US3397050A - Herbicidal method - Google Patents

Description

United States Patent O 3,397,050 HERBICIDAL METHOD Harvey M. Loux, Valley View, Del., assignor to E. l. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 590,544, Oct. 31, 1966. This application Dec. 13, 1967, Ser. No. 690,077

12 Claims. (Cl. 71-92) ABSTRACT OF THE DISCLOSURE Novel uracils of the following formula:

AF\NN 0: R2 i H wherein R and R and are as defined hereinafter are useful as herbicides.

Exemplary of such compounds is: 5-bromo-6-methyl- 3-( 1-piperidino) uracil.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of my copending application Ser. No. 590,544, filed Oct. 31, 1966, which in turn is a continuation-in-part of my copending application Ser. No. 1,416,623, filed Dec. 7, 1964, which in turn is a continuation-in-part of my then copending application Ser. No. 159.768, filed Dec. 15, 1961, all now abandoned.

BRIEF SUMMARY OF THE INVENTION This invention relates to a novel class of uracils and to compositions and methods for using these uracils as herbicides.

The uracils of this invention are represented by the following formula:

N-N 0- R: H wherein is a cycloimino group selected from the group consisting of monocyclic heter-ocyclic groups containing from 3 through 8 ring atoms and bicyclic heterocyclic groups containing 7 through 12 ring atoms, provided the cycloimino group must contain one nitrogen atom bonding the group to the uracil nucleus, provided the group can have from 0 to 2 additional hetero atoms selected from the group consisting of oxygen, nitrogen and sulfur, and further provided the group can be substituted with a member selected from the group consisting of hydroxy, alkyl of 1 through 4 carbon atoms, and hydroxy alkyl of 1 through 4 carbon atoms;

R, is hydrogen, chlorine, bromine, fluorine, iodine, alkyl 3,397,050 Patented Aug. 13, 1968 is selected from the following groups:

azacycloalkyl of 3 through 8 ring atoms, azacycloalkenyl of 5 through 7 ring atoms, azabicycloalkyl of 7 through 11 ring atoms, diazacycloalkyl of 5 through 8 ring atoms, azabicycloalkenyl of 9 through 11 ring atoms, azaoxacycloalkyl of 5 through 8 ring atoms, azaoxacycloalkenyl of 5 through 8 ring atoms, diazabicycloalkenyl of 7 through 11 ring atoms, azaoxabicycloalkyl of 8 through 10 ring atoms, azaoxabicycloalkenyl of 9 through 11 ring atoms, azadioxacycloalkyl of 5 through 9 ring atoms, azathiacycloalkyl of 5 through 7 ring atoms, azadithiacycloalkyl of 5 through 8 ring atoms, azathiacycloalkenyl of 5 through 7 ring atoms, azathiabicycloalkyl of 9 and 10 ring atoms, or azathiabicycloalkenyl of 9 and 10 ring atoms.

azolyl.

Most preferred are the compounds where KN A N is azacycloalkyl of 5 through 7 ring atoms, azaoxacycloalkyl of 5 or 6 ring atoms, and azathiacycloalkyl of 5 or 6 ring atoms, the groups being substituted with from 0 through 4 methyl groups and contain 1 or 2 hetero atoms.

Exemplary of these compounds are:

5-bromo-6-methyl-3-( 1-piperidino)uracil 5-chloro-6-methyl-3-(1-piperidino)uracil 5-bromo-6-methyl-3- 1-pyrrolidinyl)uracil 5-chloro-6-methy1-3- l-pyrrolidinyl) uracil 5-bromo-6-methyl-3- (hexahydro-l-azepinyl) uracil 5 -chloro-6-methyl-3-(hexahydro- 1-azepinyl)uracil 6-methyl-3-(hexahydro-1-azepinyl)uracil 5-br omo-6-methyl-3-(4-morpholino) uracil 5 ,6-dimethyl-3-( l-piperidino) uracil As as well known in the art, herbicidal compounds frequently are utilized in the form of a heribicidal equivalent salt, addition compound, or complex derivative thereof for some formulating or handling advantage the derivative may provide over the compound per se. Similarly, it is to be understood that also included within the scope of this invention are salts, addition compounds, and complexes of the uracils of Formula 1 which can be formed from Lewis bases and acids and which exert a herbicidal effect similar to that of the uracils per se. Lewis bases and acids are generally described in the following texts: (1) J. Hine, Physical Organic Chemistry, McGraw-Hill Book Company, Inc., New York, 1956, Chapter 2; (2)

W. F. Luder and S. Zulfanti, The Electronic Theory of Acids and Bases, John Wiley and Sons, Inc., New York, 1946; (3) E. S. Gould, Mechanism and Structure in Organic Chemistry, Holt, Rinehart and Winston, New York, 1959, Chapter 4; (4) M. Arnett, Progress in Physical Organic Chemistry, Vol. 1, Edited by S. G. Cohen, A. Streitwieser, Jr., and R. W. Taft, Interscience Publishers, Inc., New York, 1963, Chapter entitled Quantitative Comparisons of Weak Organic Bases; and (5) G. A. Olah, Editor, Friedel-Crafts and Related Reactions, Volumes 1 and 2, Interscience Publishers, Inc., New York, 1963.

Non-limiting illustrations of compounds shown in the above texts which can be used to form salts, addition compounds, or complexes with the uracils of Formula 1 for purposes of the present invention are:

BASES Sodium hydroxide Potassium hydroxide Lithium hydroxide Calcium hydroxide Magnesium hydroxide Barium hydroxide Strontium hydroxide Ferric hydroxide Manganese hydroxide Quaternary ammonium hydroxides Primary, secondary and tertiary amines Heterocyclic amines Guanidines Amidines Phenols Cresols Naphthols ACIDS Friedel-Crafts catalysts Halogenated benzoic acids Mineral acids Organic sulfonic acids Halogenated aliphatic acids Halogenated aryloxyaliphatic acids Organic aliphatic and aromatic acids The preferred derivatives of uracils of Formula 1 for purposes of the invention are salts formed with the cations sodium, potassium, and lithium. This is because these salts are readily soluble in water and can be applied as aqueous solutions.

In Formula 1, the

cycloirnino group in the 3-position of the uracil ring can include but is not limited to such groups as where R, is alkyl of 1 through 4 carbon atoms or CH CH OH and y is 04.

It is obvious from the above that the term cycloimino as used herein includes hetero atoms but it is intended in accordance with the invention that the number of hetero atoms in the group of the 3-position of the uracil ring does not exceed three and can only be oxygen, nitrogen or sulfur.

DESCRIPTION OF THE INVENTION A suitable method for preparing the uracils of the invention is illustrated by the following equations:

O O benzene acid cata yst s N-NHCNHg CH CCNzGOOCzI-I5 A 0 CH3 H I s N-NHONHC=CHC o 0 02m 0 CH3 p; (D NaO C2135 s NNH NHC=CHCOOC2H5 HCl The semicarbazide used as a starting material in Equation 2 above can be prepared according to Ann., 221, 304 (1883) or Ben, 35, 4477 (1902).

The appropriately substituted urea is treated with a fi-keto ester or an tat-substituted ,B-keto ester substituted with such radicals as alkoxy, fluorine, or alkyl, and an acid catalyst, at reflux in a solvent from which water is removed continuously. After the water has all been removed, a methanolic solution of a base such as sodium methoxide is added. After a few minutes reflux, the reaction mixture is cooled and extracted with water. Upon acidification of the water layer, the desired product separates in crystalline form.

, The product formed at the end of the first step, i.e., after the water has been removed, is a ureido compound. It can be isolated and purified if desired; however, this is neither necessary nor advantageous for the operation of step 2.

These ureido compounds referred to above are believed to exist in either or both of two tautomeric forms, as

illustrated in the following equation:

(4) CH3-C=CHOOOC2H5 CHsC-CH2C O O O I-I I IH IUI 6:0 (1:0 llTH--N s :2 NIP-N s Uracils of this invention which are substituted in the 5-position with halogen and hydroxyrnethyl groups can be conveniently prepared in accordance with general methods heretofore described in the literature for related compounds.

For example, the preparation of those compounds having a halogen substituent in the 5-position is illustrated by Equation 5 below. For more general details, see I. Am. Chem. Soc. 61, 1015 (1939), Ann. 305, 314, Ann. 352, 242, and Ann. 441, 192. In the case of the chlorination, it is sometimes convenient to use sulfuryl chloride rather than chlorine.

The reaction of uracil-s, which are not substituted in the 5-position, with formaldehyde leads to uracils substituted in the 5-position with a hydroxymethyl group as illustrated by Equation 6.

0 s N-N I otno 6 s N-N I CHZOH CH3 BMOH) 0% CHa N N n H The metal salts of this invention 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 best 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 the reaction of 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. If the solvent-free salt is desired, it can be easily prepared by removing the solvent.

Alternately, the quaternary ammonium salts of the uracils can be prepared from the corresponding sodium salts in a dry inert solvent such as toluene or xylene. The 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 vacuum.

Addition compounds of the uracils of Formula 1 with Lewis bases such as amines can be prepared by mixing together equimolar quantities of an appropriate uracil and a nitrogenous base. The mixture is gradually heated, with stirring, until a clear melt is formed. On cooling, the addition compound crystallizes. This product can then be recrystallized from a solvent such as benzene, cyclohexane, nitromethane or acetonitrile.

It is sometimes advantageous to use an inert solvent medium to carry out the reaction. Such a solvent moderates the reaction by acting as a heat sink, and allows better control of the reaction, especially if it is being carried out on a large scale. Suitable inert solvents are benzene, cyclohexane, nitromethane, acetonitrile and dioxane.

When an inert solvent is used, the addition compounds are prepared by dissolving the amine in the solvent and then adding the uracil gradually, with stirring. Stirring is continued for from ten minutes to two hours. Mild heating may be necessary. Some addition compounds precipitate and can be removed by filtration. Other addition compounds are isolated by evaporation of the solvent. The addition compounds prepared in this way are suitable for use without further purification, but can be purified by recrystallization if desired.

In some instances, the uracil and amine are highly soluble in the inert solvent, but the addition compound is not, and so it can be filtered off pure when the reaction is complete.

Complexes of the uracils of Formula 1 with a Lewis base such as phenol can be formed by comelting the uracil and phenol in a 1:1 to 2:1 (uracilzphenol) ratio. They can also be formed by codissolving the reactants, in the same ratio, in a solvent such as nitromethane or a mixture of nitromethane and cyclohexane. Process conditions and isolation procedures are the same as those described above for the addition compounds.

The uracil derivatives of this invention including the uracils of Formula 1 and their salts, addition compounds, and complexes have outstanding herbicidal effectiveness. They are particularly active as post-emergence sprays at levels of from about 2 to 40 pounds of active material per acre for the control of annual grasses and perennial grasses such as quackgrass, Johnson grass, Bermuda grass, and nutsedge growing on railroad ballast, in industrial areas, or on and adjacent to crop land in agricultural areas. They are also useful for the postand pre-emergence control of annual grass and broadleaf seedlings when used as a spray at a rate of about A to 3 pounds per acre. Still another important use for the compounds of this invention is for pre-emergence and post-emergence control of a wide spectrum of Weeds and brush on industrial and railroad ballast sites using level-s of about 5 to 40 pounds of active material per acre.

In general, one uses the compounds of this invention at levels of at least about pound of active material per acre to obtain herbicidal effectiveness, the exact amount used being dependent upon the particular situation involved.

The compounds of this invention are preferably formulated with pest-control adjuvants, modifiers, or diluents, hereinafter generically called inert carriers. Formulation facilitates handling and often actually enhances herbicidal action. Such herbicidal formulations are prepared in the form of either powdered solids, granules, pellets, or liquids.

The liquid compositions, whether solutions or dispersions of the compounds of this invention in a liquid solvent, and also the wettable powders, contain as a conditioning agent one or more surface-active agents in amounts sufiicient to render a given composition containing the compounds of this invention readily dispersible in water or in oil. By the term surface-active agent it is understood that wetting agents, dispersing agents, suspending agents, and emulsifying agents are included.

Surface active agents suitable for use in the compositions of this invention are set forth, for example, in Searle, U.S. Patent No. 2,426,417; Todd, U.S. Patent No. 2,655,447; or Jones, U.S. Patent No. 2,412,510. See also Lenher et al., US. Patent No. 2,139,276. A detailed list of surface-active agents is set forth in an article in Soap and Chemical Specialties, Vol. 31, No. 7, pages 506l; No. 8, pages 48-61; No. 9, pages 52 67; and No. 10, pages 38-67 (1955). See also McCutcheon in Soap and Chemical Specialties, December 1957; January, February, March, 1958; and Bulletin 13-607 of the Bureau of Entomology and Plant Quarantine of the U.S. Department of Agriculture.

In preparing herbicidal compositions, surface-active agents are generally employed at concentrations of from about 1-10% by weight. Levels as high as 0.5 to 6 parts for each part of uracil, however, give unusual and unexpected beneficial results. Such compositions have a greater herbicidal efiectiveness than can be expected from a consideration of the activity of the components used separately.

Powdered or dust compositions of the invention, whether or not also modified with a surface-active agent, are pre pared by mixing the active ingredient with finely divided inert solid carriers. Such carriers are preferably talcs, natural clays, pyrophyllite, diatomaceous earth, and flours such as walnut shell, wheat, redwood, soya bean, and cottonseed. Other inert solid carriers which can be used include magnesium and calcium carbonates, calcium phosphates, sulfur, lime, etc., either in powder or granular form. The percentage by weight of the active ingredient will vary according to the manner in which the composition is to be applied, but, in general, will be from about 0.5 to by weight of the herbicidal composition.

Granule or pellet compositions can be prepared by mixing the active material in finely divided form with clays (with or Without water-soluble binders), moistening the mixture with 15-20% water, extruding the mass under pressure through an orifice, then cutting the extrusions to size before drying to yield pellets or first drying, then granulating to yield granules. Alternatively, granules can be made by spraying active material in solution or suspension upon the surface of a preformed granule of clay, vermiculite, or other suitable granular material. When the active material is soluble in the spray medium so it can penetrate into the pores of the granular carrier no'binding agent is needed. When it is insoluble and suspended, a binder is needed to adhere the active material to the surface. The binder can be soluble such as goulac, or dextrin r colloidally soluble such as swollen starch, glue or polyvinyl alcohol. The final step in either case is to remove the liquid medium whether solvent or carrier.

Herbicidal compositions of this invention can also be prepared by dispersing the active ingredient in an inert non-aqueous carrier. Aliphatic and aromatic hydrocarbons, for example, hydrocarbons of petroleum origin, are preferred as carriers. These dispersions are prepared by milling the uracil with dispersing agents and suspending agents and inert carriers in mills such as pebble mills. The amount of the herbicide in the dispersion may be from 10% or less to 48 and 50% of the oil dispersion.

Preferably, the particles in such dispersions range from about 1 to 50 microns although the majority are preferably in the range of from about 5 to 20 microns in average diameters. In general, the oils used include aliphatic and aromatic hydrocarbons and mixtures thereof, particularly those derived from petroleum and having a boiling point in the range from about 125 to 400 C. A hydrocarbon oil having a lower boiling point should not be used because when sprayed from a nozzle, such a hydrocarbon tends to volatilize undesirably. Furthermore, low-boiling hydrocarbons present a serious fire hazard.

In some situations it is desirable that the active uracil herbicide be released slowly from the carrier. Such compositions are particularly useful for application to gravel and cinder drive-ways and the like, where they release their herbicidal ingredients slowly over a long period of time and thus eliminate the necessity for frequent application.

Such compositions are made by incorporating the uracil into a solid or semi-solid matrix of a material such as portland cement or calcium sulfate. The uracils will be present in these compositions in varying concentrations depending upon the ultimate use of the products. Generally, they will contain from 1% to 40%, by weight, of uracil. They can be prepared by any of the well-known techniques, such as granulating or pelletizing.

Herbicidal formulations can also be prepared containing a fungicide or bactericide. When such compositions are applied to the soil, the fungicidal or bactericidal ingredients retard the breakdown of the uracils by soil microorganisms and thus renders them stable over a longer period of time. The fungicides and bactericides which can be incorporated into these compositions can be any of the well-known products such as, for example, antibiotics such as penicillin, phenols, thiocarbamates, and the like. The amount of microbiocide to be included in such compositions will naturally vary with their ultimate use. Generally, however, they will contain from 1% to 70% of a microbiocide.

The uracils of this invention can also be incorporated into paints, particularly marine paints, for application to surfaces where the growth of plants such as algae is undesirable. Such compositions are prepared by dissolving or suspending the uracil in a paint-compatible solvent. Uracils will be present in such compositions at concentrations of from 1% to The uracils of this invention can also be dissolved in a suitable solvent or dispersed in a suitable carrier and impregnated into wooden objects such as construction timbers or railroad ties. When these objects are placed in or near the ground, the uracils slowly leach from them,

8 thus preventing the growth of weeds in the nearby areas.

Such wooden objects can also be floated on the surface of water in which undesirable aquatic growth is present. Again, the uracil is slowly leached from the wood and prevents growth of nearby aquatic weeds for extended periods.

The concentration of uracil to be impregnated into any such wooden object will vary according to the nature of the wood and the type of weed to be controlled.

Optionally, adhesives such as gelatin, blood albumin, resins, for example, rosin *alkyl resins and the like can also be used in certain compositions to increase retention or tenacity of deposits following application.

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.

Among the known herbicides which can be combined with the uracils of this invention are:

SUBSTITUTED UREAS 3 -(3,4dichlorophenyl) -1,1-dimethylurea 3-(4-chlorophenyl)-1,l-dimethylurea 3-phenyl-1,l-dimethylurea 3- 3 ,4-dichlorophenyl) -3-methoxy-1, 1-dimethylurea 3-(4-chlorophenyl)-3-methoxy-1,1-dimethylurea 3-(3,4-dichlorophenyl)-1-n-butyl-1-methylurea 3-(3,4-dichlorophenyl) -1-methoxy-1-methylurea 3- (4-chlorophenyl) -1-methoxy-1-methy1urea 3- 3 ,4-dichlorophenyl)-1,1,3trimethylurea 3-(3,4-dichlorophenyl)-1,1-diethylurea These ureas can be mixed with the uracils of this invention in proportions of from 1:4 to 4:1, respectively, the preferred ratio being 1:2 to 2: 1.

SUBSTITUTED TRIAZINES 2-chloro-4,6-bis(ethylamino)-s-triazine 2-chloro-4-ethyl-amino-6-isopropylamino-s-triazine 2-chloro-4,6-bis (methoxypropylamino -s-triazine 2-methoxy-4,6-bis isopropylamino -s-triazine 2-diethylamino-4-isopropylacetamido-6-rnethoxy-s-triazine 2-methylmercapto-4,6-bis isopropylamino -s-triazine 2-methylmercapto-4,6-bis(ethylamino)-s-triazine 2-methylmercapto-4-ethylamino-6-isopropylamino-striazine 2-methoxy-4,6-bis (ethyl-amino -striazine 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis(isopropylamino)-s-triazine These triazines can be mixed with the uracils of this invention in proportions of from 1:4 to 4:1, respectively, the preferred ratio being 122 to 2:1.

PHENOLS Dinitro-o-sec-butylphenol and its salts Pentachlorophenol and its salts These phenols can be mixed with the uracils of this invention in the proportions of 1:10 to 20: 1, respectively, the preferred ratio being 1:5 to 5:1.

CARBOXYLIC ACIDS AND DERIVATIVES These carboxylic acids and derivatives can be mixed with the uracils of this invention in the listed proportions.

2,3,6-trichlorobenzoic acid and its salts 2,3,5,6-tetrachlorobenzoic acid and its salts Z-methoxy-3,5,6-trichlorobenzoic acid and its salts 2-methoxy-3,6-dichlorobenzoic acid and its salts 3-amino-2,S-dichlorobenzoic acid and its salts 3-nitro-2,S-dichlorobenzoic acid and its salts 2,4-dichlorophenoxyacetic acid and its salts and esters 2,4,S-trichlorophenoxyacetic acid and its salts and esters (2-methyl-4-chlorophenoxy)acetic acid and its salts and esters 2-(2,4,5-trichlorophenoxy)propionic acid and its salts and esters 2-(2,4,5-trichlorophenoxy)ethyl-2,2-dichloropropionate 4-(2,4-dichlorophenoxy)butyric acid and its salts and esters 4-(2-methyl-4-chlorophenoxy)butyric acid and its salts and esters Mixed in a 1:16 to 8:1 ratio, preferably a 1:4 to 4:1

ratio.

2,6-dichlorobenzonitrile Mixed in a 1:4 to 4:1 ratio, preferably a 1:3 to 3:1 ratio.

Trichloroacetic acid and its salts Mixed in a 1:2 to 25:1 ratio, preferably a 1:1 to 8:1 ratio.

2,2-dichloropropionic acid and its salts Mixed in a 1:4 to 8:1 ratio, preferably a 1:2 to 4:1 ratio.

N,N-dipropylthiolcarbamic acid, ethyl ester n-Propyl-N,N-dipropylthiolcarbamate N-propyl-N-ethyl-n-butylthiocarbamate Mixed in a 1:2 to 24:1 ratio, preferably a 1:1 to 12:1 ratio. 7

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 1:1 to 12:1 ratio.

2,3,6-trichlorophenylacetic acid and its salts Mixed in a 1:12 to 8:1 ratio, preferably a' 1:4 to 4:1 ratio.

2-chloro-N,N-dially1acetamide Maleic hydrazide Mixed in a 1:2 to 10:1 ratio, preferably a 1:1 to :1 ratio.

INORGANIC AND MIXED INORGANIGORGANIC SALTS These salts can be mixed with the uracils of this invention in the listed proportions.

Calcium propylarsonate Disodium monomethylarsonate Octyl-dodecylammoniummethyla'rsonate Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.

Sodium arsenit-e Mixed in a 1:5 to 40:1 ratio, preferably a 1:4 to 25:1 ratio.

Lead arsenate Calcium arsenate Mixed in a 150:1 to 600:1 ratio, preferably a 100:1 to 400:1 ratio.

Sodium tetraborate hydrated, granulated Sodium metaborate Sodium pentaborate Polyborchlorate Unrefined borate ore such as borascu Mixed in a 6:1 to 150021 ratio, preferably a 3:1 to 1000: 1 ratio.

Sodium chlorate Mixed in a 2:1 to 40:1 "ratio, preferably a 1:1 to 20:1 ratio.

Ammonium sulfamate Mixed in a 1:1 to 100:1 ratio, preferably a 1:1 to 50:1 ratio.

OTHER ORGANIC HERBICIDES 5,6-dihydro- 4A,6A -dipyri-do-( 1,2-A,2',1-C)pyraziniu-m d-ibromide Mixed in a 1:20 to 16:1 ratio, preferably a 1:5 to 5:1 ratio.

3-amino-1,2,4-triazole ,Mixed in a 1:20 to 20:1 ratio, preferably a 1:5 to 5 :1 ratio.

3,6-endoxohexahyd'rophthalic acid Mixed in a 1:3 to 20:1 ratio, preferably a 1:2 to 10:1 ratio.

Hexachloroacetone Mixed in a 1:2 to 16:1 ratio, preferably a 1:1 to 8:1 ratio.

Diphenylacetonitrile N-N-dimethyl-a,a-diphenylacetamide N-N-di-n-propyl-Z,6-dinitro-4-trifluoromethylaniline N-N-di-n-propyl-2,6-dinitro-4-methylaniliue Mixed in a 1:10 to 30:1 ratio, preferably a 1:5 to 20: 1 ratio.

0- 2,4-dichlorophenyl -O-methyl-isopropylphosphoramidothiate 2,3,5,6-tetracloroterephthalic acid, dimethyl ester Mixed in a 1:4 to 20:1 ratio, preferably a 1:3 to 15:1

ratio.

OTHER SUBSTITUTED URACILS These uracils can be mixed with other substituted uracils, in the proportions listed below. Methods for the preparation of the listed uracils which are novel can be found in copending applications Ser. Nos. 233,952, filed Oct. 29, 1962; and 232,311, filed Oct. 22, 1962, now US. Patent 3,235,360.

3-cyclohexyl-6-methyluracil 3-cyclohexyl-6-ethyluracil 3 -cyclohexyl-6-sec-butyluracil 3-norbornyl-6-rnetl1yluracil 3-cyclopentyl-6-methyluracil 3-cyclohexyl-6-isopropyluracil Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.

3-cyclohexyl-5,6-t'ri'met hyleneuracil 3-sec-butyl-5,6-trimethyleneuracil 3-isopropyl-5 6-trimethyleneuracil 3-isopropyl-5,6-tetramethyleneuracil 3-isopropyl-5,6-pentamethyleneuracil Mixed in a 1:6 to 6:1 ratio, preferably a 1:4 to 4:1 ratio.

3-cyclohexyl-5 ,6-dirnethyluracil 5-bromo-3cyclohexyl-6-methyluracil 5-chloro-3-phenyl-6-methyluracil Mixed in a 1:6 to 6:1 ratio, preferably a 1:2 to 2:1 ratio.

3-isopropyll-trichloromethylthio-5- b'romo-6-methyluracil 3cyclohexy-l-1-trichloromethylthio-S bromo-6-rnethyluracil 3-sec-butyll-acetyl-S-bromo-6-rnethyluracil 3-isopropyl-1-acetyl-5-broimo-'6-n1ethyluracil 3-isopropyl-1-trichloromethylthio-S-chloro-6-methyluracil Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.

The rate of application for compounds of this invention will, of course, vary with the particular end result desired, the particular use to which the compounds are put, the particular plant involved, the formulation used, the mode of application, the prevailing weather conditions, the foliage density, and the like. Since so many variables play a role, it is not possible to indicate generally a particular rate of application suitable for all situations. Certain particular usage rates that are found to be elTe-ctive can be suggested, but it must be understood the determination of the optimum particular rate for use in any given instance is conventional procedure to those skilled In order that the invention may he better understood, the following examples are given, wherein all parts and proportions are by weight unless otherwise indicated.

Example 1.-Preparation of 3-(hexahydro-l-azepinyl)- G-methyluracil A mixture of 126 parts l-(hexahydro-l-azepinyl) urea, 104 parts of ethyl acetoacetate, 4 parts of p-toluenesulfonic acid, and 1300 parts of toluene is refluxed for 20 hours, during which time 11.3 parts of water is collected in a Dean-Stark trap. The reaction mixture is cooled, 220 parts of a 29% solution of sodium methoxide in methanol is added, and refluxing is resumed for a period of 3 hours. The reaction mixture is cooled, poured into 1000 parts of ice water and stirred vigorously. The water layer is separated from the organic layer; the sodium salt of 3-(hexahydro-l azepinyl)-6-rnethyluracil is extracted with 500 parts of water, and the combined water layers are washed with 250 parts of methylene chloride. Acidification of the water layers with 95 parts of concentrated hydrochloric acid precipitates 3-=(hexahydro-l-azepinyl)-6-methyluracil.

The product is isolated by filtration and rinsed twice with 600 parts of water.

Recrystallization from acetonitrile gives pure 3-(hexahydro-1-azepinyl)-6-methyluracil.

By substituting equivalent amounts of the appropriate fl-keto ester and urea for the ethyl acetoacetate and 1- (hexahydro-l-azepinyl)urea set forth above, the following in the art. 30 uracils listed in Table I can be made similarly:

TABLE I .T-Keto Ester Reactant Substituted Urea Reactant Uracil Product Ethyl propionoacetate 1-(hexahydro-l-azepinyl)urea 6-ethyl-3-(hexahydro-1-azepinyl)uracil. Ethyl aceto-a-methylacetate don". 5,ttdimethyl-3-(hexahydro l-azepinyl)uracil.

Ethyl aeeto-a-ethflacetate- Q-carboethoxycyclopentanone 2-earboethoxycyclohexanone Ethyl acetoacetate Ethyl propionoacetate Ethyl aceto-a-fiuoroaeetate Ethyl aceto a-methylacetate 2-carboethoxycyclopnetanone Ethyl acetoacetate Ethyl aceto-a-fluoroacetata. Ethyl aceto-wmethylacetata Ethyl aceto-aethylaeetata 2-carboethoxycyclopentanone 2-carboethoxycyclohexanone 2-carboethoxycycloheptanone Ethyl aceto-a-fluoroacetate Ethyl aeeto-a-methylacetate. Ethyl acettra-ethylacetate. 2-carboethoxyoyclopentanone- 2-carboethoxycyclohexanone 5-ethyl-3-(hexahydro-l-azepinyl)-6-methyluracil. 3-(hexahydro-l'azepinyl)-5,6ttrimethyleneuracil. S-(hexahydro-l-azepiny1)-5,6-tetra.methyleneuracil 6-methyl-3-(4-morpho1in0) uracil.

6-ethyl-3-(4-morpholino)uracil.

5-fluoro-6-methyl-3-(4-morpholino) uracil.

5,6d1methyl-3-(4-morpholino) uracil.

3-(4-morpholino) 5,6-trimethyleneuracll.

(i-methyl-B-(l-piperidino) uracil.

3-(1-piperidin0)-5,6-trimethyleneuracil.

3-(1-piperidin0) 5,(i-tetramethyleneuracil.

5,6-pentamethylene-3-(l-piperidino)uracil. 5-Iluoro-6-methyl-3-(l-pyrrolidinyl) uracil. 5,6-dimethyl-3-(l-pyrrolidinyDuracil.

5-ethyl-6-methyl-3-(l-pyrrolidinyl)uracil.

, 3-(l-pyrrolidinyD-5,fi-trimethyleneuraeil.

3-(1-pyrrolidinyD-5,B-tetramethyleneuracil.

Ethyl aceto-a-methylacetate ,3,5-dithiazin-5-yl)urea 5,tidiniethylt-(dihydro-l,3,5-dithiazin-5-yluraci Ethyl aceto-wfiuoroacetate do 3-(dihyiiro-l,3,5-dlthiazin-5-yl)-5-fiuroro-&methylm'aci Do 1-(1-aziridinyl)urea 3-(1-aziridinyl)-5-fluoro-6-methyluracil. Ethyl aeeto-a-methylacetate o 3-(l-aziridinyl)-5,6-dimethyluracil.

Ethyl acetoacetate 1-(1,2,3,fi-tetrahydro-l-pyridyl)urea 6'methy1-3-(1,2,3,6-tetrahydro-1-pyridyl)uracil.

Ethyl aceto-a-methylacetate 1-(4-methyl-1-piperazinyl)urea 5,6-dimethyl-3-(4-methyl-1-piperazinyl)uracil.

Do 1-(1,2,3-6-tetrahydro-1-pyridyl)urea .t 5,6-diInfthyl-3-(1,2,3,6-tetrahydro1-pyridyl) uraci.

Ethyl accto-a-fluoroacetate 1-(1,2,3,6-tetrahydrol-pyridyl)urea 5-fiuorqi6-methyl-3-(1,2,3,6-tetrahydro-1-pyrldyl) uraci Ethyl acetda-ethylacetate 1-(4methyl 1-piperazinyl)urea 5-ethyl-6-methy1-3-(4-methyl-1-piperazinyl)uracil.

Ethyl aceto-a-fluoroacetate ..do 5-fiu01'o1-6-methyl-3-(4-methyl-1-piperazinyl) uraci.

Ethyl acetoFa-methylacetate 1-(2,fi-dimethyM-morpholino)urea 5,ttdimfthyl-3-(2,5-dimethyl-4-morpholino)- uracl Ethyl acetoacetate .do 3-(2,5-dimethy1-4-morpholino)fi-methyluracil.

Ethyl aceto-a-methylacetate l-(2-methyl-1-piperidino)urea.. 5,6-dimethyl-3-(2-rnethyl-l-piperidino)uracil.

Ethyl acetoa-fluoroacetate "do 5-fiuoro1-6-methyl-3-(Z-methyl-l-pipcridino) uraci.

Ethyl propionoacetate l-(l-piperazinyDurea 6-ethyl-3-(l-piperazinyhuracfl.

Ethyl acetoacetate t 1-(2-methyl-4-pyrazolin-l-yDurea 6-methy1-3-(2-methyl-4-pyrazo1in-1-yl)uracil.

Ethyl aceto-a-ethylacetate .d0 5-ethyli6-methy1-3-(2-methyl-4-pyrazo1in-1-yl) uraci Ethyl aceto-a-fiuoroacetate do fi-fiuorol-6-methyl-3-(2-methyl-4-pyrazolin-l-yl) uraci Ethyl acetoacetate l-(tetrahydro-l,4-thiazin-4-yl)urea 6-methyl-3-(tetrahydro-l,4-thiazin-4-yl)uracil.

Ethyl propiono-a-methylacetate do 6-ethyl -15-methyl-8-(tetrahydro-1,4-thiazin-4-yl) Ethyl aceto-a-fluoroacetate do 5-fluorol-6-methyl-3-(tetrahydro-l,4-thlazin-4-y1) uraci Ethyl aceto-a-methylacetate 1-(dihydro-l,3,5di0xazin-5-yl)urea 3-(dihyldro-1,3-5-dioxazin-5-yl)-5,6-dimethyl- Ethyl acetoacctate d0 3-(dihydro-l.3,5-dioxazin-5-yl)-6-methylurac1l.

Do 1-(1,2,3,4-tetrahydro-2-1soqumolmyl)urea 6-Il1eth1yl-3-(1,2,3,4-tetrahydro-2-isoquinolinyl)- Ethyl aceto-a-ethylacetate l-[4-(2'hydroxyethyl)-1-piperaziny1]urea 5-ethylll-3il4-(2%1ydroxyethyl)-1-piperazinyl]-6- me y 1118.01

Ethyl acetoFa-fiuoroacetate "do 5-fi110ro-3-[4-(2-hydroxyethyl)-l-piperazinyl]-6- methyluracil.

TABLE II-Continued Uracil Starting Reactnats Parts by Weight Uracil Product Obtained of Halogen 3-[2-(-hydroxy-1,1-dirnethylethyl)-1-pyrrolidinyl]-6methy1uracil. 17.0 (Bl'z) 5brofio-ii-[Z-(fihydroxyl-l,l-dimethylethyl)-1-pyrrolidinyl]-6- me y urae 6-methyl-3-(2,3,5,6-tetramethyl-piperazin-1-yl)uracil 17.0 (Brz) 5-bromo-6-methyl-3-(2,3,5,6-tetramethyl-piperazin-l-yl)uracil.

3-(benzlrnidazol-1-yl) -6-methyluraci1 3-(octahydro-1-azocinyl)-6-methyluracil.

3-(decahydro-lquinolyl)-6-methyluraci1 17.0 (B12) 3-(11-azabicyclol4-4-1]-undee-11-yl)-6-methylurac11 17.0 (Br (i-methyl-B-(2-methyl-3-oxazolidinyl)uracil 8.0 (012)". 3- (hexahydro-2H-1,5-oxazocin-5-yl) -6-rnethyiurac1l. 84) (011).. 3-(4-oxazolin-3-yl)-6-methyluraeil 8.0 (012).. 3-(8-oxa-3azabicyclo-[3.2.11-oct-3-yl)-6methyluracil 17.0 (Brz) 3-(octahydru-2H-1,3-benzoxazin-3-yl)-6-methyluracil. 17.0 (Bra)... 3-(3-benzoxazolinyl)-6-methylu.racil 8.0 (012)-- 3-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)-6-methyluracil 8.0 (012)-".

5-bromo-348-oxa-3-azabicyclo[3.2.1]0ct3-y1)-6-methyluracil. 5-bromo-3-(octahydro-2H-1,3-benzoxazin-3-yl)-6-methyluracil. 3-(3-benzoxazolinyl) -5-chloro-6methyluracil.

5-chloro-3-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)-6-methyluracil.

Example 3.-Prepa-ration of 3-(hexahydro-l-azepinyl)-5- hydroxymethyl-6-methyluracil TABLE III Uracil Reactant Uracil Product Obtained G-methyl-3-(4-morpholino)uracil.. 5-hydroxymethyl-fi-methyi-a(4- morpholino)uracil. 6-methyl-3(1-piperidino)uracil 5-hydroxymethyl-6-methyl-3(1- piperidino)uracil. G-methyl-S- (l-pyrrolidinyl) uracil. 5-hydroxymethyl-(i-methyl-3-(1- pyri'olidinyDuracil. 5-hydroxymethyl-3-(4-methyl-1- piperazinyl)-6-methyluracil.

3-(4-mefhyl-1-piperazinyl)-6methyl 40 uraci Excess iodine which precipitates is removed by filtration, and the filtrate is diluted with 400 parts of cold water. The remaining iodine in the mixture is reduced to iodine ion by adding a sufficient quantity of a saturated, aqueous solution of sodium bisulfite to render the solution colorless.

The aqueous mixture is extracted with 800 parts of methylene chloride. The organic layer is separated, washed with saturated sodium bicarbonate solution, and then dried with magnesium sulfate.

Removal of the methylene chloride leaves 3-(hexahydro-l-azepinyl)-5-iodo-6 methyluracil.

The following 5-iodo uracils can be prepared similarly by substituting an equivalent amount of the reactant uracils listed in Table IV below one at a time for the 3-(hexahydro-l-azepinyl)-6-methyluracil set forth above.

Uracil Reactant 3-(2, 5-dimethyi-4-morpholino)-6- methyluraeil. 3-(Z-rnethyl-l-piperidino)-6methylurac 6-methyi-3-(1-pip erazinyl) uracil...

6-methyl-3-(2-methyi-4-pyrazo- 1in-1-yl)-uracil.

3-(dihydro-1, 3, 5-dioxazin-5-yD-6- methyluracil.

6-methyl-3-(1, 2, 3, ttetrahydro-Z- isoquinolinyl) uracil.

3-[4-(Q-hydroxyethyl)-1-piperazinyl]-6-methylu.racil.

3-(dihydro-1, 3, 5-dithiazin-5-yl)- fi-methyluracil.

3-[3-azabicyclo (3.2.2)nonan-3-yl]-6- methyluracil.

6-methyl-3-(1, 2, 3, G-tetrahydro-lpyridyl)uracil.

3-(dihydro-2, 4, fi-trimethyl-l, 3; 5- dithiazin-5-yl)-6-methyluracil.

3-(11-azabieyc1o[4.4.1]undec-1-en-l1- yl-6methyluracil.

6-methyl-3- (4-thiazolin-3-yl) -uracil 3-(3, 4-dihydro-2H-l, 4-benzothiazin- 4-yl)-6-methyluracil.

5-hydroxymethyl-3- (2, 5-dimethyl-4- morpholino)-6-methyluracrl.

5-l1ydroxyInethyl-3-(2-methyl-1- piperidin0)-6-In ethyluracil.

5-hydroxymethyl-6-methyl-3- (l-piperazinyhuracil.

5-hydroxymethyl-6-methyl-3-(2- methyl-4pyrazolin-1-yl) -urac1l.

5-hydroxymethyl-G-methyl-Zi-tetrahydro-1,4-thiazin-4-yi)-uraci1.

5-hydroxymethyl-3-(dihydro-l, 3, 5-

dioxazin-5yl)-6-methyluracil.

fi-hydroxymethyl-fi-methyl-ZS- (l, 2, 3, 4-tetrahydro 2-isoquinolinyl)- uracil.

5-hydroxyrnethyl-3-[4-(2-hydroxyethyl)-l-piperazinyl]-6methyluracil.

3-(dihydro-1, 3, 5-dithiazin-5-yl)- ahydroxymethyl-ti-methyluracil.

3-[3-azabicylo (3.2.2)n0nan-3-yl]- hydroxymethyl-fi-methyluracil.

(1, 2, 3, G-tetrahydro-l-pyridyl)- uracil.

3- (dihydro-2, 4, G-trimethyl-l, 3, 5-

dithiazin-5yl)-5-hydroxymethyluracil.

3-(11-azabicyclo[4.4.1]undec-1- en-l1-y1)-5-l1ydroxymethy1-6- methyluracil.

5-hydroxymethyl-dme thyl 3-(4- thiazolin-3-yl)uracil.

3-(3, 4-dihydro-2H-l, -benzothiazin-4-yl)-fi hdroxymethyl- G-methyluraeil.

Example 4.Preparation of 3-(hexahydro-1-azepinyl)-5- iodo-6-methyluracil 3-(4-methyl-1-piperazinyl)-6- methyluracil.

3-(2,5-dimethyl-4-morpholino)-6- methyluracil.

3-(2-methyl-1-piperidino)-6-methyl- 5-iodo-3-(4-methyl-1-piperazinyD- fi-methyluracil. 3-(2,5-dimethy1-4-morpholino)-5- iodo-G-methyluracil. 5-iodo-3-(2-methyl-1-piperidino)- fi-methyluracil. 5-iodo-6-methyl-3-(l-piperazinyl) uracil. 5-iodo-6-methyl-3-(2-n1ethyl-4- 0 6-methyl-3-(1,2,3,4-tetrahydro-2- A mixture of 22.3 parts of 3-(hexahydro-l-azepinyl)-6- methyluracil, parts of acetic acid, and 25.4 parts of iodine is stirred at 100 C. as 7.5 parts of fuming nitric acid are gradually added. Upon completion of addition, the solution is refluxed for /2 hour, and then cooled in an ice bath. 75

yl)uracil. pyrazolin-l-yDuracil. 6-methyl-3-(tetrahydro-1,4-thiazin- 5-iodo-6-methyl-3-tetrahydro-1,4-

methyluracrl. iodo-fi-methyluracil.

5-iodo-6-methyl-3-(1,2,3,4-tetrahydro-Z-isoquinolinyl)uracil. 3-[4-(2-hydroxyethyD-l-piperazinyl1-5-iodo-6methyluracil. 3-(dihydro-1,3,5-dithiaziu-5-yl)- fi-ioddfi-methyluracil. 5 iodo-dmethyl-3-(l-pyrrolyl) uracil. 5-iodo-6n1ethyl-3-(1,2,3,6-tetrahydro-l-pyridyDuracil.

isoquinolinyhuracil. 8-[4-(Z-hydroxyethyl)-1 piperamethyluracil. 6-methyl-3-(l-pyrroiyDuracil 6methyl-3-(1,2,3,6-tetrahydro-1- pyridyDuracil.

Example 5.-Preparation of 3-(hexahydro-1-azepinyl)-5- methoxymethyl-G-methyluracil A mixture of 22.3 parts of 3-(hexahydro-1-azepinyl)- o methyluracil, 140 parts of water, 38 parts of ethyl alcohol, 6.6 parts of para-formaldehyde, and 2 parts of barium hydroxide is heated and stirred at reflux for /2 hour. The solution is cooled in an ice bath, neutralized with dilute hydrochloric acid, and stripped free of water and alcohol under reduced pressure.

The residue is stirred with 50 parts of methanol, and the solution is filtered to remove inorganic salts. One part of chloracetic acid is added to the solution. The reactants are charged to a bomb, and heated at C. for 6 hours. The reaction mixture is heated for several minutes with 1 part of decolorizing charcoal, filtered hot, and stripped free of solvent under reduced pressure to yield 3-hexahydro-1-azepinyl-S-niethoxymethyl-6-methy1uracil.

17 18 The following 5-alkoxymethyluracils can be made simi- At concentrations of 2 to 4 pounds (active) per acre arly by substituting an equivalent amount of the uracil in 100 gallons of water, this material gives excellent conreactants and alcohols listed in Table V for the 3-(hexatrol of a wide variety of annual and broadleaf weeds hydro-1-azepinyl)-6-methyluracil and methanol set forth growing in railroad yards on railroad ballast.

above: 5

TABLE V Uracil Reactant Alcohol Reactant Uracil Product Obtained (rmethyl-lt(4-morpholino)uraeil (32H5OH 5-ethoxymethy1-6-methyl3-(morpho1ino)uracil. 6-methy1-3-(lpiperldino)uracil 03111011.- 6-methyl-3-(1-piperidlno)-5-propoxymethyluracil. 3-(4-methyl-1-piperazinyl)-6-methyluracll C2H5OH 5-eth0xymethyl-3-( i-methyl-l-plperazlnyl)-6-methy1urncil. 3-(2,5-dimethyl-4-morophollno)-6-methyluracil CH;OH- 3(2,5-dimethyM-morpholino)-5-methyoxmethyl-fi-methyluracil. 6-methyl-3-(l piperazlnyDuracil CH3OH. 6-methoxymethyl-fi-methyl-ES-(l-plperazinyDuraell. 6 methyl-3-(Z-methyl-d-pyrazolin-l-yDuracll. CH OH. 5-methoxymethyl-(i-methyl-8-(2-methyl-4-pyrazolin-1-yl)uracil. 6methyl-3-(tetrahydro-l,4-thiazin-4-yl)uracll CH3OH 5-methoxymethyl-fi-methyl-3-(tetrahy rol,4-thiazin-4-yl)uracil. 3-(dihydro-1,3,5-dioxazin-5-yl)-6-methyluracil CHaOH. 3-(dlhydro-l,3,5-dioxazln-5-yl)-5-methoxymethyl-6methyluracil. (rmethyl-3-(1,2,3,4-tetrahydro-2-isoquinolinyl)uracil CHSOH--. 5-methiaxymethyl-fi-methyl-B-(1,2,3,4-tetrahydro-2-Isoquino1iny1) 111801 3-[4-(Z-hydroxyethyl)-1-plperazinyl]-6methyluracil iso-C3H1 3-[4-(Z-gydroxyethyl)-1-piperazinyl]-5-lsopropoxymethyLB-methyb 11130 3-(dihydro-l,3,fi-dithiazln-fi-yl)-6-methyluracil CHQOH..- 3-(dihifidro-1,3,5-dlthlazln-5-yl)-5-methoxymethyl-6-methyl- 11160 3-(hexahydro-l,4-dlazepin-1-yl)-6-methyluracil 0113011.... 3-(hexahydro-1,4-dlazepin1-yl)-5-methoxymethyl-fi-methyluracil. fi-rnethyl-B-(l,2,3,G-tetrahydro-l-pyridyl)uracil CHaOH... 5-methoxymethyl-fi-methyl-S-(1,2,3,G-tetrahydro-l-pyrldyl)uracil. 6- methyl-3-(2-methylthiazolidln-3yl)uracil CHGOH 5-meth0xymethyl-6-methyl-3-(-methylthiazolidin-8-yl)uracll. 3-(hexahydro-3-benzothlazollnyl)-6-methyluracll CHQOH 3-(hexalhydro-ii-benzothlazollnyl)-5methoxymethy1-6-methyl- 11130 3-(3-benzothiazo1iny1)-6-methy1uracll CHHOH 3-(3-benzothlazolinyl)-5-methoxymethyl-fi-methyluracll- Example 6.Preparation of 5-bromo-3-(hexahydro-1- Example 8 azepinyl)-6methyluracil, sodium salt Aqueous suspension: Percent A solution of 4 parts of sodium hydroxide in 150 parts 35 :32: 5 3'(hexahydm'l'azepmyl) 6methy1' 28 of water is added to 21.7 parts of -bromo-3-(hexahydro- Sodium g g' ggg g l-azepinyl)-6-methyluracil. The suspension is stirred and H drated i u] warmed to effect solution. The water is removed from the Dglsodium solution under reduced pressure, leaving the sodium salt Sodium g fi 555 of the uracil as a white solid. 40 Water p p The following metal salts can be prepared similarly by substituting equivalent amounts of other uracils and other The above ingredients are mix-ed and pebble-milled or metallic hydroxides for the 5-bromo-3- (hexahydro-l-azesand-milled until the average particle size of the active pinyl)-6-methylur-acil and sodium hydroxide set forth material is substantially less than 5 microns. The resulting above. The following list contains examples of typical 4.5 stable th1xotropic suspension does not cake, and can be salts of the invention: readily diluted with water to form a dilute, very slowly settling suspension which re uires no a itation durin S-bromo-6-methyl-3-(4-morphol1no)uracll, hthium salt application q g g gg i -m l g mti pPtassmm Salt This aqueous suspension, applied as directed spray at romo'6'met y Sodlum salt 1 to 3 pounds of active ingredient per acre in 30 gallons 5-chloro-6-methyl-3-(1-pyrrolidinyl)uracil, lithium salt of water, ives ood re-emer ence co trol of bar d- 5,6-di'methyl-3-(1-pyrrol1dmyl)urac1l, potassium salt g g P g n nyar grass, wild mustard, green 'foxtail, and jungle ricegrass in 3-(4-morpholino) -5,6-trimethyleneuracil, lithium salt 5-bromo-6-methyl-3-(l-pyrrolidinyl)uracil, sodium salt estabhshed sugar cane' 5-ohloro-6-methyl-3 (1-piperindo)uracil, sodium salt 55 Example 9 5-iodo-6-methyl-3-(1-pyrrolidinyl)uracil, sodium salt Aqueous dispersion: Percent The following examples illustrate preparation and use gigg 3:tg zfi formulations incorporating the herbicidally active com- Sodium 55 Pounds of the mventlon' Hydrated attapulgite 1,75 Example 7 Water 54.25 Aqueous 1 ti Percent This formulation is wet-milled until the particles are 3 '(hexahydro-l-azepinyl)-6.methy1uraci1, Sodium substantially all below 10 microns in size, to yield a stable Salt 5 i p r i n. An application of 30 pounds per acre (active) Sodium lauryl sulfate 2 f hi formulation in 40 gallons of water controls annual Water 93 and perennial broadleaf and grass weeds such as quackgrass, giant foxtail, ragweed, and lambsquarters growing The solution 1s prepared by dissolving the two soluble i fire-breaks in fo e t d areas. salts in the water, with agitation. This solution is suitable for quick dilution to desired spray levels. Example 10 This aqueous solution is used for post-emergence weed Aqueous concentrate: Percent control. An application of 2 to 3 pounds of active ingredi- S-bromo 3-(hexahydro l-azepinyl) 6-methylent per acre in 30 gallons of water gives excellent control uracil, potassium salt 10 I of crabgrass, pigweed, wild mustard, ryegrass, chickweed, Sodium lauryl sulfate 1 and wild oats. Water 89 The aqueous concentrate is prepared by dissolving the two solid components in water. The concentrate can be easily diluted to use levels and sprayed.

These aqueous concentrates are conveniently applied with a pressure-type hand sprayer. One to two pounds of active ingredient per acre in 40 gallons of water gives excellent pro-emergence control of foxtail, watergrass, and Johnson grass seedlings in established sugar cane. This formulation, at 40 pounds of active ingredient per acre in 100 gallons of water, provides control of a wide variety of annual and perennial weeds on industrial sites and railroad ballast.

Example 11 Emulsifiable oil: Percent 5-bromo-6-methyl-3-(l-piperidino) uracil 20.0

Alkyl aryl polyether alcohol 2.5 Oil soluble petroleum sulfonate 2.5 Isophorone 75.0

The emulsifiable oil is prepared by mixing the above components until a homogeneous solution results. It can then be emulsified in water for application.

This emulsifiable oil is useful for weed control on railroad rights-of-way, in railroad yards, and on sidings. When this composition is diluted with 100 gallons of water per acre and sprayed from a railroad spray car at pounds of active ingredient per acre, mixed vegetation such as quack grass, crabgrass, Bermuda grass, brome grass, rag-weed, cocklebur, lambsquarters, and marestail is controlled for an extended period.

The emulsion is also highly useful for brush control when extended with water so that 10 pounds is contained in 100 gallons of water. This mixture is sprayed on undesirable brush species such as sweet gum, crab apple, oak, maple, and poplar until the foliage is thoroughly wetted whereupon excellent control of the brush species is obtained.

Example 12 Emulsifiable oil suspension: Percent 5-bromo-6-methyl-3-(l-pyrrolidinyl) uracil 25 Blend of polyalcohol carboxylic acid esters and oil-soluble petroleum sulfonates 6 Diesel oil 69 The above components are mixed together, and milled in a roller mill, pebble, mill, or sand mill until the par ticles of the active component are substantially all below 10 microns in size. The resulting suspension can be emulsified in water or diluted further with weed oils for spray application.

This formulation is diluted with 80 gallons of Lion Herbicidal Oil, No. 6 and applied at 10 to pounds of active ingredient per acre for the control of weeds such as morningglory, chickweed, pigweed, lambsquarters, yarrow, ragweed, wild carrot, quack grass, witchgrass, crabgress, and oak and maple seedlings growing along railroad rights-of-way. Excellent control is obtained.

Example 13.Tank mixes (A) Ten pounds of 5-bromo-6-methyl-3-(1-piperidino)- uracil as an 80% wettable powder and 2 pounds of 4,6- dinitroorthosecondary butylphenol in 4 gallons of oil are blended as a tank mix, and applied at 12 pounds of active herbicide per acre in 100 gallons of water to weeds growing along fence rows. Quick kill of annual and perennial broadleaf and grass weeds is obtained with excellent residual weed control.

(B) Fifteen pounds of an 80% water-dispersible powder formulation of 5-bromo-3 (hexahydro 1 azepinyl)-6- met-hyluracil and 24 pounds of 2,2-dichloropropionic acid, sodium salt, 85% are dispersed and mixed in 100 gallons of water.

This composition is good for the control of perennial grasses and broadleaf Weeds on railroad rights-of-way. An application of 100 gallons of this formulation per acre 20 gives good control of Johnson grass, Bermuda grass, nutsedge, barnyard grass, crabgrass, plantain, ragweed, and beggarticks.

(C) Nineteen pounds of an water dispersible powder formulation of 5-bromo-6-methyl-3-(l-pyrroldinyl)uracil and 20 pounds of 2,2-dichloropropionic acid, sodium salt are dispersed and mixed in 50 to 100 gallons of water. This composition, sprayed on one acre, gives good control of both annual and perennial grasses and broadleaf weeds growing along railroad rights-of-way and around loading dock installations.

Such difficult-to-kill weeds as crabgrass, dock, ragweed, lambsquarters, pigweed, goatweed, carpetweed, beggarticks, Spanish needle, nightshade, black medic, knotweed, plantain, spotted spurge, and velvetleaf are controlled by this application.

(D) Twelve pounds of 5-bromo-6-methyl-3-(l-piperidino)-uracil as an 80 Wettable powder and 35 pounds of ammonium sulfarnate are blended as a tank mix in 100 gallons of water.

This composition is sprayed on mixed brush species such as gum, Viburnum, willow, cedar, oak, and maple infesting a power line right-of-way until the undesirable plant-s are thoroughly wetted. Good control of these brush species is obtained.

Anapplication of 47 pounds per acre (active) in 100 gallons of water controls annual and perennial broadleaf, and grass weeds, giving rapid contact action and extended residual weed control. Weeds controlled by this treatment include crabgrass, broomsedge, cocklebur, flower-of-anhour, and oak, maple, and sweet gum seedlings.

SOLID COMPOSITIONS Example 14 Dusts: Percent 3-(hexahydro-l-azepinyl)-6-methyluracil 10.0 Talc These components are blended and micropulverized until the particles of uracil have been reduced to about 10 microns in diameter, then reblended.

Example 15 Granules: Percent 5-bromo-6-met'hyl-3-(lpyrrolidinyD-uracil 5 Anhydrous sodium sulfate l0 Non-swelling sub-bentonite clay 85 The compounds are blended and micropulverized, then moistened with water and granulated. The granules are then dried and screened.

The granules are applied conveniently by hand for spot treatment of undesirable bunch grasses growing in agricultural areas. An application of 20 pounds of active ingredient per acre gives good control of Muhlenbergia, Orchard, Vasey, and Kentucky 31 fescue grasses.

Example 16 Pellets: Percent 5-bromo-6-methyl-3-(l-piperidino) uracil 25 Anhydrous sodium sulfate 10 Sodium lignin sulfonate 10 Ca, Mg bentonite 55 The components are blended and micropulverized, then moistened with 1820% water and extruded through die holes. The extrusions are cut as formed to give pellets and dried.

These pellets are useful for weed control along highway guard rails, around bridges, cyclone fences, and highway signs. They are applied conveniently by hand methods at 10 to 25 pounds of active ingredient per acre. Excellent control of annual and perennial grasses and broadleaf weeds such as Johnsongrass, Bermudagrass, crabgrass, quackgrass, dogbane, milkweed, veronica, and ragweed is obtained. I

21 Example 17 Soluble powder: Percent -bromo-6-methy1-3-(4-morpholino)-uracil 50 Synthetic fine silica 2 Sodium metasilicate, anhydrous 25 Potassium chloride 22 Dioctyl sodium sul-fosuccinate l The ingredients are blended and micropulverized to give a free-flowing, noncaking powder. When added to a spray tank, the active ingredient dissolves rapidly, leaving only the silica in suspension.

Example 18 Wettable powder: Percent 5-bromo-3-(hexahydro-1-azepinyl)-6-methyluracil 80.0

Sodium lauryl sulfate 0.6 Sodium lignin sulfonate 2.0 Kaolin clay 17.4

Example 19 Wettable powder: Percent 3-piperidino-6-methyluracil 50 Sodium alkylnaphthalenesulfonate 2 Sodium ligninsulfonate 2 Attapulgite clay 46 The components are blended and then micropulverized until the solids are substantially below 50 microns in particle size. The mixture is re'blended until it is homogeneous. Application at a rate of 30 pounds per acre (active) of this formulation in 80 gallons of water controls annual and perennial broadleaf and grass weeds such as quack grass, giant foxtail, ragweed, and lambsquarters.

The other compounds of this invention set forth in Examples 1 through 6 can be formulated similarly and applied with similar results.

I claim:

1. A method for the control of undesirable vegetation said method comprising applying to a locus to be protested a herbicidally effective amount of the compound of the formula is azacycloalkyl of 3 through 8 ring atoms, azacycloalkenyl of 5 through 7 ring atoms, azabicycloalkyl of 7 through 11 ring atoms, diazacycloalkyl of 5 through 8 ring atoms, azabicycloalkenyl of 9 through 11 ring atoms, azaoxacycloalkyl of 5 through 8 ring atoms, diazabicycloalkenyl of 7 through 11 ring atoms, azaoxacycloalkenyl of 5 through 8 ring atoms, azaoxabicycloalkyl of 8 through 10 ring atoms, azaoxabicycloalkenyl of 9 through 11 ring atoms,

azadioxacycloalkyl of 5 through 8 ring atoms,

azathiacycloalkyl of 5 through 7 ring atoms,

azadithiacycloalkyl of 5 through '8 ring atoms,

azathiacycloalkenyl of 5 through 7 ring atoms,

azathiabicycloalkyl of 9 and 10 ring atoms, or

azathiabicycloalkenyl of 9 and 10 ring atoms,

provided that one nitrogen atom bonds the group to the uracil nucleus, and further provided the group can be substituted with a member selected from the group consisting of hydroxy, alkyl of 1 through 4 carbon atoms, and hydroxyalkyl of 1 through 4 carbon atoms;

R is hydrogen, chlorine, bromine, fluorine, iodine, alkyl of 1 through 3 carbon atoms; hydroxymethyl or alkoxymethyl of 2 through 4 carbon atoms;

R is methyl or ethyl; provided that R, and R can be joined together as (CH where n is an integer from 3 through 5.

2. The method of claim .1 wherein a surface-active agent is applied with the compound of the formula.

3. The method of claim 1 wherein an inert carrier is applied with the compound of the formula.

4. A method for the control of undesirable vegetation said method comprising applying to a locus to be protected a herbicidally effective amount of the compound of the formula ll A N-N y- 0: R2

wherein is azacycloalkyl of 5 through 7 ring atoms,

azaoxacycloalkyl of 5 through 6 ring atoms, or azathiacycloalkyl of 5 through 6 ring atoms, provided that one nitrogen atom bonds the group to the uracil nucleus, and further provided the group can be substituted with 0 through 4 methyl groups;

R is hydrogen, chlorine, bromine, fluorine, iodine, alkyl of 1 through 3 carbon atoms, hydroxymethyl or alkoxymethyl of 2 through 4 carbon atoms;

R, is methyl or ethyl; provided that R and R can be joined together as (CH where n is an integer from 3 through 5.

5. The method of claim 1 wherein the active compound is 5-bromo-6-methyl-3-(l-piperidino)uracil.

6. The method of claim 1 wherein the active compound is 5-chloro-6-methyl-3-(1-piperidino)uracil.

7. The method of claim 1 wherein the active compound is 5-bromo-6-methyl-3-( l-pyrrolidinyl)uracil.

8. The method of claim 1 wherein the active compound is 5-chloro-6-methyl-3 l-pyrrolidinyl) uracil.

9. The method of claim 1 wherein the active compound is 5-bromo-6-methyl-3-(hexahydro-l-azepinyl)uracil.

.10. The method of claim 1 wherein the active compounii is 5-chloro-6-methy1-3-(hexahydro-1-azepinyl) uraci 11. The method of claim 1 wherein the active compound is 6Fmethyl-3-(hexahydro-1-azepinyl)uracil.

12. The method of claim 1 wherein the active compound is 5-bromo-6-methyl-3-(4-morpholino)uracil.

References Cited UNITED STATES PATENTS 2,969,364 l/ 1961 Lyttle. 3,002,975 10/ 1961 Slezak. 3,235,357 2/1966 Loux.

JAMES O. THOMAS, JR., Primary Examiner.