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
  • C07D213/60—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
• • 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
  • C07D213/61—Halogen atoms or nitro 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
  • C07D213/62—Oxygen or sulfur atoms
  • C07D213/70—Sulfur atoms

Definitions

• the invention relates (a).to novel pyridyloxy(thio)-phenoxy propanoic acids, salts and esters thereof and pyridyl(oxy/thio)phenoxy propanols and esters and ethers thereof, and propionitriles, (b) to herbicidal compositions of such compounds and (c) to methods of using such compounds for the control of undesired plant growth.
• the compounds are particularly useful for control of grassy weeds.
• the present invention provides a trifluoromethylpyridyl(oxythio)phenoxypropionic compound corresponding to the formula
• compositions containing one or more active ingredients as well as preemergent and postemergent methods of controlling undesired plant growth, especially in the presence of valuable crops.
• Such methods comprise applying a herbicidally-effective amount of one or more active ingredients to the locus of the undesired plants, that is, the seeds, foliage, rhizomes, stems and roots or other parts of the growing plants or soil in which the plants are growing or may be found.
• the compounds of the present invention are generally oils or crystalline solids at ambient temperatures which are soluble in many organic solvents commonly employed as herbicidal carriers.
• the compounds of the present invention wherein T is oxygen can be readily prepared by the reaction of 2-(4--hydroxyphenoxy)propanoic acid or an ester thereof with a substituted pyridine having the requisite substitution in the 3-- and/or 5-ring positions in addition to 2-halo substitution.
• the pyridine compound used as starting material can be prepared from a 2-halopyridine compound, generally the 2-chloro substituted compound; having trichloromethyl substitution in either or both of the 3- and 5-ring positions in addition to any desired chloro or bromo substitution at the 3- or 5--positions, if not occupied by a CC1 3 group, by reacting the pyridine compound with a fluorinating material such as anti- money trifluoride whereupon the trichloromethyl group or groups are converted to trifluoromethyl groups.
• a fluorinating material such as anti- money trifluoride
• T is sulfur
• the compounds of the present invention wherein T is sulfur similarly can be prepared by the reaction of 2-(4--mercaptophenoxy)propanoic acid or an ester thereof with an appropriate substituted pyridine in substantially the same manner as described above.
• reaction between such a substituted pyridine and the.said hydroxy- or mercapto-phenoxy propanoic acid can be readily carried out in a polar solvent such as dimethyl sulfoxide to which has been added a small amount of aqueous or powdered sodium hydroxide. Reaction is usually carried out at a temperature in the range of about 70 to about 125°C over a period of about 1 to 3 hours under ambient atmospheric pressure. The reaction mixture is then allowed to cool and is poured into a quantity of cold water and acidified with hydrochloric acid, whereupon the product precipitates and is separated and purified as may be required.
• a polar solvent such as dimethyl sulfoxide
• the propanoate esters of the present invention may be prepared in substantially the same manner as set forth above for the propanoic acids, using the requisite ester of 2-(4-hydroxyphenoxy)propanoic acid or 2-(4-mercaptophenoxy)--propanoic acid to react with the appropriately substituted 2-halopyridine.
• the appropriate propanoic acid of the invention is esterified by first converting to the acid chloride with thionyl chloride and then reacting the acid chloride with the appropriate alcohol, or, mercaptan, such as ethyl mercaptan, propyl mercaptan, or butyl mercaptan, according to generally accepted procedures or the classic method of reacting an alcohol and an acid in the presence of a little sulfuric acid may be followed.
• mercaptan such as ethyl mercaptan, propyl mercaptan, or butyl mercaptan
• the propanoic acid compounds of the invention after conversion to the acid chloride may also be reacted with (a) ammonia to form the simple amide, (b) with an alkyl amine to form an N-alkyl amide or N,N-dialkyl amide, or (c)' with a methoxy amine to form the methoxy amide.
• the simple amide serves as preferred starting material for the manufacture of the nitriles, which are obtained upon reaction of the amide with phosphorous oxychloride.
• the propanoate metal salts are prepared from the propanoic acid form of the compound by simply reacting the carboxylic acid with the requisite inorganic base, such as NaOH, KOH, Ca(OH) 2 or Mg(OH) 2 .
• the amine salts are prepared by reacting the propanoic acid compound with the requisite amine, for example, triethanolamine or trimethylamine.
• Esterification of such alcohol is carried out according to methods generally known in the art in which, e.g., an acid chloride is reacted with the alcohol in solvent medium in the presence of a hydrogen chloride acceptor, such as triethylamine.
• a hydrogen chloride acceptor such as triethylamine.
• the hydrochloric salt is filtered off and the solvent stripped, leaving an oily product.
• Ethers of the alcohols of the invention are prepared _by reacting the alcohol with, e.g., sodium hydride in a polar solvent such as dimethyl formamide at a temperature of about 35 to 60°C, after which an alkyl bromide is added to the reaction mixture and heated to 75 to 100°C for one to two hours.
• the solvent medium is then stripped off under reduced pressure and the crude product is poured into cold water and final product taken up with water immiscible solvent such as heptane.
• the solvent on being stripped off, leaves an oily product.
• a salt e.g.. the sodium salt, of 4-methoxyphenol, or of 4-mercaptophenol
• a solvent such as dimethyl sulfoxide and the requisite trifluoromethyl-substituted 2-chloropyridine is added to the solution of the methoxy phenol and reacted in the presence of aqueous sodium hydroxide at a temperature in the range of about 70 to 130°C and over a time interval of about 30 to 45 minutes.
• the reaction mixture is then cooled and poured over ice.
• the solid product is filtered off, washed with water, taken up in a solvent mixture and reprecipitated therefrom.
• the methoxy group if present, is then cleaved off the phenyl ring by refluxing the compound in'48% by weight HBr for about an hour and after purification, precipitated from acidic solution and recovered, as by filtration, and dried.
• the 4-(trifluoromethyl-substituted 2-pyridyloxy)phenol, or 4-(trifluoromethyl-substituted 2-pyridylthio)phenol is then dissolved in a solvent such as dimethyl sulfoxide, anhydrous powdered sodium hydroxide is added thereto and reacted therewith for a few minutes at about 75 to 85°C.
• an ester such as the ethyl ester of 2-bromopropanoic acid is added to the reaction mixture and stirred for a time, such as about half an hour, at approximately 100°C or up to about 2 hours in the case of the sulfur bridged compound.
• the reaction mixture is then allowed to cool and poured over ice or simply into cold water whereupon an oily layer separates which can be recovered by taking up in a water-immiscible solvent and subsequently stripping the solvent off leaving an oily product.
• the product so obtained will be the alkyl ester of the propanoic acid compound.
• the reactants are usually mixed with a carrier medium, such as, for example, methyl ethyl ketone, methyl isobutyl ketone or an aprotic polar solvent such as dimethylformamide, dimethylacetamide,- dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, or sulfolane.
• a carrier medium such as, for example, methyl ethyl ketone, methyl isobutyl ketone or an aprotic polar solvent such as dimethylformamide, dimethylacetamide,- dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, or sulfolane.
• the first step condensation is generally carried out at a temperature of at least 50°C, preferably about 70 to about'150°C and during a reaction period of about 1 to about 20 hours, preferably about 1 to about 10 hours.
• the second condensation reaction is carried out under similar reaction conditions except that the
• the product had the following elemental analysis:
• aqueous solutions so obtained are conveniently used in herbicid applications with or without further dilution.
• the a may be recovered by evaporation of the water from the sections and purified by careful recrystallization, if desired.
• Magnesium and calcium salts are prepared in substantially the manner decribed above.
• propanoic acids identified by ring substituents, the molar amount of propanoic acid, the base employed and the estimated amounts of each base, are as follows:
• aqueous solutions so obtained are conveniently used in herbicidal applications with or without further dilution.
• the salts may be recovered by evaporation of water from the solutions and purified by recrystallization, if desired.
• amine salts such as the triethanolamine, diethanolamine, tripropylamine, or the butylamine salt, are prepared in substantially the manner described above.
• the separated hydrochloride salt was filtered off, and the toluene was stripped off.
• The-residue was poured into ice water and extracted with heptane.
• the heptane extracts were dried, and the heptane was removed by distillation, leaving an oil with a refractive index of 1.4740 at 25°C.
• the anticipated product was 2-(4-(3,5-bis(trifluoromethyl)-2-pyridyloxy)phenoxy]propyl octanoate.
• the product had the following elemental analysis:
• reaction mixture is then slowly heated to 90°C over a 30-minute period and held at 90°C for one hour and ten minutes.
• the reaction mixture is then stirred and heated at 105-115°C for 2 hours.
• the dimethylformamide is then strippe off under partial vacuum and the crude product poured into cold water and extracted with heptane. The heptane is remove by distillation, leaving an oil, 2-[4-(3,5-bis(trifluoromethyl)-2-pyridyloxy)phenoxy]propyl n-butyl ether.
• a solution of the sodium salt of 4-methoxyphenol was prepared by dissolving the methoxyphenol (7.45 g; 0.06 mole) in 45 ml of dimethylsulfoxide and adding a solution of sodium hydroxide (2.4 g; 0.06 mole) in 7 ml of water.
• a solution of 2-chloro-5-(trifluoromethyl)pyridine (9.0 g; 0.05 mole) i 40 ml of dimethylsulfoxide was then added to the above sodiu phenate solution over an 11 minute period.
• the 5-(trifluoromethyl)-2-(4-methoxyphenoxy)pyridine (10.95 g; 0.0407 mole) was refluxed with 50 ml of 48 percent by weight aqueous hydrobromic acid solution for one hour. At the end of this time, the reaction mixture was cooled, poured over ice and the separated solids collected on a filter. The product was purified by taking it up in dilute caustic solution, extracting the solution with chloroform to remove unreacted starting material and then acidifying the solution to precipitate free phenol. The dried crystalline phenol product had a melting temperature of 89-91°C and was found to contain 56.21% carbon; 3.27% hydrogen; and 5.44% nitrogen. The theoretical composition of 4-(5-trifluoromethyl-2-pyridyloxy)phenol is 56.48% carbon; 3.16% hydrogen; and 5.49% nitrogen.
• the ethyl 2-[4-(5-trifluoromethyl-2-pyridylthio)-phenoxy]propionate (13.5 gm., 0.37 mole) was dissolved in 50 ml of 95% ethanol and a solution of sodium hydroxide (3.0 gm., 0.075 mole) in 25 ml of water was added. The mixture was refluxed at 80° for about 6 minutes, then cooled, poured into 400 ml of cold water, and extracted with 250 ml of methylene chloride to remove any base-insoluble impurities. The aqueous solution containing the sodium salt of the acid was acidified to pH 1 with concentrated hydrochloric acid.
• the compounds of the present invention have been found to have advantage over prior art compounds in the control of perennial grassy weeds in that the present com- - pounds control a broader spectrum of such weeds than the counterpart compounds while exhibiting a higher level of activity or control at-like dosage rates.
• the present compounds are sufficiently tolerant towards most broad leafed crops to contemplate control of grassy weeds therein at substantially commercially practicable levels, particularly so with the preferred compounds.
• unmodified active ingredients of the present invention can be employed.
• the present invention embraces the use of the -compounds in composition form with an inert material known in the art as an 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.
• 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, pesticides and the like and can be formulated with solid particulate fertilizer carriers such as ammonium nitrate, urea and the like.
• the present compounds which are substituted propanol or propyl ethers are more effective in preemergent operations than in postemergent applications.
• the exact rate to be applied is dependent not only on a specific active ingredient being applied, but also on a particular action desired (e.g., general or selective contro] the plant species to be modified and the stage of growth thereof as well as the part of the plant to be contacted witl 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.
• the active ingredients of the invention are usually applied at an approximate rate of from about 0.5 to about 5 pounds/acre (0.56-5.6 kg./hectare), but lower or higher rates may be appropriate in some cases such as 0.01 to about 20'pounds/ac (0.011-22.4 kg./hectare).
• a dosage of about 0.05 to about 20 pounds/acr (0.056-22.4 kg./hectare) is generally applicable, a rate of 0.2 to 4 pounds/acre (0.224-4.48 kg./hectare) being preferre and about 0.75 to about 1 pound/acre (0.84-1.12 kg./hectare) being most preferred.
• a dosage: of about 0.01 to about 20 pounds/acre (0.011-22.4 kg./hectar is generally applicable, although not all compounds and equally effective and some weeds are more difficult to control.
• a dosage rate in the range of about 0.05 to about 0.75 pounds/acre (0.056-0.84 kg./hectare) is preferr in postemergent control of annual grassy weeds, while above 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 of surface active material.
• the compositions generally in the nature of an emulsion, were employed to treat separate respective seed beds of sandy loam soil of good nutrient content'wherein each seed bed contained separate groups, of viable seeds, each group being of one.plant specie.
• 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.
• Each seed bed was treated with one of the compositions as a soil drench applied uniformly throughout the surface of the bed.
• the compositions were applied to the seed beds so that different seed beds of a given plant specie were treated with one of each of the test compounds.
• Another seed bed was treated only with water to serve as a control. After treatment, the seed beds were maintained for 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 preemergent control obtained are set forth in the table below. Control refers to the reduction in growth compared to the observed results of the same specie.

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Plant Pathology (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (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)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1978
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