WO2008005831A2

WO2008005831A2 - Compositions of ppo-inhibiting compounds and n-alkylpyrrolidones

Info

Publication number: WO2008005831A2
Application number: PCT/US2007/072467
Authority: WO
Inventors: Hong Liu; Rennan Pan; Frederick W. Hotzman
Original assignee: Fmc Corporation; Hotzman, Linda, Kay
Priority date: 2006-07-05
Filing date: 2007-06-29
Publication date: 2008-01-10
Also published as: WO2008005831A3

Abstract

Herbicidal compositions comprising (a) a N-(C6-C20)alkylpyrrolidone and (b) a PPO-inhibiting compound of formula (I): where R, R1, X, and n are as described herein are disclosed. The compositions provide unexpectedly improved control of undesired weeds without adversely affecting crop tolerance combined with desired rainfast characteristics. Also disclosed are methods of controlling undesired plant growth by the application of such compositions to a locus where undesired plants or weeds are growing or are expected to grow.

Description

COMPOSITIONS OF PPO-INHIBITING COMPOUNDS AND N-ALKYLPYRROLIDONES

This application claims the benefit of U.S. Provisional Application No.

60/818,555 filed July 5, 2006.

FIELD OF THE INVENTION

The present invention relates generally to the field of herbicidal compositions. In particular, the present invention relates to novel herbicidal compositions containing a PPO-inhibiting compound and an N-alkylpyrrolidone.

The compositions improve control of weed species and have favorable rainfast characteristics, while not adversely affecting crop tolerance of these compounds.

BACKGROUND OF THE INVENTION

It is known that the performance of pesticides can be optimized by designing storage stable pesticidal compositions with suitable aqueous surfactant properties, wherein such suitable surfactant properties include i) the ability to provide solubility to an otherwise water-insoluble pesticide, ii) the ability to form and maintain an emulsion or a suspension of highly concentrated pesticide in water, and iii) the ability to provide a mechanism whereby the pesticide remains in contact with the plant for long periods of time (rainfastness), as well as other surfactant properties.

Pesticidal formulations containing N-alkylpyrrolidones and related compounds have been described in the art. US Patent No. 5,160,528, for example, sets forth emulsifiable concentrate compositions of pesticides comprised of N-alkylpyrrolidone hydrophobic solvents, wherein the composition provides, on dilution with water, a highly stable emulsion which avoids precipitation of the pesticide on extended storage. The compositions are said to be highly concentrated, making them advantageous from both economic and handling viewpoints.

US Patent No. 5,294,644 sets forth compositions of pesticides comprised of N-alkyl substituted lactams, which when diluted with water and sprayed onto the foliage of plants, provide uniform and complete application of the pesticide that is resistant to the tendency of the pesticide to wash off the plant (rainfastness).

US Patent No. 5,424,072 sets forth wetting agents comprised of higher alkyl substituted lactams, an anionic surfactant, and water, which when combined with standard compositions of, for example, the herbicides fluazifop-p-butyl and glufosinate, provide for rapid uptake of the herbicide to promote rain fastness, and to enhance the promotion of cuticular infiltration of the herbicide with no or minimal phytotoxicity.

US Patent No. 5,766,615 sets forth compositions comprised of a long-chain alkylpyrrolidone, an anionic surfactant, a film-forming water-insoluble graft polymer from 20% to 80% of N-vinylpyrrolidone and from 20% of an α-olefin of up to 20 carbon atoms, an agriculturally active chemical, wherein the relative amounts of the components being such that the composition forms a rainfast microemulsion or emulsion when added to water. A class of pesticides of particular interest in recent years are herbicides that i) are crop tolerant, or selective to certain agricultural crops, such as wheat, corn, cotton, and soybeans to name a few, ii) provide control, at low rates of application, of weed species that are economically detrimental to these crops, and iii) are environmentally safe to use. A family of selective herbicides within this class of pesticides is one that provides control of weeds through inhibition of protoporphyrinogen oxidase (PPO). PPO is a plant enzyme that is involved in the synthesis of heme and chlorophylls. Inhibition of this enzyme in photosynthetic plant cells leads to accumulation of protoporphyrinogen IX that leaks out into the cytoplasm and forms protoporphyrin IX, a tetrapyrrole pigment, which in the presence of light and oxygen causes extensive disruption of cell membranes thereby killing the plant.

PPO-inhibiting compounds provide benefits not afforded by non-selective herbicides. These benefits include, for example, i) residual weed control of up to 30 days longer when compared to weed control by non-selective herbicides, ii) control of currently difficult to control weed species, such as velvetleaf, waterhemp, pigweed and lambsquarters, and iii) quick action that causes necrosis of weeds within 24 hours and death in 2-5 days. Important PPO-inhibiting compounds include a class of 3-(2,4,6- trisubstituted benzimidazol-7-yl)-l,6-disubstituted-2,4(lH,3H)pyrimidinediones, which are disclosed and claimed in US Patent No. 6,077,812 the disclosure of which is incorporated herein by reference. Even though the PPO-inhibiting compounds are highly active in controlling undesired weeds in agricultural crops, there remains a need to optimize that herbicidal activity to provide the maximum control of weeds, while not adversely affecting crop tolerance of these herbicides, and doing so in the most economical and environmentally safe manner.

SUMMARY OF THE INVENTION

In accordance with the present invention, it has been found that control of certain undesirable weeds and rainfast characteristics are unexpectedly improved, while not adversely affecting crop tolerance, by application of a herbicidal composition comprising a N-(C₆-C₂o)alkylpyrrolidone and a PPO-inhibiting compound of formula (I):

(I) wherein

R is selected from haloalkyl;

R¹ is selected from the group consisting of hydrogen, amino, alkyl, haloalkyl, cyanomethyl, propen-2-yl, propyn-2-yl, alkoxycarbonylmethyl, or methoxymethyl; X is selected from the group consisting of fluorine, chlorine, bromine, alkyl, haloalkyl, cyano, nitro, and amino; and n is 2 or 3. The present invention also includes methods of using the herbicidal compositions wherein the compositions are applied to a locus where said undesired weeds are growing or are expected to grow.

DETAILED DESCRIPTION OF THE INVENTION

In a first embodiment of the present invention, herbicidal compositions exhibiting an unexpected improvement in control of weeds and an unexpected improvement in rainfast characteristics without adversely affecting crop tolerance are those compositions comprising (a) a N-(C6-C₂o)alkylpyrrolidone and (b) a PPO- inhibiting compound of formula (I):

(I) wherein R is selected from haloalkyl;

R¹ is selected from the group consisting of hydrogen, amino, alkyl, haloalkyl, cyanomethyl, propen-2-yl, propyn-2-yl, alkoxycarbonylmethyl, or methoxymethyl;

X is selected from the group consisting of fluorine, chlorine, bromine, alkyl, haloalkyl, cyano, nitro, and amino; and n is 2 or 3.

Preferred PPO-inhibiting compounds for use in the compositions of the present invention are those where R¹ is alkyl; X is fluorine or chlorine; and n is 2. More preferred are those where R is trifluoromethyl; R¹ is methyl; X is fluorine at position 6, and chlorine at position 4, which is the compound 3-(2-trifluoromethyl-4- chloro-6-fluorobenzimidazol-7-yl)- 1 -methyl-6-trifluoromethyl- 2,4(1 H,3H)pyrimidinedione (referred to below as "Compound A"). In the compositions of the present invention, the PPO-inhibiting compound usually comprises from about 1% to about 35% by weight of the composition, preferably from about 5% to about 25% by weight, and more preferably from about 10% to about 20% by weight. In addition, in certain cases the PPO-inhibiting compounds of formula (I), for example, Compound A, may possess asymmetric centers, which can give rise to optical enantiomorphs and diastereomers. The compounds may exist in two or more forms, i.e., polymorphs, which are significantly different in physical and chemical properties. The compounds may also possess acidic or basic moieties, which may allow for the formation of agriculturally acceptable salts or agriculturally acceptable metal complexes. This invention includes the use of such enantiomorphs, polymorphs, salts and metal complexes. Agriculturally acceptable salts and metal complexes include, without limitation, for example, ammonium salts, the salts of hydrochloric acid, sulfonic acid, ethanesulfonic acid, trifluoroacetic acid, methylbenzenesulfonic acid, phosphoric acid, gluconic acid, pamoic acid, and other acid salts, and the alkali metal and alkaline earth metal complexes with, for example, sodium, potassium, lithium, magnesium, calcium, and other metals.

Preferred N-(C6-C₂o)alkylpyrrolidones are the N-(C8-Ci₄)alkylpyrrolidones. Such N-(C8-Ci₄)alkylpyrrolidones include N-octylpyrrolidone, N-(2- ethylhexyl)pyrrolidone, N-decylpyrrolidone, N-dodecylpyrrolidone, and N- tetradecylpyrrolidone, and mixtures thereof, most preferredly, N- dodecylpyrrolidone.

The compositions of the present invention may also include additional adjuvants, such as a penetrant, an emulsifier, a solvent, or an adhesive, or mixtures thereof. It is believed that at least one or more of the various adjuvants set forth below as penetrants, as emulsifiers, solvents, or as adhesives most likely serve multiple functions in the composition. For example, adjuvants in the category of penetrants may also serve as solvents or emulsifiers, while an emulsifier may also serve as an adhesive, or a solvent. In the present invention the penetrant may be any adjuvant that aids in promoting the passing of a PPO-inhibiting compound into the leaves of the weed for which control is sought, thereby providing, for example, greater control of a broader spectrum of weeds or hastening the death of certain targeted weeds. Useful penetrants include, without limitation, vegetable oils such as radia oil, methylated seed oils, mineral oils such as Norpar 12, Norpar 13, Isopar L, and Isopar M, resins, micronutrients such as salts of iron, potassium, or zinc, cationic surfactants such as Rhodameen PN-430, and mixtures thereof. A preferred class of penetrants are methylated seed oils selected from the group consisting of methyl soyate, methyl canolate, methyl coconate, methyl oleate, methyl sunflowerate, methyl caprolate, methyl linoleate, methyl linolenate, methyl palmitoleate, methyl palmitate, methyl myristate, methyl myristoleate, methyl margarate, and other methylated seed oils, and mixtures thereof. In the compositions of the present invention, the total amount of the N-(C_O-

C₂o)alkylpyrrolidone and the penetrant, if a penetrant is used, may be from about 10% to about 90% by weight of the composition, preferably from about 30% to about 85% by weight, and more preferably, from about 45% to about 80% by weight. In the present invention, the emulsifier may be any adjuvant that promotes a stable mixture of two or more immiscible liquids, such as water, solvent, and PPO- inhibiting compound, with a dispersed phase in a continuous phase. Stable mixtures provide, for example, more uniform coverage of the leaves of the weed species with PPO-inhibiting compound when the compositions of the present invention containing one or more emulsifiers are applied. Useful emulsifiers include non- ionic surfactants, anionic surfactants, other emulsifiers, and mixtures thereof.

In the compositions of the present invention, the amount of the emulsifier may be from about 1% to about 30% by weight of the composition, preferably from about 3% to about 20% by weight, and more preferably, from about 5% to about 10% by weight.

In the present invention, the solvent may be any adjuvant that is capable of dissolving one or more other substance to form a uniformly dispersed solution or mixture at the molecular- or ionic-size level. The inclusion of one or more solvents in the compositions of the present invention aids in promoting uniform coverage of weed leaves with PPO-inhibiting compound, or by promoting cuticular uptake of PPO-inhibiting compound by the weed.

Solvents finding utility in the present invention are those with flash points of 100 ⁰F or above, preferably 150 ⁰F or above, and more preferably 200 ⁰F or above. Such solvents include, without limitation, (C6-Ci3)alkylacetates, N-(C₁- C₂o)pyrrolidones, and mixtures thereof.

In the compositions of the present invention, the amount of the solvent may be up to about 50% by weight of the composition, preferably up to about 35% by weight, if a solvent is employed. More preferably, the solvent comprises from about 2% to about 25% by weight of the composition.

In the present invention, the adhesive may be any adjuvant, either inorganic or organic, natural or synthetic that is capable of aiding in bonding a PPO-inhibiting compound to the leaves of weeds or other surfaces. The use of adhesives in the compositions of the present invention lessens the tendency of the herbicide to wash off of the surface of the leaves, i.e., improve rainfastness, thereby promoting prolonged exposure of the weed to the PPO-inhibiting compound.

Useful adhesives include, without limitation, synthetic latexes, pinolenes, pyrrolidone polymers, organosilicone surfactants, alkyl-glycosides, polyethenimines, drift control agents, deposition agents, resins, other adhesives, or mixtures thereof.

In the compositions of the present invention, the amount of the adhesive may be up to about 20% by weight of the composition, preferably up to about 12% by weight, more preferably, up to about 8% by weight, if an adhesive is used.

Generally, in the compositions of the present invention, a preferable weight ratio of PPO-inhibiting compound to N-(C6-C₂o)alkylpyrrolidone to penetrant is in the range of 1 part of PPO-inhibiting compound to from about 0.1 part to about 10 parts of N-(C6-C₂o)alkylpyrrolidone to up to about 10 parts of penetrant (1:0.1-10:0-

10), respectively. A more preferable weight ratio of PPO-inhibiting compound to N-

(C6-C₂o)alkylpyrrolidone to penetrant is in the range of 1 : to from about 0.3 to about 8 : to up to about 8 (1:0.3-8:0-8), respectively; most preferably in the range of 1 : to from about 1 to about 6 : to from about 1 to about 5 (1 : 1-6: 1-5), respectively.

In general no adjustment of the pH of the system need be made during the process of preparing the compositions of the present invention. If it is desired to adjust the pH of the finished composition as, for example, when the composition is to be combined with other herbicides, fertilizers, etc., or the pH adjustment offers improved conditions for cuticular uptake of the PPO-inhibiting compound, conventional and suitable reagents for pH adjustment may be used. Such reagents include, without limitation, hydrochloric acid, acetic acid, phosphoric acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, other reagents, and mixtures thereof.

As used in this specification and unless otherwise indicated the substituent terms alkyl, alkoxy, alkanoate, alkanoic, and haloalkyl, used alone or as part of a larger moiety, includes straight or branched chains of at least one or two carbon atoms, as appropriate to the substituent, and preferably up to 12 carbon atoms, more preferably up to ten carbon atoms, most preferably up to seven carbon atoms. The term "cycloalkyl", used alone or as part of a larger moiety, includes rings of three to twelve carbon atoms, preferably three to six carbon atoms. The term "alkenyl", used alone or as part of a larger moiety, includes straight or branched chains of at least two carbon atoms containing at least one carbon-carbon double bond, and preferably up to 12 carbon atoms, more preferably up to ten carbon atoms, most preferably up to seven carbon atoms. The term "aryl" refers to an aromatic ring structure, including fused rings, having four to ten carbon atoms. The term "heteroaryl" refers to an aromatic ring structure, including fused rings, having at least one nitrogen, sulfur, or oxygen atom. "Halogen" or "halo" refers to fluorine, bromine, iodine, or chlorine. The term "weed" refers to an unwanted plant that is growing in a place or in a manner that is detrimental to a plant of interest. The term "weed control" or "percent control", or "percent injury" refers to significant damage, caused by, for example, an herbicide, to the bulk of the weeds wherein said weeds are either dead or dying, thereby not competing with crops for subsistence. The term "rainfastness" or "rainfast" refers to the ability to provide a mechanism whereby the pesticide remains in contact with the plant over a period of time, specifically in the rain.

The compositions of the present invention may be formulated and/or applied with one or more second compounds. Second compounds include, but are not limited to, other pesticides, plant growth regulators, fertilizers, soil conditioners, or other agricultural chemicals. In applying the compositions of this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the active PPO-inhibiting compound is of course employed; the amount may vary in the range of, e.g. about 0.01 to about 3 kg/ha, preferably about 0.03 to about 1 kg/ha. For field use, where there are losses of herbicide, higher application rates (e.g., four times the rates mentioned above) may be employed. When the compositions of the present invention are used in combination with other herbicides, the herbicides may include, for example, glyphosate, 2,4-D, MCPA, MCPP, isoproturon, imazapyr, imazamethabenz, imazethapyr, imazaquin, acifluorfen, acifluorfen-sodium, bifenox, fomasafen, bromoxynil, chlorimuron, achlorsulfuron, bensulfuron, pyrazosulfuron, thifensulfuron, triasulfuron, fenoxaprop, fluazifop, quizalofop, diclofop, bentazone, butachlor, metolachlor, acetochlor, dimethenamide, dicamba, fluroxypyr, chlomethoxyfen, fluoroglycofen- ethyl, fomesafen, halosafen, lactofen, oxyfluorfen, fluazolate, pyraflufen-ethyl, cinidon-ethyl, flumioxazin, flumiclorac-pentyl, fluthiacet-methyl, thidiazimin, oxadiazon, oxadiargyl, azafenidin, carfentrazone-ethyl, sulfentrazone, pentoxazone, clomazone, benzfendizone-methyl, butafenacil, pyrazogyl, profluazol, flufenpyr, ethoxyfen-ethyl, and other herbicides.

When the compositions of the present invention are used in combination with insecticides, the insecticides may include, for example: organophosphate insecticides, such as chlorpyrifos, diazinon, dimethoate, malathion, parathion- methyl, and terbufos; pyrethroid insecticides, such as fenvalerate, deltamethrin, fenpropathrin, cyfluthrin, flucythrinate, α/p/zα-cypermethrin, έetø-cypermethrin, zetøα-cypermethrin, biphenthrin, resolved cyhalothrin, etofenprox, esfenvalerate, tralomehtrin, tefluthrin, cycloprothrin, betacyfluthrin, and acrinathrin; carbamate insecticides, such as aldecarb, carbaryl, carbofuran, and methomyl; organochlorine insecticides, such as endosulfan, endrin, heptachlor, and lindane; benzoylurea insecticides, such as diflubenuron, triflumuron, teflubenzuron, chlorfluazuron, flucycloxuron, hexaflumuron, flufenoxuron, and lufenuron; and other insecticides, such as amitraz, clofentezine, fenpyroximate, hexythiazox, and imidacloprid. When the compositions of the present invention are used in combination with fungicides, the fungicides may include, for example: benzimidazole fungicides, such as benomyl, carbendazim, thiabendazole, and thiophanate-methyl; 1,2,4- triazole fungicides, such as epoxyconazole, simeconazloe, cyproconazole, flusilazole, flutriafol, propiconazole, tebuconazole, triadimefon, and triadimenol; substituted anilide fungicides, such as metalaxyl, oxadixyl, procymidone, and vinclozolin; organophosphorus fungicides, such as fosetyl, iprobenfos, pyrazophos, edifenphos, and tolclofos-methyl; morpholine fungicides, such as fenpropimorph, tridemorph, and dodemorph; other systemic fungicides, such as fenarimol, imazalil, prochloraz, tricyclazole, and triforine; dithiocarbamate fungicides, such as mancozeb, maneb, propineb, zineb, and ziram; non-systemic fungicides, such as chlorothalonil, dichlofluanid, dithianon, and iprodione, captan, dinocap, dodine, fluazinam, gluazatine, PCNB, pencycuron, quintozene, tricylamide, and validamycin; inorganic fungicides, such as copper and sulphur products, and other fungicides.

When the compositions of the present invention are used in combination with nematicides, the nematicides may include, for example: carbofuran, carbosulfan, turbufos, aldecarb, ethoprop, fenamphos, oxamyl, isazofos, cadusafos, and other nematicides.

When the compositions of the present invention are used in combination with plant growth regulators, the plant growth regulators may include, for example: maleic hydrazide, chlormequat, ethephon, gibberellin, mepiquat, thidiazon, inabenfide, triaphenthenol, paclobutrazol, unaconazol, DCPA, prohexadione, trinexapac-ethyl, and other plant growth regulators.

Soil conditioners are materials which, when added to the soil, promote a variety of benefits for the efficacious growth of plants. Soil conditioners are used to reduce soil compaction, promote and increase effectiveness of drainage, improve soil permeability, promote optimum plant nutrient content in the soil, and promote better pesticide and fertilizer incorporation. When the compositions of the present invention are used in combination with soil conditioners, the soil conditioners may include organic matter, such as humus, which promotes retention of cation plant nutrients in the soil; mixtures of cation nutrients, such as calcium, magnesium, potash, sodium, and hydrogen complexes; or microorganism compositions which promote conditions in the soil favorable to plant growth. Such microorganism compositions include, for example, bacillus, pseudomonas, azotobacter, azospirillum, rhizobium, and soil-borne cyanobacteria.

Fertilizers are plant food supplements, which commonly contain nitrogen, phosphorus, and potassium. When the compositions of the present invention are used in combination with fertilizers, the fertilizers may include nitrogen fertilizers, such as ammonium sulfate, ammonium nitrate, and bone meal; phosphate fertilizers, such as superphosphate, triple superphosphate, ammonium sulfate, and diammonium sulfate; and potassium fertilizers, such as muriate of potash, potassium sulfate, and potassium nitrate, and other fertilizers.

The following examples further illustrate the present invention, but, of course, should not be construed as in any way limiting its scope. The examples are organized to present a protocol for the preparation of a composition of the present invention, set forth a list of compositions, and set forth certain biological data indicating the efficacy of such compositions. Unless otherwise indicated, all parts, percentages, and the like are by weight.

EXAMPLE 1

This example illustrates the preparation of a composition comprised of Compound A, an N-alkylpyrrolidone, a penetrant, an emulsifier, an adhesive, and a solvent.

In a 1000 mL beaker equipped with a mechanical stirrer was placed 163 grams of N-dodecylpyrrolidone (AGSOLEX 12; sold by International Specialty Products, Wayne, NJ 07470), 163 grams of methyl oleate (a penetrant), and 25 grams of a (C7)alkylacetate (a solvent-EXXATE 700; sold by Exxon Mobil Corporation) and stirred at slow speed for about five minutes, or until the mixture was homogeneous. With continued stirring, 84 grams of Compound A (PPO- inhbiting compound) was added portionwise. Upon completion of addition the mixture was again stirred for about five minutes, or until all of Compound A was dissolved. With further continued stirring, 25 grams of a 50% Ci₆-alkylated vinylpyrrolidone copolymer (an adhesive-AGRTMER AL-22: sold by International Specialty Products, Wayne, NJ 07470) was added. The EC composition was stirred for an additional 5-10 minutes to assure complete homogeneity of the mixture.

Using a similar process, the following compositions were prepared. In general, the N-alkylpyrrolidone was combined with the penetrant(s) and solvent(s). Compound A was added, and after Compound A was dissolved, the remaining component(s) were added. Table 1

Compositions Of Compound A Comprised Of An N-alkylpyrrolidone Penetrant-

Solvent

Percent Weight/Weight

Composition Number 1 2 3 4 5 6 7 8 9

Compound A 100 113 118 120 120 120 120 120 120

N-alkylpyrrolidone 100 220 235 230 230 230 230 230 230

Penetrant 1 - 517 549 450 450 450 450 450 450

Penetrant 2 - - - - - - - - -

Solvent 1 730 - - 50 50 50 50 50 50

Solvent 2 - - - - - - - - -

Emulsifier 1 40 - - - - - -- --

Emulsifier 2 30 - - - - - - -

Emulsifier 3 - - - - - - - - -

Emulsifier 4 - - 59 - - - - - -

Emulsifier 5 - - 39 - - - - - -

Emulsifier 6 - - - - - - - - -

Emulsifier 7 - 100 - 100 100 100 100 100 100

Adhesive 1 - 50 - 50 - - - - -

Adhesive 2 - - - - 50 - - - -

Adhesive 3 - - - - - 50 - - -

Adhesive 4 - - - - - - 50 -

Adhesive 5 -- - -- - - - - 50

Adhesive 6 - - - - - - - - 50

Adhesive 7 - - - - - - - - -

Adhesive 8 -- -- -- -- -- -- -- -- --

Total 100 100 100 100 100 100 100 100 100

Table 1 (cont.)

Percent Weight/Weight

Composition Number 10 11 12 13 14 15 16 17 18

Compound A 109 109 109 109 109 100 100 100 100

N-alkylpyrrolidone 218 218 218 218 218 100 100 100 100

Penetrant 1 509 509 509 509 509 - - - -

Penetrant 2 - - - - - - - - -

Solvent 1 - - - - - 640 640 640 640

Solvent 2 -- -- -- -- -- -- -- -- --

Emulsifier 1 - - - - - 40 40 40 40

Emulsifier 2 - - - - - 30 30 30 30

Emulsifier 3 - - - - - - - - -

Emulsifier 4 73¹ 73¹ 73¹ 73¹ 73¹ - - - -

Emulsifier 5 - - - - - - - - -

Emulsifier 6 - - - - - - - - -

Emulsifier 7 - - - - - - - - -

Adhesive 1 - - - - - 100 - - -

Adhesive 2 93 - - - - - 100 - -

Adhesive 3 -- 93 -- -- -- -- -- 100 --

Adhesive 4 - - - - - - - - 100

Adhesive 5 - - 93 - - - - - -

Adhesive 6 -- -- -- 93 -- -- -- -- --

Adhesive 7 - - - - 93 - - - -

Adhesive 8 - - - - - - - - -

Total 100 100 100 100 100 100 100 100 100

Percent Weight/Weight

Composition Number 19 20 21 22 23 24 25 26 27

Compound A 100 100 120 120 120 120 120 120 120

N-alkylpyrrolidone 100 100 120 120 120 120 60 180 240

Penetrant 1 - - 120 240 480 240 120 240 240

Penetrant 2 — — — — — —

Solvent 1 640 640 500 380 140 380 560 320 380

Solvent 2 — — — — — — — — —

Emulsifier 1 40 40 38 38 — — — —

Emulsifier 2 30 30 42 42 - 38 38 38 38

Emulsifier 3 — — — — 42 42 42 42

Emulsifier 4 — — — — — —

Emulsifier 5 - - - - - - - - -

Emulsifier 6 - - - - - -

Emulsifier 7 — — 80 — — — —

Adhesive 1 - - 60 60 60 - - - -

Adhesive 2 — — — — — —

Adhesive 3 - - - - - - - - -

Adhesive 4 — — — 60 60 60 60

Adhesive 5 100 - - - - - - - -

Adhesive 6 - 100 - - - - - - -

Adhesive 7 - - - - - -

Adhesive 8 -- -- -- -- -- -- -- -- --

Total 100 100 100 100 100 100 100 100 100 Table 1 (cont)

Percent Weight/Weight

Composition Number 28 29 30 31 32 33 34 35 36

Compound A 100 100 120 204 167 142 184 184 132

N-alkylpyrrolidone 200 200 240 596 652 690 358 358 256

Penetrant 1 - - 240 - - - - - 256

Penetrant 2 - - - - - - - - -

Solvent 1 560 620 260 100 81 68 358 269 192

Solvent 2 -- - -- -- - - -- - --

Emulsifier 1 42 42 - - - - 53 53 53

Emulsifier 2 38 38 38 -- -- -- 47 47 47

Emulsifier 3 -- - 42 -- - - -- - --

Emulsifier 4 - - - 60 60 60 - - -

Emulsifier 5 - - - 40 40 40 - - -

Emulsifier 6 - - - - - - - - -

Emulsifier 7 - - - - - - - - -

Adhesive 1 60 - 60 - - - - 89 64

Adhesive 2 - - - - - - - - -

Adhesive 3 -- - -- -- - - -- - --

Adhesive 4 - - - - - - - - -

Adhesive 5 - - - - - - - - -

Adhesive 6 -- - -- -- - - -- - --

Adhesive 7 - - - - - - - - -

Adhesive 8 -- -- -- -- -- -- -- -- --

Total 100 100 100 100 100 100 100 100 100

Percent Weight/Weight

Composition Number 37 38 39 40 41 42 43 44 45

Compound A 132 184 184 132 108 122 130 130 123

N-alkylpyrrolidone 256 358 358 256 211 239 575 574 600

Penetrant 1 256 - - 256 423 358 - - -

Penetrant 2 - - - - - - - - -

Solvent 1 256 269 269 192 158 181 137 196 117

Solvent 2 — — — — — — —

Emulsifier 1 53 53 53 53 53 53 - - 53

Emulsifier 2 47 47 47 47 47 47 — — 47

Emulsifier 3 — — — — — — —

Emulsifier 4 — — — — — — 60 60 —

Emulsifier 5 - - - - - - 40 40 -

Emulsifier 6 - - - - - - - - -

Emulsifier 7 — — — — — — —

Adhesive 1 - - - - 58 - 60

Adhesive 2 - - - - - -

Adhesive 3 - - - - - -

Adhesive 4 — 89 — 64 — — — — —

Adhesive 5 - - - - - - - - -

Adhesive 6 - - - - - - - - -

Adhesive 7 - - - - - - - - -

Adhesive 8 -- -- 89 -- -- -- -- -- --

Total 100 100 100 100 100 100 100 100 100 Table 1 (cont.)

Percent Weight/Weight

Composition Number 46 47 48 49 50 51 52 53 54

Compound A 164 123 103 123 164 123 103 107 107

N-alkylpyrrolidone 480 240 200 600 480 240 200 200 200

Penetrant 1 - 240 300 - 240 300 400 500

Penetrant 2 - - -- -- -- -

Solvent 1 176 237 247 177 256 237 247 143 43

Solvent 2 - - - - - - - - -

Emulsifier 1 53 53 53 53 53 - -

Emulsifier 2 47 47 47 47 47 -- -

Emulsifier 3 -- -- -- -- 100 100 100 100

Emulsifier 4 - - - - - - - -

Emulsifier 5 - - - - - - - -

Emulsifier 6 - - - - - -

Emulsifier 7 - - -- -- -- -

Adhesive 1 80 60 50 - 60 50 50 50

Adhesive 2 - - - - - - - -

Adhesive 3 - - - - - - - -

Adhesive 4 - - -- -- -- --

Adhesive 5 - - - - - -

Adhesive 6 - - -- -- -- --

Adhesive 7 - - - - - - - -

Adhesive 8 -- -- -- -- -- -- -- --

Total 100 100 100 100 100 100 100 100 100

Percent Weight/Weight

Composition Number 55 56 57 58 59 60 61 62 63

Compound A 82 82 82 144 123 108 97 108 153

N-alkylpyrrolidone 160 240 240 280 247 210 189 322 298

Penetrant 1 480 320 480 420 480 532 564 420 449

Penetrant 2 - - - - - - - - -

Solvent 1 128 208 48 - - - - - -

Solvent 2 — — — — — — — — —

Emulsifier 1 — — — — — — — — —

Emulsifier 2 — — — — — — — — —

Emulsifier 3 100 100 100 100 100 100 100 100 100

Emulsifier 4 — — — — — — — — —

Emulsifier 5 - - - - - - - - -

Emulsifier 6 - - - - - - - - -

Emulsifier 7 — — — — — — — — —

Adhesive 1 50 50 50 50 50 50 50 50 -

Adhesive 2 - - - - - - - - -

Adhesive 3 - - - - - - - - -

Adhesive 4 — — — — — — — — —

Adhesive 5 - - - - - - - - -

Adhesive 6 - - - - - - - - -

Adhesive 7 - - - - - - - - -

Adhesive 8 -- -- -- -- -- -- -- -- --

Total 100 100 100 100 100 100 100 100 100 Table 1 (cont.)

Percent Weight/Weight

Composition Number 64 65 66 67 68 69 70 71 72

Compound A 133 114 102 119 154 104 155 154 164

N-alkylpyrrolidone 259 221 200 232 300 200 300 300 320

Penetrant 1 518 565 598 464 300 300 300 300 320

Penetrant 2 -- - -- -- - -- -

Solvent 1 - - - 35 96 246 95 96 96

Solvent 2 - - - - - - - - -

Emulsifier 1 — — — — — — —

Emulsifier 2 - - - - - - -

Emulsifier 3 100 100 100 100 100 100 100 100 100

Emulsifier 4 - - - - - - - - -

Emulsifier 5 - - - - - - - - -

Emulsifier 6 - - - - - - -

Emulsifier 7 -- - -- -- - -- -

Adhesive 1 - - 50 50 50 50 50 -

Adhesive 2 - - - - - - - - -

Adhesive 3 - - - - - - - - -

Adhesive 4 -- - -- -- -- -- --

Adhesive 5 - - - - - - -

Adhesive 6 -- - -- -- -- -- --

Adhesive 7 - - - - - - - - -

Adhesive 8 -- -- -- -- -- -- -- -- --

Total 100 100 100 100 100 100 100 100 100

Percent Weight/Weight

Composition Number 73 74 75 76 77 78 79 80 81

Compound A 174 186 155 165 103 110 168 168 188

N-alkylpyrrolidone 333 360 300 320 200 213 326 326 357

Penetrant 1 333 360 450 400 300 320 326 408 357

Penetrant 2 - - - - - - - -

Solvent 1 10 04 15 35 247 230 48 27 20

Solvent 2 — — — — — — — — —

Emulsifier 1 - - - - - - - - -

Emulsifier 2 - - - - - - - - -

Emulsifier 3 100 90 - - 100 - - - -

Emulsifier 4 — — — — — — — — —

Emulsifier 5 - - - - - - - - -

Emulsifier 6 - - 80 80 - - - - -

Emulsifier 7 — — — — — 78 81 71 77

Adhesive 1 50 - - - 50 49 51 -

Adhesive 2 - - - - - - - - -

Adhesive 3 - - - - - - - - -

Adhesive 4 — — — — — — — — —

Adhesive 5 - - - - - - - - -

Adhesive 6 - - - - - - - - -

Adhesive 7 - - - - - - - - -

Adhesive 8 -- -- -- -- -- -- -- -- --

Total 100 100 100 100 100 100 100 100 100 Table 1 (cont.)

Percent Weight/Weight

Composition Number 82 83 84 85 86 87 88

Compound A 10 3 11 0 16 8 16 8 18 9 16 8 18 8

N-alkylpyrrolidone 25 0 21 3 32 6 32 6 35 7 32 6 35 7

Penetrant 1 35 0 32 0 32 6 40 8 35 7 32 6 35 7

Penetrant 2 — — — — — — —

Solvent 1 — — 4 8 2 7 2 0 5 0 2 0

Solvent 2 147 23 0 — — — — —

Emulsifier 1 __ __ __ __ __ __ __

Emulsifier 2 __ __ __ __ __ __ __

Emulsifier 3 __ __ __ __ __ __ __

Emulsifier 4 __ __ __ __ __ __ __

Emulsifier 5 — — — — — — —

Emulsifier 6 — — — — — — —

Emulsifier 7 10 0 7 8 8 1 7 1 7 7 8 0 7 8

Adhesive 1 5 0 4 9 5 1 __ __ 5 0 __

Adhesi Adhesi ve 3 Adhesi ve 4 Adhesi ve 5 Adhesi ve 6 Adhesi ve 7 Adhesi

Total 100 100 100 100 100 100 100

Combination of Adhesives 4 and 5

Compound A 3-(2-trifluoromethyl-4-chloro-6-fluorobenzimidazol-7-yl)-l-methyl-6-tπfluoromethyl- 2,4(1 H,3H)pyrimidinedione

N-alkylpyrrolidone N-dodecylpyrrolidone (AGSOLEX 12 sold by International Specialty Products, Wayne, NJ 07470) Penetrant 1 Methyl Oleate Penetrant 2 Rhodameen PN-430 Solvent 1 Exxate 700 Solvent 2 Exxate 800

Emulsifie r l Geronol FF/6-E

Emulsifie r 2 Geronol FF/4-E

Emulsifie r 3 Agent 1810-49

Emulsifie r 4 Henkel 33425

Emulsifie r 5 Henkel 33426

Emulsifie r 6 Witco B-2005-1

Emulsifie r 7 Agent X-2347-47

Adhesive 1 Agπmer AL- 22

Adhesive 2 Agπmox 3 H

Adhesive 3 Exhalt 800

Adhesive 4 Adsee 775

Adhesive 5 Atplus 452

Adhesive 6 Nu-Film-17

Adhesive 7 C55O,OOO

Adhesive 8 Beetle Resin 65

EXAMPLE 2

This example illustrates a method for improving the control of certain weeds with herbicidal compositions of the present invention comprising Compound A and an N-alkylpyrrolidone, while not adversely affecting crop tolerance

Two aliquots of 0.0711 gram each of a 240 gram/liter suspension concentrate (24SC) composition of Compound A were weighed into two 50 mL beakers. To one of the beakers was added 40 mL of an aqueous stock solution of 0.1% (wt/wt) N- dodecylpyrrolidone (AGSOLEX 12), while 40 mL of an aqueous stock solution of 0.02% (wt/wt) N-dodecylpyrrolidone was added to the other beaker. Each beaker contained solutions of Compound A equivalent to rates of application of 80 g/ha, in addition to N-dodecylpyrrolidone. Aliquots of 20 mL of solution were withdrawn from each beaker, and in turn placed in two additional 50 mL beakers. Each 20 mL aliquot was then further diluted with 20 mL each of distilled water to provide solutions of Compound A equivalent to a rates of application of 40 g/ha. In a like manner, each solution was serially diluted to provide additional solutions of Compound A equivalent to rates of application of 20 g/ha and 10 g/ha. Corresponding solutions were prepared that included Compound A only. Fourteen to sixteen day old crop species of field corn and wheat; and weed species of velvetleaf, common ragweed, jimsonweed, wild mustard, and common cocklebur, growing in fiber flats, were mechanically sprayed with each rate of application of each test solution prepared above in an amount sufficient to cover the canopy of the test plants. There were four replicates sprayed for each rate of application. Upon completion of spraying the treated plants were allowed to dry for about 15 minutes, then they were maintained in a greenhouse for a period of 7 to 14 days. The crop species were evaluated for percent injury at 7 and 14 days after treatment, while the weed species were evaluated for percent injury at 14 days after treatment. Table 2

Herbicidal Efficacy and Crop Tolerance of Compound A Combined With An N-Alkylpyrrolidone

Percent Injury(PI)^a

Crops Weeds

Adjuvant 1 1 2 2 3 4 5 6 7

Adjuvant %Wt/Wt 7dat^b 14dat 7dat 14dat

24SC + 0.1 7 7 5 6 69 76 93 75 73

AGSOLEX^® 12^C

24SC + 0.02 4 3 3 3 57 70 81 72 55

AGSOLEX 12

24SC^d Alone -- 2 3 0 1 49 60 68 61 52 Crop Injury Increased By Percent Increase Percentage Points⁶ of Weed lnjury^f

Adjuvant 1 1 2 2 3 4 5 6 7

Adjuvant %Wt/Wt 7dat^b 14dat 7dat 14dat

24SC + 0.1 5 4 5 5 41 27 37 23 40

AGSOLEX 12

24SC + 0.02 2 0 3 2 16 17 19 18 6

AGSOLEX 12

24SC Alone -- 0 0 0 0 0 0 0 0 0

Crop species: 1-Field Corn (Zea mays); 2-Wheat {Triticum aestivum)

Weed species: 3 - Velvetleaf (Abutilon theophrasti); 4 - Common Ragweed {Ambrosia artemisiifolia); 5 - Jimsonweed {Datura stramonium); 6 - Wild Mustard [Brassica kaber

(pinnatifida)]; 7 - Common Cocklebur {Xanthium pensylvanicum) a - Percent Injury is an average derived from the percent control for four rates of application (10, 20,

40, and 80 g/ha ) of Compound A. b - dat: Days After Treatment. c- AGSOLEX 12 is N-dodecylpyrrolidone sold by International Specialty Products, Wayne, NJ

07470. d - Standard 24SC composition of Compound A is comprised of: Compound A (23.03%-wt/wt),

Antimicrobial Agent (0.05%), Antifoam Agent (0.10%), Emulsifier-Surfactant (2.60%), Surfactant

(0.40%), Suspension Aid (0.45%), Thickener (0.35%), Antifreeze (6.00%), and Water-Dispersant

(67.02%). e - Crop Injury Increased By Percentage Points is the difference between PI caused by the composition of 24SC + AGSOLEX 12 and the PI caused by the composition of 24SC alone. f - Percent Increase of Weed Injury = [PI(24SC + AGSOLEX 12) - PI(24SC Alone)] ÷ PI(24SC

Alone) x 100

Generally, as set forth in Table 2 above, the addition of N- dodecylpyrrolidone to a composition of Compound A causes a substantial increase to weed injury with only a slight increase in crop injury.

EXAMPLE 3

Rainfastness Tests of Compositions of the Present Invention Catchweed bedstraw planted in 10-cm square plastic pots was grown for 3 weeks in a growth chamber set with a 20/15 ⁰C; 14/10 hours day/night cycle.

Two N-alkylpyrrolidones (N-octylpyrrolidone and N-dodecylpyrrolidone) were tank-mixed with a 240 gram/liter suspension conconcentrate (24SC) of a PPO- inhibiting compound (Compound A) to produce spray solutions. The N- alkylpyrrolidones were added to the tank mix in order to be at a 20 g/ha concentration. The resultant spray solutions, containing Compound A as the active ingredient, were applied to the catchweed bedstraw plants at 40 g ai/ha with 200 L/ha of spray at 271 kPa. Catchweed bedstraw plants were randomized as a split plot design with 3 replications.

Rainfall was simulated using an overhead irrigation system set to delivery 10 mm of water. The simulated rain treatment was undergone 2 hours after the spray solution was applied to the catchweed bedstraw.

To determine the amount of PPO-inhibiting compound (active ingredient) residue, one plant from each pot was cut and placed in a pre-weighed vial. The vial was weighed again and the net was the weight of the plant. 10 ml of methanol was added and the sample was sonicated for 20 minutes to extract the PPO-inhibiting compound. The extract was analyzed using a Gas Chromatograph method. The amount of PPO-inhibiting compound retained on the plant was calculated and normalized by the weight of the plant.

Compositions with no N-alkylpyrrolidone were used as the control. Results are in tables 3 and 4 below (a higher relative Chemical Residue is better).

Table 3 Rainfastness Test 1

Treatment Chemical Residue (Relative Units)

A 12

A+B 34

A+C 15 Table 4

Rainfastness Test 2

Treatment Chemical

Residue

(Relative

Units)

A 23

A+B 32

A is Compound A B is N-octylpyrrolidone

C is N-dodecylpyrrolidone

It will be appreciated by those of ordinary skill in the art that variations of the invention may be used and that it is intended that the invention may be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications encompassed within the spirit and scope of the invention as defined by the following claims.

Claims

What is claimed is:

1. A herbicidal composition comprising (a) a N-(C₆-C₂o)alkylpyrrolidone and (b) a PPO-inhibiting compound of formula (I):

(I) wherein

R is selected from haloalkyl;

R¹ is selected from the group consisting of hydrogen, amino, alkyl, haloalkyl, cyanomethyl, propen-2-yl, propyn-2-yl, alkoxycarbonylmethyl, or methoxymethyl; X is selected from the group consisting of fluorine, chlorine, bromine, alkyl, haloalkyl, cyano, nitro, and amino; and, n is 2 or 3.

2. The composition of claim 1, wherein R¹ is alkyl; X is fluorine or chlorine; and n is 2.

3. The composition of claim 2, wherein R is trifluoromethyl; R¹ is methyl; X is fluorine at position 6, and chlorine at position 4.

4. The composition of claim 1, wherein said N-(C6-C₂o)alkylpyrrolidone is a N- (C8-Ci4)alkylpyrrolidone.

5. The composition of claim 4, wherein said N-(C8-Ci₄)alkylpyrrolidone is selected from the group consisting of N-octylpyrrolidone, N-(2- ethylhexyl)pyrrolidone, N-decylpyrrolidone, N-dodecylpyrrolidone, or N- tetradecylpyrrolidone, or mixtures thereof.

6. The composition of claim 5, wherein said N-(C8-Ci₄)alkylpyrrolidone is N- dodecylpyrrolidone.

7. The composition of claim 1, further comprising a penetrant, an emulsifier, a solvent, an adhesive, or mixtures thereof.

8. The composition of claim 7, wherein said penetrant is selected from the group consisting of a vegetable oil, a methylated seed oil, a mineral oil, a resin, a micronutrient, a cationic surfactant, and mixtures thereof.

9. The composition of claim 8, wherein said methylated seed oil is selected from the group consisting of methyl soyate, methyl canolate, methyl coconate, methyl oleate, methyl sunflowerate, methyl caprolate, methyl linoleate, methyl linolenate, methyl palmitoleate, methyl palmitate, methyl, myristate, methyl myristoleate, methyl margarate, and mixtures thereof.

10. The composition of claim 7, wherein said emulsifier is a non-ionic surfactant, an anionic surfactant, or mixtures thereof.

11. The composition of claim 7, wherein said solvent is a (C₁- C₂o)alkylpyrrolidone, a (C6-Ci3)alkylacetate, or mixtures thereof.

12. The composition of claim 7, wherein said adhesive is selected from the group consisting of a synthetic latex, a pinolene, a pyrrolidone polymer, an organosilicone surfactant, an alkyl-glycoside, a polyethenimine, a drift control agent, a deposition agent, a resin, or mixtures thereof.

13. The composition of claim 7, wherein said PPO-inhibiting compound comprises from about 1% to about 35% by weight of the composition.

14. The composition of claim 13, wherein said PPO-inhibiting compound comprises from about 5% to about 25% by weight of the composition.

15. The composition of claim 14, wherein said PPO-inhibiting compound comprises from about 10% to about 20% by weight of the composition.

16. The composition of claim 7, wherein the total amount of said N-fTV C₂o)alkylpyrrolidone and said penetrant comprise from about 10% to about 90% by weight of the composition.

17. The composition of claim 16, wherein the total amount of said N-(Ce- C2o)alkylpyrrolidone and said penetrant comprise from about 30% to about 85% by weight of the composition.

18. The composition of claim 17, wherein the total amount of said N-(C_O- C₂o)alkylpyrrolidone and said penetrant comprise from about 45% to about 80% by weight of the composition.

19. The composition of claim 7, wherein said emulsifier comprises from about 1% to about 30% by weight of the composition.

20. The composition of claim 19, wherein said emulsifier comprises from about 3% to about 20% by weight of the composition.

21. The composition of claim 20, wherein said emulsifier comprises from about 5% to about 10% by weight of the composition.

22. The composition of claim 7, wherein said solvent comprises up to about 50% by weight of the composition.

23. The composition of claim 22, wherein said solvent comprises up to about 35% by weight of the composition.

24. The composition of claim 23, wherein said solvent comprises from about 2% to about 25% by weight of the composition.

25. The composition of claim 7, wherein said adhesive comprises up to about 20% by weight of the composition.

26. The composition of claim 25, wherein said adhesive comprises up to about 12% by weight of the composition.

27. The composition of claim 26, wherein said adhesive comprises up to about 8% by weight of the composition.

28. The composition of claim 7, wherein a weight ratio of said PPO-inhibiting compound to said N-(C6-C₂o)alkylpyrrolidone to said penetrant is in the range of 1 : to from about 0.1 to about 10 : to up to about 10, respectively (1:0.1-10:0-10).

29. The composition of claim 28, wherein said weight ratio is in the range of 1 : to from about 0.3 to about 8 : to up to about 8, respectively (1:0.3-8:0-8).

30. The composition of claim 29, wherein said weight ratio is in the range of 1 : to from about 1 to about 6 : to from about 1 to about 5, respectively (1 : 1-6: 1-5).

31. A method of controlling undesired plant growth comprising applying a herbicidally effective amount of a composition of claim 1 to a locus where said undesired plants are growing or are expected to grow.

32. A method of controlling undesired plant growth comprising applying a herbicidally effective amount of a composition of claim 7 to a locus where said undesired plants are growing or are expected to grow.