US3300292A - Herbicidal compositions containing uracil thiocyanate addition compounds - Google Patents

Herbicidal compositions containing uracil thiocyanate addition compounds Download PDF

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Publication number
US3300292A
US3300292A US468956A US46895665A US3300292A US 3300292 A US3300292 A US 3300292A US 468956 A US468956 A US 468956A US 46895665 A US46895665 A US 46895665A US 3300292 A US3300292 A US 3300292A
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carbon atoms
alkyl
thiocyanate
compounds
addition compound
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US468956A
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Raymond W Luckenbaugh
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to US468956A priority Critical patent/US3300292A/en
Priority to NL6604852A priority patent/NL6604852A/xx
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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
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—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
    • C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other 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
    • C07D239/553—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other 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 with halogen atoms or nitro radicals directly attached to ring carbon atoms, e.g. fluorouracil

Definitions

  • v R is alkyl of 1 through 10 carbon atoms
  • substituted alkyl of 1 through 8 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, dialkylamino, and cyano, aryl of 5 through carbon atoms, substituted phenyl of 6 through 14 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, phenylalkyl of 1 through 6 carbon atoms, chloroalkoxy of 1 through 5 carbon atoms, trifiuoromethyl, 1,2-tetramethylene, and 1,2-trimethylenylene, arylalkyl of 5 through 13 carbon atoms, substituted arylalkyl of 5 through 13 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, nitro, alkyl and alkoxy, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12
  • I g R is hydrogen, methyl, chloromethyl or bromomethyl
  • R is hydrogen or branched or unbranched alkyl of 1 through 4 carbon atoms
  • X is oxygen or sulfur
  • M is magnesium, calcium, strontium, or barium
  • n 1 or 2
  • R and R can be joined together to form an alkylene bridge of 3 through 5 carbon atoms.
  • substituted alkyl is intended to include such radicals as bromoalkyl of 1 through 8 carbon atoms chloroalkyl of 1 through 8 carbon atoms hydroxyalkyl of 1 through 8 carbon atoms alkoxyalkyl of 2 through 8 carbon atoms alkoxy carbonyl alkyl of 3 through 8 carbon atoms diaalkyl amino alkyl of 3 through 8 carbon atoms and cyanoalkyl of 2 through 8 carbon atoms Similarly, the terms aryl and substituted phenyl?
  • arallcyl and substituted aralkyl are intended to include such radicals as benzylv phenylalkyl of 8"through 11 carbon atoms (total) chlorobenzyl dichlorobenzyl alkylbenzyl of 8 :through' 11 carbon atoms (total) diallrylbenzyl of 9" through 13 carbon atoms (total) nitrobenzyl alkoxybenzyl of Stbrough 11 carbon atoms (total) naphthylmethyl and furfuryl
  • the terms-cycloalkyl, cycloalkenyl, cycloalkyl alkyl, and cycloalkenyl alkyl will incude cyclohexyl cyclohexenyl cyclohexylalkyl cyclohexenylalkyl cyclopentyl cyclopenteny
  • addition compounds are prepared by reacting the appropriate uracil with a suitable thiocyanate.
  • the uracil reactants are prepared according to the following equations:
  • the compounds of the invention are prepared by mixing 4 to 16 parts by weight of a 3560% aqueous solution of a thiocyanate with a dry uracil at room temperature. Reaction is immediate. The addition compounds precipitate and are filtered from the reaction medium. They are then washed with an organic solvent such as ether or pentane and dried in vacuo over a dehydrating agent such as P 0 or CaCI
  • the uracil-thiocyanate addition compounds hereof have a herbicidal effect similar to that of the uracils per se.
  • These addition compounds have been found, however, in accordance with the present invention to provide important formulating and handling advantages and thus herbicidal compositions of these compounds are preferred in various herbicidal applications.
  • these uracil-thiocyanate addition compounds have melting points usually greater than 300 C. which permits preparation of wettable powders having high concentrations of active ingredients and also makes sand-grinding of liquid formulations easier and more stable.
  • novel addition compounds as the corresponding uracils per se, can be used as general-purpose weed killers, as soil sterilants, in soil-foliage applications, and as selective weed killers for either preor post-emergence weed control.
  • the compounds control both annual and perennial broadleaf weeds and grasses.
  • the compounds control such germinating broadlea-f weeds as pigweed, lambsquarters, mustard, chickweed, flower-of-an-hour, ragweed and such grass weeds as crab grass, water grass, giant foxtail, green foxtail and seedling Johnson grass.
  • the compounds control existing mixed annual and perennial vegetation composed of such broadleaf and grass Weeds as crab grass, foxtail, water grass, quack grass, Bermuda grass, Johnson grass, brome grass, ragweed, cocklebur, pigweed, lambs quarters, mares tail, wild carrot, plantain and dandelion.
  • the concentration at which the compounds are to be used will naturally vary with the result desired, the type of vegetation, the formulation used, the mode of application, weather conditions, foliage density, and other similar factors. Since so many variables play a role, it is not possible to indicate a concentration suitable for all situations. Generally, however, when the compounds are used in pre-emergence treatments, they are applied at concentrations of from 0.25 to 35 pounds of active ingredient per acre. Concentrations of from 0.5 to 8 pounds per acre are preferred for selective weed control. When the compounds are used in soil-foliage applications, they are applied at concentrations of from 2 to 35 pounds per acre. More can be applied to control diflicult-to-kill species under adverse conditions.
  • Preferred for use as herbicides are the addition compounds of formula 1 where R is a A H:- l radical where A is methyl or ethyl, Y is hydrogen or methyl, and Z is alkyl or 1 through 6 carbon atoms; R is halogen, or a branched or unbranched alkyl of 1 through 6 carbon atoms;
  • R is hydrogen, or a branched or unbranched alkyl of 1 through 6 carbon atoms
  • R is hydrogen
  • X is oxygen
  • M is calcium
  • R and R can be joined to form an alkylene bridge of 3 through 5 carbon atoms.
  • the calcium thiocyanate addition compounds with '3 l-lower alkylethyl -5-ha1ogeno-6-methyluracils 3-(2- lower alkylethyl) -5-halogeno-6-methylunacils 3-( l-lower alkylisopropyl) -5-halogeno-6-methyluracils 3 (cycloalkyl) -5-halogeno-6-methyluracils 3-(cycloalkenyl)-5-halogeno-6-methy!luracils 3 (phenyl) -5 halogeno-6-methyluracils 3-(bicycloalkyl)-5-halogeno-6-methyluracils 3- (bicycloal-kenyl) -5-halogeno-G-methyluracils '3- (tr-icycloalkyl) -5-halogeno-6-methyluracils 3 (tricyclo alkenyl) -S-halogeno-6-methyl
  • herbicidal compositions of this invention incorporating the uracil-thiocyanate addition compounds hereof can readily be prepared for use by incorporating them with suitable adjuvants.
  • The'amount of addition compound in such preparations can vary over a wide nange 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 compounds of the invention with finely-divided solids such as tales, natural clays, pyrophillite, diatomaceous earth and synthetic fine silicas; flours such as walnut shell, wheat, redwood, s-oya bean and cotton seed; or inorganic substanoes such as magnesium carbonate, calcium silicate, calcium phosphate, sulfur and lime. These preparations are made by thoroughly blending the active ingredients and the solid. The particles in such preparations are preferably less than 50 microns in average diameter.
  • Granules and pellets can be made by mixing a finely- .divided addition compound with a suitable clay, 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 can also be prepared by spraying a suspension or solution of an addition compound onto the surface of a preformed granule or clay, vermiculite or other suitable granular material.
  • a binding agent such as goulac, dextrin, swollen starch, glue or polyvinyl alcohol be added to attach it more firmly to the granule surfaces.
  • Emulsifiable oil preparations can be made by dissolving a uracil-thiocyanate addition compound in an oil such as isophorone or cyclohexanone, and adding an emulsifying agent.
  • Aqueous suspensions of those addition compounds which are water-insoluble are prepared by first making a slurry of the active ingredient and suitable dispersing agent and then wet-grinding this slurry, by ball-milling or sand-grinding, until 90% of the particles of active ingredient are less than 10 microns in diameter.
  • Both of these liquid preparations can be diluted to the proper concentrations with water before application.
  • the herbicidal preparations can also contain a surface-active agent.
  • surfactant renders the preparations readily dispersible in liquids and improves their action on waxy leaves and the like.
  • surface-active agents are used in the preparations at concentrations of from about 1 to 10%, by weight.
  • levels of from 0.5 to 6 parts of surfactant for each part of uracil give unusual and unexpected results. Preparations having these higher levels of surfactants show greater herbicidal effectiveness than can be expected from a consideration of the activity of the components used separately.
  • surface-active agent is intended to include wetting agents, dispersing agents and emulsifying agents.
  • Surface-active agents suitable for use are set forth in Detergents and Emulsifiers Up-to-Date, 1962. John W. McCutcheon, Inc., Morristo-wn, New Jersey. Other surface-active agents which can be used in these preparations are listed in US. Patents 2,139,276, 2,412,- 510, 2,426,417, 2,655,477, and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the US. Department of Agriculture.
  • the preparations can also optionally contain adhesives such as gelatin, blood albumin and such resins as rosin alkyd resins. These increase retention and tenacity of deposits following application.
  • This product is essentially pure 5-bromo-3-isopropyl- 6-methyl l/l addition compound with calcium thiocyanate.
  • EXAMPLE 2 3-isopropyl-6-methyluracil (25.2 parts by weight) is added, in one portion, to a stirred aqueous solution of parts, by volume, of calcium thiocyanate (SS-60%). The temperature increases from 25 C. to 29 C. in four minutes and the mixture becomes pastelike.
  • SS-60% calcium thiocyanate
  • EXAMPLE 4 3-cyclohexyl-5,6-trimethyleneuracil (23.4 parts by weight) is added, in one portion, to ,a stirred aqueous solution of 150 parts by volume of calcium thiocyanate (SS-60%). The temperature increases from 24 to 25.5 C.
  • the product is filtered from the solution after it has been stirred overnight, washed with n-pentane and ether, and then dried in a vacuum desiccator. There are obtained 33.5 parts by Weight of the 3-cyclohexyl-5,6-trimethyleneuracil 2/1 addition compound with calcium thiocyanate. It is a tan powder, with a melting point greater than 300 C.
  • EXAMPLE 5 5 -bromo-6-methyl-3 -phenyluracil (28.1 parts by weight) is added to a stirred aqueous solution of 150 parts, by volume, of calcium thiocyanate (SS-60%) After being stirred overnight, the 5-bromo-6-methyl-3-phenyluracil 1/1 calcium thiocyanate addition compound is isolated by filtration It is washed with n-pentane and ether, and then dried in a vacuum desiccator.
  • EXAMPLE 6 Two hundred twenty-five parts, by volume, of an aqueous solution of barium thiocyanate (35-40%) are stirred at room temperature. To this, at room temperature, are added 24.7 parts, by weight of 5-bromo-3-isopropyl-6- methyluracil. The solution is stirred overnight and the 5-bromo-3-isopropyl-6-methluracil 1/1 addition compound with barium thiocyanate is isolated by filtering, washing with ether, and drying in a vacuum desiccator over calcium chloride.
  • EXAMPLE 7 One hundred eighty-five parts, by volume, of an aqueous solution of strontium thiocyanate (4550%) are stirred at room temperature. To this are added 24.7 parts by weight of S-bromo-3-isopropyl-6-methyluracil at room temperature.
  • the product is essentially pure 5-bromo-3-isopropyl-6- methyluracil 1/1 addition compound with strontium thiocyanate.
  • the resulting composition after separation from the sand by centrifugation, is a thixotropic liquid whose solids do not cake densely on the bottom of the container on extended storage.
  • this composition can be extended with water to form a nonfl-occulated stable suspension containing 0.220%, by weight, of the active ingredient.
  • this mixture When applied in 60 gallons of water to an industrial area, this mixture, at a rate of to pounds per acre of ac- 15 tive ingredient, gives excellent control of such broad-leaf and grass weeds such as crabgrass, foxtail, lambs quarters, wild carrot, barnyard grass and seedling Johnson grass.
  • the addition compounds in the following table can be Thio- Volume and Strength cyanate Thiocyanate Solution VolumeinMl.
  • Attapulgite hydrated 2.0 Goulac (sodium lignin sulfonate) 5.0 Water 53.0
  • addition compounds in the following table can be similarly formulated and used, in herb-icidally equivalent amounts 3-(5-chloronorbornenyl) 6 methyluracil 1/1 addition compound with Ca(SCN) 3-isobutyl-5-nitro-6-methyluracil 1/1 addition compound with,Ba(SCN) 3-isopropyl-5 hydroxymethyl-6-methyluracil 1/1 addition compound with Sr(SCN) EXAMPLE 1'2.WETTABLE POWDER Percent -bromo-3-isopropyl-6-methyluraci1 1/ 1 addition compound with Ca(SCN) 95 Sodium. lignin sulfonate 3 Sodium alkyl aryl su'lfonate 2 These ingredients are mixed and micropulverizcd to an average particle size below 50 microns.
  • the "resulting wettable powder is applied at the rate of 8 pounds per :acre (active) in 25 gallons water for the control of wild oats and cheatgrass along roadsides.
  • the 3-sec.-butyl-5-chloro-6-methyluracil 1/ 1 addition compound with Ca(SCN) and the 3-(2-ethylpropyl)-5- bromo-6-methyluracil 1/1 addition compound with can be similarly formulated and used, in herbicidally equivalent amounts.
  • a herbicidal composition comprising an adjuvant and, in an amount sufiicient to exert herbicidal action, a compound of the formula litgn where R is selected from the group consisting of alkyl of 1 through 10 carbon atoms, substituted alkyl of 1 through 8 carbon atoms, wherein said substituent is selected from the group consisting of bromide, chlorine, hydroxy, alkoxy, alkoxycar bonyl, dialkylamino, and cyano,
  • substituted cycloalkyl of 3 through 12 carbon atoms wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, phenylalkyl of 1 through 6 carbon atoms, chloroa-lkoxy of 1 through 5 carbon atoms, trifluoromethyl, 1,2- tetramethylene, and 1,2-trimethylenylene,
  • substituted arylalkyl of 5 through 13 carbon atoms wherein said substituent is selected from the group consisting of chlorine, nitro, alkyl and alkoxy,
  • substituted cycloalkyl of 3 through 12 carbons atoms wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and
  • R is selected from the group consisting of hydrogen, halogen, nitro, 'hydroxymethyl, alkyl of 1 through 6 carbon atoms, and a-lkoxymethyl wherein the alkoxy portion thereof contains 1 through 4 carbon atoms;
  • R is selected from the group consisting of hydrogen
  • R is selected from the group consisting of hydrogen and alkyl of 1 through 4 carbon atoms
  • X is selected from the group consisting of oxygen and sulfur
  • 1 1 1 2 M is selected from the group consisting of magnesium, References Cited by the Examiner calcium, strontium and barium; and UNITED STATES PATENTS n is selected from the group consisting of 1 and 2.

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US468956A 1965-07-01 1965-07-01 Herbicidal compositions containing uracil thiocyanate addition compounds Expired - Lifetime US3300292A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030153584A1 (en) * 2001-04-11 2003-08-14 Queen's University Pyrimidine compounds as anti-ictogenic and/or anti-epileptogenic agents

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2992089A (en) * 1959-02-13 1961-07-11 Amchem Prod Herbicidal process
FR1270771A (fr) * 1959-08-14 1961-09-01 Du Pont Nouveaux uraciles substitués et leur préparation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2992089A (en) * 1959-02-13 1961-07-11 Amchem Prod Herbicidal process
FR1270771A (fr) * 1959-08-14 1961-09-01 Du Pont Nouveaux uraciles substitués et leur préparation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030153584A1 (en) * 2001-04-11 2003-08-14 Queen's University Pyrimidine compounds as anti-ictogenic and/or anti-epileptogenic agents
US7501429B2 (en) * 2001-04-11 2009-03-10 Queen's University At Kingston Pyrimidine compounds as anti-ictogenic and/or anti-epileptogenic agents

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