EP0984681A1 - Process and compositions promoting biological effectiveness of exogenous chemical substances in plants - Google Patents

Process and compositions promoting biological effectiveness of exogenous chemical substances in plants

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Publication number
EP0984681A1
EP0984681A1 EP98925033A EP98925033A EP0984681A1 EP 0984681 A1 EP0984681 A1 EP 0984681A1 EP 98925033 A EP98925033 A EP 98925033A EP 98925033 A EP98925033 A EP 98925033A EP 0984681 A1 EP0984681 A1 EP 0984681A1
Authority
EP
European Patent Office
Prior art keywords
composition
exogenous chemical
chemical substance
amine compound
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98925033A
Other languages
German (de)
English (en)
French (fr)
Inventor
Gérard G. SOULA
Rémi Meyrueix
Alain J. L. Lemercier
Philippe G. Caisse
Anthony J. I. Ward
Jane L. Gillespie
Ronald J. Brinker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Monsanto Technology LLC
Original Assignee
Monsanto Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR9706917A external-priority patent/FR2763793B1/fr
Application filed by Monsanto Co filed Critical Monsanto Co
Publication of EP0984681A1 publication Critical patent/EP0984681A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Definitions

  • the field of the present invention is that of exogenous chemical substances applied to foliage of plants, and relates particularly to a process and to compositions applied by that process for promoting biological effectiveness of such exogenous chemical substances.
  • exogenous chemical substance means a chemical substance, whether naturally or synthetically obtained, which is applied to a plant to result in expressing a desired biological activity.
  • biological activity means elicitation of a stimulatory, inhibitory, regulatory, therapeutic, toxic or lethal response in the plant or in a pathogen, parasite or feeding organism present in or on the plant.
  • exogenous chemical substances include, but are not limited to, chemical pesticides (such as herbicides, algicides, fungicides, bactericides, viricides, insecticides, miticides, nematicides and molluscicides), plant growth regulators, fertilizers and nutrients, gametocides, defoliants, desiccants, mixtures thereof and the like.
  • chemical pesticides such as herbicides, algicides, fungicides, bactericides, viricides, insecticides, miticides, nematicides and molluscicides
  • plant growth regulators such as fertilizers and nutrients, gametocides, defoliants, desiccants, mixtures thereof and the like.
  • biological effectiveness is used herein to denote the degree to which a desired biological activity is expressed upon application of an exogenous chemical substance to foliage of a plant, or alternatively to denote the dosage or rate of application of the exogenous chemical substance that results in the desired biological activity being expressed to a given degree.
  • the exogenous chemical substance is a herbicide
  • biological effectiveness can be measured by the degree of inhibition of plant growth resulting from application of a particular rate of the herbicide, or by the application rate of the herbicide required to cause a particular degree of inhibition, e.g., 50% or 85% inhibition.
  • increased or enhanced biological effectiveness of a herbicide can be exhibited for example as an increased level of plant growth inhibition at a given rate of the herbicide, or as a reduction in the minimum rate of the herbicide giving a certain threshold level of plant growth inhibition.
  • exogenous chemical substances For many purposes in agriculture and related endeavors it is desired to treat plants with exogenous chemical substances of various kinds. Many exogenous chemical substances are applied to foliage (i.e., leaves and other non- woody above-ground parts) of a plant, and have a site of action- in the plant either close to or remote from the locus of application. Such substances are referred to herein as foliar-applied exogenous chemical substances. Typically, when an exogenous chemical substance is applied to foliage by plant treatment processes known in the art, only a small portion of the amount applied reaches sites of action in the plant where a desired biological activity of the exogenous chemical substance can be usefully expressed.
  • anionic exogenous chemical substance means an exogenous chemical substance whose molecular structure includes one or more acid, or proton-donating, sites, and is therefore capable of forming an anion in the presence of a proton acceptor.
  • the term therefore embraces substances that are zwitterionic. In describing an exogenous chemical substance as "anionic” herein, it is not implied that the exogenous chemical substance is necessarily in anionic form or that it is dissociated.
  • Benefits of a process providing greater reliability of biological effectiveness include an ability to reduce rates of application of exogenous chemical substances without sacrificing consistency of biological effectiveness. Pressures felt by the agricultural industry to reduce pesticide, particularly herbicide, usage are well evidenced by symposia on the subject, such as that held in 1993 by the Weed Science Society of America and documented in Weed Technology 8, 331-386 (1994). Reduced use rates bring rewards not only environmentally but also economically, as the cost per unit area treated decreases.
  • Foliar-applied exogenous chemical substances have frequently been applied together with amphiphilic materials, particularly amphiphilic surface-active agents, otherwise known as surfactants.
  • Surfactants can influence biological effectiveness of a foliar-applied exogenous chemical substance in numerous ways.
  • a dilute aqueous composition of an exogenous chemical substance When a dilute aqueous composition of an exogenous chemical substance is applied to foliage by conventional hydraulic spraying, the presence of surfactant in the dilute aqueous composition can alter the size distribution of the spray droplets, typically increasing the percentage of spray volume in the form of small droplets and reducing the percentage of spray volume in the form of large droplets. As smaller droplets have lower momentum than larger droplets, these smaller droplets are less likely to rebound from a foliar surface and consequently are more likely to be retained on that surface. Spray retention can also be facilitated by adhesion between surfactant molecules in a spray droplet and the foliar surface, which in most plants is waxy and hydrophobic. This adhesion reduces not only rebound but also run-off of spray droplets from the foliar surface. Surfactants also tend to increase the area of contact between a spray droplet and a foliar surface, and in many cases enhance penetration of an exogenous chemical substance from the droplet into and through cuticles
  • amphiphilic materials including surfactants have long been known to increase the biological effectiveness of exogenous chemical substances. It is therefore commonplace for one or more surfactants to be included in commercial formulations of foliar-applied exogenous chemical substances, even in formulations that do not require the presence of surfactants for acceptable physical stability or handling properties, for example as emulsifying or suspending agents or dispersants.
  • glyphosate has been used as a plant growth regulator.
  • Glyphosate in its strict sense is an acid compound, N-phosphonomethylglycine, but the word "glyphosate" is herein used in a less restrictive sense, except where the context dictates otherwise, to encompass not only glyphosate acid but also salts, adducts and esters thereof, and compounds which are converted to glyphosate in plant tissues or which otherwise provide glyphosate ions.
  • the glyphosate is present as a water-soluble salt.
  • glyphosate is typical of most exogenous chemical substances that are acids or that form anions.
  • Herbicidal salts of glyphosate are disclosed, for example, in U.S. Patent No. 3,799,758 to Franz, U.S. Patent No. 3,853,530 to Franz, U.S. Patent No. 4,140,513 to Prill, U.S. Patent No. 4,315,765 to Large, U.S. Patent No. 4,405,531 to Franz, U.S. Patent No. 4,481,026 to Prisbylla and U.S. Patent No. 4,507,250 to Bakel.
  • the counterion to glyphosate anion is a relatively low molecular weight, non- amphiphilic cation.
  • salts are alkali metal, for example sodium and potassium, salts; ammonium salt; C )-6 alkylammonium, for example dimethylammonium and isopropylammonium, salts; C 1-6 alkanolammonium, for example ethanolammonium, salts, C 1-6 alkylsulfonium, for example trirnethylsulfonium, salts; and sulfoxonium salts.
  • glyphosate salts include, for example, Roundup® brand, Accord® brand and Roundup® Ultra brand herbicides of Monsanto Company, which contain the isopropylammonium salt, Roundup® Dry brand and Rodeo® brand herbicides of Monsanto Company, which contain the ammonium salt, Roundup® Geoforce brand herbicide of Monsanto Company, which contains the sodium salt, and Touchdown® brand herbicide of Zeneca, which contains the trimethylsulfonium salt. Salts of glyphosate with higher molecular weight, amphiphilic cations have also been disclosed.
  • amphiphilic cations include those having a hydrophilic moiety such as an ammonium, ethanolammonium, polyoxyethylene ammonium, or sulfonium group, and a hydrophobic moiety comprising 1 to 4 hydrocarbyl groups having in total more than 6 carbon atoms.
  • a hydrophilic moiety such as an ammonium, ethanolammonium, polyoxyethylene ammonium, or sulfonium group
  • a hydrophobic moiety comprising 1 to 4 hydrocarbyl groups having in total more than 6 carbon atoms.
  • Patent No. 4,431,594 disclose various quaternary ammonium salts of glyphosate wherein the cation is amphiphilic.
  • U.S. Patent No. 5,668,085 discloses salts of glyphosate with amphiphilic cations derived from polyoxyethylene C 8 . 22 tertiary alkylamine surfactants, a specifically disclosed example being the N-cocoalkyl-N,N-diethanolammonium salt of glyphosate where "coalkyl” refers to a mixture of predominantly C 12 and C 14 alkyl chains, derived from coconut oil.
  • Glyphosate as a herbicide has many advantages, particularly environmental advantages including biodegradability and low ecotoxicity.
  • the small fraction of applied glyphosate which reaches sites of phytotoxic action is related to the fact that the glyphosate must go through several barriers. Among these, one of the most important is believed to be the lipophilic cuticle on the foliar surface to which the glyphosate is applied. It has therefore been theorized that it would be desirable to place the glyphosate into an amphiphilic medium which would provide greater compatibility between the lipophilic cuticle and the hydrophilic glyphosate, and thereby facilitate penetration of glyphosafe into and through the cuticle. Similar thinking has been applied to other exogenous chemical substances, particularly those typically formulated as water-soluble salts.
  • Another approach to providing an amphiphilic medium has been to apply glyphosate together with a lipophilic agent, such as an oil, in the form of a water-in-oil emulsion or microemulsion.
  • a lipophilic agent such as an oil
  • Such emulsions or microemulsions are disclosed in European Patent Application No. 0 379 852, U.S. Patent No. 4,853,026 and U.S. Patent No. 5,248,086.
  • a disadvantage of such microemulsions is that, when provided as concentrate compositions, they are subject to the phenomenon of breaking of the emulsion upon dilution with water to concentrations suitable for application, for example, 5 grams of glyphosate, expressed as acid equivalent, per liter (g a.e./l).
  • water-in-oil microemulsions tend not to withstand dilution in water. The failure of such microemulsions to provide improved cuticular penetration is perhaps related to this inability to withstand dil
  • Oil-in-water macroemulsion formulations of glyphosate have also been investigated.
  • the majority of the glyphosate is present in the continuous aqueous phase, as shown, for example, in European Patent Application No. 0 485 207.
  • Such macroemulsions, in which the glyphosate and the lipophilic component are segregated do not therefore provide glyphosate in an amphiphilic form, and have generally not enhanced delivery of glyphosate to its sites of phytotoxic action in the plant.
  • a different approach, illustrated in European Patent Specification No. 0 148 169 is to encapsulate a water-soluble herbicide such as glyphosate in a polymeric shell by interfacial polycondensation.
  • a water-in-oil emulsion having a lipophilic emulsifier based on alkylated polyvinylpyrrolidone is used.
  • Polymerization to form the shell, by reaction of comonomers, occurs at the oil-water interface of the emulsion containing the herbicide, resulting in formation of a shell that encapsulates the herbicide.
  • Another objective of the invention is to provide a composition or formulation of an exogenous chemical substance, in particular an anionic exogenous chemical substance, that is economical and simple to make.
  • Another objective of the invention is to provide a composition or formulation that meets the previously stated objectives while permitting maintenance of the non-ecotoxic and biodegradable character of glyphosate.
  • Another objective of the invention is to provide a composition or formulation of an exogenous chemical substance, particularly an anionic exogenous chemical substance, that can be applied in a dilute aqueous medium and does not lose its beneficial properties at high rates of dilution.
  • Another objective of the invention is to provide a convenient and economical method for the preparation of a composition or formulation that meets the objectives stated above.
  • FIGURE Figure 1 is a transmission electron micrograph (magnification 28,000x) of a colloidal suspension of supramolecular aggregates containing an amphiphilic salt of glyphosate prepared according to Example 1 hereof.
  • the supramolecular aggregates appear as approximately spherical beads, most easily visible in the darker areas of the micrograph. They range widely in diameter, with most falling in a range from about 50 to about 500 nm.
  • a plant treatment composition for application to foliage of a plant to elicit a desired biological response comprising an aqueous application medium, in which supramolecular aggregates are colloidally dispersed.
  • the supramolecular aggregates comprise one or more amphiphilic salt(s) of an exogenous chemical substance having anions of an anionic exogenous chemical substance and cations derived by protonation of one or more amine compound(s) each having the formula (I)
  • R and R are independently linear hydrocarbyl chains each having 6 to about 22 carbon atoms, and R is hydrogen, a C 1-5 hydrocarbyl group or a linear hydrocarbyl chain no longer than R and no longer than R .
  • the exogenous chemical substance is present in the composition in a first molar amount X in the form of said amphiphilic salt(s) and in a zero or second molar amount X in the form of one or more salt(s) having anions of the exogenous chemical substance and cations derived from one or more base(s) other than an
  • the total molar amount (X + X ) of the exogenous chemical substance in salt form is sufficient to elicit the desired biological response when the composition is applied to the foliage of the plant at a rate from about 10 to about 1000
  • the anionic exogenous chemical substance is N-phosphonomethylglycine.
  • the amine compound of formula (I) has a molecular weight of about 240 to about 700. In another embodiment of the invention the amine compound of formula (I) has a molecular weight greater than about 300 and not greater than about 560.
  • the second molar amount is preferably present in the form of one or more salt(s) having monovalent cations selected from alkali metal, ammonium, C 1-5 alkylammonium, C . 5 alkanolammonium, C ⁇ _ 5 alkanolalkylammonium and C ⁇ _ 5 alkylsulfonium cations, and cations derived from an amine compound of formula (II):
  • R 5 di wherein R 4 and R 5 are independently hydrogen, methyl groups or hydrocarbyl chains each having 2 to 5 carbon atoms, and R is a linear hydrocarbyl chain having 6 to about 22 carbon atoms.
  • X as a fraction of (X + X ) is about 0.01 to about 0.2. In another embodiment, X as a fraction of (X + X ) is about 0.3 to 1.
  • a liquid, preferably aqueous, concentrate composition is also provided, which when diluted with a suitable amount of water forms a plant treatment composition as described above.
  • a contemplated liquid concentrate composition contains in total at least about 5% by weight and up to about 40% or more by weight of the exogenous chemical substance expressed as acid equivalent (a.e.).
  • the neutralizing step comprises neutralization of a first molar amount X 1 of an anionic exogenous chemical substance with one or more amine compound(s) of formula (I) in a liquid, preferably aqueous, medium with agitation to make a liquid composition containing one or more amphiphilic salt(s) of the exogenous chemical substance.
  • the neutralizing step further comprises introducing to the liquid composition, with agitation, a second molar amount X of the exogenous chemical substance in the form of one or more salt(s) other than an amphiphilic salt formed by neutralizing the exogenous chemical substance with an amine compound of formula (I).
  • X as a fraction of (X + X ) is about 0.01 to 1.
  • the salt(s) of the second molar amount of the exogenous chemical substance can be made in situ by neutralizing, in the liquid medium with agitation, this second molar amount with one or more base(s) other than an amine compound of formula (I), before, during or after neutralization of the first molar amount; alternatively such salt(s) can be prepared separately by processes known in the art and added to the liquid medium before, during or after neutralization of the first molar amount.
  • the conditioning step comprises continuing the agitation of the liquid composition until supramolecular aggregates comprising amphiphilic salt(s) of the exogenous chemical substance formed by neutralizing the exogenous chemical substance with an amine compound of formula (I) are colloidally dispersed in the liquid medium.
  • neutralizing is to be understood to mean reacting substantially equimolar amounts of acid and base.
  • anionic exogenous chemical substance has a molecular structure with two or more acid sites, as is the case for example with N-phosphonomethylglycine
  • neutralizing is to be understood to mean reacting each mole of acid with about 1 to about 2 moles of base to form a monobasic salt, a dibasic salt, or a mixture thereof. .
  • Contemplated compositions have numerous benefits and advantages.
  • a contemplated composition When applied to foliage of plants according to the process of the invention, a contemplated composition provides enhanced biological effectiveness by comparison with commercial standard formulations of the same exogenous chemical substance.
  • a contemplated composition elicits a greater biological response than a commercial standard formulation.
  • a lower application rate is required of the exogenous chemical substance when applied in the form of a contemplated composition than in the form of a commercial standard formulation.
  • a contemplated composition is biologically effective at a given application rate on a broader spectrum of target species than commercial standard formulations.
  • a contemplated composition provides greater reliability or consistency of biological effectiveness in a range of environmental conditions than commercial standard formulations.
  • a contemplated composition is more rainfast, i.e., its biological effectiveness is less likely to be reduced by incidence of rain or overhead irrigation occurring within a short period, for example up to about 6 hours, after application, than commercial standard formulations.
  • a contemplated composition provides an observable biological response in a shorter period after application than commercial standard formulations.
  • anionic exogenous chemical substances examples include, but are not limited to, chemical pesticides (such as herbicides, algicides, fungicides, bactericides, viricides, insecticides, aphicides, miticides, nematicides and molluscicides), plant growth regulators, fertilizers and nutrients, gametocides, defoliants, desiccants, mixtures thereof and the like.
  • chemical pesticides such as herbicides, algicides, fungicides, bactericides, viricides, insecticides, aphicides, miticides, nematicides and molluscicides
  • plant growth regulators fertilizers and nutrients, gametocides, defoliants, desiccants, mixtures thereof and the like.
  • a preferred group of anionic exogenous chemical substances consists of those that are normally applied post-emergence to foliage of plants, i.e., foliar-applied anionic exogenous chemical substances.
  • An especially preferred group of foliar-applied anionic exogenous chemical substances consists of those that are systemic in plants, that is, translocated to some extent from their point of entry in the foliage to other parts of the plant where they can usefully exert their desired biological effect.
  • herbicides particularly preferred among these are herbicides, plant growth regulators and nematicides, particularly those that have a molecular weight, excluding counterions, of less than about 300.
  • an even more preferred category consists of nematicides such as those disclosed in U.S. Patent No. 5,389,680, the disclosure of which is incorporated herein by reference.
  • Preferred nematicides of this group are 3,4,4-trifluoro-3- butenoic acid or N-(3,4,4-trifluoro-l-oxo-3-butenyl)glycine.
  • the exogenous chemical substance is a herbicide.
  • Suitable herbicides include, without restriction, acifluorfen, asulam, benazolin, bentazon, bilanafos, bromacil, bromoxynil, chloramben, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, diclofop, endothall, fenac, fenoxaprop, flamprop, fluazifop, flumiclorac, fluoroglycofen, fomesafen, fosamine, glufosinate, glyphosate, haloxyfop, imazameth, imazamethabenz, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, picloram, quinclorac, quizalofop, sulfamic acid, 2,3,6-TBA, TCA and triclo
  • Especially preferred herbicides are those whose molecular structure comprises at least one of each of amine, carboxylate, and either phosphonate or phosphinate functional groups.
  • This category includes the herbicides N-phosphonomethylglycine (glyphosate) and DL-homoalanin-4-yl(methyl) phosphinate (glufosinate).
  • Another preferred group of herbicides are those of the imidazolinone class, including imazameth, imazamethabenz, imazapyr, imazaquin and imazethapyr.
  • glyphosate has three acid sites, and can therefore form tribasic salts
  • preferred aqueous compositions have a pH value not greater than about 8, at which pH value the fraction of glyphosate existing as a tribasic salt is negligibly small. Only the two acid sites that are significantly deprotonated at pH 8 are therefore considered herein. One of these is on the phosphonate moiety, and the other is on the carboxylate moiety, of the glyphosate molecule.
  • glyphosate acid is sometimes referred to as
  • GH 2 Monovalent glyphosate anions, such as predominate for example at around pH 4, are referred to as GH " .
  • compositions of the invention the amount of exogenous chemical substance present, in all forms thereof, is sufficient when applied to foliage of a plant to elicit the desired biological activity.
  • Such compositions are sometimes referred to as “spray compositions", “sprayable compositions” or “ready-to-use compositions” and typically contain about 0.02% by weight to about 2% by weight of the exogenous chemical substance, expressed as acid equivalent (a.e.).
  • spray compositions typically contain about 0.02% by weight to about 2% by weight of the exogenous chemical substance, expressed as acid equivalent (a.e.).
  • acid equivalent a.e.
  • such compositions can contain up to about 5% a.e. by weight or even 10% a.e. by weight.
  • liquid concentrate compositions of the invention the amount of exogenous chemical substance present, in all forms thereof, provides, upon dilution in a suitable volume of water and application of the diluted composition to foliage of a plant, a sufficient amount to elicit the desired biological activity.
  • Liquid concentrate compositions contain about 10% a.e. by weight to about 40% a.e. by weight or more of the exogenous chemical substance, in all forms thereof present.
  • concentration, or "loading" is physical stability of the composition under a range of storage conditions. The upper limit of loading depends on the nature and concentration of other ingredients in the composition and can be readily determined by routine experimentation using procedures known in the art.
  • compositions of the invention contain supramolecular aggregates comprising amphiphilic salt(s) formed by neutralization of a first molar amount X of the anionic exogenous chemical compound by one or more amine compound(s) each having the formula (I)
  • R (I) ⁇ 2 wherein R and R are independently linear hydrocarbyl chains each having 6 to about 22 carbon atoms, and R is hydrogen, a C ⁇ _ 5 hydrocarbyl group or a linear hydrocarbyl chain
  • R preferably each have at least 8, more preferably at least 10, carbon atoms.
  • R is preferably hydrogen or a C 2 . 5 hydrocarbyl group, more preferably hydrogen or a C ⁇ alkyl
  • R and R are saturated or unsaturated chains each having independently 12, 14, 16 or 18 carbon atoms and R is hydrogen or a methyl group.
  • R and R chains are alike, and are derived from lauric, myristic, palmitic, stearic, oleic, linolenic, linoleic or other natural fatty acids, with saturated chains such as lauryl, myristyl, palmityl or stearyl groups being preferred.
  • the molecular weight of the amine compound of formula (I) is about 240 to about 700. In a particular embodiment of the invention which has been found to provide especially pronounced enhancement of biological effectiveness, the molecular weight of the amine compound of formula (I) is greater than about 300, for example greater than about 330, and not greater than about 560.
  • amine compounds of formula (I) include dilaurylamine (molecular weight 353), available as NoramTM 2C, N,N-dilauryl-N-methylamine (molecular weight 367), available as NoramTM M2C, and N,N-distearyl-N-methylamine (molecular weight 535), available as NoramTM M2SH, all from CECA S.A. of Paris, France. Normally, by design, only one amine compound of formula (I) is used to prepare an amphiphilic salt of the exogenous chemical substance.
  • the R and R groups of the amine compound are often derived from natural sources such as coconut oil, palm oil, beef tallow, etc.
  • commercial preparations of such amine compounds can contain a range of hydrocarbyl chain lengths, sometimes with varying degrees of unsaturation.
  • amounts of an amine compound of formula (I) are specified herein, it is to be understood that such amounts are inclusive of other amine compounds of formula (I) present in the amine compound preparation used.
  • An amine compound of formula (I) is sometimes represented in its protonated (cationic) form herein as A + .
  • An amphiphilic monobasic salt of glyphosate with cations derived from an amine compound of formula (I) can therefore be represented by formula (III):
  • the amphiphilic salt(s) of the exogenous chemical substance and one or more amine compound(s) of formula (I) are the only salts of the exogenous chemical substance present in the composition.
  • the amount of A present in such embodiments is about 1 mole per mole of exogenous chemical substance in the case of a monobasic salt, and about 2 moles per mole of exogenous chemical substance in the case of a dibasic salt.
  • a mixture of monobasic and dibasic salts can be present, and in such a case the amount of A present can range from about 1 to about 2 moles per mole of exogenous chemical substance.
  • the exogenous chemical substance is glyphosate
  • a mixture of amphiphilic salts of formulas (III) and (IV) can be present.
  • the exogenous chemical substance is glyphosate
  • the monobasic salt predominate in the composition; in other words, that the amount of A + present be not substantially greater than 1 mole per mole of exogenous chemical substance.
  • the amphiphilic salt of formula (III) predominate.
  • the mole ratio of (III) to (IV) be about 80:20 to 100:0. This corresponds to a mole ratio of A + to exogenous chemical substance of about 1 :1 to about 1.2:1.
  • the amount of amphiphilic salt(s) comprising A + cations is correspondingly reduced as a fraction of all salts of the exogenous chemical substance present.
  • the amount of A present, on a molar basis should be not less than about 1% of all cations forming salts with the exogenous chemical substance, i.e., X as a fraction of (X 1 + X 2 ) is about 0.01 to 1.
  • X represents a relatively small fraction of
  • the amine compound(s) from which the A cations are derived have relatively high molecular weight, it is difficult to achieve the desired high loading except where relatively low molecular weight B + cations, for example sodium, ammonium or isopropylammonium cations, predominate.
  • B + cations for example sodium, ammonium or isopropylammonium cations, predominate.
  • X represents a larger fraction of (X 1 + X 2 ), for example about 0.1 to 1, preferably about 0.3 to 1, and more preferably about 0.35 to 1.
  • a significant fraction, for example more than about 10% by weight, preferably more than about 50% by weight, of the amphiphilic salt(s) comprising A + cations are believed to be located in the supramolecular aggregates which are colloidally dispersed in the liquid, preferably aqueous, medium of a concentrate liquid composition of the invention. This can be verified by isolating the supramolecular aggregates from the medium by techniques known in the art such as filtration or centrifugation, and analyzing the two components thus obtained.
  • amphiphilic salt(s) may be partitioned in the aqueous medium; however it is believed that even under these circumstances most or substantially all of the amphiphilic salt(s) remain in the supramolecular aggregates.
  • a second molar amount of the exogenous chemical substance is present as one or more salt(s) other than a salt comprising A cations, such second molar amount can be present predominantly in the supramolecular aggregates, predominantly in the aqueous medium, or more or less equally in both.
  • Such salt(s) can be amphiphilic or non- amphiphilic. Where a salt of the second molar amount is an amphiphilic salt, it is believed that it will be predominantly located in the supramolecular aggregates.
  • the cation(s) of salt(s) of the second molar amount of the exogenous chemical substance are other than those derived from an amine compound of formula (I).
  • Preferred such cations are monovalent cations including (i) alkali metal, for example sodium and potassium, cations, (ii) ammonium cations, (iii) alkylammonium, alkanolammonium and alkanolalkylammonium cations having 1-5 carbon atoms, (iv) alkylsulfonium cations having 1-5 carbon atoms, and (v) cations derived from an amine compound of formula (II):
  • R and R are independently hydrogen, methyl groups or hydrocarbyl chains each having 2 to 5 carbon atoms, and R 6 is a linear hydrocarbyl chain having 6 to about 22 carbon atoms.
  • R and R are preferably independently hydrogen or methyl groups.
  • R 6 preferably has at least 8, more preferably at least 10 carbon atoms.
  • R is derived from lauric, myristic, palmitic, stearic, oleic, linolenic, linoleic and other natural fatty acids, with a saturated C 12 . 18 chain such as a lauryl, myristyl, palmityl or stearyl group being even more preferred.
  • cations useful in salts of the second molar amount of the exogenous chemical substance include sodium, ammonium, dimethylammonium, isopropylammonium, monoethanolammonium, trimethylsulfonium, octylammonium, N-lauryl-N,N-dimethylammonium and N-stearyl-N,N-dimethylammonium cations.
  • the last named of these, in its unprotonated form, is available as NoramTM DMSH from CECA S.A.
  • a monobasic salt of glyphosate, or a mixture of monobasic salts of glyphosate, with such cations can therefore be represented by formula (V):
  • the exogenous chemical substance is glyphosate
  • the monobasic salt predominate in the composition in other words, that the amount of all B + cations present be not substantially greater than 1 mole per mole of exogenous chemical substance.
  • the mole ratio of (V) to (VI) be about 80:20 to 100:0. This corresponds to a mole ratio of B + to exogenous chemical substance of about 1 :1 to about 1.2:1.
  • the amount of B cations present, on a molar basis should be not greater than about 99% of all cations
  • a third molar amount X of the exogenous chemical substance can be present in the form of the acid.
  • X is small by comparison with (X + X ), for example in a mole ratio of X 3 to (X 1 + X ) not greater than about 1 :10.
  • the colloidal dispersions of supramolecular aggregates formed for example when compositions are prepared by a process as described herein, have surprisingly been found to exhibit a high degree of physical stability.
  • the supramolecular aggregates themselves, as well as the composition as a whole, are physically stable, a feature which is of great benefit in the handling, storage and use of compositions of the invention.
  • a particularly unexpected discovery is that the supramolecular aggregates substantially maintain their structural integrity even upon dilution to levels useful for direct application to foliage of plants.
  • This structural integrity is not dependent on the presence of surfactants other than the amphiphilic salt(s) of the exogenous chemical substance (if indeed such amphiphilic salt(s) can be considered "surfactants").
  • surfactants other than the amphiphilic salt(s) of the exogenous chemical substance can optionally be present in compositions of the invention.
  • aqueous concentrate compositions of the invention can be described as stable colloidal suspensions of supramolecular aggregates.
  • stable in this context it is meant that no phase separation or settling of aggregates occurs during storage of a composition without agitation at 20-25°C for 48 hours.
  • a stability test is described more fully in the Examples herein.
  • the more desirable aqueous concentrate compositions of the invention are colloidal suspensions in which no phase separation or settling occurs during storage without agitation at constant or varying temperatures from about 10°C to about 40°C for 48 hours, even more desirably from about 0°C to about 50°C for 7 days, and most desirably about -10°C to about 60°C for 30 days.
  • nanoparticle has no universally accepted definition in the art; however as used herein the term refers to bodies whose longest dimension is of a size up to about 1 ⁇ m (1000 nm), and includes bodies that are not solid particulates.
  • the mean size of the longest dimension of the supramolecular aggregates is about 10 to about 10,000 nm, more preferably about 20 to about 2000 nm, and most preferably about 100 to about 1000 nm.
  • the supramolecular aggregates can be of various shapes, including spherical, cylindrical, needle-like and other shapes. They are often liposome-like in structure.
  • supramolecular aggregates have been identified as being multilamellar, i.e., having concentric layers like scales of an onion.
  • the mean size of the aggregates can be determined, for example, by light-scattering techniques known in the art. Shapes of aggregates can be determined by observation with an electron microscope.
  • the colloidal suspension On dilution in water to a concentration of the exogenous chemical substance of 5 g a.e./l, the colloidal suspension preferably exhibits turbidity corresponding to absorbance of light of wavelength 400 nm of at least 0.5 across a 0.5 cm spectrophotometer cell.
  • turbidity test is described more fully in the Examples herein.
  • compositions of the invention can contain agriculturally acceptable materials other than an exogenous chemical substance or a salt thereof as described herein.
  • more than one exogenous chemical substance can be included.
  • An additional anionic exogenous chemical substance can be included, selected for example from those hereinbefore listed.
  • an exogenous chemical substance that is other than anionic as defined herein can be included.
  • a glyphosate composition of the invention can optionally contain, in addition to glyphosate, an anionic herbicidal compound such as acifluorfen, bilanafos, 2,4-D, dicamba, fluazifop, fluoroglycofen, glufosinate, imazapyr, imazaquin, imazethapyr, MCPA, nonanoic acid or picloram.
  • an anionic herbicidal compound such as acifluorfen, bilanafos, 2,4-D, dicamba, fluazifop, fluoroglycofen, glufosinate, imazapyr, imazaquin, imazethapyr, MCPA, nonanoic acid or picloram.
  • additional anionic compound is present as salt(s) comprising A + , and optionally B + , cations as described herein.
  • a composition of the invention containing salts of an anionic herbicide can optionally contain a herbicidal compound that is other than anionic, such as for example an ester derivative of an anionic herbicide, acetochlor, aclonifen, alachlor, atrazine, bensulfuron, bifenox, butachlor, chlorimuron, chlorsulfuron, clomazone, cyanazine, diflufenican, diquat, dithiopyr, diuron, flazasulfuron, flumetsulam, flumioxazin, fluometuron, flupoxam, halosulfuron, isoproturon, isoxaben, metolachlor, metsulfuron, nicosulfuron, oryzalin, oxyfluorfen, paraquat, pendimethalin, phenmedipham, propachlor, propanil, pyridate, sethoxydim, simazine,
  • Exogenous chemical substances useful in compositions of the invention can be selected from those listed in standard reference works such as 77ze Pesticide Manual, 10th Edition, British Crop Protection Council (1994), and Farm Chemicals Handbook '97, Meister Publishing Company (1997).
  • Various agriculturally acceptable adjuvants or excipient substances can also be included, whether or not their purpose is to contribute directly to the biological effectiveness of an exogenous chemical substance in a treated plant.
  • the exogenous chemical substance is a herbicide
  • liquid nitrogen fertilizer or ammonium sulfate can be included in the composition.
  • compositions of the invention include agents to modify color, odor, viscosity, gelling properties, freezing point, stability or texture.
  • One or more surfactant(s), other than amphiphilic salts of an exogenous chemical substance, can also be included in a contemplated composition.
  • a wide range of surfactants is available to the formulator of exogenous chemical substances and can be selected readily from standard works such as McCutcheon 's Emulsifiers and Detergents, 1997 Edition, MC Publishing Company, or Handbook of Industrial Surfactants, 2nd Edition, Gower ( 1997).
  • surfactants useful herein have a chemical structure that comprises one or more moieties each consisting of a single C 2 _ 4 alkylene oxide unit or a polymerized or copolymerized chain of C 2 ⁇ alkylene oxide units. Such surfactants are referred to as polyoxyalkylene surfactants and include nonionic, anionic, cationic and amphoteric types. Polyoxyalkylene surfactants useful in presently contemplated compositions contain about 2 to about 100 C 2-4 alkylene oxide units.
  • the alkylene oxide units form one or more chain(s) of either ethylene oxide or copolymerized ethylene oxide and propylene oxide, each chain of alkylene oxide units having a terminal hydrogen or a C 1-4 alkyl or C alkanoyl end-cap.
  • Hydrophobic moieties of surfactants useful in compositions of the invention can be essentially hydrocarbon-based, in which case the hydrophobic moieties are typically C 8-24 , preferably C 12 . 18 , alkyl, alkenyl, alkylaryl, alkanoyl or alkenoyl chains. These chains can be linear or branched.
  • the hydrophobic moieties can contain silicon atoms, for example in the form of siloxane groups such as heptamethyltrisiloxane groups, or fluorine atoms, for example as partially fluorinated alkyl or perfluoroalkyl chains.
  • nonionic surfactants especially preferred classes include polyoxyethylene alkyl, alkenyl or alkylaryl ethers, such as polyoxyethylene primary or secondary alcohols, alkylphenols or acetylenic diols; polyoxyethylene alkyl or alkenyl esters, such as ethoxylated fatty acids; sorbitan alkylesters, whether ethoxylated or not; glyceryl alkylesters; sucrose esters; and alkyl polyglycosides.
  • polyoxyethylene alkyl, alkenyl or alkylaryl ethers such as polyoxyethylene primary or secondary alcohols, alkylphenols or acetylenic diols
  • polyoxyethylene alkyl or alkenyl esters such as ethoxylated fatty acids
  • sorbitan alkylesters whether ethoxylated or not
  • glyceryl alkylesters sucrose esters
  • alkyl polyglycosides especially preferred classes include polyoxy
  • nonionic surfactants include polyoxyethylene (9) nonylphenol, NeodolTM 25-7 of Shell (a polyoxyethylene (7) C 12-15 linear primary alcohol), TergitolTM 15-S-9 of Union Carbide ( a polyoxyethylene (9) C 12 . 15 secondary alcohol), TweenTM 20 of ICI (a polyoxyethylene (20) sorbitan monolaurate), SurfynolTM 465 of Air Products ( a polyoxyethylene (10) 2,4,7,9-tetramethyl-5-decyne-4,7-diol) and AgrimulTM PG-2069 of Henkel (a C 9 . u alkyl polyglucoside).
  • anionic surfactants especially preferred classes include fatty acids, sulfates, sulfonates, and phosphate mono- and diesters of alcohols, alkylphenols, polyoxyethylene alcohols and polyoxyethylene alkylphenols, and carboxylates of polyoxyethylene alcohols and polyoxyethylene alkylphenols. These can be used in their acid form but are more typically used as salts, for example sodium, potassium or ammonium salts.
  • cationic surfactants especially preferred classes include polyoxyethylene tertiary alkylamines or alkenylamines, such as ethoxylated fatty amines, quaternary ammonium surfactants and polyoxyethylene alkyletheramines.
  • Representative specific examples of such cationic surfactants include polyoxyethylene (5) cocoamine, polyoxyethylene (15) tallowamine, distearyldimethylammonium chloride, N-dodecylpyridine chloride and polyoxypropylene (8) ethoxytrimethylammonium chloride.
  • Particularly preferred polyoxyethylene alkyletheramines are those disclosed in International Publication No. WO 96/32839.
  • quaternary ammonium surfactants of diverse structures are known in the art to be useful in combination with glyphosate and other exogenous chemical substances and can be used in compositions contemplated herein; such quaternary ammonium surfactants have formula (VII):
  • Z " is a suitable anion such as chloride, bromide, iodide, acetate, salicylate, sulfate or phosphate; k and m are integers such that the positive electrical charges on cations balance the negative electrical charges on anions; and options for R a , R , R c and R include, without limitation:
  • R a is a benzyl or C 8-24 , preferably a C 12 . 18 , alkyl or alkenyl group, and R , R c and R are independently C 1-4 alkyl, preferably methyl, groups;
  • R a and R are independently C 8 . 24 , preferably C 12 . 18 , alkyl or alkenyl groups, and R c and R are independently C alkyl, preferably methyl, groups;
  • R a is a C 8 . 24 , preferably a C 12-18 , alkyl or alkenyl group,
  • R b is a polyoxyalkylene chain having about 2 to about 100 C 2-4 alkylene oxide units, preferably ethylene oxide units, and R c and R d are independently C alkyl, preferably methyl, groups;
  • R a is a C 8 . 2 , preferably a C j2 .
  • R 18 alkyl or alkenyl group
  • R b and R c are polyoxyalkylene chains having in total about 2 to about 100 C 2-4 alkylene oxide units, preferably ethylene oxide units, and R is a C 1-4 alkyl, preferably a methyl, group; or (v) R a is a polyoxyalkylene chain having about 2 to about 100 C 2- alkylene oxide units in which C 3 ⁇ , alkylene oxide units, preferably propylene oxide units, predominate, and R , R c and R are independently C 1-4 alkyl, preferably methyl or ethyl, groups.
  • Particularly preferred quaternary ammonium surfactants of this type are those disclosed in U.S. Patent No. 5,464,807.
  • an amphiphilic quaternary ammonium compound, or mixture of such compounds is present, having formula (VIII):
  • R e is a hydrocarbyl or haloalkyl group having about 6 to about 22 carbon atoms; W and Y are independently O or NH; a and b are independently 0 or 1 but at least one of a and b is 1; X is CO, SO or SO 2 ; n is 2 to 4; R , R 8 and R are independently C 1- alkyl; and k, m and Z " have the same meanings as in formula (VII).
  • R e in one particular embodiment is a hydrocarbyl group having about 12 to about 18 carbon atoms.
  • R e can also be fluorinated. In one specific embodiment, R e is perfluorinated, and preferably has about 6 to about 12 carbon atoms.
  • R e is a saturated perfluoroalkyl group having about 6 to about 12 carbon atoms
  • X is CO or SO 2
  • Y is NH
  • a is 0, b is 1
  • n is 3
  • R , R 8 and R are methyl groups
  • k and m are each 1
  • Z " is a chloride, bromide or iodide anion.
  • Suitable examples include 3 -(((heptadecafluorooctyl)sulfony l)amino)-N,N,N-trimethyl- 1 -propaminium iodide, available for example as FluoradTM FC-135 from 3M Company, and the corresponding chloride. It is believed that FluoradTM FC-754 of 3M Company comprises the corresponding chloride.
  • amphiphilic quaternary ammonium compound(s) of formula (VIII) are present in an adjuvant amount, i.e., an amount sufficient to provide visibly improved biological effectiveness of the exogenous chemical substance by comparison with a composition lacking such compound(s).
  • "Visibly improved” in the present context means that, in a side-by-side comparison, a difference in biological effectiveness in favor of the composition containing the amphiphilic quaternary ammonium compound(s) would be evident to an experienced technician in the art relating to the particular class of exogenous chemical substance being applied, for example a weed scientist in the case where the exogenous chemical substance is a herbicide.
  • one or more amphiphilic quaternary ammonium compound(s) of formula (VIII) are preferably included in a ratio of total weight of such compound(s) to weight of the anionic exogenous chemical substance, expressed as acid equivalent, of about 1 :3 to about 1 : 100.
  • Suitable concentrations of a compound of formula (VIII) are about 0.001% to about 1% by weight in a plant treatment composition, and about 0.01% to about 10% by weight in a liquid concentrate composition of the invention.
  • compositions of the present invention is an oil, such as a triglyceride ester of fatty acids of animal, vegetable or synthetic origin, a paraffin, a polysiloxane, or a fatty acid or an ester or amide thereof.
  • oil such as a triglyceride ester of fatty acids of animal, vegetable or synthetic origin, a paraffin, a polysiloxane, or a fatty acid or an ester or amide thereof.
  • Such an oil, or mixture of oils, is present in an adjuvant amount as defined above.
  • oils examples include triglyceride esters of the coconut oil type, such as the product MiglyolTM 812 of Htils, corn oil, olive oil, C 12-15 alkyl benzoate, eicosapentaenoic and docosahexaenoic acids and alkyl and triglyceride esters thereof and triglyceride ester of caprylic acid. Oils can be fractionated or not. Fractionation permits elimination of certain fatty acid chain lengths so as to modify melting point.
  • one or more oil(s) are included, each having a chemical structure corresponding to formula (IX): R 4 -CO-Y-R 15 (IX) wherein R is a hydrocarbyl group having about 5 to about 21 carbon atoms, R 1 is a hydrocarbyl group having 1 to about 14 carbon atoms, the total number of carbon atoms in R 14 and R 15 is about 11 to about 27, and Y is O or NH.
  • R 14 and R 15 are preferably linear hydrocarbyl chains.
  • R preferably has about 11 to about 21 carbon atoms and is preferably derived from a natural saturated or unsaturated fatty acid.
  • R 15 is preferably an alkyl group with 1 to about 6 carbon atoms.
  • Especially preferred oils of formula (IX) are therefore C 1-6 alkylesters or C 1-6 alkylamides of fatty acids. It is further preferred that R 14 is saturated in about 40% to 100% by weight of all compounds of formula (IX) present in the composition.
  • an oil is included that is a C 1-4 alkylester of a
  • C 12-18 fatty acid more preferably a C alkylester of a C 12 . 18 saturated fatty acid.
  • Examples include methyl oleate, ethyl oleate, isopropyl myristate, isopropyl palmitate and butyl stearate. Butyl stearate is especially preferred.
  • one or more oil(s) of formula (IX) are preferably included in a ratio of total weight of such oil(s) to weight of the cationic exogenous chemical substance, expressed as acid equivalent, of about 1:3 to about 1 :100.
  • Suitable concentrations of an oil of formula (IX) are about 0.001% to about 1% by weight in a plant treatment composition, and about 0.01% to about 10% by weight in a liquid concentrate composition of the invention.
  • Oil(s), if present, can be emulsified in a composition of the invention by means of the amphiphilic salt(s) of the exogenous chemical substance. If desired, additional surfactant(s) can be included as emulsifier(s) for such oil(s). It is believed that the presence of oil, especially an oil of formula (IX), in the composition can further enhance penetration of the exogenous chemical substance into or through plant cuticles, perhaps as a result of the more lipophilic character imparted to the composition.
  • oil especially an oil of formula (IX)
  • Liquid concentrate compositions in accordance with the present invention can be prepared by the following general procedure; however, the invention is not limited to compositions made by this procedure.
  • the first step is a neutralizing step.
  • This step comprises neutralization of a first molar amount X of an anionic exogenous chemical substance with one or more amine compound(s) of formula (I) in a liquid medium, preferably an aqueous medium, with agitation to make a liquid composition containing one or more amphiphilic salt(s) of the exogenous chemical substance.
  • a first molar amount X of glyphosate acid is added to water together with an amine compound of formula (I), in an amount of about 1 to about 2 moles per mole of glyphosate, to make a monobasic salt [GH " ] [A + ], a dibasic salt [G " ] [A ] 2 , or a mixture of such monobasic and dibasic salts, where A + is a cation derived by protonation of the amine compound.
  • the relative molar proportions of monobasic and dibasic salts is a function of the quantity of the amine compound added per mole of glyphosate.
  • the neutralizing step further comprises introducing to the liquid composition, with agitation, a second molar amount X of the exogenous chemical substance in the form of one or more salt(s) other than an amphiphilic salt formed by neutralizing the exogenous chemical substance with an amine compound of formula (I).
  • X as a fraction of (X + X ) is in a range of about 0.01 to 1.
  • a second molar amount X of glyphosate is added in the form of a
  • the salt(s) of the second molar amount of the exogenous chemical substance can be prepared separately in advance, or made in situ by neutralizing, in the liquid medium with agitation, this second molar amount with one or more base(s) other than an amine compound of formula (I). In either case, introduction of such salt(s) can occur before, during or after neutralization of the first molar amount of the exogenous chemical substance.
  • the neutralizing step takes place with agitation, preferably moderate agitation, for example using a magnetic stirrer.
  • the neutralizing step is conducted at a temperature higher than the melting point of the amine compound(s) of formula (I) used.
  • the temperature of the liquid medium during the neutralizing step is about 50°C to about 100°C.
  • the second step is a conditioning step.
  • This step comprises continuing the agitation of the liquid composition until supramolecular aggregates comprising amphiphilic salt(s) of the exogenous chemical substance formed by neutralizing the exogenous chemical substance with an amine compound of formula (I) are colloidally dispersed in the liquid medium.
  • Agitation preferably moderate agitation, can be provided, for example, by the same device used to agitate during the neutralizing step. It is preferred to maintain an elevated temperature, similar to that provided during the neutralizing step, throughout the conditioning step.
  • the conditioning step typically lasts for a period of a few minutes to a few hours and results in spontaneous formation of a stable colloidal suspension of supramolecular aggregates.
  • Optional ingredients other than salt(s) of the exogenous chemical substance can be dissolved or dispersed in the liquid medium prior to, during or after the neutralization step and prior to, during or after the conditioning step.
  • An optimum order of addition can readily be established for any composition by routine experimentation. Application of a contemplated composition to foliage
  • Exogenous chemical substances should be applied to plants at a rate sufficient to give the desired effect. These application rates are usually expressed as amount of exogenous chemical substance per unit area treated, e.g. grams per hectare (g/ha). What constitutes a "desired effect" varies according to the standards and practice of those who investigate, develop, market and use a specific class of exogenous chemicals. For example, in the case of a herbicide, the amount applied per unit area to give 85% control of a plant species as measured by growth reduction or mortality is often used to define a commercially effective rate. Herbicidal effectiveness is one of the biological effects that can be enhanced through this invention.
  • Herbicidal effectiveness refers to any observable measure of control of plant growth, which can include one or more of the actions of (1) killing, (2) inhibiting growth, reproduction or proliferation, and (3) removing, destroying, or otherwise diminishing the occurrence and activity of plants.
  • the selection of application rates that are biologically effective for a specific exogenous chemical substance is within the skill of the ordinary agricultural scientist. Those of skill in the art will likewise recognize that individual plant conditions, weather and growing conditions, as well as the specific exogenous chemical substance and composition thereof selected, will influence the degree of biological effectiveness achieved in practicing this invention. Useful application rates for exogenous chemical substances employed can depend upon all of the above conditions.
  • Glyphosate compositions of the invention can be applied to a plant in a herbicidally effective amount, and can effectively control one or more plant species of one or more of the following genera without restriction: Abutilon, Amaranthus, Artemisia, Asclepias, Avena, Axonopus, Borreria, Brachiaria, Brassica, Bromus, Chenopodium, Cirsium, Commelina, Convolvulus, Cynodon, Cyperus, Digitaria, Echinochloa, Eleusine, Elymus, Equisetum, Erodium, Helianthus, Imperata, Ipomoea, Kochia, Lolium, Malva, Oryza, Ottochloa, Panicum, Paspalum, Phalaris, Phragmites, Polygonum, Portulaca, Pteridium, Pueraria, Rubus, Salsola, Setaria, Sida, Sinapis, Sorghum, Triticum, Typha, Ulex, Xanthium and Ze
  • Particularly important annual broadleaf species for which glyphosate compositions are used are exemplified without limitation by the following: velvetleaf (Abutilon theophrasti), pigweed (Amaranthus spp.), buttonweed (Borreria spp.), oilseed rape, canola, indian mustard, etc. (Brassica spp.), commelina (Commelina spp.), filaree (Erodium spp.), sunflower (Helianthus spp.), morningglory (Ipomoea spp.), kochia (Kochia scoparia), mallow (Malva spp.), wild buckwheat, smartweed, etc.
  • Particularly important annual narrowleaf species for which glyphosate compositions are used are exemplified without limitation by the following: wild oat (Avena fatua), carpetgrass (Axonopus spp.), downy brome (Bromus tectorum), crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crus-galli), goosegrass (Eleusine indica), annual ryegrass (Lolium multiflorum), rice (Oryza sativa), ottochloa (Ottochloa nodosa), bahiagrass (Paspalum notatum), canarygrass (Phalaris spp.), foxtail (Setaria spp.), wheat (Triticum aestivum) and corn (Zea mays).
  • glyphosate compositions are exemplified without limitation by the following: mugwort (Artemisia spp.), milkweed (Asclepias spp.), Canada thistle (Cirsium arvense), field bindweed (Convolvulus arvensis and kudzu (Puer ⁇ ri ⁇ spp.).
  • brachiaria (Brachiaria spp.), bermudagrass (Cynodon dactylon), yellow nutsedge (Cyperus esculentus), purple nutsedge (C. rotundus), quackgrass (Elymus repens), lalang (Imperata cylindrica), perennial ryegrass (Lolium perenne), guineagrass (Panicum maximum), dallisgrass (Paspalum dilatatum), reed (Phragmites spp.), johnsongrass (Sorghum halepense) and cattail (Typha spp.).
  • glyphosate compositions of the present invention can be useful on any of the above species.
  • a plant treatment composition of the invention comprising one or more amphiphilic glyphosate salt(s) of formula (III) or (IV) is applied to foliage of crop plants genetically transformed to tolerate glyphosate, and simultaneously to foliage of weeds or undesired plants growing in close proximity to such crop plants. This process results in control of the weeds or undesired plants while leaving the crop plants substantially unharmed.
  • Crop plants genetically transformed to tolerate glyphosate include those whose seeds are sold by Monsanto or under license from Monsanto bearing the Roundup Ready® trademark. These include varieties of cotton, soybean, canola and corn.
  • compositions of the present invention can be used in precision farming techniques, in which apparatus is employed to vary the amount of exogenous chemical substance applied to different parts of a field, depending on variables such as the particular plant species present, soil composition, and the like.
  • a global positioning system operated with the spraying apparatus can be used to apply the desired amount of the composition to different parts of a field.
  • a plant treatment composition is preferably dilute enough to be readily sprayed using standard agricultural spray equipment.
  • Suitable application rates for the present invention vary depending upon a number of factors, including the type and concentration of active ingredient and the plant species involved.
  • Useful rates for applying an aqueous composition to a field of foliage can range from about 25 to about 1 ,000 liters per hectare (1/ha), preferably about 50 to about 300 1/ha, by spray application.
  • a contemplated process for eliciting a desired biological activity in a plant or in a pathogen, parasite or feeding organism present in or on a plant further comprises, prior to the step of applying a plant treatment composition of the invention to foliage of the plant, a step of diluting, in a suitable volume of water, a liquid concentrate composition as provided herein to form the plant treatment composition.
  • Glyphosate acid in the form of a wet cake having a glyphosate assay of 86.5% a.e. by weight, is introduced in an amount of 0.47 g (equivalent to 2.4 mmol GH ) to a 30 ml flask.
  • N,N-distearyl-N-methylamine NoramTM M2SH of CECA S.A.
  • NoramTM M2SH of CECA S.A. N,N-distearyl-N-methylamine
  • a stable colloidal suspension is obtained which is of low viscosity and has a pH of about 4.
  • the colloidal suspension is characterized by the following procedures.
  • Turbidity of the colloidal suspension after dilution to a glyphosate concentration of 5 g a.e./l, is measured by means of a UV/visible spectrophotometer, model Lamda 2 TM of Perkin Elmer, at a wavelength of 400 nm. Spectrophotometer cells 0.5 cm in width are used. Turbidity is given by absorbance recorded per centimeter path length of light (abs/cm), i.e., in this case absorbance divided by 0.5.
  • Size of the colloidal particles is measured by light-scattering after dilution to a glyphosate concentration of 50 mg a.e./l.
  • Example 2 The procedure of Example 1 is followed, except that the amine compound used is N,N-dilauryl-N-methylamine (NoramTM M2C of CECA S.A.). The weight of amine introduced is 0.83 g. Results for Example 2 are presented in Table 1 below.
  • Example 1 The procedure of Example 1 is followed, except that the amine compound used is dilaurylamine (NoramTM 2C of CECA S.A.). The weight of amine introduced is 0.79 g. Results for Example 3 are presented in Table 1 below.
  • Example 5 The procedure of Example 1 is followed, except that the amine compound is added in an amine to glyphosate a.e. mole ratio of 2:1.
  • the amine compound is N,N-distearyl-N- methylamine (NoramTM M2SH).
  • NoramTM M2SH N,N-distearyl-N- methylamine
  • the weight of amine introduced is 2.48 g.
  • a stable colloidal suspension is obtained having a pH of about 7. Results for Example 4 are presented in Table 1 below.
  • Example 5 Example 5
  • Example 4 The procedure of Example 4 is followed, except that the amine compound is N,N-dilauryl-N-methylamine (NoramTM M2C). The weight of amine introduced is 1.66 g. Results for Example 5 are presented in Table 1 below.
  • Example 4 The procedure of Example 4 is followed, except that the amine compound is dilaurylamine (NoramTM 2C). The weight of amine introduced is 1.58 g. Results for Example 6 are presented in Table 1 below.
  • amine compound of formula (I) abbreviations for amine compounds can be understood by reference to the Examples, mole ratio of amine compound of formula (I) to glyphosate a.e.
  • Glyphosate acid in the form of a wet cake having a glyphosate assay of 86.5% a.e. by weight, is introduced in an amount of 0.47 g (equivalent to 2.4 mmol GH 2 ) to a 30 ml flask.
  • N,N-distearyl-N-methylamine NoramTM M2SH of CECA S.A.
  • NoramTM M2SH of CECA S.A. is then added in the amount of 0.43 g, calculated to be equivalent to 0.84 mmol to provide an N,N-distearyl-N- methylamine to glyphosate a.e. mole ratio of 0.35:1.
  • the flask is stoppered and placed in a water bath at 60°C for 2 hours. Magnetic agitation is applied to ensure thorough mixing. Octylamine is then added in the amount of 0.20 g, calculated to be equivalent to 1.56 mmol to provide an octylamine to glyphosate a.e. mole ratio of 0.65:1 and a total base to glyphosate a.e. mole ratio of 1 :1.
  • the flask is left in the water bath for 30 minutes while agitation is maintained.
  • a stable colloidal suspension is obtained which is of low viscosity and has a pH of about 4.
  • the colloidal suspension is characterized by the procedures of Example 1. Results for Example 7a are presented in Table 2 below.
  • Example 7a The procedure of Example 7a is followed, except that the amount of N,N-distearyl- N-methylamine added is 0.62 g, calculated to be equivalent to 1.2 mmol to provide an N,N-distearyl-N-methylamine to glyphosate a.e. mole ratio of 0.5:1; and the amount of octylamine added is 0.155 g, calculated to be equivalent to 1.2 mmol to provide an octylamine to glyphosate a.e. mole ratio of 0.5:1 and a total base to glyphosate a.e. mole ratio of 1 : 1.
  • Results for Example 7b are presented in Table 2 below.
  • Example 7a The procedure of Example 7a is followed, except that the amount of N,N-distearyl- N-methylamine added is 0.99 g, calculated to be equivalent to 1.92 mmol to provide an N,N-distearyl-N-methylamine to glyphosate a.e. mole ratio of 0.8:1; and the amount of octylamine added is 0.062 g, calculated to be equivalent to 0.48 mmol to provide an octylamine to glyphosate a.e. mole ratio of 0.2:1 and a total base to glyphosate a.e. mole ratio of 1 : 1. Results for Example 7c are presented in Table 2 below.
  • Glyphosate acid in the form of a wet cake having a glyphosate assay of 86.5% a.e. by weight, is introduced in an amount of 0.47 g (equivalent to 2.4 mmol GH 2 ) to a 30 ml flask.
  • N,N-distearyl-N-methylamine NoramTM M2SH of CECA S.A.
  • NoramTM M2SH of CECA S.A. is then added in the amount of 0.62 g, calculated to be equivalent to 1.2 mmol to provide an N,N-distearyl-N- methylamine to glyphosate a.e. mole ratio of 0.5:1.
  • the flask is stoppered and placed in a water bath at 60°C for 2 hours. Magnetic agitation is applied to ensure thorough mixing. A 1M sodium hydroxide solution is then added in the amount of 1.18 ml, to provide 1.18 mmol sodium hydroxide, giving a sodium hydroxide to glyphosate a.e. mole ratio of 0.5:1 and a total base to glyphosate a.e. mole ratio of 1:1. The flask is left " in the water bath for 30 minutes while agitation is maintained.
  • a stable colloidal suspension is obtained which is of low viscosity and has a pH of about 4.
  • the colloidal suspension is characterized by the procedures of Example 1. Results for Example 8 are presented in Table 2 below.
  • amine compound of formula (I) abbreviations for amine compounds can be understood by reference to the Examples. mole ratio of amine compound of formula (I) to glyphosate a.e.
  • Glyphosate acid in the form of a wet cake having a glyphosate assay of 86.5% a.e. by weight, is introduced in an amount of 0.47 g (equivalent to 2.4 mmol GH 2 ) to a 30 ml flask.
  • N,N-distearyl-N-methylamine NoramTM M2SH of CECA S.A.
  • the flask is stoppered and placed in a water bath at 60°C for 2 hours. Magnetic agitation is applied to ensure thorough mixing. N-stearyl-N,N-dimethylamine (NoramTM DMSH of CECA S.A.) is then added in the amount of 0.71 g, to provide 2.4 mmol N-stearyl-N,N-dimethylamine, giving an N-stearyl-N,N-dimethylamine to glyphosate a.e. mole ratio of 1 :1 and a total base to glyphosate a.e. mole ratio of 2:1. The flask is left in the water bath for 30 minutes while agitation is maintained. A stable colloidal suspension is obtained which is of low viscosity and has a pH of about 4. The colloidal suspension is characterized by the procedures of Example 1. Results for Example 9 are presented in Table 3 below.
  • amine compound of formula (I) abbreviations for amine compounds can be understood by reference to the Examples. mole ratio of amine compound of formula (I) to glyphosate a.e.
  • N,N-distearyl-N-methylamine (NoramTM M2SH) in the amount of 1.24 g and an oil comprising triglyceride ester of fatty acids (MiglyolTM 812 of H ⁇ ls) in the amount of 0.62 g are introduced to a 30 ml flask.
  • the flask is stoppered, then placed in a water bath at 60°C, with magnetic agitation, until the amine compound dissolves in the oil.
  • Glyphosate acid in the form of a wet cake having a glyphosate assay of 86.5% a.e. by weight, is then added in an amount of 470 mg (equivalent to 2.4 mmol GH 2 ).
  • 20 ml of deionized water ion-exchanged and passed through a 0.2 ⁇ m filter) is added to provide an aqueous medium for neutralization of the glyphosate with the amine compound.
  • the flask is stoppered again and placed in a water bath at 60°C for 2 hours. Magnetic agitation is applied to ensure thorough mixing.
  • a stable colloidal suspension is obtained which is of low viscosity and has a pH of about 4.
  • the colloidal suspension is characterized by the procedures of Example 1. Results for Example 10 are presented in Table 4 below.
  • Example 10 The procedure of Example 10 is followed, except that the amine compound used is N,N-dilauryl-N-methylamine (NoramTM M2C of CECA S.A.). The weight of amine introduced is 0.788 g. The weight of oil introduced is 0.62 g. Results for Example 11 are presented in Table 4 below. Table 4: Results for Examples 10-11
  • amine compound of formula (I) abbreviations for amine compounds can be understood by reference to the Examples, mole ratio of amine compound to glyphosate a.e.
  • Dioctylamine in the amount of 8.76 g, glyphosate acid (assay 96% by weight) in the amount of 11.99 g, and distilled water in the amount of 219.3 g distilled water are introduced to a 500 ml screw-topped vial.
  • the mass fraction of glyphosate introduced is thus 50 grams per kilogram (g/kg).
  • the mixture of ingredients is magnetically stirred at 50°C for 3 hours to obtain a turbid colloidal suspension containing supramolecular aggregates. The suspension is cooled to room temperature.
  • the pH of the formulation and the size of supramolecular aggregates are measured after dilution of the suspension with distilled water to a glyphosate concentration of 5 g a.e./kg.
  • the 50 g a.e./kg suspension is examined for phase separation after standing without agitation at ambient temperature for 48 hours. Results for Example 12 are presented in Table 5 below.
  • Example 12 The procedure of Example 12 is followed, except that the amine compound is trihexylamine, added in the amount of 19.2 g, glyphosate acid is added in the amount of 12.0 g and distilled water is added in the amount of 209 g. Results for Example 13 are presented in Table 5 below.
  • Example 15 The procedure of Example 12 is followed, except that the amine compound is N,N-dioctyl-N-methylamine, added in the amount of 15.2 g, glyphosate acid is added in the amount of 12.0 g and distilled water is added in the amount of 213 g. Results for Example 14 are presented in Table 5 below.
  • Example 15 The procedure of Example 12 is followed, except that the amine compound is N,N-dioctyl-N-methylamine, added in the amount of 15.2 g, glyphosate acid is added in the amount of 12.0 g and distilled water is added in the amount of 213 g. Results for Example 14 are presented in Table 5 below.
  • Example 15 The procedure of Example 12 is followed, except that the amine compound is N,N-dioctyl-N-methylamine, added in the amount of 15.2 g, glyphosate acid is added in the amount of 12.0 g and distilled water is added in the amount of 213 g. Results for Example
  • Example 12 The procedure of Example 12 is followed, except that the amine compound is didecylamine, added in the amount of 21.4 g, glyphosate acid is added in the amount of 8.8 g and distilled water is added in the amount of 195 g. Glyphosate concentration in the suspension is 39 g a.e./kg. Results for Example 15 are presented in Table 5 below.
  • Example 12 The procedure of Example 12 is followed, except that the amine compound is dilaurylamine (NoramTM 2C), added in the amount of 36.0 g, glyphosate acid is added in the amount of 12.0 g and distilled water is added in the amount of 192 g. Results for Example 16 are presented in Table 5 below.
  • Example 12 The procedure of Example 12 is followed, except that the amine compound is
  • N,N-dilauryl-N-methylamine NoramTM M2C
  • glyphosate acid is added in the amount of 10.0 g
  • distilled water is added in the amount of 175 g.
  • Glyphosate concentration in the suspension is 47 g a.e./kg. Results for Example 17 are presented in Table 5 below.
  • Example 12 The procedure of Example 12 is followed, except that the amine compound is N,N-distearyl-N-methylamine (NoramTM M2SH), added in the amount of 52.0 g, glyphosate acid is added in the amount of 12.0 g and distilled water is added in the amount of 176 g. Results for Example 18 are presented in Table 5 below.
  • NoramTM M2SH N,N-distearyl-N-methylamine
  • amine compound of formula (I) abbreviations for amine compounds can be understood by reference to the Examples, mole ratio of amine compound of formula (I) to glyphosate a.e.
  • N,N-distearyl-N-methylamine (NoramTM M2SH) in the amount of 37.5 g and glyphosate acid (assay 96% by weight) in the amount of 12.0 g are introduced to a 500 ml screw-topped vial. Next, 12.0 g of isopropanol and 12 g of n-butanol are added, followed by 218 g of distilled water. The mass fraction of glyphosate introduced is thus 50 grams per kilogram (g/kg). The mixture of ingredients is magnetically stirred at 50°C for 5 hours to obtain a turbid colloidal suspension containing supramolecular aggregates. The suspension is cooled to room temperature.
  • Example 20 The composition of Example 19 (comprising mono(N,N-distearyl-N- methylammonium) glyphosate formulated with isopropanol and n-butanol as described above) is evaluated for herbicidal effectiveness in a greenhouse test by foliar application to a representative annual broadleaf species, velvetleaf (Abutilon theophrasti, ABUTH) and a representative annual narrowleaf species, Japanese millet, a form of barnyardgrass (Echinochloa crus-galli, ECHCF).
  • ABUTH Abutilon theophrasti
  • ECHCF barnyardgrass
  • Roundup® Ultra herbicide an aqueous solution concentrate formulation of the mono(isopropylammonium) salt of glyphosate, containing 41% by weight of said salt together with a surfactant, this product being sold as an agricultural herbicide by Monsanto Company in the U.S.A.
  • MON 0139 contains glyphosate at a concentration of about 680 grams of acid equivalent per liter (g a.e./l) and Roundup® Ultra herbicide contains 356 g a.e./l. The following procedure is used for the greenhouse test.
  • Seeds of the plant species indicated are planted in 85 mm square pots in a soil mix which has previously been steam sterilized and prefertilized with a 14-14-14 NPK slow release fertilizer at a rate of 3.6 kg/m .
  • the pots are placed in a greenhouse with sub- irrigation. About one week after emergence, seedlings are thinned as needed, including removal of any unhealthy or abnormal plants, to create a uniform series of test pots.
  • the plants are maintained for the duration of the test in the greenhouse where they receive a minimum of 14 hours of light per day. If natural light is insufficient to achieve the daily requirement, artificial light with an intensity of approximately 475 microeinsteins is used to make up the difference. Exposure temperatures are not precisely controlled but average about 27°C during the day and about 18°C during the night. Plants are sub- irrigated throughout the test to ensure adequate soil moisture levels. Relative humidity is maintained at about 50% for the duration of the test.
  • Pots are assigned to different treatments in a fully randomized experimental design with 3 replications.
  • a set of pots is left untreated as a reference against which effects of the treatments can later be evaluated.
  • Two sets of 3 replications are provided for treatments with Roundup® Ultra, to ensure a sound basis is available for comparison of herbicidal effectiveness of compositions of the invention.
  • glyphosate compositions to foliage is made by spraying with a track sprayer fitted with a TeeJetTM 950 IE nozzle calibrated to deliver a spray volume of 93 liters per hectare (1/ha) at a pressure of 166 kilopascals (kPa).
  • Application is made when the plants are 2-3 weeks old. After treatment, pots are returned to the greenhouse until ready for evaluation, in this Example 15 days after treatment (DAT).
  • DAT Days after treatment
  • Treatments are made using dilute aqueous compositions, prepared by dilution with water of preformulated concentrate compositions. All comparisons are made at equal glyphosate acid equivalent rates.
  • the required degree of dilution for a glyphosate concentrate composition to make a plant treatment composition is calculated from the equation
  • A RS/VC
  • A is the volume in milliliters (ml) of the glyphosate composition to be added to the plant treatment composition being prepared
  • R is the desired glyphosate rate in grams of acid equivalent per hectare (g a.e./ha)
  • S is the total volume in milliliters (ml) of plant treatment composition being prepared
  • V is the application rate in liters per hectare (1/ha) of plant treatment composition, conventionally referred to as "spray volume”
  • C is the concentration of glyphosate in grams of acid equivalent per liter (g a.e./l) in the glyphosate composition.
  • Example 19 the colloidal suspension of mono(N,N-distearyl-N-methylammonium) glyphosate (Example 19) provided herbicidal effectiveness greatly superior to that provided by the mono(isopropylammonium) salt (MON 0139) at equal glyphosate a.e. rates.
  • effectiveness of the composition of Example 19 was similar to that obtained with Roundup® Ultra, although the composition of Example 19 contains no added surfactant.
  • Example 20 Substantially the same procedure as used in Example 20 is followed, except where noted below, in a greenhouse test by foliar application to two representative annual broadleaf species, wild radish (Raphanus sativus, RAPSN) and tall momingglory (Ipomoea purpurea, PHBPU), a representative perennial narrowleaf species, quackgrass (Elymus repens, AGRRE). Soil is prefertilized with a 6-7-8 organic NPK fertilizer at a rate of 3.9 kg/m 3 . Plants receive 16 hours of light per day. Temperatures are maintained at approximately 23 °C during the day and approximately 18°C during the night. Relative humidity is maintained at approximately 70%.
  • Example 22 Substantially the same procedure as used in Example 20 is followed in a greenhouse test by foliar application to ABUTH and ECHCF. Evaluation of herbicidal effectiveness is conducted 15 DAT.
  • the compositions included in this test are those of Examples 13 (comprising mono(trihexylammonium) glyphosate), 14 (comprising mono(N,N-dioctyl-N-methylammonium) glyphosate), 16 (comprising mono(dilaurylammonium) glyphosate), 17 (comprising mono(N,N-dilauryl-N- methylammonium) glyphosate and 18 (comprising mono(N,N-distearyl-N- methylammonium) glyphosate).
  • Results of the test of Example 22 are given in Table 9 below.
  • the colloidal suspensions of mono(dilaurylammonium) glyphosate (Example 16) and mono(N,N-distearyl-N-methylammonium) glyphosate (Example 18) provided herbicidal effectiveness on ABUTH that was superior not only to that provided by the mono(isopropylammonium) salt (MON 0139), but also to that provided by Roundup® Ultra, at equal glyphosate a.e. rates.
  • the performance of the composition of Example 16 was especially noteworthy in this regard.
  • none of the colloidal suspension formulations exhibited herbicidal effectiveness on ECHCF matching that of Roundup® Ultra.
  • Herbicidal effectiveness of the colloidal suspension of mono(N,N- dioctyl-N-methylammonium) glyphosate (Example 14) was notably weak on both test species in this test.
  • Example 21 Substantially the same procedure as used in Example 21 is followed in a greenhouse test by foliar application to RAPSN, PHBPU and AGRRE. Only one set of 3 replicates is assigned to Roundup® Ultra in this test. An early evaluation of herbicidal effectiveness is conducted 5 DAT, as an indication of enhanced early symptom development, as well as a later evaluation conducted 22 DAT.
  • compositions included in this test are those of Examples 13 (comprising mono(trihexylammonium) glyphosate), 14 (comprising mono(N,N-dioctyl-N-methylammonium) glyphosate), 16 (comprising mono(dilaurylammonium) glyphosate), 17 (comprising mono(N,N-dilauryl-N- methylammonium) glyphosate and 18 (comprising mono(N,N-distearyl-N- methylammonium) glyphosate).
  • Results of the test of Example 23 are given in Table 10 below.
  • Example 20 Substantially the same "" procedure as used in Example 20 is followed in a greenhouse test by foliar application to ABUTH and ECHCF. Evaluation of herbicidal effectiveness is conducted 21 DAT.
  • the compositions included in this test are those of Examples 16 (comprising mono(dilaurylammonium) glyphosate) and 18 (comprising mono(N,N-distearyl-N-methylammonium) glyphosate). Results of the test of Example 24 are given in Table 11 below.
  • Example 15 (comprising mono(didecylammonium) glyphosate) is included in this test. Results of the test of Example 25 are given in Table 12 below.
  • Example 15 the colloidal suspension of mono(didecylammonium) glyphosate (Example 15) provided superior herbicidal effectiveness to mono(isopropylammonium) glyphosate (MON 0139) on ABUTH, but was weaker in this regard than Roundup® Ultra. On ECHCF the performance of the composition of Example 15 did not even match that of MON 0139.

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EP98925033A 1997-05-30 1998-05-29 Process and compositions promoting biological effectiveness of exogenous chemical substances in plants Withdrawn EP0984681A1 (en)

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FR9706917A FR2763793B1 (fr) 1997-05-30 1997-05-30 Suspension colloidale de glyphosate, l'un de ses procedes de preparation et composition phytotoxique en contenant
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US8300598P 1998-04-24 1998-04-24
US8297498P 1998-04-24 1998-04-24
US83005P 1998-04-24
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