SUBSTITUTED PHENOXYPROPIONALDEHYDE DERIVATIVES

Abstract: The invention relates to substituted phenoxypropion­ aldehyde derivatives having the general formula wherein: W and W¹ are independently O, S or NH; X is CY, N or N⊕ - O⊖; Q is N or N⊕ - 0⊖; Z is CH or N; Y is hydrogen, halogen, cyano, nitro or haloalkyl of up to 10 carbon atoms; Y¹ and Y² are independently hydrogen, halogen, nitro, cyano or a radical of up to 4 carbon atoms selected from alkyl, haloalkyl and alkoxy; R is hydrogen or a radical of up to 4 carbon atoms selected from alkyl, haloalkyl and alkoxy; R¹ is cyano, vinyl, acetynyl, dialkylphosphinyl or dialkylphosphonyl; and R² is - OR³, -SR³ or -NR⁴R⁵ wherein R³ is hydrogen, a radical of up to 10 carbon atoms selected from alkyl, cycloalkyl, haloalkyl, hydroxyalkyl, oxoalkyl, alkoxyalkyl, alkenyl and alkynyl, or Ar, -COR⁶ or -CSR⁶ wherein R⁶ is a radical of up to 10 carbon atoms selected fron alkyl, cycloalkyl, haloalkyl, theoalkyl, alkoxy, alkenyloxy and alkynyl, or phenoxy, amino, Ar, -COOR⁷ or -COSR⁷ wherein R⁷ is hydrogen, alkali metal, a radical of up to 10 carbon atoms selected from alkyl, cycloalkyl, haloalkyl, alkenyl and alkynyl, or Ar; and R⁴ and R⁵ are independently hydrogen or alkyl of up to 10 (preferably up to 4) carbon atoms; formulations of such derivatives and the use thereof for pre-emergence or post-emergence control of noxious plants, namely weed.

Description: The present invention relates to substituted phenoxypropionaldehyde derivatives, compositions containing such derivatives and the use thereof for pre-emergence or post-emergence control of noxious plants, namely weeds. According to the present invention there are provided active substituted phenoxypropionaldehyde derivatives represented by the general formula: wherein Y¹ and Y² are independently hydrogen, halogen, nitro, cyano, or a radical of up to 4 carbon atoms selected from alkyl, haloalkyl and alkoxy; W is O or S; R is hydrogen or a radical of up to 4 carbon atoms selected from alkyl and alkoxy; R¹ is cyano, vinyl, acetynyl, or dialkylphosphonate; R³ is hydrogen, a radical of up to 10 carbon atoms selected from alkyl, cycloalkyl, haloalkyl, hydroxyalkyl, oxoalkyl, alkoxyalkyl, alkenyl and alkynyl, or -COR⁶ or -CSR⁶ wherein R⁶ is a radical of up to 10 carbon atoms selected from alkyl, cycloalkyl, haloalkyl, alkoxy, alkenyl, and alkynyl, or amino, -COOR⁷ or -COSR⁷ wherein R⁷ is hydrogen, alkali metal, or a radical of up to 10 carbon atoms selected from alkyl, cycloalkyl, haloalkyl, alkenyl and alkynyl. Particularly preferred compounds include those represented by the general formula: wherein Y¹ is hydrogen or halogen; R is an alkyl radical of up to 4 carbon atoms; and R³ is hydrogen, a radical of up to 10 carbon atoms selected from alkyl and haloalkyl, or -COR⁶ or -CSR⁶ wherein R⁶ is a radical of up to 10 carbon atoms selected from alkyl, and alkoxy, or -COOR⁷ or -COSR⁷ wherein R⁷ is hydrogen, alkali metal or an alkyl radical of up to 10 carbon atoms. The group Y¹ is preferably in the 2-position. Group Y¹ is also preferably chlorine when it is halogen. Preferably R is methyl. The compounds of the present invention may be prepared using techniques and starting materials known and available to those skilled in the art, and preparation of certain of the compounds of the present invention are illustrated by the following Examples, wherein a compound having the following formula is prepared: wherein Y¹, R¹ and R² are as follows: Example Y¹ R¹ R² I -H -CN -O-COO-C₂H₅ Example I Preparation of: 2-ethoxycarbonyloxy-3-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]butyronitrile. A mixture of 0.28 grams of 3-[4-(5-trifluromethyl-2-pyridyloxy) phenoxy]propionaldehyde, 1.0 gram of powdered sodium cyanide, 0.1 gram of tetrabetyl ammonium hydrogen sulphate, 3.2 millilitre of ethyl chlorocarbonate and 40 milliliters of methylene chloride was stirred overnight at room temperature under a nitrogen blanket. The reaction mixture was then diluted with 50 milliliters of methylene chloride and washed consecutively with 2 x 40 milliliter portions of water, 2 x 40 milliliter portions of saturated aqueous sodium bicarbonate and 2 x 40 milliliter portions of water. The organic phase was dried over anhydrous sodium sulfate and evaporated affording about 0.42 gram of viscous, gummy residue. The residue was eluted over silica gel using methylene chloride as the eluent, 50 milliliter fractions being collected and analyzed by TLC. Fractions 5 to 11 were combined and evaporated affording about 0.3 gram of colorless viscous material confirmed by NMR and MS analyses as the desired product. Examples II to V Following the procedure described in the foregoing Example using 3-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]-2-hydroxy butyronitrile (prepared in situ ) as a starting material, the following compounds were also prepared: II. The compound, 2-phenoxycarbonyl-3-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]butyronitrile, by reaction of said starting material with phenyl chloroformate. III. The compound, 2-acetyloxy-3-[4-(-trifluoromethyl-2-pyridyloxy)phenoxy]butyronitrile, by reaction of said starting material with acetylchloride. IV. The compound, 2-methyloxycarbonyloxy-3-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]butyronitrile, by reaction of said starting material with methylchloroformate. V. The compound, 2-allyloxycarbonyloxy-3-[4-(5-trifluormethyl-2-pyridyloxy)phenoxy]butyronitrile, by reaction of said starting material with allyl chloroformate. Weed control in accordance with this invention is effected by applying to the soil prior to emergence of weeds therefrom or to the plant surfaces subsequent to emergence from the soil, a herbicidally effective amount of a compound of this invention. It is, of course, to be understood that the term "a compound of this invention" also includes mixtures of such compounds or a formulation containing a compound or mixture of compounds of this invention. The term "herbicidally effective amount" is that amount of a compound of this invention required to so injure or damage weeds such that the weeds are incapable of recovering following application while not causing substantial injury to any valuable crop amongst which the weeds might be growing. The quantity of a compound of this invention applied in order to exhibit a satisfactory herbicidal effect may vary over a wide range and depends on a variety of factors, such as, for example, hardiness of a particular weed species, extent of weed infestation, climatic conditions, soil conditions, method of application, and the like. Typically, 11.2 or less grams/are (one or less pound per acre) of a compound of this invention would be expected to provide satisfactory weed control, although in some instances application rates in excess of one pound per acre, e.g., up to 22.4 or more gms/are (up to 2 or more pounds per acre) might be required. Of course, the efficacy of a particular compound against a particular weed species may readily be determined by routine laboratory or field testing in a manner well known to the art. It is expected that satisfactory weed control can be had at a rate of application in the range of 1.1 to 11.2 gms/are (0.1 to 1.0 pound per acre). Of course, a compound of this invention can be formulated according to routine methods with any of several known and commonly used herbicidal diluents, adjuvants and carriers. The formulations can contain liquid carriers and adjuvants such as organic solvents, as well as compounds such as, for example, emulsifiers, stabilizers, dispersants, suspending agents, spreaders, penetrants and wetting agents. Typical carriers utilized in dry formulations include clay, talc, diatomaceous earth and silica. Preferred formulations are those in the form of wettable powders, flowables, dispersible granulates or aqueous emulsifiable concentrates which can be diluted with water at the site of application. Also, dry formulations such as granules, dusts, and the like, may be used. When desired, a compound of this invention can be applied in combination with other herbicidal agents in an effort to achieve even broader vegetative control. Typical herbicides which can be conveniently combined with one or more compounds of the present invention include atrazine, hexazinone, metribuzin, ametryn, cyanazine, cyprazine, prometon, prometryn, propazine, simazine, terbutryn, propham, alachlor, acifluorfen, bentazon, metolachlor and N,N-dialkyl thiocarbamates such as EPTC, butylate or vernolate. These, as well as other herbicides described, for example, in the Herbicide Handbook of the Weed Science Society of America, may be used in combination with a compound or compounds of the invention. Typically such formulations will contain from about 5 to about 95 percent by weight of a compound of this invention. The herbicidal formulations contemplated herein can be applied by any of several methods known to the art. Generally, the formulation will be applied as an aqueous spray. Such application can be carried out by conventional ground equipment, or if desired, the sprays can be aerially applied. Soil incorporation of such surface applied herbicides is accomplished by natural leaching, and is of course facilitated by natural rainfall and melting snow. If desired, however, the herbicides can be incorporated into the soil by conventional tillage means. Compounds of this invention have been found especially useful for controlling grassy weeds but could be used for preemergence and postemergence control of a wide variety of grassy weeds. Typical of the various species of vegetative growth that may be controlled, combated, or eliminated are, for example, annuals such as foxtail, crabgrass, field pennycress, ryegrass, goose grass, wild oats, barnyardgrass, hemp nettle, spurge, pondweed, cheatgrass, fall panicum, witchgrass, watergrass, and similar annual grasses and weeds. Biennials that may be controlled include wild barley and campion. Also controlled by the compounds of this invention may be perennials such as quackgrass, Johnsongrass, horsetail and cattail. The compound prepared as described in the Examples were individually tested for herbicidal efficacy, against a variety of grassy weed species, under controlled laboratory conditions of light, humidity and temperature. A solvent solution of each compound was applied, both preemergence and postemergence, to test flats containing the various weed species, and herbicidal efficacy was determined by periodic visual inspection, after application of the compounds vis a vis an untreated control. Herbicidal efficacy was determined on a Numerical Injury Rating (NIR) scale of from 0 (no injury) to 10 (all plants dead). A NIR rating of 7 to 9 indicates severe injury; a NIR rating of 4 to 6 indicates moderate injury, that is, plant growth is reduced to the extent that normal growth could be expected, but only under ideal conditions; and a NIR rating of 1 to 3 indicates slight injury. The following Tables give the individual and average pre-emergence (Table 1) and post-emergence (Table II) NIR determined for the compound prepared as described in Example I on the grassy (GR) weed species to which the compounds were applied, at the indicated rate of application in pounds per acre. The NIR was determined three weeks subsequent to application. Compd: I YLFX 10 CBGS 10 JNGS 10 WOAT 3 BNGS 10 Rate 0.5 Average 8.6 Compd: I YLFX 8 JNGS 7 WOAT 1 BNGS 9 Rate 1.1 Average 6.3 The grassy weeds used in the screening tests were barnyardgrass (BNGS), large crabgrass (CBGS), Johnsongrass (JNGS), wild oats (WOAT) and yellow foxtail (YLFX).

Claims: A compound having the general formula: wherein Y¹ and Y² are independently hydrogen, halogen, nitro, cyano, or a radical of up to 4 carbon atoms selected from alkyl, haloalkyl and alkoxy; W is O or S; R is hydrogen or a radical of up to 4 carbon atoms selected from alkyl and alkoxy; R¹ is cyano, vinyl, acetynyl or dialkylphosphonate; R³ is hydrogen, a radical of up to 10 carbon atoms selected from alkyl, cycloalkyl, haloalkyl, hydroxyalkyl, oxoalkyl, alkoxyalkyl, alkenyl and alkynyl, or -COR⁶ or -CSR⁶ wherein R⁶ is a radical of up to 10 carbon atoms selected from alkyl, cycloalkyl, haloalkyl, alkoxy, alkenyl, and alkynyl, or amino, -COOR⁷ or -COSR⁷ wherein R⁷ is hydrogen, alkali metal, or a radical of up to 10 carbon atoms selected from alkyl, cycloalkyl, haloalkyl, alkenyl and alkynyl. A compound according to claim 1, having the general formula: wherein Y¹ is hydrogen or halogen; R is an alkyl radical of up to 4 carbon atoms; and R³ is hydrogen, a radical of up to 10 carbon atoms selected from alkyl and haloalkyl, or -COR⁶ or -CSR⁶ wherein R⁶ is a radical of up to 10 carbon atoms selected from alkyl, and alkoxy, or -COOR⁷ or -COSR⁷ wherein R⁷ is hydrogen, alkali metal or an alkyl radical of up to 10 carbon atoms. A compound according to claim 2, wherein the group Y¹ is in the 2-position. A compound according to any of claims 1 to 3, wherein the group Y¹ is chlorine. A herbicidal composition containing an agronomically acceptable carrier and a herbicidally effective amount of a compound or mixture of compounds according to any of claims 1 to 4. A herbicidal composition according to claim 5, which is in the form of a wettable powder, a flowable, a dispersible granulate or an aqueous emulsifiable concentrate which can be diluted with water at a desired site of application. A herbicidal composition according to claim 5 or 6, in which the compound or mixture of compounds according to any of claims 1 to 4 is used together with one or more other herbicidal agents. A herbicidal composition according to claim 7, which contains 5 to 95 per cent by weight of a compound or mixture of compounds according to any of claims 1 to 4. A method of controlling weeds wherein a herbicidally effective amount of herbicide is applied to a growth medium prior to emergence of weeds therefrom or to the weeds subsequent to emergence from the growth medium, the herbicide comprising a compound or mixture of compounds according to any of claims 1 to 4 or being in the form of a composition according to any of claims 5 to 8.

Inventors: RAJU, MUPPALA SARVESWARA
Applicants: PPG INDUSTRIES, INC.
Application year: 1987
Main classification: C07C255
IPC codes: A01N57, A01N47, A01N43, C07F9, A01N39, C07C329, C07D213