Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
  • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
  • C07D249/12—Oxygen or sulfur atoms

Definitions

• the invention described in this application pertains to weed control in agriculture, horticulture, or other fields where there is a desire to control unwanted plant growth. More specifically, the present application describes novel herbicidal 1-aryl- ⁇ 2 -1,2,4-triazolin-5-ones, herbicidal compositions containing the new compounds, methods for preparing the compounds, and methods for preventing or destroying undesired plant growth by preemergence or postemergence application of the herbicidal compositions to the locus where control is desired. The present compounds may be used to effectively control a variety of both grassy and broadleaf plant species.
• Various herbicidal 1-aryl- ⁇ 2 -1,2,4-triazolin-5-ones are known in the art. U.S. Patent No.
• R 1 is alkyl
• R 2 is hydrogen, alkyl, or alkenyl
• X is hydroxy, alkyl, alkoxy, alkoxyalkoxy, alkenyloxy, or alkyloxycarbonylalkyloxy.
• R is alkyl, alkenyl, or cycloalkyl
• X is chlorine or bromine
• Y is hydrogen or alkoxy
• Japanese Kokai 81-32,468 discloses herbicidal aryltriazolinones of the formula
• R is hydrogen, alkyl, or 2-propenyl, and R 1 is methyl or alkoxy.
• R n is hydrogen or represents 1 to 4 same or different radicals selected from halogen, nitro, cyano, optionally halo-substituted alkyl, alkoxy, or alkylthio, and optionally substituted phenyl or phenoxy, and R 1 is alkyl, alkoxyalkyl, dialkoxyethyl, dialkylaminoethyl, or cycloalkyl.
• U.S. Patent No. 4,315,767 discloses herbicidal bicyclic compounds of the following formula
• V is hydrogen, halogen, methyl, or alkoxy
• X is hydrogen, halogen, cyano, methyl, methoxy, or nitro
• Y is hydrogen, halogen, or methyl
• m and n are 0 to 4 (m plus n is 2 to 4)
• Q is oxygen or sulfur
• Z is oxygen, S(O) p , or NR wherein p is 0-2 and R 1 is alkyl, provided that when m plus n is 2 or 4 then Y and X are other than hydrogen, and when Z is S(O) P then n is 1 to 4.
• V is hydrogen, halogen, hydroxy, alkyl, or -OR 1 ;
• R 1 is optionally substituted alkyl, cycloalkyl, cycloalkylalkyl, optionally substituted alkenyl, alkynyl, optionally substituted benzyl, alkylarainocarbonyl, (alkyl) (methyl or methoxy)aminocarbonyl, acyl, alkoxycarbonyl, or -CHR 7 R 8 wherein R 7 is hydrogen or alkyl and R 8 is cyano, acetyl, hydroxycarbonyl, alkoxycarbonyl, hydroxymethyl, alkoxymethyl, alkylcarbonyloxymethyl, hydroxycarbonylethenyl, alkoxycarbonylethenyl, or a group -CO-NR 11 R 12 wherein R 11 is hydrogen, alkyl, alkenyl, or alkoxy, and R 12 is hydrogen or alkyl;
• X is halogen, cyano,
• R is alkyl, alkenyl, alkynyl, cycloalkyl, or optionally substituted phenyl or arylalkyl
• R 1 is haloalkyl or haloalkenyl
• R 2 is optionally substituted alkyl, alkenyl, or alkynyl, or optionally substituted aryl, arylalkyl, or alkylaryl.
• the compounds of this invention are 1-[4- bromo-2-fluoro-5-(substituted)oxyphenyl]-3-methyl- 4-difluororaethy1- 2-1,2,4-triazolin-5-ones of the formula
• R is alkyl, alkenyl, alkynyl, alkoxyalkyl, or alkyl-S(O) n -alkyl wherein n is 0 to 2.
• the present compounds are named in accordance with the numbering system shown in formula I, for the ring atoms of the heterocycle which is the same as the numbering system used in U.S. 4,318,731, supra, for similar compounds.
• R is selected from -CH 3 , -CH 2 OCH 3 , and -CH 2 C ⁇ CH.
• the present compounds which have a fluorine atom at the C-2 position of the phenyl ring, in general have herbicidal properties far superior to those of the corresponding compounds having a chlorine atom at C-2 of the phenyl ring, and are highly active at low application rates against a variety of grassy and broadleaf weed species in both preemergence and postemergence applications.
• the compounds of this invention may be prepared by methods analogous to the methods described in the references above for similar compounds or by methods within the skill of the art.
• the disclosures: in the above references pertaining to methods of: preparation are incorporated herein by reference.
• the compound of formula I in which R is hydrogen. is an important intermediate to the herbicidal compounds of formula I in which R is as defined above, as illustrated in Examples 2-7 below.
• Other compounds useful as intermediates are the compounds corresponding to formula I in which the -CHF 2 . substituent is replaced with a hydrogen atom, as illustrated in Example 1H below.
• reaction mixture was cooled to 0-10°C, and 591 g (6.15 moles) of methyl chloroformate was added dropwise over four hours. Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was stirred for 17 hours. After this time, 450 g of aqueous 50% sodium hydroxide was added to neutralize the reaction mixture. The resultant solid was collected by filtration, and the filter cake washed with two 500 mL portions of water. The solid was dried under reduced pressure to give 1211 g .of 2-bromo-4- fluorophenyl methyl carbonate; m.p. 75-78°C.
• reaction mixture was allowed to warm to ambient temperature and was stirred for two hours. After this time, 100 mL of water was added to the reaction mixture, followed by the dropwise addition of a solution of 9.4 g (0.107 mole) of pyruvic acid in 100 mL of water. Upon complete addition, the reaction mixture was stirred for 30 minutes at ambient temperature. The reaction mixture was filtered to collect a solid. The solid was dried to give 23.5 g of pyruvic acid, 4-bromo-2-fluoro-5-methoxyphenylhydrazone; m.p. 156-158°C.
• Step G 1-(4-Bromo-2-fluoro-5-methoxyphenyl)-3- methyl- ⁇ 2 -1,2,4-triazolin-5-one
• Step H 1-(4-Bromo-2-fluoro-5-methoxyphenyl)-3- methyl-4-difluoromethyl- ⁇ 2 -1,2,4- triazolin-5-one
• Step A 1-( 4-Bromo-2-fluoro-5-hydroxyphenyl)-3- methyl-4-difluoromethy1- ⁇ 2 -1,2,4-tria- zolin-5-one
• Example 1 in 25 mL of methylene chloride was added dropwise. The reaction mixture temperature was maintained at -40°C throughout the addition. Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was stirred for 16 hours. The reaction mixture was poured into ice-water, and the mixture extracted with diethyl ether. The extract was dried with sodium sulfate, filtered, and the filtrate concentrated under reduced pressure to give a residue. The residue was dissolved in diethyl ether, and the solution was passed through a pad of silica gel.
• Step B 1-(4-Bromo-2-fluoro-5-methoxymethoxyphenyl)--3--methyl--4--d fluoromethyl- ⁇ 2 - 1,2,4-triazolin-5-one
• Example 2A 1-(4-bromo-2-fluoro-5-hydroxyphenyl)-3-methyl-4-difluoromethyl- ⁇ 2 -1,2,4- triazolin-5-one (Example 2A) by an alkylation procedure analogous to that described above in either Example 2B or Example 3:
• 1,2,4-TRIAZ0LIN-5-ONE obtained as an oil.
• the ir and nmr spectra were consistent with the proposed structure.
• Example 6 1-[4-BROMO-2-FLUORO-5-(1-METHYLPROPARGYLOXY)PHENYL ]-3-METHYL-4-DIFLUOROMETHYL- ⁇ 2 - 1,2,4-TRlAZOLIN-5-ONE, m.p. 80-82°C.
• the ir and nmr spectra were consistent with the proposed structure. Analysis calc'd for C 14 H 11 BrF 3 N 3 O 2 :
• the plant test species used in demonstrating the herbicidal activity of compounds of this invention include cotton (Gossypium hirsutum var. Stoneville), soybean (Glycine max var. Williams), field corn (Zea mays var. Agway 595S), rice (Oryza sativa var. Labelle), wheat (Triticum aestivium var.
• Prodax field bindweed (Convolvulus arvensis), morningglory ( Ipomea lacunosa or Ipomea hederacea), velvetleaf (Abutilon theophrasti), barnyardgrass (Echinochloa crus galli), green foxtail (Setaria viridis), johnsongrass (Sorghum halepense), and yellow nutsedge (Cyperus esculentus).
• Seeds or tubers of the plant test species were planted in furrows in steam sterilized sandy loam soil contained in disposable fiber flats.
• the flats had been filled to a depth of about 6.5 cm with the soil.
• a topping soil of equal portions of sand and sandy loam soil was placed uniformly on top of each flat to a depth of approximately 0.5 cm.
• the flats for the preemergence tests were watered, then drenched with the appropriate amount of a solution of the test compound in a mixture of acetone and water containing a small amount (up to 0.5% v/v) of sorbitan monolaurate emulsifier/ solubilizer.
• concentration of the test compound in solution was varied to give a range of application rates, generally 8.0 kg/ha and submultiplies thereof.
• the flats were placed in a greenhouse and watered regularly at the soi l surface for 21 days at which time phytotoxicity data were recorded.
• the flats for the postemergence tests were placed in a greenhouse and watered for 8-10 days, then the foilage of the emerged test plants was sprayed with a solution of the test compound in acetone-water containing up to 0.5% sorbitan monolaurate. After spraying, the foliage was kept dry for 24 hours, then watered regularly for 21 days, and phytotoxicity data recorded.
• Phytotoxicity data were taken as percent control. Percent control was determined by a method similar to the o to 100 rating system disclosed in "Research Methods in Weed Science,” 2nd ed., B. Truelove, Ed.; Southern Weed Science Society; Auburn University, Auburn, Alabama, 1977.
• the present rating system is as follows: Herbicidal data are given for various compounds of the invention in Tables 1 and 2 below. The test compounds are identified in the tables by Example numbers. In the tables "kg/ha” is kilograms per hectare and "% C" is percent control.
• the active compounds as above defined are formulated into herbicidal compositions by admixture in herbicidally effective amounts with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application.
• the present herbicidal compounds may be formulated as granules of relatively large particle size, watersoluble or water-dispersible granules, as powdery dusts , as wettable powders , as emulsif i able concentrates, as solutions or as any of several other known types of formulations, depending on the desired mode of application.
• these herbicidal compositions are usually applied either as sprays, dusts, or granules to the areas in which suppression of vegetation is desired.
• sprays or dusts are most commonly used.
• These formulations may contain as little as 0.5% to as much as 95% or more by weight of active ingredient.
• Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns.
• a typical dust formulation useful herein is one containing 1.0 part of the herbicidal compound and 99.0 parts of talc.
• Wettable powders also useful formulations for both pre- and postemergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersant.
• the wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid.
• Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion.
• a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Frequently, additional wetting agent and/or oil will be added to the tank-mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant.
• Emulsifiable concentrates are homogeneous liquid or paste compositions dispersible in water or other dispersant, and may consist entirely of the herbicidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent.
• a liquid carrier such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent.
• these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated.
• the percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
• Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; polyhydric alcohols; and other types of surface active agents, many of which are available in commerce.
• the surface active agent when used, normally comprises 1% to 15% by weight of the herbicidal composition.
• compositions for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene or other organic solvents.
• Granular formulations, wherein the toxicant is carried on relatively coarse 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, may also be used.
• Water-soluble or water-dispersible granules are also useful formulations for herbicidal application of the present compounds.
• Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible. These soluble or dispersible granular formulations described in U.S. patent No. 3,920,442, incorporated herein by reference are useful herein with the present herbicidal compounds.
• the active herbicidal compounds of this invention may be formulated and/or applied with insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selective herbicides in agriculture.
• an effective amount and concentration of the active compound is of course employed.
• the active herbicidal compounds of this invention may be used in combination with other herbicides, e.g. they may be mixed with, say, an equal or larger amount of a known herbicide such as chloroacetanilide herbicides such as 2-chloro-N- (2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor), 2-chloro-N-(2-ethyl-6-methylphenyl)- N-(2-raethoxy-1-methylethyl) acetamide (metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)glycine (diethatyl-ethyl); benzothiadiazinone herbicides such as 3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide (bentazon); triazine herbicides such as 6-chloro-

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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)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

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Citations (5)

• 1985
  • 1985-08-23 EP EP85904377A patent/EP0231176A1/en active Pending
  • 1985-08-23 BR BR8507256A patent/BR8507256A/pt unknown
  • 1985-08-23 WO PCT/US1985/001627 patent/WO1987000730A1/en unknown
  • 1985-08-23 AU AU47296/85A patent/AU4729685A/en not_active Abandoned
  • 1985-08-27 CA CA 489430 patent/CA1262734C/xx not_active Expired
  • 1985-08-27 IL IL76199A patent/IL76199A0/xx unknown
  • 1985-08-28 DK DK390385A patent/DK390385D0/da not_active Application Discontinuation
  • 1985-09-06 ES ES546768A patent/ES8802035A1/es not_active Expired
  • 1985-09-12 PL PL25534685A patent/PL255346A1/xx unknown
  • 1985-09-13 TR TR22222A patent/TR22222A/xx unknown
• 1986
  • 1986-11-24 ES ES557223A patent/ES557223A1/es not_active Expired

Patent Citations (5)

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