ALPHA-AMINOOXY C4-ALKANOIC ACIDS AND ESTERS

Abstract: Compounds of the formula wherein X is halogen, OM in which M is an alkali metal, an alkaline earth metal, silver or ammonium cation, OH or OR³ in which R³ is an alkyl or alkoxyalkyl group containing from 1 to 10 carbon atoms; R is an alkyl group containing from 2 to 4 carbon atoms; R² is alkyl, alkenyl, optionally substituted phenyl or R¹ and R² when taken together with the carbon atom to which they are attached from a cyclic hydrocarbyl group, are useful as herbicides and plant regulators.

Description: ALPHA-AMINQOXY C -ALKXNOIC ACIDS AND ESTERS 4 The present invention relates to new alpha-aminooxy C4-C6 alkanoic acids and esters and certain derivatives thereof, their use as herbicides and plant grcwth regulators and to herbicidal plant growth regulator formulations containing these new compounds. The present invention is directed to new alpha-aminooxy C46 alka noic acid and esters of the Formula I EMI1.1 wherein X is halogen, CM in which M is an alkali metal, an alkaline earth metal, silver or alrmonium cation, HI, or OR3 in which R3 is an alkyl or alkoxyalkyl group containing from 1 to 10 carbon atoms; R is an alkyl group containing from 2 to 4 carbon atoms; R1 is a hydrogen atan or an alkyl group containing from 1 to 6 carbon atoms optionally substituted by one or more halogen atoms; and R2 is an alkyl or an alkenyl group containing up to 6 carbon atoms, a phenyl group optionally substituted by one or more substituents selected fran a halogen atom, a nitro group, an alkyl, alkythio or alkoxy group containing from 1 to 4 carbon atoms each optionally substituted by one or more halogen atoms, or by a methylenedioxy group, or R1 and R2 together with the carbon atom to which they are attached form a cyclic hydrocarbyl group containing fran 3 to 12 carbon atams. The compounds are useful as herbicides and plant growth regulators or are intermediates to such compounds or other useful esters, e.g. of the pyrethroid-tppe. Non-limiting examples of individual species within the scope of the invention include: Butanoic acid, 2-(((1-(4-bratophenyl)ethylldene)amino)- oxy)-, methyl ester, Butanoic acid, 3-methyl-2(((1-(3-(trifluorarethyl)phenyl)- ethylidene) amino) oxy) -, methyl ester, Butanoic acid, 2-(((1-(3-(trifluoromethoxy)phenyl)ethyl- idene) amino) oxy) -, tert-butyl ester, Butanoic acid, 2-(((1-(4-ethylthio)phenyl)ethylidene)- amino)oxy)-. The halogen atoms used in Formula I include chlorine, fluorine and bromine. In the Compounds of the Invention, R is preferably an ethyl or isopropyl group, R1 is preferably a hydrogen atam or a methyl, ethyl or trifluoromethyl group and R2 is preferably a methyl group, a 2-methylpropenyl group, a phenyl group substituted by one or two groups selected fran chlorine, fluorine, nitro, methyl or trifluorarethyl, or by methylenedioxy, for example 4-chiorophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, 2-methylpropenyl, 3, 4-methylenedioxyphenyl, 3-(trifluorsmethyl)phenyl, or is a tetralinyl group. When R1 is a hydrogen atan, RI is preferably a 2,4dichlorophenyl or 3-nitrophenyl group; and when RI is a methyl group RI is preferably a 3-trifluororrethylphenyl group. This invention is directed to novel chemical compounds and the use of certain active compounds in which X is OH or OR3 in which R3 is an alkyl or alkoxyalkyl group in regulating the natural growth or development of plants. In particular, this invention relates to the chemical treatment of plants to alter their natural growth or development for the purpose of enhancing various agricultural or horticultural features of the plants, and also to the control of undesirable vegetation, including killing. This invention further relates to a method of controlling plant growth by regulating the natural growth or development of plants comprising applying to said plants an effective, plant-regulating, non-lethal amount of the above compounds, as well as controlling undesirable vegetation comprising applying a herbicidally effective amount of the oompcunds to such vegetation. As employed herein, the term "natural growth or development" designates the normal life cycle of a plant in accordance with its genetics and environment, in the absence of artificial external influences. The term "regulating" is used herein to denote the bringing about through chemical means of any temporary or permanent modification or variation from the normal life cycle short of killing the plant. With properly controlled application, a growth regulating effect can be achieved without herbicidal results. The amount which constitutes an effective amount varies not only with the particular material selected for treatment, but also with the regulatory effect to be achieved, the species of plant being treated and its stage of development, and whether a permanent or transient effect is sought. Growth regulation may arise fran the effect of the canpound on either the physiological processes or the morphology of the plant, or fram both in combination or in sequence. lorphological changes are generally noticible by observable changes in the size, shape, colour or texture of the treated plant or any of its parts, as well as in the quantity of fruit or flowers produced. Changes in physiological processes on the other hand, occur within the treated plant and are usually hidden fram the eye of an observer. Changes of this type most often occur in the production, location, storage or use of chemicals naturally occurring in the plant, such as hormones. Physiological changes may be visually detectable when followed by a change in morphology. In addition, numerous analytical procedures for determining the nature and magnitude of changes in the various physiological processes are known to those skilled in the art. The active campounds of the instant invention serve to regulated the natural growth or development of treated plants in a number of diverse ways, and it is to be understood that each compound may not produce identical regulatory effects on each plant species or at every rate of application. As stated above, responses will vary in accordance with the compound, the rate, the plant, etc. The term "herbicidally effective amount" designates any amount of the compounds disclosed herein which will kill a plant or any portion thereof. By "plants" is meant germinant seeds, emerging seedlings, and established vegetation, including roots and above-ground portions. Effects include killing, defoliation, desiccation, stunting, leaf burn, and dwarfing. Herbicidal effects are generally achieved at higher application rates than growth regulating effects. The Compounds of the Invention are useful as plant growth regulators or herbicides (usually when X is OH or OR3) or as intermediates (when X is halogen, OH or OR3) to such compounds or to other useful esters, e.g. of the pyrethroid type, including those disclosed and claimed in applicants concurrently filed U.S. patent application No. 662116 filed 18th October, 1984, using conventional procedures known in the art for converting alkyl esters to acids, acids to acid halides or salts, acid halides or salts to alkyl or pyrethroid alcohol esters and alkyl esters to other alkyl esters. The Compounds of the Invention can n exhibit gecmetrical and optical isomerism. The present invention includes all the biologically active ocopounds of Formula I of the invention and the useful intermediates, and thus includes racemates and various geometric and/or optically-active isomers or mixtures enriched in such isomer forms which may be directly synthesized, resolved or mixed together. The various geametrical and optical isomers of the compounds of Formula I may have different biological activity. The alpha-aminooxy C4-C6 alkanoic isovaleric acids and esters of Formula I may be prepared by forming the alkali metal salt of an oxide with alkali metal hydroxide in an inert solvent (e.g toluene) in the presence of a catalyst (including onium catalysts) with azeotropic distillation of the water formed. After the water is removed, a 2-bromoalkanoic acid alkyl ester is added and the reaction mixture is refluxed, often for 24-48 hours. The reaction mixture was filtered to remove the salts prior to distillation in a Kugelrohr apparatus. The carboxylic acids were prepared via alkaline hydrolysis in a ternary mixture of ethanol-tetrahydrofuran and water. The oxides utilized in making the acids and alkyl esters of this invention were prepared from the corresponding carbonyl coopd and hydroxylamine hydrochloride via well known methods e.g., Vogel, A. I., Practical Organic Chemistry, Wiley and Sons, 1966, p.343. The invention is illustrated by the following examples, which are presented for the purpose of illustration, and should not be regarded as limiting the invention in any way. The identity of the products, including intermediates, was confirmed by elemental, infrared and nuclear magnetic resonance spectral (NMR) analysis as necessary. Example 1 Butanoic acid, 3-methyl-2(( (1- (3- (trifluororrrethyl) phenyl)ethyl- idine)amino)oxy-, ethyl ester. In a 500 ml round bottom flask fitted with a magnetic stirrer, Dean-Stark trap and nitrogen purge were place 2.0 g sodium hydroxide in 15 ml of water. To this was added 10.16 g of 3-(trifluoromethyl)acetophenone oxirre in 15 ml of toluene and a catalytic amount of tetrabutylammonium hydrogen sulfate and the mixture was heated to reflux overnight. After cooling, 9.75 g of ethyl 2-bromo-3-methyl butyrate was added all at once and the mixture was refluxed for three days. After cooling, the reaction mixture was filtered and the product was distilled in a Kugelrohr apparatus to yield 7.33 g of the desired product; b.p. 900C (0.05 mn). Example 2 Butanoic acid, 3-methyl-2-(( (1- (3- (trifluoramethyl) -penyl)- ethylidene) amino) oxy) -. In a 300 ml round bottom flask equipped with a magnetic stirrer and reflux condenser were placed 15 ml water, 15 ml of tetrahydrofuran, 15 ml of ethanol, 0.6 g of sodium hydroxide and 5.0 g of the above ester of Example 1. This mixture was refluxed for 36 hours. The reaction mixture was evaporated to dryness and the residue was taken up in 10% sodium hydroxide. The basic solution was then extracted with methylene chloride to remove neutral products. Acidification of the basic solution and extraction of the aqueous solution with methylene chloride yielded,.after drying of the methylene chloride with magnesium sulfate and evaporating the solvent, 4.21 g of the desired product; m.p. 49-51"C. Examples 3-64 Following the procedures similar to those described in Examples 1 and 2 above, additional alpha-aminooxy C4-C6 alkanoic acids and esters of Formula I were prepared as set forth in Table 1 below. Table 1. ALPHA-AMINOOXY C4-C6 ALKANOIC ACIDS AND ESTERS OF FORMULA I EMI7.1 <tb> Embodinent <SEP> R <SEP> R1 <SEP> R2 <SEP> x <tb> <SEP> 3 <SEP> i-C3H7 <SEP> CH3 <tb> <SEP> 3 <SEP> phenyl <SEP> OH <tb> <SEP> 4 <SEP> i-C3H7 <SEP> H <SEP> 7 <SEP> OH <tb> <SEP> 5 <SEP> 7 <SEP> CH <SEP> iC3H7 <SEP> 'CH--C <SEP> (CH3) <SEP> 2'CH2-CH <SEP> (CH3) <SEP> -CH- <SEP> OH <tb> <SEP> 6 <SEP> i-C3H7 <SEP> CH3 <SEP> -C=C(CH3)2 <SEP> OH <tb> <SEP> 7 <SEP> iC3H7 <SEP> C2H5 <SEP> phenyl <SEP> OH <tb> <SEP> ./ <SEP> ¹ <tb> <SEP> 8 <SEP> i-C3H7 <SEP> /l <SEP> !\ <SEP> OH <tb> <SEP> or <SEP> it <tb> <SEP> 9 <SEP> i-C3H7 <SEP> CH3 <SEP> v <SEP> OH <tb> <SEP> 10 <SEP> i-C3H7 <SEP> CH3 <SEP> CH3 <SEP> OH <tb> <SEP> 11 <SEP> i-C3H7 <SEP> H <SEP> 4-Cl <SEP> phenyl <SEP> OC2H5 <tb> <SEP> 12 <SEP> 3 <SEP> H <SEP> phenyl <SEP> OC2H5 <tb> <SEP> 13 <SEP> i-C3H7 <SEP> CH3 <SEP> 4-C1 <SEP> phenyl <SEP> OH <tb> <SEP> 14 <SEP> i-C3H7 <SEP> H <SEP> " <SEP> OH <tb> <SEP> 15 <SEP> i-C3H7 <SEP> CH3 <SEP> 2-C1 <SEP> phenyl <SEP> OC2H5 <tb> <SEP> 16 <SEP> C2H5 <SEP> H <SEP> phenyl <SEP> OC2H5 <tb> <SEP> 17 <SEP> C <SEP> H <SEP> H <SEP> phenyl <SEP> OH <tb> <SEP> 18 <SEP> i-C3H7 <SEP> CH3 <SEP> 2-C1 <SEP> phenyl <SEP> OH <tb> <SEP> /o <SEP> ol <tb> <SEP> 19 <SEP> i-C3H7 <SEP> \. <SEP> = <SEP> ./ <SEP> OC2H5 <tb> <SEP> o <SEP> \ <tb> <SEP> 0-0 <tb> <SEP> 20 <SEP> i-C <SEP> \o <SEP> H <SEP> \ <SEP> OH <tb> <SEP> '7 <tb> EMI8.1 <tb> Embodiment <SEP> R <SEP> Rl <SEP> R2 <SEP> X <tb> <SEP> <tb> <SEP> 21 <SEP> i-C3H7 <SEP> CH3 <SEP> ew <SEP> OC2HS <tb> <SEP> 22 <SEP> 3 <SEP> H <SEP> phenyl <SEP> OCH3 <tb> <SEP> 7-.' <tb> <SEP> o <tb> <SEP> 23 <SEP> i-C3 <SEP> H <SEP> ¯¯0 <SEP> OC2H5 <tb> <SEP> 24 <SEP> 3 <SEP> H <SEP> 4-CH3S-phenyl <SEP> OC2H5 <tb> <SEP> 25 <SEP> i-C3H7 <SEP> H <SEP> -2, <SEP> 4-Cl2phenyl <SEP> OC2H5 <tb> <SEP> 0-. <tb> <SEP> / <SEP> I <tb> <SEP> c- <SEP> o <tb> <SEP> 26 <SEP> i-C3 <SEP> H <SEP> K <SEP> OH <tb> <SEP> \. <SEP> ./ <tb> <SEP> 27 <SEP> i-C3H7 <SEP> H <SEP> 2,4-C12phenyl <SEP> OH <tb> <SEP> 28 <SEP> i-C3H7 <SEP> H <SEP> 4-thiomethylphenyl <SEP> OH <tb> <SEP> 29 <SEP> i-C3H7 <SEP> H <SEP> 4-methoxy <SEP> phenyl <SEP> OC2Hg <tb> <SEP> 30 <SEP> i-C3H7 <SEP> H <SEP> 4-CH30 <SEP> phenyl <SEP> OH <tb> <SEP> 31 <SEP> i-C3H7 <SEP> H <SEP> 2-C1 <SEP> phenyl <SEP> OC2H5 <tb> <SEP> 32 <SEP> i-C3H7 <SEP> H <SEP> 2-C1 <SEP> phenyl <SEP> OH <tb> <SEP> 33 <SEP> 7 <SEP> CH3 <SEP> 4CH3 <SEP> phenyl <SEP> OC2H5 <tb> <SEP> 34 <SEP> i-C3H7 <SEP> CH3 <SEP> 4-CH3 <SEP> phenyl <SEP> OH <tb> <SEP> 35 <SEP> i-C3H7 <SEP> H <SEP> 4-F <SEP> phenyl <SEP> OCH2H5 <tb> <SEP> 36 <SEP> C2H5 <SEP> CH3 <SEP> 4-Cl <SEP> phenyl <SEP> OC2H5 <tb> <SEP> 37 <SEP> C <SEP> H <SEP> H <SEP> 4-C1 <SEP> phenyl <SEP> OC2Hs <tb> <SEP> 38 <SEP> i-C3H7 <SEP> H <SEP> 4-F <SEP> phenyl <SEP> OH <tb> <SEP> 39 <SEP> CH5 <SEP> CH3 <SEP> 4-C1 <SEP> phenyl <SEP> OH <tb> <SEP> 40 <SEP> C <SEP> H <SEP> H <SEP> 4-C1 <SEP> phenyl <SEP> OH <tb> <SEP> 41 <SEP> i <SEP> 3 <SEP> H <SEP> 4CH3 <SEP> phenyl <SEP> OC2H5 <tb> <SEP> 42 <SEP> 3 <SEP> H <SEP> 4CH3 <SEP> phenyl <SEP> OH <tb> Embodiment R R1 R2 X 43 i-C3H7 -CH--C(CH3)-CH2-CH(CH3)-CH- OCH2OCH3 44 i-C3H7 H 4CH3 phenyl OC2H5 45 i-C3H7 CH3 phenyl OC2H5 46 i-C3H7 H 3-CF3 phenyl OC2H5 47 i-C3H7 H 3-CF3 phenyl OH 48 i-C3H7 H 3-CF3 phenyl OH 49 i-C3H7 H 3,4-Cl2 phenyl OC2H5 50 i-C3H7 CH3 3,4-C12 phenyl OH 51 i-C3H7 CH3 3-CF3 phenyl OH 52 l-C3H7 H 4-N02 phenyl OC2H5 53 i-C3H7 H 3-N02 phenyl OH 54 i-C3H7 H 4-N02 phenyl OH 55 i-C3H7 CF3 phenyl OC2H5 56 i-C3H7 CF3 phenyl OH 57 i-C3H7 H 4-methylcyclohexenyl OC2H5 58 C H H 3-N02 phenyl OH 59 n-C4Hg H 3-N02 phenyl OC2H5 60 n-C3H7 H 3-N02 phenyl OC2H5 61 i-C3H7 CH3 3-NO2 phenyl OC2H5 62 n-C4H9 H 3-N02 phenyl OH 63 C2H5 H 3-NO2 phenyl OC2H5 64 i-C3H7 CH3 CH3 OC2H5 For application, the compound of Formula I ordinarily is applied most effectively by formulating it with a suitable inert carrier or surface-active agent, or both. The invention, therefore, also includes campositions suitable for combatting unwanted plants, such compositions comprising an inert carrier or surface-active agent, or both, and as active ingredient at least one compound of Formula I. The term "carrier" as used herein means an inert solid or liquid material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated, or its storage, transport and/or handling. Any of the materials customarily employed in formulating pesticides, herbicides, or fungicides, are suitable. Suitable solid carriers are natural and synthetic clays and silicates, for example, talcs; magnesium aluminum silicates, for example attapulgites and vermiculites; aluminum silicates, for example, kaolinites, montmorillonites and micas; calcium carbonate; calcium sulfate; synthetic hydrated silicon oxides and synthetic calcium or aluminum silicates; elements such as, for example, carbon and sulfur; natural and synthetic resins such as, for example, caumarone resins, polyvinyl chloride and styrene polymers and copolymers; bitumen; waxes such as, for example, beeswax, paraffin wax, and chlorinated mineral waxes; solid fertilizers, for example, superphosphates; and ground, naturally-occurring, fibrous materials, such as ground corncobs. Examples of suitable liquid carriers are water, alcohols such as isopropyl alcohol and glycols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as cellosolves; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as kerosene, light mineral oils; chlorinated hydrobons such as carbon tetrachloride, perchloroethylene and trichloromethane. Also suitable are liquefied, normally vaporous and gaseous compounds. Mixtures of different liquids are often suitable. The surface-active agent may be an emulsifying agent or a dispersing agent or a wetting agent; it may be nonionic or ionic. Any of the surface-active agents usually applied in formulating herbicides or insecticides may be used. Examples of suitable surface-active agents are the sodium and calcium salts of polyacrylic acids and lignin sulfonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of gly glycerol, sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohols or alkyl phenols, for example, p-octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulfates or sulfonates of these condensation products, alkali or alkaline earth metal salts, preferably sodium salts, of sulfuric or sulfonic acid esters containing at least 10 carbon atoms in the molecule, for example, sodium lauryl sulfate, sodium secondary alkyl sulfates, sodium salts of sulfonated castor oil, and sodium alkylaryl sulfonates such as sodium dodecylbenzene sulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxides. The compositions of the invention may be prepared as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders are usually compounded to contain 25 to 75% by weight of active compound and usually contain, in addition to the solid carrier, 3-10% by weight of a dispersing agent, 2-15% of a surface-active agent and, where necessary, 0-10% by weight of stabilizer(s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust con concentrate having a similar composition to that of a wettable powder but without a dispersant or surf surface-active agent, and are diluted in the field with further solid carrier to give a composition usually containing 0-5-10% by weight of the active compound. Granules are usually prepared to have a size between 10 and 1000 BS mesh (1.676-0.152 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 0.5-25% by weight of the active compound, 0-1% by weight of additives such as stabilizers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, cosolvent, 10-50% weight per volume of the active compound, 2-20% weight per volume emulsifiers and 0-20% weight per volume of appropriate additives such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 10-75% weight of the active compound, 0.5-5% weight of dispersing agents, 1-5% of surface-active agent, 0.1-10% weight of suspending agents, such as defoamers, corrosion inhibitors, stabilizers, penetrants and stickers, and as carrier, water or an organic liquid in which the active compound is substantially insoluble; certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as antifreeze agents for water. Of particular interest in current practice are water-dispersible granular formulations. These are in the form of dry, hard granules that are essentially dust-free, and are resistant to attrition on handling, thus minImizing the formation of dust. On contact with water, the granules readily disintegrate to form stable suspensions of the particles of active material. Such formulations contain 90% or (up to 95%) more by weight of finely divided active material, 3-7% by weight of a blend of surfactants, which act as wetting, dispersing, suspending and binding agents, and may contain up to 3% by weight of a finely divided carrier, which acts as a resuspending agent. Aqueous dispersions and emulsions, for example, compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the present invention. The said emulsions may be of the water-in-oil or of the oil-in-water type, and may have thick, mayonnaise-like consistency. It is evident from the foregoing that this invention contemplates ccmpositions containing as little as about 0.5% by weight to as much as about 95% by weight of a compound of Formula I as the active ingredient. The ccmpositions of the invention may also contain other ingredients, for example, other copponds possessing pesticidal, especially insecticidal, acaricidal, herbicidal or fungicidal properties, as are appropriate to the intended purpose. As mentioned above, the compounds of the Invention have been found useful for influencing or regulating plant growth and controlling (the growth of) unwanted plants, being particularly active with respect to one or more grassy or broadleafed weeds or plants. For example, the compounds can change plant morphology; depress the growth of plants; inhibit germination; or totally or selectively kill plants depending on the compounds and the amount used. As herbicides, they appear to be more effective when applied preemergence or pre-plant incorporated (applied to the soil before the seeds have sprouted) than when applied posternsrgence (applied to the foliage). Protection of a locus or area from undesirable plants is effected by applying a compound of Formula I, ordinarily in a camposition of one of the aforementioned types, to soil in which the seeds of the unwanted plants are present, or to the foliage of the unwanted plants. The active compound, of course, is applied in an amount sufficient to exert the desired action. The amount of the compound of the invention to be used in caribatting undesired plants will naturally depend on the condition of the plants, the degree of activity desired, the formulation used, the mode of application, the climate, the season of the year, and other variables. Recommendations as to precise amounts are, therefore, not possible. In general, however, application to the locus to be protected of from 0.1 to 10.0 kg per hectare of the compound of Formula I will be satisfactory. Examples of Activity with Respect to Plants In the following examples, the species of plants that were tested were: Barnyardgrass (watergrass) - Echinochloa crus-galli Large crabgrass - Digitaria sanguinalis Downy broke - Branus tectorum Yellow foxtail - Setaria lutescens Redroot pigweed - Amaranthus retroflexus Sicklepod - Cassia obtusifolia Velvet leaf - Abutilon tbeophrasti Garden cress - lepidium sativum Johnson grass - Sorghum halepense Morningglory - Ipomoea purpurea L. (Roth) Test Procedures The preemergence (soil) herbicidal activity of compounds of Formula I was evaluated by planting seeds of barnyardgrass, garden cress, downy brat, velvetleaf, yellow foxtail, and either sicklepod or morningglory in test tubes, nominally measuring 25 x 200 millimeters, filled about three-quarters full of untreated soil, in each case covered on top with about 2.5 cubic centimeters of soil treated with a certain amount of the test compound. The treated soil applied to the tubes containing the barnyardgrass and cress seeds contained one milligram of the test compound per tube, and contained 0.1 milligram of the test compound per each tube containing the seeds of the other plants. The dosages were approximately 20 and 2.0 kg of test compound per hectare, respectively. The seeds were planted on top of the treated soil and covered with about 1.5 cubic centimeters of untreated soil. The planted soil was held under controlled conditions of temperature, moisture, and light for 9 to 10 days. The amounts of germination and growth in each tube were evaluated on a 0 to 9 scale, the numeric ratings having the following meanings: Rating Meaning 9 No living tissue 8 Plant severely damaged and expected to die 7 Plant badly damaged, but expected to live 6 Moderate damage, but complete recovery expected 5 Intermediate damage (probably unacceptable for crop plants) 3-4 Observable damage 1-2 Plant slightly affected, possibly by the chemical, possibly due to biological variability 0 No visible effect The postemergence (foliar) herbicidal activity of compounds of Formula I was evaluated by spraying 10-day-old large crabgrass plants, 13-day-old pigweed plants, 6-day-old Johnsongrass plants, 9-day-old velvetleaf plants, 9-day-old yellow foxtail plants and either 9-day-old sicklepod plants or 5-day-old morningglory plants to runoff with a liquid formulation of the test compound. The crabgrass and pigweed plants were sprayed with 2.4 milliliters of a 0.25% solution (about ten kg of the test compound per hectare), and other plants were sprayed with 2.4 milliliters of a 0.025% solution (about one kg of the test compound per hectare). The sprayed plants were held under controlled conditions of temperature, moisture and light for 7 to 8 days, when the effect of the test compound was evaluated visually, the results being rated on the 0 to 9 scale described above. Illustrative results of the preemergence and postemergence herbicidal activity tests are set forth below. In Preemergence tests, (a) on barnyard grass, the following compounds were rated 7 or better: Compounds of Embodiments 3, 10, 14, 16, 17, 18, 20, 26, 39, 40, 47, 48, 50, 51, 55 (b) on garden cress, the following compounds were rated 7 or better: Compounds of Embodiments 3, 4, 5, 7, 8, 9, 10, 13, 14, 16, 17, 18, 20, 23, 26, 30, 32, 34, 36, 37, 38, 39, 40, 42, 47, 48, 50, 51, 52, 53, 54, 56, 57, 58, 60, 62, 63 In Postertergence tests, (a) on large crabgrass, the following campaunds were rated 7 or better: Compounds of Embodiments 10, 50, 51 (b) on pigweed, the following compounds were rated 7 or better: : Compounds of Embodirrents 7, 9, 13, 14, 18, 20, 21, 23, 30, 32, 36, 37, 38, 39, 40, 47, 48, 49, 50, 51, 54, 56, 58, 60, 63 In addition, almost all of the compounds of the invention, demorstrated one or more effects on plants, such as depressing growth, dwarfing, inhibiting germination, chlorosis, necroses, etc. against one ore more of the test plant species.

Claims: CLAIMS 1. A compound of Formula I EMI17.1 wherein X is halogen, CM in which M is an alkali metal, an alkaline earth metal, silver or ammonium cation, OH or OR3 in which R3 is an alkyl or alkoxyalkyl group containing frcm 1 to 10 carbon atoms; R is an alkyl group containing from 2 to 4 carbon atans; R1 is a hydrogen atom or an alkyl group containing fran 1 to 6 carbon atoms optionally substituted by one or more halogen atoms; and R2 is an alkyl or an alkenyl group containing up to 6 carbon atoms, a phenyl group optionally substituted by one or more substituents selected fran a halogen atom, a nitro group, an alkyl, alkythio or alkoxy group containing fran 1 to 4 carbon atoms each optionally substituted by one or more halogen atoms, or by a methylenedioxy group, or R1 and R2 together with the carbon atan to which they are attached form a cyclic hydrorbyl group containing from 3 to 12 carbon atoms. 3 2. A compound as claimed in claim 1 wherein X is OH or OR ; R is an ethyl or isopropyl group; R1 is a hydrogen atom or methyl, ethyl or trifluoramethyl group; and R2 is a methyl group, a 2-rnethylpropenyl group, a phenyl group substituted by one or two groups selected fram chlorine, fluorine, nitro, methyl or trifluoratethyl or by methylenedioxy, or is a tetralinyl group. 3. A compound as claimed in claim 2 wherein R is a hydrogen atan and R2 is 2,4-dichlorophenyl, or 3-nitrophenyl. 4. A compound as claimed in claim 2 wherein R1 is a methyl group and R2 is a 3-trifluorsmethylphenyl group. 5. A plant growth regulating composition comprising a plant growth regulating amount of an active compound according to 3 claim 1 in which X is OH or OR , together with at least one carrier or surface-active agent. 6. A method of controlling plant growth at a locus comprises applying to the locus or the plants a controlling amount of an active compound according to claim 1 in which X is OH or oR3, or a composition as claimed in claim 5.

Inventors: SANBORN, JAMES RUSSELL, TIEMAN, CHARLES HENRY
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1985
Main classification: C07C251
IPC codes: A01N37, C07D317, A01N43