SYNERGISTIC HERBICIDAL COMPOSITIONS AND METHOD FOR CONTROLLING UNDESIRABLE VEGETATION

Abstract: Synergistic herbicidal activity is displayed by composi­ tions comprising the following two components: (a) a pyrrolidone of the formula in which: X is selected from the group consisting of hydrogen, chlo­ rine, and methyl; Y is selected from the group consisting of hydrogen, chlorine and bromine; Z is selected from the group consisting of chlorine and brom­ ine; R¹ is selected from the group consisting of hydrogen and C₁-C₄ alkyl; R² is selected from the group consisting of hydrogen, halo­ gen, C₁-C₄ alkyl, acetyl, trifluoromethyl, nitro, cyano, C₁-C₄ alkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsul­ fonyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, penta­ fluoropropionamido, and 3-methylureido; and R₃ is selected from the group consisting of hydrogen, C₁-C₄ alkyl, chlorine and trifluoromethyl; and (b) a phosphonic acid of the formula in which: R⁴ is selected from the group consisting of C₁-C₄ alkyl, C₁-C₄ haloalkyl, and -CH₂NHCH₂COOH, at a weight ratio of (a) to (b) of from about 0.1:1 to about 20:1.

Description: SYNERGISTIC HERBICIDAL COMPOSITIONS AND METHOD FOR CONTROLLING UNDESIRABLE VEGETATION. The protection of crops from weeds and other vegetation which inhibit crop growth by consuming valuable acreage or soil nutrients is a constantly recurring problem in agriculture. To help combat this problem, researchers in the field of synthetic chemistry have produced an extensive variety of chemicals and chemical formulations effective in the control of such unwanted growth. Chemical herbicides of many types have been disclosed in the literature and a large number are in commercial use. In many cases, active herbicides have been shown to be more effective in combination than when applied individually. The result is often termed "synergism", since the combination demonstrates a potency or activity level exceeding that which it would be expected-to have, based on a knowledge of the individual potencies of the components. The present invention resides in the discovery that certain pyrrolidones and certain'phosphonic acids, already known individually for their herbicidal potency, display this synergistic effect when applied in combination. The two classes of compounds forming the combination which is the subject of the present invention are independently known in the art as active herbicides. Pyrrolidones are disclosed as herbicides in U.S. Patent No. 4 110 105 (Teach, August 29, 1979), and phosphonic acids are similarly disclosed in U.S. Patent: - No. 3 853 530 (Franz, Decembre 10, 1974), - No. 3 799 758 (Franz, March 26, 1974), and -No. 3 929 450 (Hamm, Decembre 30, 1975), as well as numerous other references including: - Maynard et al., "Organophosphorus Compounds. I. 2-chloroalkylphosphonic Acids as Phosphorylating Agents", Aust. J. Clun., 16, 596)608 (1963), and - Yang, "Ethylene Evolution From 2-Chloroethylphosphonic Acid", PZant PtlysyfoZ., 44, 1203-1304 (1969). -s as now been found that synergism in the control of undesirable vegetat r, is exhibited by compositions comprising a mixture of the followir- two components: @(a) a pyrrolidone of the formula: EMI2.1 in dhich: : X is selected from the group consisting of hydrogen, chlorine and methyl; Y is selected from the group consisting of hydrogen, chlorine and bromine; Z is selected from the group consisting of chlorine and Cl-C4 alkyl; R1 is selected from the group consisting of hydrogen and C1-C4 alkyl; R2 is selected from the group consisting of hydrogen, halogen, Cr-C4 alkyl, acetyl, trifluoromethyl, nitro, cyano, C1-C4 alkoxy, C1-C4 alkylthio, C,-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, trifluoromethyl thio, tri fl uoromethyl sul fi nyl, tri fl uoromethyl sul fonyl , pentafl uoro propionamido, and 3-methylureido; and R3-is selected from the group consisting of hydrogen, C1-C4 alkyl, chlorine and trifluoromethyl; ; and i(b) a phosphonic acid of the formula: EMI2.2 in which: R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl, and -CH2NHCH2COOH. In the compositions of the present invention, pyrrolidones of the following formula are preferred: EMI2.3 in which: R2 is trifluoromethyl or cyano. -The term 'alkyl' as usen herain includes both stright-chain and branhec-crain grobss. The carbon canges are intended to be inclusive oss sth ubber and lower limits. -The terms "syanergism" and "synergistic" are used herein to convey the esult osservad when a combination of herbicides demonstrates a potency in excess o that whren the combination wou; 5e expected to produce on the of the potencies of each herbicide applied individually. - The term "herbicide" is used nerein to denote a compound which controls or modifies the growth of plants. - The term"herbicidally effective amount" is used to indicate the quantity of such a compound or combination of such compounds which is capable of producing a controlling or modifying effect. "Controlling" or "modifying effects" include all deviations from natural development, for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulating, leaf burn, dwarfing and the like. The term "plants" is used to include germinating seeds, emerging seedlings and established vehetation, including roots and above-ground portions. - rn the composirions of this invention, the (pyrrollidone):(phosphonic acid)weight ratio at which the herbicidal response is synergistic lies within the ranqe r- about 0.1:1 to about 20:1, preferably about 0.1:1 to t 10: Apt cation rates will deeend upon the weeds to be controlled and the degree o.¯ control desired. In general, the compotions of this invention are most efficiently employed at a rate of 0.01 to 50 pounds per acre (0.011 to 56 klograms per hectar) of the active ingredient, preferably 0.1 to 25 pcnuds per acre (0.11 to 28 kilograms per hectare). Examnies of pyrrolidones useful in the present invention are: #1-pnenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-phenyl-3,3-dichloro-4-chloromethyl-2-pyrrolidone. #1-(2',6'-dimethylphenyl)-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-chlorophenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-p-chlorophenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-trifluoromethylphenyl-3-chloromethyl-2-pyrrolidone. #1-phenyl-3-chloro-3-methyl-4-chloromethyl-2-pyrrolidone. #1-(2',@dichlorophenyl)-3,2-dichloro-4-chloromethyl-2-pyrrolidone. #1-m-trifluoromethylphenyl-3,2-dichloro-4-chloromethyl-2-pyrrolidone. #1-m-trifluoromethylphenyl-y-chloro-3-methyl-4-chloromethyl-2-pyrrolidone. #1-p-@@@@.-C-chloro-4-chloromethyl-2-pyrrolidone. #1-m-fluoropheyl-3-chlro-4-chloromethyl-2-pyrrolidone. #1-m-trifluoromethyl-3-bromo-4-chloromethyl-2-pyrrolidone. #1-(3',4'-dichlorophenyl)-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-nitrophenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-(3',5'-dichlorophenyl)-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-trifluoromethylphenyl-3-chloro-4-(1'-chloroethyl)-2-pyrrolidone. #1-m-cynophenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-(3',5'-dichlorophenyl)-3,3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-trifluoromethylphenyl-3,3-dichloro-4-(1'-chloroethyl)-2-pyrrolidone. #1-m-cyanophenyl-3,3-dichloro-4-chloromethyl-2-pyrrolidone. #1-(3'-trifluoromethyl-4'-chlorophenyl)-3-chloro-4-chloromethyl-2-pyrrolidone. #1-(3'-trifluoromethyl-4'-chlorophenyl)-3,3-dichloro-4-chloromethyl-2-pyrrolidone. #1-m-trifluoromethylthiophenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-methylthiophenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-trifluoromethylsulfinylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-methylsulfinylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-methylsulfonylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-trifluoromethylsulfonylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-(3',5'-bis-trifluoromethylphenyl)-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-methoxyphenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-acethylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone. 1 -m-tolyl-3-c hloro-4-chloromethyl-2-pyrroli done #1-m-trifluoromethylphenyl-4-chloromethyl-2-pyrrolidone. #1-m-bromophenyl-3-chloro-4-chloromethyl-2-pyrrolidone. 1 -o-chlorophenyl-3-chloro-4-chloromethyl-2-pyrrolidone. done. #1-m-iodophenyl-3-chloro-4-chloromethyl-2-pyrrolidone. 1 -p-methoxyphenyl-3-chloro-chloromethyl-1 -pyrrolidone #1-o-trifluoromethylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #1-m-pentafluoropropionamidophenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #cis-1-m-trifluoromethylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone. #trans-1-m-trifluoromethylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone. These and other pyrrolidones within the scope of the invention can be prepared by the procedures described in U.S. Patent No. 4 110 105. Examples of substituted phosphonic acids useful in the present invention are: #methylphosphonic acid #buthalphosphonic acid #2-chloroethylphosphonic acid ethyl phosphonic acid t-butylphosphonic acid 2-bromoethylphosphonic acid #propylphonic acid #s-buthylphosphonic acid #N-phosphonomethylglycine. These and other substituted phosphonic acids within the scope of the invention can be prepared by the procedures described in U.S. Patent No. 3 799 758 and the Maynard et al. articles mentioned above. The following examples provide further illustration demonstrating the synergistic herbicidal response of the present compositions. EXAMPLE 1 This example demonstrates the synergistic response of 1-m-trifluoromethylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone and 2-chloroethylphosphonic acid in combined postemergence application to a veriety of weeds. Aluminum flats measuring 15.2#22.9#7.0 centimeters (cm) were filled to a depth of 5.0 cm with loamy sand soil containing 50 parts per million (ppm) each of the commercial fungicide cis-N[(trichloromethyl)thio]-4-cyclo- hexene-1,2-dicarboximide (Cptan) and 18-18-18 fertilizer (percentages of N-P205-K20 on a weight basis). Several rows were impressed across the width of each flat and each row was seeded with a single weed species. The weed species included: ^ yellow nut sledge (Cyperus esculentus), * nightshade (Solanum nigrwn), johnsongrass (Sorghum haZopense) * wild oat (Avena fatua) . velvetleaf (AbutiZon theophrasti), v jimsonweed (Datura stramonium) and a annual morning glory (Ipomoea purpurea). Ample seeds were planted to give about 20 to 50 seedlings per row after emergence depending on the size of the plants. The flats were then placed in a greenhouse for two weeks, where they were watered regularly. At the end of this period, the foliage on the emergent weeds was sprayed with aqueous solutions of the test compounds.The quantities sprayed were such that the amount of each test compound applied per flat corresponded to the desired application rate in pounds per acre. In control flats, the test compounds were applied alone at various application rates, whereas in the test flats, solutions containing both compounds were applied. Additional flats not treated at all were used as a standard for measuring the extent of weed control occuring in the treated flats. Three weeks after treatment, the control and test flats were compared to the standard and each row was rated visually in terms of percent control ranging from 0% to 100%, with 0% representing the same degree of growth as the same row in the standard and 100% representing complete kill of all weeds in the row. All types of plant injury were taken into consideration. The results of these tests are listed in Table I herein-after, in the columns headed by the symbol "0" (indicating the "observed" results). These results are compared with the expected results, shown in the columns headed by the symbol "E", derived from the control date using Limpel's formula (Limpel and al., 1962, "Weed Control by Dimethylchloroterephtalate Alone and in Certain Combinations", Proc. NEWCC, Vol. 16, pp. 48-53): E = X + y ¯ 1XY 100 where: X = observed percent injury when one of the herbicides is used alone, and Y = observed percent injury when the other herbicide is used alone. An at asterisk (#)is is used to indicate the tests where the results show synergism, i.e., where the observed result exceeds the expected result. Since synergism can only be detected when the expected result is less than 100, tests where both the E and 0 values are 100 are left blank. It is clear from the table that synergisms was widely evident over the entire range of application rates tested. TABLE I -HERBICIDE SYNERGISM TEST RESULTS¯ Pyrrolidone: EMI7.1 Application Rates Percent Control- O : Observed E : Expected (lb/A) Night- Jimson- Velvet- Morning- Johson Phosphonic Shane weed leaf Nutsedge glory grass Wild Oat Pyrrolidone Acid O E O E O E O E O E O E O E Control Data: 0.25 - 20 30 20 0 0 5 0 0.5 - 40 65 60 10 10 15 20 1.0 - 95 100 98 40 30 60 40 - 0.25 0 0 0 0 0 0 0 - 0.5 0 0 0 0 0 0 0 - 1.0 10 30 0 0 0 10 0 Test Data: : 0.25 0.25 40# 20 100# 30 20# 20 0 0 0 0 0 5 0 0 0.25 0.5 60# 20 100# 30 40# 20 0 0 10# 0 0 5 0 0 0.25 1.0 70# 28 100# 51 100# 20 0 0 20# 0 20# 15 30# 0 0.5 0.25 80# 40 100# 65 85# 60 0 10 20# 10 30# 15 20 20 0.5 0.5 100# 40 100# 65 100# 60 10 10 20# 10 65# 15 25# 20 0.5 1.0 100# 46 100# 76 100# 60 10 10 30# 10 60# 24 30# 20 1.0 0.25 100# 95 40 40 20 30 90# 60 50# 40 1.0 0.5 100# 95 60# 40 25 30 98# 60 100# 40 1.0 1.0 100# 96 65# 40 30 30 98# 64 100# 40 # Synergistic effect show. Blank space indicate 100% control in both observed and expected results, precluding evalution of synergism. EXAMPLE 2 In this example, the same herbicides used in Example 1 were used. Here, however, the pyrrolidone was applied in pre-emergence fashion it was sprayed over the soil surface on the same day on which the weed seeds were planted, i.e., before the weeds were able to emerge from the soil. The phosphonic acid was applied in postemergence fashion as in Example 1. The application rates were varied somewhat to show a wider range and the injury ratings were taken four weeks after planting rather than five. Otherwise, the procedure were identical to those of Example I. The results are shown in Table II herein-after, where a strong degree of synergism is evident at higher application rates. EXAMPLE 3 This example demonstrates the synergistic response of l-m-trifluoro- methylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone and N-phosphonomethylglycine in combined post-emergence application. The weed species used in this test included: shattercane (Sorghum bicoZor) and n annual ryegrass (LoZiwn mu itiflorum) as well as the yellow nutsedge, wild oat, johnsongrass, and morning glory species listed above. Fiber flats were used rather than aluminum. The emergent weeds were treated three weeks after seeding and injury ratings were taken four weeks later. Otherwise, the procedure was the same as that described in Example 1. The results are shown in Table III herein-after, where a strong degree of synergism is evident in many of the tests. TABLE II -HERBICIDE SYNERGISM TEST RESULTS- Pyrrolidone: EMI9.1 Application Rates Percent Control- O : Observed E : Expected (lb/A) Night- Jimson- Velvet- Morning- Johson Phosphonic Shane weed leaf Nutsedge glory grass Wild Oat Pyrrolidone Acid O E O E O E O E O E O E O E Control Data: 0.0625 - 0 0 10 0 0 0 0 0.125 - 30 20 30 0 10 10 20 0.25 - 50 60 65 10 40 20 40 - 0.5 0 0 0 0 0 0 0 - 1.0 0 0 0 0 0 0 0 - 2.0 0 0 0 0 0 0 0 Test Data: : 0.0625 0.5 0 0 0 0 10 10 0 0 0 0 0 10 0 0 0.0625 1.0 0 0 0 0 10 10 0 0 0 0 0 10 0 0 0.0625 2.0 0 0 0 0 10 10 0 0 0 0 0 10 0 0 0.125 0.5 30# 30 20 20 10 30 0 0 10 10 10 20 10 10 0.125 1.0 30 30 20 20 30 30 0 0 10 10 10 20 10 10 0.125 2.0 30 30 20 20 30 30 0 0 10 10 10 20 10 10 0.25 0.5 100# 50 60 60 100# 65 10 10 40 40 100# 30 30# 20 0.25 1.0 100# 50 65# 60 100# 65 10 10 40 40 100# 30 60# 20 0.25 2.0 100# 50 70# 60 100# 65 10 10 40 40 100# 30 65# 20 # Synergistic effect shown. TABLE III -HERBICIDE SYNERGISM TEST RESULTS- EMI10.1 Application Rates Percent Control- O : Observed E : Expected (lb/A) Shatter- Morning- Johnson Phosphonic cane Nutsedge Ryegrass glory Wild Oat grass Pyrrolidone Acid O E O E O E O E O E O E Control Data: 0.125 - 10 0 0 0 10 30 0.25 - 20 0 30 0 60 40 0.5 - 30 10 65 0 70 60 - 0.125 0 70 40 0 0 0 - 0.25 0 70 60 0 30 0 - 0.5 65 80 90 30 60 0 Test Data: : 0.125 0.125 10 10 30 70 40 40 0 0 40# 10 100# 30 0.125 0.25 0 10 75# 70 70# 60 20# 0 100# 37 100# 30 0.125 0.5 50 69 75 80 95# 90 60# 30 100# 64 100# 30 0.25 0.125 20 20 50 70 70# 58 60# 0 100# 60 100# 40 0.25 0.25 20 20 60 70 95# 72 60# 0 100# 72 60# 40 0.25 0.5 60 72 70 80 98# 93 100 30 100# 84 70# 40 0.5 0.125 40# 30 80# 76 70 79 40# 0 100# 70 100# 60 0.5 0.25 30 30 60 76 70 86 50# 0 100# 79 60 60 0.5 0.5 40 76 98# 84 99# 97 75# 30 100# 88 100# 60 # Synergistic effet shown. EXAMPLE 4 The same herbicides tested in Example III were tested in the data shown in this example, the main difference being that the pyrrolidone was applied pre-emergence, rather than postemergence with the phosphonic acid. The latter was applied two weeks after planting, and injury ratings were taken two weeks later. The procedure was otherwise identical to that of Example 1. The results are shown in Table IV, herein after, where.synerism is indicated at all application rates. EXAMPLE 5 The tests shown in this example were run with l-m-cyanophenyl-3-chloro- 4-chloromethyl-2-pyrrolidone and N-phosphonomethylglycine in combined postemergence application. The weed species included: watergrass foxtail in addition to the- wild oat, x yellow nutsedge, annual morning glory, and annual ryegrass previously tested, in fiber flats. The weeds were treated ten days after seeding, and injury ratings were taken 17 days later. Since the tests were performed during the winter season, low growth rates occurred rendering comparisons with the standard more difficult. Synergism, however, is shown in many of the tests results, which are listed in Table V herein-after. TABLE IV -HERBICIDE SYNERGISM TEST RRESULTS EMI12.1 Application Rates Percent Control- O : Observed E : Expected (lb/A) Night- Jimson- Velvet- Morning- Johson Phosphonic Shane weed leaf Nutsedge glory grass Wild Oat Pyrrolidone Acid O E O E O E O E O E O E O E Control Data: 0.0625 - 0 0 10 0 0 10 0 0.125 - 30 20 30 0 10 20 10 0.25 - 50 60 65 10 40 30 20 - 0.5 30 20 0 10 10 0 0 - 1.0 60 30 20 20 15 10 0 - 2.0 100 50 100 40 30 60 100 Test Data: : 0.0625 0.125 75# 30 20 20 0 10 10 10 10 10 10 10 10 0 0.0625 0.25 100# 60 30 30 40# 28 30# 20 10 15 15 19 40 0 0.0625 0.5 60# 50 50# 40 40# 30 60 64 65 100 0.125 0.125 100# 51 20 36 20 30 10 10 10 19 40# 20 20# 10 0.125 0.25 100# 72 30 44 60# 44 40# 20 20 24 60# 28 40# 10 0.125 0.5 100# 60 90# 40 30 37 85# 68 0.25 0.125 100# 65 40 68 100# 65 30# 19 40 46 100# 30 100# 20 0.25 0.25 100# 85 50 72 100# 72 60# 28 50# 49 100# 37 95# 20 0.25 0.5 60 80 75# 46 60# 58 100# 72 # Synergistic effet shown. Blank spaces indicate 100% control in both observec and expected results, precluding synergism evaluation. TABLE V -HERBICIDE SYNERGISM TEST RESULTS- EMI13.1 Application Rates Percent Control- O : Observed E : Expected (lb/A) Wild Water- Morning Phosphonic Oat grass Nutsedge glory Ryegrass Foxtail Pyrrolidone Acid O E O E O E O E O E O E Control Data: 0.062 - 0 0 0 0 0 0 0.125 - 0 0 0 0 0 0 0.25 - 0 0 0 0 0 30 - 0.125 0 0 0 0 0 50 - 0.25 0 0 0 0 0 65 - 0.5 0 0 20 10 0 75 Test Data: 0.062 0.125 0 0 0 0 0 0 10# 0 0 0 40 50 0.062 0.25 0 0 0 0 40# 0 20# 0 20# 0 65# 60 0.062 0.5 0 0 20# 0 60# 20 30# 10 40# 0 75 75 0.125 0.125 0 0 0 0 0 0 0 0 0 0 50 50 0.125 0.25 0 0 0 0 0 0 0 0 0 0 50 60 0.125 0.5 0 0 0 0 20 20 10 10 10# 0 60 75 0.25 0.125 0 0 0 0 0 0 0 0 0 0 30 65 0.25 0.25 0 0 0 0 10# 0 20# 0 10# 0 60 76 0.25 0.5 0 0 40# 0 60# 20 30# 10 30# 0 100# 83 #Synergistic effect shown. The compositions of this invention are useful as herbicides demonstrating synergistic activity for the control of undesirable vegetation. The compositions can be formulated in the same manner in which herbicides are generally formulated. The compounds may be applied either separately or combined as part of a two-part herbicidal system. The object of the formulation is to apply the compositions to the locus where control is desired by a convenient method. The "locus" may include soil, seeds, seedlings, and vegetation. Formulations will generally contain several additives. Among these are some inert ingredients and diluent carriers such as organic solvents, water, oil and water, water in oil emulsions, carriers of dust and granules, and surface active, wetting, dispersing, and emulsifying agents. Fertilizers, e.g., ammonium nitrate, urea and superphosphate may also be added. Aids to rooting and growth, e.g., compost, manure, humus, sand, etc., may likewise be added. The formulations are commonly dusts, wettable powders, granules, solutions of emulsifiable concentrates. Dusts are free-flowing powder compositions containing the herbicidal compound impregnated on a particulate carrier. The particle size of the carrier is usually in the approximate range of 30 to 5P microns. Examples of suitable carriers are talc, bentonite, diatomaceous earth, and pyrophyllite. Anticaking and antistatic agents can be added, if desired. The composition generally contains up to 50% of active ingredient. Dusts, like liquid compositions, can be applied from boom and hand or power sprayers or airplanes. Wettable powders are finely divided compositions comprising a particulate carrier impregnated with the herbicide compound and additionally containing one or more surface active agents. The surface active agent promotes rapid dispersion of the powder in aqueous medium to form stable, sprayable suspensions. A wide variety of surface active agents can be used, for example, long chain fatty alcohols; salts of sulfonic acid; esters of long chain fatty acids; and polyhydric alcohols; in which the alcohol groups are free, omega-substituted polyethylene glycols of relatively long chain length. A list of surface active agents suitable for use in agriculture formulations can be found in Wade Van Valkenburg, "Pesticide Formulations" (Marcel Dekker, Inc., New York, 1973) at pages 79-84.

Claims: n(b) a phosphonic acid of the formula: EMI15.1 in which: R4 iS selected from the group consisting of C1-C4 alkyl, C1-C4 halo alkyl, and -CH2NHCH2COOH, at a weight ratio of (a) to (b) of from about 0.1:1 to about 20:1. 3.- A synergistic herbicidal composition comprising a mixture of: 1(a) a pyrrolidone of the formula: EMI15.2 in which: in which; Rê is cyano, and n(b) a phosphonic acid of the formula: EMI15.3 in which: R4 is selected from the group consisting of C1 -C4 alkyl, C1 -C4 halo alkyl, and -CH2NHCH2COOHt at a weight ratio of (a) to (b) of from about 0.1:1 to about .20:1. 4.- A composition according to Claim 2 or 3 in which the weight ratio of (a) to (b) is from about 0.1:1 to about 10:1. 5.- A composition according to Claim 2 in which: R2 is m-trifluoromethyl, and R4 is 2-chloroethyl. 6.- A composition according to Claim 2 in which: R2 is m-trifluoromethyl, and R4 is -CH2NHCH2COOH. 7.- A composition according to Claim 3 in which: R2 is m-cyano, and R4 is 2-chloroethyl. 3.- A composition acccording to Ciai.ii 3 i which: is m-cyano, anc is -CH2NHCH2COOH. 9. A method of controlling ungestrable vegetation which comprisee applying to the locus where control is desired a herbicydally effective amount of a composition comprising a mixture Of: @(a) a pyrrolidone of the formula: EMI16.1 in which: ' is selected from the group consisting of hydrogen, chlorine sand methyl; # is selected from the group consisting of hydrogen, chlorine sNc bromine; # is selected from the group consisting of chlorine and bromine; ; RÚ is selected from the group consisting of hydrogen and C1-C4 alkyl Rê is selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, acetyl, trifluoromethyl, nitro, cyano, C1-C4alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, trifluorothylthio, trifluoromethylsulfinyl, trifluoromethyl sulfonyl, pentafluoropropianamido, and 3-methylureido; and R is selected from the group consisting of hydrogen, C1-C4 alkyl, chlorine and trifluoromethyl; and @(b) a phosphonic acid of the formula: EMI16.2 in which: R4 is selected from the group consisting of Ct-C4 alkyl, C1 -C4 halo alkyl and -CH2NHCH2COOH, at a weight ratio of (a) to (b) from about 0.1:1 to about 20:1. 10.- A method of controlling undesirable vegetation which comprises applying o the locus where control is desired a herbicidally effective amount cf a composition comprising a mixture of: @(a) a pyrrolidone of the formula: EMI17.1 in which: R2 is trifluoromethyl, and n(U) a phosphonic acid of the formula: EMI17.2 in which: R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 halo alkyl, and -CH2NHCH2COOH, at a weight ratio of (a) to (b) of from about 0.1:1 to about 20:1. 11.- A method of controlling undesirable vegetation which comprises applying to the locus where control is desired a herbicidally effective amount of a composition comprising a mixture of: n(a) a pyrrolidone of the formula: EMI17.3 in which: R2 is cyano, and @(b) a phosphonic acid of the formula: EMI17.4 in which: R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 halo alkyl, and -CHNHCH2COOH, at a weight ratio of (a) to (b) of from about 0.1:1 to about 20:1. 12.- A method according to Claim 10 or 11 in which the weight ratio o (a) to (b) is from about 0.1:1 to about 10:1. 13.- A method according to Claim 10 in which: R2 is m-trifluoromethyl , and R4 is 2-chloroethyl. 14.- A method according to Claim 10 in which: R2 is m-trifluoromethyl, and R4 is -CH2NHCH2COOH. 15.- A method according to Claim 11 in which: R2 is m-cyano, and R4 is 2-chloroethyl. 16.- A method according to Claim 11 in which: R2 is m-cyano, and R4 is -CH2NHCH2COOH.

Inventors: STAMP, DAVID LEE, THIELE, GERALD HERMAN
Applicants: STAUFFER CHEMICAL COMPANY
Application year: 1980
Main classification: A01N57
IPC codes: A01N57, A01N43, A01P13, A01N25