US3235360A - Control of undesirable vegetation - Google Patents

Control of undesirable vegetation Download PDF

Info

Publication number
US3235360A
US3235360A US232311A US23231162A US3235360A US 3235360 A US3235360 A US 3235360A US 232311 A US232311 A US 232311A US 23231162 A US23231162 A US 23231162A US 3235360 A US3235360 A US 3235360A
Authority
US
United States
Prior art keywords
trimethyleneuracil
salt
carbon atoms
alkyl
butyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US232311A
Inventor
Edward J Soboczenski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE594076D priority Critical patent/BE594076A/xx
Priority to CA731651A priority patent/CA731651A/en
Priority to IT635567D priority patent/IT635567A/it
Priority to NL254838D priority patent/NL254838A/xx
Priority to DK106253D priority patent/DK106253A/da
Priority to SE7792/60A priority patent/SE305770B/xx
Priority to DE19601240698 priority patent/DE1240698C2/en
Priority to CH921360A priority patent/CH482402A/en
Priority to GB17418/64A priority patent/GB968664A/en
Priority to GB28141/60A priority patent/GB968661A/en
Priority to GB17419/64A priority patent/GB968665A/en
Priority to GB17417/64A priority patent/GB968663A/en
Priority to FR835959A priority patent/FR1270771A/en
Priority to US217521A priority patent/US3235357A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US232311A priority patent/US3235360A/en
Priority to GB619166A priority patent/GB1035092A/en
Priority to GB619566A priority patent/GB1035096A/en
Priority to GB619366A priority patent/GB1035094A/en
Priority to GB619466A priority patent/GB1035095A/en
Priority to NO14675262A priority patent/NO117095B/no
Priority to DK534662A priority patent/DK113254B/en
Priority to SE13294/62A priority patent/SE350496B/xx
Priority to CH923466A priority patent/CH489201A/en
Priority to CH923566A priority patent/CH490007A/en
Priority to CH923666A priority patent/CH490008A/en
Priority to BR14539162A priority patent/BR6245391D0/en
Priority to CH1449962A priority patent/CH487591A/en
Priority to US284835A priority patent/US3254082A/en
Priority to OA51234A priority patent/OA01145A/en
Priority to DK185565A priority patent/DK129315B/en
Priority to BR17145265A priority patent/BR6571452D0/en
Priority to BR171453/65A priority patent/BR6571453D0/en
Priority to US516686A priority patent/US3360521A/en
Priority to MY1965116A priority patent/MY6500116A/en
Priority to MY1965103A priority patent/MY6500103A/en
Priority to MY1965102A priority patent/MY6500102A/en
Priority to MY1965115A priority patent/MY6500115A/en
Application granted granted Critical
Publication of US3235360A publication Critical patent/US3235360A/en
Priority to MY6900393A priority patent/MY6900393A/en
Priority to MY6900392A priority patent/MY6900392A/en
Priority to MY6900391A priority patent/MY6900391A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D239/22—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C07D239/72—Quinazolines; Hydrogenated quinazolines
    • C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
    • C07D239/96—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3

Definitions

  • this invention is directed to the herbicidal use of compounds of the formula 1 O O O u 1 RN RN m cro 2 Benin EX where R is alkyl of 1 through carbon atoms, substituted alkyl of 1 through 10 carbon atoms, aryl of 6 through 14 carbon atoms, substituted aryl of 6 through 14 carbon atoms, aralkyl of 7 through carbon atoms, substituted aralkyl of 7 through 15 carbon atoms, alkenyl of 3 through 10 carbon atoms, alkynyl of 3 through 10 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, cycloalkenyl of 4 through 12 carbon atoms, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of 5 through 13 carbon atoms, (substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, (substituted cycloalkenyhal
  • X is oxygen or sulfur
  • n 3, 4, or 5.
  • salts of these compounds can also be used accord ing to this invention.
  • salts are meant those compounds formed with such cations as sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese and quaternary ammonium.
  • the uracils of Formula 1 also form novel 1:1 addition compounds with excesses of certain nitrogenous bases.
  • the exact structure of these compounds is not known. Although the compounds are, generally speaking, poorly soluble in water, they are, according to the best available information, believed to be essentially salt-like in structure. They will be symbolized by the following formula, with the understanding that it is representative only, and is not intended to illustrate actual structure:
  • n 3 4, or 5
  • NB is a nitrogenous base having an ionization constant K of IO- in water.
  • Suitable nitrogeneous bases are substituted, unsubstituted, cyclic and acylic Amines, Amidines, and Guanidines
  • the amines can be primary, secondary or tertiary amines, polyamines, arylamines, or heterocyclicarnines. Illustrative of such amines are:
  • Ethanolamine Dodecylamine Ethylenediamine Hexamethylenediamine Cocoadiamine Tallowdiamine Hexamethyleneimine Cyclohexylamine Methoxypropylamine Methylamine Dimethylamine Trimethylamine Ethylamine Propylamine Butylamine Octylamine Pyridine Piperidine Tetramethylguanidine Acetamidine Benzylamine Diethylenediamine Z-aminobutanol-l 2-aminooctanol-1 Sec.-butylamine 2-amino-2-methyl-1,3 propanediol Trimethylenediamine Some of the uracils of Formula 1 also form Water stable,
  • Z is hydrogen, chlorine, nitro, alkyl of 1 through 3 carbon atoms, bromine or OR (where R, is alkyl of 1 through 3 carbon atoms),
  • Y is chlorine or'alkyl of 1 through 3 carbon atoms
  • n 3, 4 or 5
  • p is /2, 1 or 2.
  • This invention is also directed to novel uracils, within the scope of Formula 1.
  • uracils are of the formula R is substituted or unsubstituted cycloalkyl radical containing 3 through 10 carbon atoms, a substituted or unsubstituted cycloalkenyl radical containing 4 through 10 carbon atoms, or a B1 CRz a radical, where R is methyl or ethyl, R is an alkyl radical containing 1 through carbon atoms, and R is hydrogen or methyl, and n is 3, 4 or 5.
  • substituted alkyl is intended to include such radicals as Bromoalkyl of 1 through carbon atoms, Chloroalkyl of 1 through 10 carbon atoms, Hydroxyalkyl of 1 through 10 carbon atoms, Alkoxyalkyl of 2 through 12 carbon atoms, Alkoxy carbonyl alkyl of 3 through 12 carbon atoms, Dialkyl amino alkyl of 3 through 12 carbon atoms, and Cyanoalkyl of 2 through 10 carbon atoms.
  • aryl and substituted aryl embrace radicals such as The terms aralkyl and substituted aralkyl are intended to include such radicals as Furfuryl,
  • cycloalkyl, cycloalkenyl, cycloalkyl alkyl, and cycloalkenyl alkyl will incude Cyclopropyl
  • cyclic substituents can be further substituted with alkyl groups containing 1 through 4 carbon atoms, methoxy, chlorine and bromine.
  • the uracils of Formulae 1 through 4 represent a new class of herbicides offering farmers and property owners a new and effective method for the control of undesirable vegetation.
  • uracils exhibit selective action in crops.
  • weeds growing in fields of such economic crops as corn, cotton, asparagus, sugar beets, red beets, bobs, spinach, potatoes, peanuts and pineapple can be controlled. This selective activity is described in more detail in the examples Which follow.
  • These compounds are also useful for general weed control on industrial sites, railroad rights-of-Way, and areas adjacent to croplands.
  • concentrations at which the compounds of this invention are to be used will vary according to the result desired, the type of vegetation, the formulation used, the mode of application, weather conditions, foliage density, and other similar factors. Since so many factors play a role, it is not possible to indicate a concentration suitable for all situations. Generally, when they are used for preemergence treatment in crops, these uracils are used at concentrations of at least about 0.5 pound of active ingredient per acre. Concentrations of from 0.5 to 3 pounds per acre are preferred.
  • the uracils When used in non-crop applications, the uracils are used at concentrations of from to 30 pounds of active ingredient per acre. The optimum concentrations to be used in any particular application Will be readily apparent to one skilled in the art.
  • R is an alkyl or alkenyl radical containing 3 through 6 carbon atoms, phenyl, substituted phenyl, cycloalkyl radical of 3 through 10 carbon atoms or cycloalkenyl radical of 4 through 10 carbon atoms,
  • X is oxygen
  • n 3, 4, or 5
  • R, X, and n have the same meaning as in Formula 1;
  • R is an alkyl radical of 1-6 carbon atoms, H+ is an acid, and B is a base.
  • the reaction sequence consists of two steps: first, the acid catalyzed condensation of a l-substituted urea or thiourea with an alkyl 2-cycloalkanone-l-carboxylate to give the ureido intermediate; and, second, the alkaline ring closure of this intermediate to the salt of the uracil product, followed by treatment with acid to liberate the free uracil.
  • the first step is best carried out by dissolving or suspending the l-substituted urea or thiourea in a solvent such as xylene, benzene or a 6 mixture of benzene and dioxane, and heating to reflux.
  • a solvent such as xylene, benzene or a 6 mixture of benzene and dioxane
  • Suitable acid catalysts are phosphoric, poly- 5 phosphoric, formic, chloroacetic, or Lewis acids such as BF ⁇ ; and AlCl
  • the mixture is stirred and heated to reflux until the water, split out during the reaction and collected in a suitable apparatus, ceases to be given off.
  • the clear solution is decanted or filtered and then con- 10 centrated to give the intermediate ureido derivative.
  • the ureido intermediate is dissolved in alcohol containing a slight excess of base, preferably an alkali metal alkoxide or hydroxide, and the solution is refluxed for a short time.
  • base preferably an alkali metal alkoxide or hydroxide
  • This step effects the ring closure.
  • the salt of the uracil is obtained by concentrating this solution to dryness.
  • the free uracil is prepared by acidifying an aqueous solution of the salt, and then isolating the solid.
  • the salt of the compounds of Formula 1 are prepared by conventional methods such as dissolving the free uracil in an aqueous or nonaqueous solution of at least an equimolar amount of a base or basic salt containing the desired cation.
  • a sodium salt can be prepared by dissolving the uracil in water containing an equimolar amount of sodium hydroxide. The salt can then be isolated from the solution by removal of the water.
  • the uracil salts which are not soluble in water can be prepared by treating an aqueous solution of an alkali metal salt of the uracil with an aqueous solution of a water-soluble salt of the metal.
  • the quaternary ammonium salts of the compounds of Formula 1 are prepared by reacting the substituted uracil with an appropriate quaternary ammonium hydroxide.
  • the quaternary ammonium salts of the uracils can be prepared in a dry inert solvent such as toluene or xylene.
  • the sodium salt of the uracil is first prepared and appropriate quaternary ammonium halide is then added with stirring and, if necessary, mild heating.
  • the sodium halide which forms is removed by filtration, leaving the quaternary ammonium salt of the uracil in solution.
  • the solvent-free salt can be prepared by removing the solvent, preferably in vacuo.
  • the nitrogenous base-uracil addition compounds of Formula 2 are prepared by mixing an appropriate uracil with a 4 to 20-f0ld weight excess of nitrogenous base. The mixture is heated gently until a clear solution forms.
  • addition compounds thus formed are stable in the presence of excess amine and can be diluted with suitable solvents for herbicidal applications.
  • the complexes of Formula 3 are formed by co-melting a uracil and a phenol in a 1:2. to 2:1 (uracilzphenol) ratio. They can also be formed by co-dissolving the reactants, in the same ratio, in a nonpolar solvent such as nitromethane or a mixture of nitromethane and cyclohexane.
  • the phenol complexes are formed by co-melting, it is not necessary to purify them further for herbicidal uses. If solvents are used in their preparation, they can be isolated by filtration or evaporation of the solvent. The complexes so obtained are also suitable for herbicidal use without further purification.
  • HERBICIDAL COMPOSITIONS The uracil compounds described in Formulae 1 through 4 can be prepared for use by incorporating them with adjuvants.
  • the amount of herbicide in such preparations can vary 7 over a wide range according to need. Generally speaking, they will contain from about 0.5% to 95%, by weight of a uracil.
  • Powder and dust preparations can be made by mixing uracils of the invention with finely-divided solids such as talcs, natural clays, pyrophyllite, diatomaceous earth; flours such as walnut shell, wheat, redwood, soya bean and cotton seed; or inorganic substances such as magnesium carbonate, calcium carbonate, calcium phosphate, sulfur and lime. These preparations are made by thoroughly blending the active ingredient and the solid.
  • the particles in such preparations should be less than 50 microns in average diameter, preferably about 20 microns.
  • Water-soluble powders can be prepared by blending a suitable uracil with such water-soluble alkaline powders as silicates, carbonates, phosphates or hydroxides, and optionally with water-soluble diluents such as urea or dextrose.
  • Granules and pellets can be be made by mixing a finely-divided uracil with a suitable clay such as kaolinite, montmorillonite or attapulgite, moistening this mixture with from 15 to 20% by weight of water, and then extruding the mass through a suitable die under pressure. The extrusions are cut into pro-determined lengths and then dried. These pellets can be granulated if desired.
  • a suitable clay such as kaolinite, montmorillonite or attapulgite
  • Granules or pellets can also be prepared by spraying a suspension or solution of a uracil onto the surface of a preformed granule of clay, vermiculite or other suitable granular material. If the uracil is in solution, it will penetrate into the pores of the granules and so will adhere without the aid of a binding agent. When the active material is insoluble in the liquid and is carried as a suspension, it is preferable that a binding agent such as goulac, dextrin, swollen starch, glue or polyvinyl alcohol be added. In either case, the granule is then dried and ready for use.
  • a binding agent such as goulac, dextrin, swollen starch, glue or polyvinyl alcohol
  • the uracils can also be prepared in liquids.
  • Water and aliphatic and aromatic hydrocarbons especially those derived from petroleum and having boiling points of from 125 C. to 400 C. are preferred. Hydrocarbons having lower boiling points should not be used because of their undesirable volatilization characteristics and infiammability.
  • These liquid preparations are made by dissolving the active in the liquid, or, if the active is insoluble in the liquid, by milling the components in a mill such as a pebble mill until the particles have average diameters of from 1 to 50 microns, preferably 5 to 20 microns.
  • the herbicidal preparations can also contain a surface-active agent.
  • the surfactant renders the preparations readily dispersible in liquids and improves their action on waxy leaves and the like.
  • surface-active agents are used in the preparations at concentrations of from about 1 to 10% by weight.
  • surface-active agen is intended to include wetting agents, dispersing agents, suspending agents and emulsifying agents.
  • Surface-active agents suitable for use are set forth in Detergents and Emulsifiers upto-date, 1962, John W. McCutcheon, Inc., Morristown, New Jersey. Other surface-active agents which can be used in these preparations are listed in US. Patents 2,139,- 276; 2,412,510; 2,426,417; 2,655,447; and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the US. Department of Agriculture.
  • the preparations can also contain adhesives, corrosion inhibitors, antifoam agents, dyes and pigments, anticaking agents, and hard water stabilizers.
  • the salts of the compounds of Formula 1 are especially advantageous for use as herbicides because many are soluble in water and can be applied as aqueous solutions.
  • the compounds of Formula 2 can be formulated as aqueous solutions or as oil-emulsifiable or oil-extendable formulations.
  • the nitrogenous base-addition compounds give formulation and application advantages, while still maintaining the desirable herbicidal characteristics of the parent uracils.
  • the herbicidal compositions of this invention can be formulated to contain two or more of the uracils. They can also be formulated to contain other known herbicides in addition to the uracils to give compositions which have advantages over the individual components.
  • PHENOLS Dinitro-o-sec-butylphenol and its salts Pentachlorophenol and its salts These phenols can be mixed with the uracils in the proportions of 1:10 to 20:1, respectively, the preferred ratio being 1:5 to 5:1.
  • N,N-di(n-propyl)thiolcarbarnic acid ethyl ester N,N-di(n-propyl)thiolcarbamic acid, n-propyl ester N-ethyl-N-(n-butyl)thiolcarbamic acid, ethyl ester N-ethyl-N-(n-butyl)thiolcarbamic acid, n-propyl ester Mixed in a 1:2 to 24:1 ratio, preferably a 1:1 to 12:1 ratio.
  • B Sodium arsenite Mixed in a 1:10 to 40:1 ratio, preferably a 1:5 to 25:1 ratio.
  • G Ammonium sulfamate Mixed in a 1:1 to 100:1 ratio, preferably a 1:1 to 50:1ratio.
  • uracils of this invention can be mixed with other substituted uracils, in the respective proportions listed below. Methods for the preparation of the listed uracils can be found in copending applications Serial Nos. 159,746, filed December 15, 1961; 167,434, filed February 1 1 1, 1962; 89,673, filed February 16, 1961; and 89,672, filed February 16, 1961.
  • the remaining unrecrystallized solid is dissolved in 2360 parts by Weight of absolute alcohol containing 248 parts by weight of sodium methoxide, and is refluxed for 10 minutes.
  • the solvent is stripped at reduced pressure and the residue dissolved in water, cooled, and acidified.
  • the solid is filtered 01f, dried, and recrystallized from ethanol to give the desired 3-isopropyl-5,6-trimethyleneuracil, melting at 222223.5 C.
  • Example 2 Preparati0n of 3-cycl0hexyl-5,6- trimethyleneuracil
  • a mixture of 343 parts by weight of ethyl Z-cyclopentanone-l-carboxyl-ate, 284 parts by weight of cyclohexylurea, 10 parts by weight of p-toluene sulfonic acid, and 1750 parts by weight of xylene is stirred at reflux for 6 hours. During this time the Water given off by the reaction is trapped out. The solvent is stripped from the resulting solution at reduced pressure. The residue is then dissolved in 793 parts by weight of absolute ethyl alcohol.
  • Example 3 Preparati0n of 3-allyl-5,6- trimethyleneuracil To a warm stirred slurry of 300 parts by weight of allylurea and 1758 parts by weight of benzene is added a solution of 40 parts by weight .of 100% phosphoric acid in 468 parts by weight of ethyl 2-cyelopentanone-l-carboxylate. The slurry is refluxed for 16 hours during which the water given off .by the reaction is trapped out.
  • the resulting solution is decanted and concentrated to an oil.
  • a solution of 180 parts by weight of sodium methoxide in 1400 parts by weight of ethyl alcohol is added to this oil and the mixture is refluxed for ten minutes. The solution is then concentrated to dryness and the residue dissolved in 2000 parts by weight of water.
  • aqueous basic solution is extracted free of neutral impurities with 1500 parts by weight of ether. It is then cooled and acidified to a pH of 2 with hydrochloric acid. Solid, white 3-allyl-5,-6-trimethyleneuracil, melting at 163.5-166 C., precipitates, which is filtered and dried.
  • n-Butylurea 162 3-n-butyl-5,G-trimethylcneuracil.
  • n-I-Iexylurea 162 3-n-hexyl-5,(i-trimethyleneuracil.
  • Isooctylurea 162 3-iso0ctyl-5 ,fi-trirnethyleneuracil.
  • a-Naphthylurea 162 3-(a-naphthyl)-5.6-trimethylene uraei Tcrt-butymrea 116 Ethyl 2 cyelohexanonel-carboxylate... 187 3-tert.-butyl-5,6-tetramethyleneuracil.
  • n-Octylurea 172 .dO 187 3-n-octyl-5,6-tetrarnethyleneuracl Cyclooctylurea Methyl 2-cyclopentanone-1-carboxylate.. 156 3-eycloocty1-5,G-trimethylene uracil.
  • Cyclopentylurea 128 Ethyl 2-cyclohexanone-l'carboxylate... 187 3-cyclopentyl-5,6-tetramethyleneuracil.
  • urac Isopropylurea 102 ...do 162 3-is pr lipyl-5,fi-pentamethyleneuraci n-Amylurea 130 Ethyl 2'cycloheptanone-Lcarboxylate 202 3-n-am yl-5,fi-pentamethylene- 1112101 Bromonorbornylurea 231 ..do 202 3-bromonorb0rnyl-5,6-pentamethyleneuracil. Cyeloheptenylurea 156 do 202 3-cyeloheptenyl-5,6-pentamethyleneuracil. Norbornylurea 152 Methyl 2-cyclopentanone-l-carboxylate.
  • denyl)urea methandS-indenyl)-5,6-trimethyleneuraeil. 1 (3a,4,5,6,7,7a-hexahydr0-5-indeny1)-urea- 196 Ethyl 2-cyclohexanone-Lcarboxylate. 187 3-(3a,4,5,6,7,7a-hexahydr0-5-in.
  • Example 5 Preparati0n of 3-is0pr0pyl-5,6- trimethyleneuracil, barium salt
  • a mixture of 194 parts by weight of 3-isopropyl-5,6- trimethyleneuracil, 600 parts by Weight of methyl alcohol, and 54 parts by Weight of sodium methoxide is stirred until the components are completely dissolved.
  • To this mixture is added a solution of 224 parts by weight of barium chloride dihydrate in 1000 parts by Weight of 5 water. The resulting solution is quickly filtered free of foreign matter. A 'White solid gradually separates and is filtered off. This is 3-isopropyl-5,6-trirnethyleneuraoil, barium salt.
  • trimethyleneuracil and 865.8 parts of a one-molar solution of tetrabutylammonium hydroxide in methanol is stirred and heated slightly until solution is complete.
  • the solvent is removed by distillation under reduced pressure.
  • the resulting white solid is essentially pure 3-cy-clohexyl-S,6-trimethyleneuracil, tetrabutylamrnonium salt.
  • quaternary ammonium salts can be similarly prepared by reacting equivalent amounts of an appropriately substituted uracil and a suitable quaternary ammonium hydroxide.
  • the following compounds can be prepared in this fashion:
  • trimethyleneuracil-piperidine addition compound A mixture containing one part of 3-(2-methylcyclohexyl)-5,G-trimethyleneuracil and 20 parts of piperidine is stirred and gently heated until a clear solution is obtained.
  • butyl-5,6-tetrametlzyleneuracil with phenol A mixture of 222 parts of 3-sec.-butyl-5,6-tetramethyleneuracil and 94 parts of phenol is gradually heated until a clear melt forms. The liquid is stirred to assure complete mixing and is then allowed to cool.
  • Example 10 Preparation of the complex of 3-sec.-butyl- 5,6-tetramethyleneuracil with p-chlorophenol
  • a mixture of 222 parts of 3-sec.-butyl-5,G-tetramethyleneuracil and 128 parts of p-chlorophenol is gradually heated until a clear melt forms.
  • the liquid is stirred and allowed to cool.
  • the resulting solid is recrystallized twice from cyclohexane.
  • the resulting white p-chlorophenol complex of 3-sec.butyl-S,fi-tetramethyleneuracil melts at 9193 C.
  • Example 12 A queous dispersion The following ingredients (except the water) are mixed, micropulverized, blended with the water and then sand ground until the particles of active material are less than 5 microns in diameter:
  • This stable suspension when diluted with water and when applied at the rate of 25 pounds of active ingredient per acre in 100 gallons of water, gives excellent control of such annual weeds as crab grass, foxtail, wild rye, wild barley, bachelor buttons, and lambs-quarters growing in a parking lot.
  • Example 13 A qneous suspension The following ingredients are mixed and pebble-milled or sand-milled until substantially all the particles of the active material are under 5 microns in size. The resulting stable thixotropic suspension does not cake on storage and is readily diluted with water to form a very slow settling suspension which requires no agitation during application.
  • This suspension when applied as a directed spray at 2 pounds of active ingredient per acre in 30 gallons of water, gives good pre-emergence control of crab grass, mustard species, lambs-quarters, and rice grass germinating in sugar cane.
  • Example 14 -A qneous solution Percent 3-sec.-butyl-5,6-tetramethyleneuracil 20 Piperidine 80 The components are mixed together at room temperature until a clear solution is formed. Ths solution is extendable with water.
  • the sixty gallons are sprayed on an area of one acre along roadsides. Excellent kill and residual control of such species as wild oats, cheatgrass, annual bluegrass, crab grass, foxtails, ryegrass, filaree, wild mustard, and beggar tick is obtained.
  • the mix is wet-milled until all particles are below 10 microns in size.
  • the pH of the slurry is then adjusted to about 8.5.
  • This formulation gives exceptional control of vegetation around Warehouses and industrial sites. It is dispersed in suflicient water to give good coverage of the area to be sprayed. Applied at the rate of 30 pounds of active ingredients per acre, it gives good control of existing weeds and keeps the area weed-free. Good control of such troublesome weeds as crabgrass, fall panicum, mares tail, goatweed, smartweed, spotted spurge, morning glory, ragweed, pigweed, lambs-quarters, buttonweed, foxtail, broomsedge, and Russian thistle is obtained.
  • Example 16 Emulsifiable oil An emulsifiable oil is prepared by mixing the components to give a homogeneous solution. This solution can then be emulsified in water for application.
  • This emulsifiable oil is useful for directed postemergence weed control in cotton at lay-by. When applied at 2 pounds of active ingredient per acre in 30 gallons of water, it gives excellent control of germinating annual weeds such as crab grass, cockleburr, and water grass.
  • Example Z7.Emulsifiable oil suspension The following components are mixed together and milled in a roller mill, pebble mill, or sand mill until substantially all the particles of the active component are under 10 microns in size. The resulting suspension may be emulsified in Water or diluted further with weed oils for spray application.
  • Parafiinic hydrocarbon (at least 90% unsulfonatable) 72.0 Soya lecithin 3.0
  • This formulation is dispersed in 80 gallons of diesel oil and sprayed, in a blanket treatment, on vegetation and bare areas along railroad ballast. It is sprayed at a rate of 30 pounds of active ingredients per acre. Good control of Bermuda grass, ragweed, goldenrod, smartweed, seedling Johnson grass, spotted spurge, dogbane, and flower-of-an-hour is obtained.
  • Example 20 Oil dispersion Percent 3-sec-butyl-5,6-trimethyleneuracil 20.0 2-(2,4,5-trichlorophenoxy)propionic acid 5.0 Diesel oil 75.0
  • This formulation is used for the control of a wide variety of woody and herbaceous perennial weeds and grasses along highway rights-of-way. Dispersed in No. 2 fuel oil, it is sprayed at -20 pounds per acre of active ingredients on dense growths of weeds and brush on highway shoulders. Honeysuckle, brambles, water grass, goldenrod, ragweed, leafy spurge, seedling sassafras, maples, sweet gum, and poison ivy are controlled,
  • Example 21 -Oil dispersion Percent 3-cyclohexyl-5,6-tetramethyleneuracil 20.0 2,3,6-trichlorobenzoic acid 10.0 Diesel oil 70.0
  • This formulation is dispersed in 100 gallons of herbicidal oil and sprayed along an oil pipeline at the rate of 30 pounds of active ingredients per acre. Excellent control of leafy spurge, bindwced, panic grass, big bluestem, purpletop, poison ivy, quack grass, seedling oaks, maples, sweet gum, ragweed, goldenrod, honeysuckle, and brambles is obtained. The area is kept clear of troublesome weeds for an extended period.
  • Example 22 --Oil-extendable formulation Percent 3-sec.-butyl-5,6-tetramethyleneuracil 1 1 complex with phenol 75.0 Soya lecithin 2.6 Calcined montmorillonite clay (Pikes Peak clay) 22.4
  • uracil-phenol complexes can be formulated in a like manner, and when used in hcrbicidally equivalent amounts, will give excellent results:
  • a wettable powder is prepared with these ingredients by blending and micropulverizing them.
  • Example 24 Tank mix A wettable powder is prepared by blending and micropulverizing the following components:
  • This wettable powder and an emulsifiable oil containing 6 pounds per gallon of N,N-dipropylthiolcarbamic acid, ethyl ester are added to a spray tank to form a dilute mixture, in water, of to 1%. pounds of uracil formulation and /2 gallon of the ester formulation per gallons.
  • This dilute suspension-emulsion is applied at the volume rate of 100 gallons per acre to spring-seeded alfalfa. Good control of such weeds as checkweed, smartweed, portulaca, penny Cress, yellow rocket, shepherds purse, ragweed, redroot pigweed, crab grass, annual bluegrass, and henbit is obtained.
  • Example 25 -Tank mix Percent 3-sec.-butyl-5,6-trimethyleneuracil 60.0 Mixed polyoxyethylene esters of fatty acids and oilsoluble petroleum sulfonates 5.0 Attapulgite clay 35.0
  • An oil-dispersible powder of these ingredients is prepared by blending and then grinding them to a particle size of less than 50 microns.
  • a wettable powder is prepared by blending the components and then micropulverizing them until the particles of the active ingredient are substantially all under 50 microns in size, and then reblending to homogeneity.
  • this formulation When applied at 1 pound of active ingredient per acre in 40 gallons of water, this formulation gives excellent pre-emergence control of crab grass, foxtail, cocklebur, lambs quarters, and burdock in a newly planted field of cotton.
  • One to three pounds of active ingredient per acre gives good weed control in asparagus, sugar cane, and pineapple.
  • One to two pounds per acre gives excellent pre-emergence control annual weeds such as crab grass, foxtail, wild mustard, ryegrass, and velvetleaf in a newly planted field of spinach.
  • uracils can be similarly formulated, and when use in herbicidally equivalent amounts, will give good general weed control:
  • Example 28 -Wettable powder The following components are blended, then micropulverized until substantially all the solids are under 50 microns in particle size, then reblended to homogeneity:
  • Example 29 Wettable powder
  • the following powder is prepared in the same manner as Example 28, but in addition is passed through an air 22 attrition m-ill, such as an air-reductionizer, to reduce the particle size to under 10 microns:
  • Percent 3-tert.-butyl-5,G-trimethyleneuracil 80.0 Dioctyl sodium sulfosuccinate concreted with sodium benzoate (Aerosol OTB) Partially desulfonated sodium lignin sulfonate Calcined, non-swelling montmorillonite type clay (Pikes Peak clay)
  • This composition is used for pre-emergence application in agricultural crops such as sugar cane, asparagus, and safflower. It is dispersed in gallons of water and sprayed with a pressure sprayer. At 0.5 to 2.0 pounds of active ingredient per acre, excellent control of pigweed, lambs-quarters, purslane, mustard, crab grass, foxtail, and water grass is obtained.
  • Example 30 Wettable powder The following are blended, then micropnlverized until the particles are below microns in diameter, and reblended:
  • Each of the following uracils can be similarly formulated and applied in gallons of herbicidal oil. At rates of 2030 pounds (active) per acre, they will give good Weed control.
  • This wettable powder is prepared by blending the components and then micropulverizing the mixture until the particles are under 50 microns in size.
  • This formulation is dispersed in water and sprayed preemergence at 5 pounds of active ingredients per acre on a planting of red table beets. Excellent control of crab grass, chickweed, annual morning glory, carpetweed, purslane, smartweed, lambs-quarters, ragweed, black nightshade, giant foxtail, and velvet leaf is obtained. The crop shows no visible injury.
  • Example 33 Wettable powder Percent 3-sec.-butyl-5,6-trimethyleneuracil 40.0 3-(4-chlorophenyl)-1,l-dimethylurea 20.0 Alkyl naphthalene sulfonate, Na salt 1.5 Low viscosity methyl cellulose 0.5 Attapulgite clay 38.0
  • a wettable powder is prepared by blending these components and then micropulverizing the mixture until the particles are below 50 microns in size.
  • This formulation controls weeds along railroad rightsof-way. Applied in the spring in about 100 gallons of water and at the rate of pounds of active ingredients per acre, the formulation gives good control of annual ryegrass, bromegrass, ragweed, henbit, goldenrod, field daisy, buckhorn, plantain, water grass, and volunteer rye.
  • Example 34 Wettable powder Percent 3-cyclohexyl-5,6-tetramethyleneuracil 40.0 2-chloro-4-ethylamino-6-isopropyl-amino-s-triazine 20.0
  • a wettable powder is prepared by blending these ingredients and then grinding them until the particles are below 50 microns in size.
  • a tractor-mounted sprayer which sprays four rows at a time is used to apply this formulation to a field of potatoes, before the potatoes emerge.
  • the formulation is used at a rate of 3 pounds of active ingredients per acre.
  • Such weeds as crabgrass, chickweed, smartweed, purslane, giant foxtail, annual morning glory, Johnson grass seedlings, barnyard grass, bedstraw, and henbit are controlled without visible injury to the potatoes. Excellent yields of potatoes are obtained, with minimum cultivation.
  • Example 35 -Wettable powder Percent 1-(3,4-dichlorophenyl)-3,3-dimethylurea 80.00 Low viscosity methyl cellulose 0.25 Alkyl naphthalene sulfonic acid, sodium salt 1.75 Disodium phosphate 0.80
  • Example 36 Pellets Percent 3-cyclohexyl-5,6-tetramethyleneuracil 25 Anhydrous sodium sulfate 10 Sodium lignin sulfonate 10 Ca, Mg bentonite 3-cyclopropyl-5,6-tetramethyleneuracil 3- (chloronorbornyl -5,6-tetramethyleneuracil 3 -cyclopentyl-5 ,6-tetramethyleneuracil 3-r1orbornyl-5,6-tetramethyleneuracil 3-indenyl-5 ,6-tetramethyleneuracil 3-naphthylmethyl-5,6-trimethyleneuracil 3 (p-cumyl -5, 6-trimethyleneuracil 3- (3 ,4,5-trichlorophenyl -5,6-tetramethyleneuracil 3- (4-isopropylcyclohexyl -5 ,6-tetramethyleneu ra cil 3-(de
  • trimethyleneuracil Example 37 Pellets Percent 3-cyclohexyl-5,6-trimethyleneuracil 4 3-(p-chlorophenyl)-1,1-dimethylurea 2 Kaolin clay 37 Mississippi sub-bentonite clay 37 Sodium sulfate 10 Sodium lignin sulfonate 10 These ingredients are blended, micropulverized, pugmilled with 17%20% water, and then extruded through -inch die holes. The extrusions are cut into A -inch lengths and dried.
  • This formulation controls annual grasses and herbaceous broadleaved weeds in asparagus beds.
  • the pellets are distributed evenly over the top of the beds at a rate of 3 pounds of active ingredients per acre just before the cutting season begins and again at the end of the cutting season.
  • Excellent control of crabgrass, blackeyed Susan, beggar-ticks, prickly lettuce, ragweed, barnyard grass, green foxtail, pigweed, and fall panicum is obtained.
  • Example 38 Percent 3-isopropyl-5,6-trimethyleneuracil 3.33 Phenyldimethylurea 6.67 California sub-bentonite clay 80.00 Sodium sulfate, anhydrous 10.00
  • This formulation is used to control all vegetation in a fire lane.
  • the pellets are distributed from the air in remote areas of the fire lane at the rate of 40 pounds of active ingredients per acre. Excellent control of elm, sweet gum, oaks, maples, brambles, goldenrod, blackeyed Susan, and honeysuckle is obtained.
  • Example 39 Pellets Percent 3-cyclohexyl-5,6-trimethyleneuracil 6.67 3-sec.-butyl-5-chloro-6-methyluracil 3.33 Sodium sulfate, anhydrous 10.00 California sub-bentonite clay 80.00
  • This formulation keeps lumber yards free of weeds.
  • the pellets are distributed in the spring with a seeder at pounds (actives) per acre.
  • the lumber-yard stacking area is kept free of such pernicious weeds as crabgrass, ragweed, pigweed, Russian thistle, fall panicum, goat weed, cheatgrass, and seedling Johnson grass.
  • Example 40 -Granules Percent 3-isopropyl-5,6-trimethyleneuracil, Na salt 5 8-15 mesh granular, expanded vermiculite 95
  • This granular composition is prepared by dissolving the active material in water and spraying it upon the granules while they are being tumbled. The granules are then dried.
  • Granular 8-15 mesh attapulgite clay 96 These granules are applied by hand or by special spreaders at 2.5 pounds of active ingredient per acre for the pre-emergence control of annual weeds in potatoes. They control crabgrass, chickweed, barnyard grass, goose grass, foxtail, velvetleaf, and germinating Johnson grass without visible inujry to the crop.
  • Example 42 The following components are blended and micropulverized, then moistened with water and granulated. The granules are then dried and screened.
  • Non-swelling sub-bentonite clay 86 The granules are applied with a granule spreader at 3 pounds of active ingredient per acre for pre-emergence control of annular weeds in asparagus.
  • potassium salt 5 Preformed attapulgite clay granules, +8 to +15 mesh A granular composition is prepared with these components 'by dissolving the active material in water and spraying it upon the granules while they are being tumbled. The granules are then dried.
  • uracil salts can be substituted for the 3- chloronorbornyl-5,6-pentamethyleneuracil, potassium salt. When applied at equivalent rates, good weed control is observed.
  • potassium salt 3-isoamyl-5,6-tetramethylene-Z-thiouracil, potassium salt 3-allyl-5,6-pentamethyleneuracil, potassium salt 3-(2-decyl)-5,6-trimethyleneuracil, lithium salt 3-methyl-5,fi-trimethyleneuracil, lithium salt 3-sec.-butyl-5,6-tetramethyleneuracil, lithium salt 27
  • the ingredients are blended and micropulverized, then pug-milled with to water, and moist-granulated. After drying, the granules are screened to 8-30 mesh.
  • Example 45 Granules Percent 3-isopropyl-5,6-trimethyleneuracil 2.00 Polyoxyethylene tall oil acid ester 0.02
  • the surfactant and uracil are first mixed and micropulverized, then suspended in water and sprayed on the remaining granular components While they are being tumbled.
  • Example 46 Granules Percent 3-cyclohexyl-5 ,6-trimethyleneuracil 1.0 Trichloroacetic acid, sodium salt 3.0
  • Example 47 Waler-s0luble powder Percent 3- Z-methoxyethyl -5 ,6-pentamethyleneuracil Sodium silicate 74 Sodium dioctyl sulfosuccinate 1 These components are blended. and micropulverized.
  • a method for the control of undesirable vegetation comprising applying to a locus to be protected from such vegetation a herbicidally effective amount of a compound selected from the group consisting of (a) compounds of the formula 28 where:
  • R is selected from the group consisting of alkyl of 1 through 10 carbon atoms, substituted alkyl of 1 through 10 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, dialkylamino, and cyano, aryl of 6 through 14 carbon atoms, substituted aryl of 6 through 14 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, phenyl, alkoxy, alkyl, nitro, trifiuoromethyl, 1,2- tetramethylene, and 1,2-trimethylenylene, aralkyl of 7 through 15 carbon atoms, substituted aralkyl of 7 through 15 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, alkyl, nitro, and alkoxy, tetrahydronaphthylalkyl, alkenyl of 3 through 10 carbon atoms,
  • herbicidal active compound is 3-cyclohexyl-5,6-trimethyleneuracil.
  • herbicidal active compound is 3-isopropyl-5,6-trimethy1eneuracil.
  • herbicidal active compound is 3-sec-butyl-5,6-tetramethyleneuracil.
  • herbicidal active compound is 3-cyclohexyl-5,6-tetramethyleneuracil.
  • herbicidal active compound is 3-isopropyl-5,6-trimethyleneuracil, sodium salt.
  • herbicidal active compound is 3-cyclohexyl-5,6-trimethyleneuracil potassium salt.
  • a method for the control of undesirable vegetation comprising applying to a locus to be protected from such vegetation a herbicidally effective amount of a compound selected from the group consisting of (a) compounds of the formula it i where R is selected from the group consisting of alkyl of 1 through 10 carbon atoms,
  • substituted alkyl of 1 through 10 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, dialkylamino, and cyano,
  • substituted aryl of 6 through 14 carbon atoms wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, phenyl, alkoxy, alkyl, nitro, trifluoromethyl, 1,2- tetramethylene, and 1,2-trimethylenylene,
  • substituted aralkyl of 7 through 15 carbon atoms wherein said substituent is selected from the group consisting of chlorine, alkyl, nitro, and alkoxy,
  • substituted cycloalkyl of 3 through 12 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,
  • substituted cycloalkenyl of 4 through 12 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,
  • X is selected from the group consisting of oxygen and sulfur; and n is a number 3 through 5;
  • R and n are as defined above, and 15 NB is a nitrogenous base having an ionization constant K l0 in water; and (d) compounds of the formula H o Z 0 ll RN @ECHDD H O ⁇ N p 111-1 where R and n are as defined above, Z is selected from the group consisting of hydrogen,
  • R is an alkyl of 1 through 3 carbon atoms
  • Y is selected from the group consisting of chlorine and alkyl of 1 through 3 carbon atoms; in is a number 1 through 5; and
  • p is selected from the group consisting of /2, 1 and 2.

Description

United States Patent ()iifiee 3,235,360 Patented Feb. 15, 1966 This invention relates to 3-substituted-5,6-alkylene uracils and to compositions and methods employing these compounds as herbicides.
More particularly, this invention is directed to the herbicidal use of compounds of the formula 1 O O O u 1 RN RN m cro 2 Benin EX where R is alkyl of 1 through carbon atoms, substituted alkyl of 1 through 10 carbon atoms, aryl of 6 through 14 carbon atoms, substituted aryl of 6 through 14 carbon atoms, aralkyl of 7 through carbon atoms, substituted aralkyl of 7 through 15 carbon atoms, alkenyl of 3 through 10 carbon atoms, alkynyl of 3 through 10 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, cycloalkenyl of 4 through 12 carbon atoms, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of 5 through 13 carbon atoms, (substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, (substituted cycloalkenyhalkyl of 5 through 14 carbon atoms, or cyano;
X is oxygen or sulfur; and
n is 3, 4, or 5.
The salts of these compounds can also be used accord ing to this invention. By salts are meant those compounds formed with such cations as sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese and quaternary ammonium.
The uracils of Formula 1 also form novel 1:1 addition compounds with excesses of certain nitrogenous bases. The exact structure of these compounds is not known. Although the compounds are, generally speaking, poorly soluble in water, they are, according to the best available information, believed to be essentially salt-like in structure. They will be symbolized by the following formula, with the understanding that it is representative only, and is not intended to illustrate actual structure:
where R is defined as in Formula 1, n is 3, 4, or 5, and NB is a nitrogenous base having an ionization constant K of IO- in water. Suitable nitrogeneous bases are substituted, unsubstituted, cyclic and acylic Amines, Amidines, and Guanidines The amines can be primary, secondary or tertiary amines, polyamines, arylamines, or heterocyclicarnines. Illustrative of such amines are:
Ethanolamine Dodecylamine Ethylenediamine Hexamethylenediamine Cocoadiamine Tallowdiamine Hexamethyleneimine Cyclohexylamine Methoxypropylamine Methylamine Dimethylamine Trimethylamine Ethylamine Propylamine Butylamine Octylamine Pyridine Piperidine Tetramethylguanidine Acetamidine Benzylamine Diethylenediamine Z-aminobutanol-l 2-aminooctanol-1 Sec.-butylamine 2-amino-2-methyl-1,3 propanediol Trimethylenediamine Some of the uracils of Formula 1 also form Water stable,
novel complexes with phenol and substituted phenols. These complexes have the formula where R is as defined in Formula 1,
Z is hydrogen, chlorine, nitro, alkyl of 1 through 3 carbon atoms, bromine or OR (where R, is alkyl of 1 through 3 carbon atoms),
Y is chlorine or'alkyl of 1 through 3 carbon atoms,
In is a number 1 through 5,
n is 3, 4 or 5, and
p is /2, 1 or 2.
These complexes are also herbicidal, and in this respect, have some advantages over the uracils per se, viz., higher solubility in oils and solvents. They are formulated into herbicidal compositions in the same way as are the uracils themselves.
This invention is also directed to novel uracils, within the scope of Formula 1. These uracils are of the formula R is substituted or unsubstituted cycloalkyl radical containing 3 through 10 carbon atoms, a substituted or unsubstituted cycloalkenyl radical containing 4 through 10 carbon atoms, or a B1 CRz a radical, where R is methyl or ethyl, R is an alkyl radical containing 1 through carbon atoms, and R is hydrogen or methyl, and n is 3, 4 or 5.
To be included in this formula, as defined for Formula 1, are the salts of these compounds.
In Formulae 1 to 4 the term substituted alkyl is intended to include such radicals as Bromoalkyl of 1 through carbon atoms, Chloroalkyl of 1 through 10 carbon atoms, Hydroxyalkyl of 1 through 10 carbon atoms, Alkoxyalkyl of 2 through 12 carbon atoms, Alkoxy carbonyl alkyl of 3 through 12 carbon atoms, Dialkyl amino alkyl of 3 through 12 carbon atoms, and Cyanoalkyl of 2 through 10 carbon atoms.
Similarly, the terms aryl and substituted aryl embrace radicals such as The terms aralkyl and substituted aralkyl are intended to include such radicals as Furfuryl,
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 Naphthylmethyl.
The terms cycloalkyl, cycloalkenyl, cycloalkyl alkyl, and cycloalkenyl alkyl will incude Cyclopropyl,
Cyclohexyl,
Cyclohexenyl,
Cyclohexylalkyl,
Cyclohexenyalkyl,
Cyclopentyl,
Cyclopentenyl,
Cylclopentylalkyl, Cyclopentenylalkyl,
Norbornyl,
Norbornenyl,
Norbornenylalkyl, Bicyclo(2,2,2)octyl, Bicyclo(2,2,2)octenyl,
Bicyclo (2,2,2) octylalkyl, Bicyclo(2,2,2)octenylalkyl, Cyclopropyl,
Cyclobutyl,
Cyclobutylalkyl,
Cyclobutenyl,
Cyclobutenylalkyl,
Hexahydroindanyl, Tetrahydroindanyl, HeXahydroindenyl,
Hexahydroindenyl alkyl, Tetrahydroindanyl alkyl, I-Iexahydroindanyl alkyl, Hexahydro-4,7-methanoindenyl, Tetrahydro-4,7-rnethanoindanyl, Hexahydro-4,7-methanoindanyl, Hexahydro-4,7-methanoindanyl alkyl, Tetrahydro-4,7-methanoindanyl alkyl, HeXahydro-4,7-methanoindanyl alkyl, Decahydronaphthyl, Decahydronaphtyl alkyl, Decahydronaphthyl alkyl, Tetrahydronaphthyl, Tetrahydronaphthyl alkyl, Decahydro-1,4-methanonaphthyl, Decahydro-1,4-methanonaphthyl alkyl, Octahydro-l,4-methanonaphthyl, Octahydro-l,4-methan0naphthyl alkyl, Decahydro-1,4-5,S-dimethanonaphthyl, Decahydro-1,4-5 ,S-dimethanonaphthyl alkyl, Octahydro-l,4-5,8-dimethanonaphthyl, and Octahydro-1,4-5,8-dimethanonaphthyl alkyl.
These cyclic substituents can be further substituted with alkyl groups containing 1 through 4 carbon atoms, methoxy, chlorine and bromine.
UTILITY The uracils of Formulae 1 through 4 represent a new class of herbicides offering farmers and property owners a new and effective method for the control of undesirable vegetation.
Certain of these uracils exhibit selective action in crops. By properly selecting a uracil of the invention and a rate and time of application, weeds growing in fields of such economic crops as corn, cotton, asparagus, sugar beets, red beets, mangels, spinach, potatoes, peanuts and pineapple can be controlled. This selective activity is described in more detail in the examples Which follow.
These compounds are also useful for general weed control on industrial sites, railroad rights-of-Way, and areas adjacent to croplands.
The concentrations at which the compounds of this invention are to be used will vary according to the result desired, the type of vegetation, the formulation used, the mode of application, weather conditions, foliage density, and other similar factors. Since so many factors play a role, it is not possible to indicate a concentration suitable for all situations. Generally, when they are used for preemergence treatment in crops, these uracils are used at concentrations of at least about 0.5 pound of active ingredient per acre. Concentrations of from 0.5 to 3 pounds per acre are preferred.
When used in non-crop applications, the uracils are used at concentrations of from to 30 pounds of active ingredient per acre. The optimum concentrations to be used in any particular application Will be readily apparent to one skilled in the art.
The preferred compounds for use according to this invention are the compounds of Formula 1 where R is an alkyl or alkenyl radical containing 3 through 6 carbon atoms, phenyl, substituted phenyl, cycloalkyl radical of 3 through 10 carbon atoms or cycloalkenyl radical of 4 through 10 carbon atoms,
X is oxygen, and
n is 3, 4, or 5,
and their sodium, and potassium salts, nitrogenous base addition compounds and phenol complexes.
PREPARATION OF COMPONDS The substituted ur-acils of Formula 1 can be prepared according to the following equations:
In Equations 5 and 6 R, X, and n have the same meaning as in Formula 1; R is an alkyl radical of 1-6 carbon atoms, H+ is an acid, and B is a base.
The reaction sequence consists of two steps: first, the acid catalyzed condensation of a l-substituted urea or thiourea with an alkyl 2-cycloalkanone-l-carboxylate to give the ureido intermediate; and, second, the alkaline ring closure of this intermediate to the salt of the uracil product, followed by treatment with acid to liberate the free uracil.
The first step, illustrated by Equation 5, is best carried out by dissolving or suspending the l-substituted urea or thiourea in a solvent such as xylene, benzene or a 6 mixture of benzene and dioxane, and heating to reflux. To this solution is then added a mixture of the acid catalyst in slight excess of the alkyl 2-cycloalkanone-l-carboxylate. Suitable acid catalysts are phosphoric, poly- 5 phosphoric, formic, chloroacetic, or Lewis acids such as BF}; and AlCl The mixture is stirred and heated to reflux until the water, split out during the reaction and collected in a suitable apparatus, ceases to be given off. The clear solution is decanted or filtered and then con- 10 centrated to give the intermediate ureido derivative.
In the second step, illustrated by Equation 6 the ureido intermediate is dissolved in alcohol containing a slight excess of base, preferably an alkali metal alkoxide or hydroxide, and the solution is refluxed for a short time.
1 This step effects the ring closure. The salt of the uracil is obtained by concentrating this solution to dryness. The free uracil is prepared by acidifying an aqueous solution of the salt, and then isolating the solid.
These compound can also be prepared as described in Archives of Biochem. and Biophys, 83, 141 (1959).
The salt of the compounds of Formula 1 are prepared by conventional methods such as dissolving the free uracil in an aqueous or nonaqueous solution of at least an equimolar amount of a base or basic salt containing the desired cation. For example, a sodium salt can be prepared by dissolving the uracil in water containing an equimolar amount of sodium hydroxide. The salt can then be isolated from the solution by removal of the water. The uracil salts which are not soluble in water can be prepared by treating an aqueous solution of an alkali metal salt of the uracil with an aqueous solution of a water-soluble salt of the metal.
The quaternary ammonium salts of the compounds of Formula 1 are prepared by reacting the substituted uracil with an appropriate quaternary ammonium hydroxide.
Since these hydroxides are generally available in solution, the reaction is most conveniently carried out in the same solvent. It the solventafree salt is desired, it can be easily prepared by removing the solvent.
Alternatively, the quaternary ammonium salts of the uracils can be prepared in a dry inert solvent such as toluene or xylene. The sodium salt of the uracil is first prepared and appropriate quaternary ammonium halide is then added with stirring and, if necessary, mild heating. The sodium halide which forms is removed by filtration, leaving the quaternary ammonium salt of the uracil in solution. If desired, the solvent-free salt can be prepared by removing the solvent, preferably in vacuo.
The nitrogenous base-uracil addition compounds of Formula 2 are prepared by mixing an appropriate uracil with a 4 to 20-f0ld weight excess of nitrogenous base. The mixture is heated gently until a clear solution forms.
The addition compounds thus formed are stable in the presence of excess amine and can be diluted with suitable solvents for herbicidal applications.
The complexes of Formula 3 are formed by co-melting a uracil and a phenol in a 1:2. to 2:1 (uracilzphenol) ratio. They can also be formed by co-dissolving the reactants, in the same ratio, in a nonpolar solvent such as nitromethane or a mixture of nitromethane and cyclohexane.
When the phenol complexes are formed by co-melting, it is not necessary to purify them further for herbicidal uses. If solvents are used in their preparation, they can be isolated by filtration or evaporation of the solvent. The complexes so obtained are also suitable for herbicidal use without further purification.
HERBICIDAL COMPOSITIONS The uracil compounds described in Formulae 1 through 4 can be prepared for use by incorporating them with adjuvants.
The amount of herbicide in such preparations can vary 7 over a wide range according to need. Generally speaking, they will contain from about 0.5% to 95%, by weight of a uracil.
Powder and dust preparations can be made by mixing uracils of the invention with finely-divided solids such as talcs, natural clays, pyrophyllite, diatomaceous earth; flours such as walnut shell, wheat, redwood, soya bean and cotton seed; or inorganic substances such as magnesium carbonate, calcium carbonate, calcium phosphate, sulfur and lime. These preparations are made by thoroughly blending the active ingredient and the solid. The particles in such preparations should be less than 50 microns in average diameter, preferably about 20 microns.
Water-soluble powders can be prepared by blending a suitable uracil with such water-soluble alkaline powders as silicates, carbonates, phosphates or hydroxides, and optionally with water-soluble diluents such as urea or dextrose.
Granules and pellets can be be made by mixing a finely-divided uracil with a suitable clay such as kaolinite, montmorillonite or attapulgite, moistening this mixture with from 15 to 20% by weight of water, and then extruding the mass through a suitable die under pressure. The extrusions are cut into pro-determined lengths and then dried. These pellets can be granulated if desired.
Granules or pellets can also be prepared by spraying a suspension or solution of a uracil onto the surface of a preformed granule of clay, vermiculite or other suitable granular material. If the uracil is in solution, it will penetrate into the pores of the granules and so will adhere without the aid of a binding agent. When the active material is insoluble in the liquid and is carried as a suspension, it is preferable that a binding agent such as goulac, dextrin, swollen starch, glue or polyvinyl alcohol be added. In either case, the granule is then dried and ready for use.
The uracils can also be prepared in liquids. Water and aliphatic and aromatic hydrocarbons, especially those derived from petroleum and having boiling points of from 125 C. to 400 C. are preferred. Hydrocarbons having lower boiling points should not be used because of their undesirable volatilization characteristics and infiammability. These liquid preparations are made by dissolving the active in the liquid, or, if the active is insoluble in the liquid, by milling the components in a mill such as a pebble mill until the particles have average diameters of from 1 to 50 microns, preferably 5 to 20 microns.
The herbicidal preparations, whatever physical form they take, can also contain a surface-active agent. The surfactant renders the preparations readily dispersible in liquids and improves their action on waxy leaves and the like. For general application, surface-active agents are used in the preparations at concentrations of from about 1 to 10% by weight. Levels of from 0.5 to 6 parts of surfactant for each part of uracil, however, give unusual and unexpected results. Preparations having these higher levels of surfactants show greater herbicidal elfectiveness than can be expected from a consideration of activity of the components used separately.
The term surface-active agen is intended to include wetting agents, dispersing agents, suspending agents and emulsifying agents. Surface-active agents suitable for use are set forth in Detergents and Emulsifiers upto-date, 1962, John W. McCutcheon, Inc., Morristown, New Jersey. Other surface-active agents which can be used in these preparations are listed in US. Patents 2,139,- 276; 2,412,510; 2,426,417; 2,655,447; and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the US. Department of Agriculture.
The preparations can also contain adhesives, corrosion inhibitors, antifoam agents, dyes and pigments, anticaking agents, and hard water stabilizers.
The salts of the compounds of Formula 1 are especially advantageous for use as herbicides because many are soluble in water and can be applied as aqueous solutions.
With respect to the nitrogenous base-addition compounds of Formula 2, it has been found that preparation with polar low-molecular weight amines, such as ethanolamines, propanolarnines and butanolamines gives addition compounds which are extendable in water when the amine is present in excess. Other amines, such as piperidine and octanolamines give addition compounds (in an excess of the amine) which are soluble in both water and hydrocarbon solvents. At the other end of the scale, amines such as dodecylamines, oleyldiamines and tallowamines give addition compounds (in the presence of an excess of the amine) with high hydrocarbon solubility.
Thus, it is apparent that by properly selecting an amine and forming an addition compound with it, the compounds of Formula 2 can be formulated as aqueous solutions or as oil-emulsifiable or oil-extendable formulations. In this way, the nitrogenous base-addition compounds give formulation and application advantages, while still maintaining the desirable herbicidal characteristics of the parent uracils.
FORMULATION WITH OTHER HERBICIDES The herbicidal compositions of this invention can be formulated to contain two or more of the uracils. They can also be formulated to contain other known herbicides in addition to the uracils to give compositions which have advantages over the individual components.
Among the known herbicides which can be combined with the uracils are:
SUBSTITUTED UREAS 3- (3 ,4-dichlorophenyl l l-dimethylurea 3 -(4-ch1orophenyl) -1, l-dirnethylurea 3 -phenyl-1,1-dimethylurea 3- 3 ,4-dichlorophenyl -3 -methoxy-1, l-dimethylurea 3-(4-chlorophenyl)-3-methoxy-1,1-dimethylurea 3 (3 ,4-dichlorophenyl) -1-n-butyl-l-methylurea 3- 3 ,4-dichlorophenyl) -1-methoxy-1-methylurea 3-(4-chlorophenyl) -1-methoxy-1-methylurea 3-(3,4-dichlorophenyl)-1,1,3-trimethylurea 3-( 3,4-dichlorophenyl) -1, l-diethylurea 3-(p-chlorophenoxyphenyl)-1,1-dimethylurea These ureas can be mixed with the uracils in proportions of from 1:4 to 4: 1, respectively, the preferred ratio being 1:2 to 2:1.
portions of from 1:4 to 4:1, respectively, the preferred ratio being 1:2 to 2: 1.
PHENOLS Dinitro-o-sec-butylphenol and its salts Pentachlorophenol and its salts These phenols can be mixed with the uracils in the proportions of 1:10 to 20:1, respectively, the preferred ratio being 1:5 to 5:1.
9 CARBOXYLIC ACIDS AND DERIVATIVES The following carboxylic acids and derivatives can be mixed with the uracils in the listed respective proportions:
Mixed in a 1:20 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.
B. 2,6-dichlorobenzonitrile Mixed in a 1:4 to 4:1 ratio, preferably a 1:3 to 3:1 ratio.
C. Trichloroacetic acid and its salts Mixed in a 1:4 to 25:1 ratio, preferably a 1:2 to 10:1 ratio.
D. 2,2-dichloropropionic acid and its salts Mixed in a 1:4 to 10:1 ratio preferably a 1:2 to 5:1 ratio.
E. N,N-di(n-propyl)thiolcarbarnic acid, ethyl ester N,N-di(n-propyl)thiolcarbamic acid, n-propyl ester N-ethyl-N-(n-butyl)thiolcarbamic acid, ethyl ester N-ethyl-N-(n-butyl)thiolcarbamic acid, n-propyl ester Mixed in a 1:2 to 24:1 ratio, preferably a 1:1 to 12:1 ratio.
F. N-phenylcarbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, 4-chloro-2- butynyl ester Mixed in a 1:2 to 24:1 ratio, preferably a 1:2 to 12:1 ratio.
G. 2,3,6-trichlorophenylacetic acid and its salts Mixed in a 1:20 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.
H. 2-chloro-N,N-diallylacetamide Maleic hydrazide Mixed in a 1:2 to 10:1 ratio, preferably a 1:1 to 5:1 ratio.
INORGANIC AND MIXED INORGANIC-ORGANIC SALTS The following salts can be mixed with the uracils in the listed proportions:
A. Calcium propylarsonate Disodiurn monomethylarsonate Octyl-dodecylammoniummethylarsonate Dimethylarsinic acid Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.
B. Sodium arsenite Mixed in a 1:10 to 40:1 ratio, preferably a 1:5 to 25:1 ratio.
C. Lead arsenate Calcium arsenate Mixed in a 150:1 to 600:1 ratio, preferably a :1 to 400:1 ratio.
D. Sodium tetraborate hydrated, granulated Sodium metaborate Sodium pentaborate Polychlorborate Unrefined borate ore, such as borascu Mixed in a 3:1 to 1500:1 ratio, preferably a 6:1 to 1000:1 ratio.
E. Ammonium thiocyanate Mixed in a 1:10 to 20:1 ratio, preferably a 1:5 to 5:1 ratio.
F. Sodium chlorate Mixed in a 1:1 to 40:1 ratio, preferably a 2:1 to 20:1 ratio.
G. Ammonium sulfamate Mixed in a 1:1 to 100:1 ratio, preferably a 1:1 to 50:1ratio.
OTHER ORGANIC HERBICIDES The following herbicides can be mixed with the uracils in the listed respective proportions:
A. 5,6-dihydro-(4A,6A) dipyrido- (1,2A,2',1-C)pyra Zinium dibromide Mixed in a 1:20 to 16:1 ratio, preferably a 1:5 to 5:1 ratio.
B. 3-amino-1,2,4-triazole Mixed in a 1:20 to 20:1 ratio, preferably a 1:5 to 5:1 ratio.
C. 3,6-endoxohexahydrophthalic acid Mixed in a 1:4 to 20:1 ratio, preferably a 1:2 to 10:1 ratio.
D. Diphenylacetonitrile N,N-dimethyl-ot,a-diphenylaceta-mide N,N-di(n-propyl)-2,6-dinitro-4-trifluorornethylaniline N,N-di- (n-propyl)-2,6-dinitro-4-rnethylaniline Mixed in a 1:10 to 30:1 ratio, preferably a 1:5 to 20:1 ratio.
E. O-(2,4-dichlorophenyl)-O-methyl-isopropyl-phosphoramidothioate 2,3,5,6-tetrachloroterephthalic acid, dimethyl ester Mixed in a 1:4 to 20:1 ratio, preferably a 1:3 to 15:1 ratio.
F. 2,4-dichloro-4-nitrodiphenyl ether Mixed in a 1:10 to 30:1 ratio, preferably a 1:5 to 20:1 ratio.
OTHER SUBSTITUTED URACILS The uracils of this invention can be mixed with other substituted uracils, in the respective proportions listed below. Methods for the preparation of the listed uracils can be found in copending applications Serial Nos. 159,746, filed December 15, 1961; 167,434, filed February 1 1 1, 1962; 89,673, filed February 16, 1961; and 89,672, filed February 16, 1961.
3 -isopropyl-5-bromo-6-methyluracil 3 -isopr-opyl-5-chloro-6-methyluracil 3 -sec.-butyl-5-bromo-6-methyluracil 3 -sec.-butyl-5-chloro-6-methyluracil 3 -cyclohexyl-5-bromo-6-methyluracil 3 -cyclol1exyl-5-chloro-6-methyluracil 3 -tert.-butyl-5-bromo-6-methyluracil 3 -tert.-butyl-5-chloro-6-methyluracil Mixed in a 1:6 to 6:1 ratio, preferably a 1:4 to 4:1 ratio.
3 -cyclohexyl-6-methyluracil 3 -cyclohexyl-6-ethyluracil 3 -cyclohexyl-6-sec.-butyluracil '3 -cyclohexyl-6-propyluracil 3-cyclopentyl-6-methyluracil 3 -cyclohexyluracil Mixed in a 1:6 to 6:1 ratio, preferably a 1:4 to 4:1 ratio.
3 -isopropyl-5-bromouracil 3-sec.-butyl-5-bromouracil 3 -sec.-butyl-S-chlorouracil 3 -cyclohexyl-5 -bromouracil 3 -cyclohexyl-5-chlorouracil Mixed in a 1: 4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.
3 -isopropyl-1-trichloromethylthio-S-bromo-6-methyluracil 3 -cyclohexyll-trichloromethylthio-5-bromo-6-methyluracil 3-sec.-butyl-1-acetyl-5-bromo-6-methyluracil 3 -isopropyl-1-acetyl-5-bromo6-rnethyluracil 3 -isopropyll-trichloromethylthio-5-chloro-6-methyluracil Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.
EXAMPLES This invention will be better understood by referring to the following illustrative examples:
PREPARATION OF COMPOUNDS Example I.--Preparation of 3-is0pr0pyl-5,6-trimethyleneuracil A mixture of 404 parts by weight of isopropylurea, 686 parts by weight of ethyl 2-cyclopentanone-l-carboxylate, 40 parts by weight of phosphoric acid, 1000 parts by weight of dioxane, and 879 parts by Weight of benzene is stirred at reflux for 4 hours. During this time, the water given off by the reaction is trapped out. The solvent is stripped at reduced pressure and a portion of the resulting solid is recrystallized from cyclohexane to give 2-(3- isopropylurido)-1-cyclopentene carboxylic acid, ethyl ester.
The remaining unrecrystallized solid is dissolved in 2360 parts by Weight of absolute alcohol containing 248 parts by weight of sodium methoxide, and is refluxed for 10 minutes. The solvent is stripped at reduced pressure and the residue dissolved in water, cooled, and acidified. The solid is filtered 01f, dried, and recrystallized from ethanol to give the desired 3-isopropyl-5,6-trimethyleneuracil, melting at 222223.5 C.
Example 2.Preparati0n of 3-cycl0hexyl-5,6- trimethyleneuracil A mixture of 343 parts by weight of ethyl Z-cyclopentanone-l-carboxyl-ate, 284 parts by weight of cyclohexylurea, 10 parts by weight of p-toluene sulfonic acid, and 1750 parts by weight of xylene is stirred at reflux for 6 hours. During this time the Water given off by the reaction is trapped out. The solvent is stripped from the resulting solution at reduced pressure. The residue is then dissolved in 793 parts by weight of absolute ethyl alcohol.
To this solution is added a mixture of parts by weight of sodium methoxide in 400 parts by weight of absolute ethyl alcohol. The mixture is then refluxed for 10 minutes. The solvent is stripped from this mixture 5 and the resulting solid is dissolved in 3000 parts by Weight of water.
This solution is cooled, acidified with excess hydrochloric acid and the solid is filtered off. Recrystallization of this solid from dirnethylformamide gives light gray crystals of the desired uracil, melting at 3l0-313 C.
Example 3.-Preparati0n of 3-allyl-5,6- trimethyleneuracil To a warm stirred slurry of 300 parts by weight of allylurea and 1758 parts by weight of benzene is added a solution of 40 parts by weight .of 100% phosphoric acid in 468 parts by weight of ethyl 2-cyelopentanone-l-carboxylate. The slurry is refluxed for 16 hours during which the water given off .by the reaction is trapped out.
The resulting solution is decanted and concentrated to an oil.
A solution of 180 parts by weight of sodium methoxide in 1400 parts by weight of ethyl alcohol is added to this oil and the mixture is refluxed for ten minutes. The solution is then concentrated to dryness and the residue dissolved in 2000 parts by weight of water.
The aqueous basic solution is extracted free of neutral impurities with 1500 parts by weight of ether. It is then cooled and acidified to a pH of 2 with hydrochloric acid. Solid, white 3-allyl-5,-6-trimethyleneuracil, melting at 163.5-166 C., precipitates, which is filtered and dried.
The compounds listed in the following table can be prepared according to the procedures of Examples 1, 2 0r 3 by substituting equivalent amounts of the listed ureas, thioureas and alkyl-Z-cycloalkanone-l-canboxylates for those used in the examples:
Substituted urea Parts by Ester of the cycloalkanone carboxylate Parts by Substituted uracil product Weight weight ltlethyluthiourea 90 Ethyl 2-cyclopentanone-l-carboxylate.. 162 3-methyl-5,6-trimethylene-2-tl1iouracil.
n-Butylurea 162 3-n-butyl-5,G-trimethylcneuracil.
n-I-Iexylurea 162 3-n-hexyl-5,(i-trimethyleneuracil.
Isooctylurea 162 3-iso0ctyl-5 ,fi-trirnethyleneuracil.
a-Naphthylurea 162 3-(a-naphthyl)-5.6-trimethylene uraei Tcrt-butymrea 116 Ethyl 2 cyelohexanonel-carboxylate... 187 3-tert.-butyl-5,6-tetramethyleneuracil.
n-Octylurea 172 .dO 187 3-n-octyl-5,6-tetrarnethyleneuracl Cyclooctylurea Methyl 2-cyclopentanone-1-carboxylate.. 156 3-eycloocty1-5,G-trimethylene uracil.
Cyclopentenylurca 126 .....do 156 3-cycl0pentenyl-5,6-trimethyleneuraci Fenchylurea 216 do 156 3-l'enchyl-5,6-trimethyleneuracil.
Cyclopentylurea 128 Ethyl 2-cyclohexanone-l'carboxylate... 187 3-cyclopentyl-5,6-tetramethyleneuracil.
1-(4-methoxyeyclohcxylurea) 172 do 187 3-(4-methoxycyclohexyl)-5,6-
tetramethyleneuracil.
1-(3,4-dlClllOlOGyClOllOXylllI'Cfi) 211 Ethyl 2-cycl0pcntanone-l-earboxylate. 187 3-(3,4-dichlorocyclohexyl)-5,6-
trimethyleneuracll.
Table-Continued Substituted urea Parts by Ester of the cycloalkanone carboxylate Parts by Substituted uracil product weight weight Cyclooctenylurea 168 Methyl 2-cyclohexanone-1-carboxylate 162 3-cyclrifctenyl-5,6-tetrameth 1en urac Carvacrylurea 191 Methyl Z-cycloheptanoned-carboxylate 187 3 carva lcryl-5,fi-pentamethylene.
urac Isopropylurea 102 ...do 162 3-is pr lipyl-5,fi-pentamethyleneuraci n-Amylurea 130 Ethyl 2'cycloheptanone-Lcarboxylate 202 3-n-am yl-5,fi-pentamethylene- 1112101 Bromonorbornylurea 231 ..do 202 3-bromonorb0rnyl-5,6-pentamethyleneuracil. Cyeloheptenylurea 156 do 202 3-cyeloheptenyl-5,6-pentamethyleneuracil. Norbornylurea 152 Methyl 2-cyclopentanone-l-carboxylate. 156 3-norbgrnyl-5,fi-trimethylene- 11126 Chloronorbornylurea 188. 5 ..do 156 3-(Clll0r0n01b0rnyl)-5,6-trimeth.
yleneuracil. Bornylurea 216 do 156 3-b0rnyl-5,6-trimethyleneuraoiL 1-cyclohexyl-2-thi0urea .l 154 Ethyl 2rcyclopentanone-l-carboxylate. 162 3%yl0hoX}il-5,fi-trimethyleneZ- nouraci Norobornylurea 154 do 162 3-norbqrnyl-dfi-trimethylene- 111301 3-cyclopropylmethylurea 115 Ethyl 2-cycloheptanone-Lcarboxylate 202 3cycl0propylmethyl-5,6pentamethyleneuracil. 2-rnethoxyethylurea 118 do 202 3-(Q-Inethoxyethyl)-5,6-pentameth.
yleneuracil. Allylurea.-. 100 Ethyl 2-eyclohexanone-l-carboxylate 187 3-ally -5,6 methyleneuracll.
200 Ethyl Z-cycloheptanone-l-carboxylate 202 3-dec y -5,6De tamethylene- 111301 1-allyl-2-thiourea 100 Ethyl 2-cyclopentanone-l-carboxylate 162 S-allyh?,6-trimethylene-2-thio.
' uraci Decahydronaphthylurea 162 3 decahydronaphthyl-5,6-trimeth yleueuracil. 1-( l-isopropylcyclohexyl)urea 162 3-(4-is0pr0pylcy0lohexy1)-5,6 tri methyleneuracil. 1(1-ethylhexyl)urea 162 3-(l-ethlylhexyl)-5,6trimetl1yleneuraei l-(l,l-diinethylbutyhurea 144 Ethyl 2-eycloheptanone-l-earboxylate 202 3-(1,Ldimethylbutyl)-5,6-pentamethyleneuracil. 1-(3a,4,5,6,7,7ahexahydro-4,7-methan0-5dn- 196 Ethyl 2-cyclopentanone-1-carboxylate 162 3-(321,4,5,6,7,7a-hexahydr0-4,7-
denyl)urea. methandS-indenyl)-5,6-trimethyleneuraeil. 1 (3a,4,5,6,7,7a-hexahydr0-5-indeny1)-urea- 196 Ethyl 2-cyclohexanone-Lcarboxylate. 187 3-(3a,4,5,6,7,7a-hexahydr0-5-in.
denyg)-5,6-tetramethyleneurac Example 4.-Preparati0n of 3-is0pr0pyl-5,6-trimethyleneuracil, sodium salt Into a solution of 12 parts by Weight of sodium hydroxide and 100 parts by Weight of Water is added 58 parts by Weight of 3-isopropyl-5,6-tri'methyleneuracil. This slurry is heated and stirred until the solids are completely dissolved. The sodium salt of the uracil separates on cooling. More of the solid can be forced out of solution by dilution with acetonitrile. The salt is filtered ofI and dried.
Example 5.--Preparati0n of 3-is0pr0pyl-5,6- trimethyleneuracil, barium salt A mixture of 194 parts by weight of 3-isopropyl-5,6- trimethyleneuracil, 600 parts by Weight of methyl alcohol, and 54 parts by Weight of sodium methoxide is stirred until the components are completely dissolved. To this mixture is added a solution of 224 parts by weight of barium chloride dihydrate in 1000 parts by Weight of 5 water. The resulting solution is quickly filtered free of foreign matter. A 'White solid gradually separates and is filtered off. This is 3-isopropyl-5,6-trirnethyleneuraoil, barium salt.
The following salts are prepared according to this method by substituting equivalent quantities of an appropriate substituted uracil for the 3-isopropyl-5,6-trimethyleneuracil and the proper diand polyvalent metal chlorides for barium chloride:
3-cyclohexyl-5,6-trimethyleneuracil, magnesium salt 3-n-butyl-5,6-trirnethyleneuracil, calcium salt 3-sec.-butyl-5,6-trimethyleneuracil, iron salt 3-allyl-5,6-trimethy1eneuracil, manganous salt Example 6.Preparati0n of 3-cycl0hexyl-5,6-trimethyleneuracil, tetrabutylammanium salt A mixture containing 234 parts of 3-cyclohexyl-5,6-
trimethyleneuracil and 865.8 parts of a one-molar solution of tetrabutylammonium hydroxide in methanol is stirred and heated slightly until solution is complete. The solvent is removed by distillation under reduced pressure. The resulting white solid is essentially pure 3-cy-clohexyl-S,6-trimethyleneuracil, tetrabutylamrnonium salt.
Other quaternary ammonium salts can be similarly prepared by reacting equivalent amounts of an appropriately substituted uracil and a suitable quaternary ammonium hydroxide. The following compounds can be prepared in this fashion:
3-cyclopentenyl-5,6-tetramethyleneuracil, tetramethylammonium salt 3-bornyl-5,6-trimethyleneuracil, trimethylbenzylammonium salt 3-isopropyl-5,6-trimethyleneuracil, trimethyldodecylammonium salt Example 7.Preparazi0n of 3-sec.-butyl-5,6tetramethyleneuracil-piperidine addition compound A mixture containing one part of 3-sec.-butyl-5,6-tetramethyleneuracil and 4 parts of piperidine is stirred and gently heated until a clear solution is obtained.
By similarly employing equivalent amounts of appropriate uracils and nitrogenous bases in place of the 3-sec.- butyl-S,G-trimethyleneuracil and piperidine, the following uracil-nitrogenousbase-addition products can be prepared:
3-sec.-butyl-5,6-pentamethyleneuracil, triethylenediarnine addition compound 3-sec.-butyl-5,6-pentamethyleneuracil, ethylenediamine addition compound 3-sec.-butyl-5,6-pentamethyleneuracil, octylamine addition compound 3-sec.-butyl-5,6-pentamethyleneuracil, dodecylamine addition compound 3-sec.-butyl-5,6-pentamethyleneuracil, cocoadiamine addition compound 3-(2-pentyl)-5,6-tetramethyleneuracil, piperidine addition compound 3- (3 ,4-dimethylcyclohexyl) ,6-trimethyleneuracil, piperidine addition compound Example 8.Preparation of 3-(methylcyclohexyl)-5,6-
trimethyleneuracil-piperidine addition compound A mixture containing one part of 3-(2-methylcyclohexyl)-5,G-trimethyleneuracil and 20 parts of piperidine is stirred and gently heated until a clear solution is obtained.
The following can be prepared in the same fashion by substituting equivalent amounts of appropriate uracils and amines for the 3-(2-methylcyclohexyl)-5,6-trimethyleneuracil and piperidine:
Example 9.Preparation of the 1 :1 complex of 3-sec.-
butyl-5,6-tetrametlzyleneuracil with phenol A mixture of 222 parts of 3-sec.-butyl-5,6-tetramethyleneuracil and 94 parts of phenol is gradually heated until a clear melt forms. The liquid is stirred to assure complete mixing and is then allowed to cool.
The solid residue is recrystallized twice from cyclohexane. The resulting 3-sec.-buty1-5,6-tetramethyleneuracil phenol complex melts at 103104 C.
Example 10.Preparation of the complex of 3-sec.-butyl- 5,6-tetramethyleneuracil with p-chlorophenol A mixture of 222 parts of 3-sec.-butyl-5,G-tetramethyleneuracil and 128 parts of p-chlorophenol is gradually heated until a clear melt forms. The liquid is stirred and allowed to cool. The resulting solid is recrystallized twice from cyclohexane. The resulting white p-chlorophenol complex of 3-sec.butyl-S,fi-tetramethyleneuracil melts at 9193 C.
The following complexes can be prepared in a similar fashion by replacing the 3-sec.-butyl-5,G-tetramethyleneuracil and p-chlorophenol with equivalent amounts of appropriate uracils and phenols:
3-isopropyl-5,6-trin1ethyleneuracil, pentachlorophenol complex 3-butyl-5,6-tetramethyleneuracil, 2,4-dichlorophenol complex 3-(2-hexyl)-5,6-trimethyleneuracil, p-nitrophenol complex 3-(3-methylcyclohexyl) -5,6-trimethyleneuracil, p-chlorophenol complex 3-sec.-butyl-5,6-tetramethyleneuracil, p-methoxyphenol complex HERBICIDAL COMPOSITIONS LIQUID FORMULATIONS Example 11.A queous concentrate A. An aqueous concentrate is prepared by dissolving the two solid components in water. The product can be readily diluted to use levels and sprayed.
Percent 3-sec.-amyl-5,6-trimethyleneura-cil, potassium salt 5 Sodium lauryl sulfate 1 Water 94 This aqueous concentrate is applied with a pressuretype hand sprayer. Three pounds of active ingredient per acre in 40 gallons of water gives excellent preemergence control of foxtail, watergrass, Johnson grass seedlings in sugar cane.
B. The following substituted uracils in equivalent amounts can also be formulated as aqueous concentrates according to this procedure:
3-cyclopentenyl-5,6-trimethyleneuracil, sodium salt 3-cyclohexyl-5,6-trimethylene-2-thiouracil, sodum salt 3-sec.-butyl-5,G-tetramethyleneuracil, sodium salt 3-cyclopentenyl-5,6-tetramethyleneuracil, sodium salt 3-cyclooctyl-5,6-tetramethyleneuracil, sodium salt 3-cyclohexyl-5,6-tetran1ethylene-Z-thiouracil, sodium salt 3-cyclol1eptenyl-5,6-pentamethylene-2-thiouracil, sodium salt 3-decahydro-2-naphthyl-5,6-trimethyleneuracil, sodium salt 3-bornyl-5,6-trimethyleneuracil, sodium salt 3-(3-methoxypropyl)-5,6-tetramethyleneuracil, sodium salt 3-(5-cyanopentyl) -5,6-trimethyleneuracil, tetramethylammonium salt 3-cyclobutylmethyl-5,G-trimethyleneuracil, sodium salt 3-fenchyl-5,6-trimethyleneuracil, tetraethylammonium salt 3-norbornyl-5,6-tetramethyleneuracil, tetrapropylammonium salt 3-chloronorbornyl-5,6-tetramethyleneuracil, tetramethylammonium salt 3-norbornenyl-5,6-trimethyleneuracil, benzyltrimethylammonium salt 3-cyclohexyl-5,6-trimethyleneuracil, 2/ 1 6,7-dihydrodipyrido[1,2-a:2',l'-C]pyrazinium salt 3-sec.-butyl-5,6-trimethyleneuracil, 2/ 1 6,7-dihydrodipyrido[1,2-a:2,l'-C]pyrazinium salt These formulations, applied at the rate of 20 pounds (active) in gallons of water to weeds growing around bridge abutments, give excellent control of wild barley, bedstraw, hedge bindweed, wild carrot, cheatgrass, cocklebur, dog fennel and goose grass.
Example 12.A queous dispersion The following ingredients (except the water) are mixed, micropulverized, blended with the water and then sand ground until the particles of active material are less than 5 microns in diameter:
Percent 3-[(m trifluoromethyl)phenyl] 5,6-trimethylencuracil 30.0 Sodium lignin sulfonate 5.0 Hydrated attapulgite 1.5 Water 63.5
This stable suspension, when diluted with water and when applied at the rate of 25 pounds of active ingredient per acre in 100 gallons of water, gives excellent control of such annual weeds as crab grass, foxtail, wild rye, wild barley, bachelor buttons, and lambs-quarters growing in a parking lot.
The following substituted uracils can be formulated similarly. When applied in a like fashion, in equivalent amounts, they also give good herbicidal results:
B-(m-pyridyl) -5,6-trimethyleneuracil 3- 3-chloro-4-ethoxyphenyl -5 ,6-trimethyleneuracil 3 (p-amyloxyphenyl) -5,6-trimethyleneuracil 3- (p-methoxyphenyl -5 ,6-trimethyleneuracil 3 -(2,5-dichloro-4-nitrophenyl -5 ,G-trimethyleneuracil 3 -(m-chlorophenyl -5 ,dtrimethyleneuracil 3- (3 ,4-dimethylphenyl -5,6-trimethyleneuracil 3- [psec.-butyl phenyl] -5 ,6-trimethylcneuracil 3- (3 -nitro-4-chlorophenyl) -5,6-trimethyleneuracil 3-cyclopentenyl-5,6-trimethyleneuracil, iron salt 1 7 3 321,4,5 ,6,7,7a-hexahydro-4,7-methano-5 -indanyl) -5 ,6-
trimethyleneuracil, calcium salt 3-sec.-butyl-5,6-tetramethyleneuracil, manganous salt 3-isopropyl-5,6-tetramethyleneuracil, barium salt 3-methyl-5,6-pentamethyleneuracil, magnesium salt Example 13.-A qneous suspension The following ingredients are mixed and pebble-milled or sand-milled until substantially all the particles of the active material are under 5 microns in size. The resulting stable thixotropic suspension does not cake on storage and is readily diluted with water to form a very slow settling suspension which requires no agitation during application.
This suspension, when applied as a directed spray at 2 pounds of active ingredient per acre in 30 gallons of water, gives good pre-emergence control of crab grass, mustard species, lambs-quarters, and rice grass germinating in sugar cane.
Example 14.-A qneous solution Percent 3-sec.-butyl-5,6-tetramethyleneuracil 20 Piperidine 80 The components are mixed together at room temperature until a clear solution is formed. Ths solution is extendable with water.
Twenty pounds (active) of this formulation are mixed with 60 gallons of water in a spray tank. Eight pounds of trimethylnonyl ether of polyethylene glycol are added. Only slight agitation is required for complete mixing.
The sixty gallons are sprayed on an area of one acre along roadsides. Excellent kill and residual control of such species as wild oats, cheatgrass, annual bluegrass, crab grass, foxtails, ryegrass, filaree, wild mustard, and beggar tick is obtained.
The following compounds can be substituted for 3-sec.- butyl-5,6-tetramethyleneuracil-piperidine addition compound, in herbicidally equivalent amounts, and when used in a like fashion, will give good weed control:
3-isopropyl-5,6-pentamethyleneuracil, piperidine addition compound 3-tert.-butyl-5,6-tetramethyleneuracil, piperidine addition compound 3-tert.-butyl-5,6-pentamethyleneuracil, ethylenediamine addition compound 3-n-butyl-5,6-pen-tamethyleneuracil, piperidine addition compound 3-sec.-butyl-5,6-tetramethyleneuracil, hexamethylenediamine addition compound 3-sec.-butyl-5,6-penta methyleneuracil, sec.-butylamine addition compound 3-sec.-butyl-5,6-pentamethyleneuracil, cyclohexylamine addition compound 3-sec.-butyl-5,6-tetramethyleneuracil, piperazine addition compound Example 15.Aque0us dispersion Percent 3-cyclohexyl-5,6-trimethyleneuraci1 22.50 3-cyclohexyl-5-bromo-6-methyluracil 7.50 Sodium lignin sulfonate 15.00 Hydrated attap ulgite clay 1.75 Water 52.95-52.65 NaOH (as needed) 0.30-0.60
The mix is wet-milled until all particles are below 10 microns in size. The pH of the slurry is then adjusted to about 8.5.
This formulation gives exceptional control of vegetation around Warehouses and industrial sites. It is dispersed in suflicient water to give good coverage of the area to be sprayed. Applied at the rate of 30 pounds of active ingredients per acre, it gives good control of existing weeds and keeps the area weed-free. Good control of such troublesome weeds as crabgrass, fall panicum, mares tail, goatweed, smartweed, spotted spurge, morning glory, ragweed, pigweed, lambs-quarters, buttonweed, foxtail, broomsedge, and Russian thistle is obtained.
Example 16.-Emulsifiable oil An emulsifiable oil is prepared by mixing the components to give a homogeneous solution. This solution can then be emulsified in water for application.
Percent 3- 3pentyl) -5,6-tetramethyleneuracil 20.0 Alkyl aryl polyether alcohol 2.5 Oil soluble petroleum sulfonate 2.5
Methyl isobutyl ketone 75.0
This emulsifiable oil is useful for directed postemergence weed control in cotton at lay-by. When applied at 2 pounds of active ingredient per acre in 30 gallons of water, it gives excellent control of germinating annual weeds such as crab grass, cockleburr, and water grass.
Example Z7.Emulsifiable oil suspension The following components are mixed together and milled in a roller mill, pebble mill, or sand mill until substantially all the particles of the active component are under 10 microns in size. The resulting suspension may be emulsified in Water or diluted further with weed oils for spray application. Percent 3-phenyl-5,6-trirnethyleneuracil 25 Blend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates 6 Isophorone 69- This formulation is diluted with gallons of Lion Herbicidal Oil No. 6 and applied at 20 pounds of active ingredient per acre for the control of morning glory,
yarrow, ragweed, wild carrot, Water grass, witch grass, and crab grass growing along fence rows. Excellent control is obtained.
Similarly formulated and used in equivalent amounts, with excellent results, are 3-cyclohexyl-5,6-trirnethylene- Z-thiouracil and 3-(2,3dichloro-Ba,4,5,6,7,7a-hexahydro- 4,7-methano-5-indanyl) -5,6-trimethyleneuracil.
Example 18.-0il suspension Percent 3salilyl-5.6-tetramethylene-2-thiouracil 22 Blend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates 7 Xylene 71 3-cycloheptenyl-5,6-trimethylene-2-thiouracil 3-rnethyl-5,6-tetramethylene-Z-thiouracil 3-isoamyl-5,6-tetramethylene-Z-thiouracil 3-( l-decahydronaphthyl)-5,6-trimethyleneuracil 3-(3a,4,5,6,7,7a-hexahydro-4,7-methano-5-indenyl)- 5 ,6-trimet-hyleneuracil 3-cyclopentenyl-5 ,6-tetramethylene-2-thi0uracil 3-tert.-butyl-5 ,6-pentamethylene-2-th-iouracil 3-norbornylmethyl-5 ,6-trimethylene-Z-thiouracil 3-cyclohexyl-5,6-pentamethylene-Z-thiouracil 3-cyclooctyl-5,6-pentamethylene-2-thiouracil 3-phenyl-5 ,6-trimethylene-Z-thiouracil 3-cyclooctyl-S,6-trimethylene-2-thiouracil Example 19.Oil dispersions Percent 3 cyclohexyl-5,6-trimethyleneuracil 12.5 3-(3,4-dichlorophenyl) -1,l-dimethylurea 12.5
Parafiinic hydrocarbon (at least 90% unsulfonatable) 72.0 Soya lecithin 3.0
These components are mixed together and then wetmilled until the particles are below microns in size. The resulting oil suspension can be diluted further with oil for application.
This formulation is dispersed in 80 gallons of diesel oil and sprayed, in a blanket treatment, on vegetation and bare areas along railroad ballast. It is sprayed at a rate of 30 pounds of active ingredients per acre. Good control of Bermuda grass, ragweed, goldenrod, smartweed, seedling Johnson grass, spotted spurge, dogbane, and flower-of-an-hour is obtained.
Example 20.Oil dispersion Percent 3-sec-butyl-5,6-trimethyleneuracil 20.0 2-(2,4,5-trichlorophenoxy)propionic acid 5.0 Diesel oil 75.0
These ingredients are mixed and then wet-milled until the particles of uracil are below 10 microns in size.
This formulation is used for the control of a wide variety of woody and herbaceous perennial weeds and grasses along highway rights-of-way. Dispersed in No. 2 fuel oil, it is sprayed at -20 pounds per acre of active ingredients on dense growths of weeds and brush on highway shoulders. Honeysuckle, brambles, water grass, goldenrod, ragweed, leafy spurge, seedling sassafras, maples, sweet gum, and poison ivy are controlled,
Example 21.-Oil dispersion Percent 3-cyclohexyl-5,6-tetramethyleneuracil 20.0 2,3,6-trichlorobenzoic acid 10.0 Diesel oil 70.0
These components are mixed and then wet-milled until the insoluble particles are under 10 microns in size.
This formulation is dispersed in 100 gallons of herbicidal oil and sprayed along an oil pipeline at the rate of 30 pounds of active ingredients per acre. Excellent control of leafy spurge, bindwced, panic grass, big bluestem, purpletop, poison ivy, quack grass, seedling oaks, maples, sweet gum, ragweed, goldenrod, honeysuckle, and brambles is obtained. The area is kept clear of troublesome weeds for an extended period.
Example 22.--Oil-extendable formulation Percent 3-sec.-butyl-5,6-tetramethyleneuracil 1 1 complex with phenol 75.0 Soya lecithin 2.6 Calcined montmorillonite clay (Pikes Peak clay) 22.4
These ingredients are blended and micropulverized until the particles are under 50 microns in diameter and then reblended until homogeneous.
Eight pounds of this formulation are applied in 80 gallons of Lion Herbicidal Oil No. 6 as a foliar spray to annual weeds growing under electric power line towers. Exce lent initial kill and're d al c n ol of a P pulation of crab grass, foxtail, wild mustard, lambs-quarters, cheatgrass, mustard and shepherds purse is obtained.
The following uracil-phenol complexes can be formulated in a like manner, and when used in hcrbicidally equivalent amounts, will give excellent results:
3-neopentyl-5,6-tetramethyleneuracil, p-cresol complex 3-(3-pentyl)-5,6-tetramethyleneuracil, 2,4-dichlorophenol complex 3 4-methoxycyclohexyl -5 ,G-trimethyleneuracil, p-nitro- Attapulgite clay 17.25
A wettable powder is prepared with these ingredients by blending and micropulverizing them.
Fifteen pounds of this wettable powder are dispersed in 100 gallons of a water solution containing 20 pounds of a formulation of 2,2-dichloropropionic acid, sodium salt. This composition eradicates grasses and other troublesome weeds from warehouse areas. Excellent control of existing Bermuda grass, quack grass, Johnson grass, ragweed, crab grass, panicum species, and knotweed is obtained by an application of this spray mixture at 150 gallons per acre.
Example 24.Tank mix A wettable powder is prepared by blending and micropulverizing the following components:
Percent 3-cyclohexyl-S,6-trimethyleneuracil 80.00 Alkyl naphthalene sulfonic acid, Na salt 1.75 Partially desulfonated sodium lignin sulfonate 2.00 Attapulgite clay 17.25
This wettable powder and an emulsifiable oil containing 6 pounds per gallon of N,N-dipropylthiolcarbamic acid, ethyl ester are added to a spray tank to form a dilute mixture, in water, of to 1%. pounds of uracil formulation and /2 gallon of the ester formulation per gallons.
This dilute suspension-emulsion is applied at the volume rate of 100 gallons per acre to spring-seeded alfalfa. Good control of such weeds as checkweed, smartweed, portulaca, penny Cress, yellow rocket, shepherds purse, ragweed, redroot pigweed, crab grass, annual bluegrass, and henbit is obtained.
Example 25 .-Tank mix Percent 3-sec.-butyl-5,6-trimethyleneuracil 60.0 Mixed polyoxyethylene esters of fatty acids and oilsoluble petroleum sulfonates 5.0 Attapulgite clay 35.0
An oil-dispersible powder of these ingredients is prepared by blending and then grinding them to a particle size of less than 50 microns.
Twenty pounds of this formulation are mixed in 100 gallons of 0.5% pentachlorophenol in diesel oil. The mixture is sprayed uniformly over an acre of weedinfested railroad right-of-way to give superior control 21 of existing Johnson grass seedlings, big bluestem, cheat grass, fall panicum, smart weed, velvet leaf, ragweed, pigweed, and broomsedge.
Calcined, non-swelling montmorillonite type clay (Pikes Peak clay) 17.25
A wettable powder is prepared by blending the components and then micropulverizing them until the particles of the active ingredient are substantially all under 50 microns in size, and then reblending to homogeneity.
When applied at 1 pound of active ingredient per acre in 40 gallons of water, this formulation gives excellent pre-emergence control of crab grass, foxtail, cocklebur, lambs quarters, and burdock in a newly planted field of cotton. One to three pounds of active ingredient per acre gives good weed control in asparagus, sugar cane, and pineapple. One to two pounds per acre gives excellent pre-emergence control annual weeds such as crab grass, foxtail, wild mustard, ryegrass, and velvetleaf in a newly planted field of spinach.
The following uracils can be similarly formulated, and when use in herbicidally equivalent amounts, will give good general weed control:
3-norbornyl-S,6-trimethyleneuracil 3-cycloheptyl-5,6-trimethyleneuracil 3-cyclooctyl-5,6-trimethyleneuracil Example 27.--Wettable powder A wettable powder is prepared by blending the following components, micropulverizing them until substantially all the particles are under 50 microns in size, and then reblending:
Percent 3-sec.-butyl-5,6trimethyleneuracil 80.00 Low viscosity methylcellulose 0.25
' Alkyl naphthalene sulfonic acid, Na salt 1.75 Disodium phosphate (corrosion inhibitor) 0.80 Attapulgite clay 17.20
Example 28.-Wettable powder The following components are blended, then micropulverized until substantially all the solids are under 50 microns in particle size, then reblended to homogeneity:
Percent 3-cyclohexyl-5,6-trimethyleneuracil, barium salt 80.0 Sodium lauryl sulfate 0.6 Sodium lignin sulfonate 2.0 Kaolin clay 17.4
This formulation is used in the manner described in Example 27, with good results.
Example 29.Wettable powder The following powder is prepared in the same manner as Example 28, but in addition is passed through an air 22 attrition m-ill, such as an air-reductionizer, to reduce the particle size to under 10 microns:
Percent 3-tert.-butyl-5,G-trimethyleneuracil 80.0 Dioctyl sodium sulfosuccinate concreted with sodium benzoate (Aerosol OTB) Partially desulfonated sodium lignin sulfonate Calcined, non-swelling montmorillonite type clay (Pikes Peak clay) This composition is used for pre-emergence application in agricultural crops such as sugar cane, asparagus, and safflower. It is dispersed in gallons of water and sprayed with a pressure sprayer. At 0.5 to 2.0 pounds of active ingredient per acre, excellent control of pigweed, lambs-quarters, purslane, mustard, crab grass, foxtail, and water grass is obtained.
Example 30.Wettable powder The following are blended, then micropnlverized until the particles are below microns in diameter, and reblended:
Percent 3-bornyl-5,6-trimethyleneuracil e 25 Alkylnaphthalene sulfonic acid, sodium salt 1 Partially desulfonated sodium lignin sulfonate 1 Attapulgite clay 73 This wettable powder is suspended in water at a concentration of 15-20 pounds of active ingredient per 100 gallons of water. This suspension is sprayed at the rate of 100 gallons per acre for control of crabgrass, water grass and lambs-quarters growing around telephone poles.
Each of the following uracils can be similarly formulated and applied in gallons of herbicidal oil. At rates of 2030 pounds (active) per acre, they will give good Weed control.
3 a,2,4-trimethylbenzyl -5,6-trimethyleneuracil 3 -p-chlorobenzyl-5 ,6-tetramethylene-2-thiouracil 3 -a-phenethyl-5 ,6-trimethylene-2-thiouracil 3-cyano-5 ,6-trimethyleneuracil 3- p-fiuorophenyl) -5 ,6-trimethyleneuracil 3 (3 ,4-dichlorophenyl -5 ,6-trimethyleneuracil 3- (4-bromophenyl -5 ,6-trimethyleneuracil 3- (m-nitrophenyl) -5,6-trimethyleneuracil 3 3-chloro-p-tolyl) -5,6-trimethyleneuracil 3-benzy1-5 ,6-trimethyleneuracil 3 p-methylbenzyl -5,6-trimethyleneuracil 3 -phenethyl-5 ,6-trimethyleneuracil 3 -(p-rnethoxybenzyl -5 ,6-tetramethyleneuracil 3 (p-sec.-butylphenethyl -5,6-trimethyleneuracil 3 -p-nitrobenzyl-5,6trimethyleneuracil 3 -p-chlor-obenzyl-5,6-trimethyleneuracil 3 a,2,4-trichlorobenzyl) -5 ,G-pentamethyleneuracil 3-cycloheptylene-S ,G-pentamethyleneuracil 3 -cyclooetenyl-5,6-tetramethyleneuracil 3-carvacryl-5 ,6-pentamethyleneuracil 3-isopropoyl-5 ,6-pentamethyleneuracil 3 -n-amyl-5,6-pentamethyleneuracil 3 -isooctyl-5 ,6-pentamethyleneuracil 3-cyclopentyl-5 ,6-pentamethyleneuracil 3-tetrahydronaphthyl-5 ,6-trimethyleneuracil 3 -bromonorbornyl-5 ,6-pentamethyleneuracil 3-cyclopropyl-5 ,6-trimethyleneuracil 3- Z-cyanoethyl) -5 ,6-trimethyleneuracil 3- 3-hydroxypropyl -5 ,G-tetramethyleneuracil 3 buten-2-yl) -5 ,6-trimethyleneuracil 3 propyn-Z-yl -5 ,6-trimethyleneuracil 3- cyclopentenylmethyl -5 ,6-trimethyleneuracil 3- 2-methylcyclohexylmethyl) -5,6-trimethyleneuracil 3 (4-methoxycyclohexylmethyl -5 ,6-tetramethyleneuracil 3 -(4-methylcyclohexenylmethyl -5 ,6--trimethyleneuracil 3-furfuryl-5 ,6-tetramethyleneuracil 23 Example 31.Wettable powder Percent 3-(norbornenylmethyl)-5,6-trimethyleneuracil 75.0 Dioctylsodium sulfosuccinate 0.5 Ditertiary acetylenic glycol 0.5 Coconut acid ester of sodium isethionate 0.5 Precipitated sodium silico aluminate 23.5
These components are mixed, and micropulverized until the particles are less than 50 microns in diameter.
An application of this formulation at 25 pounds (active) in 80 gallons water controls beggar tick, wild mustard, lambs-quarters, plantain, velvetleaf, annual bluegrass, Canadian bluegrass, crabgrass, foxtail, and seedling Johnson grass growing around radar installations.
The following compounds can be formulated in a similar fashion. When used in the same way, at equivalent rates, they give good weed control.
3-( 1,4,5 ,6-tetrachloro-7,7-dimethoxybicyclo[2,2, 1] hept-S-en-Z-ylmethyl)-5,6-trimethyleneuracil 3-( wethylbicyclo [2,2,2] oct--en-2-ylmethyl) -5,6-
trimethyleneuracil 3-( 4-bromobutyl)-5,6-tetramethyleneuracil 3-( 3-chloro-1-methylpropyl)-5,6-pentamethyleneuracil 3- 5 ,6,7,8-tetrahydronaphthyl -5 ,6-trimethyleneuracil 3-(n-hexyl)-5,6-tetramethyleneuracil '3 -isopropyl-5,6-trimethyleneuracil Example 32.Wettable powder Percent 3-cyclohexyl-5,6-trimethyleneuraci1 16.0 3,6endoxohexahydrophthalic acid 64.0 Polyoxyethylene tall oil acid ester 3.0 Low viscosity polyvinyl alcohol 0.5 Synthetic fine silica 16.5
This wettable powder is prepared by blending the components and then micropulverizing the mixture until the particles are under 50 microns in size.
This formulation is dispersed in water and sprayed preemergence at 5 pounds of active ingredients per acre on a planting of red table beets. Excellent control of crab grass, chickweed, annual morning glory, carpetweed, purslane, smartweed, lambs-quarters, ragweed, black nightshade, giant foxtail, and velvet leaf is obtained. The crop shows no visible injury.
Example 33.Wettable powder Percent 3-sec.-butyl-5,6-trimethyleneuracil 40.0 3-(4-chlorophenyl)-1,l-dimethylurea 20.0 Alkyl naphthalene sulfonate, Na salt 1.5 Low viscosity methyl cellulose 0.5 Attapulgite clay 38.0
A wettable powder is prepared by blending these components and then micropulverizing the mixture until the particles are below 50 microns in size.
This formulation controls weeds along railroad rightsof-way. Applied in the spring in about 100 gallons of water and at the rate of pounds of active ingredients per acre, the formulation gives good control of annual ryegrass, bromegrass, ragweed, henbit, goldenrod, field daisy, buckhorn, plantain, water grass, and volunteer rye.
Example 34.Wettable powder Percent 3-cyclohexyl-5,6-tetramethyleneuracil 40.0 2-chloro-4-ethylamino-6-isopropyl-amino-s-triazine 20.0
Dioctyl sodium sulfosuccinate concreted 85-15 with sodium benzoate 1.0 Low viscosity methyl cellulose 0.3 Calcined montmorillonite clay 38.7
A wettable powder is prepared by blending these ingredients and then grinding them until the particles are below 50 microns in size.
A tractor-mounted sprayer which sprays four rows at a time is used to apply this formulation to a field of potatoes, before the potatoes emerge. The formulation is used at a rate of 3 pounds of active ingredients per acre. Such weeds as crabgrass, chickweed, smartweed, purslane, giant foxtail, annual morning glory, Johnson grass seedlings, barnyard grass, bedstraw, and henbit are controlled without visible injury to the potatoes. Excellent yields of potatoes are obtained, with minimum cultivation.
Example 35.-Wettable powder Percent 1-(3,4-dichlorophenyl)-3,3-dimethylurea 80.00 Low viscosity methyl cellulose 0.25 Alkyl naphthalene sulfonic acid, sodium salt 1.75 Disodium phosphate 0.80
Attapulgite clay 17.20
These ingredients are blended, micropulverized until all particles are below microns in diameter, and then reblended.
Percent 3-cyclohexyl-5,6-trirnethyleneuracil 80.00 Alkylnaphthalene sulfonic acid, sodium salt 1.75 Partially desulfonated sodium lignin sulfonate 1.00 Calcined non-swelling montmorillonite clay 17.25
These ingredients are blended, micropulverized until all particles are below 50 microns in diameter, and then reblended.
Nine parts (active) of the uracil formulation are mixed with one part (active) of the urea formulation.
This mixture, applied at 1.25-2 pounds (total active herbicides) per acre in 40 gallons of water to a new planting of sugar beets, gives excellent control of foxtail, crabgrass, barnyard grass, pigweed, lambs-quarters, ragweed and velvetleaf.
Example 36.Pellets Percent 3-cyclohexyl-5,6-tetramethyleneuracil 25 Anhydrous sodium sulfate 10 Sodium lignin sulfonate 10 Ca, Mg bentonite 3-cyclopropyl-5,6-tetramethyleneuracil 3- (chloronorbornyl -5,6-tetramethyleneuracil 3 -cyclopentyl-5 ,6-tetramethyleneuracil 3-r1orbornyl-5,6-tetramethyleneuracil 3-indenyl-5 ,6-tetramethyleneuracil 3-naphthylmethyl-5,6-trimethyleneuracil 3 (p-cumyl -5, 6-trimethyleneuracil 3- (3 ,4,5-trichlorophenyl -5,6-tetramethyleneuracil 3- (4-isopropylcyclohexyl -5 ,6-tetramethyleneu ra cil 3-(decahydro-1,4-5,8-din1ethanonaphth-Z-ylmethyl) -5,6-
trimethyleneuracil Example 37.Pellets Percent 3-cyclohexyl-5,6-trimethyleneuracil 4 3-(p-chlorophenyl)-1,1-dimethylurea 2 Kaolin clay 37 Mississippi sub-bentonite clay 37 Sodium sulfate 10 Sodium lignin sulfonate 10 These ingredients are blended, micropulverized, pugmilled with 17%20% water, and then extruded through -inch die holes. The extrusions are cut into A -inch lengths and dried.
This formulation controls annual grasses and herbaceous broadleaved weeds in asparagus beds. The pellets are distributed evenly over the top of the beds at a rate of 3 pounds of active ingredients per acre just before the cutting season begins and again at the end of the cutting season. Excellent control of crabgrass, blackeyed Susan, beggar-ticks, prickly lettuce, ragweed, barnyard grass, green foxtail, pigweed, and fall panicum is obtained.
Example 38.-Pellets Percent 3-isopropyl-5,6-trimethyleneuracil 3.33 Phenyldimethylurea 6.67 California sub-bentonite clay 80.00 Sodium sulfate, anhydrous 10.00
These ingredients are blended, micropulverized, pugmilled with %20% Water, and extruded through Aa-inch holes. The extrusions are cut into As-inch lengths, dried, and screened.
This formulation is used to control all vegetation in a fire lane. The pellets are distributed from the air in remote areas of the fire lane at the rate of 40 pounds of active ingredients per acre. Excellent control of elm, sweet gum, oaks, maples, brambles, goldenrod, blackeyed Susan, and honeysuckle is obtained.
Example 39.Pellets Percent 3-cyclohexyl-5,6-trimethyleneuracil 6.67 3-sec.-butyl-5-chloro-6-methyluracil 3.33 Sodium sulfate, anhydrous 10.00 California sub-bentonite clay 80.00
These ingredients are pelletized in the manner of Example 38.
This formulation keeps lumber yards free of weeds. The pellets are distributed in the spring with a seeder at pounds (actives) per acre. The lumber-yard stacking area is kept free of such pernicious weeds as crabgrass, ragweed, pigweed, Russian thistle, fall panicum, goat weed, cheatgrass, and seedling Johnson grass.
Example 40.-Granules Percent 3-isopropyl-5,6-trimethyleneuracil, Na salt 5 8-15 mesh granular, expanded vermiculite 95 This granular composition is prepared by dissolving the active material in water and spraying it upon the granules while they are being tumbled. The granules are then dried.
These granules are applied at pounds of active ingredient per acre to mixed annual and perennial vegetation growing under cyclone fences, around highway markers, along fence rows, and around oil tank installations. Excellent weed control is obtained.
The following compounds can be formulated in a like manner, and when used in herbicidally equivalent amounts, will give good weed control:
3-cycl0hexyl-5,6trimethyleneuracil, tetramethylammonium salt 3-sec.-butyl-5,6-trimethyleneuracil, tetrabutylammonium salt 3-tert.-butyl-5,6-trimethyleneuracil, tetrabutylammonium salt 3-sec.-amyl-5,6-trimethyleneuracil, sodium salt 3-naphthy1-5,6-trimethyleneuracil, potassium salt 3-isopropyl-5,6-trimethyleneuracil, trimethylbenzylammonium salt 3-(0ct-7-enyl)-5,6-trimethyleneuracil, trimethylbenzylammonium salt 2x3 3-(a-decahydro1,45,8-dimethanonaphthyl)-5,6-trimethyleneuracil, sodium salt 3 -(5, 6,7,8,10,10-hexachlo-ro-l,2,3 ,4,4a,5,8,8a-octahydro- 1,4,5,8-dimethano-2-naphthyl) -5,6-trimethyleneuracil, atetrapr-opylammonium salt Example 41.Granules The following composition is prepared by dissolving the active ingredient in water and spraying the solution upon the attapulgite granules while they are being tumbled. The granules are then dried.
Percent 3-isopropyl-5,6-trimethyleneuracil, sodium salt 4 Granular 8-15 mesh attapulgite clay 96 These granules are applied by hand or by special spreaders at 2.5 pounds of active ingredient per acre for the pre-emergence control of annual weeds in potatoes. They control crabgrass, chickweed, barnyard grass, goose grass, foxtail, velvetleaf, and germinating Johnson grass without visible inujry to the crop.
Example 42 .-Granules The following components are blended and micropulverized, then moistened with water and granulated. The granules are then dried and screened.
Percent 3-n-butyl-5,G-trimethyleneuracil 4 Anhydrous sodium sulfate 10 Non-swelling sub-bentonite clay 86 The granules are applied with a granule spreader at 3 pounds of active ingredient per acre for pre-emergence control of annular weeds in asparagus.
Example 43.Granules Percent 3-chloronorbornyl-5,6-pentamethy1eneuracil,
potassium salt 5 Preformed attapulgite clay granules, +8 to +15 mesh A granular composition is prepared with these components 'by dissolving the active material in water and spraying it upon the granules while they are being tumbled. The granules are then dried.
These granules are applied at the rate of 20 to 30 pounds of active ingredient per acre to mixed annual and perennial weeds growing in a lumber storage yard. EX- cellent control of such weed species as crabgrass, foxtails, seedling Johnson grass, quack grass, dandelion, plantain, lambs quarters, and beggar tick is obtained with spring applications.
The following uracil salts can be substituted for the 3- chloronorbornyl-5,6-pentamethyleneuracil, potassium salt. When applied at equivalent rates, good weed control is observed.
3-cyclohexyl-5,6-trimethyleneuracil, potassium salt 3-cyclopentenyl-5,6-tetramethylenethiouracil, potassium salt 3 ethoxycarbonylmethyl 5,6-trirnethyleneuracil, lithium salt 3-ethyl-5,fi-tetramethyleneuracil, lithium salt 3-tert.-'butyl-5,fi-trimethyleneuracil, potassium salt 3-fenchyl-5,6-trimethylene-2-thiouracil, potassium salt 3-isopropyl-5,6-trimethyleneuracil, potassium salt 3-sec.-butyl-5,6-tetramethyleneuracil, potassium salt 3-( l-ethyl-l-methylbutyl -5,6-pentamethyleneuracil,
potassium salt 3-isoamyl-5,6-tetramethylene-Z-thiouracil, potassium salt 3-allyl-5,6-pentamethyleneuracil, potassium salt 3-(2-decyl)-5,6-trimethyleneuracil, lithium salt 3-methyl-5,fi-trimethyleneuracil, lithium salt 3-sec.-butyl-5,6-tetramethyleneuracil, lithium salt 27 Example 44.Granules Percent 3-cyclohexyl-5,6-trimethyleneuracil 16.67
2 ethylamino 4 isopropylamino-6-methylthio-striazine 8.33
Kaolin clay 72.00
Low viscosity methyl cellulose 3.00
The ingredients are blended and micropulverized, then pug-milled with to water, and moist-granulated. After drying, the granules are screened to 8-30 mesh.
These granules are distributed along the banks of a drainage canal. Applied at 120 pounds of granules per acre, good control of an existing rank growth of canary grass, smartweed, pigweed, and goldenrod is obtained.
Example 45 .Granules Percent 3-isopropyl-5,6-trimethyleneuracil 2.00 Polyoxyethylene tall oil acid ester 0.02
Sodium chlorate, 40%sodium metaborate, 60% 97.98
The surfactant and uracil are first mixed and micropulverized, then suspended in water and sprayed on the remaining granular components While they are being tumbled.
These granulesare distributed by hand at the rate of about 1.5 pounds per 100 square feet around airport sign-a1 lights. Excellent control of Johnson grass, brambles, poison ivy, honeysuckle, pigweed, ragweed, bindweed, Bermuda grass, cheatgrass, and big bluestem is obtained.
Example 46.Granules Percent 3-cyclohexyl-5 ,6-trimethyleneuracil 1.0 Trichloroacetic acid, sodium salt 3.0
Example 47.Waler-s0luble powder Percent 3- Z-methoxyethyl -5 ,6-pentamethyleneuracil Sodium silicate 74 Sodium dioctyl sulfosuccinate 1 These components are blended. and micropulverized.
Forty pounds of this formulation are dissolved in 100 gallons of water containing 0.4% of trimethylnonyl ether of polyethylene glycol. Three hundred gallons of this solution per acre are applied to a germinating stand of crabgrass, annual bluegrass, chickweed and wild mustard. Good control of these Weeds is obtained.
The embodiments of the invention in which an exclusive property or privilege is claimed are:
1. A method for the control of undesirable vegetation, said method comprising applying to a locus to be protected from such vegetation a herbicidally effective amount of a compound selected from the group consisting of (a) compounds of the formula 28 where:
R is selected from the group consisting of alkyl of 1 through 10 carbon atoms, substituted alkyl of 1 through 10 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, dialkylamino, and cyano, aryl of 6 through 14 carbon atoms, substituted aryl of 6 through 14 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, phenyl, alkoxy, alkyl, nitro, trifiuoromethyl, 1,2- tetramethylene, and 1,2-trimethylenylene, aralkyl of 7 through 15 carbon atoms, substituted aralkyl of 7 through 15 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, alkyl, nitro, and alkoxy, tetrahydronaphthylalkyl, alkenyl of 3 through 10 carbon atoms, alkynyl of 3 through 10 carbon atoms, alkenyl of 3 through 10 carbon atoms, substituted cycloalkyl of 3 through 12 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkenyl of 4 through 12 carbon atoms, substituted cycloalkenyl of 4 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of 5 through 13 carbon atoms, (substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, substituted cycloalkenyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, and cyano; X is selected from the group consisting of oxygen and sulfur; and n is a number 3 through 5; and (b) the sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese and quaternary ammonium salts of the compounds of Formula a.
2. The method of claim 1 wherein the herbicidal active compound is 3-cyclohexyl-5,6-trimethyleneuracil.
3. The method of claim 1 wherein the herbicidal active compound is 3-isopropyl-5,6-trimethy1eneuracil.
4. The method of claim 1 wherein the herbicidal active compound is 3-sec-butyl-5,6-tetramethyleneuracil.
5. The method of claim 1 wherein the herbicidal active compound is 3-cyclohexyl-5,6-tetramethyleneuracil.
6. The method of claim 1 wherein the herbicidal active compound is 3-isopropyl-5,6-trimethyleneuracil, sodium salt.
7. The method of claim 1 wherein the herbicidal active compound is 3-tert-butyl-5,6-trirnethyleneuracil.
8. The method of claim 1 wherein the herbicidal active compound is 3-cyclohexyl-5,6-trimethyleneuracil potassium salt.
9. A method for the control of undesirable vegetation, said method comprising applying to a locus to be protected from such vegetation a herbicidally effective amount of a compound selected from the group consisting of (a) compounds of the formula it i where R is selected from the group consisting of alkyl of 1 through 10 carbon atoms,
substituted alkyl of 1 through 10 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, dialkylamino, and cyano,
aryl of 6 through 14 carbon atoms,
substituted aryl of 6 through 14 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, phenyl, alkoxy, alkyl, nitro, trifluoromethyl, 1,2- tetramethylene, and 1,2-trimethylenylene,
aralkyl of 7 through 15 carbon atoms,
substituted aralkyl of 7 through 15 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, alkyl, nitro, and alkoxy,
tetrahydronaphthylalkyl,
alkenyl of 3 through 10 carbon atoms,
alkynyl of 3 through 10 carbon atoms,
cycloalkyl of 3 through 12 carbon atoms,
substituted cycloalkyl of 3 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,
cycloalkenyl of 4 through 12 carbon atoms,
substituted cycloalkenyl of 4 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,
cycloalkyl alkyl of 4 through 13 carbon atoms,
cycloalkenyl alkyl of through 13 carbon atoms,
(substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,
(substituted cyc1oalkenyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, and
cyano;
X is selected from the group consisting of oxygen and sulfur; and n is a number 3 through 5;
(b) the sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese, and quaternary ammonium salts of the compounds of Formula a;
(c) compounds of the formula RN W a om)n where:
R and n are as defined above, and 15 NB is a nitrogenous base having an ionization constant K l0 in water; and (d) compounds of the formula H o Z 0 ll RN @ECHDD H O \N p 111-1 where R and n are as defined above, Z is selected from the group consisting of hydrogen,
chlorine, bromine, nitro, alkyl of 1 through 3 carbon atoms, and --OR;, (where R is an alkyl of 1 through 3 carbon atoms); Y is selected from the group consisting of chlorine and alkyl of 1 through 3 carbon atoms; in is a number 1 through 5; and p is selected from the group consisting of /2, 1 and 2.
References Cited by the Applicant UNITED STATES PATENTS 2,567,651 9/1951 Papesch et al 260260 2,688,020 8/1954 Mackay et al. 260260 2,969,364 1/1961 Lyttle 71--2.5 X 3,002,975 10/1961 Slezak 712.5 X 3,078,154 2/1963 Gysin et al. 71--2.5 3,086,854 4/1963 Harvey 71--2.5
OTHER REFERENCES Bonner et al.: Proc. Natl. Acad. Sci., 25, 184-188 (1939). Thompson et al.: Botanical Gazette, 107, 475-507 LEWIS GOTTS, Primary Examiner.
JULIAN S. LEVITT, Examiner.

Claims (1)

  1. 9. A METHOD FOR THE CONTROL OF UNDESIRABLE VEGETATION, SAID METHOD COMPRISING APPLYING TO A LOCUS TO BE PROTECTED FROM SUCH VEGETATION A HERBICIDALLY EFFECTIVE AMOUNT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (A) COMPOUNDS OF THE FORMULA
US232311A 1959-08-14 1962-10-22 Control of undesirable vegetation Expired - Lifetime US3235360A (en)

Priority Applications (40)

Application Number Priority Date Filing Date Title
BE594076D BE594076A (en) 1959-08-14
CA731651A CA731651A (en) 1959-08-14 Substituted uracils
IT635567D IT635567A (en) 1959-08-14
NL254838D NL254838A (en) 1959-08-14
DK106253D DK106253A (en) 1959-08-14
DE19601240698 DE1240698C2 (en) 1959-08-14 1960-08-12 WEED KIDS
SE7792/60A SE305770B (en) 1959-08-14 1960-08-12
CH921360A CH482402A (en) 1959-08-14 1960-08-13 Herbicides
GB17418/64A GB968664A (en) 1959-08-14 1960-08-15 3-substituted uracils
GB28141/60A GB968661A (en) 1959-08-14 1960-08-15 Herbicidal compositions containing 3-substituted uracils
GB17419/64A GB968665A (en) 1959-08-14 1960-08-15 3-substituted uracils
GB17417/64A GB968663A (en) 1959-08-14 1960-08-15 3-substituted uracils
FR835959A FR1270771A (en) 1959-08-14 1960-08-16 New substituted uracils and their preparation
US217521A US3235357A (en) 1959-08-14 1962-08-17 Method for the control of undesirable vegetation
US232311A US3235360A (en) 1959-08-14 1962-10-22 Control of undesirable vegetation
GB619566A GB1035096A (en) 1959-08-14 1962-12-07 Improvements relating to herbicides
GB619366A GB1035094A (en) 1959-08-14 1962-12-07 Improvements relating to herbicides and novel 3-substituted uracils
GB619466A GB1035095A (en) 1959-08-14 1962-12-07 Improvements relating to herbicides and novel 3-substituted uracils
GB619166A GB1035092A (en) 1959-08-14 1962-12-07 Improvements relating to herbicides and novel 3-substituted uracils
DK534662A DK113254B (en) 1959-08-14 1962-12-10 Herbicide.
NO14675262A NO117095B (en) 1959-08-14 1962-12-10
SE13294/62A SE350496B (en) 1959-08-14 1962-12-10
CH923466A CH489201A (en) 1959-08-14 1962-12-11 Herbicides
CH923566A CH490007A (en) 1959-08-14 1962-12-11 Herbicides
CH923666A CH490008A (en) 1959-08-14 1962-12-11 Herbicides
BR14539162A BR6245391D0 (en) 1959-08-14 1962-12-11 HERBICIDAL COMPOSITES
CH1449962A CH487591A (en) 1959-08-14 1962-12-11 Herbicides
US284835A US3254082A (en) 1959-08-14 1963-06-03 Process for preparing substituted uracils
OA51234A OA01145A (en) 1961-12-11 1964-12-30 Substituted uracils, herbicidal compositions containing them, their preparation and use.
DK185565A DK129315B (en) 1959-08-14 1965-04-12 Herbicide.
BR171453/65A BR6571453D0 (en) 1959-08-14 1965-07-20 HERBICIDAL COMPOSITIONS AND PROCESS TO PREPARE ACTIVE INGREDIENTS FROM THE SAME
BR17145265A BR6571452D0 (en) 1959-08-14 1965-07-20 HERBICIDIC COMPOSITIONS AND PROCESS OF PREPARING USABLE PHENOL URACIL COMPLEXES AS ACTIVE INGREDIENTS OF THE SAME
US516686A US3360521A (en) 1959-08-14 1965-12-27 3-substituted-5, 6-alkyleneuracils
MY1965103A MY6500103A (en) 1959-08-14 1965-12-31 3- substituted uracils
MY1965102A MY6500102A (en) 1959-08-14 1965-12-31 Herbicidal compositions containing 3- substituted uracils
MY1965115A MY6500115A (en) 1959-08-14 1965-12-31 3- substituted uracils
MY1965116A MY6500116A (en) 1959-08-14 1965-12-31 3- substituted uracils
MY6900393A MY6900393A (en) 1959-08-14 1969-12-31 Improvements relating to herbicides and novel-3-substituted uracils
MY6900392A MY6900392A (en) 1959-08-14 1969-12-31 Improvements relating to herbicides and novel3-substituted uracils
MY6900391A MY6900391A (en) 1959-08-14 1969-12-31 Improvements relating to herbicides

Applications Claiming Priority (15)

Application Number Priority Date Filing Date Title
US83370459A 1959-08-14 1959-08-14
US83370559A 1959-08-14 1959-08-14
US1295760A 1960-03-07 1960-03-07
US1295660A 1960-03-07 1960-03-07
US1295860A 1960-03-07 1960-03-07
US1296860A 1960-03-07 1960-03-07
US1295960A 1960-03-07 1960-03-07
US1296760A 1960-03-07 1960-03-07
US4883760A 1960-08-11 1960-08-11
US8498061A 1961-01-26 1961-01-26
US8967461A 1961-02-16 1961-02-16
US12363661A 1961-07-13 1961-07-13
US15974661A 1961-12-15 1961-12-15
US232311A US3235360A (en) 1959-08-14 1962-10-22 Control of undesirable vegetation
US284835A US3254082A (en) 1959-08-14 1963-06-03 Process for preparing substituted uracils

Publications (1)

Publication Number Publication Date
US3235360A true US3235360A (en) 1966-02-15

Family

ID=27585449

Family Applications (2)

Application Number Title Priority Date Filing Date
US232311A Expired - Lifetime US3235360A (en) 1959-08-14 1962-10-22 Control of undesirable vegetation
US284835A Expired - Lifetime US3254082A (en) 1959-08-14 1963-06-03 Process for preparing substituted uracils

Family Applications After (1)

Application Number Title Priority Date Filing Date
US284835A Expired - Lifetime US3254082A (en) 1959-08-14 1963-06-03 Process for preparing substituted uracils

Country Status (12)

Country Link
US (2) US3235360A (en)
BE (1) BE594076A (en)
BR (1) BR6571453D0 (en)
CA (1) CA731651A (en)
CH (1) CH482402A (en)
DE (1) DE1240698C2 (en)
DK (1) DK106253A (en)
GB (2) GB968661A (en)
IT (1) IT635567A (en)
MY (4) MY6500103A (en)
NL (1) NL254838A (en)
SE (1) SE305770B (en)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330640A (en) * 1964-05-27 1967-07-11 Du Pont Method for the control of undesirable vegetation
US3436207A (en) * 1965-02-23 1969-04-01 Du Pont Control of undesirable vegetation
US3462435A (en) * 1966-11-15 1969-08-19 United States Borax Chem Alkyleneiminoquinazoline-2,4-diones
US3464989A (en) * 1967-05-19 1969-09-02 United States Borax Chem 3-alkyleneiminoquinazoline-4-imino-2-ones
US3471282A (en) * 1968-07-12 1969-10-07 Du Pont Herbicidal compositions containing poly uracils
US3532699A (en) * 1968-07-12 1970-10-06 Du Pont Herbicidal poly uracils
US3539333A (en) * 1968-08-21 1970-11-10 Gulf Research Development Co Combating weeds in sugar beets
US3869275A (en) * 1970-12-04 1975-03-04 Schering Ag Herbicidal mixtures
US3931171A (en) * 1970-02-05 1976-01-06 Bayer Aktiengesellschaft Process for the production of 2,3-dihydro-1,3-oxazinedione-(2,4)-compounds
US4111681A (en) * 1976-09-09 1978-09-05 E. I. Du Pont De Nemours And Company Cycloalkanapyrazole-3-carbonitrile herbicides
FR2498894A1 (en) * 1981-02-04 1982-08-06 Lecalvez Robert Herbicidal compsns. contg. lenacil and a urea (deriv.) - esp. for treatment of ornamental shrubs and conifers
US4859229A (en) * 1986-07-31 1989-08-22 Hoffmann-La Roche Inc. 3-Aryluracils having an ether (thio) carbomyloxy or sulphomyloxy substituent on the aromatic moiety
US5017211A (en) * 1987-09-23 1991-05-21 Ciba-Geigy Corporation Heterocyclic compounds
US5183492A (en) * 1989-06-29 1993-02-02 Ciba-Geigy Corporation Herbicidal 3-aryluracils
US5310723A (en) * 1993-08-05 1994-05-10 Fmc Corporation Herbicidal 3-(1-substituted-quinolin-2-on-7-yl)-1-substituted-6-trifluoromethyluracils
US5391541A (en) * 1993-08-11 1995-02-21 Fmc Corporation Herbicidal 3-(substituted-benzyl)-1-methyl-6-trifluoromethyluracils
US6409988B1 (en) 1999-07-01 2002-06-25 3-Dimensional Pharmaceuticals, Inc. Radiolabeled 1-aryl pyrazoles, the synthesis thereof and the use thereof as pest GABA receptor ligands
US6506784B1 (en) 1999-07-01 2003-01-14 3-Dimensional Pharmaceuticals, Inc. Use of 1,3-substituted pyrazol-5-yl sulfonates as pesticides
US6518266B1 (en) 1999-07-22 2003-02-11 3-Dimensional Pharmaceuticals 1- Aryl-3-thioalkyl pyrazoles, the synthesis thereof and the use thereof as insecticides
US6545033B1 (en) 1999-10-06 2003-04-08 3-Dimensional Pharmaceuticals, Inc. Fused 1-(2,6-dichloro-4-trifluoromethylphenyl)-pyrazoles, the synthesis thereof and the use thereof as pesticides
EP2052608A1 (en) 2007-10-24 2009-04-29 Bayer CropScience AG Herbicide combination
EP2090166A1 (en) 2008-02-14 2009-08-19 Bayer CropScience AG Liquid herbicidal preparations
DE102008037631A1 (en) 2008-08-14 2010-02-18 Bayer Cropscience Ag Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL272286A (en) * 1960-12-27
ZA731789B (en) * 1972-03-24 1973-12-19 American Cyanamid Co 2,3,5-substituted-6-trifluoromethyl-1,3-diazin-4-ones
US4189366A (en) * 1979-01-15 1980-02-19 Eastman Kodak Company Radiation curable compositions containing 5-halo-6-halomethyluracil derivatives as photoinitiators
EP0260621A3 (en) * 1986-09-18 1989-03-15 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft 3-aryl uracil-enol ethers and their use as herbicides
US5149810A (en) * 1988-04-22 1992-09-22 Imperial Chemical Industries Plc Pyrimidine compounds
EP0338686B1 (en) * 1988-04-22 1994-06-22 Zeneca Limited Pyrimidinone derivatives
DE58908208D1 (en) * 1988-07-29 1994-09-22 Ciba Geigy Ag Thiouracile as stabilizers for chlorine-containing polymers.
GB8908638D0 (en) * 1989-04-17 1989-06-01 Ici Plc Novel compounds
US6344460B1 (en) 1999-03-19 2002-02-05 Lonza Inc. Propynyl uracils
CN114656408A (en) * 2022-04-12 2022-06-24 药源药物化学（上海）有限公司 Synthetic process of plant protectant intermediate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2567651A (en) * 1951-09-11 J-dialkyl-g-amino-l
US2688020A (en) * 1952-01-17 1954-08-31 American Cyanamid Co Preparation of dihydrouracils
US2969364A (en) * 1957-12-26 1961-01-24 Upjohn Co Derivatives of 5-amino uracil
US3002975A (en) * 1958-08-25 1961-10-03 Diamond Alkali Co Process for the preparation of 1,3-dihalo-uracils
US3078154A (en) * 1956-11-07 1963-02-19 Geigy Ag J R Method for inhibiting the growth of plants
US3086854A (en) * 1959-02-05 1963-04-23 Du Pont Method for the control of plant growth

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2899435A (en) * 1959-08-11 S-neopentyl s-aixyl barbituric acid
US2937175A (en) * 1960-05-17 Preparation of orotic acid
US2444024A (en) * 1948-06-29 Sydney archer
GB693912A (en) * 1949-04-01 1953-07-08 Us Rubber Co Plant growth regulants and phytocides
US2820035A (en) * 1953-10-07 1958-01-14 Boehringer Sohn Ingelheim Barbituric acid derivatives
BE553585A (en) * 1955-12-21
NL100471C (en) * 1956-04-04

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2567651A (en) * 1951-09-11 J-dialkyl-g-amino-l
US2688020A (en) * 1952-01-17 1954-08-31 American Cyanamid Co Preparation of dihydrouracils
US3078154A (en) * 1956-11-07 1963-02-19 Geigy Ag J R Method for inhibiting the growth of plants
US2969364A (en) * 1957-12-26 1961-01-24 Upjohn Co Derivatives of 5-amino uracil
US3002975A (en) * 1958-08-25 1961-10-03 Diamond Alkali Co Process for the preparation of 1,3-dihalo-uracils
US3086854A (en) * 1959-02-05 1963-04-23 Du Pont Method for the control of plant growth

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330640A (en) * 1964-05-27 1967-07-11 Du Pont Method for the control of undesirable vegetation
US3436207A (en) * 1965-02-23 1969-04-01 Du Pont Control of undesirable vegetation
US3462435A (en) * 1966-11-15 1969-08-19 United States Borax Chem Alkyleneiminoquinazoline-2,4-diones
US3464989A (en) * 1967-05-19 1969-09-02 United States Borax Chem 3-alkyleneiminoquinazoline-4-imino-2-ones
US3471282A (en) * 1968-07-12 1969-10-07 Du Pont Herbicidal compositions containing poly uracils
US3532699A (en) * 1968-07-12 1970-10-06 Du Pont Herbicidal poly uracils
US3539333A (en) * 1968-08-21 1970-11-10 Gulf Research Development Co Combating weeds in sugar beets
US3931171A (en) * 1970-02-05 1976-01-06 Bayer Aktiengesellschaft Process for the production of 2,3-dihydro-1,3-oxazinedione-(2,4)-compounds
US3869275A (en) * 1970-12-04 1975-03-04 Schering Ag Herbicidal mixtures
US4111681A (en) * 1976-09-09 1978-09-05 E. I. Du Pont De Nemours And Company Cycloalkanapyrazole-3-carbonitrile herbicides
FR2498894A1 (en) * 1981-02-04 1982-08-06 Lecalvez Robert Herbicidal compsns. contg. lenacil and a urea (deriv.) - esp. for treatment of ornamental shrubs and conifers
US4859229A (en) * 1986-07-31 1989-08-22 Hoffmann-La Roche Inc. 3-Aryluracils having an ether (thio) carbomyloxy or sulphomyloxy substituent on the aromatic moiety
US5017211A (en) * 1987-09-23 1991-05-21 Ciba-Geigy Corporation Heterocyclic compounds
US5183492A (en) * 1989-06-29 1993-02-02 Ciba-Geigy Corporation Herbicidal 3-aryluracils
US5310723A (en) * 1993-08-05 1994-05-10 Fmc Corporation Herbicidal 3-(1-substituted-quinolin-2-on-7-yl)-1-substituted-6-trifluoromethyluracils
US5391541A (en) * 1993-08-11 1995-02-21 Fmc Corporation Herbicidal 3-(substituted-benzyl)-1-methyl-6-trifluoromethyluracils
US6409988B1 (en) 1999-07-01 2002-06-25 3-Dimensional Pharmaceuticals, Inc. Radiolabeled 1-aryl pyrazoles, the synthesis thereof and the use thereof as pest GABA receptor ligands
US6506784B1 (en) 1999-07-01 2003-01-14 3-Dimensional Pharmaceuticals, Inc. Use of 1,3-substituted pyrazol-5-yl sulfonates as pesticides
US6518266B1 (en) 1999-07-22 2003-02-11 3-Dimensional Pharmaceuticals 1- Aryl-3-thioalkyl pyrazoles, the synthesis thereof and the use thereof as insecticides
US6545033B1 (en) 1999-10-06 2003-04-08 3-Dimensional Pharmaceuticals, Inc. Fused 1-(2,6-dichloro-4-trifluoromethylphenyl)-pyrazoles, the synthesis thereof and the use thereof as pesticides
EP2052608A1 (en) 2007-10-24 2009-04-29 Bayer CropScience AG Herbicide combination
EP2090166A1 (en) 2008-02-14 2009-08-19 Bayer CropScience AG Liquid herbicidal preparations
DE102008037631A1 (en) 2008-08-14 2010-02-18 Bayer Cropscience Ag Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides
US20100062941A1 (en) * 2008-08-14 2010-03-11 Bayer Cropscience Ag Herbicide Combination Comprising Dimethoxytriazinyl-Substituted Difluoromethanesulfonylanilides

Also Published As

Publication number Publication date
SE305770B (en) 1968-11-04
MY6500103A (en) 1965-12-31
CA731651A (en) 1966-04-05
BR6571453D0 (en) 1973-05-10
DE1240698C2 (en) 1973-01-04
DK106253A (en) 1900-01-01
MY6500115A (en) 1965-12-31
MY6500102A (en) 1965-12-31
GB968663A (en) 1964-09-02
US3254082A (en) 1966-05-31
NL254838A (en) 1900-01-01
DE1240698B (en) 1973-01-04
GB968661A (en) 1964-09-02
IT635567A (en) 1900-01-01
MY6500116A (en) 1965-12-31
BE594076A (en) 1900-01-01
CH482402A (en) 1969-12-15

Similar Documents

Publication Publication Date Title
US3235360A (en) Control of undesirable vegetation
US3235361A (en) Method for the control of undesirable vegetation
US3235357A (en) Method for the control of undesirable vegetation
EP0104532B1 (en) O-halobenzoic acid derivatives, process for their preparation, herbicidal compositions and their use
US3235363A (en) Method for the control of undesirable vegetation
US3235358A (en) Control of undesirable vegetation
US3322526A (en) Herbicidal composition and method
US3360521A (en) 3-substituted-5, 6-alkyleneuracils
CA1291761C (en) Certain substituted 4-benzoyl-3,5-dioxotetrahydropyrans and thiopyrans
US3374083A (en) Method for the control of undesirable vegetation with 3, 5, 6-substituted uracils
US3436207A (en) Control of undesirable vegetation
US3497515A (en) 3,5,6-substituted uracils
US3189431A (en) Method for the control of undesirable plant growth
US4160037A (en) Compounds, compositions and methods of combatting pest employing thioureas
US3235362A (en) Method for the control of weeds
US3352863A (en) 3, 5-disubstituted uracils
US3244503A (en) Methods for the control of plants
US3803148A (en) Isoxazolopyrimidine herbicides and method of controlling plant growth
US3988300A (en) Benzophenone ureas and method for utilizing the same
IL32113A (en) 1-alkoxycarbonyl uracils,their preparation and herbicidal compositions containing them
US3216816A (en) Herbicidal composition and method
US3360522A (en) 3-bicycloalkyl-6-methyluracil
US3388153A (en) 3-phenyl-3-hydroxyureas and thioureas
US3089765A (en) Herbicidal method
US3512955A (en) Method of protecting plant growth