513, 134+188+381+524, 134+188+459+460
134+188+459+461 134+188+459+513, 134+188+459+524, 134+188+460+461
134+188+460+513 134+188+460+524, 134+188+461+513, 134+188+461+524
134+188+513+524 134+379+381+459, 134+379+381+460, 134+379+381+461
134+379+381+513 134+379+381+524, 134+379+459+460, 134+379+459+461
134+379+459+513 134+379+459+524, 134+379+460+461, 134+379+460+513
134+379+460+524 134+379+461+513, 134+379+461+524, 134+379+513+524
134+381+459+460 134+381+459+461, 134+381+459+513, 134+381+459+524
134+381+460+461 134+381+460+513, 134+381+460+524, 134+381+461+513
134+381+461+524 134+381+513+524, 134+459+460+461, 134+459+460+513
134+459+460+524 134+459+461+513, 134+459+461+524, 134+459+513+524
134+460+461+513 134+460+461+524, 134+460+513+524, 134+461+513+524
136+188+379+381 136+188+379+459, 136+188+379+460, 136+188+379+461
136+188+379+513 136+188+379+524, 136+188+381+459, 136+188+381+460
136+188+381+461 136+188+381+513, 136+188+381+524, 136+188+459+460
136+188+459+461 136+188+459+513, 136+188+459+524, 136+188+460+461
136+188+460+513 136+188+460+524, 136+188+461+513, 136+188+461+524
136+188+513+524 136+379+381+459, 136+379+381+460, 136+379+381+461
136+379+381+513 136+379+381+524, 136+379+459+460, 136+379+459+461
136+379+459+513 136+379+459+524, 136+379+460+461, 136+379+460+513
136+379+460+524 136+379+461+513, 136+379+461+524, 136+379+513+524
136+381+459+460 136+381+459+461, 136+381+459+513, 136+381+459+524
136+381+460+461 136+381+460+513, 136+381+460+524, 136+381+461+513
136+381+461+524 136+381+513+524, 136+459+460+461, 136+459+460+513
136+459+460+524 136+459+461+513, 136+459+461+524, 136+459+513+524
136+460+461+513 136+460+461+524, 136+460+513+524, 136+461+513+524 188+379+381+459, 188+379+381+460, 188+379+381+461, 188+379+381+513,
188+379+381+524, 188+379+459+460, 188+379+459+461, 188+379+459+513,
188+379+459+524, 188+379+460+461, 188+379+460+513, 188+379+460+524,
188+379+461+513, 188+379+461+524, 188+379+513+524, 188+381+459+460,
188+381+459+461, 188+381+459+513, 188+381+459+524, 188+381+460+461,
188+381+460+513, 188+381+460+524, 188+381+461+513, 188+381+461+524,
188+381+513+524, 188+459+460+461, 188+459+460+513, 188+459+460+524,
188+459+461+513, 188+459+461+524, 188+459+513+524, 188+460+461+513,
188+460+461+524, 188+460+513+524, 188+461+513+524,
379+381+459+460, 379+381+459+461, 379+381+459+513, 379+381+459+524,
379+381+460+461, 379+381+460+513, 379+381+460+524, 379+381+461+513,
379+381+461+524, 379+381+513+524, 379+459+460+461 , 379+459+460+513,
379+459+460+524, 379+459+461+513, 379+459+461+524, 379+459+513+524,
379+460+461+513, 379+460+461+524, 379+460+513+524, 379+461+513+524,
381+459+460+461, 381+459+460+513, 381+459+460+524, 381+459+461+513,
381+459+461+524, 381+459+513+524, 381+460+461+513, 381+460+461+524,
381+460+513+524, 381+461+513+524,
459+460+461+513, 459+460+461+524, 459+460+513+524, 459+461+513+524,
460+461+513+524.
According to a further embodiment, Septoria tritici comprises at least five mutations in the CYP51 gene.
According to a further embodiment, Septoria tritici comprises at least six mutations in the CYP51 gene.
According to a further embodiment, Septoria tritici comprises at least seven mutations in the CYP51 gene.
According to a further embodiment, Septoria tritici comprises at least eight mutations in the CYP51 gene.
According to specific embodiments, Septoria tritici comprises at least the following mutation combinations:
L50S (M.1) + 1381V (M.16) + Y461H (M.26);
L50S (M.1) + V136A (M.4) + Y461S (M.29);
L50S (M.1) + V136A (M.4) + 1381V (M.16) + Y461S (M.29) + S524T (M.35);
L50S (M.1) + D134G (M.3) + V136A (M.4) + 1381V (M.16) + Y461H (M.26);
L50S (M.1) + V136A (M.4) + 1381V (M.16) + Y461H (M.26);
L50S (M.1) + S188N (M.8) + 1381V (M.16) + Del459 (M.22) + Del460 (M.24) + N513K (M.34); • L50S (M.1) + D134G (M.3) + V136A (M.4) + 1381V (M.16) + Y461H (M.26) + S524T (M.35);
• L50S (M.1) + S188N (M.8) + A379G (M.15) + 1381V (M.16) + Del459 (M.22) + Del460 (M.24) + N513K (M.34);
• L50S (M.1) + V136A (M.4) + S188N (M.8) + A379G (M.15) + 1381V (M.16) + Del459 (M.22) + Del460 (M.24) + S524T (M.35);
• L50S (M.1) + V136C (M.5) + S188N (M.8) + A379G (M.15) + 1381V (M.16) + Del459 (M.22) + Del460 (M.24) + S524T(M.35);
• V136A + S524T;
• V136A + 1381V + S524T;
• A379G + 1381V;
• V136C + DEL459 + DEL460;
• A379G + 1381V + S524T + DEL459 + DEL460.
In one embodiment, the method comprises applying a fungicidally effective amount of com pound (I) or compound (II) to the cereal plants.
In a further embodiment, the method comprises applying a fungicidally effective amount of compound (I) or compound (II) to the cereal seeds.
The term “cereal” as used herein comprises wheat and triticale.
Thus, in a preferred embodiment, the present invention relates to a method for controlling Sep- toria tritici that is resistant to DM I fungicides on wheat or triticale, comprising applying to the plants, their seed or the soil a fungicidally effective amount of compound (I) or compound (II).
In a further preferred embodiment, the method comprises applying to the wheat or triticale plants a fungicidally effective amount of compound (I) or compound (II).
In a further preferred embodiment, the method comprises applying to the wheat or triticale seeds a fungicidally effective amount of compound (I) or compound (II).
In a more preferred embodiment, the present invention relates to a method for controlling Sep- toria tritici that is resistant to DM I fungicides on wheat, comprising applying to the plants, their seed or the soil a fungicidally effective amount of compound (I) or compound (II).
In a further more preferred embodiment, the method comprises applying to the wheat plants a fungicidally effective amount of compound (I) or compound (II).
In a further more preferred embodiment, the method comprises applying to the wheat seeds a fungicidally effective amount of compound (I) or compound (II).
Application of the compound (I) or compound (II) to the plants, their seed or the soil in the method according to present invention may be carried out in spray application, in seed treat- merit, in drip and drench applications, in-furrow applications, on-seed application and overall soil incorporation, chemigation, i.e. by addition of the active ingredients to the irrigation water, and in hydroponic/mineral systems.
In the context of the present invention, fungicidal action against Septoria tritici means a signifi cant reduction in primary infection by Septoria tritici, compared with the untreated plant, prefer ably a significant reduction (by a value of between 40-79% compared to an untreated control plant), compared with the untreated plant (100%); more preferably, the primary infection by Septoria tritici is entirely suppressed (by a value of between 80-100% compared to an untreated control plant). The control is for protection of plants which have not yet been infected.
In a preferred embodiment, the above reduction in primary infection by Septoria tritici, compared with the untreated plant is of at least 40%, more preferably at least 60%, even more preferably at least 70%.
In another preferred embodiment, the above reduction of at least 40%, more preferably at least 60%, even more preferably at least 70% is achieved by using at most 200 g a.i. / 100kg seed, such as at most 150 g a.i. / 100kg seed or such as at most 140 g a.i. / 100kg seed.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant in particular seeds
Plants and as well as the propagation material of said plants, which can be treated with fungi- cidally effective amount of compound (I) or compound (II) include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecti cides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by tradi tional breeding methods and/or the generation of mutants, or by recombinant procedures.
For example, compounds (I) or (II) in a method according to the present invention can be ap plied (as seed treatment, spray treatment, in furrow or by any other means) also to plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agri_products.asp). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modi fications also include but are not limited to targeted post-transitional modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
For use according to the present invention, compound (I) or compound (II) can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, pow- ders, pastes granules, pressings, capsules, and mixtures thereof. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound I or compound (II). The formulations are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: ’’Agglomeration”, Chemical Engi neering, Dec. 4, 1967, 147-48, Perry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701, US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Con trol as a Science (J. Wiley & Sons, New York, 1961), Hance et al. : Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation tech nology (Wiley VCH Verlag, Weinheim, 2001).
Examples for composition types (see also “Catalogue of pesticide formulation types and interna tional coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International) are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecti cidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation mate rials, such as seeds (e. g. GF).
The formulations may comprise auxiliaries which are customary in agrochemical formulations. The auxiliaries used depend on the particular application form and active substance, respective ly.
Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment formulations).
The formulations generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substances.
The active substance concentrations in the ready-to-use preparations can be varied within rela tively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1% by weight of compound (I) or compound (II).
Compound (I) or compound (II) may be used together with other pesticides, such as herbicides, fungicides, insecticides or bactericides. These agents can be admixed with compound (I) or compound (II) in a weight ratio of 1:100 to 100:1, preferably 1 :10 to 10:1, if appropriate immedi ately prior to use (tank mix).
Compound (I) or compound (II) may also be used together with fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and saf- eners. These may be used sequentially or in combination with the above-described composi tions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with the fertilizers.
Compound (I) or compound (II) are applied by treating the fungi or the plants, plant propagation materials (preferably seeds), materials or soil to be protected from fungal attack with a pesti- cidally effective amount of compound (I) or compound (II). The application can be carried out both before and after the infection of the materials, plants or plant propagation materials (pref erably seeds) by the pests.
In general, "pesticidally effective amount" means the amount of compound (I) or compound (II) or of compositions comprising compound (I) or or compound (II) needed to achieve an observa ble effect on growth, including the effects of necrosis, death, retardation, prevention, and re moval, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary. A pesticidally effective amount will also vary accord ing to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
In the method of combating harmful fungi depending on the desired effect, the application rates of compound (I) or compound (II) are from 0,1 g/ha to 10000 g/ha, preferably 2 g/ha to 2500 g/ha, more preferably from 5 to 1000 g/ha, most preferably from 10 to 750 g/ha, in particular from 20 to 700 g/ha.
In an alternative embodiment of the invention, the compound (I) or compound (II) are used for the protection of the seed and the seedlings' roots and shoots, preferably the seeds as set forth above.
The compositions comprising compound (I) or compound (II) can be applied to plant propaga tion materials, particularly seeds, diluted or undiluted. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, prefer ably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting and soaking application methods of the propa gation material (and also in furrow treatment). In a preferred embodiment, the compounds or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
In the treatment of plant propagation material (preferably seed), the application rates of the in ventive mixture are generally for the formulated product (which usually comprises from 10 to 750 g/l of the active(s)) .
The invention is further illustrated, but not limited by the following practical examples:
Examples: The compounds were dissolved in a mixture of acetone and/or dimethylsulfoxide and the wet ting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a ratio (volume) solvent-emulsifier of 99 to 1 to give a total volume of 5 ml. Subsequently, water was added to total volume of 100 ml. This stock solution was then diluted with the described solvent- emulsifier-water mixture to the final concentration given in the table below.
1. Curative control of leaf blotch on wheat caused by Zymoseptoria tritici (SEPTTR K4)
Leaves of potted wheat seedlings were inoculated with an aqueous spore suspension of Zy moseptoria tritici. Then the plants were immediately transferred to a humid chamber at 18-22°C and a saturated relative humidity. After 4 days, the plants were sprayed to run-off with the pre viously described spray solution. The plants were allowed to air-dry and then transferred to a greenhouse chamber at 18-22°C and a relative humidity of about 70 %. After 4 weeks the se verity of fungal attack on leaves was visually assessed as % diseased leaf area.
2. Preventative control of leaf blotch on wheat caused by Zymoseptoria tritici (SEPTTR P7)
Leaves of potted wheat seedlings were sprayed to run-off with the previously described spray solution. The plants were allowed to air-dry and then placed in a greenhouse chamber at 19°C and a relative humidity of about 55 %. Seven days later the plants were inoculated with an aqueous spore suspension of Zymoseptoria tritici. Thereafter the plants were immediately trans ferred to a humid chamber at 18-22°C and a saturated relative humidity. After 4 days the plants were placed in chamber at 18-22°C and a relative humidity of about 70 %. After 4 weeks, the severity of fungal attack on leaves was visually assessed as % diseased leaf area.
Inoculation of different strains:
Trials were inoculated with two different isolates of Zymoseptoria tritici.
Isolate (A) carries the following mutations in CYP 51: L50S, V136A and Y461S.
Isolate (B) carries the following mutations in CYP 51: L50S, V136C, S188N, A379G, 1381V, Del Y459, DelG460, S524T
Table E1. Fungicidal activity of against Zymoseptoria tritici having specified combinations of mutations
Figure imgf000021_0001
Comparative examples

Claims

Claims
1. A method for controlling Septoria tritici resistant to DMI fungicides in cereals, comprising applying to the plants, their seed or the soil a fungicidally effective amount of 4-[[6-[2-(2,4- difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-thioxo-4,5-dihydro-1,2,4-triazol-1-yl)propyl]-3- pyridyl]oxy]benzonitrile (I) or 4-[[6-[2-(2,4-difluorophenyl)-1 , 1 -difluoro-2-hydroxy-3-(1 ,2,4- triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (II), wherein the Septoria tritici comprises at least one mutation in the CYP51 gene.
2. A method according to claim 1 , wherein the mutation occurs in the amino acid positions selected from 50, 107, 134, 136, 137, 178, 188, 208, 259, 284, 303, 311, 312, 379, 381 , 410, 412, 459, 460, 461 , 476, 490, 510, 513 or 524.
3. A method according to claims 1 or 2, wherein the mutation occurs in the amino acid posi tions selected from 50, 134, 136, 188, 379, 381, 459, 460, 461 , 513 or 524.
4. A method according to any one of claims 1 to 3, wherein the mutation is selected from
M.1 L50S, M.2 D107V, M.3 D134G, M.4 V136A, M.5 V136C, M.6 Y137F, M.7 N178S, M.8 S188N, M.9 S208T, M.10 S259F, M.11 N284H, M.12 H303Y, M.13 A311G, M.14 G312A, M.15 A379G, M.16 1381V, M.17 A410T, M.18 G412A, M.19 Y459C, M.20 Y459D, M.21 Y459S, M.22 Del459, M.23 G460D, M.24 Del460, M.25 Y461G, M.26 Y461 H, M.27 Y461 L M.28 Y461 N, M.29 Y461S, M.30 Del461 , M.31 G476S, M.32 V490L, M.33 G510C, M.34 N513K, M.35 S524T.
5. A method according to to any one of claims 1 to 4, wherein the Septoria tritici comprises at least two mutations in the CYP51 gene.
6. A method according to any one of claims 1 to 5, wherein Septoria tritici comprises the mutations selected from the following combinations:
. L50S (M.1) + 1381V (M.16) + Y461H (M.26);
. L50S (M.1) + V136A (M.4) + Y461S (M.29);
. L50S (M.1) + V136A (M.4) + 1381V (M.16) + Y461S (M.29) + S524T (M.35);
. L50S (M.1) + D134G (M.3) + V136A (M.4) + 1381V (M.16) + Y461 H (M.26);
. L50S (M.1) + V136A (M.4) + 1381V (M.16) + Y461H (M.26);
. L50S (M.1) + S188N (M.8) + 1381V (M.16) + Del459 (M.22) + Del460 (M.24) + N513K (M.34);
. L50S (M.1) + D134G (M.3) + V136A (M.4) + 1381V (M.16) + Y461H (M.26) + S524T (M.35);
. L50S (M.1) + S188N (M.8) + A379G (M.15) + 1381V (M.16) + Del459 (M.22) + Del460 (M.24) + N513K (M.34);
. L50S (M.1) + V136A (M.4) + S188N (M.8) + A379G (M.15) + 1381V (M.16) + Del459 (M.22) + Del460 (M.24) + S524T (M.35);
. L50S (M.1) + V136C (M.5) + S188N (M.8) + A379G (M.15) + 1381V (M.16) + Del459 (M.22) + Del460 (M.24) + S524T (M.35);
. V136A (M.4) + S524T (M.35);
. V136A (M.4) + 1381V (M.16) + S524T (M.35);
. A379G (M.15) + 1381V (M.16);
. V136C (M.5) + DEL459 (M.22) + DEL460 (M.24);
. A379G (M.15) + 1381V (M.16) + DEL459 (M.22) + DEL460 (M.24) + S524T (M.35).
7. A method according to any one of claims 1 to 6, wherein compound (I) or compound (II) is applied to the plants, soil or seed of plants.
8. A method according to any one of claims 1 to 7, wherein compound (I) or compound (II) is applied to the plants.
9. A method according to any one of claims 1 to 7, wherein compound (I) or compound (II) is applied to the soil.
10. A method according to any one of claims 1 to 7, wherein compound (I) or compound (II) is applied to the seed of plants.
11. A method according to any of claims 1 to 9, wherein compound (I) or compound (II) is applied to plants or soil in an amount from 5 g/ha to 2500 g/ha.
12. A method according to any one of claims 1 to 7 or 10, wherein compound (I) or compound (II) is applied to seeds in an amount from 0.01 g to 10 kg per 100 kg.
13. A method according to any of claims 1 to 12, wherein the cereal is wheat or triticale.
14. Use of 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4,5-dihydro-1,2,4- triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (I) or 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro- 2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (II) to control Septoria triti- ci, that is resistant to DMI fungicides, in cereals, wherein Septoria tritici comprises at least one mutation in the CYP51 gene.
15. Use according to claim 14, wherein the cereal is wheat or triticale.
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Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3060084A (en) 1961-06-09 1962-10-23 Du Pont Improved homogeneous, readily dispersed, pesticidal concentrate
US3299566A (en) 1964-06-01 1967-01-24 Olin Mathieson Water soluble film containing agricultural chemicals
US3920442A (en) 1972-09-18 1975-11-18 Du Pont Water-dispersible pesticide aggregates
US4144050A (en) 1969-02-05 1979-03-13 Hoechst Aktiengesellschaft Micro granules for pesticides and process for their manufacture
US4172714A (en) 1976-12-20 1979-10-30 E. I. Du Pont De Nemours And Company Dry compactible, swellable herbicidal compositions and pellets produced therefrom
GB2095558A (en) 1981-03-30 1982-10-06 Avon Packers Ltd Formulation of agricultural chemicals
WO1991013546A1 (en) 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Water-dispersible or water-soluble pesticide granules from heat-activated binders
US5180587A (en) 1988-06-28 1993-01-19 E. I. Du Pont De Nemours And Company Tablet formulations of pesticides
US5208030A (en) 1989-08-30 1993-05-04 Imperial Chemical Industries Plc Active ingredient dosage device
US5232701A (en) 1990-10-11 1993-08-03 Sumitomo Chemical Company, Limited Boron carbonate and solid acid pesticidal composition
EP0707445A1 (en) 1993-07-03 1996-04-24 Basf Ag Stable, ready-to-use, multi-phase aqueous pesticide formulations and methods of preparing them
WO2016187201A2 (en) * 2015-05-18 2016-11-24 Viamet Pharmaceuticals, Inc. Antifungal compounds
WO2017029179A1 (en) * 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Triazole derivatives, intermediates thereof and their use as fungicides
WO2017162564A1 (en) * 2016-03-24 2017-09-28 Bayer Cropscience Aktiengesellschaft Method to control septoria leaf blotch caused by resistant zymoseptoria tritici strains

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3060084A (en) 1961-06-09 1962-10-23 Du Pont Improved homogeneous, readily dispersed, pesticidal concentrate
US3299566A (en) 1964-06-01 1967-01-24 Olin Mathieson Water soluble film containing agricultural chemicals
US4144050A (en) 1969-02-05 1979-03-13 Hoechst Aktiengesellschaft Micro granules for pesticides and process for their manufacture
US3920442A (en) 1972-09-18 1975-11-18 Du Pont Water-dispersible pesticide aggregates
US4172714A (en) 1976-12-20 1979-10-30 E. I. Du Pont De Nemours And Company Dry compactible, swellable herbicidal compositions and pellets produced therefrom
GB2095558A (en) 1981-03-30 1982-10-06 Avon Packers Ltd Formulation of agricultural chemicals
US5180587A (en) 1988-06-28 1993-01-19 E. I. Du Pont De Nemours And Company Tablet formulations of pesticides
US5208030A (en) 1989-08-30 1993-05-04 Imperial Chemical Industries Plc Active ingredient dosage device
WO1991013546A1 (en) 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Water-dispersible or water-soluble pesticide granules from heat-activated binders
US5232701A (en) 1990-10-11 1993-08-03 Sumitomo Chemical Company, Limited Boron carbonate and solid acid pesticidal composition
EP0707445A1 (en) 1993-07-03 1996-04-24 Basf Ag Stable, ready-to-use, multi-phase aqueous pesticide formulations and methods of preparing them
WO2016187201A2 (en) * 2015-05-18 2016-11-24 Viamet Pharmaceuticals, Inc. Antifungal compounds
WO2017029179A1 (en) * 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Triazole derivatives, intermediates thereof and their use as fungicides
WO2017162564A1 (en) * 2016-03-24 2017-09-28 Bayer Cropscience Aktiengesellschaft Method to control septoria leaf blotch caused by resistant zymoseptoria tritici strains

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
"Advances in Applied Microbiology", vol. 90, 30 September 2014, ACADEMIC PRESS, United States, ISBN: 978-0-12-002658-6, ISSN: 0065-2164, article JOHN A. LUCAS ET AL: "The Evolution of Fungicide Resistance", pages: 29 - 92, XP055561097, DOI: 10.1016/bs.aambs.2014.09.001 *
"Technical Monograph", 2008, CROPLIFE INTERNATIONAL, article "Catalogue of pesticide formulation types and international coding system"
AHDB FUNGICIDE PERFORMANCE UPDATE, December 2017 (2017-12-01), pages 24, Retrieved from the Internet <URL:https://cereals.ahdb.org.uk/media/1326769/Fungicide-performance-data-2017-7-December-2017.pdf>
BROWNING: "Agglomeration", CHEMICAL ENGINEERING, 4 December 1967 (1967-12-04), pages 147 - 48
COOLS H.J.FRAAIJE B.A.: "Update on mechanisms of azole resistance in Mycosphaerella graminicola and implications for future control", PEST MANAGEMENT SCIENCE, vol. 69, 2013, pages 150 - 155, XP055266573, DOI: 10.1002/ps.3348
FRAAIJE B. A.BRUNETT F. J.CLARK W. S.MOTTERAM J.LUCAS J. A.: "Resistance development to Qol inhibitors in populations of Mycosphaerella graminicola in the UK. Modern fungicides and antifungal compounds II", 14TH INTERNATIONAL REINHARDSBRUNN SYMPOSIUM, BCPC, 2005, pages 63 - 71
HANCE ET AL.: "Weed Control Handbook", 1989, BLACKWELL SCIENTIFIC
HUF A.REHFUS A.LORENZ K.-H.BRYSON R.VOEGELE R.T.STAMMLER G.: "Proposal for a new nomenclature for CYP51 haplotypes in Zymoseptoria tritici and analysis of their distribution in Europe", PLANT PATHOLOGY, 2018
KLINGMAN: "Weed Control as a Science", 1961, J. WILEY & SONS
MOLLET, H.GRUBEMANN, A.: "Formulation technology", 2001, WILEY VCH VERLAG
PERRY'S: "Chemical Engineer's Handbook", 1963, MCGRAW-HILL, pages: 8 - 57
THIES MARTEN HEICK ET AL: "Resistance of wheat pathogen Zymoseptoria tritici to DMI and QoI fungicides in the Nordic-Baltic region - a status", EUROPEAN JOURNAL OF PLANT PATHOLOGY, vol. 149, no. 3, 28 March 2017 (2017-03-28), NL, pages 669 - 682, XP055659697, ISSN: 0929-1873, DOI: 10.1007/s10658-017-1216-7 *
TOM ALLEN-STEVENS: "Fungicide chemistry - Disease control 'enters a new phase' - cpm magazine", 31 July 2019 (2019-07-31), XP055647431, Retrieved from the Internet <URL:http://www.cpm-magazine.co.uk/2019/07/31/fungicide-chemistry-disease-control-enters-new-phase/> [retrieved on 20191128] *

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