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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
• • 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

• This invention relates to novel herbicides for weed control in agriculture, horticulture and other fields where it is desired to control unwanted plant growth, such as grassy or broadleaf plant species.
• the information also relates to intermediates for the production of such herbicides.
• Z may be O, S, NH or alkylamino (such as lower alkylamino, e.g. methylamino).
• R 4 may be H or CH 3 and R 3 may be OH, alkoxy
• lower alkoxy such as methoxy or ethoxy
• lower alkenyloxy or alkynyloxy e.g. allyloxy or propargyloxy
• amino, arylamino e.g. phenylamino
• alkylamino e.g. lower alkylamino such as methylamino or dimethylamino
• alkenylamino e.g. diallylamino
• alkoxyamino e.g.
• R 5 and R 6 may be independently alkyl (e.g. lower alkyl such as methyl, ethyl or propyl), haloalkyl (e.g. halo lower alkyl such as trifluoromethyl) or aryl such as phenyl or substituted phenyl, (e.g. alkoxy-substituted and/or halo-substituted phenyl).
• alkyl e.g. lower alkyl such as methyl, ethyl or propyl
• haloalkyl e.g. halo lower alkyl such as trifluoromethyl
• aryl such as phenyl or substituted phenyl, (e.g. alkoxy-substituted and/or halo-substituted phenyl).
• R' may be H, alkyl (e.g. lower alkyl such as methyl), halogen such as Cl, Br or F, haloalkyl (e.g. lower haloalkyl such as CF CH 2 F or CHF 2 ), nitro, NH 2 , lower alkoxy or alkylthio (e.g. OCH 3 or SCH 3 ) or cyano.
• alkyl e.g. lower alkyl such as methyl
• halogen such as Cl, Br or F
• haloalkyl e.g. lower haloalkyl such as CF CH 2 F or CHF 2
• nitro NH 2
• lower alkoxy or alkylthio e.g. OCH 3 or SCH 3
• R a and R b on the triazolinone ring may be any of those known in the art.
• each may, independently, be lower alkyl or lower haloalkyl (e.g. fluoroalkyl); some examples ofR a and R b substituents are found in Table 1.
• “Ar” carries a substituent (i.e. other than H) at the 2-position or the 4-position of the phenyl radical, most preferably at both the 2- and 4-positions.
• X may be H, halogen such as Cl, Br or F (preferably F), alkyl (e.g. lower alkyl such as methyl), haloalkyl (e.g. lower haloalkyl such as CF 3 , CH 2 F or CHF 2 ) or nitro; and
• Y may be H, halogen such as Cl, Br or F (preferably Br or Cl), alkyl (e.g. lower alkyl such as methyl), alkoxy (e.g. lower alkoxy such as methoxy), haloalkyl (e.g. lower haloalkyl such as fluoroalkyl), -SOCF 3 or halo lower alkoxy such as -OCHF 2 .
• X, Y substituents are: 2-F, 4-Cl; 2-F, 4-Br; 2,4-Cl; 2-Br, 4-Cl; and 2F,4-CF 3 .
• a broader aspect of the invention relates to herbicidal compounds of the formula
• R 2 may be H, halogen (such as Cl, Br or F), alkyl (such as lower alkyl, e.g. methyl), haloalkyl (such as halo lower alkyl, e.g. CF3, CHF 2 , C 2 ,F 5 or CH F), alkoxy (such as lower alkoxy, e.g. methoxy), haloalkoxy (such as halo lower alkoxy, e.g. OCHF 2 and OCF 3 ), nitro, amino, alkylthio (such as lower alkyl- thio, e.g. methylthio), -COOH, -CONHSO R 5 , -CONH 2 ,
• R 1 , R 3 , R 4 , R 5 , and R 6 (as well as Ar, R a , R b , X and Y) are as described earlier.
• Ar, R a and R b are so chosen that the Methoxy Analog or Propargyloxy Analog (in which Q' is methoxy or propargyloxy instead of the Q' described above) is a herbicide.
• R a and R b and Ar are so chosen that the Methoxy Analog or the Propargyloxy Analog of such preferred compound has marked herbicidal properties, such Analog showing at least 50% kill of at least one of the following plant species when applied under at least one of the following modes at the rate of 0.5 kg/ha, and more preferably showing such 50% kill when applied at the rate of 0.1 kg/ha:
• Example 1 the starting material is the Hydroxy Analog of the compound (which Hydroxy Analog may be obtained by treatment of the corresponding Methoxy Analog as described in Example IE of published International Application WO 85/04307).
• the Hydroxy Analog is treated to form the nitrophenyl ether, which is then treated to form the hydroxyphenyl ether, followed by etherification with the appropriate moiety.
• Other methods are illustrated below.
• Method B the process is illustrated with a compound in which "M" is N instead of CH; in that method the hydroxypyridyl ether is produced, by treating the methoxypyridyl ether with BBr 3 .
• Method C the first step is an etherification to introduce the R 2 group followed by a reduction of the nitro substituent (on the Ar group) to form an amino group which is then converted to a chlorine substituent.
• Methods D and E relate to processes for making the Q'-Ar-NH 2 compound whose NH 2 group can then be converted to the final triazolinone moiety in a conventional manner.
• Method D the NH 2 group has been acylated to protect it during the various reactions.
• Method E that NH 2 group is introduced by nitration followed by reduction. While these methods are illustrated specifically with reagents chosen to form the product of Example 1 (or, in Method B, the corresponding pyridyl compound), it will be understood by those skilled in the art that analogous reactants may be used to form other compounds disclosed herein.
• Method B React 1-(4-chloro-2-fluoro-5-hydroxy- phenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4- triazol-5(1H)-one first with sodium hydride (e.g. in
• N,N-dimethylformamide C'DMF followed by reaction with an appropriately substituted 5-methoxypyridine (e.g.
• Method C React 1-(2,5-difluoro-4-nitrophenyl)-4- difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol- 5(1H)-one with an alkyl (e.g. ethyl) 2-(4-hydroxy- phenoxy)propionate in the presence of a base (such as sodium hydride in N,N-dimethylformamide) to form the alkyl 2-[4-C4-fluoro-2-nitro-5-(4-difluoromethyl-4,5- dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]- phenoxy]propionate.
• a base such as sodium hydride in N,N-dimethylformamide
• Method D React 4-chloro-2-fluoro-5-hydroxyaceta- nilide with 4-fluoronitrobenzene (e.g. by heating in the presence of a base, such as sodium hydride, and DMF) to form 4-chloro-2-fluoro-5-(4-nitrophenoxy)acetanilide.
• Method E React 2,5-difluoronitrobenzene with 4-methoxyphenol (e.g. in the presence of a base, such as sodium hydride and DMF) to form 5-fluoro-2-(4-methoxy- phenoxy)nitrobenzene.
• a base such as sodium hydride and DMF
• Reduce the nitro group (as by hydrogenation in ethanol with a catalytic amount of platinum oxide) to form 5-fluoro-2-(4-methoxyphenoxy)- aniline.
• Nitrate the latter (as with nitric acid and sulfuric acid) to form 5-fluoro-2-(4-methoxyphenoxy)-4- nitroaniline.
• Treat the latter e.g.
• substituents present in the final product may be introduced at various stages.
• the methoxy group may be converted to a Q group such as a C 2 H 5 O-CO-CH(CH 3 )-O- group at a subsequent stage in the process, or the latter group may be introduced earlier, as by using ethyl 2-bromopropionate in place of the methyl iodide in Method D or by using ethyl 2-(4-hydroxy ⁇ henoxy)propionate in place of the 4-methoxyphenol in Method E.
• Step A 1-[4-Chloro-2-fluoro-5-(4-nitrophenoxy)phenyl]- 4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4- triazol-5 ( 1H) -one
• 30 mL of N,N-dimethylformamide was added slowly a solution of 5.50 g (0.019 mole) of 1-[4- chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5- dlhydro-3-methyl-1,2,4-triazol-5(1H)-one in 30 mL of N,N-dimethylformamide.
• Step B 1-[5-(4-Aminophenoxy)-4-chloro-2-fluorophenyl]- 4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-tri- azol-5(1H)-one Hydrogenation of 5.80 g (0.015 mole) of 1-[4-chloro- 2-fluoro-5-(4-nitrophenoxy)phenyl]-4-difluoromethyl-4,5- dihydro-3-methyl-1,2,4-triazol-5(1H)-one dissolved in 100 mL of ethanol in the presence of a catalytic amount (0.30 g) of platinum oxide produced 4.6 g of 1-[5-(4- aminophenoxy)-4-chloro-2-fluorophenyl]-4-difluoromethoxy- 4, 5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid, mp 133-135°
• Step C 1-[4-Chloro-2-fluoro-5-(4-hydroxyphenoxy)- phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl- 1,2,4-triazol-5(1H)-one While maintaining a temperature of 20 to 25°C, 4.4 g (0.011 mole) of 1-[5-(4-aminophenoxy)-4-chloro-2-fluoro- phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-tri- azol-5 (1H)-one was added to 4.0 mL. of stirred, concentrated sulfuric acid.
• Step D Ethyl 2-[4-[(2-chloro-4-fluoro-5-(4-difluoro- methyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4- triazol-1-yl)phenoxy]phenoxy]propionate
• 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), wheat (Triticum aestivium var. Prodax), rice ( Oryza sativa var.
• Seeds or tubers of the plant test species were planted in furrows in steam sterilized sandy loam soil contained in disposable fiber flats.
• 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 test 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 submultiples thereof.
• the flats were placed in a greenhouse and watered regularly at the soil surface for 21 days at which time phytotoxicity data were recorded.
• the flats for the postemergence test were placed in a greenhouse and watered for 8-10 days, then the foliage 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.
• the compound is 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, as water-soluble or water-dis- persible granules, as powdery dusts, as wettable powders, as emulsifiable 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 in 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.
• Other useful formulations for herbicidal applications are emulsifiable concentrates.
• 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 su ⁇ fates 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.
• Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a solvent 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.
• a low boiling dispersant solvent carrier such as the Freons
• 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.
• the soluble or dispersible granular formulations described in U.S. patent No. 3,920,442 are useful herei i h 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 amount may be as low as, for example, 2 g/ha or lower, e.g. about 1 to 250 g/ha preferably about 4 to 30 g/ha.
• 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-(meth- oxymethyl)acetamide (alachlor), 2-chloro-N-(2-ethyl-6- methylphenyl)-N-(2-methoxy-l-methylethyl)acetamide (metolachlor), and N-chloroacetyl-N-(2,6-diethyl- phenyl) glycine (diethatyl-ethyl); benzothiadiazinone herbicides such as 3-(1-methylethyl)-(1H)-2,1,3-benzo- thiadiazin-4-(3H)-one-2,2-dioxide (bentazon); triazine herbicides such

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• 1987
  • 1987-08-05 HU HU874354A patent/HUT48799A/hu unknown
  • 1987-08-05 WO PCT/US1987/001928 patent/WO1988001133A1/en not_active Application Discontinuation
  • 1987-08-05 JP JP62505029A patent/JPH02500271A/ja active Pending
  • 1987-08-05 EP EP19870905518 patent/EP0322413A4/de not_active Withdrawn
  • 1987-08-05 BR BR8707779A patent/BR8707779A/pt unknown
  • 1987-08-20 CN CN87105742A patent/CN1032005A/zh active Pending
  • 1987-08-20 ZA ZA876179A patent/ZA876179B/xx unknown
• 1988
  • 1988-04-19 KR KR1019880700414A patent/KR880701527A/ko not_active Application Discontinuation

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