WO1988001133A1

WO1988001133A1 - Herbicides

Info

Publication number: WO1988001133A1
Application number: PCT/US1987/001928
Authority: WO
Inventors: George Theodoridis
Original assignee: Fmc Corporation
Priority date: 1986-08-20
Filing date: 1987-08-05
Publication date: 1988-02-25
Also published as: EP0322413A1; EP0322413A4; CN1032005A; JPH02500271A; HUT48799A; KR880701527A; BR8707779A; ZA876179B

Abstract

Herbicidal compounds which are ring-substituted aryloxyphenoxytriazolinones, such as compounds of formula (1) where R2 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 information also relates to intermediates for the production of such herbicides.

A particularly effective aspect of this invention relates to herbicidal compounds of the formula

(F ormula I)

where Q-Ar- is a substituted phenyl radical (e.g. of the formula

in which the substituent Q is at the 5-position (meta to the nitrogen of said formula I); Q is

Z may be O, S, NH or alkylamino (such as lower alkylamino, e.g. methylamino).

R⁴ may be H or CH₃ and R³ may be OH, alkoxy

(e.g. 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. lower alkoxyamino such as methoxyamino) or alkyl-, haloalkyl- or arylsulfonylamino of the formula -NHSO₂R⁵ or -N(SO₂R⁵)SO₂R⁶. R⁵ and R⁶ 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).

"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 CH₂F or CHF₂), nitro, NH₂, lower alkoxy or alkylthio (e.g. OCH₃ or SCH₃) or cyano. There may be a plurality of R' substituents on the same benzene ring.

In Formula I above, Ar, R^a and R^b are so chosen that when Q is methoxy or propargyloxy (instead of Q having the formula given above) the compound is a herbicide. 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 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^a and R^b on the triazolinone ring may be any of those known in the art. For instance, 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.

Preferably, "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 CF₃, CH₂F or CHF₂) 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), -SOCF₃ or halo lower alkoxy such as -OCHF₂. Presently preferred X, Y substituents are: 2-F, 4-Cl; 2-F, 4-Br; 2,4-Cl; 2-Br, 4-Cl; and 2F,4-CF₃.

A broader aspect of the invention relates to herbicidal compounds of the formula

in which Q (which generically includes Q) is;

in which R² 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, CHF₂, C₂,F₅ or CH F), alkoxy (such as lower alkoxy, e.g. methoxy), haloalkoxy (such as halo lower alkoxy, e.g. OCHF₂ and OCF₃), nitro, amino, alkylthio (such as lower alkyl- thio, e.g. methylthio), -COOH, -CONHSO R⁵, -CONH₂,

-CONHR 5, -CONHOR⁷ (where R⁷ is lower alkyl such as methyl), -COOCH(R⁴)COOR³, -NHSO₂R⁷, -N(SO₂R⁷),

-SCH(R⁴)COR³ or -NHCH(R⁴) COR³ or R³[CO-CH(R⁴)-O]_n or NCCH(R⁴)O-[CO-CH(R⁴)-O]_m, and M is CH or N.

Z, R¹, R³, R⁴, R⁵, and R⁶ (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.

In the preferred compounds of this invention, R^a and R^b and Ar (or X and Y) 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:

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 (including 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 hydroxypyridyl ether is produced, by treating the methoxypyridyl ether with BBr₃. 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 amino group which is then converted to a chlorine substituent. Methods D and E relate to processes for making the Q'-Ar-NH₂ compound whose NH₂ group can then be converted to the final triazolinone moiety in a conventional manner. In Method D the NH₂ group has been acylated to protect it during the various reactions. In Method E that NH₂ 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.

2-fluoro- or 2-chloro-5-methoxypyridine) to form 1-[4- chloro-2-fluoro-5-(5-methoxypyridin-2-yl)oxyphenyl]-4- difluoromethyl-4, 5-dihydro-3-methyl-1,2,4-triazol-5(1H)- one. Then treat with boron tribromide (e.g. in methylene chloride) followed by reaction with an alkyl (e.g. ethyl) 2-bromopropionate (e.g. in the presence of potassium carbonate and acetone) to form the corresponding alkyl 2-[5-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5- dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]- pyridin-2-yl]oxypropionate.

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. Reduce the nitro group by hydrogenation (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-1-yl)phenoxy]phenoxy]propionate. Then treat (as with sodium nitrite and hydrochloric acid, followed by copper (I) chloride) to form the corresponding alkyl 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5- dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]- phenoxy]propionate. 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 NO₂ 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)acetanilide. 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-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. first with sodium nitrite and hydrochloric acid followed by copper (I) chloride) to form 4-chloro-2-fluoro-5-(4-methoxyphenoxy)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 C₂H₅O-CO-CH(CH₃)-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-hydroxyρhenoxy)propionate in place of the 4-methoxyphenol in Method E.

EXAMPLE 1 ETHYL 2-[4-[(2-CHL0RO-4-FLUORO-5-(4-DIFLUORO- METHYL-4, 5-DIHYDRO-3-METHYL-5-OXO-1H-1,2,4-TRIAZ0L- 1-YL) PHENOXY]PHENOXY]PROPIONATE

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 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 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. To this mixture was added 2.68 g (0.019 mole) of 4-fluoronitrobenzene. The resultant mixture was stirred at room temperature for approximately 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 evaporated under reduced pressure to yield 6.0 g of 1-[4- chloro-2-fluoro-5-(4-nitrophenoxy)phenyl]-4-difluoro- methyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid, mp 115-117°C, Compound 4 of Table 1.

The nmr spectrum was consistent with the proposed structure. 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°C, Compound 3 of Table 1.

The nmr spectrum was consistent with the proposed structure.

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. 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, refluxing mixture of 32.0 g (0.13 mole) of copper (II) sulfate pentahydrate, 80 mL of water and 30 mL 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 concentrated hydrochloric acid , causing a precipitate to form. The solid was collected by filtration to yield 2.3 g of 1-[4-chloro-2-fluoro-5-(4-hydroxyphenoxy)- phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4- triazol-5(1H)-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-1H-1,2,4- triazol-1-yl)phenoxy]phenoxy]propionate

A stirred mixture of 0.60 g (0.0015 mole) of 1-[4- chloro-2-fluoro-5-(4-hydroxyphenoxy)phenyl]-4-difluoro- methyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, 0.54 g (0.0030 mole) of ethyl 2-bromopropionate, and 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, eluting with methylene chloride to yield 0.43 g of ethyl 1-[4-[(2-chloro-4-fluoro-5-(4-difluoromethyl-4,5- dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-l-yl)phenoxy]- phenoxy]propionate as a solid, mp 128-129°C, Compound 5 of Table 1. The nmr spectrum was consistent with the proposed structure.

EXAMPLE 2 N-METHYLSULFONYL-2-[4-[2-CHLORO-4-FLU0RO-5-(4- DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL-5-OXO-1H- 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 1-[4-chloro-2- fluoro-5-(4-hydroxyphenoxy)phenyl]-4-difluoromethyl- 4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, 0.32 g (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-1H-1,2,4-triazol-l-yl)phenoxy]phenoxy]- propionamide 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 bindweed (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 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. 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 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. 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 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. For example, 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. 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 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. 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. In applying an active compound 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 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 as 6-chloro-N-ethyl-N-(1-methylethyl)- 1, 3, 5-triazine-2,4-diamine (atrazine), and 2-[4- chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino -2- methylpropanenitrile (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 -[3-(trifluoro- methyl)phenyl]urea (fluometuron).

It is apparent that various modifications may be made in the formulation and application of the compounds of this invention without departing from the inventive concepts herein as defined in the claims.

Other representative compounds are identical with the foregoing compounds 1 - 92, respectively, except that in each case the aromatic ring bearing the R² substituent is a pyridine ring of the formula

with the R² and R' 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. Identifying

Claims

Claims :

1. A compound characterized by the formula

in which Q' is

in which R² is H, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, amino, alkylthio, -COOH, -CONHSO₂R⁵, -CONH₂, -CONHR⁵, -CONHOR⁷ (where R⁷ is lower alkyl such as methyl), -COOCH(R⁴)COOR³, -NHSO₂R⁷, -N(SO₂R⁷)₂, -SCH(R⁴)COR³, -NHCH(R⁴)COR³, R³[CO-CH(R⁴)-O]_n or NCCH(R⁴)O-[CO-CH( R⁴) -O]m ; M is CH or N;

Z is O, S, NH or alkylamino; R⁴ is H or CH₃; R ³ is OH, alkoxy, alkenyloxy, alkynyloxy, ammo, arylamino, alkylamino, alkenylammo, alkoxyamino, alkyl-, haloalkyl- or arylsulfonylammo of the formula -NHSO₂R⁵ or -N(SO₂R )SO₂R⁶ where R⁵ and R⁶ are independently alkyl, haloalkyl or aryl; "n" is 1 or 2; "m" is zero or 1. R' is H, alkyl, halogen, haloalkyl, nitro, alkoxy, alkylthio or cyano;

Ar is a substituted benzene ring with Ar, R^a and R^b being so chosen that when Q' is methoxy or propargyloxy, instead of Q' having the formula given above, the compound is a herbicide.

2. A compound as in claim 1 characterized in that

R² is R³[CO-CH(R⁴)-O]_n or NCCH(R⁴)O-[CO-CH(R⁴)-O]_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 R² is R³[CO-CH(R⁴)-O]_n.

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^b is methyl andR^a 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 composition 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 composition 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.