IL32113A - 1-alkoxycarbonyl uracils,their preparation and herbicidal compositions containing them - Google Patents

1-alkoxycarbonyl uracils,their preparation and herbicidal compositions containing them

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Publication number
IL32113A
IL32113A IL32113A IL3211369A IL32113A IL 32113 A IL32113 A IL 32113A IL 32113 A IL32113 A IL 32113A IL 3211369 A IL3211369 A IL 3211369A IL 32113 A IL32113 A IL 32113A
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carbon atoms
formula
alkyl
methyluracil
uracil
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IL32113A
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IL32113A0 (en
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Du Pont
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    • 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
    • C07D239/60—Three or more oxygen or sulfur 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

l-ALKQXYCARBQNYL URACILS, THEIR PH PAHATION AND HKRBIGIDAL COMPOSITIONS COSTAIHI THEM 32113/2 ' This invention relates to novel 1-alkoxycarbonyl substituted uracils and to compositions and methods for using these uracils as herbicides.
The uracils of this invention are represented by the general ormula where R-^ is alkyl of 1 through 10 carbon atoms, substituted alk l of 1 through 8 carbon atoms, having one or more substituents selected from the group consisting of bromine, chlorine, fluorine, hydroxy, alkoxy, and cyano, aryl of 6 through 10 carbon atoms, furyl, pyridyl, substituted phenyl having one or more identical or different substituents selected from the group consisting of chlorine, bromine, fluorine, phenyl, alkyl or alkoxy of 1 through 6 carbon atoms, trifluoro-methyl, 1,2-tetramethylene, and 1, -trimeth lene, aralkyl of 7 through 13 carbon atoms, furfuryl, pyridylalkyl, substituted aralkyl of 7 through 13 carbon atoms, having one or more identical or different substituents selected from the group consisting of chlorine, nltro, alkyl, and alkoxy, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, 32113/3 is one of the radicals- (a) cycloalkyl, (b) cycloalkenyl, (c) cycloalkyl alkyl, (d) cycloalkenyl alkyl each optionally substituted with bromine, chlorine, methoxy or alkyl; with the proviso that: (1) the unsubstituted and halo-substituted radicals have respectively: . i . 3-12 carbon atoms for radical (a) 4-12 carbon atoms for radical (b) .4-13 carbon atoms for radical (c) -13 carbon atoms for radical (d); (2) the methoxy or alkyl substituted radicals have, respectively: 4-13 carbon atoms for radicals (a) and (b) -14 carbon atoms for radicals (c) and (d); R2 is hydrogen, halogen, methyl, ethyl ^ methoxy, ethoxy, nitro, alkoxymethyl of 2 through 4 carbon atoms, hydroxyalkyl of 1 through 4 carbon atoms, mercaptomethyl, methylthio, ethylthio, methylthiomethyl, bromomethyl, chloromethyl and fluoromethyl; R5 is hydrogen or alkyl of 1 through 3 carbon atoms; -3a- 32113/3 is alkyl of 1 through 10 carbon atoms, optionally substituted vjith one or more chlorine, bromine or fluorine atoms or with alkoxy of 1 through 4 carbon atoms; alkynyl of 3 ¾o 6 carbon atoms, aryl of 6 through 10 carbon atoms, phenyl substituted with chlorine, fluorine or alkylthio, "benzyl, furfuryl, thienyl or pyridyl, alkenyl of 3 through 4 carbon atoms, cyclo-alkyl of 4 through 8 carbon atoms and cycloalkylalkyl of 4 through 13 carbon atoms, X is oxygen or sulfur; with the proviso that R2 and can be taken together as -(CH2)n,- to form a ring . where n' is 3, 4 or 5· As is well known in the art, herbicide1 compounds frequently are utilized in the form of a herbicide 1 equivalent salt, addition compound or complex derivative" thereof for some formulating or handling advantage the derivative may provide ' over the compound per se. Therefore, it is to be understood that also included within the scope of this invention are such « derivatives 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. P. Luder and S. Zuffanti, The Electronic Theory of. Acids and Bases, John Wiley and Sons, Inc., New York, 19½; ,(3) E. S. Gould, Mechanism and Structure in Organic Chemistry. Holt, Rinehart and Winston, New York, 1959, Chapter 4; (4) Ε. Μ. 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, 19^3· Illustrative of such derivatives of the uracils of Formula (l) are complexes which are formed with phenol and substituted phenol. These complexes have the formula: where i, 2, 3i R-ii and X are as defined in Formula (l); A is hydrogen, bromine, chlorine, nitro, alkyl of 1 through 3 carbon atoms or an -OR5 radical where R5 is alkyl of 1 through 3 carbon atoms; Y is chlorine or alkyl of 1 through 3 carbon atoms; m is a number 1 through 5j an n is 1/2, 1 or 2; with the proviso again that R2 and R3 can be taken together as -(CHa)n- , to form a ring where n is 3, 4, or 5.
These complexes have a higher solubility in oils and solvents than the corresponding uracils per se.
The compounds of this invention are useful as herbicides. The ma be used to control e ro o - 5 - ! 32113/2 in industrial areas, along power line rights-of-way, railroads, roads, etc. When the proper compound is chosen it will control such hard to kill perennial weeds as Bermudagrass (Cynodo dactylon), Johnsongrass (Sorghum halQpense), and quackgrass (Agropyron repen.s) .
If the proper compound rate and time of application is selected, certain of these compounds can be used to control weeds in such crops as sugar cane, pineapple, peppermint, aspara gus, sisal, citrus, corn, flax, alfalfa, sunflower, and peanuts.
The precise rate of application of the compound to use will depend on several factors, including the weed to be controlled, the season, rainfall, temperature and the crop if any. Broadly, the rates utilized will be between 1/4 and 30 kilograms per hectare. For selective weed control the rates that may be used usually fall between 1/4 and 10 kilograms per hectare. For the proper compound the proper rate may be selected from this range by one skilled in the art.
Herbicidally active uracil compounds similar to those of the present invention have been disclosed in Australian Paten According No. 255,402. /to. that specification one of the possible substitu at the nitrogen atom in the 1-position of the uracil may be a carbalkoxy group, but no specific eompounds containing such substituents have been named.
;In contrast thereto, wherein the compounds according to this invention the substituent of the nitrogen in the 1-position is an alkoxycarbonyl group, the alkyl moiety of this group is defined as comprising from 1 - 10 carbon atoms, and these compounds have been found to be superior to the similar compound actually known before the present invention, especially in that they resist leaching and are thus not carried, by rain or irriga — 5®. — ltogether these comno^nds as well *?s' the other compounds according to the invention, hr.ve been found to have a better herbieidal activity than those described in earlier publications such fas the aforesaid Australian specification md the Israeli s ecification Mo, 8350.
Thus l-nset!. O2ycarbonyl«-3**sec.butyl^5-bx0no Particularly good results ave also boen achieved with l-hexyloxyc rbonyl-'-sec .butyl->5-bromo-6-met yluracil and the corresponding l-decyloxycarbonyl compound.
Fo the f omul^e (1) and (2), the expression "substituted allcyl" for the term R^ is intended to include such radicals as Bromoalkyl of 1 through 10 carbon atoms Chloroclkyl of 1 through 10 carbon atoms Hydroxyalkyl of 1 through 10 carbon atoms Alkoxyalkyl of 2 through 10 carbon atoms Cyanoalkyl of 2 through 10 carbon atoms.
For formulae (1) ¾nd (2), the expression "aryl" for the terms R. and R„ is intended to include such radicals as Phenyl Naph hyl _o-Biphenyl Pyridyl Chlorophenyl Bromophenyl Dichlorophenyl Dibromopheny1 Fluorophenyl Trichlorophenyl Alkylphenyl of 7 through 11 carbon atoms Di lkylphenyl of 8 through 12 carbon atoms Chloroalkylphenyl of 7 through 10 carbon atoms tgopfeefty3r Chloroalkoxyphenyl of 7 through 11 carbon atoms Trlfluoromethylphenyl Alkylnaphthyl of 11 through 16 carbon atoms Chloronaphthyl Tetrahydronaphthyl and Indenyl .
For Formulae (1) and (2), the expression "aralkyl" he term Ri is intended to include such radicals as Benzyl Phenylalkyl of 8 through 11 carbon atoms Chlorobenzyl Dichlorobenzyl Alk lbenzyl of 8 through 11 carbon atoms Dialkylbenzyl of 9 through 11 carbon atoms -■t Alkoxybenzyl of 8 through 11 carbon atoms and Naphthylmethy1.
For Formulae (l) and (2), the expression "cycloalkyl" for the terms Ri and R and the expression "cycloalkenyl", "cycloalkyl alkyl", and "cycloalkenyl alkyl" for the term Rx are intended to include radicals such as Cyclopropyl Cyclohexyl Cyclohexenyl Cyclohexylalkyl Gyclohexenylalkyl Cyclopentyl Cyclopentenyl CyclopentylaIky1 Cyclopentenylalkyl Norbornyl Norbornenyl Norbornylalkyl Norbornenylalkyl Bicyclo( 2.2.2)octyl Bicyclo(2.2.2)octenyl Bicyclo(2.2.2)octylalkyl Bicyclo(2.2.2)octenylalkyl Cyclopropyl Cyclobutyl Cyclooctyl Cyclododecyl Cyclobutylalkyl Cyclobutenyl CyclobutenylaIky1 Hexahydroindany1 Tetrahydroindanyl Hexahydroindenyl Hexahydroindenylalkyl Tetrahydroindanylalkyl Hexahydrolndanyla lkyl Hexahydro- ,7-me hanoindeny1 Te rahydro- ,7-me hanoindKny1 Hexahydro-4,7-methanoindanyl Tetrahydro-4,7-methanoindanyl Hexahydro- ,7-methanoindenylaIky1 Tetrahydro-4,7-methanoindanylaIky1 Hexahydro-4,7-methanoindanylalkyl Decahydronaphthyl Decahydronaphthylalkyl Tetrahydronaphthyl Tetrahydronaphthylalkyl Decahydro-1,4-methanonaphthyl Decahydro-l,4-methanonaphthylalkyl Octahydro-1, -methanonaphthy1 0ctahydro-l34-methanonaphthylalkyl Decahydro-la4-5j8-dimethanonaphthyl Decahydro-li4-5,8-dimethanonaphthylalkyl Octahydro-1,4-5,8-dimethanonaphthy1 Octahydro-l^-SjS-dimethanonaphthylalkyl Fenchyl and Bornyl .
For Formulae (1) and (2) substituted) cy&oalkyl cycloalkyl alkyl*", /and ^substituted cycloalkenyl alkyl" for the term Ri are intended to include the cyclic groups substituted with a substituent such as alkyl groups containing 1 through 4 carbon atoms, methoxy, chlorine, and bromine.
For Formulae (1) and (2), the expression "substituted alkyl" for the term R4 is intended to include alkoxy of 1 through 4 carbon atoms, bromoalkyl of 1 through 10 carbon atoms, chloroalkyl of 1 through 10 carbon atoms, and fluoroalkyl of 1 through 10 carbon atoms.
The uracils of this invention can be prepared in the manner illustrated by the following reaction equation: Detailed descriptions for the preparation of the tri-substituted uracils used as starting materials in Equation (a) are given in the following references: U.S. Patent 3,235,357 U.S. Patent 3, 23 ,360 U.S. Patent 3, 235, 361 U.S. Patent 3,235,362.
As may be noted from Equation (a), the sodium salt of the trisubstituted uracil starting material is prepared by mixing the uracil and a solution of a suitable sodium alkoxide such as sodium methoxide in a suitable organic solvent, such as methanol.
The solvent is next evaporated, most conveniently at reduced pressure and the resulting salt is dried under Excess reagents are decomposed by stirring with suitable base, for example, 10$ aqueous sodium hydroxide.
The product is isolated by extraction of the mixture with a water-immiscible organic solvent, such as benzene, chloroform or methylene chloride. The solution of product is then dried with magnesium sulfate or other suitable drying agent and recovered by evaporation of the solvent. The products are usually either viscous oils or low-melting solids. Many possess good solubility in hydrocarbon solvents.
In addition, the compounds of this invention can be prepared without isolation of the intermediate salt, as illustrated in Equation (b) A solution of the uracil in a suitable organic solvent, such as tetrahydrofuran, is added to a suspension of sodium hydride in the same solvent. After gas evolution ceases, an excess of the chlorocarbonyl reagent is added and the mixture is boiled under reflux until the reaction is complete. On coolin the insoluble salt is filtered and the solvent is removed from the filtrate by evaporation to yield the desired product as an oil that may be further purified as described above.
Complexes of the compounds of Formula (l) with a Lewis base such as phenol can be formed by comelting the uracil and phenol in a 1:1 to 2:1 ratio. They can also be formed by co-dissolving the reactants, in the same ratio, in a solvent such as nitromethane or a mixture of nitromethane and cyclohexane.
These methods are described in Israel Patent Spec. No. 24137 When a solvent is used, the complex is prepared by gradually with stirring. Stirring is continued for from minutes to 2 hours. Mild heating may be necessary. Some complexes precipitate and can be removed by filtration.
Other complexes are isolated by evaporation of the solvent.
The complexes prepared in this way are suitable for use without further purification, but can be purified by recrystal-lization if desired.
The compounds of the invention can be prepared for use as herbicides by incorporating them with adjuvants.
The amount of active ingredient uracil in such preparations can vary 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, pyrophillite, 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 made by mixing a finely-divided uracil with a suitable clay such as kaolinite, mont-morillonite or attapulglte, 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 pre-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 granule 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 00° C. are preferred. Hydrocarbons having lower boiling points should not be used because of their undesirable volatilization characteristics and inflammability. 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 # 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 effectiveness than can be expected from a consideration of activity of the components used sep.'irately.
The term "surface-active agent" 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 Annual" - 19^7, John W. McCutcheon, Inc., Morristown, New Jersey.
The preparations can also contain adhesives, corrosion inhibitors, antifoam agents, dyes and pigments, anticaking agent and hard water stabilizers.
In accordance with the invention, herbicidal compositions can be formulated to contain 2 or more of the uracils of the invention. They can also be formulated to contain other known herbicides in addition to the uracil of this invention to give compositions which have advantages over the individual components. Among the herbicides which can be combined with the uracils are: Substituted Ureas 3-(3,4-dichlorophenyl)-1,1-dimethylurea 3-(4-chlorophenyl) -1,1-dimethylurea 3-phenyl-l,l-dimethylurea 3- (3i^-dichlorophenyl)-3-methoxy-l,1-dimeth lurea 3-(4-chlorophenyl)-3-methoxy-l,1-dimethyluren •jr 3-(3^-dichlorophenyl)-l-n-butyl-l-meth lurea 3-( *4-dichlorophenyl)-l-methoxy-l-methylurea 3-(4-chlorophenyl)-l-methoxy-l-methylurea 3-(3»4-dichlorophenyl)-1,1, -1rimethylurea 3-(3,4-dichlorophenyl)-1,1-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.
Substituted Triazines 2-chloro-4,6-bis (ethylamino)-s-triazine 2-chloro-4-ethylamino-6-isopropylamino- -triazine 2-chloro-4,6-bis (methoxypropylamino) -s-triazine 2-methoxy-4,6-bis ( isopropylamino) -s-triazine 2-ethylamino-4-(2-methoxyethylamine )-6-chloro- - triazine 2-isopropylamino-4-methoxyethylamino-6-methyl- thio-ffi©**-eei*o~_s-triazine 2-methyIm roap-¾e-4,6-bis ( isopropylamino ) -_s- triazine 2-methylme*,e€tpitee—4,6-bis (ethylamino ) -s-triazine thio , _ 2-methylme-reep-te-4-ethylamino-6-isopropylamino-s- triazine 2-methoxy-4,6-bis (ethylamino) -s-1riazine 2-methoxy-4-ethylamino-6-isopropylamino-s- triazine 2-chloro-4,6-bis (isopropylamino ) -s^-tria zine . - thio 2-tert-butylamino-4-ethylamino-6-methyIroarcap-tG- js-triazine These triazines 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.
Phenols 4-cyano-2,6-diiodophenol and Its salts -cyano-2,6-dibromophenol and its salts dlnitro-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.
Carboxylic Acids and Derivatives The following carboxylic acids and derivatives can be mixed with the uracils in the listed respective proportions A. 2,3*6-trichlorobenzoic acid and its salts 2,3a j6-tetrachlorobenzoic acid and its salts 2-methoxy-3,5i6-trichlorobenzoic acid and its salts 2-methoxy-3,6-dichlorobenzoic acid and its salts 3-amino-2,5-dichlorobenzoic acid and its salts 3-nitro-2,5-dichlorobenzoic acid and its salts 2-methyl-2j6-dichlorobenzoic acid and its salts 2,3-dichloro-6-methylbenzoic acid and its salts 2, -dichlorophenoxyacetic acid and its salts and esters 2. .5-trichlorophenoxyacetic acid and its salts and esters (2-methyl-4-chlorophenoxy)acetic acid and its salts and esters 2-(2, ,5-trichlorophenoxy)propionic acid and its salts and esters 2-(2,4,5-trichlorophenoxy)ethyl-2,2-dichloro- propionate 4-(2, -dichlorophenoxy)butyric acid and its salts and esters 4-(2-methyl-4-chlorophenoxy)butyric acid and its salts and esters 2.3.6-trichlorobenzyloxypropanol 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 :1 ratio.
E. N,N-di (n-propyl)thio!j/carbamic acid, ethyl ester N,N-di (n-propyl)thioicarbaniic acid, n-propyl ester o N-ethyl-N-(n-butyl)thio¾carbamic acid, ethyl ester o N-ethyl-N-(n-butyl)thio^6arbamic acid, n-propyl ester Mixed in a 1:2 to 24:1 ratio, preferably a 1:1 to 12:1 ratio.
F. N-phen lcarbamic 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. 2i3,6-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 V Mixed in a 1:2 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 prop larsonate disodium xnonomethylarsonate oc tyl-dodecy lananoniumme thy la r sona te dime h larsinic 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 100:1 to 400:1 ratio.
D. sodium tetraborate hydrated, granulated sodium me ta borate sodium pentaborate polychlorbora te unrefined borate ore, such as borascu Mixed in a 5:1 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.
P. sodium chlorate 4 0. ammonium sulfamate Mixed in a 1:1 to 100:1 ratio, preferably a 1:1 to 50:1 ratio.
Other Organic Herbicides The following herbicides can be mixed with the uracils in the listed respective proportions: A. 5,6-dihydro-(4A,6A)-dipyrido-(l,2-A,2' ,1'-C) pyrazinium dibromide l,l'-dimethyl-4,4'-dipyrldinium di- (methyl sulfate) Mixed in a 1:20 to 16:1 ratio, preferably a 1:5 to 5:1 ratio.
B. 3-amino-l,2, -triazole Mixed in a lr20 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-a,o diphenylacetamide N,N-di-(n-propyl)-2,6-dinitro-4-methylaniline N-methyl-N-n-butyl-2,6-dinitro-4-trifluoromethyl- aniline Mixed in a 1:10 to 30:1 ratio, preferably a 1:5 to 20:1 ratio.
E . 0-(2,4-dichlorophenyl ) -O-methyl-isopropyl- phosphoramidothioate 2,3,5,6-tetrachloroterephthalic acid, dimethyl ester thiomethyl ester of 2,3,5,6-tetrachloro-4-carbo- methoxy benzoic acid Mixed in a 1:4 to 20:1 ratio, preferably a 1:3 to P. 2,4-dichloro-V-nitrodiphenyl ether Mixed in a 1:10 to 30:1 ratio, preferably a 1:5 to 20:1 ratio.
G. l-(3, -dichlorophenyl)-3,5-dimethylhexahydro- l*3»5-triazinone-2 l-phenyl-3-methyl-5-allyl-hexahydro-l, 3, 5- triazinone-2 Mixed in a 1:4 to 4:1 ratio, preferably 1:2 to 2:1 ratio.
Substituted Uracils The uracils of this invention can be mixed with other classes of substituted uracils, in the respective proportions listed below. -bromo- -sec-butyl-6-methylurac11 -bromo-3-sec-butyl-6-methyluracil, sodium salt 5-chloro-3-sec-butyl-6-methyluracil -bromo-3-tert-butyl-6-methyluracil -chloro-3-tert-butyl-6-methyluracil -bromo-3-(l-ethylpropyl)-6-methyluracil -chloro-3-(l-ethylpropyl)-6-methyluracil -bromo-3-isopropyl-6-methyluracil -chloro-3-isopropyl-6-methyluracil -bromo-3-cyclohexylmethyl-6-methyluracil -chloro-3-cyclohexylmethyl-6-methyluracil 3-cyclohexy1-5-methox -6-methyluraci1 3-sec-butyl-5,6-dimethyluracil -bromo-6-methyl-3-norbornylmethyluracil 3-sec-butyl-6-methyl-5-nitrouracil 3-cyclohexyl-5,6-dime hyluracil -bromo-3-cyclohexyl-6-methyluracil -chloro-3-phen 1-6-me h luraci1 -bromo-6-methyl-3-(l-piperidino)uracil -chloro-6-methyl-3-(l-piperidino)uracil -bromo-6-methyl-3-(l-pyrrolidinyl)uracil -chloro-6-methyl- -(l-pyrrolidinyl) uracil -bromo-6-methyl-3- (hexahydro-l-azepinyl)uracil -chloro-6-methyl-3-(hexahydro-l-azepinyl) uracil 6-methyl-3-(hexahydro-l-azepinyl)uracil -bromo-6-methyl-3-(4-niorpholino)uracil Mixed in a 1:6 to 6:1 ratio, preferably a 1:4 to :1 ratio. 3-cyclohexyl-6-methyluracil 3-cyclohexyl-6-ethyluracil 3-eyelohexyl-6-sec-bu yluraci1 3-cyclohexyl-6-propyluracil 3-cyclopentyl-6-methyluracil 3-cyclohexyluracil Mixed in a 1:6 to 6:1 ratio, preferably a 1:4 to :1 ratio. 3-isopropyl-5-bromouracil 3-sec-butyl-5-bromouracil 3-sec-butyl-5-chlorouracil 3-cyclohexyl-5-broniouracil 3-cyclohexyl-5-chlorouracil Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to :1 ratio. 3-isopropyl-l-trichlororaethylthio-5-bromo-6- methyluracil 3-cyclohexyl-l-trichloromethylthio-5-bromo-6- methyluracil • V 3-sec-butyl-l-acetyl~5-bromo-6-methyluracil 3-isopropyl-l-acetyl-5-bromo-6-methyluracil 3-isopropyl-l-trichloromethylthio-5-chloro- 6-methyluracil Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.
EXAMPLES The invention will be better understood by referring to the following illustrative examples; parts and percents are by weight unless otherwise specified: Preparation of Compounds Example 1 - Preparation of l-ethoxycarbonyl-3-sec-butyl-5- bromo-6-methyluracil Forty parts of 58.6$ sodium hydride dispersion in oil is washed 3 times with pentane. Eight hundred parts of anhydrous methanol is added and the solution is stirred under a condenser until gas evolution ceases. To this solution is gradually added 26l parts of 5-bromo-3-sec-butyl-6-methyluracll and the brown solution formed is then stirred for 3 hours at ambient temperature. The solvent is evaporated and the residual solid is dried.
A mixture of 11.3 parts of the above salt and 8.68 parts of ethyl chloroformate are boiled under reflux under anhydrous conditions for 2 hours. After cooling, the mixture is treated with a solution of 6 parts of sodium hydroxide in parts of water. After stirring 15 minutes, the mixture is extracted with methylene chloride and the methylene chloride solution is dried over magnesium sulfate. The dried solution is filtered and the solvent is evaporated to give 1-ethoxy- carbonyl-3-sec-butyl-5-bromo-6-methyluracil as a viscous, Anal, cal'd for 012Η1γΒΓ 2θ : C, 3.25; Hj 5-15; Br, 23.99; N, 8. i.
Found: C, 43.06; H, 5-34; Br, 23-45; N, 8.12.
Example 2 - Preparation of 1-methoxycarbonyl-3-tert-butyl- 5-chloro-6-methyluracil A solution of 10 parts of 3-tert-butyl-5-chloro- 6-methyluracil, 2.38 parts of sodium methoxide and 180 parts of anhydrous methanol is stirred at ambient temperature for 3 hours. The solvent is removed under reduced pressure and the salt is dried. The dried salt is mixed with 12.5 parts of methyl chloroformate and boiled under reflux for 5 hours. After cooling, the reaction mixture is mixed with 8 parts of sodium hydroxide dissolved in 100 ml. of water. The mixture is extracted with methylene chloride and the extracts are combined and dried over magnesium sulfate. The solvent is allowed to evaporate and the resulting solid is triturated with hexane to yield l-methoxycarbonyl-3-tert-butyl-5-chloro-6-methyluracil as a white solid, .m.p. 101-103°.
The following 1-substituted uracil products can be prepared in a similar fashion by substituting a listed uracil reactant and an excess of a chlorocarbonyl reactant for the uracils and chloroformates in Examples 1 and 2.
Example No. Uracil Reactant Chlorocarbonyl Reacta 3 3-sec-buty1-5- romo-6-methy1- hexyl chloroformate uracil 4 3-_te_rt-buty1-5-chloro-6-methy1- butyl chloroformate uracil 3-isopropyl-5-bromo-6-methyl- ethyl chloroformate uracil 6 5-isopropyl-5-bromo-6-methyl- methyl chlorothiolfor uracil 7 3-phenyl-5-bromo-6-methyluracil cyclohexyl chloroforma 8 -benzyl-5-chloro-6-methyluracil allyl chloroformate 9 5-bromo-3,6-dimethyluracil methylchloroformate 3-cyclohexyl-5-bromo-6-methyl- proper yl chloroforma uracil 11 3-tert-butyl-6-methyluracll methoxymethyl chlorof 12 ryl-5-lodo-6-me hyluracil furfuryl chloroformat 13 3-cyclododecen-2-ylmethyl-5- butyl chloroformate bromo-6-methyluracil 14 3-propa yl-5-fluoro-6-methyluracil 2-fluoroethyl chlorof 3-cyclopropyl-5,6-dimethyluracil phenyl chloroformate xample 16 3-cyclohexylmethyl-5,6-dimethyl- thienyl chloroformate uracil 17 3- ( 2, 3-dichlorocyclododecylmethyl- eyelopropylmethyl chl -chloro-6-methyluracil formate 18 3-(l32, 3,4-tetrahydronaphth-5-yl)- benzyl chloroformate 5j6-dimethyluracil 19 3-cyclobutenylmethyl-5-methoxy-6- buten-5-yl chloroform methyluracil 3-allyl-5-nitro-6-ethyluracil 3, -dichlorophenyl c formate 21 3-(a-naphthyl)-5-bromo-6-iso- 3-bromopropyl chlorof propyluracil 22 3-cyclopentyl-5-mercaptomethyl- -chlorophenyl chlor 6-methyluracil formate 3-(6-ethoxyhexyl)-5-iodo-6-methyl- m-pyridyl cHLoroforma uracil 24 3-octenyl-5-ethyl-6-methyluracil a-naphthyl chloroform 3- (3-nitro- -chlorophenyl) 5 docyl chloroformatC' chloromethyl-6-methyluracil Exanrole No*. Uracil Re8ctant Chlorocarbonyl Reactant 3-phenyl-5-chloro-6-methyluracil ethyl chloroformate 3-phenyl-5-bromo-6-methyluracil methyl chloroformate 3-sec-butyl-5-bromo-6-methyluracll isopropyl chloroformate 3-n-decyl-5-methylthio-6-methyl- benzyl chlorothiolformat uracil -cyclopentenyl-5-iodo-6-methyl butyl chlorothiolformate uracil 3-m-pyridyl-5-fluoromethyl-6- 2-fluoroethyl chlorothi methyluracil formate 3-m-methoxyphenyl-5-bromo-6-lso- ethyl chlorothiolformate propyluracil 3-norbornenyl-5-(J~hydroxybutyl)- ally! chloroformate 6-methyluracil 3-(3,^-dlchlorophenyl)-5-fluoro- 2, 2,2-trichloroethyl methyl-6-meth luracil chloroformate Example No. Uracil Reactant Chlorocarbonyl React 58- ^-(S^-dimethylcyclohexylmethyl)- hexyl chlorothiolform _3- 3-(2-chloroethyl)-5-bromo-6- ei¾rl chloroformate ethyluracil - or 3-methyl-5-methylthiomethyl-6- metlyl chlorothioifor methyluracil 39 Example 4i - Preparation of l-ethoxycarbonyl-3-cyclohexyl- 5j6-trimethyleneuracil A sodium hydride suspension is prepared by washing 1.64 parts of 58.6$ sodium hydride oil suspension with pentane and slurrying the residue in 270 parts of tetra-hydrofuran. To this suspension is added 9· 36 parts of 3-cyclohexyl-5,6-trimethyleneuracil and the resulting mixture is stirred at ambient temperature until evolution of hydrogen ceases. Ethyl chloroformate (9·4 parts) is added and the white suspension is boiled under reflux for 8 hours. The reaction mixture is allowed to cool. The white precipitate is filtered and discarded. The solvent is allowed to evaporate from the filtrate, and the residue is mixed well with 100 parts of 10$ aqueous sodium hydroxide. This mixture is extracted with methylene chloride and the organic layer is dried over magnesium sulfate. Removal of the drying a ent by filtration and evaporation of the solvent yields a clear oil that crystallizes on standing. Trituration of the crystals with pentane gives l-ethoxycarbonyl-3-cyclohexyl-5,6-trimethyleneuracil as a white solid, .p. 68-72° . 40 Example -4-3- - Preparation of l-methylthiocarbonyl-3-sec-butyl -bromo-6-methyluracil A sodium hydride suspension, prepared from 1.84 parts of 58.6$ sodium hydride oil dispersion (washed with pentane) and 45 parts of tetrahydrofuran, is added to 10 parts of 3-sec-butyl-5-bromo-6-methyluracil in 135 parts of tetrahydrofuran.
The mixture is stirred at ambient temperature until evolution of hydrogen ceases. To this suspension is added 12.7 parts of methj c hlorothiplformate and the reaction mixture is boiled under reflux for 5 hours. On cooling, the salt formed is removed by filtration and the solvent is allowed to evaporate from the filtrate. 1-Methy11hiocarbony1-3-sec-buty1- -bromo-6-methy1-uracil is obtained as a viscous, yellow oil. Anal, cal'd for CiiH15BrN203S: C, 39-42j H, .51; N, 8.36. Found: C, 39-54; 41 Example - $ - Preparation of l-methoxycarbonyl-3-tert-butyl-5- chloro-6-methyluraci1 ^ Pentane washing of 1.86 parts of 8.6$ sodium hydride oil suspension gives a gray solid which is suspended in 5 parts of tetrahydrofuran. A solution of 10 parts of 3 tert-butyl-5-chloro-6-methyluracil in 90 parts of tetrahydrofuran is added dropwise and the mixture is stirred at ambient temperature until gas evolution ceases. Methyl chloroformate (12.5 parts) is added and the mixture is boiled under reflux for 5 hours. On cooling, the salt formed is removed by filtration and the solvent is allowed to evaporate from the filtrate. The residue is treated with 100 parts of 10$ sodium hydroxide and then extracted with methylene chloride. The organic layer is dried over magnesium sulfate. The solution is filtered and the filtrate is allowed to evaporate. The residual white solid is triturated with hexane to yield 1-methoxy-carbonyl-3-tert-butyl-5-chloro-6-methyluracil, m.p. 101-103°.
The following 1-substituted uracil products can be prepared in a similar fashion by substituting a listed uracil reactant and an excess of a chlorocarbonyl reactant for the uracils and chloroformates in Example 43.
Example No. Uracil Reactant Chlprocarbonyl Reacta 3-benzyl-5-chloro-6-methyluracil et }># 5- ert-butyl-5-chloro-6-methyl- et uracil 3-isopropyl-5-bromo-6-methyluracil et 3-cyclohexyl-5,6-trimethylene- me uracil 3-benzyl-5-chloro-6-methyluracil methyl chloroformate 3-sec-butyl-5-bromo-6-methyluracil hexyl chloroformate 3-tert-butyl-5-chloro-6-methyl- methyl chlorothiol orm uracil 3-benzyl-5-chloro-6-methyluracil methyl chlorothiolform 3-sec-butyl-5-bromo-6-meth luracil methyl chloroformate 3-phenyl-5-chloro-6-methyluracil hexyl chloroformate 3-benzyl-5-chloro-6-methyluracil allyl chtorofor ate 3-cyclohexyl-5,6-trimethylene- 2-methoxyetl¾i chlorof uracll Example No. Uracil Reactant Chlorocarbonyl React ^ 3-tert-butyl-5-chloro-6-methyl- eyelopropylmethyl ch s S S% 3-cyclopentyl-5-chloro-6-methyl- isopropyl chloroforma uracil 3-sec_-butyl-5,6-trimethyleneuracil hexyn-5-yl chloroform (g>Q 3-cyclopropylmethyl-5,6-tetra- ethyl chloroformate methyleneuracil (>Λ βί 5-isopropyl-5,6-pentamethylene- benzyl chlorothiolfor uracil 3-phenethyl-5-ethylthio-6-methyl- 2-fluorophenyl chlor uracil formate 3-(2,3-difluorocyclobuten-2- ethyl chloroformate yImethy1)-5- droxymethy1-6- methyluracil Example No. Uracil Reactant Chlorocarbonyl Reactant (^ 3-(cyclohexen-2-ylmethyl)- 2-methoxyethyl chloro- <≤> 3-hexen-3-y1-5-methoxymethyl- methyl chlorothiol ormat 6-methyluracil (o I -TtJ 3-bromophenyl-5-isopropoxy- methyl chloroformate 6-methyluracil 65 (o-fluorophenyl)-5-iodo-6- cyclohexyl chloroformate methyluracil 3-octyn-7-yl-5,6-dimethyluracll ethyl chlorothiolformat 3-cyclododecylmethyl-5-bromo- ethyl chloroformate 6-methyluracil -(5-chloro- -methoxyphenyl)· furfuryl chloroformate -methylthio-6-methyluracil -methylcyclopropylmethyl-5- methyl cHLoroformate fluoromethyl-S-methyluracil f 5-cyclodecyl-5-bromo-6- ethyl chloroformate ethyluracil Example No. Uracil Reactant Chlorocarbonyl Reactan 3-norbornyl-5-chloro-6-methyl- allyl chloroformate uracil - (o-pyridylmethyl ) -5,6-di- butyl chlorothiolforma me Kyluracil 3-tertrbutyl-5j6-tetramethylene- 3,^-dichlorophenyl chl « I j*i 3-cyclohexyl-5,6-trimethylene- methyl chlorothiolform uracil Formulation and Use of Compounds Example -8-580 -chloro-l-ethoxycarbonyl- 6-methyl-3-phenyluracil 25.0$ attapulgite clay 68.0$ dioctyl sodium sulfosuccinate 1.0$ sodium lignin sulfonate 2.0$ finely divided synthetic silica 4.0$ The above components are blended, micropulverized in a hammer mill until the particles are essentially smaller than 50 microns and then reblended until the mixture is homogeneous. All other compounds of this invention can be formulated in like manner.
Five kilograms of the active ingredient in the above formulation are suspended in 200 liters of water and sprayed evenly over a hectare of established asparagus before the spears have begun to emerge in the spring. This treatment provides control of such weeds as chickweed (Stellaria media), henbit (Lamium amplexicaule ) , crabgrass (Dlgltaria spp.), goosegrass (Eleusine indlca), ragweed (Ambrosia spp.) and lambsquarter (Chenopodium album) for an extended period. The crop provides an excellent yield of spears.
Example -84- 81 3-cyclohexyl-l-ethoxycarbonyl- 5,6-trimethyleneuracil 50.0$ montmorillonite clay 46.0$ sodium alkyl naphthalene sulfonate * 2.0$ calcium lignin sulfonate 2.0 The above ingredients are blended, micropulverized to a particle size below 100 microns, and reblended until Two kilograms of the above active ingredient are suspended in water and sprayed over an acre of dormant alfalfa in the late fall. This treatment provides control of winter annuals such as chickweed, bachelor's button (Centura sp.)a henbit, squirreltailed barley (Hordeum jubatum) , and chess (Bro us sp . ) .
E am le^" -bromo-3-sec-butyl-l-ethoxycarbonyl- 6-methyluracil 90.0$ trimethylnonyl polyethylene glycol ether 10.0$ The above high-strength composition is prepared by blending the ingredients until a homogeneous solution results. This composition is suitable for further formulation but can also be applied directly as an emulsifiable concentrate in equipment with efficient agitation.
The above material is emulsified in water and applied at 30 kg/ha to an area around a tank farm. This treatment gives long term control of Johnsongrass, crabgrass, annual bluegrassj dandelion (Taraxacum vulgare)^ fall panicum (Panicum sp. )3 wild carrot (Daucus carota), plantain (Plantago lanceolata) and other weeds in the area.
Example > ¾2 3-cyclohexyl-l-methoxycarbonyl-5j6- tri ethyleneuracil 25.0$ hydrated attapulgite 2.0$ disodium hydrogenphosphate 1.0$ sodium lignum sulfonate 5·0# sodium penta chlorophenate 0.5$ water 66.5$ All the ingredients except the water are ground to pass an 0.42 mm. screen. The water is then added and the composition is sandground to a particle size essentially below 5 microns.
Two kilograms per hectare of the above material as a water dispersion are applied to a field of peppermint. The treatment provides long term control of crabgrass, goose-grass, barnyard grass (Echinochloa crusgalli), lambsquarter, ragweed and other weeds.
Example #f S¥ 3-benzyl-5-chloro-l-ethoxycarbonyl- 6-methyluracil 5.0$ attapulgite clay 25.0$ talc 70.0$ The active ingredient is micropulverized with the minor diluent to a particle size essentially below 50 microns.
This composition is then blended thoroughly with the major diluent to form a 5$ active dust.
The following compounds can be formulated in like manner: 3-benzyl-5-chloro-l-methylthiocarbonyl-6-methyluracil 5-chloro-l-methylthiocarbonyl-6-methyl-3-phenyluracil 3-benzyl-5-chloro-l-methoxylcarbonyl-6-methyluracil -chloro-l-hexylox lcarbonyl-6-methyl-3-phenyluracil l-allyloxycarbonyl-3-benzyl-5-chloro-6-methyluracil One kilogram per hectare of the above chemical is applied pre-emergence to a hectare of flax. The treatment provides control of crabgrass, ba nyardgrass , kochia and other weeds without lasting damage to the flax.
Example T -bromo-3-sec-butyl-l-ethoxycarbonyl 6-methyluracil 35-0$ xylene 59-0$ alkylphenyl polyethylene glycol ether 3.0$ oil-soluble calcium alkylbenzene sulfonate 3.o$ The above ingredients are blended until homogeneous to form an emulsifiable concentrate. The followin compounds can be formulated in like manner: 3-tert-butyl-5-chloro-l-ethoxycarbonyl-6-methyluracll -bromo-1-ethoxycarbonyl-6-methy1-3-isopropyluraci1 -bromo-3-sec-butyl-l-methylthiocarbonyl-6-methyluracil 3-tert-butyl-5-chloro-l-methylthiocarbonyl-6-me hyluracil 5-bromo-3-sec-butyl-l-methoxycarbonyl-6-methyluracll oxy 3-tert-butyl-5-chloTO-l-cycloprop carbonyl-6-meth luraclL Four kilograms per hectare of the above chemical are applied as an emulsion in 400 liters of water per hectare to a field of newly transplanted sisal. The treatment provides long terra control of many weeds in the crop.
This material may also be used without dilution for spot treatment.
Example 3-eyelohexy1-1-ethoxycarbonyl-5,6- trimethyleneuraeil 24.0$ fuel oil 68.0$ alkylaryl polyethylene glycol ether 4.0$ oleyl ester of polyethylene glycol 4.0$ The above ingredients are blended until homogeneous to form an emulsifiable concentrate. The following compounds can be formulated in like manner: -bromo-3-sec-butyl-6-methyluracil-l-phenoxycarbonyl 3-cyclohexyl-l-(2~methoxyethoxycarbonyl)-5,6- trimethyleneuracil -bromo-3-sec-butyl-l-hexyloxycarbonyl-6-meth luracil 3-tert-butyl-5-chloro-l-hexyloxycarbonyl-6-methyluracil Eight kilograms of the chemical (active ingredient) formulated as described above are emulsified in 500 liters of •water and applied as a directed spray in sugar cane 20-30 cm. tall. The material is applied when the weeds are small or . have not yet emerged. This treatment controls barnyard grass, mustard species, and junglevine in the cane.
ExampleJ#T -bromo- -sec-butyl-1-ethoxycarbon 1- 6-methyluracil 50.0$ aromatic weed oil 50.0$ The above composition is prepared by blending the two components. It can be sprayed directly as a low volume concentrate or it can be diluted with additional oil before application.
The following compounds can be formulated in like manner: -bromo-l-ethoxycarbonyl-6-methyl-3-isopropyluracil -bromo-3-sec-butyl-l-methylthiolcarbonyl-6-methyluracil 5-bromo-3-sec-butyl-l-hexyloxycarbonyl-6-meth luracil This compound is applied at the rate of 20 kilograms of active ingredient per hectare in 400 liters of water for the control of annual and perennial broadleaved weeds growing along a pipeline right-of-way. Excellent control of broomsedge (Andropogon virginicus), crabgrass, nutsedge (Cyperus spp.), Johnsongrass, goldenrod (Solidago spp.) and eveningprimrose (Oenothera spp.) is obtained.
Example Jc % . 3-tert-buty 1 - 5-chioro- 1-ethox - carbonyl-6-methyluracll 24.0$ trimeth lnonyl polyethylene glycol ether 48.0$ heavy aromatic naphtha " 28.0$ The above components are blended to form an emulsifiable concentrate containing a high surfactant level.
The following compounds can be formulated in like manner: -tert-butyl-5~chlor0-l-methylthiocarbonyl-6-meth luracll 3-tert-butyl-5-ehloro-l-he'xyloxycarbonyl-6-methyluracil Five kilograms of active ingredient formulated as described above are emulsified in 500 . liters of water. This emulsion is sprayed to runoff in a block under 2-year transplanted citrus trees. The treatment provides control of seedling Bermudagrass, seedling crabgrass, goosegrass, ragweed, seedling morningglory ( Ipomoca spp ♦ ) and other weeds.
One kilogram of 3-tert-butyl-5-chloro-l-ethoxycarbonyl- 6-methyluracil which has been formulated as a 5 $ wettable powder according to the recipe and method shown in Example 84 is suspended in 200 liters of water and sprayed pre-emergence over a hectare of peanuts. The treatment gives control of numerous weed species including crabgrass, goosegrass, ragweed, lambsquarter, smartweed, and barnyardgrass. The peanuts grow free of weed competition and produce an excellent yield.
ExampleJT 3 3-cyclohexyl-l-ethoxycarbonyl- 5,6-trimethyleneuracil 20.0$ sodium sulfate anhydrous 10.0$ sodium lignin sulfonate 2.0$ sodium alkyl naphthlene sulfonate 1.0$ The above ingredients are ground to pass an O.30 mm. . ' screen and are then charged to a blender where sufficient water (l8-21 ) is added to form an extrudable composition. This composition is extruded through an orifice and cut into pellets which are then dried. The pellets can be used directly or may be further subdivided in granules by passage through a Stobar granule tor.
The following compounds can be formulated in like manner: -chloro-l-ethoxycarbonyl-6-methyl-3-phenyluracil 3-benzyl-5-chloro-l-ethoxycarbonyl-6-methyluracil -chloro-l-methylthiocarbonyl-6-methyluracil l-allyloxycarbonyl-3-benzyl-5-chloro-6-methyluracil 3-cyclohexyl-l-methoxycarbonyl-5,6-trimethyleneuracil Example ^ <$Q -bromo-3-sec-butyl-1-ethoxycarbony1- 6-methyluracTl 10.0$ trimethylnonyl polyethylene glycol ether o.5# aromatic weed oil 5·0 attapulgite granular (0.6-1.2 mm) 8 .5$ The above components except the granules are blended by warming and stirring and are then sprayed on the granules which are tumbled in a blender. The resulting herbicidal granules can be used without further treatment.
The following compounds can be formulated in like manner: 3-tert-butyl-5-chloro-l-ethoxycarbonyl-6-methyluracil -bromo-3-sec_-butyl-l-methylthiocarbonyl-6-methyluracil 5-bromo-3-sec-butyl-l-methoxycarbonyl-6-methyluracil 3-tert-butyl-5-chloro-l-hexyloxycarbonyl-6-methyluracll 3- tert-butyl-5-chloro-l-cyclopropylca rbonyl-6-methyluracil The granules or pellets formed as described above may or oak or may be applied with a spreader at the rate of kilograms of active ingredient per hectare to give control of all vegetation in an industrial site.
Example Sfi 3-benzyl-5-chloro-l-methylthiocarbonyl- 6-methyluracil 50.0$ montmorillonite clay 46.0 sodiumalkyl naphthalene sulfonate 2.0$ calcium lignin sulfonate 2.0$ The above ingredients are blended, micropulverized to a particle size below 100 microns, and reblended until homogeneous.
Two kilograms of the above active ingredient are suspended in 400 liters of water and applied pre-emergence to a hectare of corn. This treatment provides control of such weeds as bamyardgrass, crabgrass, goosegrass, dock (Rumex spp. ) , giant foxtail (Setoria spp.), and ragweed. The crop provides a good yield of corn.
Example & 0 3-tert-butyl-5-chloro-6-methyluracil, 1-carboxylic acid, propyl ester 25.0$ attapulgite clay 68.0$ dioctyl sodium sulfosuccinate 1.0$ sodium lignin sulfonate 2.0$ finely divided synthetic silica 4.0$ The above components are blended, micropulverized in a hammer mill until the particles are essentially smaller than 0 microns and then reblended until the mixture is homogeneous.
One kilogram of the active ingredient in the above formulation is suspended in 250 liters of water and applied pre-emergence to a hectare of sunflowers. The treatment controls the existing weeds including crabgrass, ryegrass, ragweed, wild oats, smartweed, and mustard (Brassica sp.). The sunflowers grow free from weed competition and produce an excellent crop of seed of high oil content.

Claims (12)

UJ CLAIMS 32113/2
1. Uracyl compounds of the formula C = 0 X R '4 where ^ is alkyl of 1 through 10 carbon atoms, substituted alkyl of 1 through 8 carbon atoms, having one or more subatitbromine uents selected from the group consisting of ¾©«a£«e, chlorine, fluorine, hydroxy, alkoxy, and cyano, aryl of 6 through 10 carbon atoms, furyl, pyridyl, substituted phenyl having one or more identical or different subatituents seleoted from the group consisting of chlorine, bromine, fluorine, or phenyl, alkyl alkoxy of 1 through 6 carbon atoms, t ifluorometh l, j ' 1,2-tetramethylene, and 1,2-trimethylene, aralkyl of 7 through 13 carbon atoms, furfuryl, pyridylalkyl, substituted aralkyl of 7 through 13 carbon atoms, having one or more identical or different subatituents selected from the group consisting of ohlorine, nitro, alkyl, and alkoxy. - 42 - 32113/3 ^ - 43 - alkenyl of 3 hrough 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, or R1 is one of themdicals- (a) cycloalkyl, (b) cycloalkenyl, (c) cycloalkyl alkyl, (d) cycloalkenyl alkyl each optionally substituted with bromine, chlorine, methoxy or alkylί with the proviso tha i (1) the unsubstituted and halo-substituted radicals have respectively: 3-12 carbon atoms for radical (a) 4-12 carbon atoms for radical (b) 4-13 carbon atoms for radical (c) 5-13 carbon atoms for radical (d); (2) th<§ methoxy or alkyl substituted radicals have, respectively. 4-13 carbon atoms for radicals (a) and (b) 5-14 carbon atoms for radicals (c) and (d)j Rg is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, nitro, alkoxymethyl of 2 through 4 carbon atoms, hydroxyalkyl of 1 through 4 carbon atoms, mereaptoraethyl, methylthio, ethylthio, methylthiomethyl, broiaomethyl, chloromethyl and fluoromethyl; is hydrogen or alkyl of 1 through 3 carbon atomsi 32113/2 R^ is alkyl of 1 through 10 carbon atoms, optionally substituted with one or more chlorine, bromine, or fluorine atoms or with alkyhyl of 3 to 6 carbon atoms, alkoxy of 1 through 4 oarbon atoms } /aryl of 6 through 10 carbon atoms, phenyl substituted with chlorine, fluorine or alk lthio, benzyl, furfuryl, thienyl or pyridyl, alkenyl of 3 through 4 parbon atoms, cycloalkyl of 4 through 8 carbon atoms and cycloalky-^lkyl of 4 through 13 carbon atoms, X is Oxygen or sulfur; with the proviso that R„ and can be taken together as -(0H )-f to form a ring where n' is 3, 4, or 5, and their complexes with phenol of the formula where ^, g» ^, ^ » an<^ ^ aro as defined in Formula (1); A is hydrogen, bromine, chlorine, nitro, alkyl of 1 through 3 carbon atoms or an -OR., radical where is alkyl of 1 through 3 carbon atoms; Y is chlorine or alkyl of 1 through 3 carbon atoms; m is a number 1 through 5; and n is 1/2* 1 or 2.
2. l-Methoxycarbonyl-3-sec-butyl-5-bromo-6-methyluracil.
3. l- ethoxycarbonyl-3-tert-butyl-5-chloro-6-methyluracil.
4. l-Methoxycarbonyl-3-cyclohexyl-5,6-trimethyleneuracil.
5. l-Ethoxycarbonyl-3-^ec-butyl-5-bromo-6-methyluracil. - 44 - 32113/2
6. Uracil compounds of formula (l) in Claim 1 and their complexes with phenols of the formula (2) in Claim 1, substantially as described herein with reference to the Examples.
7. A process for preparing the compounds of formula (1) in Claim 1 which comprises (1) reacting in the presence of an organic solvent a uracil having the formula 0 with sodium metboxide; and (2) reacting the product of step (1) with an excess of a chlorocarbony1 having the formula 0 R.X - 4 I! - 01 and, if desired, cornelting or codissolving the uracil compound of formula (1) thus obtained with phenol to form the corresponding phenol complex of formula (2).
8. A process for preparing the uracil compounds of formula (l) in Claim 1 which comprises (l) mixing a uracil having the formula 0 with sodium hydride; and 32113/2 (2) reacting the product of step (1) with an excess of a chlorocarbonyl having the formula 0 R.X - 4 h - 01 and, if desired cornelt ing or codissolving the uracil!compound of formula (1) thus obtained with phenol to form the corresponding phenol complex of formula (2). j
9. Processes or the preparation of compounds of formula I (1) in Claim 1, substantially as described herein with reference to the Examples.
10. Herbicidal compositions comprising a herbicidal amount of a compound of formula (1) or (2) in Claim 1, and an ad uvant.
11. A composition according to Claim 10 containing 2 or more uracils of formula (1) in Claim 1 and also other known herbicides.
12. A method for the control of undesirable vegetation which comprises applying to a locus to be protected a herbi-oidally effective amount of a compound of formula (l) or (2) in Claim 1 alone or in the form of a composition according to Claim 10 or 11. PC/rb
IL32113A 1968-05-13 1969-04-30 1-alkoxycarbonyl uracils,their preparation and herbicidal compositions containing them IL32113A (en)

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DE1283665B (en) * 1966-02-03 1968-11-21 Interelectric Ag Card for congratulatory and visitation purposes and process for their manufacture
JPS5633918U (en) * 1979-08-21 1981-04-02
FR2549060B1 (en) * 1983-07-11 1986-06-27 Roussel Uclaf NOVEL SUBSTITUTED URACILS COMPRISING IN POSITION 1 A SUBSTITUTED PHENYLOXY GROUP, THEIR PREPARATION METHOD AND THE HERBICIDAL COMPOSITIONS CONTAINING THEM
DK167280B1 (en) * 1985-03-20 1993-10-04 Ciba Geigy Ag 3-ARYLURACIL DERIVATIVES, PROCEDURES FOR PREPARING THEREOF, WEED POLLUTANTS CONTAINING THESE DERIVATIVES AND THE USE OF THE DERIVATIVES FOR THE WEED PREVENTION
DK366887A (en) * 1986-07-31 1988-05-13 Hoffmann La Roche pyrimidine
JPH02501388A (en) * 1987-09-23 1990-05-17 チバ　―　ガイギー　アクチエンゲゼルシャフト heterocyclic compound
HU219159B (en) * 1989-06-29 2001-02-28 Novartis Ag. 3-aryluracyl derivatives, herbicidal compositions comprising 3-aryluracyl derivatives as active ingredient and process for producing the active ingredient and for combating weeds

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OA03321A (en) 1970-12-15
FR2008386A1 (en) 1970-01-23
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JPS4831898B1 (en) 1973-10-02
GB1257259A (en) 1971-12-15

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