Patent Publication Number: US-6218338-B1

Title: Herbicidal composition

Description:
This application is a 371 of PCT/JP98/00577 filed Feb. 13, 1998. 
    
    
     TECHNICAL FIELD 
     The present invention relates to a herbicidal composition, and more particularly, it relates to a herbicidal composition for foliar treatment and a weeding method by foliar treatment of weeds therewith. 
     BACKGROUND ART 
     At the present time, numerous herbicides are commercially available and they are widely used. There are, however, many species of weeds to be controlled and their growth extends over a long time. For this reason, requested are herbicides with higher herbicidal activity, wide herbicidal spectrum, and safety to crops. 
     DISCLOSURE OF INVENTION 
     The present inventor has intensively studied to find out excellent herbicides. As a result, he has found that various weeds growing in crop lands or non-crop lands can be effectively controlled by foliar treatment of these weeds with a herbicidal composition containing as active ingredients, (a) a compound of the general formula:                    
     wherein R is C 1 -C 7  alkyl, C 5 -C 6  cycloalkyl, C 2 -C 6  alkenyl, dimethylamino, or diethylamino; and 
     (b) a compound selected from the group consisting of 2-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-N, N-dimethylnicotinamide (common name, nicosulfuron; hereinafter referred to as nicosulfuron), 3-[4,6-bis(difluoromethoxy)pyrimidin-2-yl]-1-(2-methoxycarbonylphenylsulfonyl)urea (common name, primisulfuronmethyl; hereinafter referred to as primisulfuron-methyl), 1-(4,6-dimethoxypyrimidin-2-yl)-3-(3-ethylsulfonyl-2-pyridylsulfonyl)urea(common name, rimsulfuron; hereinafter referred to as rimsulfuron), methyl 5-{[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonylaminosulfonyl}-3-chloro-1-methyl-1H-pyrazole-4-carboxylate (common name, halosulfuron-methyl; hereinafter referred to as halosulfuron-methyl), N-(4-methoxy-6-methyltriazin-2-yl)aminocarbonyl-2-(3,3,3-trifluoropropyl)-benzenesulfonamide (common name, prosulfuron; hereinafter referred to as prosulfuron), methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylate (common name, thifensulfuron-methyl; hereinafter referred to as thifensulfuron-methyl), ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-benzoate (common name, chlorimuron-ethyl; hereinafter referred to as chlorimuron-ethyl), and 2-[[[[(4,6-dimethyl-2-pyrimidinyl)-amino]carbonyl]amino]sulfonyl]benzoic acid, 3-oxetanyl ester (common name, oxasulfuron; hereinafter referred to as oxasulfuron). He has further found that the herbicidal activity is synergistically increased as compared with the cases where the active ingredients are independently used, and the herbicidal composition can, therefore, be applied at a lower amount; and that the herbicidal spectrum is expanded and a wide variety of weeds can be selectively controlled, particularly in corn fields by a mixture of compound [1] and nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron-methyl, prosulfuron, or thifensulfuronmethyl, and in soybean fields by a mixture of compound [1] and thifensulfuron-methyl, chlorimuron-ethyl, or oxasulfuron, thereby completing the present invention. 
     Thus, the present invention provides a herbicidal composition for foliar treatment comprising as active ingredients, (a) a compound of general formula [1] as depicted above, and (b) a compound selected from the group consisting of nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron-methyl, prosulfuron, thifensulfuron-methyl, chlorimuron-ethyl, and oxasulfuron (hereinafter referred to as the present composition); and a weeding method by foliar treatment of weeds therewith. 
    
    
     MODE FOR CARRYING OUT THE INVENTION 
     Compound [1] can be produced by the methods as described in the following production examples. 
     PRODUCTION EXAMPLE 1 
     To a solution of 5.3 g (53.3 mmol) of sodium acetate mixed with about 100 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoroacetone, and the mixture was stirred at 70° C. for 20 minutes. The reaction mixture was cooled to room temperature, to which a solution of 5.8 g (21.5 mmol) of 2-fluoro-4-chloro-5-isopropoxyphenylhydrazine dissolved in about 20 ml of diethyl ether was added, and the mixture was stirred at room temperature for 1 hour. The ether layer was separated and then concentrated. About 60 ml of tetrahydrofuran (hereinafter referred to as THF) was added to the residue, to which 8.3 g (23.0 mmol) of (carbethoxyethylidene)triphenylphosphorane was added, and the mixture was heated under reflux for 2 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.8 g (10.5 mmol) of 2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethylpyridazin-3-one. 
     Then, 3.5 g (9.7 mmol) of 2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethylpyridazin-3-one was dissolved in about 10 ml of concentrated sulfuric acid under ice cooling, and the solution was warmed to room temperature. After ten minutes, about 100 ml of water was added to the reaction mixture. The deposited crystals were collected by filtration, and then washed twice with 20 ml of water and once with 10 ml of hexane in this order. The crystals thus obtained were recrystallized from isopropanol, which afforded 3.2 g (9.9 mmol) of 2-[2-fluoro-4-chloro-5-hydroxyphenyl]-4-methyl-5-trifluoromethylpyridazin-3-one. 
     Then, 3.2 g (9.9 mmol) of 2-[2-fluoro-4-chloro-5-hydroxyphenyl]-4-methyl-5-trifluoromethylpyridazin-3-one was dissolved in about 50 ml of N,N-dimethylformamide, to which 0.44 g (11 mmol) of sodium hydride (60 wt % oil dispersion) was added at room temperature. The mixture was left stand at room temperature for 30 minutes and then cooled with ice, to which 1.8 g (11 mmol) of ethyl bromoacetate was added. The mixture was stirred at room temperature for 1 hour, to which diethyl ether and water were added in this order to make an extraction. The organic layer was washed with 10% aqueous hydrochloric acid solution, saturated aqueous sodium hydrogencarbonate solution, and saturated aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The solvent was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 2.4 g (5.5 mmol) of ethyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate (compound [1] wherein R is ethyl; hereinafter referred to as compound A), m.p., 102.0° C. 
     PRODUCTION EXAMPLE 2 
     The same procedure as described in Production Example 1 is repeated, except that the following reaction reagents are substituted for ethyl bromoacetate. Thus, the desired ester derivatives of 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetic acid can be obtained. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                   
                 Ester 
                 Compound 
                 Physical 
               
               
                 Reaction reagent* 
                 produced* 
                 symbol 
                 property (m.p.) 
               
               
                   
               
             
            
               
                 Methyl bromoacetate 
                 Methyl ester 
                 B 
                 80.4° C. 
               
               
                 Propyl bromoacetate 
                 Propyl ester 
                 C 
                 82.9° C. 
               
               
                 Butyl bromoacetate 
                 Butyl ester 
                 D 
                 75.6° C. 
               
               
                 Pentyl chloroacetate 
                 Pentyl ester 
                 E 
               
               
                 Hexyl bromoacetate 
                 Hexyl ester 
                 F 
               
               
                 Heptyl bromoacetate 
                 Heptyl ester 
                 G 
                 63.2° C. 
               
               
                 i-Propyl bromoacetate 
                 i-Propyl ester 
                 H 
               
               
                 i-Butyl bromoacetate 
                 i-Butyl ester 
                 I 
               
               
                 t-Butyl bromoacetate 
                 t-Butyl ester 
                 J 
               
               
                 c-Pentyl bromoacetate 
                 c-Pentyl ester 
                 K 
               
               
                 c-Hexyl bromoacetate 
                 c-Hexyl ester 
                 L 
               
               
                 Allyl bromoacetate 
                 Allyl ester 
                 M 
               
               
                 Vinyl chloroacetate 
                 Vinyl ester 
                 N 
               
               
                   
               
               
                 *: “i-”, “t-”, and “c-” mean iso-, tertiary-, and cyclo-, respectively.  
               
            
           
         
       
     
       1 H-NMR (250 MHz or 300 MHz, CDCl 3 , TMS, δ (ppm)) 
     Compound E 
     0.88 (3H, t, J=7 Hz), 1.2-1.4 (4H, m), 1.55-1.70 (2H, m), 2.43 (3H, q, J=2 Hz), 4.19 (2H, t, J =7 Hz), 4.68 (2H, s), 6.98 (3H, d, J =7 Hz), 7.33 (1H, d, J =8 Hz), 7.99 (1H, s) 
     Compound H 
     1.26 (6H, d, J=6.3 Hz), 2.43 (3H, q, J=2 Hz), 4.65 (2H, s), 5.05-5.18 (1H, m), 6.98 (1H, d, J=7 Hz), 7.33 (1H, d, J=8 Hz), 7.98 (1H, s) 
     Compound I 
     10 0.90 (6H, d, J=6.6 Hz), 1.85-2.03 (1H, m), 2.42 (3H, q, J=1.8 Hz), 3.98 (2H, d, J=6.5 Hz), 4.70 (2H, s), 6.99 (1H, d, J=6.3 Hz), 7.33 (1H, d, J=9.1 Hz), 7.98 (1H, s) 
     Compound J 
     1.45-1.53 (9H, m), 2.39-2.45 (3H, m), 4.58-4.60 (2H, m), 6.96-7.00 (1H, m), 7.30-7.36 (1H, m), 7.96-8.00 (1H, m) 
     Compound K 
     1.5-1.9 (8H, m), 2.43 (3H, q, J =2 Hz), 4.65 (2H, s), 5.2-5.4 (1H, m), 6.97 (1H, d, J=7 Hz), 7.33 (1H, d, J=8 Hz), 7.98 (1H, s) 
     Compound M 
     2.42 (3H, q, J=1.9 Hz), 4.67-4.72 (2H, m), 5.23-5.37 (2H, m), 5.84-5.98 (1H, m), 7.00 (1H, d, J =6.3 Hz), 7.33 (1H, d, J=9.2 Hz), 7.99 (1H, s) 
     Compound N 
     2.42 (3H, q, J=1.8 Hz), 4.68-4.71 (1H, m), 4.77 (2H, s), 4.94-5.01 (1H, m), 7.03 (1H, d, J=6.3 Hz), 7.26-7.31 (1H, m), 7.34 (1H, d, J=9.0 Hz), 7.99 (1H, s) 
     PRODUCTION EXAMPLE 3 
     First, 1.0 g of the above compound A was dissolved in 15 ml of 1,4-dioxane, to which 15 ml of concentrated hydrochloric acid was added. This solution was warmed to 60° C., stirred for 6 hours, and then extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The solvent was distilled out under reduced pressure. The residue was dissolved in 5 g of thionyl chloride, heated under reflux for 1 hour, and then concentrated under reduced pressure. The residue was dissolved in 20 ml of THF at room temperature, to which 0.65 g of N,N-diethylhydroxylamine was added dropwise, and the mixture was then concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, which afforded 1.1 g of O-[2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetyl]-N,N-diethylhydroxylamine (compound [1] wherein R is diethylamino; hereinafter referred to as compound 0). 
       1 H-NMR (250 MHz, CDCl 3 , TMS, δ (ppm)) 1.10 (6H, t, J=7.1 Hz), 2.42 (3H, , J=1.9 Hz), 2.94 (4H, q, J=7.1 Hz), 4.74 (2H, s), 7.01 (1H, d, J=6.3 Hz), 7.33 (1H, , J=9.1 Hz), 7.97 (1H, s) 
     PRODUCTION EXAMPLE 4 
     The same procedure described in Production Example 3 is repeated, except that N,N-dimethylhydroxylamine is substituted for N,N-diethylhydroxylamine. Thus O-[2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetyl]-N,N-dimethylhydroxylamine (compound [1] wherein R is dimethylamino; hereinafter referred to as compound P) can be obtained. 
     Nicosulfuron, primisulfuron-methyl, halosulfuron-methyl, thifensulfuronmethyl, and chlorimuron-ethyl are compounds as described in Farm Chemicals Handbook, 1995 (published by Meister, Publishing Co., 1995), at pages C266, C45, C286, C293, and C91, respectively. 
     Rimsulfuron is a compound as described in AG CHEM NEW COMPOUND REVIEW, VOLUME 10, 1992 (published by AG CHEM INFORMATION SERVICES, 1992), page 51. 
     Prosulfuron is a compound as described in AG CHEM NEW COMPOUND REVIEW, VOLUME 13, 1995 (published by AG CHEM INFORMATION SERVICES, 1995), page 23. 
     Oxasulfuron is a compound as described in AG CHEM NEW COMPOUND REVIEW, VOLUME 15, 1997 (published by AG CHEM INFORMATION SERVICES, 1997), page 38. 
     The present invention provides a herbicidal composition that is effective for control of a wide variety of weeds with crop selectivity and for application to a new cultivation method such as non-tillage cultivation. In particular, the herbicidal composition of the present invention effectively controls the main weeds in corn fields and/or in soybean fields, e.g., dicotyledonous plants such as wild buckwheat ( Polygonum convolvulus ), pale smartweed ( Polygonum lapathifolium ), pennsylvania smartweed ( Polygonum pensylvanicum ), common purslane ( Portulaca oleracea ), common lambsquarters ( Chenopodium album ), redroot pigweed ( Amaranthus retroflexus ), wild mustard ( Sinapis arvensis ), hemp sesbania ( Sesbania exaltata ), sicklepod ( Cassia obtusifolia ), velvetleaf ( Abutilon theophrasti ), prickly sida ( Sida spinosa ), ivyleaf morningglory ( Ipomoea hederacea ), tall morningglory ( Ipomoea purpurea ), entireleaf morningglory ( Ipomoea hederacea  var.  integriuscula ), jimsonweed ( Datura stramonium ), black nightshade ( Solanum nigrum ), common cocklebur ( Xanthium strumarium ), common sunflower ( Helianthus annuus ), field bindweed ( Convolvulus arvensis ), sun spurge ( Euphorbia helioscopia ), devils beggarticks ( Bidens frondosa ), and common ragweed ( Ambrosia artemisiifolia ); and monocotyledonous plants such as barnyardgrass ( Echinochloa crus - galli ), green foxtail ( Setaria viridis ), giant foxtail ( Setaria faberi ), yellow foxtail ( Setaria glauca ), southern crabgrass ( Digitaria ciliaris ), goosegrass ( Eleusine indica ), johnsongrass ( Sorghum halepense ), quackgrass ( Agropyron repens ), and shattercane ( Sorghum bicolor ), while it exhibits no significant phytotoxicity on crops such as corn and/or soybean. 
     In the present composition, the mixing ratio of component (a) to component (b), although it may vary with the species of weeds to be controlled, situation and conditions of application, and other factors, is usually in the range of 1:0.2 to 20 by weight. 
     The present composition may be usually used in the form of formulations such as emulsifiable concentrates, wettable powders, or flowables, which can be prepared by mixing the composition with solid carriers, liquid carriers, or other bulking agents, and if necessary, adding surfactants or other adjuvants to this mixture. In such a formulation, component (a) and component (b) are usually contained at the total amount of 0.5 to 90 wt %, preferably 1 to 80 wt %. 
     The solid carrier to be used in the formulation may include, for example, the following materials in fine powder or granule form: clays (e.g., kaolinite, diatomaceous earth, synthetic hydrated silicon oxide, Fubasami clay, bentonite, acid clay); talc and other inorganic minerals (e.g., sericite, powdered quartz, powdered sulfur, activated carbon, calcium carbonate); and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride, urea). The liquid carrier may include, for example, water; alcohols (e.g., methanol, ethanol); ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone); aromatic hydrocarbons (e.g., toluene, xylene, ethylbenzene, methylnaphthalene); non-aromatic hydrocarbons (e.g., hexane, cyclohexane, kerosine); esters (e.g., ethyl acetate, butyl acetate); nitriles (e.g., acetonitrile, isobutyronitrile); ethers (e.g., dioxane, diisopropyl ether); acid amides (e.g., dimethylformamide, dimethylacetamide); and halogenated hydrocarbons (e.g., dichloroethane, trichloroethylene). 
     The surfactant may include, for example, alkylsulfate esters; alkylsulfonate salts; alkylarylsulfonate salts; alkyl aryl ethers and their polyoxyethylene derivatives; polyethylene glycol ethers; polyhydric alcohol esters; and sugar alcohol derivatives. 
     The other adjuvants may include, for example, adhesive agents and dispersing agents, such as casein, gelatin, polysaccharides (e.g., powdered starch, gum arabic, cellulose derivatives, alginic acid), lignin derivatives, bentonite, and, synthetic water-soluble polymers (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid); and stabilizers such as PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-/3-tert-butyl-4-methyoxyphenol), vegetable oils, mineral oils, fatty acids, and fatty acid esters. 
     The present composition can also be prepared by making the active ingredients into the respective formulations using the above formulation technique and then mixing these formulations. 
     The present composition thus formulated may be applied to plants as such, or after diluted with water or other solvents. The present composition may also be used in admixture with other herbicides, in which case the herbicidal activity can be expected to be enhanced. The present composition can also be used together with insecticides, bactericides, fungicides, plant growth regulators, fertilizers, soil conditioners, or other agents. 
     The application amount of the present composition, although it may vary with the mixing ratio of component (a) to component (b) as the active ingredient compounds, weather conditions, formulation types, application times, application methods, application places, weeds to be controlled, and crops to be protected, is usually in the range of 5 to 500 g as the total amount of active ingredient compounds per hectare. In the case of emulsifiable concentrates, wettable powders, flowables, or other similar formulations, they are usually applied after diluted in their prescribed amounts with water at a ratio of 100 to 1000 liters per hectare. 
     The following will describe formulation examples, in which parts are by weight. 
     FORMULATION EXAMPLE 1 
     Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, 0, or P, 40 parts of nicosulfuron, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 35 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 2 
     Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 40 parts of primisulfuron-methyl, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 35 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 3 
     Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, parts of rimsulfuron, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 55 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 4 
     Fifteen parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 50 parts of halosulfuron-methyl, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 30 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 5 
     Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 5 parts of thifensulfuron-methyl, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 70 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 6 
     Forty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 10 parts of thifensulfuron-methyl, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 45 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 7 
     Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 20 parts of prosulfuron, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 55 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 8 
     Thirty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 30 parts of prosulfuron, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 35 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 9 
     Ten parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 20 parts of nicosulfuron, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 64 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 10 
     Ten parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 20 parts of primisulfuron-methyl, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 64 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 11 
     Ten parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 10 parts of rimsulfuron, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 74 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 12 
     Five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 18 parts of halosulfuron-methyl, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 71 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 13 
     Ten parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 2.5 parts of thifensulfuron-methyl, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 81.5 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 14 
     Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 20 parts of prosulfuron, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 54 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 15 
     Two and a half parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 2.5 parts of prosulfuron, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 89 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 16 
     Ten parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 5 parts of chlorimuron-ethyl, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 80 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 17 
     Thirty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 15 parts of chlorimuron-ethyl, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 50 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 18 
     Ten parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 2.5 parts of thifensulfuron-methyl, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 82.5 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 19 
     Ten parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 5 parts of chlorimuron-ethyl, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 79 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 20 
     Five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 2.5 parts of chlorimuron-ethyl, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 86.5 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 21 
     Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, parts of thifensulfuron-methyl, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 69 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 22 
     Thirty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 7.5 parts of thifensulfuron-methyl, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 56.5 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     FORMULATION EXAMPLE 23 
     Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 40 parts of oxasulfuron, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurylsulfate, and 35 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound. 
     FORMULATION EXAMPLE 24 
     Ten parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 20 parts of oxasulfuron, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose), and 64 parts of water are mixed and wet pulverized until the particle size comes to 5 microns or smaller to give a flowable for each compound. 
     The following will describe test examples. 
     Evaluation Criteria The herbicidal activity is evaluated at 11 levels with indices of 0 to 10, i.e., shown by numeral “0”, “1”, “2”, “3”, “4”, “5”, “6”, “7”, “8”, “9”, or “10”, wherein “0” means that there was no or little difference in the degree of germination or growth between the treated plants and the untreated plants at the time of examination, and “10” means that the test plants died completely or their germination or growth was completely inhibited. The herbicidal activity is excellent when ranked at “7”, “8”, “9”, or “10”, but insufficient when ranked at “6” or lower. The phytotoxicity is shown by “no injury” when no significant phytotoxicity was observed; “low” when low phytotoxicity was observed; “moderate” when moderate phytotoxicity was observed; or “high” when high phytotoxicity was observed. 
     TEST EXAMPLE 1 
     Cylindrical plastic pots each having a diameter of 14 cm and a depth of 12.5 cm were filled with upland soil, and then seeded with corn ( Zea mays ), morningglories (Ipomoea spp.), and velvetleaf ( Abutilon theophrasti ). These test plants were grown in a greenhouse for 24 days. 
     A flowable of compound A, which had been obtained by mixing 10 parts of compound A, 2 parts of a mixture of polyoxyethylene alkylarylphosphate and polyoxyethylene alkyl aryl ether, and 25 parts of water, pulverizing the mixture by wet grinding method so that the particle size came to 5 microns or smaller, adding 11 parts of a thickening agent (xanthan gum and smectite clay) and an antifreezing agent (propylene glycol) to the pulverized mixture, and further adding water so that the total amount came to 100 parts, and a mixture of the flowable of compound A and the formulation product of nicosulfuron (trade name, Accent; Du Pont Co.) were independently diluted in their prescribed amounts with water. Each dilution was uniformly sprayed over the est plants with a small sprayer. Before and after the herbicidal treatment, the inside of he greenhouse was kept under the excess humidity conditions such that the phytooxicity on corn was easily caused. After the application, the test plants were grown in the greenhouse, and the herbicidal activity and safety to corn were then examined. 
     The results are shown in Table 2. The number of days shows how many days it was after the herbicidal treatment. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 2 
               
             
            
               
                   
                   
               
               
                   
                 Herbicidal activity 
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 morning- 
                   
                 Phytotoxicity 
               
               
                   
                 Dosage 
                 glories 
                 velvetleaf 
                 corn 
               
            
           
           
               
               
               
               
               
               
            
               
                 Compound 
                 (g/ha) 
                 14 days 
                 14 days 
                 7 days 
                 14 days 
               
               
                   
               
               
                 Compound A 
                 20 
                 10 
                 10 
                 low 
                 no injury 
               
               
                 Compound A + 
                 20 + 20 
                 10 
                 10 
                 no injury 
                 no injury 
               
               
                 nicosulfuron 
               
               
                   
               
            
           
         
       
     
     TEST EXAMPLE 2 
     Plastic pots each having an area of 26.5×19 cm 2  and a depth of 7 cm were filled with upland soil, and then seeded with corn ( Zea mays ), giant foxtail ( Setaria faberi ), and southern crabgrass ( Digitaria ciliaris ). These test plants were grown in a greenhouse: corn for 16 days, and giant foxtail and southern crabgrass for 23 days. 
     An emulsifiable concentrate of compound E, which had been obtained by well mixing 10 parts of compound E, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 35 parts of cyclohexanone, a formulation product of nicosulfuron as described above, and a mixture of the emulsifiable concentrate of compound E and the formulation product of nicosulfuron were independently diluted in their prescribed amounts with water. Each dilution was uniformly sprayed over the test plants with a small sprayer. The same procedure was repeated for compound 0. After the application, the test plants were grown in the greenhouse for 4 days, and the herbicidal activity and safety to corn were then examined. The results are shown in Table 3. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 3 
               
             
            
               
                   
                   
               
               
                   
                 Herbicidal activity 
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Dosage 
                 southern 
                   
                 Phytotoxicity 
               
               
                 Compound 
                 (g/ha) 
                 crabgrass 
                 giant foxtail 
                 corn 
               
               
                   
               
               
                 Compound E 
                 20 
                 3 
                 4 
                 no injury 
               
               
                 Compound O 
                 20 
                 3 
                 4 
                 no injury 
               
               
                 Nicosulfuron 
                 20 
                 1 
                 1 
                 no injury 
               
               
                 Compound E + 
                 20 + 20 
                 8 
                 9 
                 no injury 
               
               
                 nicosulfuron 
               
               
                 Compound O + 
                 20 + 20 
                 8 
                 9 
                 no injury 
               
               
                 nicosulfuron 
               
               
                   
               
            
           
         
       
     
     TEST EXAMPLE 3 
     Plastic pots each having an area of 26.5×19 cm 2  and a depth of 7 cm were filled with upland soil, and then seeded with soybean ( Glycine max ), giant foxtail ( Setaria faberi ), and southern crabgrass (Digitaria ciliaris). These test plants were grown in a greenhouse for 23 days. 
     An emulsifiable concentrate of compound A, which had been obtained by well mixing 10 parts of compound A, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 35 parts of cyclohexanone, a formulation product of chlorimuron-ethyl (trade name, Classic; Du Pont Co.), and a mixture of the emulsifiable concentrate of compound A and the formulation product of chlorimuron-ethyl were independently diluted in their prescribed amounts with water. Each dilution was uniformly sprayed over the test plants with a small sprayer. The same procedure was repeated for compounds E and O. After the application, the test plants were grown in the greenhouse for 4 days, and the herbicidal activity and safety to soybean were then examined. The results are shown in Table 4. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 4 
               
             
            
               
                   
                   
               
               
                   
                 Herbicidal activity 
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Dosage 
                 southern 
                   
                 Phytotoxicity 
               
               
                 Compound 
                 (g/ha) 
                 crabgrass 
                 giant foxtail 
                 soybean 
               
               
                   
               
               
                 Compound A 
                 20 
                 3 
                 4 
                 no injury 
               
               
                 Compound E 
                 20 
                 3 
                 4 
                 no injury 
               
               
                 Compound O 
                 20 
                 3 
                 4 
                 no injury 
               
               
                 Chlorimuron- 
                 20 
                 0 
                 0 
                 no injury 
               
               
                 ethyl 
               
               
                 Compound A + 
                 20 + 20 
                 7 
                 7 
                 no injury 
               
               
                 chlorimuron- 
               
               
                 ethyl 
               
               
                 Compound E + 
                 20 + 20 
                 7 
                 7 
                 no injury 
               
               
                 chlorimuron- 
               
               
                 ethyl 
               
               
                 Compound O + 
                 20 + 20 
                 7 
                 7 
                 no injury 
               
               
                 chlorimuron- 
               
               
                 ethyl 
               
               
                   
               
            
           
         
       
     
     TEST EXAMPLE 4 
     Plastic pots each having an area of 26.5×19 cm 2  and a depth of 7 cm were filled with upland soil, and then seeded with corn ( Zea mays ), giant foxtail ( Setaria faberi ), southern crabgrass ( Digitaria ciliaris ), and barnyardgrass ( Echinochloa crus - galli ). These test plants were grown in a greenhouse for 23 days. 
     An emulsifiable concentrate of compound A, which had been obtained by well mixing 10 parts of compound A, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 35 parts of cyclohexanone, a formulation product of primisulfuron-methyl (trade name, Beacon; Ciba-Geigy Ltd.), a formulation product of thifensulfuron-methyl (trade name, Pinnacle; Du Pont Co.), a mixture of the emulsifiable concentrate of compound A and the formulation product of primisulfuron-methyl, and a mixture of the emulsifiable concentrate of compound A and the formulation product of thifensulfuron-methyl were independently diluted in their prescribed amounts with water. Each dilution was uniformly sprayed over the test plants with a small sprayer. After the application, the test plants were grown in the greenhouse for 5 days, and the herbicidal activity and safety to corn were then examined. The results are shown in Table 5. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 5 
               
             
            
               
                   
                   
               
               
                   
                 Herbicidal activity 
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Dosage 
                 giant 
                 southern 
                 barn- 
                 Phytotoxicity 
               
               
                 Compound 
                 (g/ha) 
                 foxtail 
                 crabgrass 
                 yardgrass 
                 corn 
               
               
                   
               
               
                 Compound A 
                 20 
                 4 
                 4 
                 6 
                 no injury 
               
               
                 Primisulfuron- 
                 40 
                 1 
                 1 
                 1 
                 no injury 
               
               
                 methyl 
               
               
                 Thifensulfuron- 
                 10 
                 0 
                 0 
                 0 
                 no injury 
               
               
                 methyl 
               
               
                 Compound A + 
                 20 + 40 
                 8 
                 8 
                 8 
                 no injury 
               
               
                 primisulfuron- 
               
               
                 methyl 
               
               
                 Compound A + 
                 20 + 10 
                 7 
                 7 
                 8 
                 no injury 
               
               
                 thifensulfuron- 
               
               
                 methyl 
               
               
                   
               
            
           
         
       
     
     TEST EXAMPLE 5 
     Plastic pots each having an area of 26.5×19 cm 2  and a depth of 7 cm were filled with upland soil, and then seeded with soybean (Glycine max), giant foxtail ( Setaria faberi ), southern crabgrass ( Digitaria ciliaris ), and barnyardgrass ( Echinochloa crus - galli ). These test plants were grown in a greenhouse for 23 days. 
     An emulsifiable concentrate of compound A, which had been obtained by well mixing 10 parts of compound A, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 35 parts of cyclohexanone, a formulation product of thifensulfuron-methyl (trade name, Pinnacle; Du Pont Co.), and a mixture of the emulsifiable concentrate of compound A and the formulation product of thifensulfuron-methyl were independently diluted in their prescribed amounts with water. Each dilution was uniformly sprayed over the test plants with a small sprayer. After the application, the test plants were grown in the greenhouse for 5 days, and the herbicidal activity and safety to soybean were then examined. The results are shown in Table 6. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 6 
               
             
            
               
                   
                   
               
               
                   
                 Herbicidal activity 
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Dosage 
                 giant 
                 southern 
                 barn- 
                 Phytotoxicity 
               
               
                 Compound 
                 (g/ha) 
                 foxtail 
                 crabgrass 
                 yardgrass 
                 soybean 
               
               
                   
               
               
                 Compound A 
                 20 
                 4 
                 4 
                 6 
                 no injury 
               
               
                 Thifensulfuron- 
                 10 
                 0 
                 0 
                 0 
                 no injury 
               
               
                 methyl 
               
               
                 Compound A + 
                 20 + 10 
                 7 
                 7 
                 8 
                 no injury 
               
               
                 thifensulfuron- 
               
               
                 methyl 
               
               
                   
               
            
           
         
       
     
     INDUSTRIAL APPLICABILITY 
     A wide variety of weeds in upland fields, particularly in corn fields and in soybean fields, can be effectively controlled by the present composition.