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EP0215778A1 - Derives de phenoxyalcenylpyridine, compositions fongicides les contenant, procedes fongicides les utilisant et procedes de preparation de ces derives - Google Patents

Derives de phenoxyalcenylpyridine, compositions fongicides les contenant, procedes fongicides les utilisant et procedes de preparation de ces derives

Info

Publication number
EP0215778A1
EP0215778A1 EP19850901761 EP85901761A EP0215778A1 EP 0215778 A1 EP0215778 A1 EP 0215778A1 EP 19850901761 EP19850901761 EP 19850901761 EP 85901761 A EP85901761 A EP 85901761A EP 0215778 A1 EP0215778 A1 EP 0215778A1
Authority
EP
European Patent Office
Prior art keywords
compound
pyridine
enyl
phenyl
lower alkyl
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP19850901761
Other languages
German (de)
English (en)
Inventor
Allan F. Rose
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron USA Inc
Original Assignee
Chevron Research and Technology Co
Chevron Research Co
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 Chevron Research and Technology Co, Chevron Research Co filed Critical Chevron Research and Technology Co
Publication of EP0215778A1 publication Critical patent/EP0215778A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • This invention relates to certain fungicidal phenoxyalkenylpyridine derivatives and to methods of pre ⁇ paring such derivatives.
  • the inven ⁇ tion relates to the application of said derivatives as fungicides.
  • the present invention provides compounds having fungicidal activity and having especially excellent activity against bean powdery mildew pathogen and celery late blight pathogen. Moreover, certain of the compounds are active against bean rust pathogen. This is surprising since the corresponding saturated alkyl analogs and keto analogs of the present compounds, such as described in U.S. Patent No. 4,262,000, although exhibiting activity against bean powdery mildew pathogen fail to exhibit any significant eradicant activity against celery late blight pathogen nor against bean rust pathogen. The present compounds thus afford a significant and unexpected advan ⁇ tage in the treatment of these diseases.
  • Ar is phenyl, naphthyl, substituted phenyl or substituted naphthyl in each case substituted with one or two substituents independently selected from the group of halo, lower alkyl, lower alkoxy, or phenyl;
  • R is phenyl or the group having the formula:
  • the preferred compounds in terms of their substituents, are those wherein Ar is 4-halophenyl, especially 4-chloro- phenyl, or 2,4-dihalophenyl, especially 2,4-dichloro- j e phenyl, or biphenyl.
  • the preferred R substituent is t- butyl.
  • the preferred R 1 substituent is hydrogen.
  • the preferred compounds are those having one or more of the above preferred substituents and most prefer ⁇ ably having a preferred substituent at each respective 20 position.
  • halo or halogen atom
  • lower alkyl carbonyl refers to the group having the formula
  • R 6 is lower alkyl
  • compatible salt refers to salts of the parent compound which do not significantly adversely o effect the fungicidal properties of the parent compound and are substantially non-phytotoxic at the appropriate fungicidal dosage.
  • fungicidal is a broad term and refers to either or both preventative (prevents fungicidal infec- 5 tions) and eradicant (fungalstatic - prevents the growth of fungi ultimately producing destruction of the fungus through failure to reproduce and more rarely curatic: directly causes the destruction of the fungus).
  • compatible carrier refers to sub- Q stances which can be mixed with the fungicidal compounds of the present invention which do not signi icantly adversely affect the properties of the active compound save to dilute it and are substantially non-phytotoxic. Examples of suitable compatible carriers are given in the Utility section set forth hereinbelow. Synthesis
  • the compounds of Formula I can be prepared by the following process schematically represented by the following overall reaction equation:
  • R ⁇ is lower alkyl, benzyl, allyl, or halo ⁇ allyl and X is an anion (e.g. halide, sulfate) and n is its valence.
  • this process is conducted at tempera- tures in the range of about from -20 to 100°C, preferably about from 0 to 20°C, for about from 0.5 to 12 hours, preferably about from 0.5 to 1.5 hours using about from 1 to 3, preferably about from 1 to 1.2 mole equivalents of compound R (X) ⁇ / n per mole of compound la.
  • Suitable inert organic solvents which can be used include, for example, tetrahydrofuran, dimethylformamide, toluene, and the like and compatible mixtures thereof.
  • esters of Formula I wherein R is lower alkyl carbonyl ' can be conveniently prepared via the following schematically represented process:
  • This process can be effected by contacting com- pound la with compound F under reactive conditions prefer ⁇ ably in an inert organic solvent and in the presence of a base.
  • the second step of this process can be effected by contacting compound B with 3-pyridinecarboxaldehyde under reactive conditions, preferably in an inert organic solvent and in ' the presence of base.
  • this reaction is conducted at temperatures in the range of about from 0 to 100°C, preferably about from 10 to 25°C for about from 1 to 48 hours, preferably 12 to 24 hours using about from 1 to 3 moles, preferably 1 to 1.5 moles of 3-pyridinecarboxaldehyde per mole of compound B.
  • Suitable inert organic solvents which can be used include, for example, methanol, ethanol, methylene chloride, toluene, and the like and compatible mixtures thereof.
  • the anion salts of the compounds of Formula I can be prepared by reacting the free base of Formula I with an acid having the appropriate anion or by ion exchange of one salt of Formula I with the appropriate anion exchange resin.
  • the procedures for preparing salts described in U.S. Patent No. 4,262,000, Column 12, which procedures are hereby incorporated by reference, can also be applied to prepare the salts of the present invention. Unless expressly stated to the contrary, it is preferred to separate the desired product of the above process steps before proceeding with the next step in the process. Any suitable separation procedure can be used to effect separation such as, for example, where appropriate, extraction, filtration, evaporation, distillation, chroma- tography, etc. Illustrations of suitable separation pro ⁇ cedures can be found in the appropriate example given hereinbelow.
  • the compounds of the present invention exhibit fungicidal activity and especially preventative activity against plant fungal diseases.
  • the compounds are especially effective against powdery mildew fungal diseases caused by organisms such as Erysiphe polyqoni and also against celery late blight producing organisms such as Septoria apii.
  • certain of the present com ⁇ pounds are highly effective against rust causing organisms such as Uromyces phaseoli tipica.
  • the compounds of the invention can be applied in fungicidally effective amounts to fungi and/or their habi- tats, such as vegetative hosts and non-vegetative hosts, e.g., animal products.
  • the amount used will, of course, depend on several factors such as the host, the type of fungus and the particular compound of the invention.
  • the compounds of the invention are usually not applied as pure compunds, but are generally incorporated with carriers to facilitate dispersion of the active fungicidal compounds. Generally, the carriers are biologically inert.
  • the fungicides of the invention can be formulated and applied as granules, powdery dusts, wettable powders, emulsifiable concentrates, solutions, or as any of several other known types of formulations, depending on the desired mode of application.
  • Wettable powders are finely divided particles which disperse readily in water or other dispersant. These compositions normally contain from about 5% to 80% fungicide, and the rest carriers, dispersing agents, emulsifying agents and/or wetting agents. The powder may be applied to the soil as a dry dust, or as a suspension in water. Typical carriers include fuller's earth, kaolin clays, silicas and other highly absorbent, readily wett ⁇ able, inorganic diluents.
  • Typical wetting, dispersing or emulsifying agents include, for example, aryl and alkyl- aryl sulfonates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, and polyvinyl alcohols; polyethylene oxides, sulfonated animal and vegetable oils; sulfonated petroleum oils, fatty acid esters of polyhydric alcohols and the ethylene oxide addi ⁇ tion products of such esters; and the addition products of long-chain mercaptans and ethylene oxide.
  • alkylamide sulfonates including fatty methyl taurides
  • alkylaryl polyether alcohols sulfated higher alcohols, and polyvinyl alcohols
  • polyethylene oxides sulfonated animal and vegetable oils
  • sulfonated petroleum oils fatty acid esters of polyhydric alcohols and the ethylene oxide addi ⁇ tion products of
  • the surface-active agent when used, normally comprises from 1% to 15% by weight of the fungicidal composition.
  • Dusts are freely flowing admixtures of the active fungicide with finely divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk, diatoma- ceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant.
  • finely divided solids have an average particle size of less than about 50 microns.
  • a typical dust formulation useful herein contains 75% silica and 25% of the toxicant.
  • Useful liquid concentrates include the emulsifi ⁇ able concentrates, which are homogeneous liquid or paste compositions which are readily dispersed in water or other dispersant, and can consist entirely of the fungicide with a liquid or solid emulsifying agent, or can also contain a liqid carrier such as xylene, heavy aromatic naphthas, isophorone, and other nonvolatile organic solvents.
  • these concentrates are dispersed in water or other liquid carrier, and are normally applied as a spray to the area to be treated.
  • fungicidal appli ⁇ cations include simple solutions of the active fungicide in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naph- thalenes, xylene, or other orqanic solvents.
  • Granular formulations wherein the fungicide is carried in rela ⁇ tively course particles, are of particular utility for aerial distribution or for penetration of cover-crop canopy.
  • Pressurized sprays typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier, such as the Freons, can also be used. All of those techniques for formulating and applying fun ⁇ gicides are well known in the art.
  • the percentages by weight of the fungicide can vary according to the manner in which the composition is to be applied and the particular type of formulation, but in general comprise 0.05% to 95% of the toxicant by weight of the fungicidal composition, typically depending on whether the composition is intended for direct application or dilution prior to application.
  • the compounds are typically applied at rates in the range of about from 0.1 to 5 kg/hectare, preferably 0.2 to 3 kg/hectare.
  • the fungicidal compositions can be formulated and applied with other active ingredients, including other fungicides, insecticides, nematocides, bactericides, plant growth regulators, fertilizers, etc.
  • active ingredients including other fungicides, insecticides, nematocides, bactericides, plant growth regulators, fertilizers, etc.
  • equivalent refers to a reagent equal in moles, to the moles of the preceding or succeeding reac- tant recited in that example in terms of finite moles or finite weight or volume.
  • E- and Z-isomers are generated where appropriate and are not separated.
  • geometric isomer and racemic mixtures are used as starting materials and correspondingly isomer mixtures are obtained as products.
  • Example 4 Similarly, by following the procedures set forth 5 in Examples 1-3 but using the appropriately substituted phenol and ketone starting materials the following illus ⁇ trative compounds can be prepared.
  • the title compound can be prepared by reacting 0.06 mole of methyl sulfate with 0.1 mole of 3-[2-(2,4- dichlorophenoxy)-3-hydroxy-4,4-dimethylpent-1- enyl] yridine in 200 ml tetrahydrofuran at room tempera- 10 ture.
  • the title compound can then be recovered from the reaction product mixture by appropriate laboratory proce ⁇ dures such as, for example, described in the preceding examples set forth herein.
  • methoxy ethers of the products ⁇ 5 listed in Example 4 hereinabove can be prepared by following the same procedures, including, for example: 3-[2-(2,6-dichlorophenoxy)-3-methoxy-4,4-dimethyl- pent-1-enyl]pyridine;
  • the title compound can be prepared by reacting a mixture containing 0.11 mole of acetyl chloride; 0.1 mole Q of 3-[2-(2,4-dichlorophenoxy)-3-hydroxy-4,4-dimethylpent-
  • Example 4 can be prepared by following the same procedure, including, for example:
  • Example 7 the compounds of Formula I listed in Table I and the intermediate of Formula A listed in Table II were prepared by following the procedures of Examples 1-3 but using the appropriately substituted phenol and ketone as starting materials. Also for com ⁇ parison purposes the compounds listed in Table III were prepared from the corresponding compound of Formula I via reduction of the alkene double bond via treatment with zinc dust in acetic acid.
  • Example 8 In this example, the compounds of Example 7,
  • Tables I, II and III were tested for effectiveness against a number of different fungi organisms. The parti ⁇ cular organisms and test procedures used are described below. In these tests the compounds were compared against check plants which were also sprayed with the test vehicle
  • Tomato Early Blight Compounds of the invention were tested for the control of the Tomato Early Blight organism Alternaria solani conidia.
  • Tomato (variety Bonny Best) seedlings of 6 to 7 weeks old were used.
  • the tomato plants were sprayed with a 250-ppm solution of the test compound in an acetone-and-water solution containing a small amount of a nonionic emulsifier.
  • the sprayed plants were inoculated one day later with the organism, placed in an environmen ⁇ tal chamber and incubated at 66° to 68°F and 100% relative humidity for 24 hours. Following the incubation, the plants were maintained in a greenhouse for about 12 days. Percent disease control was based on the percent disease development on untreated check plants. Two replicates (plants) were used for each compound and the check. The compounds tested and the averaged results are tabulated in Table IV.
  • Bean Rust test was made using pinto bean plants and was conducted as an eradicant test.
  • the pathogen was Uromyces phaseoli tipica.
  • the plants were inoculated with the pathogen and then incubated in an environmental chamber for approximately 24 hours at 100% relative humidity and a temperature of 68° to 70°F.
  • the plants were then removed from the chamber, allowed to dry.
  • the pinto bean plants were then sprayed with a
  • test compound 250-ppm solution of the test compound in an acetone-water mixture containing a small amount nonionic emulsifier.
  • the plants were dried and then maintained in a greenhouse at a 40 to 80% relative humidity and 66° to 72°F for 7 days. The plants were then evaluated for the percent disease control.
  • the percent disease control provided by a given test compound was based on the percent disease reduction relative to untreated check plants.
  • Rice Blast Compounds of this invention were tested for control of the Rice Blast organism Piricularia oryzae, using 10- to 14-day old rice plant seedlings (Calrose M-9 variety). Seedling plants were sprayed with a 625-ppm solution of the test compound in acetone, water and a nonionic emulsifier. The sprayed plants were inoculated 1 day later with the organism in an environmental chamber. After inoculation, the plants were kept in an environmental chamber for about 48 hours under conditions of about 72° to 75°F and about 100% relative humidity. Following the incubation period, the plants were placed in a greenhouse with a temperature of about 72°F and maintained with bottom watering for about 12 to 16 days. The percent disease control provided by a given test compound is based on a comparison of the percentage disease relative to the percent disease development on the untreated check plants.
  • *ED 50/90 are calculated values of the dosage rate (ppm) needed to obtain 50% control and 90% control. The lower ED 50/90 value, the better the activity.
  • compound No. 1 has superior preventative activity over compound No. 6 with respect to Tomato Late Blight, Celery Late Blight and Bean Powdery Mildew and has particularly good preventative activity with respect to Bean Powdery Mildew.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Pyridine Compounds (AREA)

Abstract

On décrit une 3- AD2-aryloxy-3-hydroxy-3-phenyl ou 3-t-butyl-prop-1-enyl BD pyridine et ses dérivés. Ces composés sont utiles en tant que fongicides, notamment des fongicides agricoles.
EP19850901761 1985-03-18 1985-03-18 Derives de phenoxyalcenylpyridine, compositions fongicides les contenant, procedes fongicides les utilisant et procedes de preparation de ces derives Withdrawn EP0215778A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1985/000433 WO1986005358A1 (fr) 1985-03-18 1985-03-18 Derives de phenoxyalcenylpyridine, compositions fongicides les contenant, procedes fongicides les utilisant et procedes de preparation de ces derives

Publications (1)

Publication Number Publication Date
EP0215778A1 true EP0215778A1 (fr) 1987-04-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19850901761 Withdrawn EP0215778A1 (fr) 1985-03-18 1985-03-18 Derives de phenoxyalcenylpyridine, compositions fongicides les contenant, procedes fongicides les utilisant et procedes de preparation de ces derives

Country Status (2)

Country Link
EP (1) EP0215778A1 (fr)
WO (1) WO1986005358A1 (fr)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2909287A1 (de) * 1979-03-09 1980-09-18 Bayer Ag 3-substituierte pyridin-derivate, verfahren zu ihrer herstellung sowie ihre verwendung als fungizide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8605358A1 *

Also Published As

Publication number Publication date
WO1986005358A1 (fr) 1986-09-25

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