MXPA00002524A - Synergistic herbicidal methods and compositions - Google Patents

Abstract

The present invention provides a method for the synergistic control of undesirable plants such as Ipomoea, Cyperus, Sida and Euphorbia which comprises applying to the plants or their locus a synergistically effective amount of a combination of glyphosate and an imidazolinone compound. Further provided are synergistic herbicidal compositions comprising glyphosate and an imidazolinone compound, and specifically concentrated aqueous herbicidal compositions of imidazolinyl acid salts and glyphosate salts.

Description

METHODS AND COMPOSITIONS SYNERGIC HERBICIDES Field of Invention The invention relates to a method for the synergistic control of undesirable plants, which comprises applying to the plants or to the site an inefficiently effective amount of a combination of glyphosate and a compound of imidazolinone. Also provided are synergistic herbicidal compositions comprising glyphosate and an imidazolinone compound, and specifically concentrated aqueous herbicidal compositions of imdazolinyl acid salts and glyphosate salts.

Background of the Invention Certain herbs such as Ipom or ea, 20 Cypeurs, S i da and Euph orbi a are particularly difficult to control. Their presence throughout the year can reduce crop yields and cause significant economic losses in production in row crops. One of the 25 most common practices to control these herbs Ref: 32954 S bothers is to apply a herbicide after the emergency, however, a simple selective herbicide that can give economic control of these herbs is not currently available. 5 Glyphosate [(N-fos fonome til) glycine] is a highly effective herbicide with a broad spectrum of activity. However, certain species of agronomically important herbs require relatively high glyphosate application rates for effective control. The high glyphosate ratios may begin to have an undesirable increased selection pressure. Tolerance to glyphosate, particularly of the Ipomo ea, is a recognized problem in the field. Therefore, new methods and compositions for controlling herbs with effectively lower glyphosate application rates are highly desirable. while providing a broad spectrum of herb control.

Aqueous compositions containing imidazolinyl acid salts are described in U.S. 4,816,060 and the aqueous compositions that ^ B¡ & ^ ~ *** ¡****. contain glyphosate salts are described in the E.P. 220.902-A2. However, aqueous, concentrated compositions comprising an imidazolinyl acid salt and a glyphosate salt have not been described. The main reason that aqueous compositions containing both of those compounds that have not been described, is that the imidazolinyl acid salts and the glyphosate salts are not, in general, mutually compatible. The aqueous glyphosate salt compositions generally have a pH value of about 4. However, the imidazolinyl acid salts are not completely stable in an environment having a pH value of about 4. Conversely, the salts of glyphosate are not completely stable at the pH values required to provide stable aqueous compositions of imidazolinyl acid salts.

To overcome the problems of incompatibility associated with aqueous compositions containing imidazolinyl acid salts and glyphosate salts, concentrated emulsifiable emulsion suspension compositions containing irnidazolinyl acids and glyphosate have been described (see, for example, US 5,268,352) . However, the concentrated emulsifiable suspension compositions are not completely satisfactory since they require the use of heavy aromatic solvents.

What is necessary in the art is an aqueous composition for overcoming incompatibility problems associated with imidazolinyl acid salts and glyphosate salts without requiring the use of heavy aromatic solvents.

Brief Description of the Invention Surprisingly, it has now been found that the combination of glyphosate with an imidazolinone compound7 provides synergistic herb control. Advantageously, the synergistic combination of the invention allows low application rates of glyphosate with the concomitant increase in spectrum in the control of the herb. On the other hand, the synergistic herbicidal methods and compositions of the invention allow for resistant and effective targeting programs and provide improved control of pestiferous herbs such as Ipomoea in glyphosate-resistant production crops.

The present invention provides a method for the synergistic control of undesirable plants such as Ipom oea, Cyperu s, Si da or Euph orbi which comprises applying to the locus of said plants or to the foliage or stem of said plants an ineffectively effective amount of a combination of glyphosate and at least one imidazolinone compound selected from the group consisting of imazetapyr, the R-isomer thereof or a salt thereof; imazaquin, the R-isomer thereof or a salt thereof; imazapic, the R-isomer thereof or a salt thereof; imazamox, the R-isomer thereof or a salt thereof; imazapyr, the R-isomer thereof or a salt thereof; and mixtures thereof.

The present invention also relates to an aqueous, concentrated herbicidal composition comprising about 0.1% w / v to about 7% w / v of a salt of imidazolinyl acid, about 15% w / v to about 45% p / v of a glyphosate salt, about 0.5% w / v to about 6% w / v of dimethyl sulfoxide, - ^^^^^^^ - about 0.5% w / v up to about 15% w / v of a wetting agent, more than about 10% w / v of an antifreeze agent, more than about 1 % p / v of an antifoam agent, more than about 3% w / v of a base, and water, with the proviso that the composition has an initial pH from about 6.0 to about 7.0.

The present invention also relates to a process for the preparation of the concentrated, aqueous herbicidal compositions of this invention.

Detailed description of the invention.

Glyphosate [(N-fos fonomethyl) glycine] is a highly effective broad-spectrum herbicide. However, certain pesky herbs such as Ipom oea, S i da, Cype urs and Euph orbi a may require very high glyphosate application rates for effective control. High glyphosate application rates can reduce the safety margin of the crop, increasing the tolerance development potential of the herb < ~ jaM * d? -l_- ^ »i ^ a-? J and resulting in the loss of an economical grass control.

Surprisingly, it has been found that the application of a combination of glyphosate plus at least one imidazolinone compound selected from imazethapyr, the R-isomer thereof or a salt thereof; imazaquin, the R-isomer thereof or a salt thereof; imazapic, the R-isomer thereof or a salt thereof; imazamox, the R-isomer thereof or a salt thereof; imazapyr, the R isomer thereof or a salt thereof provide synergistic control of annoying weeds, particularly of Ipomoea, Si da, Cypeurs and Euph orb, especially Ipomo ea. Therefore, the application of the combination of the invention gives a mutually reinforcing action in such a way that the application rate of the individual herbicidal components can be reduced and still the same herbicidal effect is executed or, alternatively, the application of the combination of the herbicidal components demonstrates a greater herbicidal effect than expected from the effect of the application of "herbicidal components H SHM individual when applied simply (synergistic effect).

As used in the specification and claims, the term glyphosate designates the compound N- (fos fonomethyl) -glycine or the agriculturally acceptable salts thereof. Similarly, the terms used for the imidazolinone imazatapyr, imazaquin, imazapic, imazamox and imazapyr compounds as they appear in the specification and claims designates the compound, the R isomer thereof, an agriculturally acceptable salt thereof or mixtures thereof except that in the context, something else is dictated. The imidazolinone compounds and their corresponding chemical names are listed below.

Imazetapyr designates 5-ethyl-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid, the R-isomer thereof, a salt thereof, or mixtures thereof .

Imazaquin designates 2 - (- isopropyl-4-5-oxo-2-imide zol in-2-i 1) quinol inoca rboxi 1 ico acid, the R isomer thereof, a salt thereof, or mixtures thereof.

Imazapic designates 2- (4-isopropyl-5-methyl-5-oxo-2-imidazolin-2-yl) -5-methylnicotinic acid, the R-isomer thereof, a salt thereof, or mixtures thereof.

Imazamox designates 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5- (me t oxime t il) nicotinic acid, the R isomer thereof, a salt of the same, or mixtures thereof.

Imazapir denotes the acid 2 - (4 -i-sopropyl-4-methyl-1-5-oxo-2-imidazolin-2-yl) nor cotico, the R-isomer thereof, a salt thereof, or mixtures thereof .

In the context of the present invention, the term salt acceptable in agriculture includes alkali metal, ammonium, alkyl sulphonium salt or alkyl phosphonium or the quaternary salt of an amine having a molecular weight of less than 300. In particular, the term includes isopropylammonium, ammonium, sodium and trimesium, especially isopropylammonium and ammonium.

As used in the specification and claims, the term isomer R designates the optical isomer of an imidazolinone compound having the R configuration assigned to the asymmetric carbon in the imidazolinone ring which is substituted by a methyl and an isopropyl group, For example, the R isomer of the imidazolinone imazapyr compound is shown below.

In general, commercial glyphosate formulations are aqueous solutions of an agriculturally acceptable salt such as glyphosate-sopropi ammonium, sodium glycoside, glyphosate trimesium and the like. Similarly, imidazolinone herbicides and their salts acceptable in agriculture are commercially available as ^ ¡¡HHj gHn ^ aqueous solutions. Additionally, imidazolinone herbicides are commercially available as dispersible granules, soluble granules and the like. In current practice, the combination of the invention can be applied simultaneously (as a tank mix or a pre-mix), separately or sequentially.

Thus, in accordance with the method 10 of the invention, a synergistically effective amount of a combination of glyphosate and an imidazolinone compound selected from the group consisting of imazetapyr, imazaquin, imazapic, imazamox and imazapir is applied in place, foliage 15 or stems of the undesirable plants, particularly the selected plants of the genus Ipomoea, Sida and Euphorbia, preferably Ipomoea lacunbosa, Cyperus rotundus, Sida spinosa and Euphorbia macula ta, more preferably Ipomoea 20 la cumosa.

Preferred combinations for the method of the invention are those combinations wherein the weight / weight (w / w) ratio of glyphosate is: of imidazolinone is around 3: 1 up 65: 1. More preferably, the combinations of the invention are combinations of glyphosate and imazatapyr wherein the ratio p / p of glyphosate to imazatapyr is from about 8: 1 to 12: 1 or combinations of glyphosate and imazaquin wherein the ratio p / p. p of gli pit to: imazaquin is around 3: 1 to 10: 1 or combinations of glyphosate and imazapic where the ratio p / p of gli pit to: imazapic is around 15: 1 to 65: 1 or combinations of glyphosate and imazamox in which the ratio w / w of glyphosa to: imazamox is around 20: 1 to 65: 1.

The synergistically effective amount of the combination of glyphosate and an imidazolinone compound selected from imazethapyr, imazaquin, imazapic, imazamox and imazapyr may vary in accordance with prevailing conditions such as the particular imidazolinone compound present, grass pressure, time of application, climatic conditions, soil conditions, mode of application, topographic character, objective crop species and the like. In general, a synergistic effect can be realized at application rates from about 200 g / ha to 800 g / ha of glyphosate in combination with about 8.0 g / ha - 150 g / ha of an imidazolinone compound, preferably around 480 g / ha - 720 g / ha of glyphosate in combination with around 60 g / ha - 80 g / ha of imazetapir.

In current practice, a tank mixture of a commercially suitable presentation or association of glyphosate and an imidazolinone compound selected from imazethapyr, imazaquin, imazapic, imazamox and imazapyr can be applied to the foliage of the culture, or the glyphosate and said imidazolinone compound can applied separately or sequentially, or the combination compositions of the invention may be applied in a simple combined form as described herein.

The sterically effective amount of a combination of glyphosate and an imidazole compound suitable for use in the composition of the invention is sufficient to provide about 200 g / ha - 1200 g / ha of glyphosate and about 8.0 g / ha. ha - 150 g / ha of an imidazolinone compound, preferably about 400 g / ha - 800 g / ha of glyphosate and about 55 g / ha - 100 g / ha of imazetapir, more preferably about 480 g / ha - 720 g / ha of glyphosate and around 60 g / ha up to 80 g / ha of imaze t api r.

The synergistic herbicidal compositions of the invention provide effective resistance targeting programs, including in production crops, for example glyphosate-resistant soybean, safflower, beet, corn, wheat, rice and similar production crops, preferably soybean production crops. resistant to glyphosate.

In a particular embodiment of the invention, the storage stable herbicidal compositions of this invention comprise about 0.1 w / v to about 7% w / v of an imidazolinyl acid salt, about 15% w / v to about 45 w / v. % w / v of a glyphosate salt, about 0.5% w / v to about 6% w / v dimethylsulfoxide, about 0.5% w / v up to about 15% w / v of an agent Ülfflifr -i -mua ** ^ * - • J humectant, more than about 10% p / v of an antifreeze agent, more than about 1% p / v of an antifoaming agent, more than about 3% p / v v of a base, and water, with the proviso that the composition has an initial pH from about 6.0 to about 7.0.

In a preferred embodiment of the present invention, the aqueous herbicidal compositions 0 comprises about 0.5% w / v to about 5% w / v of an imidazolinyl acid salt, about 20% w / v to about 35% p / v of a glyphosate salt, about 0.5% w / v to about 4% w / v of dimethyl sulfoxide, about 1% w / v to about 15% w / v of a wetting agent, about 1% p / v up to about 5% w / v of an anti- freezing agent, more than about 0.5% w / v of an antifoaming agent, more than about 2.5% of a base, and water, with the proviso that the composition has an initial pH from about 6.0 to about 6.8.

Advantageously, it has been found that the compositions of the present invention ^^^ gygi provide physically and chemically stable concentrates, aqueous herbicidal compositions of imidazolinyl acid salts and glyphosate salts. The stability of the compositions of this invention is realized by including dimethyl sulfoxide in the compositions and limiting the initial pH of the compositions to a pH value from about 6.0 to about 7.0. Beneficially, the compositions of this invention overcome the incompatibility problems associated with the imidazolinyl acid salts and glyphosate salts without requiring the use of heavy aromatic solvents.

Imidazolinyl salts suitable for use in the stable compositions of this invention have the structural formula I (I) where w is oxygen or sulfur; Ri is alkyl C? -C4 R2 is Ci-C4 alkyl or C3-C6 cycloalkyl; and where Ri and R2 are taken together with the carbon to which they have been attached and which may represent C3-C6 cycloalkyl optionally substituted with methyl; X is hydrogen, halogen, hydroxyl or methyl; Y and Z are independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxymethyl, lower hydroxyalkyl, C 1 -C 6 alkoxy, C 1 -C 4 alkylthio, phenoxy, C 1 -C 4 haloalkyl, nitro cyano, C 1 alkylamino C4, lower dialkylamino, or C?-C4-sulfonyl alkyl or phenyl optionally substituted with C?-C4 alkyl, C?-C4 alkoxy or halogen, and where taken together, Y and Z form a ring in which YZ are represented by the structure: - (CH2) n-, where n is an integer of 3 or 4, with the proviso that X is hydrogen, or L M i? c = c- c = c- where L, M, Q and R are independently hydrogen, halogen, C? -C alkyl or C? -C4 alkoxy; Y R3 is ammonium, organic ammonium, trialkyl sulphonium or an alkali metal cation.

The term "lower alkyl" means alkyl C? - ß f preferably C 1 -C 4 alkyl.

Preferred imidazolinyl acid salts for use in the compositions of this invention include: salts of imazethapyr or its R-isomer; salts of imazaquin or its R-isomer; salts of imazapic or its R isomer; 10 salts of imazamox its R-isomer; salts of imazapir or its R-isomer; and mixtures of the same. Suitable glyphosate salts for use in the compositions of the present invention include, but are not limited to, glyphosate salts wherein the cation portion of the salt is an ammonium, organic ammonium, rialkylsulphonium or alkali metal cation. Preferred glyphosate salts are the organic amine salts of glyphosate such as Ci-Ce alkylamine salts, di- (C? -C6alkyl) -amine salts and t- (C? -C6alkyl) -25 amine salts being the most preferred are the salts of .. ^^^^ ^^^ mm alkylamine C? -C6. The isopropylamine salt of glyphosate is especially suitable for use in the compositions of this invention.

In another preferred embodiment of the present invention, the cation moiety of the imidazolinyl acid salt and the glyphosate salt are the same. In particular, it has been found that compositions comprising isopropylamine salt of imazetapir and the isopropylamine salt of glyphosate are physically and chemically stable.

In order to provide effective amounts in herbicides of active ingredients, the ratio of the imidazolinyl acid salt to the glyphosate salt in the compositions of this invention is preferably from about 1: 4 to about 1:15, more preferably around 1: 7 until around of 1:12, on a weight basis volume.

Wetting agents suitable for use in the compositions of this invention include, but are not limited to, wetting agents conventional such as tallow amines S "ethoxylated, alpha-olefin sulfonate salts, alkylphenol polyethylene oxide condensates and the like and mixtures thereof. Preferred wetting agents include ethoxylated tallow amines having 15 moles of ethyl oxide per molecule (such as SURFOM 5204-CS available from Oxiteno, Maua, Sao Paulo, Brazil); sodium alpha-olefin sulfonates (such as Witconate AOK available from Witco, Sao Paulo, Sao Paulo, Brazil); and nonylphenol ethoxylates (such as FLO MO®9N, available from Witco, New York, New York, United States of America); and mixtures thereof. The ethoxylated tallow amines are especially suitable for use in the stable compositions of this invention.

Antifreeze agents suitable for use in the compositions of the present invention include, but are not limited to, glycols such as propylene glycol and ethylene glycol, N-me t-ilpyr rolidone, cyclohexanone, and alcohols such as ethanol and methanol. . Preferred antifreeze agents include glycols with propylene glycol with the antifreeze agent being especially preferred. Suitable antifoam agents for use in this invention are conventional anti-foaming agents including, but not limited to, silica-based antifoam agents such as SE 47 antifoam (available from Wacker, Santo Amaro, Sao Paulo, Brazil).

In addition, the compositions of this invention may contain conventional additives used in aqueous compositions such as antimicrobial agents, antioxidants, buffering agents (including a K2HP04 / KH2P04 mixture), pigments and the like and mixtures thereof.

The most preferred, concentrated, aqueous herbicidal composition of this invention comprises about 2% w / v to about 4% w / v of isopropylamine imazethapyr salt, about 20% w / v to about 35% w / v salt of isopropylamine glyphosate, about 0.5% w / v to about 4% w / v of dimethyl sulfoxide, about 5% w / v to about 15% w / v of an ethoxylated tallow amine, about 1% w / v to about of 5% w / v of propylene glycol, about 0.001% w / v to about 0.1% w / v of an antifreeze agent, about 0.5% w / v to about 2.5% w / v of a base, and water, with the proviso that the composition has an initial pH from about 6.0 to about 5.8 and the ratio of the isopropylamine salt imazetapir to the isopropylamine glyphosate salt is from about 1: 7 to about 1:12. .

The present invention also relates to a process for the preparation of aqueous, concentrated herbicidal compositions. The process of this invention comprises: (a) providing a first aqueous solution containing a salt of imidazolinyl acid; (b) Disperse in the first aqueous solution, dimethyl sulfoxide and optionally an agent ant i freezing to produce a second aqueous solution; (c) adding in the second aqueous solution, an aqueous solution of a glyphosate salt for produce a homogenous solution while ^^^ ^^^^^^^^ ^ ^ maintains the pH above about pH 6.0 with a base; (d) adjusting the pH of the homogeneous solution produced in step (c) to about pH 6.0 to about 7.0, if necessary; (e) adding to the pH-adjusted solution obtained in step (d), a wetting agent and optionally an antifoaming agent; Y (f) add water Suitable bases for maintaining the pH of the solution produced in the above step (c) of about pH 6.0 include, but are not limited to, ammonium and organic amines and the like and mixtures thereof. Preferred bases include organic amines such as isopropylamine.

In a preferred process of the present invention, the pH is adjusted in step (d) with an acid. Suitable acids for use in the process of this invention include mineral acids and organic acids with organic acids such as acetic acid being preferred.

The concentrated, aqueous herbicidal compositions of this invention are diluted with water and applied as diluted aqueous sprays to the place where the control of the herb is desired. While the compositions of this invention are effective in controlling herbs when used alone, they can also be used in combination with other biological chemicals, including other herbicides.

For a clearer understanding of the invention, specific examples thereof are shown below. These examples are merely illustrative, and are not to be understood as limiting the scope and fundamental principles of the invention in any way.

In the following examples, the synergy is determined by the Colbyl method, that is, the expected (or predicted) response of the combination is calculated by taking the product of the observed response for each individual component of the combination when only split is applied per 100 and subtracting this value from the sum of the observed response for each component when applied alone. The synergy of the combination is then determined by comparing the observed response of the combination to the expected (or predicted) response as calculated from the observed responses of each individual component alone. If the answers observations of the combination are significantly greater than expected (or predicted) the response is determined by Fisher's Protected Minor Significant Difference (LSD) test using a significant level of 0.05, that the combination is said to be synergistic.

The aforementioned is maternally illustrated below, where a combination, C, is composed of a component A plus a component B and Obs. designates the observed response of the combination C.

. ^^^^^ X ^^^^. ^^^^ ^ AB (A + B) - = expected response (Exp.) 100 Synergy = (Obs. - Exp.) > LSD xColby, S R Weeds, 1967 (15), pages 20-22 EXAMPLE 1 Evaluation of the Herbicidal Activity of a Combination of Glifosate and Imazetapir.

In this evaluation, pitted marigold plants (Ipomoea lacunosa) are planted in standard greenhouse soil until they reach the 6-leaf stage. Said plants are then sprayed with an aqueous solution of the test compound using an atomizing injector operating at 30 psi for a predetermined period of time to obtain a range of application of ratio of about 20 g / ha to 720 g / ha. Each treatment is reapplied 3 times. After atomized, the plants are placed in greenhouse benches and are cared for in a manner commensurate with standard greenhouse practices. After 4 weeks of treatment, the plants are examined, and% grass control as compared to the untreated check, is recorded. Also after 4 weeks of treatment, the height of the plant is measured and recorded as the% reduction in height compared to the height of the untreated check. The heights of the plants are measured by squeezing the veins and measuring the land surface to the tip of the vein.

The data obtained is analyzed using conventional statistical analysis techniques to determine the minor significant difference (LSD) or standard deviation. Colby's method of analysis was used to determine the biological effect resulting from the combination treatment by comparing the biological effect of each component of the combination when applied alone.

COMPONENTS OF 9J $ # BBA SOURCE Glif osato, salt of tisojíropil ammonium 4AS ROUNDUP®1 Imazetapir 100AS PIVOT®H 'manufactured by Monsanto "manufactured by American Cyanamid Co TABLE I Evaluation of the Control of Glyphosate Grass g / ha Imazetap r g / ha% Control of Expected Observed Grass (Cbs. -Exp) 1 0 0 0.00 - 0 60 3.33 - 0 80 0.00 - or 100 30.00 - 480 0 3.33 - 720 0 23.33 - 480 60 82.67 6.67 76. .00 * 480 80 86.00 3.33 82. .67 * 480 100 84.33 42.00 42. .33 * 720 60 85.00 26.00 59. .00 * 720 80 86.67 23.33 63, .33 * 720 100 88.33 54.00 34 .33 * C - * ^ ^ • SD (0.05) = 17.4 * Synergistic, this is (obbs. -exp.) > LSD As can be seen from * JL * © s data shown in Table I, the application of a combination of glyphosate plus imazetapir gives a grass control significantly greater than what can be predicted from the grass control result of the application either alone imazetapir or only glyphosate.

TABLE II Evaluation of the Height Reduction of the Glyphosate Imazetapir Plant Height% of Reduction in Height g / ha g / ha (cm) Observed Expected (Cbs. -Exp) 1 0 0 169 0.00 0 60 143 15.35 0 80 143 15.37 0 100 115 31.47 480 0 141 16.75 720 0 106 37.11 480 60 61 63.49 29.75 33.74 * fc »^ -« **? ~ * «* ^ 480 80 60 64.58 29.58 35.00 * 480 100 59 64.87 43.71 21.16 * 720 60 62 63.55 46.40 17.15 720 80 53 68.70 46.64 22.06 * 720 100 52 68.94 55.81 13.14 XLSD (0.05) = 17.4 * Synergistic, this is (obs.-exp.) > LSD As can be seen from the data shown in Table II, the application of a combination of glyphosate plus imazetapir in 4 of the 6 relationships tested gives a reduction in height significantly greater than what can be predicted from the application of either glyphosate alone or only imazetapir.

EXAMPLE 2 Evaluation of the Herbicidal Activity of a Combination of glyphosate and Imazapic In this evaluation, pitted marigold plants (Ipomo ea l a c un o sa) are sown in a 1: 1 mixture of sandy loam and sandy soil.

^^^^ ^^^^^ M ^ m ^ ^ masonry until it was tw? Had the state of sheet 5. Said plants were then sprayed with an aqueous solution of the test compound using a spray chamber pressurized with C02. Each treatment was reapplied 4 times. After the roclo, the plants were placed in greenhouse benches and cared for in a manner commensurate with conventional greenhouse practices. At 4 weeks after treatment, the plants were visually examined and% grass control as compared to the untreated check was recorded. Also at 4 weeks after treatment, the number of leaves was counted and recorded as the% leaf reduction as compared to the untreated check. After visual relationships, the plant was removed from the soil surface and the vegetation removed was weighed and measured. Fresh plants weighed and measured were recorded as% reduction in weight as compared to the untreated check and as a% reduction in height as compared to the untreated check.

The data were analyzed using standard statistical analysis techniques to determine the significant difference -tffefior (LSD) or standard deviation.The Colby method was used to determine if the test combination demonstrated a synergistic interaction.

TEST COMPONENTS SOURCE Glyphosate, isopropylammonium salt ROUNDUP ^ ULTRA1 Imazetapir 100AS PIVOT®H 'Manufactured by Monsanto "manufactured by American Cyanamid Co TABLE III Evaluation of the Control of Glyphosate Grass c / ha Imazetapir g / ha% Control of Expected Observed Grass (Cbs. -Exp) l 0 0 0 - 0 8.97 35.00 - 0 13.45 28.75 - 0 17.93 20.00 - 280.2 0 23.75 - 560.4 0 5.00 - 280.2 8.97 51.25 50.38 0.88 280. 2 13.45 73.75 45.81 27.94 * 280. 2 17.93 77.50 39.00 38.50 * 560.4 8.97 55.00 38.25 16.75 * 560.4 13.45 78.75 32.31 46.44 * 560.4 17.93 86.25 24.00 62.25 * aLSD (0.05) = 10.76 * Synergistic, this is (obs exp.) > LSD TABLE IV E valuation of the Hoj Reduction. as Glyphosate Imazetapir Number% Reduction of Leaves g / ha g / ha of leaves Observed Expected (Gbs.-Exp) 1 0 0 13.3 0 - 0 8.97 8.8 26.34 - 0 13.45 9.0 32.46 - 0 17.93 6.0 50.89 - 280.2 0 10.8 6.66 - 560.4 0 12.5 0.17 - 280.2 8.97 5.3 58.80 16.24 42.56 * 280.2 13.45 3.8 69.44 36.62 32.81 * 280.2 17.93 5.5 55.23 46.61 8.62 560.4 8.97 5.5 54.48 19.71 34.77 * 560.4 13.45 4.5 65.52 32.22 33.30 * 560.4 17.93 3.0 77.29 47.34 29.96 * agg ^ jl ^ gfc XLSD (0.05) = 23.28 * Synergistic, this is (obs.-exp.) > LSD EXAMPLE 3 5 Evaluation of the Herbicidal Activity of a Combination of Glifosate and Imazamox.

Using essentially the same procedure described in Example 2 above, chopped 5-leaf marigold plants were treated with the test compounds and eventually 3 weeks after treatment. Each treatment was reapplied 4 times. The data is averaged and 15 are shown in Tables V and VI below.

TEST COMPONENTS SOURCE Glyphosate, isopropylammonium salt ROUNDUP ^ ULTRA1 Imazetapir 100AS PIVOT®H "manufactured by Monsanto" manufactured by American Cyanamid Co twenty TABLE V Evaluation of the Control of Grass Glyphosate g ha Xmazamox g / ha% of Control of Expected Observed Grass (Obs. -Exp) 1 0 0 0 - 0 8.97 5.00 - 0 17.93 32.50 - or 26.90 66.25 - 560.4 0 7.50 - 560.4 8.97 45.00 12.13 32.88 * 560. 4 17.93 78.75 37.63 41.13 * 560. 4 26.90 78.75 68.81 9.94 1LSD (0.05) = 15.55 * Synergistic, this is (obs.-exp.) > LSD TABLE VI Eva! Cool Weight Reduction Glyphosate Imazamox Weight% of Leaf Reduction g / ha g / ha M Observed Expected (Obs. -Exp) 1 0 0 4.38 0 0 8.97 4.19 4.19 0 17.93 4.49 -4.55 0 26.90 3.02 30.41 560.4 0 5.22 -22.39 560.4 8.97 3.61 14.02 -17.06 31.08 560. 4 17.93 2.82 32.80 -31.26 64.06 * 560. 4 26.90 2.30 47.16 -13.86 33.30 1LSD (0.05) 35.34 Synergistic, this is (obs.-exp.) > LSD TABLE VII Evaluation of the Leaves Reduction Glyphosate Imazamox Number of Reduction of Leaves g / ha g / ha of leaves Observed Expected (Cbs. -Exp) í 0 0 21.75 0 - 0 8.97 17.50 15.00 - 0 17.93 11.00 47.98 - 0. 26.90 7.00 66.21 - 560.4 0 23.00 -16.18 - 560.4 8.97 9.25 56.33 -8.80 65.13 * 560. 4 17.93 7.25 64.17 37.47 26.70 * 560. 4 26.90 6.50 67.93 57.22 10.71 XLSD (0.05) = 21.86 * Synergistic, this is (obs.-exp.) > LSD E ^ ase & ^? Iau EXAMPLE 4 Evaluation of the Herbicidal Activity of a Combination of glyphosate and the R-Isomer of a Imidazolinone compound In this evaluation, pitted marigold plants (Ipomo ea l a c a bear) and purple round sedge (Cyperu s ro t un du s) in a mixture are sown 1: 1 of sandy loam soil and masonry sand until they had the state of leaf 5-7 for the pitted marigold plants and the state of leaf 10-15 for the round purple sedge. These plants were then sprayed with a aqueous solution of the test compound using a spray chamber pressurized with C02 at a volume of 15 gallons / acre. Each treatment was reapplied 4 times. After the roclo, the plants were placed in greenhouse benches and took care of themselves in a manner commensurate with conventional greenhouse practices. At regular intervals, the plants were examined visually and% grass control as compared to the untreated check was recorded. The data were analyzed using analysis techniques -. ^^^ ñ? ^ & ^. ^ m Standard statistical test to determine the minor significant difference (LSD) or standard deviation. The Colby method was used to determine if the test combination demonstrated a synergistic interaction.

Test Compounds Glyphosate, isopropylammonium salt ROUNDUP® ULTRA)? 10 Compound A = imazapyr R isomer Compound B = imazapic R isomer Compound C = imazamox R isomer R Compound D = imazetopyr R isomer R • • • Manufactured by Monsanto 15 formulated as an aqueous concentrate in accordance with US 4,816, 060 TABLE VIII Evaluation of the Control of the Marigold Chopped after 5 Weeks of Treatment Glyphosate Compound of% of Control of Grass (g / ha) T i dazolinone Expected Observation (Obs. -Exp) x (g / ha) 0 0 0 mmi (fES ÍYS¿ -: .... '.. \ ± mnm ^ m 0 A 5.6 47.50 - 0 B 9.0 22.50 - 0 C 12.3 22.50 - 0 D 23.5 22.50 - 560 0 3.75 - 560 A 5.6 71.25 49.50 21.75 * 560 B 9.0 67.50 25.50 42.00 * 560 C 12.3 75.00 25.38 49.63 * 560 D 23.5 71.25 25.50 45.75 * ^ SD (0.05 12.6 Smérgico, this is ob s exp.) > LSD TABLE IX Evaluation of Control of Purple Round Beech after 4 Weeks of Treatment Glyphosate Composite of% of Control of Grass (g / ha) Tpii azolinone Observed Expected (Cbs.-Exp) 1 (g / ha) 0 0 0 0 A 5.6 0 0 B 9.0 0 0 C 12.3 0 0 D 23.5 0 60 0 15.00 560 A 5.6 38.33 15.00 23.33 * 560 B 9.0 40.00 15.00 25.00 * 560 C 12.3 38.33 15.00 23.33 * 560 D 23.5 60.00 15.00 45.00 * XLSD (0.05) = 9.7 Synergistic, this is (obs.-exp.) > LSD EXAMPLE 5 Preparation of aqueous, concentrated herbicidal compositions containing isopropylamine salt of imazethapyr and isopropylamine salt of glyphosate The concentrated, aqueous herbicidal compositions identified in the following Table X were prepared in accordance with the following generic procedure: (1) a first aqueous solution of isopropylamine salt of imazethapyr of imazethapyr and isopropylamine was prepared; (2) Dimethylsulfoxide and optionally pr-Butanol glycol were added to the first aqueous solution to obtain a second aqueous solution; (3) add an aqueous solution of isopropylamine salt of glyphosate to the second aqueous solution to obtain a homogeneous solution while keeping the pH below about pH 6.2 with a base; (4) adjust the pH of the homogeneous solution to a pH value of around pH 6.2 up to around pH 6.8 with an acid solution % acetic acid w / w; (5) add SURFOM 5204-CS (ethoxylated tallow amine wetting agent) and antifoam SE 47 (foaming agent) to adjust the pH of the solution; Y 6) add water.

TABLE X Compositions Aqueous Herbicides, Concentrated Ingredient /% w / v Comp. Salt IBA of Salt IPAd? DMSO Fride Base1 SUR OM Anti-Acid K2HPO | No. Opazßtapix Glyphosate Glycol KHzi = i Water pH 5204-CS Acé xco SE47 1 2.70 32.40 1.35 3.00 a / 0.81 15.66 0.01 0.16 up to 6.1 100 2 2.50 30.00 1.25 3.00 a / 0.75 14.50 0.01 0.15 _ _ up to 6.1 100 3 2.00 24.00 1.00 3.00 a / 0.80 11.80 0.01 0.12 _ _ has a 6.0 100 100 8 3.00 21.00 1.50 3.00 b / 1.50 10.15 0.01 0.12 0.05 0.02 up to 6.2 100 9 3.00 21.00 1.50 3.00 a / 0.78 10.15 0.01 0.07 0.05 0.02 up to 6.1 100 10 4.00 28.00 2.00 3.00 b / 2.00 13.63 0.01 0.01 0.02 0.07 up to 6.2 100 11 4.00 28.00 2.00 3.00 a / 1.04 13.53 0.01 0.01 0.02 0.07 to 6.4 100 12 3.00 21.00 2.00 3.00 a / 0.90 10.15 0.01 0.18 - _ has a 6.7 100 13 4.00 28.00 2.00 3.00 a / 1.20 13.53 0.01 0.24 - - up to 6.7 100 1 a . isoprop ilamine b. ammonium TABLE X (cont.) Comp. Salt HA of Salt HA of DMSO Propilen Base1 SURFOM Anti- Acid K2HP04 KH2P04 Water pH No. Imazetapir Glyphosate Glycol 5204-CS GSC? XOSi Acetic SE47 14 4.00 28.00 2.00 3.00 a / 1.20 13.53 0.01 0.24 - has a 6.4 100 15 3.00 21.00 2.00 3.00 a / 0.90 10.15 0.01 0.18 - up to 6.4 100 16 3.00 21.00 1.50 3.00 a / 0.90 10.15 0.01 0.18 - up to 6.1 17 4.00 28.00 2.00 3.00 a / 1.90 13.53 0.01 0.24 - 18 4.00 28.00 3.50 1.60 a / 1.20 13.53 0.01 0.24 - 19 4.00 28.00 3.50 - a / 1.20 13.53 0.01 0.24 - 20 4.00 28.00 2.00 1.50 a / 1.20 13.53 0.01 0.24 - 21 4.00 28.00 2.00 3.00 a / 1.20 13.53 0.01 0.24 - 22 4.00 28.00 2.00 - a / 1.20 13.53 0.01 0.24 - up 6.2 100 23 3.70 26.00 0.80 - b / 1.92 12.55 0.01 0.18 - has a 6.1 100 24 3.70 26.00 0.80 - b / 1.92 12.55 0.01 0.18 - up 6.1 100 25 4.00 28.00 1.00 - b / 2.06 13.53 0.01 0.24 _ up to 6.1 100 EXAMPLE 6 - * »* / Evaluation of storage stability of aqueous, 5 concentrated herbicidal compositions The storage stability of the concentrated, aqueous herbicidal compositions prepared in Example 5 was evaluated by storage samples of the compositions at room temperature (RT), 45 ° C and 5 ° C. The samples were periodically removed and visually inspected for physical changes in the appearance of the compositions. The results 15 are summarized in Table XI. As can be seen from the data in Table XI, the compositions of the present invention are especially stable for extended periods of time when stored above 5 ° C.

TABLE XI Storage Stability of Aqueous, Concentrated Herbicide Compositions Storage Period Comp. TßgDerature Storage Number 1 week 2 weeks 3 weeks 1 month 2 months 3 months TA without change without change without change without change without change without no 4 5 ° C without change without change without change without change without change without caKftfoio 5 ° C without change without change without change without change without change without carafctio TA without change without change without change without change without change without change 4 5 ° C without change without change without change without change without change without change 5 ° C without change without change without change without change without change without change TA without change without change without change without change without change without change 45 ° C without change without change without change without change without change without change 5 ° C without change without change without change without change without change without change TABLE XI (cont.) Storage Period Comp. Storage Temperature Number 1 week 2 weeks 3 weeks 1 month 2 months 3 months 4 TA - - - - - without change 4 5 ° C - - - - - without change 5 ° C crystal growth .c- TA without change without change without change without change without change without change 45 ° C without change without change without change without change without change without change 5 ° C without change without change without change without change without change without change TA without change 45 ° C without change 5 ° C crystal growth TABLE XI (cont.) Storage Period Comp. Temgera ura_de Storage Number 1 week 2 weeks 3 weeks 1 month 2 months 3 months TA without change without change without change without change without change without change 45 ° C without change without change without change without change without change without change 5 ° C without change without change without change without change without change without change .t- TA without change without change without change without change without change without cap &bio 8 45 ° C without change without change without change without change without change without change 5 ° C without change without change without change without change without change without change TA without change without change without change without change without change without change 45 ° C without change without change without change without change without change without change 5 ° C without change without change without change without change without change without change TA without change without change without change without change without change without change 45 ° C without change without change without change without change without change without change 5 ° C without change without change without change without change without change without change TABLE XI (cont.) Storage Period Comp. Tßg3eratura_de Storage Number 1 week 2 weeks 3 weeks 1 month 2 months 3 months 11 TA without change without change without change without change without change without change 45 ° C without change without change without change without change without change without change 5 ° C without change without change without change without change -, < ** 12 TA without change without change without change without change without change without CAS > 45 ° C without change without change without change without change without change without ca. 5 ° C without change without change without change without change without change without change 13 TA without change without change without change without change without change without change 45 ° C without change without change separation separation separation without change 5 ° C without change without change without change without change without change without change 14 TA without change without change without change without change without change without change 45 ° C without change without change without change without change without change without change 5 ° C without change without change without change without change without change without change TABLE XI (cont.) Storage Period Comp. Storage space Number 1 week 2 weeks 3 weeks 1 month 2 months 3 months TA without change without change without change without change without change without change 45 ° C without change without change without change without change without change without change 5 ° C without change without change without change without change without change without change 16 TA without change without change without change without change without change without change 4 5 ° C without change without change without change without change without change without change or 5 ° C without change without change without change without change without change without change 17 TA without change without change without change without change without change without change 4 5 ° C without change without change ßin change without change without change without change 5 ° C without change without change without change without change without change without change TA without change without change without change without change without change without change 45 ° C without change without change without change without change without change without change 5 ° C without change without change growth growth growth growth of crystal crystals of crystal crystals TABLE XI (cont.) Storage Period Comp. Storage Temperature Number 1 week 2 weeks 3 weeks 1 month 2 months 3 months 19 TA without change without change without change without change without change without change 45 ° C without change without change without change without change without change without change 5 ° C without change without change growth growth growth growth of crystal crystals of crystal crystals TA without change without change without change Vestige of Vestige of growth growth growth of crystal crystals of 45 ° C without change without change without change without change - without change 5 ° C without change growth growth growth growth of crystals growth crystals crystals TABLE XI (cont.) Storage Period Comp. Storage Temperature Number 1 week 2 weeks 3 weeks 1 month 2 months 3 months 21 TA without change without change without change Vestige of Vestige of growth growth growth of crystal crystals of 45 ° C without change without change without change without change - without change 5 ° C without change growth growth growth growth growth of crystals of crystal crystals crystals crystals 22 TA without change without change without change Vestige of Vestige of growth growth growth of crystal crystals of 4 5 ° C without change without change without change without change - without change 5 ° C without change growth growth growth growth of crystals of crystals of crystals of crystals of crystals TABLE XI (cont.) Storage Period Comp. Storage Temperature Number 1 week 2 weeks 3 weeks 1 month 2 months 3 months 23 TA without change without change without change Vestige of Vestige of growth growth growth of crystal crystals of 45 ° C without change without change without change without change - without change 5 ° C without change growth growth growth growth growth of crystals of crystal crystals crystals crystals 2 4 TA without change without change without change Vestige of Vestige of growth growth growth of crystals of crystals of crystals 4 5 ° C without change without change without change without change "without change 5 ° C without change growth growth growth growth growth of crystals of crystals of crystals of crystals of crystals TABLE XI (cont.) Storage Period Comp. Storage Tauparature Number 1 week 2 weeks 3 weeks 1 month 2 months 3 months 2 5 TA without change growth growth growth growth of crystals of crystal crystals crystals 4 5 ° C without change s ^ -n change without change without change without change without change 5 ° C growth growth of crystal crystals of crystals -C- EXAMPLE 7 Comparative evaluations of the storage stability of the concentrated aqueous herbicidal compositions.

The storage stability of compositions 20, 21 and 22 of Example 5 are compared with comparative compositions A, B and C. Comparative compositions A, B and C are essentially identical to compositions 20, 21 and 22, respectively, except that the compositions A, B and C each have an initial pH value of 5.8. the compositions are evaluated according to the procedure described in Example 6, and the results are summarized in Table XII.

As can be seen from the data in Table XII, the compositions of the present invention, which have an initial pH value of 6.2, are more stable to storage than comparative compositions having an initial pH value of 5.8.

Table XII Storage Period Composition pH Temperature Initial number Storage 1 week 2 weeks 3 weeks 1 month 6.2 TA without change without change without change Vestige of stales growth 6.2 45 ° C without change without change without change of cri without change growth growth without change 6.2 5 ° C of crystal crystals growth of crystals A 5.8 TA growth or growth growth of crystal crystals growth crystals 5 45 ° C without change without change without change without change cree imi ent or 5 ° growth growth growth 5 C crystal crystals crystals crystals Table XII (Cont.) Storage Period Composition pH Temperature Initial number Storage 1 week 2 weeks 3 weeks 1 month 21 6.2 TA without change Without change without change Growth vestige in change without change without change of crystals 6.2 45 ° C s without change growth growth without change 6.2 5 ° C of crystal crystals growth of crystals . 8 TA cr eci ient Growth growth crystal growth of crystal crystals 5 45 ° C without change without change without change without change 5 growth growth growth growth 5 ° C of crystal crystals of crystal crystals Table XII (Cont.) Storage Period Composition pH Temperature Initial number Storage 1 week 2 weeks 3 weeks 1 month 22 6.2 TA without change without change without change Growth vestige without change without change without change of crystals 6.2 45 ° C without change 6.2 5 ° C without change growth growth of crystal crystals growth of crystals 5. TA growth or growth growth of crystal crystals of crystal crystals 5. 45 ° C without change without change without change without change u? cr ecimient or growth growth oo 5. 5 ° C growth of crystals crystals crystals crystals It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property. ^ ÑUtiaeAá *

Claims (11)

Claims

1. A method for the synergistic control of plants Ipom oea, Cypeurs, Si da and Euph orbi undesirable, characterized in that it comprises applying to the place of said plants or to the foliage or the stems of said plants a synergistically effective amount of a glyphosate combination. and an imidazolinone compound selected from the group consisting of imazetapyr; imazaquin; imazapic; imazamox; imazapyr; and mixtures thereof.

2. The method according to claim 1, characterized in that the plants are Ipom or ea or Cyperu s.

3. The method according to claim 1, characterized in that the imidazolinone compound is selected from the group consisting of imazetapyr, the R isomer thereof; imazapic, the R isomer thereof; and imazamox, the R isomer thereof.

4. The method according to claim 1, characterized in that the glyphosate and imidazolinone compound are present at a weight / weight ratio of about 3: 1 to 65: 1.

5. The method according to claim 1, characterized in that the synergistically effective amount is about 200 g / ha-1200 g / ha of glyphosate and about 8.0 g / ha-150 g / ha of an imidazolinone compound.

6. An herbicidal, synergistic, aqueous, concentrated composition characterized in that it comprises about 0.1% w / v to about 7% w / v of a salt of imidazolinyl acid, about 15% w / v to about 45% w / v of a glyphosate salt, about 0.5% w / v to about 6% w / v of dimethyl sulfoxide, about 0.5% w / v to about 15% w / v of a wetting agent, more than about 10% p / v of an antifreeze agent, more than about 1% w / v of an antifoaming agent, more than about 3% w / v of a base, and water, with the proviso that the composition has an initial pH from around 6.0 to around 7.0.

7. The composition according to claim 6, characterized in that they comprise about 0.5% w / v up to about 5% w / v of the imidazolinyl acid salt, about 20% w / v up to about 35% w / v of the glyphosate salt, around 0.5% w / v to around 10 of 4% w / v of dimethyl sulfoxide, about 1% w / v to about 15% w / v wetting agent, about 1% w / v to about 5% w / v antifreeze agent, more than about 0.5% w / v of the antifoaming agent, more than about 15 2.5% w / v of the base, and water, with the proviso that the composition has an initial pH from about 6.0 to about 6.8.

8. The composition in accordance with the Claim 6, characterized in that the cation moiety of the imidazolinyl acid salt and the glyphosate salt is an ammonium, organic ammonium, t rialisulphonium or alkali metal cation. ^^, !! ^^^^^^^ ..! tto J »^ * ^

9. The composition according to claim 1, characterized in that the salt of the imidazolinyl acid is selected from the group consisting of an imazethapyr salt or its R-isomer; a salt of imazamox or its R isomer; an imazapic salt or its R isomer; a salt of imazapir or its R-isomer; and an imazaquin salt or its R. isomer

10. The composition according to claim 6, characterized in that it comprises about 2% w / v up to about 4% w / v salt of i sopropilamma imazetapyr, about 20% w / v up to about 35% w / v of isopropylamine glyphosate salt, about 0.5% w / v 5 to about 4% w / v of dimethyl sulfoxide, about 5% w / v up to about 15% w / v of an ethoxylated tallow amine, about 1% % p / v up to about 5% w / v of propylene glycol, around 0.001% w / v up to about 0.1% w / v of an antifoaming agent, about 0.5% w / v up to about 2.5% w / w v of a base, and water, with the proviso that the composition has an initial pH from about 6.0 to about 6.8 and the ratio of the isopropylamine salt imazetapyr to the salt of ^^^^ gj ^ | ^ jl isopropylamine glyphosate from about 1: 7 to about 1:12.

11. A process for the preparation of an aqueous, concentrated herbicidal composition, characterized in that: (a) providing a first aqueous solution containing a salt of imidazolinyl acid; (b) dispersing in the first aqueous solution, dimethyl sulfoxide and optionally a freezing agent to produce a second aqueous solution; (c) adding in the second aqueous solution, an aqueous solution of a glyphosate salt to produce a homogeneous solution while maintaining the pH above about pH 6.0 with a base; (d) adjusting the pH of the homogeneous solution produced in step (c) to about pH 6.0 to about 7.0, if necessary; (e) adding to the pH-adjusted solution obtained in step (d), a wetting agent and optionally an antifoaming agent; Y f) add water ? gjJtt! '