IL29833A - The use of esters and amides of 2-substituted-3-ureido-acrylic and crotonic acids as herbicides and certain novel 2-halo-3-phenylureido-crotonamides - Google Patents

Description

.'. :; · iuxai.n q* TORSI O'IOOKS i_nn*wn nnaniB η»ϊΐ8ηρ-ι η» ?»ιρκ-ι·τ'»κ**ηκ-■■-π»κ'τι » 3D-3~i Kn-2-i o^aws? '^t a 2 mays The use of. esters and amides of 2-substitu'bed- 3^ureido-acrylic and crotonic acids as herbicides and certain novel 2-halo-3-phenylureido-crotonaroides B.I.DU PONT DE NEMOURS AND COMPANY C: 28262 This invention relates to the use of esterB and amides of 2-substituted-3-ureido-S0?ylic and crotonic acids as herbicides to herbicidal compoeitions containing these compounds as active ingredients, and to certain novel 2-halo^3-phenylureido-crotonamidos.

The h^rbicidally. ac ive compounds used in the method" according to the present invention and constituting the active ingredients in the novel composition of the invention, are represented by the general formula* 0 0 il li R- MI - C - NH - G s C - C - R, I I ¾ x wherein R is selected from the grou consisting of alkyl of 1-10 carbon atoms? substituted alkyl of 1-8 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy of 1-3 carbons, alkoxycarbonyl furyl of 2-4 carbon atoms/and cyano; • 6 aryl of $-10 carbon atoms; substituted phenyl wherein said Bubstituent is selected from the group consisting of chlorine, fluorine, bromine, alkoxy of 1-5 carbon atoms, alkyl of 1-6 carbon atoms, nitro, trifluoromethyl, 2,3-tetramethylene and 2,3-trimethylenylene; aralkyl of $-13 carbon atoms; substituted 7 aralkyl of -13 carbon atoms, wherein said substituent is • fluorine , selected from the group consisting of chlorine,/nitro, alkyl and alkoxy; tetrahydronaphthylalkyl; alkenyl of 3-8 carbon atoms; alkynyl of 3-8 carbon atoms; cycloalkyl of 3-12 carbon atoms; substituted cycloalkyl of 3-12 carbon atoms, wherein said Bubstituent is selected from the group consisting of bromine, chlorine, alkoxy of 1-3 carbon atoms, and alkyl of 1-4 carbon atoms; cycloalkenyl of 4-12 carbon atoms; substituted cycloalkenyl of 4-12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, alkoxy of 1-3 carbon atoms, and alkyl of 1-4 carbon atoms; cycloalkylalkyl of 4-13 carbon atoms; cycloalkenylalkyl of -13 carbon atoms; substituted cycloalkylalkyl of 5-l4 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, alkoxy of 1-5 carbon atoms and alkyl of 1-4 carbons; substituted cycloalkenylalkyl of 5-l4 carbon atoms wherein said substitutent is selected from group consisting of bromine, chlori alkoxy of 1-3 carbon atoms, alkyl of 1-4 carbon atoms, and cyano. hydrogensor R, is /alkyl of 1-3 carbon atoms; In the formulas, the terms aryl and substituted phenyl embrace such radicals as Phenyl, Na hth 1, O-biphenyl, Pyridyl, Chlorophenyl, Bromophenyl, Alkoxyphenyl, Dibromophenyl, Fluorophenyl, · Trichlorophenyl, Alkylphenyl of † through 11 carbon atoms, Dialkylphenyl of 8 through 12 carbon atoms, Chloroalkylphenyl of 7 through 10 carbon atoms, Nitrochloropheny1, Nitrophenyl, Dichloronitrophenyl, Chloroalkoxyphenyl of 7 through 11 carbon atoms, Trifluoromethylphenyl, Tetrahydronaphthyl, and Indenyl.

The terms "aralkyl" and ^substituted aralkyl" are intended to include such radicals as -Purfuryl, Benzyl, Phenylalkyl of 8 through 11 carbon atoms (total), Chlorobenzyl, Dichlorobenzyl, Alkylbenzyl of 8 through 11 carbon atoms (total), Dialkylbenzyl of 9 through 13 carbon atoms (total), Nitrobenzyl, Alkoxybenzyl of 8 through 11 carbon atoms (total), and Naphthylmethy1.

The terms "cycloalkyl", "cycloalkenyl", "cycloalkyl alkyl and "cycloalkenyl alkyl" villi include Cyclohexyl, Cyclohexenyl, [ Cyclohexylalkyl, Cyclohexenylalkyl, ; Cyclopentyl, Cyclopentenyl, Cyclopentylalkyl, Cyclopentenylalkyl , Norbornyl, Norborncnylj Norbornylalkyl , Norbornenylalkyl , Bicyclo 2,2,2 oct l Bicyclo(2,2,2)octenyl, Bicyclo(2,2,2)octylalkyl, Bicyclo( 2,2,2Joctenylalkyl, Cyclopropyl, Cyclobutyl, Cyclobutylalkyl, Cyclobutenyl Cyclobutenylalkyl, Hexahydroindanyl, Tetrohydroindanyl, Hexahydroindenyl, .' Hexahydroindenyl alkyl, Tetrahydroindanyl alkyl, Hexahydroindanyl alkyl, Hexahydro-4.7-methanoindenyl, Tetrahydro-4,7-methanoindanyl, Hexahydro-4,7-methanoindanyl, Hexahydr0-4,7-methanoindenyl alkyl, Tetra ydro-4,7-methaioindanyl alkyl, Hexohydro-4,7-methanoindanyl alkyl, Decahydronaphthyl, Decahydronaphthyl alkyl, Tetrahydronaphthyl, Tetrahydronaphthyl alkyl, Decahydro-1, -methanonaphthyl, Decahydro-1,4-methanonaphthyl alkyl, Oc ahydro-1, -methanonaphthyl, Octahydro-1,4-methanonaphthyl alkyl, Decahydro-1,4-5j 8-dimethanonaphthyl, Decahydro-l,4-5,8-dimethanonaphthyl alkyl Octahydro-1,4-5,8-dimethanonaphthyl, and Octahydro-1,4-5,8-dimethanonaphthyl alkyl.

~J The preferred compounds are particularly preferred because of their outstanding herbicidal activity and economy of preparation.

Those compounds which are most preferred, having the best use-cost ratio are the following: 2-iodo-N-phenylcarbamoyl-3- (3-phenylureido) -crotonamide 2-bromo-N-phenylcarbamoyl-3-(3-phenylureido)-crotonamide 2-chloro-N-phenylcarbamoyl-3- (3-phenylureido)-crotonamid 2-fluoro-N-phenylcarbamoyl-3- (3-phenylureido) -crotonamid ethyl-2-methyl-3- (3-phenylureido)crotonate ethyl-2-chloro-3- (3-phenylureido)crotonate PREPARATION Illustrative of the general preparation of the compounds of the invention which are esters and crotonamides is the following reaction scheme: R-NH-C-NH2 + CH3-C-CH-C-OCH3 — > 0 X R-NH C=0 N-H 0 R-NH C=0 N-H 0 X and R are defined above.

A substituted urea is reacted with an a-substituted acetoacetic acid ester in the presence of a small amount of an acid catalyst such as p-toluenesulfonic acid or sulfuric acid in an inert water-immiscible solvent such as benzene or toluene. removed from the reaction site as quickly as possible, as for example by azeotropic distillation.

The reaction mix is cooled and stripped free of solvent under reduced pressure yielding a mixture of products.

This mixture is generally of sufficient purity to be formulated directly as a herbicidal composition without further purification. The technical materials obtained above may however be recrystallize from a variety of solvents such as ethanol, water and cyclo-hexane. Alternatively, the reaction mixture is cooled and filtered if necessary. The solid, a mixture of starting urea and 1,3-disubstituted urea, is discarded. The organic layer is extracted with sodium hydroxide solution which yields on acidification with a suitable acid, the crotonamide which may be recrystallized from a solvent such as acetonitrile.

The organic layer is stripped of solvent and the residue recrystallized from a solvent such as ethanol yielding the ureidocrotonate.

When X is a chlorine, bromine or iodine atom, the compounds may also be made by synthesizing the unsubstituted ureidocrotonate or crotonamide first and then halogenating these with a suitable reagent such as sulfuryl chloride, N-bromosucci- ' nimide or iodine and nitric acid.

UTILITY The compounds used in this invention are useful for controlling the growth of many unwanted weeds and vegetation. Examples of some of the weeds and vegetation which may be controlled with the compounds used in this invention are the following: In accordance with the present invention, these crotonamides and crotonates hereof have been found useful for controlling the growth of unwanted vegetation. When applied at rates of 1/2 to 50 lb./acre, they control many species of herbaceous and woody plants. As will be obvious to those skilled in the art, the preferred rate depends on the time and method of application and the species to be controlled. In general, the lower rates are used in crops to control annual weeds and the higher rates for control of perennial or established annual vegetation in non-crop land.

COMPOSITIONS The herbicidal compounds defined herein may normally be incorporated with various materials to prepare compositions i suitable for application by conventional agricultural equipment.; Suitable compositions o the present invention can be prepared by admixing at least one of the active components with pest control adjuvants or modifiers to provide solid or liquid compositions in the form of dusts, granules, pellets, water-dispersible and water-soluble powders, high-strength concentrates aqueous dispersions or emulsions and solutions or dispersions ini organic liquids. Suitable solid carriers are natural clays such as kaolinite, attapulgite. and montmorillonite. In addition, talcs, pyrophillite, diatomaceous silica, synthetic fine silicas:, calcium aluminosilicates, sodium aluminosilicates and tricalcium phosphate are suitable solid carriers. Organic materials such as walnut shell flour, wood flour or redwood bark flour may also be used as a suitable solid carrier. The percentages by weight of the essential active ingredient will vary with the manner in : which the composition is to be applied. The content of active component may be as low as 0.5$ when applied as a dust or as high as when used as a spot treatment in small isolated areas Liquid herbicidal compositions consist, for example, of the active compounds homogeneously dispersed in water or other non-solvent medium such as a substantially aliphatic hydrocarbon oil. Since certain of the active compounds of this ; invention are water soluble in the presence of alkali, liquid compositions may also be true solutions in water if combined vdth a strong base such as sodium hydroxide or sodium metasilicate . , Oil solutions may also be prepared with solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, esters and ketones. In order to secure homogeneous dispersions in non-solvent media, surface active agents are used. In fact, ! preferred herbicidal compositions of this invention whether liquid or solid contain the active component homogeneously admixed with one or more surfactants as well as carriers. These surface active agents are those commonly known as wetting agents, dispersing agents and emulsifying agents. They may act as wetting agents for wettable powders, pellets, granules, high strength concentrates and dusts, as dispersing agents for wettable poviders and suspensions and as emulsifying agents for emulsifiable concentrates. Surfactants may also enhance the biological activity of the compounds of this invention.

Such surface active agents can include anionic, cationic and nonionic substances.

In general, less than 10$ by weight of the surface-active agent will be used in compositions of this invention and ordinarily the amount of surface-active agents will range from 1-56 but may even be less than 1% by weight.

Additional surface-active agents can be added to the formulations to increase the ratio of surfactant :active ingredient up to as high as 5:1 by weight. Such compositions have a greater herbicidal effectiveness than can be expected from a consideration of the activity of the components used separately. When used at higher rates it is preferred that the surfactant be present in the range of one-fifth to five parts surfactant for each one part of active agent.

A few dispersants of nonionic type such as low viscosity^methyl-cellulose, low viscosity polyvinylalcohol and acacia gum are not; listed in the above Annual but have also been found to be suitable Suitable surface active agents for use in compositions of this invention include polyethylene glycol esters with fatty acids and rosin acids, polyethylene glycol ethers with alkylated phenols or with long-chain aliphatic alcohols, polyethylene glycol ethers with sorbitan fatty acid esters, and polyoxyethylene [ thioethers. Still other suitable surfactants include amine, alkali and alkaline earth salts of alkylaryl sulfonic acids, amine, alkali and alkaline earth fatty alcohol sulfates, dialkyl! esters of alkali metal sulfosuccinates, fatty acid esters of amine, alkali and alkaline earth isethionates and taurates, amine, alkali and alkaline earth salts of lignin sulfonic acids, hydroxyethylate cellulose, amine, alkali and alkaline earth salts of polymerized alkylnaphthalene sulfonic acids, and long-chain quarternary ammonium compounds. Anionic and nonionic surface active agents are preferred.

Among preferred wetting agents are sodium alkyl-naphthalene sulfonates, sodium dioctylsulfosuccinate, sodium dodecylbenzene sulfonate, ethylene oxide condensates with alkylated phenols such as octyl, nonyl, or dodecylphenol, sodium! lauryl sulfate, and trimethylnonyl polyethylene glycol.

Among preferred dispersing agents are sodium, calcium, and magnesium lignin sulfonates, low viscosity methyl cellulose, polymerized sodium alkylnaphthalene sulfonate, sodium N-oleyl or N-lauryl isethionates, sodium N-methyl - N-oleyl taurate, : sodium dodecyldiphcnyloxide disulfonate, and polyethylene oxide ; Among preferred emulsifying agents are ethylene oxide adducts to sorbitan esters of lauric, oleic, stearic, or palmitic acid, polyethylene glycol esters with lauric, oleic, stearic, palmitic, or rosin acids, oil soluble alkylaryl sulfonates, oil soluble polyoxyethylene ethers with octyl-, nonyl-, and dodecylphenol, polyoxyethylene adducts to long-chain mercaptans, and mixtures of these surfactants.

Compositions of the herbicidal crotona ides and crotonates with inert solid diluents are ordinarily prepared in ; two forms ; as wettable powders or dusts with finely divided diluents and as granules or pellets with agglomerated forms of the diluent. When the composition is a wettable powder, a mixture of the active ingredient, inert diluent, wetting agent, dispersing agent and optionally corrosion inhibitor and/or anti-foaming agent is intimately blended and ground until substantially all particles are below 50 microns. The content of active component may vary from 20^-9 but 50#-80# is generally preferred.

Thus, wettable powder formulations of the invention will contain from about 20 to 95 weight per cent active material, from 0.5 to 2.0 weight per cent wetting agent, from 0.25 to 5.0 ; weight per cent dispersant, and from 4.25 to 79 · 2 weight per cent inert extender, as these terms are described above.

When the wettable powder contains a corrosion inhibitor or an anti-foaming agent or both, the corrosion inhibitor will not exceed about 1 per cent of the composition, and the anti-foaming agent will not exceed about 0.5 per cent by weight of the composition, both replacing equivalent amounts of the inert ' Dusts are dense powder compositions which are intended for application in dry form, in accordance with the preferred compositions and methods of the invention.

Dusts are characterized by their free-flowing and rapid settling properties so that they are not readily windborne to areas where their presence is not desired. They contain primarily an active material and a dense, free-flowing, solid extender.

Their performance is sometimes aided by the inclu-sion of a wetting agent, and convenience in manufacture frequently demands the inclusion of an inert, absorptive grinding aid. For the dust compositions of this invention, the inert extender may be either of vegetable or mineral origin, the wetting agent is preferably anionic or non-ionic, and suitable absorptive grinding aids are of mineral origin.

Suitable classes of inert solid extenders for use in the dust compositions are. those organic or inorganic powders which possess high bulk density and are very free-flowing. They are also characterized by possessing relatively low surface areas and are poor in liquid absorption. Suitable classes of grinding aids are natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica or silicate. Among ionic and non-ionic wetting agents, the most suitable are the members of the group known to the art as wetting agents and emulsifiers. Although solid agents are preferred because of ease in incorporation some liquid non-ionic agents are also suitable in the dust formulations.

Preferred inert solid extenders for the dusts of this invention are micaceous talcs, pyrophyllite, dense kaolin clays, tobacco dust and ground calcium phosphate rock, such as that known as "Phosphodust", a trademark of the American Agricultural Chemical Company.

Preferred grinding aids are attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic calcium and magnesium silicates. Preferred wetting agents are those previously described under wettable powder formulations The inert solid extenders in the dusts of this invention are usually present in concentrations of from about 30 to 90 weight per cent of the total composition. The grinding aid will usually constitute 5 to 50 weight per cent of the composition, and the wetting agent will constitute from about 0 to 1.0 weight per cent of the composition. Dust compositions can also contain other surfactants such as dispersing agents in concentrations of up to about 0.5 weight per cent.

The wettable powders described above can also be used in the preparation of dusts. While such wettable powders could be used directly in dust form, it is more advantageous to, dilute them by blending with the dense dust diluent. In this manner, dispersing agents, corrosion inhibitors, and anti-foam, agents may also be found as components of a dust.

Thus, the dust compositions of this invention will comprise about 5 "to 20 weight per cent active material, 5 to 50 weight per cent absorptive filler, 0 to 1.0 weight per cent wetting agent, and about 30 to 90 weight per cent dense, free-flowing dust diluent, as these terms are used herein. Such dust formulations can contain, in addition, minor amounts of ! dispersants, corrosion inhibitors, and anti-foam agents, derived r from the wettable powders used to make the dusts.

Granules and pellets are physically stable, particulate compositions containing an active compound which adheres to or is distributed through a basic matrix of a coherent, inert carrier with macroscopic dimensions. In order to aid leaching of the active ingredient from the granule or pellet, a surfactant can be present. i For the compounds of this invention, the inert carrier is preferably of mineral origin.

Suitable carriers are natural clays, some pyro-phyllites and vermiculite. Suitable wetting agents are anionic or non-ionic.

For the granule compositions of this invention, most ! suitable carriers are of two types. The first are porous, absorptive, preformed granules, such as preformed and screened granular attapulgite or heat expanded, granular, screened vermiculite. On either of these, a solution or suspension of the active agent can be sprayed and will be absorbed or adsorbed at concentrations up to 25 weight per cent of the total weight. ; The second, which are also suitable for pellets, are initially powdered kaolin clays, hydrated attapulgite, or bentonite clays in the form of sodium, calcium or magnesium bentonites. Water-soluble salts, such as sodium salts, may also be present to aid ; in the disintegration of granules or pellets in the presence of moisture. These ingredients are blended with the active component to give mixtures that are granulated or pelleted, followed by drying, to yield formulations with the active component distribute uniformly throughout the mass. Such granules and pellets can also be made with 25 to 30 weight per cent active component, but more frequently a concentration of about 10 weight per cent is desired for optimum distribution. The granular compositions of : this invention are most useful in a size range of 15 - 60 mesh.

The most suitable wetting agents for the granular compositions of this invention depend upon the type of granule used. When preformed granules are sprayed with active material in liquid form the most suitable wetting agents are non-ionic, liquid wetters miscible with the solvent. These are compounds more generally known to the art as emulsifiers, and comprise alkylaryl polyether alcohols, alkyl polyether alcohols, poly-oxyethylene sorbitan fatty acid esters, polyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, oil soluble petroleum or vegetable oil sulfonates, or mixtures of these. Such agents will usually comprise up to about 5 weight per cent of the total composition.

When the active ingredient is first mixed with a powdered carrier and subsequently granulated, or pelleted, liquid non-ionic wetters can still be used, but it is usually preferable to incorporate at the mixing stage one of the solid, povidered anionic wetting agents such as those previously listed for the wettable powders. Such agents will comprise from about 0 to 2 weight per cent of the total composition.

Thus, the preferred granular or pelleted formulations of this invention comprise about 5 to 30 weight per cent active material, about 0 to 5 weight per cent wetting agent, and about 6 to 95 weight per cent inert mineral carrier, as these terms are used herein.

High-strength compositions generally consist of 90 to 99·5# active ingredient and 0.5 to 10 of a liquid or solid surfactant. Small amounts of conditioning agents may also be included, replacing an equal weight of surfactant. Such high-strength compositions can often be used in a manner similar to the wettable powders but they are also suitable for further formulation.

The aqueous suspension concentrates are prepared i by mixing together and sandgrinding an aqueous slurry of water-insoluble active ingredient in the presence of dispersing, agents. Thus, there is obtained a concentrated slurry of very finely divided particles in which the active ingredient is . substantially all below 5 microns in size. This concentrated aqueous suspension is characterized by its extremely small particle size so that upon diluting and spraying, a very uniform coverage is obtained.

These aqueous suspension concentrates will contain from 15 to ko o of active ingredient, from 5 to 70# water with the remainder made up of surfactants, corrosion inhibi-tors, and suspending agents.

Suspensions in organic liquids can be prepared in a similar manner such as by replacing the water with mineral oil. ■ Emulsifiable oils are usually solutions of active material in non-water miscible solvents together with a surfactan For the compounds of this invention, emulsifiable oils can be made by mixing the active ingredient with a solvent ; and surfactant. Suitable solvents for the compounds of this invention are aromatic hydrocarbons including many weed oils, chlorinated solvents, and non-water miscible ethers, esters, or ketones. Suitable surfactants are those anionic or non-ionic agents known to the art as emulsifying agents.

Emulsifying agents most suitable for the emulsifiable oil compositions of this invention are long-chain alkyl or mercaptan polyethoxy alcohols, alkylaryl polyethoxy alcohols, sorbitan fatty acid esters, polyoxyethylene ethers with sorbitan fatty acid esters, polyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, calcium and amine salts of fatty alcohol sulfates, oil soluble petroleum sulfonates or, preferably, mixtures of these emulsifying agents. Such emulsifying agents will comprise from about 1 to 10 weight per cent of the total composition. As described above, however, up to 5 parts of emulsifying agent for each part of active compound can be used.

Thus, emulsifiable oil compositions of the present invention will consist of from about 15 to 50 weightier cent active material, about o to 82 weight per cent solvent, and about 1 to 10 weight per cent emulsifier, as these terms are defined and used above.

In some instances the oil solution may be intended merely for extension with other oils, such as weed oils. In this instance,the emulsifying agents may be omitted and may be replaced by additional solvent.

Water-soluble formulations can be prepared by combining certain compounds of this invention with alkaline phosphates and carbonates. Such compositions will consist of -80$ active compound, 5-4o# of alkali metal hydroxide, phosphate or silicate and 15- o# of alkali metal carbonate.

APPLICATION The compounds used in this invention are generally applied to a locus to be protected from undesirable vegetation.

The locus to be protected is the soil. It may be barren of vegetation at the time the compounds are applied or vegetation may have begun to appear or be even fully developed. The locus to be protected also includes the surface of various weeds whose ; destruction is desired. Undesired vegetation can be any plants which are generally classified as weeds or for that matter any plant which is growing in an area in which the plant is not desired.

The herbicidally effective amount of a compound used in 1 this invention which will control undesired vegetation depends on climatic conditions and soil type. The exact quantity required will be apparent to one skilled in the art. Generally, the compounds used in this invention are applied to sandy soils at rates of 2 to 60 kilograms per hectare, and the preferred rate is in the range of 5 to o kilograms per hectare. It was noted that the compounds in Formula I are most advantageously applied to the soil in the early spring before the new growth of vegetation begins.

The following examples illustrate the preparation, formulation and application of the herbici'dal compounds of the invention. , PREPARATION Example I A mixture of 11 parts of p-fcolylurea, 5.9 parts of ethyl 2-methylacetoacetate, 0.5 parts of p_- toluenesulfonic ! acid, and 0 parts of "benzene is refluxed for four days with stirring and continuous removal of water by means of a suitable condenser trap. Six-tenths parts of water is collected. The mixture is filtered. About 2 parts of l,3-(p-tolyl)urea is obtained. One-half of the solution is stripped of solvent under reduced pressure and the remaining cake is dried and pulverized.

The other half of the benzene solution is extracted with 100 parts of 5$ sodium hydroxide solution and the latter is acidified with concentrated hydrochloric acid. The resulting precipitate is collected on a filter and washed thoroughly with water. Four parts of 2-methyl-N-(p-tolylcarbamoyl)^3- 3-(P-tolyl)ureido7crotonamide is obtained.

The benzene of the organic layer is evaporated in ethyl vacuo. The residue consists of 1 part of/2-methyl-3-(3-p-tolyl ureido) crotonate.

In an analogous manner the following compounds were made : , 3-dimethyl-3- (3-phenylureido )acrylic acid, methyl ester 2,3-dimethyl-3-(3-phenylureido)acryiic acid tthyl ester f 2-ethyl-3-methyl-3-(3-phenylureido) acrylic acid, methyl ester 2~ethyl-3-methyl-3-(3-phenylureido) acrylic acid, ethyl ester 2-ethyl-3-(3-phenylureido) crylic acid, methyl ester 2-ethyl-3-(3-phenylureido) acrylic acid, ethyl ester 2-methyl-3-ethyl-3-(3-phenylureido) acrylic acid, ethyl ester 2-methyl-3-propyl-3-(3-phenylureido) acrylic acid, methyl ester 2-methyl-3-isopropyl-3-(3-phenylureido) acrylic acid methyl ester 2,3-dimethyl-3-(3-benzylureido)acrylic acid, ethyl ester 2,3-diethyl-3-(3-phenylureido) acrylic acid, ethyl ester 2-fluoro-3-ethyl-3-(3-phenylureido) acrylic acid, methyl ester 2-fluoro-3-ethy1-3- (3-phenylureido) acrylic acid, ethyl ester 2-fluoro-3-methyl-3~[3-(0-chlorophenylureido) ]acrylic acid, ethyl ester 2,3-dimethyl-3- [3- (m-trifluoromethylphenylureido) ] -acrylic acid, sec. -butyl ester 2-fluoro-3-me thyl-3- [3- (3-fluorobenzylureido) ] acrylic acid, methyl ester - 2-fluoro-N- ( henylcarbamoy1 ) -3-(3 -phen lureido ) -crotonamide Example II A mixture of 20.0 parts by weight of phenylurea, 24.2 parts by weight of ethyl-a-chloroacetoacetate, 1 part by weight of p_-toluenesulfonic acid, and 88 parts by weight of benzene is refluxed and stirred in a vessel equipped with a Dean-Stark Trap until water ceases to evolve from the reaction. The mixture is cooled and filtered to remove 1,3-diphenylurea.

The organic layer is washed with 5 sodium hydroxide solution to remove simultaneously formed 5-chloro-6-methyl-3-phenyluracil and stripped of the benzene in vacuo. The residue is re-crystallized from an ethanol-water mixture to separate from 2 i -methyl-^-oxo-3-phenyl-4-¾idazoline- -carboxylic acid ethyl ; ester. Pure 2-chloro-3-methyl-3-(3-phenylureido) acrylic acid, ethyl ester is obtained.

The following compounds are synthesized in an ; analogous fashion: 2-chloro-3-methyl-3-(3-phenylureido) acrylic acid, methyl ester 2-chloro-3-methyl-3-(3-phenylureido) acrylic acid, butyl ester 2-chloro-3-ethyl-3-(3-phenylureido) acrylic acid, propyl ester 2-chloro-3-ethyl-3-(3-phenylureido) acrylic acid, ethyl ester 2-chloro-3-(3-phenylureido) acrylic acid, ethyl ester 2-chloro-3-ethyl-3-(3-phenylureido) acrylic acid, propyl ester 2-chloro-3-ethyl-3-(3-phenylureidp)acrylic acid, ethyl ester 2-chloro-3-methyl-3-(3-benzylureido) acrylic acid, methyl ester 2-chloro-3-ethyl-3-(3-benzylureido) acrylic acid, ethyl ester 2-chloro-3-methyl-3-(3-benzylureido) acrylic acid, ethyl ester 2-chloro-3-methyl-3-[3-(p-chlorophenyl reido) ]acrylic acid, ethyl ester 2-chloro-3-methyl-3-[3-(3, -dichlorophenylureido) ]-acrylic acid, methyl ester 2-chloro-3-[3-(p-bromophenylureido) ]acrylic acid, ethyl ester 2-chloro-3-methyl-3-[3-(0-fluorophenylureido) ]acrylic ' acid, ethyl ester 2-chloro-3-methyl-3-[3-(m-chlorophenylureido) ]acrylic · acid, methyl ester 2-chloro-3-methyl-3-[3-(p-tolylureido) ]acrylic acid, methyl ester 2-chloro-3-methyl-3-[3-(p-methoxyphenylureido) ]acrylic! acid, ethyl ester 2-chloro-3-methyl-3- [3- (O-bromophenylureido )] acrylic ; acid, ethyl ester 2-chloro-3-methyl-3-[3-(3-chloro- -methoxyphenylureido) ] acrylic acid, methyl ester 2-chloro-3-methyl-3-[3-(3-chloro-4-methylphenylureido) ]-acrylic acid, ethyl ester 2-chloro-3-methyl-3-[3-(m-trifluoromethylphenylureido) ]-acrylic acid, methyl ester 2-chloro-3-methyl-3-[3-(3j ~xylylureido) ]acrylic acid, ethyl ester . 2-chlorO-3-ethyl-3- [3-(m-methoxyphenylureido) ]acrylic acid, methyl ester 2-chloro-3-methyl-3-[3-(p-chlorobenzylureido) ]acrylic acid, ethyl ester · 2-chloro-3-methyl-3-[3-(p-methylbenzylureido) ]acrylic acid, methyl ester 2-chloro-3-methyl-3-[3-(3i4-dichlorobenzylureido) Jacryli acid, methyl ester Example III 2-bromo-3-methyl-3-(3-phen lureido)acryllc acid, ethyl ester Four parts of 3-methyl~3- (3-phenylureido)acrylic acid, ethyl ester is dissolved in 20 parts of carbon tetrachloride. 2.8 parts of N-bromosuccinimide and 0.4 parts of beuroyl peroxide are added and the mixture stirred overnight at room temperature.1 The mixture is filtered and washed with water to remove succinimid The carbon tetrachloride is removed in vacuo after drying over anhydrous magnesium sulfate and the residue is recrystallized from an ethanol-water mixture. parts of 2-bromo-3-methyl-3-(3-phenylureido)acrylic acid, ethyl ester, m.p. 101 - 103eC. is. obtained.

Starting with the appropriate acrylic ester, the · following analogs may be synthesized in an analogous manner: 2-bromo-3-isopropyl-3-(3-phenylureido)acrylic acid, ethyl ester 2-bromo-3-ethyl-3-(3-phenylureido)acrylic acid, methyl ester 2-bromo-3-methyl-3-(3-benzylureido)acrylic and ethyl ester 2-bromo-3-methyl-3-[3-(0-fluorophenylureido) ]acrylic acid, ethyl ester n 2-bromo-3-methyl-3-[3-(^-tolylureido)]acrylic acid, : ethyl ester 2-bromo-3-methyl-3-[3-(p-'bromobenzylureido)]acrylic acid, ethyl ester 2-bromo-3-methyl-3- [3- (sec . -butylureido) ]acrylic acid± methyl ester 2-bromo-3-methyl-3- [3- (tert. -butylureido) ]acrylic acid, ethyl ester 2-bromo-3-methyl-3-(3-butylureido)acrylic acid, ethyl ester 2-bromo-3-methyl-3-[3-(u-hexylureido) ]acrylic acid, methyl ester 2-bromo-3-propyl-3-(3-methylureido) acrylic acid, ethyl ester 2-bromo-3-isopropyl-3-(3-methylureido) acrylic acid, ; butyl ester Example IV 2-chloro-3-methyl-3-(3-butylureido) acrylic acid, ethyl ester A mixture of 0 parts of butylurea, 56.6 parts of ethyl a-chloroacetoacetate, 2 parts of p_-toluenesulfonic acid and l60 parts of benzene is refluxed overnight under continuous removal of water by means of a Dean-Stark Trap. 5 parts of water is collected. The reaction mixture is cooled and filtered to remove unreached urea, and the organic layer extracted with 5 sodium hydroxide solution to remove unreacted ethyl a-chloroacetoacetate and with 10$ hydrochloric acid in order to remove 3-butyl-5-methyl-2-oxo-4-imidazoline-4-carboxylic acid, ethyl ester. The organic layer is dried over anhydrous magnesium sulfate, filtered and the benzene removed in vacuo. The residue is recrystallized from ethyl acetate yielding 2-chloro-3-methyl-(3-butylureido) acrylic acid, ethyl ester, m.p. 97 - 99eC.

Starting with the appropriate acrylic esters and ureas, the following analogs may be synthesized in an analogous manner:; 2-chloro-3-methyl-3-(3-sec.-butylureido) acrylic acid,i ethyl ester ' 2-chloro-3-methyl-3-(3-tert.-butylureido) acrylic acid, ethyl ester , 2-chloro-3-ethyl-3-(3-methylureido) acrylic acid, methyl ester 3- (3-amylureido)-2-chloro-3-methylacrylic acid, ethyl es Example V 3-(3-butylureido)-2,3-dimethylacrylic acid, ethyl ester A mixture of 10 parts of butylurea, 6.2 parts of ethyl a-methylacetoacetate, and 0.5 parts of £-toluene sulfonic acid is refluxed in 80 parts of benzene under continuous removal of water by means of a Dean-Stark Trap overnight. 0.5 parts of water is collected. The reaction mixture is cooled, filtered, and the solvent evaporated. The residue is recrystallized from ethyl acetate yielding parts of 3-(3-butylureido)-2,3-dimethyl> acrylic acid, ethyl ester, m.p. 66 - 68°C.

Starting with the appropriately substituted acrylic esters and ureas, the following analogs may be prepared in an analogous manner: 2,3-dimethyl-3-(3-methylureido) acrylic acid, ethyl ester 3-(3-amylureido)-2-ethyl-3-methylacrylic acid, ethyl ester 3-(3-amylureido)-2-fluoro-3-methylacrylic acid, ethyl1 ester 3-(3-isoamylureido)-2-fluoro-3-methyiacrylic acid, ethyl ester 3-(3-a£krylureido)-2,3-dimethylacrylic acid ethyl ester 3-[3-(2-buten-l-ylureido)]-2,3-diethylacrylic acid, methyl ester , 2-bromo-N-(phenylcarbamoyl) -3- ( 3-phenylureldo)- crotonamide · 3· 3 parts of N-(phenylcarbamoyl) -3- ( 3-phenylureido)-crotonamide Is dissolved in 0 parts of glacial acetic acid together with 0.7 parts of anhydrous sodium acetate. A solution; of 1.8 parts of bromine in 10 parts of lacial acetic acid is added gradually over a 20 min. period. The mixture is poured onto an ice-water mixture, filtered, and washed thoroughly with water. The solid is recrystallized from an ethanol-water mixture yielding 2-bromo-N-(phenylcarbamoyl)- 3- ( 3-phenylureido)-crotonamide, m.p. 2β0 - 262eC.

Example VII 2-chloro- - (phenylcarbamoyl) -3- ( 3-phenylureido)- crotonamide 1 3 parts of N-phenylcarbamoyl-3- ( 3-phenylureido)-crotonamide is slurried up in 100 ml. of xylene at 65 eC. 1.2 parts of sulfuryl chloride in 10 ml. of xylene is added drop-wise over a 10 min. period. The mixture is stirred at 65eC. for 30 minutes, cooled, and extracted with aqueous ioditun hydroxid solution. The alkaline solution ig acidified with hydrochloric aci and the precipitate filtered off and washed thoroughly with water and air dried, m.p. 212 - 212.5eC Example VIII 2^iodo-N-('phenylcarbamoyl) -3- ( 3-phenylureido)- crootonamiae 3.4 parts of N- (phenylcarbamoyl) -3- ( 3-phenylureido)-crotonamide and 1.3 parts of iodine is dissolved in 25 ml. of glacial acetic acid. The solution is heated to 5°C. and 1.1. part of fuming nitric acid added. The reaction mixture is stirred FORMULATION AND APPLICATION Example IX 2-bromo-3-ethyl-3- ( 3-phenylureido)- acrylic acid, methyl ester 25 Montmorillonite clay 73 Dioctyl ester of sodium sulfosuccinic acid 1 Sodium lignin sulfonate 1 These components are blended in a ribbon blender, micropulverized in a hammer mill until the particles are under 50 microns in diameter, and then reblended until homogeneous. All other compounds of this invention can be formulated in a similar manner.

Forty kilograms of the active ingredient in this formulation is suspended in 200 liters of water and sprayed on a hectare of area around a tank farm. The soil in the area is beach sand containing little clay or organic matter. The treatment results in season long control of such annual and perennial vegetation as crabgrass, goosegrass, white clover, broomsedge, povertygrass, dune sandspur and carpetweed.

Example X Percent 2-chloro-3-ethyl-3- ( 3-phenylureido)- . 80.00 acrylic acid, ethyl ester Attapulgite clay 18.25 Alkyl naphthalene sulfonic acid, Na salt 1.50 Low viscosity methylcellulose 0.25 These components are blended in a ribbon blender micropulverized in a hammer mill until the particles are under 50 microns in diameter and then reblended until the powder is homogeneous.

This wettable powder is suspended in water at a rate to give 2 Kg. in 200 liters and the suspensions applied to a hectare of asparagus beds in the spring just before the spears emerge. The treatment gives good control of such weeds as chickweed, both ouseear and common, downy brome, crabgrass, carpetweed and purslane.

Example XI A water suspension is prepared by blending the following dry ingredients in a ribbon blender and then grinding them with water in a ball or roller mill until the solids are finely dispersed in the water and the average particle size is less than 5 microns: Percent 2-chloro-3-methyl-3-(3-phenylureido)- acrylic acid, ethyl ester 25 Hydrated attapulgite 2 Lignin sulfonic acids, Na salt 5 Water 68 Ten kilograms of the above material is suspended in 250 liters of water and applied to an acre of gravel driveway. The treatment provides season long control of crabgrass, foxtail and other annual grasses which infest the area. The mixture obtained in Example I can be formulated and applied in like manner.

Example XII A water suspension is prepared by blending the following dry ingredients in a ribbon blender and then grinding with water in a sand-mill: Percent 2-bromo-3-methyl-3- (3-phenylureido)- aorylic acid, athyl ootor 2JJ Hydrated attapulgite 2 Na2HP0^ 1 Lignin sulfonic acid, Na salt 5 Sodium pentachlorophenate 0.5 Water 66.5 Grinding is continued until essentially all the particles in the suspension have been reduced to diameters of less than 5 microns.

This aqueous suspension is diluted with sufficient water to give a concentration of 3 Kg. of the substituted ureido-r-acrylic acid ester in 100 liters of water and sprayed at a volume rate of approximately 300 liters per hectare along highway ground rails and sign posts. Excellent control of crabgrass, ragweed, mustard, lambsquarters, morningglory, foxtail and fall panicum is obtained.

Example XIII An oil suspension is prepared by grinding the ; following ingredients in a ball or roller mill until the solids are finely dispersed in the oil and the average particle size is less than 5 microns: Percent Methyl ester of 2-fluoro-3-roethyl-3- (3-phenylureido)acrylic acid 25 Diesel oil 67 Alkyl aryl polyether alcohol 8 Sufficient oil suspension to contain 60 Kg. of active ingredient is diluted with 500 liters of a herbicidal oil such as Lion Oil No. 6 and sprayed on a hectare of railroad right-of-way.

This treatment provides extended control of quackgrass, seedlings, foxtail, smooth brome grass, ragweed, nutsedge, Johnson grass, annual morningglory, wild carrot and other weeds growing along the right-of-way.

Example XIV An oil suspension is prepared by grinding the following ingredients together in a ball or roller mill until the solids are finely dispersed in the oil and the average particle size of the active ingredient is less than 5 microns: Percent 2-bromo-3-isopropyl-3- ( 3-phenylureido)— acrylic acid, ethyl, ester 25 Diesel oil 67 Polyoxy ethylene sorbitan ester of mixed rosin and fatty acids 8 This oil suspension can be diluted with water to form a water emulsion.

Sufficient of the above formulation to provide 20 Kg. of the substituted acrylic acid ester is suspended in 500 liters ; of diesel oil and sprayed along foot trails in a park. The application covers one hectare and is applied when the weeds are 5 to 1 inches in height. Such weeds as crabgrass, chickweed, cheatgrass and the foxtails are controlled.

Example XV Percent 2-chloro-3-methyl-3- (3-phenylureido)— acr lic acid meth l ester 20 Attapulgite clay 78 Alkyl naphthalene sulfonic acid, Na salt 1 Lignin sulfonic acid, Na salt 1 These ingredients are mixed in a ribbon blender until homogeneous and then charged to a pug mill where sufficient water is blended in to form a thick paste. The paste is extruded from the pug mill. These extrusions are dried and then broken by a rotary crusher into irregular granules ranging in diameter from 0.25 - 1·0 mm.

The following compounds can be formulated in like manner : 2,3-dimethyl-3-(3-phenylureido)acrylic acid, ethyl ester 2-methyl-3-isopropyl-3-(3-phenylureido)acrylic acid methyl ester 2-chloro-3-methyl-3-[3-(p-chlorophenylureido) ]acrylic acid, ethyl ester These granules may be applied by hand or with a spreader at rates sufficient to give 15 - 3P Kg./ha. to boundary fences, industrial sites, in parking areas and under billboards. They provide control of goosegrass, quackgrass, chickweed, peppergrass, crabgrass, the foxtails, and ragweed.

Example XVI Percent 2-chloro-3-ethyl-3-(3-phenylureido)- acrylic acid, propyl ester 12 Sand (20-30 mesh) . 8l Sodium silicate (28$ SiO ; ratio The sand and sodium silicate solution are mixed active ingredient is then dusted into the mixture as it is being agitated. The granules are then discharged from the blender and dried.

This preparation is applied with a spreader around oil and gas wells prior to the rainy season.

Thirty kilograms of active ingredient per hectare will effectively control weeds such as crabgrass, cheatgrass, chickweed, and wild oats in these areas.

Example XVII Percent 2-fluoro-3-ethyl-3- ( 3-phenylureido)- acrylic acid, ethyl ester 10 6-15 mesh expanded vermiculite 0 A granular preparation is made by dissolving the active ingredient in methylene chloride, spraying it on the vermiculite, and then drying the product.

These granules are applied at the rate of 20 Kg./Ha. around sign posts, guard rails, and bridge abutments to control such weeds as Johnson grass poison ivy, witchgrass, the foxtails, and morningglory.

Example XVIII Percent 2-chloro-3-me thyl-3- ( 3-phenylureido)- acrylic acid, butyl ester 25 Alkyl naphthalene sulfonic acid, Na salt 1 Anhydrous sodium sulfate 10 Non-swelling clay 6 These components are blended and micropulverized, then mixed with 15 - 20$ of water and extruded under pressure through an orifice to produce rods which are then cut into This formulation is used for dry application to the soil for the control of undesirable woody plants in fence rows and utility rights-of-way. An application of one heaping tablespoonful of granules for each inch of trunk diameter at the base of each brush cluster gives control of such plants as birch, box elder, willow, oaks, sweetgum, and wild cherry.

Example ΐχχ Percent 2-ethyl-3-(3-phenylureido)acrylic acid, methyl ester 5.0 Attapulgite clay 30.0 Talc 65.Ο The active ingredient is micropulverized with the minor diluent to a particle size essentially below 50 microns. This composition is then blended thoroughly with the major diluent to form a 5$ active dust.

The following compounds can be formulated in like manner: 2-chloro-3-methyl-3-(3-butylureido)acrylic acid, ethyl ester 2-chloro-3-methyl-3-(3-tert. butylureido)acrylic acid, ethyl ester 3- (3-amylureido)-2-chloro-3-methylacrylic acid, ethyl ester 3-(3-butylureido)-2,3-dimethylacrylic acid, ethyl ester 3-(3-isoamylureido)-2-fluoro-3-methylacrylic acid, ethyl ester Example XX Percent 3~(3-butylureido)-2,3-d3jTiethylacrylic acid, ethyl ester 20.0 00 Isophorone 24.0 Trimethylnonyl polyethylene glycol ether 6.0 The above ingredients are blended until a homogeneous ; emulsifiable solution is obtained. A high surfactant composition can be obtained by replacing up to one-half of the xylene in the above formulation with additional trimethylnonyl polyethylene glycol ether. ' Sufficient material to provide an application of 20 Kg./ of active ingredient is emulsified in 250 liters of water and applied to a hectare of material storage area in an industrial plant. This treatment provides season-long control of crabgrass, goosegrass, ragweed, carpetweed, and other vegetation in the area.

Example XXI Percent 3- ( 3-amylureido) - 2-ethyl-3-methylacrylic acid, ethyl ester 10.0 Aromatic weed oil 90.0 The above ingredients are blended with warming to form an oil concentrate suitable for aerial application or for further dilution prior to ground spraying.

Thirty kilograms of the above liquid are applied with a helicopter to a hectare of an asparagus field in the early , spring before the spears begin to emerge. This treatment controls weeds such as the chickweeds, annual bluegrass, ragweed, lambs-quarters, and purslane for an extended period.

Examplexxn Percent 2-bromo-3-methyl-3- ( 3-phenylureido)acrylic acid, ethyl ester 95 · 0 Finely divided synthetic silica Nonyl phenyl polyethylene glycol The above ingredients are coarsely ground to give a high-strength composition which can be applied directly or used in further formulation.

Example XXIII Percent 2-chloro- -(phenylcarbamoyl)-3-(3- phenylureiJo ) -crotonamide 80 Alkyl naphthalene sulfonic acid, Na salt 2 Partially desulfonated sodium lignin sulfonate 2 Diatomaceous silica ^ Kaolin clay 12 The above components are blended and mlcropulverlzed until substantially all particles are less than 50 microns.

The following compounds can be formulated in like manner: -bromo-N-(phen lcarbamo 1 ) -3-(3-phenylureido ) - crotonamide -iodo-N- (phenylcarbamoyl ) -3- (3-phenylureido ) - crotonamide Example XXIV Percent 2-Fluoro-N-phenylcarbamoyl-3-(3- phenylureido)crotonamide 30 Ca, Mg Lignin sulfonate 15 Hydrated attapulgite 1.8 Sodium carbonate anhydrous 2.5 Sodium pentachlorophenate 0.7 Water 50.0 The above components are premixed to a uniform slurry, then sand ground until substantially all particles are less than 5 microns. The resulting stable, aqueous, suspension is readily diluted with water to use level.

Example XXV Percent 2-chloro-N-phenylcarbamoyl ) -3-(3- phenylureido )crotonamide 25 Anhydrous sodium sulfate 10 Non-swelling Ca., Mg. bentonite 64 Alkyl naphthalene sulfonic acid, Na salt 1 The active component, the sodium sulfate and the surfactant are first blended and micropulverized, then blended with bentonite and moistened with 15$ to 19$ water. A uniform paste is obtained by pug milling. The resulting paste is extruded through 1/8" die holes, fitted with cutting knives that form pellets 1/8" x 1/8", which are subsequently dried.

The active component above may be replaced by any of the crotonamldes disclosed in this invention to yield a similar Example XXVI Percent 2-Bromo-N-phenylcarbamoy1-3- (3-phenylureido )crotonamlde 10 Propylene glycol 10 Granular vermicullte (Zonollte No. 4) 80 The active component is first micropulverized to a fine powder, then blended briefly with the vermiculite. The propylene glycol is then sprayed rapidly upon the tumbling . mix to prevent segregation in storage and handling.

Any of the crotonamides disclosed in this invention may be substituted for the active named component above to yield a similar granular formulation.

Example XXVH Percent 2-Bromo-N-(phenylcarbamoyl)-3- (3-phenylureido)crotonamide 95.0 Finely divided synthetic silica 3.0 Trimethylnonyl polyethylene glycol ether 2.0 The above ingredients are coarsely ground to pass a 0.42 millimeter screen. This high-strength composition can be applied directly or used for further formulation.

The following series of examples (Examples 32 - 39) illustrate the methods of employing the above formulations to control undesired vegetation.

Example XXVIII The formulation of Example 23 is extended with water in such a manner that a rate of 50 pounds active ingredient per acre is applied in 100 gallons of water to weed infested areas along power line rights-of-way. The treatment results in kill of annual and perennial weeds such as plantain, crabgrass, horsenettle, foxtail, and panic grass. Woody plants such as willow, alder, and sumac are controlled.

Example XXIX One-half to one pound of the formulation of Example 24 is extended with 3 gallons of water to which 2 ounces of a surfactant, such as trimethylnonyl polyethylene glycol ether, has been added. The resultant mixture is sprayed on existing vegetation around lumberyards. Sufficient volume is used to thoroughly wet the foliage and the exposed soil surface. The treatment results in control of annual and perennial weeds such as purslane, knotweed, chicory, foxtail, touch-me-not and quack-grass.

Example XXX The formulation of Example 24 is diluted with oil so that 25 pounds per acre (active ingredient) are applied in 80 gallons of herbicidal oil to vegetation growing around oil tank farms or grain elevators. The application results in control of annual and perennial vegetation.

Example XXXI The pellets formed In Example 25 are scattered by-helicopter over a stand of arborvitae at a rate of 8 pounds (active ingredient) per acre. Treatment is made early in the spring before weeds emerge. The treatment results in kill of crabgrass, foxtail mustard, ragweed, and barnyardgrass while allowing conifers to grow normally.

Example XXXII The granules of Example 25 are spread with a fertilizer spreader in late summer at a rate of 8 pounds (active Ingredient) per acre on an area which is to be planted with young Christmas trees the following spring. The application is made on rows 18 inches wide coinciding with the rows to be planted to trees. The treatment results in control of weeds under the small seedlings for the next summer and allows easier maintenance of the young tree..

Claims (27)

WHAT IS CLAIMED IS

1. A method for the control of undesired vegetation, comprising applying to tho locus to bo protoctod a horbicidally effective amount of a compound of the formula: 0 0 R - NH - C - NH - C = C - C - R2 R1 X wherein R is selected from the group consisting of alkyl of 1 — 10 carbon atoms, substituted alkyl of 1 - 8 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy of 1 - 3 carbons, alkoxycarbonyl of 2- furyl 4 carbon atoms»and cyano; 6 . ' aryl of $ - 10 carbon atoms; substituted phenyl wherein said substituent is selected from the group consisting of chlorine, fluorine, bromine, alkoxy of 1 - 5 carbon atoms, alkyl o 1 - 6 carbon atoms, nitro, trifluoromethyl, 2,3-tetramethylene 7 and 2,3-trimethylenylene; aralkyl.of $ - 13 carbon atoms; 7 substituted aralkyl of ^ - 13 carbon atoms wherein said substituen fluorine, is selected from the group consisting of chlorine,/nitro, alkyl and alkoxy; tetrahydronaphthylalkyl, alkenyl of 3 - 8 carbon atoms, cycloalkyl of 3 - 12 carbon atoms; substituted cycloalkyl of 3 - 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, alkoxy of 1 - 3 carbon atoms, and alkyl of 1 - carbon atoms; cycloalkenyl of h - 12 carbon atoms; substituted cycloalkenyl of - 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, alkoxy of 1 - 3 carbon atoms, and alkyl of 1 - carbon atoms; cycloalkylalkyl of 4 - 13 carbon atoms; cycloalkenyl-alkyl of 5 - 13 carbon atoms/ substituted cycloalkylalkyl of 5 - 14 carbon atoms, wherein said substituent is selected from! the group consisting of bromine, chlorine, alkoxy of 1 - 5 carbon atoms and alkyl of 1 -4 carbons; substituted cycloalkenylalkyl of 5 - 14 carbon atoms wherein said substituent is selected from the group consistin of bromine, chlorine, alkoxy of 1 - 3 carbon atoms, alkyl of 1 R2 is selected from the group consisting of -OR3 and -NH-C-NH-R ; II 0 R^ is selected from the group consisting of alkyl of ; 1-4 carbon atoms and cycloalkyl of 5-6 carbon atoms; R is selected from the group consisting of phenyl and substituted phenyl wherein said substituont is selected ] from the group consisting of bromine, chlorine, fluorine, alkoxy of 1-5 carbons, alkyl of 1-6 carbon atoms, nitro, tri-fluoromethyl, 2, 3-tetramethylene and 2, 3-trimethylene; with the limitation that when R is -NH-C-NH-R , 0 ; R is phenyl or substituted phenyl and the further limitation that when X is alkyl R and R^ cannot both be phenyl.

2. A method for the control of undesired vegetation comprising applying to the locus to be protected a herbicidally effective amount of a compound of the formula of Claim 1 wherein R is phenyl is methyl and X is selected from the group consisting of alkyl of 1 - carbon atoms, and halogen.

3. A method for the control of undesired vegetation comprising applying to the locus to be protected a herbicidally! effective amount of a compound as described in Claim 2 . wherein X is alkyl of 1 - 4 carbon atoms.

4. A method for the control of undesired vegetation : comprising applying to the locus to be prptected a herbicidally; effective amount of a compound as described in Claim 2 wherein X is selected from the group consisting of fluorine, chlorine, and bromine.

5. A method according to Claim 2 wherein the compound s 2-chloro-N-(phenylcarbamoyl)-3-(3-phenylureido)crotonamide. '

6. A method according to Claim 2 wherein the compound s 2-bromo-N-(phenylcarbamoyl)-3-(3-phenylureido)cr0tonamide.

7. A method according to Claim 2 wherein the compound is 2-fluoro-N-(phenylcarbamoyl)-3-(3-phenylureido)crotonamide.

8. A method for the control of undeslred vegetation comprising applying to the locus to be protected a herbicidally effective amount of a compound as described in Claim 1 wherein R is phenyl R-j^ is methyl R2 is O ^ R^ is selected from the group consisting of alkyl of 1 - 4 carbon atoms and cycloalkyl of 5 - 6 carbon atoms, and X is selected from the group consisting of alkyl of 1 - 4 carbon atoms and halogen.

9. A method according to Claim 8 wherein the compound is ethyl-2-methyl-3-(3-phenylureido)crotonate.

10. A method according to Claim 8 wherein the compound is ethyl-2-chloro-3-(3-phenylureido)crotonate.

11. A method according to Claim 8 wherein the compound is ethyl-2-fluoro-3-(3-phenylureido)crotonate.

12. A method according to Claim 8 wherein the compound is ethyl-2-bromo-3-(3-phenylureido)crotonate. - 44 -

13. A herbicidal composition comprising an inert diluent and a herbicidally effective amount of a compound of the following formula: 0 . 0 It « R — NH — C — NH — C = C — C — R_ wherein R is selected from the group consisting of alkyl of 1 - 10 carbon atoms} substituted alkyl of 1 - 8 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy of 1 - 3 carbons, alkoxycarbonyl of ffeyl 2 - 4 carbon atoms/and cyano; 6 ' aryl of £ - 10 carbon atoms; substituted phenyl wherein said substituent is selected from the group consisting of chlorine, fluorine, bromine, alkoxy of 1 - 5 carbon atoms, alkyl of 1 - 6 ' carbon atoms, nitro, trifluoromethyl, 2,3-tetramethylene and 7 2,3-trimethylene; aralkyl of fj - 13 carbon atoms; substituted 7 aralkyl of - 13 carbon atoms wherein said substituent is fluorine selected from the group consisting of chlorine,/nitro, alkyl and alkoxy; tetrahydronaphthylalkyl; alkenyl of 3 - 8 carbon atoms; cycloalkyl of 3 - 12 carbon atoms; substituted cycloalkyl of 3 - 1 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, alkoxy of 1 - 3 carbon atoms, and alkyl of 1 - 4 carbon atoms; cycloalkenyl of - 12 carbon atoms; substituted cycloalkenyl of - 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, alkoxy of 1 - 3 carbon atoms, and alkyl of 1 - carbon atoms; cycloalkylalkyl of - 13 carbon atoms; cycloalkenylalkyl of 5 - 13 carbon atoms; substituted cycloalkylalkyl of 5 - 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, alkoxy of 1 - 5 carbon : atoms and alkyl of 1 - 4 carbons; substituted cycloalkenylalkyl of 5 - 14 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, alkoxy of 1 - 3 carbon atoms, alkyl of 1 - 4 carbon atoms, and cyano; or alkoxy or alky X is alkyl of 1-4 carbon atoms, halogen, -©fi«— o-v -SR. th hydrogen or of l-¾ carbon ato R^ is/alkyl of 1 - 3 carbon atoms; Rg is selected from the group consisting of -OR^ and .: 0 R^ is selected from the group consisting of alkyl of 1 - 4 carbon atoms and cycloalkyl of 5 - 6 carbon atoms; R^ is selected from the group consisting of phenyl and substituted phenyl wherein said substituent is selected from the group consisting of bromine, chlorine, fluorine, alkoxy of i 1 - 5 carbons, alkyl of 1 - 6 carbon atoms, nitro, trifluoromethyl 2,3-tetramethylene and 2,3-trimethylene; with the limitation that when R2 is -NH-C-NH-R^, 0 R is phenyl or substituted phenyl and the further limitation that when X is alkyl R and R cannot both be phenyl.

14. A herbicidal composition comprising an inert diluent and a herbicidally effective amount of a compound of the" formula of Claim 15 wherein R is phenyl is methyl . ί X is selected from the group consisting of alkyl of 1 - carbon atoms and halogen.

15. A herbicidal composition comprising an inert diluent and a herbicidally effective amount of a compound as described in Claim 14 wherein X is alkyl of 1 - 4 carbon atoms.

16. A herbicidal composition comprising an inert diluent and a herbicidally effective amount of a compound as described in Claim 14 wherein X is selected from the group consisting of fluorine, chlorine, and bromine.

17. A herbicidal composition according to Claim 13 wherein said herbicidally effective compound is 2-chloro-N- i (phenylcarbamoyl)-3- (3-phenylureido)crotonamide.

18. A herbicidal composition according to Claim 13 wherein said herbicidally effective compound is 2-bromo-N- (phenylcarbamoyl) -3- ( 3-phenylureido)crotonamide. -48- 29833/4

19. A herbicidal composition according to Claim 13, wherein said horbicidally effective compound is 2-fluoro-N-(phenylearbamoyl)-3- (3-phenylureido)crotonamide.

20. A compound of the formula: wherein X' is halogen.

21. A compound as claimed in Claim 20, wherein X· is chlorine, fluorine or bromine.

22. 2-Chloro-I!I-(phenylcarbamoyl)-3-(3^phenylureido)-crotonamide.

23. · 2-Brorao-N- (phenylcarbamoyl )-3- (3-phenylureido )-crotonamide.

24. 2-Fluoro-N- (phenylcarbamoyl)-3- (3-phenylureido)-, crotonamide.

25. A method for the control of undesired vegetation according to Claim 1, substantially as described and exemplifiedjherein.

26. Herbicidal compositions according to Claim 13, substantially as described and exemplified herein,. 29833/2 f

27. Compounds according to Claim 20, substantially as described and exemplified herein. - 49- -