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WO1998015180A1 - Compositions fongicides et leur utilisation pour lutter contre les champignons phytopathogenes - Google Patents

Compositions fongicides et leur utilisation pour lutter contre les champignons phytopathogenes Download PDF

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Publication number
WO1998015180A1
WO1998015180A1 PCT/EP1997/005579 EP9705579W WO9815180A1 WO 1998015180 A1 WO1998015180 A1 WO 1998015180A1 EP 9705579 W EP9705579 W EP 9705579W WO 9815180 A1 WO9815180 A1 WO 9815180A1
Authority
WO
WIPO (PCT)
Prior art keywords
enantiomer
tetraconazole
fungicidal
group
general formula
Prior art date
Application number
PCT/EP1997/005579
Other languages
English (en)
Inventor
Ottorino Palla
Ernesto Signorini
Lucio Filippini
Original Assignee
Isagro S.P.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Isagro S.P.A. filed Critical Isagro S.P.A.
Priority to AU48661/97A priority Critical patent/AU4866197A/en
Publication of WO1998015180A1 publication Critical patent/WO1998015180A1/fr

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Classifications

    • 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

  • This invention relates to fungicidal compositions. More particularly the invention relates to fungicidal compositions comprising a triazole compound either in its pure more active enantio eric form or as an enantiomer mixture having a content of the more active enantiomer equal to or greater than 70%, and their use in agriculture for controlling phytopathogenic fungi.
  • the triazole fungicides effectively control many important fungine diseases typical of man and plants.
  • triazole fungicides are widely used in agronomic practice because they are able to effectively control phytopathogens of the more important agricultural crops.
  • triazole fungicides are used for treating the leaf or other vegetative portions, in both preventive (pre-infection) and curative (post-infection) applications.
  • Triazole fungicides are also conveniently used for seed treatment.
  • triazole fungicides are characterised by the presence of a 1H-1 ,2,4-triazole ring.
  • compounds of the following general formula (I) present high fungicidal activity: R2
  • Ri represents a hydrogen atom, a hydroxyl group or a cyano group
  • - R2 represents a linear or branched C1-C10 alkyl group, said C1-C10 alkyl group being optionally substituted with one or more halogen atoms chosen from chlorine, fluorine, bromine and iodine; a linear or branched C -C.
  • haloalkoxy group; an R group; or R1 and R2, conjointly with the carbon atom C* can represent an oxirane ring optionally substituted with an R4 group; R3 and R4, which can be equal or different, represent a phenyl group substituted with one or more halogen atoms chosen from fluorine and chlorine; or a t-butyl group.
  • the asterisked carbon atom C is a chiral atom, R1 , R2 and R3 always being different.
  • triazole compounds of general formula (I) can be used either in one of the two enantiomeric forms, (+) dextrorotatory or (-) levorotatory, or in any mixture of the two.
  • compounds of general formula (I) can also present centres of asymmetry, in which case they can be used as a single diastereoisomer or as a mixture of the possible diastereoisomers.
  • raceme mixtures of compounds of general formula (I) are always used, ie equimolar mixtures of the possible enantiomers or diastereoisomers.
  • Said compounds are characterised by zero rotatory power and conventionally are indicated by placing the symbol ( ⁇ ) before the product name.
  • the compounds of general formula (I) are generally selective, they interfering mainly with the biosynthesis of fungine ergosterol and only partially with the metabolism of the host plant.
  • the effect on the host plant is usually considered acceptable because of the benefit achieved by controlling the phytopathogens.
  • the present applicant has now surprisingly found that the problem of interference with the metabolism of the host plant and its aforesaid consequent growth limitation can be solved either by using in its pure form that enantiomer of compounds of general formula (I) which is more active towards phytopathogens or by using a mixture of the enantiomers of the compound of general formula (I) in which the more active enantiomer is present in greater quantity.
  • the present applicant has found that with the greater fungicidal activity of one of the two enantiomers of the compounds of general formula (I) there corresponds a much lesser degree of interference with the metabolism of the host plant than that determined by a raceme mixture of the compounds of general formula (I).
  • This lesser interference with the metabolism of the host plant results in more vigorous growth of the plant, with a consequent greater production yield.
  • the use of the more effective enantiomer in controlling phytopathogenic fungi also enables smaller quantities of active principle to be used, resulting in a further reduction in side effects and lesser environmental impact.
  • the present invention therefore provides fungicidal compositions comprising a triazole compound of general formula (I):
  • Ri represents a hydrogen atom, a hydroxyl group or a cyano 0
  • R2 represents a linear or branched C1-C10 alkyl group, said C1-C10 alkyl group being optionally substituted with one or more halogen atoms chosen from chlorine, fluorine, bromine and iodine;
  • a linear or branched C -C haloalkoxy group can represent an oxirane ring optionally substituted with an 4 group;
  • R3 and R4 which can be equal or different, represent a phenyl group substituted with one or more halogen atoms chosen from fluorine and chlorine; or a t-butyl group; wherein the compound of general formula (I) is present either in its pure more active enantiomeric form or as an enantiomer mixture having a content of the more active enantiomer equal to or greater than 70%.
  • Enantiomers preferred for the purpose of the present invention are those comprising from 1% to 55% of a compound of general formula (I) as enantiomer in its pure state, or from 1% to 55% of an enantiomer mixture having a content of the more active enantiomer equal to or greater than 70%.
  • the percentage of compound of general formula (I) relates only to the active principle and hence does not consider the presence of possible impurities.
  • Specific examples of compounds of general formula (I) useful for the purposes of the present invention are: tetraconazole; - epoxyconazole; tebuconazole; fenbuconazole; cyproconazole hexaconazole; yclobutanyl ; penconazole.
  • That compound of general formula (I) preferred for the purposes of the invention is tetraconazole.
  • the commercial active principle consists of an equimolar mixture of the two (+) and (-) enantiomers. The two enantiomers are prepared separately by the procedures reported for example in "Agricul ural Food Chemistry" (1991), vol. 39, pp. 197- 201.
  • the dextrorotatory enantiomer ie ( ⁇ )-tetraconazole (proposed ISO name “rectusazole") is more active in controlling phytopathogens than the raceme mixture or the levorotatory enantiomer, as reported for example in "Agricul ural Food Chemistry” (1991), vol. 39, pp. 197-201.
  • (+)-tetraconazole can be obtained by the procedures described, for example, in "Agricul ural Food Chemistry” (1991), vol. 39, pp. 197-201, which use biocatalytic reactions. In this respect, (+)- tetraconazole was obtained, with good optical purity (>95%), by enantioselective acetylation of the alcohol of formula (Ila):
  • compositions comprising pure (+)-tetraconazole or a tetraconazole mixture containing at least 70% of the (+) enantiomer (w/w). More preferred is a composition comprising a tetraconazole mixture containing more than 80% of the (+) enantiomer (w/w), and in particular more than 90% of the (+) enantiomer (w/w), and, preferably, more than 95% of the (+) enantiomer (w/w), and especially more than 97% of the (+) enantiomer (w/w). Even more preferred is a composition comprising a tetraconazole mixture the (-) enantiomer content of which is less than 1% (w/w).
  • compositions of the present invention possess high fungicidal activity towards fungine phytopathogen pertaining to various genera.
  • They are particularly effective against sugar beet fungi, cereal fungi, Cucurbi taceae fungi and fruit tree fungi. They can also be active as antimycotics, for example for controlling phytopathogenic fungi pertaining to the genus Candida or to the genus Tricophytum.
  • Rhynocosporium secalis on cereals Pyrenofora teres on barley; Cercospora beticola on sugar beet;
  • Venturia pyrina on fruit-bearing plants - Sphaeropsis malorum on fruit-bearing plants;
  • fungicidal compositions are formulated in accordance with the known art using opportune formulative ingredients.
  • compositions of the present invention can be applied to any part of the plant, for example on leaves, stems, branches and roots, or on the seeds themselves before sewing, or even on the soil in which the plant grows.
  • compositions used can be in the form of dry powder, wettable powder, e ulsifiable concentrates, microemulsions, paste, granulates, solutions, suspensions etc.
  • the choice of the type of composition depends on the specific use.
  • the compositions are prepared in known manner, for example by diluting or dissolving the active substance with a solvent medium and/or a solid diluent, possible with surfactants present.
  • the following can be used as solid diluents or supports: silica, kaolin, bentonite, talc, kieselguhr, dolomite, calcium carbonate, magnesia, chalk, clays, synthetic silicates, attapulgite, sepiolite.
  • suitable liquid diluents include various solvents, for example aromatic (xylenes or alkyl-benzene mixtures), chloroaromatic solvents (chlorobenzene) , paraffins (petroleum fractions), alcohols ( ethanol , propanol , butanol , octanol , glycerin), amines, amides (N,N-dimethylformamide, N- ethylpyrrol idone) , ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone) , esters (isobutyl acetate).
  • solvents for example aromatic (xylenes or alkyl-benzene mixtures), chloroaromatic solvents (chlorobenzene) , paraffins (petroleum fractions), alcohols ( ethanol , propanol , butanol , octan
  • Usable surfactants include sodium, calcium, triethanolamine or triethylamine salts, alkyl sulphonates, alkylarylsulphonates, polyethoxylated alkyl phenols, fatty alcohols condensed with ethylene oxide, polyoxyethylated fatty acids, polyoxyethylated sorbitol esters, 1 igninsulphonates.
  • compositions can also contain special additives for particular purposes, for example adhesive-forming additives such as gum arabic, polyvinyl alcohol, polyvinylpyrrol idone.
  • adhesive-forming additives such as gum arabic, polyvinyl alcohol, polyvinylpyrrol idone.
  • other compatible active principles can be added to the compositions of the present invention, such as fungicides, phytoregulators, antibiotics, herbicides, insecticides, fertil izers.
  • fungicides which an be included in the composition of the invention are alanicarb, ampropylfos, anilazine, azaconazole, azoxyst robin, BA3490 F, BAY KTU 3616 benalaxyl, benomyl , bilosazol, binapacryl, bitertanol, blasticidin S, bromoconazole, bupirimate, butenaclor, buthiobate, captafol, captan, carbendazim, carbox, chinoethionat , chlorobenzothiazone, chloroneb, chlorothalonil , clozolinate, clozylacon, copper salts, cyclohexyl imide, cy oxanil, cyproconazole, cyprofurane, cyprodinyl, CGA 245 704, diclofluanid, dichlone, diclobutrazole, diclomez
  • the present invention also relates to the use of said compositions in agriculture for controlling phytopathogenic fungi.
  • the appl icational doses of said compositions can vary between 1 g/ha and 10 g/ha for treatment of fruit-bearing plants and vegetables and between 50 g/ha and 250 g/ha for cereals and sugar beet.
  • the quantities can in any event vary according to climatic conditions and the infection.
  • the doses used for seed treatment (doses referred to the active principle) can vary between 0.5 g and 10 g per kg of seeds.
  • (+)-tetraconazole and ( ⁇ )-tetraconazole on the growth of wheat seeds
  • Four samples of wheat seeds (10 g) are moistened with a solution of (+)-tetraconazole or ( ⁇ )-tetraconazole in acetone at doses of 1.2 g and 2.4 g per kg of seeds.
  • each plant is measured for the length of the epicotyl, the interligula, and the first and second leaf respectively.
  • the mean values of the data obtained for each plant group are shown in Table 1. Said data clearly show the lesser interference of the ( ⁇ )-tetraconazole towards the host plant than the ( ⁇ )-tetraconazole.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des compositions fongicides comprenant un composé triazole de la formule générale (I) et dans lesquelles ce composé est présent soit sous sa forme énantiomère pure et plus active, soit en tant que mélange d'énantiomères dont la teneur en énantiomère le plus actif est égale ou supérieure à 70 %. Ces compositions sont utiles dans l'agriculture pour lutter contre les champignons phytopathogènes.
PCT/EP1997/005579 1996-10-08 1997-10-04 Compositions fongicides et leur utilisation pour lutter contre les champignons phytopathogenes WO1998015180A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU48661/97A AU4866197A (en) 1996-10-08 1997-10-04 Fungicidal compositions and their use in controlling phytopathogenic fungi

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT96MI002068A IT1284926B1 (it) 1996-10-08 1996-10-08 Composizioni fungicide e loro utilizzo per il controllo di funghi fitopatogeni
ITMI96A002068 1996-10-08

Publications (1)

Publication Number Publication Date
WO1998015180A1 true WO1998015180A1 (fr) 1998-04-16

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Application Number Title Priority Date Filing Date
PCT/EP1997/005579 WO1998015180A1 (fr) 1996-10-08 1997-10-04 Compositions fongicides et leur utilisation pour lutter contre les champignons phytopathogenes

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AU (1) AU4866197A (fr)
IT (1) IT1284926B1 (fr)
WO (1) WO1998015180A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005056548A1 (fr) * 2003-12-11 2005-06-23 Cheminova A/S Epoxiconazole enantiomeriquement pur et ses utilisations en tant qu'agent phytosanitaire
US7595338B2 (en) 2005-04-29 2009-09-29 Wyeth Process for preparing 3,3-disubstituted oxindoles and thio-oxindoles

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0132283A2 (fr) * 1983-07-25 1985-01-30 Imperial Chemical Industries Plc Diaryltriazolyléthanols, optiquement actifs comme fongicides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0132283A2 (fr) * 1983-07-25 1985-01-30 Imperial Chemical Industries Plc Diaryltriazolyléthanols, optiquement actifs comme fongicides

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
"1. Chemistry of plant Protection, Sterol Biosynthesis Inhibitors and anti-feeding compounds", SPRINGER VERLAG, BERLIN, XP002055193 *
CARELLI, ANGELINA ET AL: "Interaction of tetraconazole and its enantiomers with cytochrome P450 from Ustilago maydis", PESTIC. SCI. (1992), 35(2), 167-170 CODEN: PSSCBG;ISSN: 0031-613X, XP002055191 *
CHEMICAL ABSTRACTS, vol. 114, no. 7, 1991, Columbus, Ohio, US; abstract no. 62017s, BIANCHI, DANIELE ET AL: "Chemoenzymic synthesis and biological activity of both enantiomeric forms of tetraconazole, a new antifungal triazole" XP002055198 *
CHEMICAL ABSTRACTS, vol. 116, no. 7, 1992, Columbus, Ohio, US; abstract no. 53503m, GOZZO, F. ET AL: "Enantiomers and racemate of M 14 360: investigation on their antifungal activity" XP002055197 *
CHEMICAL ABSTRACTS, vol. 117, no. 23, 1992, Columbus, Ohio, US; abstract no. 233951k, BIANCHI, DANIELE ET AL: "Enzymic preparation of optically active fungicide intermediates in aqueous and in organic media" XP002055196 *
CHEMICAL ABSTRACTS, vol. 118, no. 17, 1993, Columbus, Ohio, US; abstract no. 169052j, BIANCHI, DANIELE ET AL: "Enzymatic preparation of optically active fungicide intermediates in aqueous and in organic media" XP002055195 *
CHEMICAL ABSTRACTS, vol. 123, no. 21, 1995, Columbus, Ohio, US; abstract no. 278610p, GOZZO, FRANCO ET AL: "Stereoselective interaction of tetraconazole with 14.alpha.-demethylase in fungi" XP002055194 *
INDIAN J. CHEM., SECT. B (1993), 32B(1), 176-80 CODEN: IJSBDB;ISSN: 0376-4699 *
J. AGRIC. FOOD CHEM. (1991), 39(1), 197-201 CODEN: JAFCAU;ISSN: 0021-8561 *
PESTIC. BIOCHEM. PHYSIOL. (1995), 53(1), 10-22 CODEN: PCBPBS;ISSN: 0048-3575 *
PURE APPL. CHEM. (1992), 64(8), 1073-8 CODEN: PACHAS;ISSN: 0033-4545 *
TAGUNGSBER. - AKAD. LANDWIRTSCHAFTSWISS. (1990), 291(SYST. FUNGIC. ANTIFUNGAL COMPD., VOL. 1), 87-94 CODEN: TALAEW *
W. KÖLLER: "Isomers of Sterol Synthesis Inhibitors: Fungicidal effects and plant growth regulator activities", PESTICIDE SCIENCE, vol. 18, no. 2, 1987, pages 129 - 147, XP002055192 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005056548A1 (fr) * 2003-12-11 2005-06-23 Cheminova A/S Epoxiconazole enantiomeriquement pur et ses utilisations en tant qu'agent phytosanitaire
US7595338B2 (en) 2005-04-29 2009-09-29 Wyeth Process for preparing 3,3-disubstituted oxindoles and thio-oxindoles

Also Published As

Publication number Publication date
IT1284926B1 (it) 1998-05-28
AU4866197A (en) 1998-05-05
ITMI962068A1 (it) 1998-04-08

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