HERBICIDES

Abstract: Herbicidal compounds which are ring-substituted aryloxyphenoxytriazolinones, such as compounds of formula (1) where R<2> is, for instance, C2H5OCO-CH(CH3)-O- or CH3SO2-NH-CO-CH(CH3)-O-.

Description: HERBICIDES 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 informa¬ tion also relates to intermediates for the production of such herbicides. A particularly effective aspect of this invention relates to herbicidal compounds of the formula (Itaπnula I) where Q-Ar- is a substituted phenyl radical (e.g. of the formula X in which the substituent Q is at the 5-position (meta to the nitrogen of said formula I); Q is NCCH(R 4 )0-[CO-CH(R 4 ) Z may be 0, S, NH or al ylamino (such as lower alkylamino, e.g. methyla ino) . 4 3 R may be H or CH- and R may be OH, alkoxy (e.g. lower alkoxy such as methoxy or ethoxy) , lower alkenyloxy or alkynyloxy (e.g. allyloxy or propargyl¬ oxy), amino, arylamino (e.g. phenylamino) , alkylamino (e.g. lower alkylamino such as methylamino or dimethyl- amino) , alkenylamino (e.g. diallylamino) , alkoxyamino (e.g. lower alkoxyamino such as methoxyamino) or alkyl-, haloalkyl- or arylsulfonylamino of the formula -NHSO R 5 or -N(S0 2 R 5 )S0 2 R 6 . R and R 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-substi- tuted and/or halo-substituted phenyl) . "n" may be 1 or 2 and "m" may be zero or 1. 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-F or CHF ) , nitro, NH , lower alkoxy or alkylthio (e.g. OCH or SCH ) or cyano. There may be a plurality of R' substituents on the same benzene ring. _a "_ In Formula I above, Ar, R- and R are so chosen that when Q is methoxy or propargyloxy (instead of Q having the formula given above) the compound is a herbi¬ cide. Compounds in which Q in Formula I is methoxy or propargyloxy are, for convenience, here designated as the Methoxy Analogs and the Propargyloxy Analogs of the claimed novel compounds. Such Methoxy Analogs and Propargyloxy Analogs are well -known in the art. " For instance, the Methoxy Analog of Compounds 1-7, 26-72 and 88-91 of this application (see Table I below) is the compound 1-(4-chloro-2-fluoro-5-methoxyphenyl)-3-methyl- 4-difluoromethyl- Δ 2- 1, 2,4-trιazolιn-5-one of Example ID of International Application WO 85/04307 published October 10, 1985, and the Propargyloxy Analog of said numbered compounds 1-7, 26-72 and 88-91 is the compound 5 of Example 2 of that same International Application, while the Methoxy and Propargyloxy Analogs of compounds 82 and 92 are described in U.S. Patent 4,398,943. The substituents R and R on the triazolinone ring- may be any of those known in the art. For _0; instance, each may, independently, be lower alkyl or lower haloalkyl (e.g. fluoroalkyl) ; some examples of ___ . R and R substituents are found in Table 1. Preferably, "Ar" carries a substituent (i.e. other than H) at the 2-position or the 4-position of the 5 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 ) 0 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, or 5 halo lower alkoxy such as -OCHF_. Presently preferred X, Y substituents are: 2-F, 4-C1; 2-F, 4-Br; 2,4-Cl; 2-Br, 4-C1; and 2F,4-CF 3 . A broader aspect of the invention relates to herbicidal compounds of the formula in which Q (which generically includes Q) is; 2 in which R 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. CF_, CHF 2 , C_,F 5 or CH F), alkoxy (such as lower alkoxy, e.g. methoxy), haloalkoxy (such as halo lower alkoxy, e.g. OCHF and OCF_), nitro, amino, alkylthio (such as lower alkyl- thio, e.g. methylthio), -COOH, -CONHSO R 5 , -CONH , -CONHR 5, -CONHOR7 (where R7 is lower alkyl such as methyl), -COOCH(R 4 )COOR 3 , -NHSO_,R 7 , -N(S0 2 R 7 ), -SCH(R 4 )COR 3 or -NHCH(R 4 )COR 3 or R 3 [C0-CH(R 4 )-0] or NCCH.(R )0-[CO-CH(R )-0] , and M is CH or N. Z, R , R , R , R , and R (as well as Ar, ___ _ _a R , R , X and Y) are as described earlier. Ar, R and R are so chosen that the Methoxy Analog or Pro¬ pargyloxy Analog (in which Q' is methoxy or propargyloxy instead of the Q' described above) is a herbicide. In the preferred compounds of this invention, R and R and Ar (or X and Y) are so chosen that the Methoxy Analog or the Propargyloxy Analog of such pre¬ ferred 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: Species: velvetleaf (Abutilon theophrasti) , green foxtail (Setaria viridis) ; Modes: pre-emergent, post- emergent. Testing for such herbicidal activity may be carried out in the manner described below (under the heading "Herbicidal Activity"). Representative compounds of this invention (includ¬ ing certain intermediates) are listed in Table 1. The compounds of this invention may be prepared by the use of steps generally described in the literature or by methods analogous or similar thereto and within the skill of the art. In Example 1 below, 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. In Method B the process is illustrated with a compound in which "M" is N instead of CH; in that method the hydroxy- pyridyl ether is produced, by treating the methoxypyridyl ether with BBr_. In 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 a ino group which is then converted to a chlo¬ rine substituent. Methods D and E relate to processes for making the Q'-Ar-NH_ compound whose NH_ group can then be converted to the final triazolinone moiety in a conventional manner. In Method D the NH,, group has been acylated to protect it during the various reactions. In 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 l-(4-chloro-2-fluoro-5-hydroxy- phenyl)-4-difluoromethyl-4, 5-dihydro-3-methyl-l,2,4- triazol-5(lH)-one first with sodium hydride (e.g. in N,N-dimethylformamide C'DMF"] followed by reaction with an appropriately substituted 5-methoxypyridine (e.g. 2-fluoro- or 2-chloro-5-methoxypyridine) to form l-[4- chloro-2-fluoro-5-(5-methoxypyridin-2-yl)oxyphenyl]-4- difluoromethyl-4, 5-dihydro-3-methyl-l, 2,4-triazσl-5(lH)- one. Then treat with boron tribromide (e.g. in meth- ylene chloride) followed by reaction with an alkyl (e.g. ethyl) 2-bromopropionate (e.g. in the presence of potas¬ sium carbonate and acetone) to form the corresponding alkyl 2-[5-[2-chloro-4-fluoro-5-(4-difluoromethyl-4, 5- dihydro~3-methyl-5-oxo-lH-l, 2,4-triazol-l-yl)phenoxy]- pyridin-2-yl]oxypropionate. Method C: React l-(2, 5-difluoro-4-nitrophenyl)-4- difluoromethyl-4, 5-dihydro-3-methyl-l, 2,4-triazol- 5(lH)-one with an*alkyl (e.g. 'ethyl) 2-( -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-lH-l, 2,4-triazol-l-yl)phenoxy]- phenoxy]propionate. Reduce the nitro group by hydro- genation (e.g. in ethanol with a catalytic amount of platinum oxide) to form the alkyl 2-[4-[2-amino-4- fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo- 1H-1, 2,4-triazol-l-yl)phenoxy]phenoxy]propionate. Then treat (as with sodium nitrite and hydrochloric acid, followed by copper (I) chloride) to form the correspond- ing alkyl 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4, 5- dihydro-3-methyl-5-oxo-lH-l, 2,4-triazol-l-yl)phenoxy]- phenoxy]propionate. - 7 - 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. Reduce the NO.- group (as by hydrogenation in ethanol with a catalytic amount of platinum oxide) to form 5-(4-aminophenoxy)-4-chloro-2-fluoroacetanilide. Treat the latter (e.g. with sodium nitrite and sulfuric acid followed by copper (II) sulfate) to form 4-chloro-2- fluoro-5-(4-hydroxyphenoxy)acetanilide. Then react with an alkyl halide, such as methyl iodide (e.g. in the presence of potassium carbonate and acetone) to form the alkyl 4-chloro-2-fluoro-5-(4-methoxyphenoxy)aceta- nilide. Hydrolyze the latter (as with hydrochloric acid) to form the corresponding aniline, e.g. 4-chloro- 2-fluoro-5-(4-methoxyphenoxy)aniline. 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. Reduce the nitro group (as by hydrogenation in ethanol with a catalytic amount of platinum oxide) to form 5-fluoro-2-(4-methoxyphenox )- 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. first with sodium nitrite and hydrochloric acid followed by copper (I) chloride-) to form 4-chloro-2-fluoro-5-(4-methoxyphen¬ oxy)nitrobenzene. Reduce the nitro group (e.g. by hydrogenating in ethanol with a catalytic amount of platinum oxide) to form the corresponding 4-chloro-2- fluoro-5-(4-methoxyphenoxy)aniline. It will be understood that substituents present in the final product may be introduced at various stages. For instance in methods D and E the methoxy group may be converted to a Q group such as a C H 0-CO-CH(CH )-0- 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-hydroxyρhenoxy)propio- nate in place of the 4-methoxyphenol in Method E. EXAMPLE 1 ETHYL 2-C4-C(2-CHL0R0-4-FLU0R0-5-(4-DIFLU0R0- METHYL-4, 5-DIHYDRO-3-METHYL-5-OXO-1H-1, 2, 4-TRIAZ0L- 1-Y )PHENOXY]PHENOXY]PROPIONATE Step A l-[4-Chloro-2-fluoro-5-(4-nitrophenoxy)phenyl]- 4-difluoromethyl-4, 5-dihydro-3-methyl-l,2,4- triazol-5(1H)-one To a stirred mixture of 0.91 g (0.019 mole) of sodium hydride In 30 mL of N,N-dimethylformamide was added slowly a solution of 5.50 g (0.019 mole) of l-[4- chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethy1-4,5- dlhydro-3-methyl-l,2,4-triazol-5(lH)-one in 30 mL of N,N-dimethylformamide. To this mixture was added 2.68 g (0.019 mole) of 4-fluoronitrobenzene. The resultant mixture was stirred at room temperature for approxi¬ mately 18 hours and then was heated at 80°C for one hour. The mixture was allowed to cool and was poured into ice water. The aqueous mixture was extracted with diethyl ether. The extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evap¬ orated under reduced pressure to yield 6.0 g of l-[4- chloro-2-fluoro-5-(4-nitrophenoxy) henyl]-4-difluoro- methyl-4, 5-dihydro-3-methyl-l, 2,4-triazol-5(lH)-one as a solid, mp 115-117°C, Compound 4 of Table 1. The n r spectrum was consistent with the proposed structure. Step B l-[5-(4-Aminophenoxy)-4-chloro-2-fluorophenyl]- 4-difluoromethyl-4, 5-dihydro-3-methyl-l, 2, 4-tri- azol-5(lH)-one Hydrogenation of 5.80 g (0.015 mole) of l-[4-chloro- 2-fluoro-5-(4-nitrophenoxy)phenyl]-4-difluoromethyl-4, 5- dihydro-3-methyl-l, 2,4-triazol-5(lH)-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 l-[5-(4- aminophenoxy)-4-chloro-2-fluorophenyl]-4-difluoromethoxy- 4, 5-dihydro-3-methyl-l,2,4-triazol-5(lH)-one as a solid, mp 133-135°C, Compound 3 of Table 1. The nmr spectrum was consistent with the proposed structure. Step C l-[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 l-[5-(4-aminophenoxy)-4-chloro-2-fluoro- phenyl]-4-difluoromethyl-4, 5-dihydro-3-methyl-l, 2, 4-tri- azol-5(lH)-one was added to 4.0 mL. of stirred, concen¬ trated sulfuric acid. To this was added a solution of 0.89 g (0.13 mole) of sodium nitrite dissolved in 6.0 mL of water, while continuing to maintain a temperature of about 20°C. After complete addition, the mixture was stirred at 20°C for 30 minutes. This mixture was added through a glass tube to the bottom of a stirred, reflux- ing mixture of 32.0 g (0.13 mole) of copper (II) sulfate pentahydrate, 80 mL of water and 30 L of xylene. After complete addition the mixture was refluxed for one hour. The mixture was cooled, and the organic phase was separated from the aqueous phase. The organic phase was extracted with an aqueous, sodium hydroxide solution (6.0 g of sodium hydroxide pellets dissolved in 250 mL of water). The basic extract as neutralized with con¬ centrated hydrochloric acid, causing a precipitate to form. The solid was collected by filtration to yield 2.3 g of l-[4-chloro-2-fluoro-5-(4-hydroxyphenoxy)- 5 phenyl]-4-difluoromethyl-4, 5-dihydro-3-methyl-l, 2,4- triazol-5(lH)-one, m.p. 162-165°C, Compound 2 of Table 1, Step D Ethyl 2-[4-[(2-chloro-4-fluoro-5-(4-difluoro¬ methyl-4,5-dihydro-3-methyl-5-oxo-lH-l, 2,4- Q_- triazol-l-yl)phenoxy]phenoxy]propionate A stirred mixture of 0.60 g (0.0015 mole) of l-[4- chloro-2-fluoro-5-(4-hydroxyphenoxy)phenyl]-4-difluoro¬ methyl-4, 5-dihydro-3-methyl-l, 2, -triazol-5(lH)-one, 0.54 g (0.0030 mole) of ethyl 2-bromopropionate, and 5 0.32 g (0.0023 mole) of potassium carbonate in 30 mL of acetone was heated at reflux for six days. The mixture was cooled and- filtered. The filtrate was evaporated under reduced pressure leaving a residue. This residue was purified by column chromatography on silica gel, 0 eluting with methylene chloride to yield 0.43 g of ethyl l-[4-[ (2-chloro-4-fluoro-5-(4-difluoromethyl-4, 5- dihydro-3-methyl-5-oxo-lH-l, 2,4-triazol-l-yl)phenoxy]- phenoxy]propionate as a solid, mp 128-129°C, Compound 5 of Table 1. 5 The nmr spectrum was consistent with the proposed structure. EXAMPLE 2 N-METHYLSULF0NYL-2-C4-C2-CHL0R0-4-FLU0R0-5-(4- DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL-5-OXO-lH- 0 1,2,4-TRIAZ0L-1-YL)PHEN0XY]PHEN0XY]PR0PI0NAMIDE In a manner similar to Step D of Example 1, the reaction of 0.60 g (0.0015 mole) of l-[4-chloro-2- fluoro-5-(4-hydroxyphenoxy) henyl]-4-difluoromethyl- 4,5-dihydro-3-methyl-l,2,4-triazol-5(lH)-one, 0.32 g 5 (0.0014 mole) of N-methylsulfonyl-2-bromopropionamide, and 0.24 g (0.0017 mole) of potassium carbonate in 20 mL of acetone produced 0.3 g of N-methylsulfonyl 2-[4-[2- chloro-4-fluoro-5-(4-difluoromethyl-4, 5-dihydro-3- methyl-5-oxo-lH-l, 2,4-triazol-l-yl)phenoxy]phenoxy]- propiona ide as an oil, Compound 32 of Table 1. The nmr spectrum was consistent with the proposed structure. Other compounds of the invention may be prepared by the methods exemplified above or by methods within the skill of the art. HERBICIDAL ACTIVITY 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. Labelle) , field bind¬ weed (Convolvulus arvensis) , morningglory (Ipomea lacunosa or Ipomea hederacea) , velvetleaf (Abutilon theophrasti) , barnyardgrass (Echinochloa crus galli ) , green foxtail (Setaria viridis) , and johnsongrass (Sorghum halepense) , wild mustard (Brassica raber) . 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 approxi¬ mately 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. The 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. Herbicidal data at selected application rates are given for various compounds of the invention in Table 3 and Table 4 below. The test compounds are identified therein by numbers which correspond to those in Table 1. In Tables 3 and 4 below: "kg/ha" is kilograms per hectare, and "% C" is percent control. For herbicidal application, the compound is formu¬ lated 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 formula¬ tion and mode of application of a toxicant may affect the activity of the material in a given application. Thus, for agricultural use 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. For preemergence application these herbicidal compositions are usually applied either as sprays, dusts, or granules in the areas in which suppression of vegetation is desired. For postemergence control of established plant growth, sprays or dusts are most commonly used. These formulations may contain as little 5 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 10. 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 15 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 0 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 inor¬ ganic diluents. . Wettable powders normally are prepared 5 to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also con¬ tain a small amount of a wetting, dispersing or emul¬ sifying agent to facilitate dispersion. For example, a useful wettable powder formulation contains 80.8 parts 0 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 5 facilitate dispersion on the foliage and absorption by the plant. Other useful formulations for herbicidal applica¬ tions are emulsifiable concentrates. Emulsifiable concentrates are homogeneous liquid or paste composi¬ tions 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. For herbicidal application 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 suϊfates 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 applica¬ tions 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. 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 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. In applying an active com¬ pound of this invention, whether formulated alone or with other agricultural chemicals, 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 herbi¬ cides 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-(l-methylethyl)-(lH)-2,1, 3-benzo- thiadiazin-4-(3H)-one-2, 2-dioxide (bentazon); triazine herbicides such as 6-chloro-N-ethyl-N-(1-methylethyl)- 1, 3, 5-triazine-2,4-diamine (atrazine), and 2-[4- chloro-6-(ethylamino)-l, 3, 5-triazin-2-yl]amino -2- me hylpropanenitrile (cyanazine) ; dinitrolaniline herbicides such as 2,6-dinitro-N,N-dipropyl-4-(tri- fluoromethyl)benzeneamine (trifluralin) ; and aryl urea herbicides such as N'-(3,4-dichlorophenyl)-N,N-di- methylurea (diuron) and N,N-dimethyl-N * -C3-(trifluoro- methyl)phenyl]urea (fluometuron) . It is apparent that various modifications may be made in the formulation and application of the com¬ pounds of this invention without departing from the inventive concepts herein as defined in the claims. - 17 - TABLE Cmpd No. R a CHF CH 4-NO 3-CN Cl CHF. CH. 4-OH CHF. CH. 4-NH CHF. CH_ 4~N0_ CHF, CH. 4-OCH.CH )CO C H CHF. CH. 4-OCH C=CH Cl CHF, CH. 4-OCH (CH ) CO CH Cl CH. CH. 4-0CH(CH )CO CH Cl CH(CH ) CH. 4-0CH(CH )CO CH Cl CH. 4~OCH(CH,)C0 CH, C 2 H 5 3 2 3 CH CH CH F CH. 4-OCH (CH )CO CH, Cl 2 2 2 3 2 3 - 18 - TABLE I - Continued Cmpd No. R a 12 CH_CH„F CH. 4-0CH(CH,)C0 o CH, Cl 2 2 3 2 3 13 CH_CH 2 CH_ CH. 4-OCH(CH )CO CH Cl 14 CH_CH=CH„ CH. 4-OCH(CH )C0 CH Cl 2 2 15 CH C=CH CH. 4-OCH(CH )CO CH Cl 2 16 CHF. Ci 4-OCH(CH )CO CH- Cl 17 CHF. Br 4-OCH(CH )CO CH Cl 18 CHF. 4-OCH(CH,)CO CH, Cl 3 2 3 19 CHF. CH(CH ) 4-OCH(CH )CO CH Cl 32 3 2 3 20 CHF. SCH. 4-OCH(CH,)C0 CH, Cl 3 2 3 21 CHF„ SO CH 4-OCH(CH )C0 CH Cl 22 CHF. SCF, 4-OCH(CH )CO CH Cl - 19 - TABLE I - Continued Cmpd No. 23 CHF. S0 2 CF 3 4-OCH (CH )C0 CH Cl 24 CHF. 4-0CH(CH )C0 CH Cl C 2 H 5 3 2 3 25 CHF. HXH(CH )C0 CH Cl 3 2 3 26 CHF. CH. 4-0CH(CH )C0 H Cl 3 2 27 CHF. CH. 4 -CCH(CH )CONH C! 3 2 28 CHF. CH. 4-OCH (CH )CONHCH Cl 29 CHF. CH. 4-OCH (CH )C0N(CH ) Cl 3 3 2 30 CHF. CH. 4-OCH ( CH ) CON (CH )OCH 31 CHF. CH. 4-OCH (CH )C0N(CH CH=CH ) . H 3 2 2 2 32 CHF. CH. 4-OCH (CH )CONHSO CH Cl 3 2 3 33 CHF. CH. 4-OCH (CH )C0N(CH )SO CH H Cl - 20 - TABLE I - Continued Cmpd No. R a 34 CHF. CH_ 4-OCH (CH ) CON (C H ) SO CH C ! 35 CHF. CH. 4-OCH ( CH ) CONHSO CF Cl 36 CHF. CH. 4-OCH(CH )CONCCH )SO CF Cl 37 CHF. CH. 4-OCH(CH,)C0NHSO_C_H_ Cl 3 225 38 CHF. CH. -CCH(CH )C0NHS0_C_H 7 Cl 39 CHF. CH. 4-OCH(CH )CONHSO C H Cl 40 CHF. CH. 4-OCH(CH )C0NHS0 (4-CICH ) Cl 41 CHF. CH. 4-OCH(CH )C0NHS0 (4-CH 00 H ) Cl 42 CHF, CH. 4-OCH_C0NHSO 2 CH_ Cl 43 CHF. CH. 4-OCH CO H Cl 2 2 44 CHF. CH. 4-OCH.CO„C_H_ Cl 2 225 - 21 - TABLE I - Continued Cmpd No. R a 45 CHF. CH 4-OCH C=N Cl 2 46 CHF. CH. 4-0CH(CH )CN 47 CHF. CH. 4-0CH(CH )C0 CH(CH )C=CH Cl 48 CHF. CH. 4-OCH COCH, Cl 2 3 49 CHF CH. 3-0CH(CH )CO C H Cl 50 CHF. CH. 3-0CH(CH )CO H Cl CHF. CH. 3-OCH(CH CONH Cl 52 CHF. CH. 3-OCH(CH 5C0NHS0 CH Cl 53 CHF. CH. 3-OCH<CH,)C0NHSO„C H Cl 3 265 54 CHF. CH. 4-OCH(CH )CO C H 2-CI Cl 55 CHF. CH. 4-OCH(CH )CO C H 2-F Cl - 22 - TABLE I - Continued Cmpd No. R a R2 56 CHF. CH. 4-0CH(CH )C0 C H 3-CI Cl 57 CHF. CH. 4-0CH(CH )CO C H 3-F C! 58 CHF. CH. 4 -0CH(CH )C0 C H 2-CH Cl 59 CHF. CH. 4-OCH.CH >C0 C H 3-CH Cl 60 CHF. CH. 4-OCH(CH )CO C H 2-OCH. Cl 61 CHF. CH. 4-OCH ( CH ) CO C H 3-OCH. Cl 62 CHF. CH_ 4-OCH (CH )CO C H 2-NO. Cl 63 CHF. CH. 4 ~OCH(CH )C0 C H. 3-NO Cl 3 225 64 CHF. CH. 4 -OCH(CH )C0 C H 2,6-F F Cl 65 CHF. CH. 4-0CH ( CH ) C0 C H 2,3-F, F Cl 66 CHF. CH. 3-OCH (CH )CO C H 4-N0 Cl - 23 - TABLE I - Continued Cmpd No. R a 67 CHF. CH. 3-0CH<CH,)C0-C_H- 4-CI Cl 3 2 2 5 68 CHF. CH. 3-OCH(CH,)CO_C_,H_ 4-Br Cl 3 2 25 69 CHF. CH. 3-OCH(CH_)C0 C H = 4-F 3 225 70 CHF. CH. 3-OCH(CH )CO C H 6-F Cl 71 CHF. CH. 3-0CH(CH,)C0„C H 4-CN 3 2 2 5 72 CHF. CH. 3-0CH(CH,)C0_C_H_ 4-OCH. Cl 3 2 2 5 73 CHF, CH. 4-OCH(CH )CO C H 74 CHF, CH. 4-OCH(CH,)C0^C H c Br 3 225 75 CHF. CH. 4-CCH(CH_)CO_C_H_ CH. 3 22 5 76 CHF, CH. 4-OCH(CH_)CO_C.H_ F NO. 3 2 2 5 77 CHF. CH. 4-OCH(CH_)CO_C H F OCHF. 3 2 2 5 - 24 - TABLE I - Continued Cmpd No. R a Rb 78 CHF CH. 4-0CH(CH )C0 C H CF 3 225 79 CHF. CH. 4-OCH(CH )CO C H H . 80 CHF. CH. 4-OCH(CH )CO C H SCH 81 CHF. CH. 4-CCH(CH )C0 C H Cl 82 CHF. CH. 4-OCH(CH )CO C H Cl Cl 83 CHF CH. 4-OCH(CH )CO C H Br Cl 3 225 84 CHF CH 4-OCH(CH )C0 C H CH Cl 3 225 85 CHF. CH_ 4-OCH(CH )CO C H 86 CHF. CH. 3-OCH(CH )CO C H 2,4-CI H H 87 CHF. CH. 3-0CH(CH )C0 C H 2F.4CI H H TABLE I - Continued Cmpd No. R a Rb R 2 88 CHF, 4-OCHCCH )C0 Na 2 CH 3 89 CHF 2 CH 3 4-OCH(CH )CO K Cl 90 CHF CH 3 4-∞H(CH 3 )C0 2 N + (C 2 H 5 ) 4 91 CHF. CH. 4-0CH(CH )C0 CH(CH ) Cl 92 CHF. CH. 4-N0. Cl Cl Other representative compounds are identical with the fore¬ going compounds 1 - 92, respectively, except that in each 2 case the aromatic ring bearing the R substituent is a pyridine ring of the formula with the R and R 1 being in the same positions with respect to the free valence (connected to 0) as in said compounds 1 - 92; see for instance the compounds produced by method B above. TABLE 2 ___ent±£ying Properties Cmpd Empirical Elemental Analysis No. M.P. (°C) FαrmuLa _ C H N 1 164-165.5 C17H9CLF3N5O4 C 46.43 2.06 15.93 F 46.60 2.28 15.84 2 162-165 C 16 H 11 dF3 3θ 3 3 133-135 C 6 Hι 2 ClF3 4θ2 4 115-117 C 16 H 10 CLF 3 4θ4 5 128-129 C 2 lH 19 C__F3 3θ5 C 51.91 3.94 8.65 F 51.81 3.69 8.79 86-88 C 19 H L3 ClF3N3θ3 C 53.84 3.09 9.91 F 53.43 3.07 9.80 136-138 C20HUCIF3 3O5 C 50.89 3.64 8.91 F 50.58 3.53 8.78 32 σil C 2 θHi8dF 3 4θ 6 S 91 113.5-115 C 2 2H21 LF 3 N 3 0 5 92 thick cdl c 16 H 10 α -2 F 2 N 4°4 1252 30123W md - 27 - Table 3 Preemergence Herbicidal Activity Compound No. 1 2 3 4 Rate (kg/ha) 8.0 4.0 4.0 4..0 %C %C %C %C Species Cotton 10 70 10 0 Soybean 10 100 80 10 Corn 50 85 60 20 Rice 0 95 60 20 Wheat 20 100 60 10 Morningglory 20 90 70 10 Wild Mustard 100 100 70 Velvetleaf 80 100 100 80 Barnyardgrass 90 100 95 30 Green Foxtail 50 100 100 70 Johnsongrass 0 85 100 70 Compound No. 5 6 7 Rate (kg/ha) 4.0 0.5. 0.5 %C %C %C Species Cotton 70 10 50 Soybean 70 30 90 Corn 60 10 95 Rice 70 10 80 Wheat 80 10 95 Morningglory 100 40 100 Wild Mustard 100 40 100 Velvetleaf 100 80 100 Barnyardgrass 100 95 95 Green Foxtail 100 100 100 Johnsongrass 100 40 95 - 28 - Table 4 Postemergence Herbicidal Activity Compound No. 1 2 3 4 Rate (kg/ha) 8.0 4.0 4.0 4.0 %C %C %C %C Species Cotton 60 100 95 70 Soybean 60 95 70 50 Corn 50 95 100 60 Rice 30 95 70 20 Wheat 20 100 95 20 Morningglory 60 100 100 90 Wild Mustard - 70 95 70 Velvetleaf 100 100 100 100 Barnyardgrass 40 100 95 30 Green Foxtail 80 95 100 30 Johnsongrass 30 95 85 30 Compound No. 5 6 7 Rate (kg/ha) " 4.0 0.5 0.5 %C %C %C Species • Cotton 100 95 100 Soybean 100 ao 100 Corn 100 100 105 Rice 95 60 100 Wheat 100 95 100 Morningglory 100 100 100 Wild Mustard 100 95 100 Velvetleaf 100 100 100 Barnyardgrass 100 90 100 Green Foxtail 100 95 100 Johnsongrass 100 95 100 1253W30123Wmd

Claims: Claims 1. A compound characterized by the formula 0 LI Q'-Ar— '^^ -R 3 R b in which Q' is 2 in which R is H, halogen, alkyl, haloalkyl, alkoxy, 15 haloalkoxy, nitro, amino, alkylthio, -COOH, -CONHS0 2 R , -CONH 2 , -CONHR , -CONHOR (where R is lower alkyl such as methyl), -COOCH(R 4 )COOR 3 , -NHS0 2 R 7 , -N(S0 2 R 7 ) 2 , -SCH(R 4 )COR 3 , -NHCH(R 4 )COR 3 , R 3 [CO-CH(R 4 )-0] or NCCH(R 4 )0-[CO-CH(R 4 )-0] m ; 20 M is CH or N; Z is 0, S, NH or alkylamino; y, alkenyloxy, alkynyloxy, am o, arylamino, alkylamino, alkenylammo, alkoxyamino, alkyl-, 25., haloalkyl- or arylsulfonylammo of the formula -NHSO-R or -N(S0 2 R )S0 2 R where R and R are independently alkyl, haloalkyl or aryl; "n" is 1 or 2; "m" is zero or 1. 30 R' is H, alkyl, halogen, haloalkyl, nitro, alkoxy, alkylthio or cyano; Ar is a substituted benzene ring with Ar, R and R being so chosen that when Q' is methoxy or pro¬ pargyloxy, instead of Q' having the formula given above, 5 the compound is a herbicide. 2. A compound as in claim 1 characterized in that R 2 is R 3 [CO-CH(R 4 )-0]n or NCCH(R 4 )0-[CO-CH(R 4 )-0]m. 3. A compound as in claim 2 characterized in that n is 1 and m is zero. 4. A compound as in claim 3 characterized in that M is CH. 5. A compound as in claim 1 characterized in that R 2 is R 3 [CO-CH(R 4 )-0] . 6. A compound as in claim 5 characterized in that M is CH. 7. A compound as in claim 6 characterized in that Ar is a benzene ring having Q' at its 5-position and halogens at its 2- and 4-positions, R is methyl and R is difluoromethyl. 8. A compound as in claim 7 characterized in that Ar has chlorine, fluorine or bromine at its 2-position and chlorine or bromine at its 4-position. 9. A compound as in claim 8 characterized in that Ar has F at its 2-position. 10. An herbicidal composition characterized by an herbicidally effective amount of the compound of claim 1 in admixture with a suitable carrier. 11. A method for controlling undesired plant growth characterized by applying to the locus where control is desired an herbicidally effective amount of the composi¬ tion of claim 10. 12. An herbicidal composition charaterized by an herbicidally effective amount of the compound of claim 5 in admixture with a suitable carrier. 13. A method for controlling undesired plant growth characterized by applying to the locus where control is desired an herbicidally effective amount of the composi¬ tion of claim 12. 14. An herbicidal composition charaterized by an herbicidally effective amount of the compound of claim 9 in admixture with a suitable carrier. 15. A method for controlling undesired plant growth characterized by applying to the locus where control is desired an herbicidally effective amount of the composition of claim 14.

Inventors: THEODORIDIS GEORGE, THEODORIDIS, GEORGE
Applicants: FMC CORP, FMC CORPORATION
Application year: 1987
Main classification: A01N43
IPC codes: A01N43, C07D249, C07D401