WO2020078942A1 - 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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Publication number
WO2020078942A1
WO2020078942A1 PCT/EP2019/077852 EP2019077852W WO2020078942A1 WO 2020078942 A1 WO2020078942 A1 WO 2020078942A1 EP 2019077852 W EP2019077852 W EP 2019077852W WO 2020078942 A1 WO2020078942 A1 WO 2020078942A1
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WIPO (PCT)
Prior art keywords
mutation
compound
trifluoromethyl
triazol
septoria tritici
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PCT/EP2019/077852
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French (fr)
Inventor
Dieter Strobel
Christian Winter
Andreas Koch
Markus Gewehr
Gerd Stammler
Martin Semar
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BASF Agro B.V.
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Publication date
Application filed by BASF Agro B.V. filed Critical BASF Agro B.V.
Priority to EP19789647.5A priority Critical patent/EP3866602A1/en
Publication of WO2020078942A1 publication Critical patent/WO2020078942A1/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 treating the plants, their seed or the soil with a fungi- cidally effective amount of a compound of formula (I)
  • A is CH or N
  • R 1 is selected from hydrogen, (Ci-C 6 )-alkyl, C(0)CH 3 ;
  • R 2 is selected from hydrogen, (Ci-C 6 )-alkyl or (C3-C6)-cycloalkyl;
  • R 3 is selected from hydrogen, halogen, (Ci-C 6 )-alkyl or (Ci-C 6 )-haloalkyl;
  • R 4 is selected from halogen, (Ci-C 6 )-alkyl, (Ci-C 6 )-haloalkyl, (Ci-C 6 )-alkoxy or (Ci-Ce)- haloalkoxy;
  • n 0, 1 , 2, 3.
  • 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.
  • 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 ).
  • DMI Demethlyation inhibitor
  • DMI 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 treating the plants, their seed or the soil with a fungi- cidally effective amount of a compound of formula (I)
  • A is CH or N
  • R 1 is selected from hydrogen, (Ci-C 6 )-alkyl or C(0)CH 3 ;
  • R 2 is selected from hydrogen, (Ci-C 6 )-alkyl or (C3-C6)-cycloalkyl;
  • R 3 is selected from hydrogen, halogen, (Ci-C 6 )-alkyl or (Ci-C 6 )-haloalkyl;
  • R 4 is selected from halogen, (Ci-C 6 )-alkyl, (Ci-C 6 )-haloalkyl, (Ci-Ce)-alkoxy or (O I -O Q )- haloalkoxy;
  • n 0, 1 , 2, 3.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • Ci-C 6 -alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,
  • C2-C4-alkyl refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1-methylethyl (iso-propoyl), butyl, 1-methylpropyl (sec. -butyl), 2-methylpropyl (iso-butyl), 1 ,1-dimethylethyl (tert-butyl).
  • Ci-C 6 -haloalkyl refers to an alkyl group having 1 or 6 carbon atoms, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1- chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2- chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl.
  • C3-C6-cycloalkyl refers to monocyclic saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Ci-C 6 -alkoxy refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen at any position in the alkyl group.
  • Examples are “C1-C4- alkoxy” groups, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1- methyhpropoxy, 2-methylpropoxy or 1 ,1-dimethylethoxy.
  • Ci-C 6 -haloalkoxy refers to a Ci-C 6 -alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • a preferred embodiment of a Ci-C 6 -haloalkoxy is a Ci-C4-haloalkoxy.
  • C1- C4-haloalkoxy groups include substituents, such as OCH2F, OCHF2, OCF 3 , OCH2CI, OCHC , OCCI 3 , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro- 2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichlorcnethoxy, OC2F 5 , OCF2CHF2, OCHF-CF 3 , 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy,
  • resistance refers to an acquired, heritable reduction in sensitivity of a fungus to a specific anti-fungal agent (or fungicide).
  • A is CH or N. According to one embodiment, A is CH. Ac- cording to another embodiment, A is N.
  • R 1 is selected from hydrogen, (Ci-C 6 )-alkyl or C(0)CH 3 ; preferably from hydrogen or (Ci-C 6 )-alkyl, more preferably from hydrogen, CH 3 , C2H 5 or CH(CH 3 ) 2 .
  • R 1 is hydrogen
  • R 1 is (Ci-C 6 )-alkyl, preferably CH 3 , C2H 5 or
  • R 1 is C(0)CH 3 .
  • R 2 is selected from hydrogen, (Ci-C 6 )-alkyl or (C 3 -C 6 )- cycloalkyl, preferably from hydrogen, CH 3 , C 2 H 5 or cyclopropyl, more preferably from hydrogen, CH 3 or cyclopropyl.
  • R 2 is hydrogen
  • R 2 is (Ci-C 6 )-alkyl, preferably CH 3 or C 2 H 5 .
  • R 2 is (C3-C6)-cycloalkyl, preferably cyclopropyl.
  • R 3 is selected from hydrogen, halogen, (Ci-C 6 )-alkyl or (C1- C 6 )-haloalkyl; preferably from halogen or (Ci-C 6 )-haloalkyl, more preferably from (O I -O Q )- haloalkyl.
  • R 3 is hydrogen
  • R 3 is halogen, preferably F or Cl.
  • R 3 is (Ci-C 6 )-alkyl, preferably CH 3 or C 2 H 5 .
  • R 3 is (Ci-C 6 )-haloalkyl, preferably CF 3 .
  • R 4 is selected from halogen, (Ci-C 6 )-alkyl, (Ci-C 6 )-haloalkyl, (Ci-Ce)-alkoxy or (Ci-C 6 )-haloalkoxy; preferably from preferably from halogen, (Ci-C 6 )-alkyl, (C1- C 6 )-haloalkyl or (Ci-C 6 )-haloalkoxy, more preferably from halogen;
  • R 4 is selected from halogen, (Ci-C 6 )-haloalkyl or (O-I-OQ)- haloalkoxy; preferably from hydrogen, F, Cl, Br, CH3, CF3 or OCF3.
  • R 4 is halogen, preferably from Cl or Br.
  • R 4 is (Ci-C 6 )-alkyl, preferably CH 3 .
  • R 4 is (Ci-C 6 )-haloalkyl, preferably CF 3 .
  • R 4 is (Ci-C 6 )-alkoxy, preferably OCH 3 .
  • R 4 is (Ci-C 6 )-haloalkoxy, preferably OCF 3 .
  • n is 0, 1 , 2 or 3, preferably 0, 1 or 2, more preferably 1. According to one specific embodiment, n is 0.
  • n is 1. According to another specific embodiment, n is 2.
  • n 3.
  • R 1 is selected from hydrogen or (Ci-C 6 )-alkyl
  • R 2 is selected from hydrogen, (Ci-C 6 )-alkyl or (C3-C6)-cycloalkyl;
  • R 3 is selected from halogen or (Ci-C 6 )-haloalkyl
  • R 4 is selected from halogen, (Ci-C 6 )-alkyl, (Ci-C 6 )-haloalkyl or (Ci-C 6 )-haloalkoxy; n is 0, 1 or 2.
  • R 1 is selected from hydrogen, CH3, C2H5 or CH(CH3)2;
  • R 2 is selected from hydrogen, CH 3 , C2H 5 or cyclopropyl
  • R 3 is selected from F, Cl or CF 3 ;
  • R 4 is selected from F, Cl, Br, CH 3 , CF 3 or OCF 3 ;
  • n 0, 1 or 2.
  • R 1 is hydrogen
  • R 2 is selected from hydrogen, (Ci-Ce)-alkyl or (C3-C6)-cycloalkyl;
  • R 3 is (Ci-C 6 )-haloalkyl
  • R 4 is selected from halogen, (Ci-C 6 )-alkyl, (Ci-C 6 )-haloalkyl or (Ci-C 6 )-haloalkoxy; n is 1.
  • R 2 is selected from hydrogen, CH 3 , C2H 5 or cyclopropyl
  • R 3 is CF 3 ;
  • R 4 is selected from F, Cl, Br, CH 3 , CF 3 or OCF 3 ;
  • n 1.
  • R 1 is hydrogen
  • R 2 is selected from hydrogen, (Ci-Ce)-alkyl or (C3-C6)-cycloalkyl;
  • R 3 is (Ci-C 6 )-haloalkyl
  • R 4 is halogen
  • n 1.
  • R 1 is hydrogen
  • R 2 is selected from hydrogen, CH 3 or cyclopropyl
  • R 3 is CF 3 ;
  • R 4 is Cl or Br
  • n 1
  • the compounds of formula (I) are selected from
  • the compounds of formula I are selected from
  • Compounds of formula (I) comprise chiral centers and are generally obtained in the form of racemates.
  • the R- and S-enantiomers of compounds of formula (I) can be separated and iso- lated in pure form with methods known by the skilled person, e.g. by using chiral HPLC.
  • compounds of formula (I) especial- ly compounds of formula 1.01 , 1.02, 1.03, 1.04 or 1.05, can be used in form of
  • compound 1.01 is used.
  • Compound 1.01 may be present as racemic composition of the (R)-enantiomer and (S)-enantiomer, but the (R)-enantiomer and the (S)-enantiomer may also be present in any other proportion, for exam- pie the pure enantiomer (R) or the pure enantiomer (S) of 1.01.
  • the compound 1.01 is provided and 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%.
  • an enantiomeric excess e.e.
  • the compound 1.01 is provided and used as (S)- 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 (R)-l.01 (R)-2-(6-(4-chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1 -(1 H-1 ,2,4- triazol-1 -yl)propan-2-ol;
  • compound 1.02 is used.
  • Compound 1.02 may be present as racemic composition of the (R)-enantiomer and (S)-enantiomer, but the (R)-enantiomer and the (S)-enantiomer may also be present in any other proportion, for exam- pie the pure enantiomer (R) or the pure enantiomer (S) of 1.02.
  • the compound 1.02 is provided and 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%.
  • an enantiomeric excess e.e.
  • the compound 1.02 is provided and used as (S)- 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%.
  • an enantiomeric excess e.e.
  • compound 1.03 is used.
  • Compound 1.03 may be present as racemic composition of the (R)-enantiomer and (S)-enantiomer, but the (R)-enantiomer and the (S)-enantiomer may also be present in any other proportion, for exam- pie the pure enantiomer (R) or the pure enantiomer (S) of 1.03.
  • the compound 1.03 is provided and 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%.
  • an enantiomeric excess e.e.
  • the compound 1.03 is provided and used as (S)- 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%.
  • an enantiomeric excess e.e.
  • compound 1.04 is used.
  • Compound 1.04 may be present as racemic composition of the (R)-enantiomer and (S)-enantiomer, but the (R)-enantiomer and the (S)-enantiomer may also be present in any other proportion, for exam- pie the pure enantiomer (R) or the pure enantiomer (S) of 1.04.
  • the compound 1.04 is provided and 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%.
  • the compound 1.04 is provided and used as (S)- 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%.
  • an enantiomeric excess e.e.
  • compound 1.05 is used.
  • Compound 1.05 may be present as racemic composition of the (R)-enantiomer and (S)-enantiomer, but the (R)-enantiomer and the (S)-enantiomer may also be present in any other proportion, for exam- pie the pure enantiomer (R) or the pure enantiomer (S) of 1.05.
  • the compound 1.05 is provided and 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%.
  • an enantiomeric excess e.e.
  • the compound 1.05 is provided and used as (S)- 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%.
  • an enantiomeric excess e.e.
  • 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.
  • 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.1 1.
  • 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. According another specific embodiment, 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
  • 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.
  • 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 treating the cereal plants with a fungicidally effective amount of a compound of formula (I). In a further embodiment, the method comprises treating cereal seeds with a fungicidally effec- tive amount of a compound of formula (I).
  • cereal plants as used herein comprises wheat and triticale.
  • the present invention relates to a method for controlling Sep- toria tritici that is resistant to DMI fungicides on wheat or triticale, comprising treating the plants, their seed or the soil with a fungicidally effective amount of a compound of formula (I).
  • the method comprises treating the wheat or triticale plants with a fungicidally effective amount of a compound of formula (I).
  • the method comprises treating wheat and triticale seeds with a fungicidally effective amount of a compound of formula (I).
  • the present invention relates to a method for controlling Sep- toria tritici that is resistant to DMI fungicides on wheat, comprising treating the plants, their seed or the soil with a fungicidally effective amount of a compound of formula (I).
  • the method comprises treating the wheat plants with a fungicidally effective amount of a compound of formula (I).
  • the method comprises treating wheat seeds with a fungicidally effective amount of a compound of formula (I).
  • Treating the plants, their seed or the soil in the method according to present invention may be carried out in spray application, in seed treatment, 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 a compound of formula (I) include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified char- acteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.
  • compounds I in a method according to the present invention can be applied (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 ag- ricultural biotech products on the market or in development (cf.
  • 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.
  • a compound of formula (I) can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, 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.
  • the formulations are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: “Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff.
  • 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.
  • 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- iy-
  • 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 of formula (I).
  • Compound of formula (I) may be used together with other pesticides, such as herbicides, fungi- cides, insecticides or bactericides. These agents can be admixed with compound of formula (I) in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1 , if appropriate immediately prior to use (tank mix).
  • Compound of formula (I) may also be used together with fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These may be used sequentially or in combination with the above-described compositions, 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 ferti- lizers.
  • fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners.
  • Compounds of the formula (I) 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 of formula (I).
  • the application can be carried out both be- fore and after the infection of the materials, plants or plant propagation materials (preferably seeds) by the pests.
  • pesticidally effective amount means the amount of compound of formula (I) or of compositions comprising compound of formula (I) needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruc- tion, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidal ly effective amount can vary.
  • a pesticidally effective amount will also vary according to the pre- vailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the application rates of compound of formula (I) 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 of formula (I) is used for the pro- tection of the seed and the seedlings' roots and shoots, preferably the seeds as set forth above.
  • compositions comprising compound of formula (I) can be applied to plant propagation ma- terials, 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, re- spectively, on to plant propagation material, especially seeds are known in the art, and include dressing, coating, pelleting, dusting and soaking application methods of the propagation materi- al (and also in furrow treatment).
  • the compounds or the composi- tions 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 from10 to 750 g/l of the active(s)) .
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the spores of Zymoseptoria tritici (formerly known as Septoria tritici) were harvested with a cot- ton swab from an MYA agar plate (1 Og/I malt, 4 g/l yeast extract, 4 g/l glucose, 20 g/l agar) and this is dipped in 3 ml of double concentrated YBG-medium, double concentrated (20 g/l yeast extract, 20 g/l pacto pepton, 40 g/l glycerol) and the suspension is adjusted to a spore density of 1.6x10 4 /ml. Compounds were diluted from stock solution in (dimethylsulfoxide) DMSO in 7 steps.
  • the compound solutions were diluted 1/5 with sterile deionized water before use. 50 pi of the corn- pound solutions were transferred into empty microplates. The plates were then filled with 50 mI of a spore suspension (spore density adjusted to 1 ,6x10 4 spores/ml) of each strain.
  • the antifungal activity was determined by measuring the turbidity of a culture in 96-well micro- plates in the presence of test compounds. Fungal growth was measured by recording the optical density at 405 nm after 7 days. A blank value for each concentration (growth media + compound, but without spores) was substracted from the spore suspension. The relative antifungal activity was calculated by comparison of the effect of the test compounds with the effect of a DMSO control and a standard fungicide.
  • ICso-values concentration of test compound resulting in 50% inhibition of fungal growth

Abstract

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 treating the plants, their seed or the soil with a fungicidally effective amount of a compound of formula (I).

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 treating the plants, their seed or the soil with a fungi- cidally effective amount of a compound of formula (I)
Figure imgf000002_0001
wherein
A is CH or N;
R1 is selected from hydrogen, (Ci-C6)-alkyl, C(0)CH3;
R2 is selected from hydrogen, (Ci-C6)-alkyl or (C3-C6)-cycloalkyl;
R3 is selected from hydrogen, halogen, (Ci-C6)-alkyl or (Ci-C6)-haloalkyl;
R4 is selected from halogen, (Ci-C6)-alkyl, (Ci-C6)-haloalkyl, (Ci-C6)-alkoxy or (Ci-Ce)- haloalkoxy;
n = 0, 1 , 2, 3.
Compounds of formula (I) wherein A is CH are known from WO 2013/007767.
Compounds of formula (I) wherein A is N are known from WO 2018/145921.
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.
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, DMI (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 10.1 11 1/ppa.12891.
DMI 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 compounds of formula (I) shows an unex- pected fungicidal activity towards Septoria tritici being resistant against DMI fungicides, in par- ticular, 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 treating the plants, their seed or the soil with a fungi- cidally effective amount of a compound of formula (I)
Figure imgf000003_0001
wherein A is CH or N;
R1 is selected from hydrogen, (Ci-C6)-alkyl or C(0)CH3;
R2 is selected from hydrogen, (Ci-C6)-alkyl or (C3-C6)-cycloalkyl;
R3 is selected from hydrogen, halogen, (Ci-C6)-alkyl or (Ci-C6)-haloalkyl;
R4 is selected from halogen, (Ci-C6)-alkyl, (Ci-C6)-haloalkyl, (Ci-Ce)-alkoxy or (OI-OQ)- haloalkoxy;
n = 0, 1 , 2, 3.
The term "halogen" refers to fluorine, chlorine, bromine and iodine.
The term "Ci-C6-alkyl" refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,
2.2-dimethylpropyl, 1-ethylpropyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl,
1.3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,
2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl and 1 -ethyl-2- methylpropyl. Likewise, the term "C2-C4-alkyl" refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1-methylethyl (iso-propoyl), butyl, 1-methylpropyl (sec. -butyl), 2-methylpropyl (iso-butyl), 1 ,1-dimethylethyl (tert-butyl).
The term "Ci-C6-haloalkyl" refers to an alkyl group having 1 or 6 carbon atoms, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1- chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2- chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl.
The term "C3-C6-cycloalkyl" refers to monocyclic saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
The term "Ci-C6-alkoxy" refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen at any position in the alkyl group. Examples are "C1-C4- alkoxy" groups, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1- methyhpropoxy, 2-methylpropoxy or 1 ,1-dimethylethoxy.
The term "Ci-C6-haloalkoxy" refers to a Ci-C6-alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above. A preferred embodiment of a Ci-C6-haloalkoxy is a Ci-C4-haloalkoxy. Examples of C1- C4-haloalkoxy groups include substituents, such as OCH2F, OCHF2, OCF3, OCH2CI, OCHC , OCCI3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro- 2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichlorcnethoxy, OC2F5, OCF2CHF2, OCHF-CF3, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy,
2.3-difluoro~,propoxy, 2 chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bro- mo-'propoxy, 3 bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1-fluoromethyl-2-fluoroethoxy, 1-chloromethyl-2-chloroethoxy, 1-bromomethyl-2- bromo^ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.
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).
According to the present invention, A is CH or N. According to one embodiment, A is CH. Ac- cording to another embodiment, A is N.
According to the present invention, R1 is selected from hydrogen, (Ci-C6)-alkyl or C(0)CH3; preferably from hydrogen or (Ci-C6)-alkyl, more preferably from hydrogen, CH3, C2H5 or CH(CH3)2.
According to one specific embodiment, R1 is hydrogen.
According to another specific embodiment, R1 is (Ci-C6)-alkyl, preferably CH3, C2H5 or
CH(CH3)2.
According to another specific embodiment, R1 is C(0)CH3.
According to the present invention, R2 is selected from hydrogen, (Ci-C6)-alkyl or (C3-C6)- cycloalkyl, preferably from hydrogen, CH3, C2H5 or cyclopropyl, more preferably from hydrogen, CH3 or cyclopropyl.
According to one specific embodiment, R2 is hydrogen.
According to another specific embodiment, R2 is (Ci-C6)-alkyl, preferably CH3 or C2H5.
According to another specific embodiment, R2 is (C3-C6)-cycloalkyl, preferably cyclopropyl.
According to the present invention, R3 is selected from hydrogen, halogen, (Ci-C6)-alkyl or (C1- C6)-haloalkyl; preferably from halogen or (Ci-C6)-haloalkyl, more preferably from (OI-OQ)- haloalkyl.
According to one specific embodiment, R3 is hydrogen.
According to another specific embodiment, R3 is halogen, preferably F or Cl.
According to another specific embodiment, R3 is (Ci-C6)-alkyl, preferably CH3 or C2H5.
According to another specific embodiment, R3 is (Ci-C6)-haloalkyl, preferably CF3.
According to the present invention, R4 is selected from halogen, (Ci-C6)-alkyl, (Ci-C6)-haloalkyl, (Ci-Ce)-alkoxy or (Ci-C6)-haloalkoxy; preferably from preferably from halogen, (Ci-C6)-alkyl, (C1- C6)-haloalkyl or (Ci-C6)-haloalkoxy, more preferably from halogen;
According to one specific embodiment, R4 is selected from halogen, (Ci-C6)-haloalkyl or (O-I-OQ)- haloalkoxy; preferably from hydrogen, F, Cl, Br, CH3, CF3 or OCF3.
According to another specific embodiment, R4 is halogen, preferably from Cl or Br.
According to another specific embodiment, R4 is (Ci-C6)-alkyl, preferably CH3.
According to another specific embodiment, R4 is (Ci-C6)-haloalkyl, preferably CF3.
According to another specific embodiment, R4 is (Ci-C6)-alkoxy, preferably OCH3.
According to another specific embodiment, R4 is (Ci-C6)-haloalkoxy, preferably OCF3.
According to the present invention, n is 0, 1 , 2 or 3, preferably 0, 1 or 2, more preferably 1. According to one specific embodiment, n is 0.
According to another specific embodiment, n is 1. According to another specific embodiment, n is 2.
According to another specific embodiment, n is 3.
According to a preferred embodiment,
R1 is selected from hydrogen or (Ci-C6)-alkyl;
R2 is selected from hydrogen, (Ci-C6)-alkyl or (C3-C6)-cycloalkyl;
R3 is selected from halogen or (Ci-C6)-haloalkyl;
R4 is selected from halogen, (Ci-C6)-alkyl, (Ci-C6)-haloalkyl or (Ci-C6)-haloalkoxy; n is 0, 1 or 2.
According to a more preferred embodiment,
R1 is selected from hydrogen, CH3, C2H5 or CH(CH3)2;
R2 is selected from hydrogen, CH3, C2H5 or cyclopropyl;
R3 is selected from F, Cl or CF3;
R4 is selected from F, Cl, Br, CH3, CF3 or OCF3;
n is 0, 1 or 2.
According to a further preferred embodiment,
R1 is hydrogen;
R2 is selected from hydrogen, (Ci-Ce)-alkyl or (C3-C6)-cycloalkyl;
R3 is (Ci-C6)-haloalkyl;
R4 is selected from halogen, (Ci-C6)-alkyl, (Ci-C6)-haloalkyl or (Ci-C6)-haloalkoxy; n is 1.
According to a further more preferred embodiment,
R1 hydrogen;
R2 is selected from hydrogen, CH3, C2H5 or cyclopropyl;
R3 is CF3;
R4 is selected from F, Cl, Br, CH3, CF3 or OCF3;
n is 1.
According to a still further preferred embodiment,
R1 is hydrogen;
R2 is selected from hydrogen, (Ci-Ce)-alkyl or (C3-C6)-cycloalkyl;
R3 is (Ci-C6)-haloalkyl;
R4 is halogen;
n is 1.
According to a still further more preferred embodiment,
R1 is hydrogen;
R2 is selected from hydrogen, CH3 or cyclopropyl;
R3 is CF3;
R4 is Cl or Br;
n is 1. Preferably, the compounds of formula (I) are selected from
1.01 2-(6-(4-chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-(1 H-1 ,2,4-triazol-1-yl)propan-2- ol;
1.02 2-(6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-(1 H-1 ,2,4-triazol-1-yl)propan-
2-ol;
1.03 1-(6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-cyclopropyl-2-(1 H-1 ,2,4-triazol-
1-yl)ethanol;
1.04 1-(6-(4-chlorohenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-cyclopropyl-2-(1 H-1 ,2,4-triazol-
1-yl)ethanol and
1.05 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl) phenyl]-1-(1 , 2,4-triazol-1-yl) propan-2-ol
(mefentrifluconazole).
More preferably, the compounds of formula I are selected from
1.01 2-(6-(4-chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-(1 H-1 ,2,4-triazol-1-yl)propan-2- ol;
1.02 2-(6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-(1 H-1 ,2,4-triazol-1-yl)propan-
2-ol and
1.05 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl) phenyl]-1-(1 , 2,4-triazol-1-yl) propan-2-ol
(mefentrifluconazole).
Compounds of formula (I) comprise chiral centers and are generally obtained in the form of racemates. The R- and S-enantiomers of compounds of formula (I) can be separated and iso- lated 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, compounds of formula (I), especial- ly compounds of formula 1.01 , 1.02, 1.03, 1.04 or 1.05, 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 a particular embodiment of the present invention, compound 1.01 is used. Compound 1.01 may be present as racemic composition of the (R)-enantiomer and (S)-enantiomer, but the (R)-enantiomer and the (S)-enantiomer may also be present in any other proportion, for exam- pie the pure enantiomer (R) or the pure enantiomer (S) of 1.01.
According to one specific embodiment, the compound 1.01 is provided and 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 further specific embodiment, the compound 1.01 is provided and used as (S)- 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 (R)-l.01 : (R)-2-(6-(4-chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1 -(1 H-1 ,2,4- triazol-1 -yl)propan-2-ol;
Compound (S)-l.01 : (S)-2-(6-(4-chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1 -(1 H-1 ,2,4- triazol-1 -yl)propan-2-ol.
According a particular embodiment of the present invention, compound 1.02 is used. Compound 1.02 may be present as racemic composition of the (R)-enantiomer and (S)-enantiomer, but the (R)-enantiomer and the (S)-enantiomer may also be present in any other proportion, for exam- pie the pure enantiomer (R) or the pure enantiomer (S) of 1.02.
According to one specific embodiment, the compound 1.02 is provided and 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 further specific embodiment, the compound 1.02 is provided and used as (S)- 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 (R)-l.02: (R)-2-(6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1 -(1 H-1 ,2,4- triazol-1 -yl)propan-2-ol;
Compound (S)-l.02: (S)-2-(6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1 -(1 H-1 ,2,4- triazol-1 -yl)propan-2-ol.
According a particular embodiment of the present invention, compound 1.03 is used. Compound 1.03 may be present as racemic composition of the (R)-enantiomer and (S)-enantiomer, but the (R)-enantiomer and the (S)-enantiomer may also be present in any other proportion, for exam- pie the pure enantiomer (R) or the pure enantiomer (S) of 1.03.
According to one specific embodiment, the compound 1.03 is provided and 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 further specific embodiment, the compound 1.03 is provided and used as (S)- 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 (R)-l.03: (R)-1 -(6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1 -cyclopropyl-2- (1 H-1 ,2,4-triazol-1 -yl)ethanol;
Compound (S)-l.03: (S)-1 -(6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1 -cyclopropyl-2- (1 H-1 ,2,4-triazol-1 -yl)ethanol.
According a particular embodiment of the present invention, compound 1.04 is used. Compound 1.04 may be present as racemic composition of the (R)-enantiomer and (S)-enantiomer, but the (R)-enantiomer and the (S)-enantiomer may also be present in any other proportion, for exam- pie the pure enantiomer (R) or the pure enantiomer (S) of 1.04. According to one specific embodiment, the compound 1.04 is provided and 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 further specific embodiment, the compound 1.04 is provided and used as (S)- 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 (R)-l.04: (R)-1-(6-(4-chlorohenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-cyclopropyl-2- (1 H-1 ,2,4-triazol-1-yl)ethanol;
Compound (S)-l.04: (S)-1-(6-(4-chlorohenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-cyclopropyl-2- (1 H-1 ,2,4-triazol-1-yl)ethanol.
According a particular embodiment of the present invention, compound 1.05 is used. Compound 1.05 may be present as racemic composition of the (R)-enantiomer and (S)-enantiomer, but the (R)-enantiomer and the (S)-enantiomer may also be present in any other proportion, for exam- pie the pure enantiomer (R) or the pure enantiomer (S) of 1.05.
According to one specific embodiment, the compound 1.05 is provided and 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 further specific embodiment, the compound 1.05 is provided and used as (S)- 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 (R)-l.05: (R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl) phenyl]-1-(1 , 2,4-triazol-1- yl)propan-2-ol;
Compound (S)-l.05: (S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 , 2,4-triazol-1-yl) propan-2-ol.
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, 31 1 , 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 : 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.1 1.
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+31 1 , 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+31 1 , 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+31 1 , 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+31 1 , 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 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) + Y461 H (M.26);
• L50S (M.1 ) + V136A (M.4) + 1381V (M.16) + Y461 S (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) + Y461 H (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) + Y461 H (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 treating the cereal plants with a fungicidally effective amount of a compound of formula (I). In a further embodiment, the method comprises treating cereal seeds with a fungicidally effec- tive amount of a compound of formula (I).
The term cereal plants 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 DMI fungicides on wheat or triticale, comprising treating the plants, their seed or the soil with a fungicidally effective amount of a compound of formula (I).
In a further preferred embodiment, the method comprises treating the wheat or triticale plants with a fungicidally effective amount of a compound of formula (I).
In a further preferred embodiment, the method comprises treating wheat and triticale seeds with a fungicidally effective amount of a compound of formula (I).
In a more preferred embodiment, the present invention relates to a method for controlling Sep- toria tritici that is resistant to DMI fungicides on wheat, comprising treating the plants, their seed or the soil with a fungicidally effective amount of a compound of formula (I).
In a further more preferred embodiment, the method comprises treating the wheat plants with a fungicidally effective amount of a compound of formula (I).
In a further more preferred embodiment, the method comprises treating wheat seeds with a fungicidally effective amount of a compound of formula (I).
Treating the plants, their seed or the soil in the method according to present invention may be carried out in spray application, in seed treatment, 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 a compound of formula (I) include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified char- acteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.
For example, compounds I in a method according to the present invention can be applied (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 ag- ricultural 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, a compound of formula (I) can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, 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. The formulations are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration”, Chemical Engineering, 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 Control 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 technology (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- iy-
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 of formula (I).
Compound of formula (I) may be used together with other pesticides, such as herbicides, fungi- cides, insecticides or bactericides. These agents can be admixed with compound of formula (I) in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1 , if appropriate immediately prior to use (tank mix).
Compound of formula (I) may also be used together with fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These may be used sequentially or in combination with the above-described compositions, 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 ferti- lizers.
Compounds of the formula (I) 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 of formula (I). The application can be carried out both be- fore and after the infection of the materials, plants or plant propagation materials (preferably seeds) by the pests.
In general, "pesticidally effective amount" means the amount of compound of formula (I) or of compositions comprising compound of formula (I) needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruc- tion, or otherwise diminishing the occurrence and activity of the target organism. The pesticidal ly effective amount can vary. A pesticidally effective amount will also vary according to the pre- vailing 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 of formula (I) 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 of formula (I) is used for the pro- tection of the seed and the seedlings' roots and shoots, preferably the seeds as set forth above.
The compositions comprising compound of formula (I) can be applied to plant propagation ma- terials, 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, re- spectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting and soaking application methods of the propagation materi- al (and also in furrow treatment). In a preferred embodiment, the compounds or the composi- tions 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 from10 to 750 g/l of the active(s)) .
The invention is further illustrated, but not limited by the following practical examples:
Microtest:
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
Activity against leaf blotch on wheat caused by Septoria tritici (Septtr)
The spores of Zymoseptoria tritici (formerly known as Septoria tritici) were harvested with a cot- ton swab from an MYA agar plate (1 Og/I malt, 4 g/l yeast extract, 4 g/l glucose, 20 g/l agar) and this is dipped in 3 ml of double concentrated YBG-medium, double concentrated (20 g/l yeast extract, 20 g/l pacto pepton, 40 g/l glycerol) and the suspension is adjusted to a spore density of 1.6x104 /ml. Compounds were diluted from stock solution in (dimethylsulfoxide) DMSO in 7 steps. The compound solutions were diluted 1/5 with sterile deionized water before use. 50 pi of the corn- pound solutions were transferred into empty microplates. The plates were then filled with 50 mI of a spore suspension (spore density adjusted to 1 ,6x104 spores/ml) of each strain.
The antifungal activity was determined by measuring the turbidity of a culture in 96-well micro- plates in the presence of test compounds. Fungal growth was measured by recording the optical density at 405 nm after 7 days. A blank value for each concentration (growth media + compound, but without spores) was substracted from the spore suspension. The relative antifungal activity was calculated by comparison of the effect of the test compounds with the effect of a DMSO control and a standard fungicide.
ICso-values (concentration of test compound resulting in 50% inhibition of fungal growth) were cal- culated from the resulting dose-response for each compound and strain.
Table E1 . Sensitivity of isolates of Zymoseptoria tritici having specified combinations of muta- tions against DMI fungicides. ED5o-values are shown in ppm (mg/L-1).
Figure imgf000026_0001
*comparative examples
Table E2. Sensitivity of isolates of Zymoseptoria tritici having specified combinations of muta- tions against DMI fungicides. ED5o-values are shown in ppm (mg/L 1).
Figure imgf000026_0002
*comparative examples

Claims

Claims
1 . A method for controlling Septoria tritici resistant to DMI fungicides in cereals, comprising treating the plants, their seed or the soil with a fungicidally effective amount of a corn- pound of formula (I)
Figure imgf000027_0001
wherein
A is CH or N;
R1 is selected from hydrogen, (Ci-C6)-alkyl, C(0)CH3;
R2 is selected from hydrogen, (Ci-C6)-alkyl or (C3-C6)-cycloalkyl;
R3 is selected from hydrogen, halogen, (Ci-C6)-alkyl or (Ci-C6)-haloalkyl;
R4 is selected from halogen, (Ci-C6)-alkyl, (Ci-C6)-haloalkyl, (Ci-Ce)-alkoxy or (OI-OQ)- haloalkoxy;
n = 0, 1 , 2, 3; 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, 31 1 , 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 or 524.
4. A method according to claim 1 or 2, 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.1 1 N284H, M.12 H303Y, M.13 A31 1 G, 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 Y461 G, M.26 Y461 H, M.27 Y461 .L M.28 Y461 N, M.29 Y461 S, M.30 Del461 , M.31 G476S, M.32 V490L, M.33 G510C, M.34 N513K, M.35 S524T.
5. A method according to claim 1 or 2, wherein the Septoria tritici comprises at least two mu- tations in the CYP51 gene.
6. A method according to any of claims 1 to 4, wherein Septoria tritici comprises the muta- tions selected from the following combinations:
• L50S (M.1 ) + 1381V (M.16) + Y461 H (M.26);
• L50S (M.1 ) + V136A (M.4) + 1381V (M.16) + Y461 S (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) + Y461 H (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) + Y461 H (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 of claims 1 to 5, wherein the compound of formula (I) is ap- plied to the plants, soil or seed of plants.
8. A method according to any of claims 1 to 6, wherein the cereal is wheat or triticale.
9. A method according to any of claims 1 to 7, wherein R1 is hydrogen.
10. A method according to any of claims 1 to 8, wherein R3 is CF3.
1 1 . A method according to any of claims 1 to 9, wherein R4 is halogen.
12. A method according to any of claims 1 to 10, wherein n is 1 .
13. A method according to any of claims 1 to 1 1 , wherein the compounds of formula (I) are selected from
1.01 2-(6-(4-chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1 -(1 H-1 ,2,4-triazol-1 - yl)propan-2-ol;
1.02 2-(6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1 -(1 H-1 ,2,4-triazol-1 - yl)propan-2-ol;
1.03 1 -(6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1 -cyclopropyl-2-(1 H-1 ,2,4- triazol-1 -yl)ethanol; 1.04 1-(6-(4-chlorohenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-cyclopropyl-2-(1 H-1 ,2,4- triazol-1-yl)ethanol and
1.05 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl) phenyl]-1-(1 , 2,4-triazol-1-yl) propan-2- ol (mefentrifluconazole).
14. A method according to any of claims 1 to 12, wherein the compounds of formula (I) are selected from
1.01 2-(6-(4-chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-(1 H-1 ,2,4-triazol-1- yl)propan-2-ol;
1.02 2-(6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-(1 H-1 ,2,4-triazol-1- yl)propan-2-ol and
1.05 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl) phenyl]-1-(1 , 2,4-triazol-1-yl) propan-2- ol (mefentrifluconazole).
15. Use of the compound of formula (I) as defined in claim 1 to control Septoria tritici, that is resistant to DMI fungicides, in cereals, wherein Septoria tritici comprises at least one mu- tation in the CYP51 gene.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022034892A1 (en) * 2020-08-11 2022-02-17 株式会社クレハ Disease control agent and disease control method for agricultural and horticultural use
WO2023209045A1 (en) 2022-04-26 2023-11-02 Syngenta Crop Protection Ag Enantiomerically enriched fungicides for the control of resistant phytopathogenic fungi

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
WO2013007767A1 (en) 2011-07-13 2013-01-17 Basf Se Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
WO2017029179A1 (en) * 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Triazole derivatives, intermediates thereof and their use as fungicides
WO2018145921A1 (en) 2017-02-10 2018-08-16 Bayer Aktiengesellschaft Composition for controlling harmful microorganisms comprising 1 -(phenoxy-pyridinyl)-2-(1,2,4-triazol-1 -yl)-ethanol derivatives

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
WO2013007767A1 (en) 2011-07-13 2013-01-17 Basf Se Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
WO2017029179A1 (en) * 2015-08-14 2017-02-23 Bayer Cropscience Aktiengesellschaft Triazole derivatives, intermediates thereof and their use as fungicides
WO2018145921A1 (en) 2017-02-10 2018-08-16 Bayer Aktiengesellschaft Composition for controlling harmful microorganisms comprising 1 -(phenoxy-pyridinyl)-2-(1,2,4-triazol-1 -yl)-ethanol derivatives

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
"Advances in Applied Microbiology", vol. 90, 30 September 2014, ACADEMIC PRESS, United States, 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 *
"Perry's Chemical Engineer's Handbook", 1963, MCGRAW-HILL, pages: 8 - 57
"Technical Monograph", 2008, article "Catalogue of pesticide formulation types and international coding system"
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.: "Modern fungicides and antifungal compounds II", 2005, INTERNATIONAL REINHARDSBRUNN SYMPOSIUM, article "Resistance development to Qol inhibitors in populations of Mycosphaerella graminicola in the UK", 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
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] *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022034892A1 (en) * 2020-08-11 2022-02-17 株式会社クレハ Disease control agent and disease control method for agricultural and horticultural use
WO2023209045A1 (en) 2022-04-26 2023-11-02 Syngenta Crop Protection Ag Enantiomerically enriched fungicides for the control of resistant phytopathogenic fungi

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