SYNERGISTIC HERBICIDAL COMPOSITIONS

Abstract: Synergistic herbicidal activity is demonstrated by com­ position comprising aa mixture of (a) a trialkylsulfonium salt of N-phosphono-methylglycine having the formula (a) a her­ bicidally effective amount of a trialkylsulfonium salt of N-­ phosphonomethylglycine having the formula in which R is C₁-C₃ alkyl and n is 0 or 1, and (b) an herbicidally effective amount of a pyrrolidone compound of the formula X′ O in which X′ is hydrogen, chlorine or methyl; Y is hydrogen, chlorine, or bromine; Z is chlorine or bromine: R¹ is hydro­ gen, alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluo­ romethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, tri­ fluoromethylsulfonyl, pentafluoropropionamido or 3-meth­ ylureido; R² is hydrogen, alkyl, chlorine or trifluoromethyl; and R³ is alkyl or hydrogen; in a pyrrolidone: N-phosphono-­ methylglycine weight ratio of from about 1:6 to about 4:1.

Description: SYNERGISTIC HERBICIDAL COMPOSITIONS Background of the Invention 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 herbicide field 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 carmercial use. In many cases, active herbicides have been shown to be mDre 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 might be expected fran a mere addition of the individual potencies of the components. The e present invention resides in the discovery that two classes of compounds already known individually for their herbicidal potency display this synergistic effect when applied in combination. Prior Art The t D classes of herbicides forming the combination which is the subject of the present invention are both knows in the art of chemical herbicides for their activity independent of each other. The N-phospbonanethylglycine salts which ccmprise one of the constituents of the herbicidal composition of the invention are disclosed in U.S. Patent 4,315,765, Large. N-phenyl pyrrolidones which comprise the other class of cDm- pounds in the compositions of the invention are disclosed in U.S. Patent 4,110,105 (Teach), issued August 29, 1978. Description of the Invention It has now been discovered that synergism in the control of undesired vegetation is exhibited by compositions comprising (a) a herbicidally effective amount of a trialkylsulfonium salt of N-phosphonomethylglyelne having the formula EMI2.1 in which R is C1-C3 alkyl and n is O or 1, and (b) an herbicidally effective amount of a pyrrolidone compound of the formula EMI2.2 in which X' is hydrogen, chlorine or methyl; Y is hydrogen, chlorine, or bromine; z is chlorine or ksxsnine; ; R1 is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio, tri flcroaraaethylsulf inyl, triflcrcrranethylsulfonyl pentafluoro propionamide or 3-methylureido; R2 is hydrogen, alkyl, chlorine or trifluoranethyl; and R3 is alkyl or hydrogen. The e term "alkyl" as used herein are intended to include both straight- and branched-chain groups. All carbcn atom ranges are intended to be inclusive of both upper and lower limits. A "herbicide", as the term is used herein, is a compound which controls or modifies the growth of plants. The term "herbicidally" effec- tive amount is used to indicate any quantity of such a compound Which is capable of producing such an effect. Controlling or modifying effects include all deviations fran natural development, for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, leaf burn, dwarfing and the like. The term "plants" is used to include germinating seeds, emerging seedlings, and established vegetation, including roots and above-ground portions. The term "synergism" is employed in its traditional sense and describes the result obtained when the herbicidal effect of a composition containing two or more active herbicidal compounds is greater than the sum of the herbicidal effects of the compounds when used alone. In the compositions of this invention, the (pyrrolidone): (N-phosphonomethylglycine salt) weight ratio lies within the following approximate limits, 1:6 to 4:1. Application rates will depend upon the weeds to be controlled and the degree of control desired. In general, the compositions of this invention are most efficiently employed at a rate of 0.01 to 50 pounds per acre (0.011 to 56 kilograms per hectare) of the active ingredients, preferably 0.1 to 25 pounds per acre (0.11 to 28 kilograms per hectare). Representative N-phosphonomethylglycine salts suitable for use in the compositions of the invention include the mono-trimethylsulfonium salt df N-phospnonomethylglycine. Preferred pyrrolidones for use in the synergistic herbicidal compositions of the invention include 1-m-trifluoromethylphenyl-3-chloro- 4-chlorcmethyl-2-pyrrolidone. Herbicidal compositions illustrative of those embodied in the instant application were prepared and evaluated for synergistic herbicidal effect. The results are shown in the following examples. EXAMPLES In the tables set forth below, the results of a series of tests are indicated which show synergistic activity between the two classes of zDounds which make up the composition of the present invention. The protocol for these tests is set forth below. Test 1 - Tables 1, 2 and 3 Test layout : randomized complete block Number of replications : 3 Plot size : 20 mR Spray equipment : knapsack sprayer Spray volume : 167 L/ha Application time : post-emergence Growth stage of weeds : Agropyron repens: quackgrass: 30-40 cm Test 2 - Table 4 Test layout : randomized complete block Number of replications : 3 Plot size : 20 mê Spray equipment : knapsack sprayer Spray volume : 167 LJha Application time : post-emergence Growth stage of weeds : Poa trivialis: blugrass: flowering Taraxacum: dandelion: pre-flowering Test 3 - Tables 5 and 6 Test layout : randomized tlete block Number of replications : 2 Plot size : 20 m2 Spray equipnent : knapsack sprayer Spray volume : 500 L/ha Application time : post-emergence Growth stage of weeds : Cyperus rotundus: purple nutsudge: pre-fiowerin Sorghum halepense: johnsongrass: boot stageg Test 4 - Table 7 Test layout : randomized complete block Number of replications : 3 Plot size : 16 m2 Spray equipment : knapsack sprayer Spray volume : 400 L/ha Application time : post-emergence forth stage of weeds : Convolvulus arvenis: field bindweed: flowering Test 5 - Table 8 Test layout : randamized complete block Number of replications : 3 Plot size : 9 m2 Spray equipment : tractor mounted CO2 sprayer Spray volume : 200 L/ha Application time : post-emergence Growth stage of weeds : Rumex crisps: curly dock: just prior to flowering Test 6 - Table 9 Test layout : randomized oonplete block Number of replications : 3 Spray equipment : tractor boon sprayer Spray volume : 21.7 gal/acre Application time : post-emergence Growth stage of weed : pre-flowering The results of these tests are listed in Tables 1-9 in the columns headed by the symbol "0" (indicating the "observed" results). These results were then compared with the expected results, shown in the columns headed by the symbol "E", derived from Limpel's formula (Limpel et al., 1962, "Weed Control by Dimethylchloroterephthalate Alone and in Certain Combinations."Proc. NEWCC, Vol. 16, pp. 48-53): XY E = X + Y - 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. A single asterisk (*) is used to indicate the tests where the results show synergism, i.e., where the observed result exceeds the expected result. In the tables below, the abbreviation "TCCP" stands for 1-m-trifluoromethylphenyl-3-chloro-4-chloromethyl-2-pyrrolidone; whereas "PMG" stands for trimethylsulfonium salt of N-phosphonomethylglycine. TABLE 1 % % Desiccation - Rumex Crispus Rate T T + 12 T + 18 T + 25 Treatment (L/ha) O E O E O E Untreated 2 2 38 55 73 3 3 23 48 90 TCCP 1 1 13 10 43 TCCP 2 2 20 20 18 TCCP 4 33 18 23 PMS + TCCP 2 + 1 38 46 70* 59 98* 85 PMG + TCCP 2 + 2 33 50 75* 64 93* 78 PMG + TCCP 2 + 4 48 58 73* 63 100* 79 PMG + TCCP 3 + 1 30 33 83* 53 99* 94 PMG + TCCP 3 + 2 55* 38 83* 58 100* 92 PMG + TCCP 3 + 4 43 48 80* 57 100* 92 *Indicates synergism. TABLE 2 Control of Poa trivialis (%) Rate T + 12 T + 18 T + 25 Treatment (L/ha) O E O E O E Untreated PMG 2 63 88 100 PMG 3 3 31 85 100 TCCP 1 5 15 70 TCCP 2 1 10 40 TCCP 4 5 15 63 PMG + TCCP 2 + 1 48 65 78 . 90 100 100 PMG + TCCP 2 + 2 63* 56 93* 89 100 100 PMG + TCCP 2 + 4 68* 65 80 90 100 100 PMG + TCCP 3 + 1 65* 34 100* 87 100 100 PMG + TCCP 3 + 2 98* 29 100* 86 100 100 PMG + TCCP 3 + 4 93* 34 100* 86 100 100 *Indicates synergism. TABLE 3 Control of Agropyron repens (%) Rate T + 12 T + 18 T + 25 Treatment (L/ha) O E O E O E Untreated PMG 2 59 70 98 PMG 3 3 44 58 90 TCCP 1 11 23 43 TCCP 2 15 20 10 TCCP 4 11 15 23 PMG + TCCP 2 + 1 33 64 60 -77 100* 99 PMG + TCCP 2 + 2 63 66 83* 76 100* 98 PMG + TCCP 2 + 4 53 64 68 74 100* 98 PMG + TCCP 3 + 1 60* 50 100* 68 100* 94 PMG + TCCP 3 + 2 98* 52 95* 66 100* 91 PMG + TCCP 3 + 4 93* 50 100* 64 100* 92 * Indicates synergism. TABLE 4 Control of Poa trivialis (8) Rate T + 12 T + 18 T + 25 Treatment (L/ha) O E O . E O E Untreated PMG 4 83 100 100 PMG 6 6 68 100 100 TCCP 3 5 50 100 TCCP 4 6 40 78 TCCP 6 5 30 73 PMG + TCCP 4 + 3 65 84 100 100 100 100 PMG + TCCP 4 + 4 80 84 100 100 100 100 PMG + TCCP 4 + 6 90* 84 100 100 100 100 PMG + TCCP 6 + 3 75* 70 100 100 100 100 PMG + TCCP 6 + 4 73* 70 100 100 100 100 PMG + TCCP 6 + 6 88* 70 100 100 100 100 T = time of application. * Indicates synergism. TABLE 5 % Desiccation -Rumex Crispus Rate T + 23 T + 30 T + 44 Treatment (L/ha) O E O E O E Untreated 4 4 50 65 95 PMG 6 6 77 80 95 TCCP 3 7 7 0 TCCP 4 4 7 7 0 TCCP 6 6 7 ? 2 PMG + 4 + 3 65* 53 80* 67 90 95 PMG + + TCCP 4 + 4 80 53 82* 67 90 95 PMG + TCCP 4 + 6 77* 53 85* 67 90 95 PMG + TCCP 6 + 3 80* 72 85* 81 90 95 PMG + TCCP 6 + 4 85* 72 90* 81 97* 95 PMG + TCCP 6 + 4 90* 72 90* 81 97* 95 * Indicates synergism. TABLE 6 Control of Sorghum halepense (%) Rate T + 11 T + 17 T + 23 Treatment (L/ha) O E O E O E Untreated Pg; 4 50 82 95 PMG 6 80 82 95 TCCP 3 3 5 5 0 TCCP 4 5 5 0 TCCP 6 5 5 0 PMG + TCCP 4 + 3 75* 52 80 83 97 95 PMG + TCCP 4 + 4 80* 52 80 83 90 95 PMG + TCCP 4 + 6 80* 52 82 83 90 95 PMG + TCCP 6 + 3 75 81 85* 83 92 95 Pg; + TCCP 6 + 4 80 81 90* 83 97* 95 PMG + TCCP 6 + 6 90* 81 90* 83 97* 95 * Indicates synergism. TABLE 7 Control of Convolvulus arvenis (8) Rate T + 7 T + 14 T + 21 T + 28 Treatment (L/ha) O E O E O E O Untreated PMG 4 11 77 87 98 Pg; 6 36 92 87 98 TCCP 3 6 35 30 51 TCCP 4 6 43 56 54 TCCP 6 9 57 65 67 PMG + TCCP 4 + 3 36* 16 92* 85 95* 91 97 99 PMG + TCCP 4 + 4 23* 16 83 87 94 94 99 99 + + TCCP 4 + 6 34* 19 93* 90 97* 95 98 99 PMG + TCCP 6 + 3 40 40 99* 95 99* 98 99 99 PMG + TCCP 6 + 4 60* 40 100* 95 100* 99 99 99 PMG + TCCP 6 + 6 60* 42 99* 97 100* 99 99 99 * Indicates synergism. TABLE 8 % Desiccation - Rumex Crispus Rate T + 23 T + 30 T + 44 Treatment (L/ha) O E O E O E Untreated - 0 0 0 PMG 4 78 78 90 Pg; 6 85 87 97 TCCP 3 45 42 37 TCCP 4 45 43 38 TCCP 6 53 50 40 PMG + TCCP 4 + 3 87 88 98* 87 100* 94 PMG + TCCP 4 + 4 82 88 96* 87 97* 94 PMG + TCCP 4 + 6 86 90 97* 89 100* 94 PMG + TCCP 6 + 3 92 92 99* 92 100* 98 PMG + TCCP 6 + 4 92 92 98* 93 100* 98 PMG + TCCP 6 + 6 97* 93 100* 93 100* 98 T = time of application * Indicates synergism. TABLE 9 Yellow Nutsedge % % % % % Desiccation Necrosis Chlorosis Necrosis Chlorosis Rate T + 5 T + 11 T + 11 T + 17 T + 17 Treatment Ib ai/ O E O E O E O E O E PMG 0.5 2 1 0 1 0 PMG 1 4 2 0 2 0 TCCP 2 18 12 0 12 0 TCCP 0.5 2 1 5 1 2 TCCP 1 4 3 10 3 3 TCCP 2 4 4 12 . 4 3 PMG + TCCP 0.5+0.5 3 4 2 2 13* 5 6* 2 15* 2 Pg; + TCCP 1 + 1 17* 8 15* 5 40* 10 15* 5 22* 3 PMG + TCCP 2 + 2 30* 21 35* 16 43* 12 47* 16 35* 3 The compositions of the present invention are useful as herbicides in controlling the growth of undesirable vegetation by postemergence application to the locus where control is desired. The compositions are generally embodied in formulations suitable for convenient application. In general, such formulations will contain inert or occasionally active ingredients or diluent carriers in addition to the active compound. Exampies of such ingredients or carriers are water, organic solvents, surface active agents, oil and water, water in oil emulsions, wetting agents, dispersing agents, and emulsifying agents. The herbicidal formulations generally take the form of wettable powders, solutions, or enwlsifiable concentrates. Wettable powders are finely divided compositions comprising a particulate carrier impregnated with the herbicidal compound and additionally containing one or more surface active agents. The e 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 and alkali metal salts of the sulfated fatty alcohols; salts of sulfonic acid; esters of longchain fatty acids; and polyhydric alcohols, in which the alcohol groups are free, atiega-substituted polyethylene glycols of relatively long chain length. A list of surface active agents suitable for use in agriculture VIY?ICJ formulations can be found in Pesticide Formulations by Wade Van Valkenburg, Marcel Deter, Inc., N.Y., 1972 at pages 79-84. The herbicidal compositions can be applied to weed surfaces in the form of a solution in a suitable solvent. Solvents frequently used in herbicidal formulations include kerosene, fuel oil, xylene, petroleum fractions with boiling ranges above xylene, and aromatic petroleum fractions rich in methylated naphthalenes. Emulsifiable concentrates consist of an oil solution of the herbicide along with an emulsifying agent. Prior to use the concentrate is diluted with water to form a suspended emulsion of soil droplets. The emulsifiers used are usually a mixture of anionic and nonionic surfactants. Other additives such as spreading agents and stickers can be included in the emulsifiable concentrate. The formulations described above, employing phytotoxic or herbicidally effective amounts of the compositions described herein, are applied to the loci where control is desired in any conventional manner. The loci referred to above include seedlings and actual plants. Liquid compositions can be applied by the use of boom and hand sprayers. The compositions can also be applied fran airplanes as sprays because they are effective in very low dosages. The compositions of the invention are applied postemergent to weed plant surfaces. The amount of a composition of the present invention which oon- stitutes a phytotoxic or herbicidally effective amount depends upon the nature of the plants to be controlled. The rate of application of active ingredient varies from about 0.01 to about 50 pounds per acre, preferably about 0.1 to about 25 pounds per acre with the actual amount used depending on the overall cost and the desired result. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosage rate for the same degree of control than more active compounds.

Claims: CLAIMS: 1. A synergistic herbicidal compositions comprising a mixture of (a) a herbicidally effective amount of a trialkylsulfonium salt of N-phosphonemethylglycine having the formula EMI12.1 in Which R is C1-C3 alkyl and n is O or 1, and (b) an herbicidally effective amount of a pyrrolidone compound of the formula EMI12.2 in which X' is hydrogen, chlorine or methyl; Y is hydrogen, chlorine, or bromine; z is chlorine or branine; R1 is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio, tri Fluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoro propionamido or 3-methylureido; R2 is hydrogen, alkyl, chlorine or trifluoromethyl; and R3 is alkyl or hydrogen; in a pyrrolidone:N-phosphonemethylglycine weight ratio of fran about 1:6 to about 4:1. 2. A synergistic herbicidal composition comprising an herbicidally effective amount of a mixture of 1-m-trifluoromethyipbenyi-3- chloro-4-chloromethyl-2-pyrrolidone and the trimethylsulfoniun salt of N-phosphonomethylglycine 3. A synergistic herbicidal composition comprising a mixture of (a) a herbicidally effective amount of a trialkylsulfonium salt of N-phDsphcncmethylglycine having the formula EMI13.1 in which R is C1-C3 alkyl and n is O or 1, and (b) an herbicidally effective amount of a pyrrolidone compound of the formula EMI13.2 in which X' is hydrogen, chlorine or methyl; Y is hydrogen, chlorine, or branine; Z is chlorine or branine; ; R1 is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoranethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio, tri fluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoro propionamido or 3emethylureido; R2 is hydrogen, alkyl, chlorine or trifluoromethyl; and R3 is alkyl or hydrogen; and (c) an inert diluent carrier; in a pyrrolidone:N-phosphonomethylglycine weight ratio of from about 1:6 to about 4:1. 4. The composition of Claim 3 wherein said pyrrolidone is 1-m-trifluoromethylphenyl-3chloro-4-chloromethyl-2-pyrrolidone and said N-phosphonomethylglycine is the ntrimethylsulfonium salt of N-phosphono methyiglycine. 5. A method of controlling undesirable vegetation Which com- prises the application to the locus desired of a synergistic herbicidal composition comprising an herbicidally effective amount of a trialkylsulfonium salt of N-phosphonomethylglycine having the formula (a) a herbicidally effective amount of a trialkylsulfonium salt of N-phosphonomethylglycine having the formula EMI14.1 in which R is C1-C3 alkyl and n is O or 1, and (b) an herbicidally effective amount of a pyrrolidone compound of the formula EMI14.2 in which X' is hydrogen, chlorine or methyl; Y is hydrogen, chlorine, or bromine; Z is chlorine or bromine; ; R1 is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyans, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio, tri fluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoro propionamido or 3-methylureido; R2 is hydrogen, alkyl, chlorine or trifluoromethyl; and R3 is alkyl or hydrogen; in a pyrrolidone: N-phosphonomethylglycine weight ratio of from about 1:6 to about 1:4. 6. The method of Clam 5 wherein said trialkylsulfonium salt of N-phosphonomethylglycine is the trimethylsulfonium salt of N-phosphono methylglycine and Wherein said pyrrolidone is 1 1-mrtrifluoromethylphenyl-3- chloro-4-chloromethyl-1-pyrrolidone.

Inventors: GROENWOLD, BARELD EGGE, PEREIRO, FERNANDO
Applicants: STAUFFER CHEMICAL COMPANY
Application year: 1985
Main classification: A01N57
IPC codes: A01N57, C07F9, A01P13, A01N37