WO1982000401A1 - Certain 2-(4-((5-trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-n-pyridinyl propanamide and derivatives thereof and a method for selectively controlling grassy weeds in rice - Google Patents

Certain 2-(4-((5-trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-n-pyridinyl propanamide and derivatives thereof and a method for selectively controlling grassy weeds in rice Download PDF

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Publication number
WO1982000401A1
WO1982000401A1 PCT/US1980/001018 US8001018W WO8200401A1 WO 1982000401 A1 WO1982000401 A1 WO 1982000401A1 US 8001018 W US8001018 W US 8001018W WO 8200401 A1 WO8200401 A1 WO 8200401A1
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Prior art keywords
chloro
hydrogen
bromo
pyridinyl
alkyl
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PCT/US1980/001018
Other languages
French (fr)
Inventor
Chem Co Dow
Original Assignee
Tobol H
Johnston H
Troxell L
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 Tobol H, Johnston H, Troxell L filed Critical Tobol H
Priority to AU71588/81A priority Critical patent/AU7158881A/en
Priority to GB8206189A priority patent/GB2091735A/en
Priority to BR8009096A priority patent/BR8009096A/en
Priority to EP19810901348 priority patent/EP0056807A4/en
Priority to PCT/US1980/001018 priority patent/WO1982000401A1/en
Priority to IL8163376A priority patent/IL63376A0/en
Priority to ZA815054A priority patent/ZA815054B/en
Priority to CA000382341A priority patent/CA1137480A/en
Priority to IT23184/81A priority patent/IT1138114B/en
Priority to BE0/205520A priority patent/BE889773A/en
Priority to GR65660A priority patent/GR75730B/el
Publication of WO1982000401A1 publication Critical patent/WO1982000401A1/en
Priority to DK142082A priority patent/DK142082A/en

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    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
    • 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
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C07D213/77—Hydrazine radicals
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3

Definitions

  • U.S. Patent 3,816,092, issued June 11, 1974, teaches the selective control of weeds in a variety of crops, including rice.
  • This reference teaches, Col. 1, lines 42-45, that herbicidally active agents cannot be predicted from the prior knowledge of compounds that have herbicidal activity.
  • the principal weed of rice is an annual grass, Echinochloa crusgalli. This grass and its close relatives are troublesome weeds in many countries of the world. Although a number of chemicals and techniques have been developed to attack this problem, there has not yet been a completely acceptable method for controlling such grassy weeds in the presence of desirable crops such as rice.
  • Y is hydrogen, chloro or bromo; T is 0 or S, and R is a radical having the formula
  • K is hydrogen, bromo, chloro or fluoro
  • L is hydrogen, bromo, chloro, fluoro, C 1 -C 3 alkyl or C 1 -C 3 alkoxy
  • M is L or trichloromethyl, with the proviso that when -NJ is in the 2-position, at least one of K, L or M must be other than hydrogen, and further that when M is trichloromethyl, L is hydrogen or halogen; a radical having the formula
  • Z is S, O or N;
  • Q is H, halo, C 1 -C 3 alkyl or C 1 -C 3 alkoxy;
  • R is H, bromo, chloro, fluoro, C 1 -C 3 alkyl or C 1 -C 3 alkoxy; a radical having the formula.
  • Y is hydrogen, methyl, bromo or chloro
  • W is hydrogen or methyl
  • V is H or methyl and m is 1 or 2;
  • Y is hydrogen, chloro, or bromo
  • X' is bromo or chloro and n is 1-3;
  • D is hydrogen, bromo, chloro, fluoro, alkyl having 1-3 carbon atoms or cyano and n is 1-3 when D is bromo, chloro or fluoro and n is 1 or 2 when D is alkyl or cyano;
  • X" is at least one of bromo, chloro, C 1 -C 3 alkyl or C 1 -C 3 alkoxy and n is 1 or 2;
  • OR is phenyl or R" is hydrogen, C 1 -C 3 alkyl
  • the alkyl and alkoxy groups are methyl and methoxy groups, respectively and R is a radical having the configuration of Formula II.
  • R is a radical having the configuration of Formula II.
  • the compounds of the above formulae have been found to be especially active as herbicides for the control of undesired vegetation, for example, grassy or graminaceous weeds.
  • the invention also provides a method for selectively controlling grassy weeds in the presence of rice which comprises applying to the weeds at least a herbicidally effective amount, but less than an amount which is phytotoxic to the rice, of a compound of Formula I as set forth hereinabove.
  • the compounds employed in the method of the present invention are novel compounds and may be prepared using the requisite starting materials by the methods illustrated in the following Examples through VI.
  • This acid chloride was dissolved in 18 ml toluene and added to 1.65 g (.011 mole) of 2-amino-benzothiazole and 1.11 g (0.011 mole) triethylamine dissolved in 45 ml warm toluene.
  • the reaction flask was flushed with nitrogen prior to the addition.
  • the reaction mixture stirred at 60°C for .5 hr, at 70°C for .3 hr, at 80°C for .75 hr and at 85°C for .5 hr.
  • the solid material was crystallized from hexane, followed by recrystallization from methyl cyclohexane resulting in two products.
  • the bis compound is a white crystalline product with a M.P. 78°-80°C.
  • the mono compound is a cream colored solid with a M.P. 77o_79oC.
  • 3-Amino-pyridine (1.1 g, 0.0117 mole) and triethylamine (2.3 g, 0.23 mole) were put in a 125 ml flat-bottomed flask, dissolved in toluene (25 ml), flushed with nitrogen and warmed to 62oC.
  • the acid chloride solution was added over a 6 minute period. During this time the temperature rose to 65oC.
  • the reaction mixture was then taken on up to reflux and refluxed for one hour and 50 minutes. At the end of this time the salt formed was filtered off and the toluene solvent was removed on a rotary evaporator.
  • the compounds utilized in the method of the present invention provide selective control of grassy weeds in rice (Oryza sativa), and give particular and advantageous selective postemergent control of Echinochloa crusgalli (commonly known as bamyardgrass or watergrass) in the presence of rice.
  • unmodified active ingredients of the present invention can he employed.
  • the present invention embraces the use of the compounds in composition form with an inert material known in the art as an agricultural adjuvant or carrier in solid or liquid form.
  • an active ingredient can be dispersed on a finely-divided solid and employed therein as a dust or granule.
  • the active ingredients, as liquid concentrates or solid compositions comprising one or more of the active ingredients can be dispersed in water, typically with aid of a wetting agent, and the resulting aqueous dispersion employed as a spray.
  • the active ingredients can be employed as a constituent of organic liquid compositions, oil-in- water and water-in-oil emulsions or water dispersions, with or without the addition of wetting, dispersing, or emulsifying agents.
  • Suitable adjuvants of the foregoing type are well known to those skilled in the art.
  • the concentration of the active ingredients in solid or liquid compositions generally is from about 0.0003 to about 95 percent by weight or more. Concentrations from about 0.05 to about 50 percent by weight are often employed. In compositions to be employed as concentrates, the active ingredient can be present in a concentration from about 5 to about 98 weight percent.
  • the active ingredient compositions can also contain other compatible additaments, for example, phytotoxicants, plant growth regulants and other biologically active compounds used in agriculture.
  • the compounds of the present invention or compositions containing the same can be advantageously employed in combination with one or more additional pesticidal compounds.
  • additional pesticidal compounds may be insecticides, nematocides, arthropodicides, herbicides, fungicides or bactericides that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds.
  • the pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use or as an additament.
  • the compounds in combination can generally be present in the ratio of from 1 to 100 parts of the compound of the present invention with from 100 to 1 parts of the additional compound(s).
  • the exact rate to be applied is dependent not only on a specific active ingredient being applied, but also on a particular action desired, the plant species to be modified and the stage of growth thereof as well as the part of the plant to be contacted with the toxic active ingredient.
  • all of the active ingredients of the present invention and compositions containing the same may not be equally effective at similar concentrations or against the same plant species.
  • a dosage of about 0.01 to about 20 pounds/acre (0.01122.4 kg/hectare) is generally applicable, although not all compounds are equally effective and some weeds are more difficult to control.
  • a dosage rate in the range of about 0.05 to about 1.0 pound/acre (0.056-1.12 kg/hectare) is preferred in postemergent control of annual grassy weeds, while about 0.5 to about 5 pounds/acre (0.56-5.6 kg/hectare) is a preferred dosage range for the postemergent control of perennial grassy weeds.
  • each compound to be utilized in a series of tests is dissolved in acetone to one-half of the final volume (twice the final concentration) to be used and the acetone solution in each case is admixed with an equal volume of water containing 0.1 percent by weight ⁇ f surface active material.
  • the compositions generally in the nature of an emulsion, were employed to spray separate respective plant species which had been grown to a height of 2-6 inches in soil of good nutrient content in a greenhouse. Sufficient amounts were employed to provide various application rates as listed in the table.
  • the various beds were positioned side by side and exposed to substantially identical conditions of temperature and light. Each bed was maintained so as to prevent any interaction with test compounds in different seed beds.
  • Control refers to the reduction in growth compared to the observed results of the same untreated specie. Note that "NT" means "not tested”.
  • Enantiomorphs often show the same biological effect but to a very different degree.
  • a general discussion of this phenomenon may be found in A. Albert, Selective Toxicity, 4th Ed. Met Luen & Co., Ltd., London, 1968, pp. 387-390 and more particular discussions in A. Fredga and B. Aberg, "Stereoisomerism in plant growth regulators of the auxin type", Ann. Rev. Plant Physiology 16:53-72, 1965 and in E. J. Lien, J. F. R. DeMiranda and E. J. Ariens "Quantitative structure-activity correlation of optical isomers", Molecular Pharmacology 12:598-604, 1976.

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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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyridine Compounds (AREA)

Abstract

Selectively controlling grassy weeds in the presence of rice by applying to the weeds or their habitats a herbicidally effective amount of certain 2-(4-(5-trifluoromethyl)2-pyridinyl)oxy)phenoxy N-pyridinyl propanamides and closely related derivatives thereof.

Description

CERTAIN2-(4-((5-TRIFLUOROMETHYL)-2-PYRIDINYL)OXY)PHENOXY)-N-PYRIDINYL PROPANAMIDEANDDERIVATIVESTHEREOFANDAMETHOD FORSELECTIVELY CONTROLLINGGRASSYWEEDSINRICE
Background of the Invention
Belgian Patent 868,875 to Ishihara Sangyo Kaisha Ltd. discloses and claims a number of 4-(5- trifluoromethyl-2-pyridyloxy)phenoxy alkanoic acids and their derivatives as well as their use as herbicides in broad-leaved crops.
British Patent 1,550,574 to Ciba Geigy AG discloses and claims a number of pyridyloxyphenoxy propionic acid compounds and their herbicidal use. This reference teaches the use of such compounds as plant growth regulators, as for controlling tobacco sucker growth.
Other pyridyloxyphenoxy propionic acid products and methods are disclosed in copending application S.N. 817,943 filed July 22, 1977 corresponding to European Patent Application 483.
U.S. Patent 3,816,092, issued June 11, 1974, teaches the selective control of weeds in a variety of crops, including rice. This reference teaches, Col. 1, lines 42-45, that herbicidally active agents cannot be predicted from the prior knowledge of compounds that have herbicidal activity. The principal weed of rice is an annual grass, Echinochloa crusgalli. This grass and its close relatives are troublesome weeds in many countries of the world. Although a number of chemicals and techniques have been developed to attack this problem, there has not yet been a completely acceptable method for controlling such grassy weeds in the presence of desirable crops such as rice.
Summary of the Invention This invention provides novel compounds having the formula:
Figure imgf000004_0001
wherein Y is hydrogen, chloro or bromo; T is 0 or S, and R is a radical having the formula
Figure imgf000004_0002
wherein J is hydrogen or methyl,
K is hydrogen, bromo, chloro or fluoro, L is hydrogen, bromo, chloro, fluoro, C1-C3 alkyl or C1-C3 alkoxy and
M is L or trichloromethyl, with the proviso that when -NJ is in the 2-position, at least one of K, L or M must be other than hydrogen, and further that when M is trichloromethyl, L is hydrogen or halogen; a radical having the formula
Figure imgf000005_0001
wherein Z is S, O or N; Q is H, halo, C1-C3 alkyl or C1-C3 alkoxy; R is H, bromo, chloro, fluoro, C1-C3 alkyl or C1-C3 alkoxy; a radical having the formula.
Figure imgf000005_0002
where Y is hydrogen, methyl, bromo or chloro;
Figure imgf000005_0003
where W is hydrogen or methyl ;
Figure imgf000006_0001
where V is H or methyl and m is 1 or 2;
Figure imgf000006_0002
where P is a -NH group in the 6- or 7- position and R' is H or
Figure imgf000006_0003
where Y is hydrogen, chloro, or bromo;
Figure imgf000006_0004
where X' is bromo or chloro and n is 1-3;
Figure imgf000006_0005
where D is hydrogen, bromo, chloro, fluoro, alkyl having 1-3 carbon atoms or cyano and n is 1-3 when D is bromo, chloro or fluoro and n is 1 or 2 when D is alkyl or cyano;
Figure imgf000007_0001
where X" is at least one of bromo, chloro, C1-C3 alkyl or C1-C3 alkoxy and n is 1 or 2;
Figure imgf000007_0002
where OR" is phenyl or R" is hydrogen, C1-C3 alkyl,
Na+ or K+; or
Figure imgf000007_0003
where g is 0 or 1.
Advantageously, the alkyl and alkoxy groups are methyl and methoxy groups, respectively and R is a radical having the configuration of Formula II. The compounds of the above formulae have been found to be especially active as herbicides for the control of undesired vegetation, for example, grassy or graminaceous weeds.
The invention also provides a method for selectively controlling grassy weeds in the presence of rice which comprises applying to the weeds at least a herbicidally effective amount, but less than an amount which is phytotoxic to the rice, of a compound of Formula I as set forth hereinabove.
Detailed Description of the Invention
The compounds employed in the method of the present invention are novel compounds and may be prepared using the requisite starting materials by the methods illustrated in the following Examples through VI.
Example I Method A N-2-benzothiazolyl-2-(4-((3-chloro- 5-(trifluoromethyl)-2-pyridinyl)- oxy)phenoxγ) propanamide
Figure imgf000008_0001
Thirty six milliliters of thionyl chloride and 4 grams (.011 mole) of 2-(4-((3-chloro-5-(tri-fluoromethyl)-2-pyridinyl)oxy)phenoxy) propanoic acid were held under reflux conditions for .5 hour (hr). After most of the thionyl chloride was removed under reduced pressure the last traces of thionyl chloride were removed by adding 7 ml toluene to the residue and heating under reduced pressure to 60°C. This acid chloride was dissolved in 18 ml toluene and added to 1.65 g (.011 mole) of 2-amino-benzothiazole and 1.11 g (0.011 mole) triethylamine dissolved in 45 ml warm toluene. The reaction flask was flushed with nitrogen prior to the addition. The reaction mixture stirred at 60°C for .5 hr, at 70°C for .3 hr, at 80°C for .75 hr and at 85°C for .5 hr.
After cooling, the salt was removed by filtration and the toluene was removed under reduced pressure. When the sample was washed with water it solidified. An off-white solid with a M.P. 63°-65°C was obtained.
Expected: C, 53.5; H, 3.06; N, 8.51 Found: C, 53.22; H, 3.20; N, 8.72
Example II
Method A 2-(4-((3-chloro-5-(trifluoromethyl)- 2-pyridinyl)oxy)-phenoxy)-N-2- thiazolyl propanamide
2-(4-( (3-Chloro-5-(trifluoromethyl)pyridinyl)-oxy)phenoxy) propionic acid (4 g, .011 mole) was converted to the corresponding acid chloride by refluxing in thionyl chloride (35 ml) for 30 min. and then removing excess thionyl chloride on the still under aspirator vacuum. The last traces were removed by adding toluene (approx. 20 ml) and distilling it out and taking the pot to 100°C again under aspirator vacuum. The acid chloride residue was then dissolved in toluene (35 ml) and transferred to a dropping funnel.
2-Aminothiazole (1.1 g, .011 mole) and triethylamine
(1.1 g .011 mole) were put in solution in 50 ml of toluene and warmed to 80ºC. The acid chloride solution was then added dropwise over a 15 min period and heating continued, at 80ºC for one hour longer. At the end of this time the salt formed was filtered out and the reaction mixture was treated with decolorizing carbon. Most of the toluene solvent was then removed and hexane added to bring down the white solid product, wt. 3.2 g - 65.5% of theoretical, M.P. 85º-87°C.
Analysis:
Calc'd: C, 48.7; H, 2.95; N, 9.46; Cl, 7.99
Found: C, 48.94; H, 3.13; N, 9.25; Cl, 8.14.
Example III Method B - 2-(4-((3-Chloro-5-(trifluoromethyl)- 2-pyridinyl)oxy)phenoxy)-N-(6-methoxy- 2-benzothiazolyl)propanamide
Figure imgf000010_0001
Thirty six ml of thionyl chloride and 4 g (.011 mole) of 2-(4-((3-chloro-5-(trifluoromethyl)- 2-pyridinyl)oxy)phenoxy) propanoic acid were held under reflux conditions for .5 hour. The thionyl chloride was removed under reduced pressure. The acid chloride was dissolved in 10 ml toluene and added to a reaction flask flushed with nitrogen and containing 1.98 g (.011 mole) of 2-amino-6-methoxy benzothiazole and 2.22 g (.022 mole) triethylamine dissolved in 25 ml pyridine. The reaction mixture was stirred at 50ºC for 2.5 hours, cooled and added to 250 ml water. Carefully 34 g of hydrochloric acid was added to neutralize the pyridine.
The resulting oil was crystallized from hexane after drying the hexane fraction with sodium sulfate and treating with activated charcoal. White crystals with a M.P. 72°-74°C were obtained. Additional compound was obtained by extracting the water fraction with methylene chloride. Expected: C, 52.72; H, 3..27; N, 8.02 Found: C, 52.35; H, 3.30; N, 7.91
Example IV Method C 2-(4-( (3-Chloro-5-(trifluoromethyl)-2- pyridinyl)oxy)phenoxy)-N-(1H-indazol- 6-yl)propanamide
2-(4-((3-Chloro-5-(trifluoromethyl)-2- pyridinyl)oxy)phenoxy)-N-(2-((4-((3- chloro-5-trifluoromethyl)-2-pyridinyl) oxy)phenoxy) 1-oxopropyl)-1H indazol-6- yl propanamide
Figure imgf000012_0001
Thirty six ml of thionyl chloride, and 4 g
(.011 mole) of 2-(4-( (3-chloro-5-(trifluoromethyl)-2- pyridinyl)oxy)phenoxy) propanoic acid were held under reflux conditions for .5 hr. After most of the thionyl chloride was removed under reduced pressure and heating the pot to 30ºC, the last traces of thionyl chloride were removed by adding 15 ml toluene to the residue and heating to 60°C. After flushing with nitrogen the acid chloride dissolved in 25 ml toluene was added to a flask containing 1.46 g (.011 mole) 6-amino indazole and 2.22 g (.022 mole) triethylamine partially dissolved in 40 ml toluene. The temperature was 50ºC. After the reaction mixture was stirred at 50°-60°C for 1.75 hours it was cooled and salt was removed by filtration.
The solid material was crystallized from hexane, followed by recrystallization from methyl cyclohexane resulting in two products.
The bis compound, where R' = R was more soluble in hexane and in methyl cyclohexane than the mono compound, where R' = H The bis compound is a white crystalline product with a M.P. 78°-80°C. The mono compound is a cream colored solid with a M.P. 77º_79ºC.
Example V Method D 2-(4-((3-Chloro-5-(trifluoromethyl)-2- pyridinyl)oxy)phenoxy)propanethioic acid-, S-(2,3,5-trichloro-4-pyridinyl) ester
Figure imgf000013_0001
2-(4-((3-Chloro-5-(trifluoromethyl)-2-pyri-dinyl)oxy)phenoxy)propionic acid (4.0 g, .011 mole) was converted to the corresponding acid chloride by refluxing in thionyl chloride (35 ml) for 30 min. and then removing the excess thionyl chloride on a still under aspirator vacuum. The last traces were removed by adding dry toluene (20 ml) and distilling it out and taking the pot to 100°C again under aspirator vacuum.
Sodium hydride (50% in wax, .53 g, .011 mole) was put in a 250 ml flat-bottomed flask equipped with a thermometer, stirring bar and condenser. Hexane (80 ml) was added and the mixture warmed to 65ºC to dissolve the wax then allowed to stand 5 min. to allow the sodium hydride to settle out. The hexane was decanted and dry dimethylformamide (50 ml) was added forming a sodium hydride suspension. Solid 2,3,5-trichloro-4-pyridinethiol (2.36 g, .011 mole) was added all at once and the mixture warmed to 55ºC. After about one minute the yellow thiol color faded indicating sodium salt formation. An additional 25 ml of dimethylformamide was added and then the acid chloride (.011 mole) dissolved in ~10 ml toluene was poured in all at once. The reaction mixture was heated at 70°-75ºC for 1.5 hr. then poured into 400 ml of cold water. The supernatant was decanted from the crude semisolid product and the latter was washed with fresh water and crystallized from hexane. The white crystalline product (3.4 g, 55%) melted at 122°-125°C. Analysis: Calcd: C, 43.03; H, 1.98; N, 5.01; Cl, 25.41; S, 5.7 Found: C, 43.35; H, 2.16; N, 4.96; Cl, 24.7; S, 5.35
Example VI 13 Method A 2-(4-((3-Chloro-5-(trifluoromethyl)- 2-pyridinyl)oxy)phenoxy)-N-3-pyridinyl- propanamide
Figure imgf000015_0001
2-(4-( (3-Chloro-5-(trifluoromethyl)-2- pyridinyl)oxy)phenoxy)propionic acid (4.0 g, 0.0111 mole) was converted to-the corresponding acid chloride by refluxmg in thionyl chloride (36 ml) for 40 min. and then removing the excess thionyl chloride on the still under aspirator vacuum. The last traces were removed by adding toluene (8 ml) and distilling, it out and taking the pot to 80°C again under aspirator vacuum. The acid chloride residue was then dissolved in toluene (25 ml) and transferred to a dropping funnel.
3-Amino-pyridine (1.1 g, 0.0117 mole) and triethylamine (2.3 g, 0.23 mole) were put in a 125 ml flat-bottomed flask, dissolved in toluene (25 ml), flushed with nitrogen and warmed to 62ºC. The acid chloride solution was added over a 6 minute period. During this time the temperature rose to 65ºC. The reaction mixture was then taken on up to reflux and refluxed for one hour and 50 minutes. At the end of this time the salt formed was filtered off and the toluene solvent was removed on a rotary evaporator. The crude product was taken up in methyl cyclohexane, decanted from some tarry gum, treated with Norit® charcoal or carbon and crystallized, 1.9 g of crystalline product was obtained which had a M.P. of 127º-128°C. Elemental analysis: C, 54.70; H, 3.56; N, 9.64; Cl, 8.14 Theory: C, 54.86; H, 3.45; N, 9.60; Cl, 8.10.
Employing the above described procedures and the appropriate starting materials the following compounds were prepared by the methods indicated. In each case Y is chlorine and T is oxygen. The R substituents are noted.
® = Registered Trademark
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
The compounds utilized in the method of the present invention provide selective control of grassy weeds in rice (Oryza sativa), and give particular and advantageous selective postemergent control of Echinochloa crusgalli (commonly known as bamyardgrass or watergrass) in the presence of rice.
For such uses, unmodified active ingredients of the present invention can he employed. However, the present invention embraces the use of the compounds in composition form with an inert material known in the art as an agricultural adjuvant or carrier in solid or liquid form. Thus, for example, an active ingredient can be dispersed on a finely-divided solid and employed therein as a dust or granule. Also, the active ingredients, as liquid concentrates or solid compositions comprising one or more of the active ingredients can be dispersed in water, typically with aid of a wetting agent, and the resulting aqueous dispersion employed as a spray. In other procedures, the active ingredients can be employed as a constituent of organic liquid compositions, oil-in- water and water-in-oil emulsions or water dispersions, with or without the addition of wetting, dispersing, or emulsifying agents. Suitable adjuvants of the foregoing type are well known to those skilled in the art.
The concentration of the active ingredients in solid or liquid compositions generally is from about 0.0003 to about 95 percent by weight or more. Concentrations from about 0.05 to about 50 percent by weight are often employed. In compositions to be employed as concentrates, the active ingredient can be present in a concentration from about 5 to about 98 weight percent. The active ingredient compositions can also contain other compatible additaments, for example, phytotoxicants, plant growth regulants and other biologically active compounds used in agriculture.
In further embodiments, the compounds of the present invention or compositions containing the same, can be advantageously employed in combination with one or more additional pesticidal compounds. Such additional pesticidal compounds may be insecticides, nematocides, arthropodicides, herbicides, fungicides or bactericides that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use or as an additament. The compounds in combination can generally be present in the ratio of from 1 to 100 parts of the compound of the present invention with from 100 to 1 parts of the additional compound(s).
The exact rate to be applied is dependent not only on a specific active ingredient being applied, but also on a particular action desired, the plant species to be modified and the stage of growth thereof as well as the part of the plant to be contacted with the toxic active ingredient. Thus, all of the active ingredients of the present invention and compositions containing the same may not be equally effective at similar concentrations or against the same plant species.
In selective postemergent operations a dosage of about 0.01 to about 20 pounds/acre (0.01122.4 kg/hectare) is generally applicable, although not all compounds are equally effective and some weeds are more difficult to control. Thus, a dosage rate in the range of about 0.05 to about 1.0 pound/acre (0.056-1.12 kg/hectare) is preferred in postemergent control of annual grassy weeds, while about 0.5 to about 5 pounds/acre (0.56-5.6 kg/hectare) is a preferred dosage range for the postemergent control of perennial grassy weeds.
The following examples illustrate effects of the compounds of this invention-
Example VII
In representative operations, each compound to be utilized in a series of tests is dissolved in acetone to one-half of the final volume (twice the final concentration) to be used and the acetone solution in each case is admixed with an equal volume of water containing 0.1 percent by weight αf surface active material. The compositions, generally in the nature of an emulsion, were employed to spray separate respective plant species which had been grown to a height of 2-6 inches in soil of good nutrient content in a greenhouse. Sufficient amounts were employed to provide various application rates as listed in the table. The various beds were positioned side by side and exposed to substantially identical conditions of temperature and light. Each bed was maintained so as to prevent any interaction with test compounds in different seed beds. Other portions of the plants were left untreated to serve as controls. After treatment, the plants were maintained for about two weeks under greenhouse conditions conducive for good plant growth and watered, as necessary. The specific plant specie, test compound and dosage and the percent post-emergent control obtained are set forth in the table below. Control refers to the reduction in growth compared to the observed results of the same untreated specie. Note that "NT" means "not tested".
Plant species in these tests were the following
Common Name Scientific Name
Rice Oryza sativa
Barnyardgrass
(Watergrass) Echinochloa crusgalli
Crabgrass Digitaria sanquinalis Yellow foxtail Setaria lutescens
Johnson grass Sorghum halepense
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
The compounds of this case exist with an optically active center,
Figure imgf000040_0001
Enantiomorphs often show the same biological effect but to a very different degree. A general discussion of this phenomenon may be found in A. Albert, Selective Toxicity, 4th Ed. Met Luen & Co., Ltd., London, 1968, pp. 387-390 and more particular discussions in A. Fredga and B. Aberg, "Stereoisomerism in plant growth regulators of the auxin type", Ann. Rev. Plant Physiology 16:53-72, 1965 and in E. J. Lien, J. F. R. DeMiranda and E. J. Ariens "Quantitative structure-activity correlation of optical isomers", Molecular Pharmacology 12:598-604, 1976. The finding that the D-enantiomers of substituted phenoxy-propionates were twice as active as grass control herbicides as the L-form (DT 2623558) suggests that the D-enantiomers of the present case should also be the more active of the enantiomorphs.

Claims

WHAT IS CLAIMED IS:
1. A compound having the formula
Figure imgf000041_0001
wherein Y is hydrogen, chloro or bromo; T is O or S, and R is a radical having the formula
Figure imgf000041_0002
wherein J is hydrogen or methyl,
K is hydrogen, bromo, chloro or fluoro, L is hydrogen, bromo, chloro, fluoro, C1-C3 alkyl or C1-C3 alkoxy and
M is L or trichloromethyl, with the proviso that when -NJ is in the 2-position, at least one of K, L or M must be other than hydrogen, and further that when M is trichloromethyl, L is hydrogen or halogen; a radical having the formula
Figure imgf000042_0001
wherein Z is S, O or N; Q is H, halo, C1-C3 alkyl or C1-C3 alkoxy; R is H, bromo, chloro, fluoro, C1-C3 alkyl or C1-C3 alkoxy; a radical having the formula
Figure imgf000042_0002
where Y is hydrogen, methyl, bromo or chloro;
Figure imgf000042_0003
where W is hydrogen or methyl;
Figure imgf000043_0001
where V is H or methyl and m is 1 or 2;
Figure imgf000043_0002
where P is a -NH group in the 6- or 7- position and R' is H or
Figure imgf000043_0003
where Y is hydrogen, chloro, or bromo;
Figure imgf000043_0004
where X' is bromo or chloro and n is 1-3;
Figure imgf000043_0005
where D is hydrogen, bromo, chloro, fluoro, alkyl having 1-3 carbon atoms or cyano and n is 1-3 when D is bromo, chloro or fluoro and n is 1 or 2 when D is alkyl or cyano;
Figure imgf000044_0001
where X" is at least one of bromo, chloro, C1-C3 alkyl or C1-C3 alkoxy and n is 1 or 2;
Figure imgf000044_0002
where OR" is phenyl or R" is hydrogen, C1-C3 alkyl, Na + or K+; or
Figure imgf000044_0003
where g is 0 or 1.
2. Compound of Claim 1 wherein R is a radical having the Formula II.
3. Compound of Claim 2 wherein J is hydrogen.
4. Compound of Claim 3 wherein L is methyl.
5. Compound of Claim 3 wherein L is chloro.
6. 2-(4-((3-chloro-5-(trifluoromethyl)-2- pyridinyl)oxy)phenoxy)-N-3-pyridinyl propanamide.
7. A method for selectively controlling grassy weeds in the presence of rice which comprises applying to the weeds or their habitats at least a herbicidally effective amount, but less than the amount which is phytotoxic to rice, of a compound having the formula
Figure imgf000045_0001
wherein Y is hydrogen, chloro or bromo; T is O or S, and R is a radical having the formula
Figure imgf000045_0002
wherein J is hydrogen or methyl,
K is hydrogen, bromo, chloro or fluoro,
L is hydrogen, bromo, chloro, fluoro, C1-C3 alkyl or C1-C3 alkoxy and
M is L or trichloromethyl, with the proviso that when -NJ is in the 2-position, at least one of K, L or M must be other than hydrogen, and further that when M is trichloromethyl, L is hydrogen or halogen; a radical having the formula
Figure imgf000046_0001
wherein Z is S, O or N; Q is H, halo, C1-C3 alkyl or C1-C3 alkoxy; R is H, bromo, chloro, fluoro, C1-C3 alkyl or C1-C3 alkoxy; a radical having the formula
Figure imgf000046_0002
where Y is hydrogen, methyl, bromo or chloro;
Figure imgf000046_0003
where W is hydrogen or methyl;
Figure imgf000046_0004
where V is H or methyl and m is 1 or 2;
Figure imgf000047_0001
where P is a -NH group in the 6- or 7- position and R' is H or
Figure imgf000047_0002
where Y is hydrogen, chloro, or bromo;
Figure imgf000047_0003
where X' is bromo or chloro and n is 1-3;
Figure imgf000047_0004
where D is hydrogen, bromo, chloro, fluoro, alkyl having 1-3 carbon atoms or cyano and n is 1-3 when D is bromo, chloro or fluoro and n is 1 or 2 when D is alkyl or cyano;
Figure imgf000048_0001
where X" is at least one of bromo, chloro, C1-C3 alkyl or C1-C3 alkoxy and n is 1 or 2;
Figure imgf000048_0002
where OR" is phenyl or R" is hydrogen, C1-C3 alkyl, Na+ or K+; or
Figure imgf000048_0003
where g is 0 or 1.
8. Method of Claim 7 wherein in the compound employed R is a radical having the Formula II.
9. Method of Claim 8 wherein in the compound employed J is hydrogen.
10. Method of Claim 9 wherein in the compound employed L is methyl.
11. Method of Claim 9 wherein in the compound employed L is chloro.
12. Method of Claim 7 wherein the compound employed is 2-(4-((3-chloro-5-(trifluoromethyl)-2- pyridinyl)oxy)phenoxy)-N-3-pyridinyl propanamide.
PCT/US1980/001018 1980-07-30 1980-07-30 Certain 2-(4-((5-trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-n-pyridinyl propanamide and derivatives thereof and a method for selectively controlling grassy weeds in rice WO1982000401A1 (en)

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AU71588/81A AU7158881A (en) 1980-07-30 1980-07-30 Compounds and method for selectively controlling grassy weedsin rice
GB8206189A GB2091735A (en) 1980-07-30 1980-07-30 Certain 2-(4(5-trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-npyridinyl propanamide and derivatives thereof and a method for selectively controlling grasst weeds in rice
BR8009096A BR8009096A (en) 1980-07-30 1980-07-30 COMPOUND AND PROCESS FOR SELECTIVE CONTROL OF GRASS WEAKNESSES PRESENT IN RICE
EP19810901348 EP0056807A4 (en) 1980-07-30 1980-07-30 Certain 2-(4-((5-trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-n-pyridinyl propanamide and derivatives thereof and a method for selectively controlling grassy weeds in rice.
PCT/US1980/001018 WO1982000401A1 (en) 1980-07-30 1980-07-30 Certain 2-(4-((5-trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-n-pyridinyl propanamide and derivatives thereof and a method for selectively controlling grassy weeds in rice
IL8163376A IL63376A0 (en) 1980-07-30 1981-07-21 Substituted 2-phenoxyalkanone derivatives and method for selectively controlling grassy weeds in rice
ZA815054A ZA815054B (en) 1980-07-30 1981-07-23 Compounds and method for selectively controlling grassy weeds in rice
CA000382341A CA1137480A (en) 1980-07-30 1981-07-23 Compounds and method for selectively controlling grassy weeds in rice
IT23184/81A IT1138114B (en) 1980-07-30 1981-07-28 COMPOUNDS AND METHOD FOR SELECTIVELY CONTROL OF HERBACEOUS PLANTS RICE CULTURES
BE0/205520A BE889773A (en) 1980-07-30 1981-07-28 COMPOUNDS AND METHOD FOR DESTRUCTION OF WEEDS
GR65660A GR75730B (en) 1980-07-30 1981-07-29
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EP0226411A1 (en) * 1985-12-06 1987-06-24 Rohm And Haas Company Controlling weeds in crops of cereals
EP0324359A1 (en) * 1988-01-11 1989-07-19 Hoechst-Roussel Pharmaceuticals Incorporated Pyrazol- and indazolpyridin amines, a process for their preparation and their use as medicaments
WO1996010016A1 (en) * 1994-09-28 1996-04-04 Hoechst Schering Agrevo Gmbh Use of substituted pyridines as pest-control agents and fungicides
CN105315199A (en) * 2014-07-14 2016-02-10 湖南化工研究院有限公司 N-pyridine aryloxyphenoxy carboxylic acid derivatives, preparation method and applications thereof
CN107434804A (en) * 2016-05-29 2017-12-05 湖南大学 N- (thiazol-2-yl) -2- [4- (pyridine -2- epoxides) phenoxy group] amide derivatives
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Cited By (10)

* Cited by examiner, † Cited by third party
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EP0092706A1 (en) * 1982-04-20 1983-11-02 Nihon Tokushu Noyaku Seizo K.K. Oxadiazole derivatives
EP0226411A1 (en) * 1985-12-06 1987-06-24 Rohm And Haas Company Controlling weeds in crops of cereals
EP0324359A1 (en) * 1988-01-11 1989-07-19 Hoechst-Roussel Pharmaceuticals Incorporated Pyrazol- and indazolpyridin amines, a process for their preparation and their use as medicaments
WO1996010016A1 (en) * 1994-09-28 1996-04-04 Hoechst Schering Agrevo Gmbh Use of substituted pyridines as pest-control agents and fungicides
US5852042A (en) * 1994-09-28 1998-12-22 Hoechst Schering Agrevo Gmbh Substituted pyridines, processes for their preparation and their use as pesticides and fungicides
CN105315199A (en) * 2014-07-14 2016-02-10 湖南化工研究院有限公司 N-pyridine aryloxyphenoxy carboxylic acid derivatives, preparation method and applications thereof
CN105315199B (en) * 2014-07-14 2020-11-20 湖南化工研究院有限公司 N-pyridine aryloxy phenoxy carboxylic acid derivative and preparation method and application thereof
CN107434804A (en) * 2016-05-29 2017-12-05 湖南大学 N- (thiazol-2-yl) -2- [4- (pyridine -2- epoxides) phenoxy group] amide derivatives
CN110627782A (en) * 2019-10-14 2019-12-31 杨子辉 Preparation method and application of pyridyl phenoxyl propionamide compound containing disulfide bond
CN110627782B (en) * 2019-10-14 2023-03-31 山东胜邦绿野化学有限公司 Preparation method and application of pyridyloxy phenoxypropionamide compound containing disulfide bond

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IT1138114B (en) 1986-09-17
ZA815054B (en) 1982-09-29
CA1137480A (en) 1982-12-14
EP0056807A1 (en) 1982-08-04
GB2091735A (en) 1982-08-04
IT8123184A0 (en) 1981-07-28
BR8009096A (en) 1982-06-22
GR75730B (en) 1984-08-02
EP0056807A4 (en) 1982-12-09
AU7158881A (en) 1982-03-02

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