Patent Publication Number: US-4650512-A

Title: Oxazolidone herbicides and methods of use

Description:
BACKGROUND OF THE INVENTION 
     The present invention relates to certain oxazolidinone compounds which are particularly useful as pre-emergent herbicides against annual and perennial grasses and broadleaf weed pests. 
     Herbicides are widely used by farmers, commercial agricultural companies, and other such industries in order to increase crop yields for such staple crops as corn, soybeans, rice, and the like, and to eliminate weed growth along highways, railroad rights-of-way, and other areas. Herbicides are effective in killing or controlling unwanted weeds which compete for soil nutrients with the crop plants, and by reason of the fact that kill weeds, are responsible for improving the aesthetic appearance of highway and railroad rights-of way. 
     There are a number of different types of herbicides presently sold commercially, and these fall into two general categories. The categories are pre-emergence and post-emergence herbicides. The pre-emergence herbicides are normally incorporated into or applied to the soil prior to the emergence of the plants from the soil, and the post-emergence herbicides are generally applied to plant surfaces after emergence of the weeds or other unwanted plants from the soil. 
     THE PRIOR ART 
     There are a number of prior art references in the literature relating to oxazolidinone and/or oxazolidine compounds. None of these references, however, disclose oxazolidinone compounds of the type herein described to be effective herbicides. 
     DESCRIPTION OF THE INVENTION 
     It has now been discovered that certain new and novel oxazolidinone compounds have good herbicidal and plant growth regulating activity, particularly when applied as pre-emergent herbicides and used against annual and perennial grasses and broadleaf weeds. 
     As used herein, the term &#34;herbicide&#34; means a compound or composition which controls or modifies the growth of plants. By the term &#34;herbicidally effective amount&#34; is meant any amount of such compound or composition which causes a modifying effect upon the growth of plants. By &#34;plants&#34; is meant germinant seeds, emerging seedlings and established vegetation, including roots and above-ground portions. Such controlling or modifying effects include all deviations from natural development, such as killing, retardation, defoliation, desiccation, regulation, stunting, tillering, leaf burn, dwarfing and the like. 
     The new and novel compounds of this invention are substituted oxazolidinone compounds. 
     Of these compounds, certain ones are preferred. The preferred compounds have the formula ##STR2## wherein Ar 1  and Ar 2  are the same or different and are aromatic or a substituted aromatic group wherein the substituent is selected from chlorine, bromine, chloride or trifluoromethyl, and R is lower alkyl having from 1 to 6 carbon atoms. 
     Representative compounds falling within the scope of the formula as set forth above include: 
     2-phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone; 
     2-phenyl-3-(3-trifluoromethyl)phenyl-5-phenyl-4-oxazolidinone; 
     2-(3-trifluoromethyl)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone; 
     2-(4-chloro)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone; 
     2-(2-chloro)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone; 
     2-[3-(3-trifluoromethyl)phenoxy]phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone; 
     2-(3-chloro)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone; 
     2-(3-methyl)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone; 
     2-(3-bromo)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone; 
     2-(3-bromo)phenyl-3-(4-chloro)phenyl-5-ethyl-4-oxazolidinone; 
     2-(3-chloro)phenyl-3-(4-chloro)phenyl-5-ethyl-4-oxazolidinone; 
     2-(3-trifluoromethyl)phenyl-3-(4-chloro)phenyl-5-ethyl-4-oxazolidinone; 
     2-(3-chloro)phenyl-3-(3-trifluoromethyl)phenyl-5-butyl oxazolidinone; 
     2,3-di-(3-trifluoromethyl)phenyl-5-butyl oxazolidinone; 
     2-(3-bromo)phenyl-3-(3-trifluoromethyl)phenyl-5-propyl oxazolidinone; 
     2-(3-chloro)phenyl-3-(3-trifluoromethyl)phenyl-5-propyl oxazolidinone; 
     2,3-di-(3-trifluoromethyl)phenyl-5-propyl oxazolidinone; and 
     2-(3-bromo)phenyl-3-(3-trifluoromethyl)phenyl-5-butyl oxazolidinone. 
     The most preferred compound for use in the practice of the invention is (2)-(3-trifluoromethyl)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone. 
     The preferred compound, as set forth above, has been found to have especially good herbicidal activity against perennial and annual grasses when applied as a pre-emergent herbicide. It is also effective as a post-emergent herbicide and plant growth regulator, but not to the same extent as when applied preemergent. 
    
    
     Examples 1 and 2 below illustrate various methods of making intermediates used to make the compounds of the invention. 
     EXAMPLE 1 
     Preparation of N-(3-Trifluoromethyl)phenyl-2-bromobutyramide 
     Thirty-seven grams (37 g) m-aminobenzotrifluoride (0.23 mole) was dissolved in 200 milliliters (ml) of methylene chloride and combined at 0° C. with 40 g of 50% aqueous sodium hydroxide (0.5 mole) in 200 ml ice water. Cooling at 0° C. and vigorous stirring were maintained while 46.3 g of 2-bromobutyryl chloride (0.25 mole) was added dropwise to the mixture. Upon completion of the chloride addition, the reagents were allowed to stir one hour without cooling and then phase separated. The organics were washed with 500 ml water, separated, dried over MgSO 4  and stripped to yield 87.4% technical product. 
     EXAMPLE 2 
     Preparation of N-(4-chloro)phenyl-2-hydroxy butyramide 
     Twenty grams of N-(4-chloro)phenyl-2-bromobutyramide (0.0645 mole) was combined with 20 ml of toluene. Twenty ml of water, 18 g of sodium formate (0.265 mole), 2 g of tetrabutylphosphonium bromide (phase transfer catalyst) and the mixture was heated to reflux with vigorous stirring. A check by nuclear magnetic resonance (NMR) indicated 50% ester/50% alcohol. Three ml of 50% aqueous sodium hydroxide was added which brought the mixture to pH 13. The mixture was refluxed an additional 5 hours, cooled, extracted with ether, washed with water, dried over MgSO 4  and stripped to yield 94% white solids. 
     EXAMPLE 3 
     Preparation of 2-(3-trifluoromethyl)phenyl-3-(4-chloro)phenyl-5-ethyl-4-oxazolidinone 
     3-(Trifluoromethyl)benzaldehyde dimethyl acetyl (1.98 g, 0.009 mole), 20 ml of toluene, 1.92 g N-(4-chloro)-phenyl-2-hydroxybutyramide (0.009 mole) and 1/8 ml of borontrifluoride etherate were combined and methanol/toluene were azeotroped off at 65° C. The reaction mixture was diluted with 100 ml of ether and washed with 100 ml 1M sodium bicarbonate, separated, dried over MgSO 4  and stripped to yield 81.1% technical product. 
     EXAMPLE 4 
     Preparation of 2-(3-Trifluoromethyl)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone 
     3-(Trifluoromethyl)benzaldehyde dimethyl acetal (2.8 g, 0.0127 mole), 30 ml of toluene, 3.14 g of N-(3-trifluoromethyl)phenyl-2-hydroxybutyramide (0.0127 mole) and 1/8 ml of borontrifluoride etherate were combined and methanol/toluene azeotroped off at 65° C. The reaction mixture was diluted with 100 ml of ether and washed with 100 ml of 1M sodium bicarbonate, separated, dried over MgSO 4  and stripped to yield 81.9% product. 
     EXAMPLE 5 
     Preparation of 2,3-di(trifluoromethyl)phenyl-5-butyl-4-oxazolidinone 
     3-Trifluoromethylbenzaldehyde dimethyl acetal (2.41 g, 0.011 mole), 30 ml of toluene, 3.3 g N-3-(trifluoromethyl)phenyl-2-hydroxyhexanamide (91% purity) (0.012 mole) and 1/8 ml of borontrifluoride etherate were combined and methanol/toluene azeotroped off at 65° C. Reaction mixture with 100 ml of 1M sodium bicarbonate, separated, dried over MgSO 4  and stripped to yield 78.7% product. 
     The herbicidal activity of representative ones of the compounds of the invention is exhibited by means of tests in accordance with the procedure set forth in Example 6 below. 
     EXAMPLE 6 
     Herbicidal Activity Tests 
     This example offers herbicidal activity test data to show the effectiveness of the oxazolidinone compounds of the invention. The effect is observed by comparing the extent of weed control in test flats treated with the compounds against that occurring in similar control flats. The soil used in these tests was a sandy loam soil from the Livermore, Calif. area. 
     Also added to the soil was 17-17-17 fertilizer (N--P 2  O 5  K 2  O on a weight basis), amounting to 50 ppm by weight with respect to the soil and 100 ppm Captan, a soil fungicide. 
     The treated soil was then placed in flats which were 3 inches deep, 6 inches wide, and 10 inches long. The soil was tamped and leveled with a row marker to impress six rows across the width of the flat. The test weeds were as follows: 
     
         ______________________________________                                    
COMMON NAME     SCIENTIFIC NAME ABR                                       
______________________________________                                    
Broadleaf Weeds:                                                          
annual morningglory                                                       
                Ipomoea purpurea                                          
                                AMG                                       
hemp sesbania   Sesbania exaltata                                         
                                SESB                                      
velvetleaf      Abutilon theophrasti                                      
                                VL                                        
mustard         Brassica sp.    MD                                        
Grasses:                                                                  
yellow nutsedge Cyperus exculentus                                        
                                YNS                                       
foxtail         Setaria sp.     FT                                        
watergrass      Echinochloa crusgalli                                     
                                WG                                        
wild oat        Avena fatua     WO                                        
curly dock      Rumex crispus   CD                                        
______________________________________                                    
 
    
     Crop plants were also planted at the same time. These were as follows: 
     
         ______________________________________                                    
CROP PLANTS    SCIENTIFIC NAME                                            
                              ABR                                         
______________________________________                                    
rice           Oryzae sativa  RC                                          
______________________________________                                    
 
    
     Sufficient seeds were planted to produce several seedlings per inch in each row. The flats were then placed in a greenhouse maintained at 70° to 85° F. (21° to 30° C.) and watered daily by sprinkler. 
     In the case of pre-emergent testing the herbicide was incorporated into the soil prior to planting of the seeds, at a rate equivalent to the indicated amounts in the Table. 
     In post-emergent testing chemical application is made by spraying 12 days after planting. The spray solution is prepared by dissolving 60 mg of herbicide compound in 20 ml of acetone containing 1% Tween®20 (polyoxysorbitan monolaurate), then adding 20 ml of water to the resulting solution. The solution is sprayed at 80 gallon/acre, resulting in a 4 lb/acre rate of chemical application. Other rates were achieved by varying the solution concentration and/or the rate of spray. 
     In both instances, either pre- or post-emergent testing, approximately 12-14 days after treatment, the degree of weed control was estimated and recorded as percentage control compared to the growth of the same species in an untreated check flat of the same age. The rating scale ranges from 0 to 100%, where 0 equals no effect with plant growth equal to the untreated control, and 100 equals complete kill. 
     The results are listed in the Tables below. 
     
                                           TABLE I                                 
__________________________________________________________________________
HERBICIDE TEST RESULTS                                                    
Cmpd.                                                                     
    Application Percent Control                                           
No. Rate (lb/A)                                                           
           Method                                                         
                FT WG WO AMG VL MD CD YNS                                 
                                         AVG                              
__________________________________________________________________________
1   4.00   PRE  100                                                       
                   10 25 0   0   0 0  0  45                               
    4.00   POST  0 0  0  20  60 60 30 0  0                                
2   4.00   PRE   0 0  0  0   0   0 0  0  0                                
    4.00   POST  0 0  0  0   20 60 0  0  0                                
3   4.00   PRE  100                                                       
                   70 65 0   98 100                                       
                                   65 0  78                               
    4.00   POST.                                                          
                70 40 40 90  90 80 40 25 50                               
4   4.00   PRE.  0 0  0  0   0   0 0  0  0                                
    4.00   POST.                                                          
                 0 0  0  25  70 70 15 0  0                                
5   4.00   PRE.  0 0  0  0   0   0 0  0  0                                
    4.00   POST.                                                          
                 0 0  0  15  10 40 0  0  0                                
6   4.00   PRE.  0 0  0  0   0   0 0  0  0                                
    4.00   POST.                                                          
                 0 0  0  0   0   0 0  0  0                                
7   4.00   PRE. 65 0  0  0   0   0 0  0  22                               
    4.00   POST.                                                          
                10 15 0  30  30 75 30 0  8                                
8   4.00   PRE. 45 0  0  0   0   0 0  0  15                               
    4.00   POST.                                                          
                 0 0  0  20  30 45 0  0  0                                
9   4.00   PRE. 100                                                       
                   0  0  0   0   0 0  0  33                               
    4.00   POST.                                                          
                10 0  15 30  60 70 20 0  8                                
10  4.00   PRE.  0 0  0  0   0   0 0  0  0                                
    4.00   POST.                                                          
                 0 0  0  0   0   0 0  0  0                                
11  4.00   PRE.  0 0  0  0   0   0 0  0  0                                
    4.00   POST.                                                          
                 0 0  0  0   0   0 0  0  0                                
12  4.00   PRE.  0 0  0  0   0   0 0  0  0                                
    4.00   POST.                                                          
                 0 0  0  0   0   0 0  0  0                                
1. 2-phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone           
2. 2-phenyl-3-(3-trifluoromethyl)phenyl-5-phenyl-4-oxazolidinone          
3. 2-(3-trifluoromethyl)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazo
   lidinone;                                                              
4. 2-(4-chloro)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone 
   4                                                                      
5. 2-(2-chloro)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone 
   .                                                                      
6. 2-[3-(3-trifluoromethyl)phenoxy]phenyl-3-(3-trifluoromethyl)phenyl-5-et
   hyl-4-oxazolidone                                                      
7. 2-(3-chloro)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone 
8. 2-(3-methyl)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone 
9. 2-(3-bromo)phenyl-3-(3-trifluoromethyl)phenyl-5-ethyl-4-oxazolidinone  
10.                                                                       
   2-(3-bromo)phenyl-3-(4-chloro)phenyl-5-ethyl-4-oxazolidinone           
   2-(3-chloro)phenyl-3-(4-chloro)phenyl-5-ethyl-4-oxazolidinone          
   2-(3-trifluoromethyl)phenyl-3-(4-chloro)phenyl-5-ethyl-4-oxazolidinone 
__________________________________________________________________________
 
    
     EXAMPLE 7 
     A postflood-postemergence test was performed in a simulated rice paddy as follows: 
     Plastic tubs measuring 10×7.5×5.75 inches (25.4×19.0×14.6 centimeters (cm)) were filled to a depth of 2 inches (5.1 cm) with 8 pounds (3.6 kilograms (kg)) of a loamy sand soil, containing 100 parts per million (ppm) of cis-N[(trichloromethyl)thio]-4-cyclohexene-1,2-dicarboximide (a commercial fungicide designated as Captan®) and 200 ppm of 18-18-18 fertilizer (containing 18% N, 18% P 2  O 5 , and 18% K 2  on a weight basis). One One pint (0.47 liter) of the soil was removed, the remaining soil was leveled and seven rows were impressed across the width of the flat. Yellow nutsedge tubers (Cyperus esculentus) (YNS), and seeds of annual morning glory (Ipomoea purpurea) (AMG), sesbania (Sesbania sp.) (SESB), and rice (Oryza sativa) (RC) were planted in separate rows. The pint of soil was then used to place a 0.5 inch (1.27 cm) layer over the seeds and tubers. The planted soil was placed in a greenhouse, and irrigated by sprinkling as needed to keep the soil moist. One to three days after the initial seeding another row was impressed 0.5 inches (1.27 cm) deep across the width of the flat and seeds of watergrass (Echinochloa crusgalli) (WG) were planted and covered by pinching together with the soil on either side of the seeder row. Seven to ten days after the original seeding, the soil was flooded with 2 inches (5.1 cm) of water. At flooding time the grass species were in the two leaf stage 1 to 2 inches (2.54 to 5.1 cm) high and the nutsedge was 1 inch (2.54 cm) high. 
     Test compounds or combinations were then applied by pipeting 5.0 milliliters (ml) of a stock solution of appropriate concentration into the flood water to produce the desired application rate in pounds of active ingredient per acre (lb/A) or its equivalent in kilograms per hectare (kg/ha). For the particular tubs used, 5.5 milligrams (mg) of active ingredient per tub is equivalent to 1.0 lb/A. The stock solution for the pyrrolidone corresponding to an application rate of 1.0 lb/A therefore consisted of 22 mg of the compound dissolved in 20 ml of acetone containing 1% polyoxyethylene sorbitan monolaurate, a commercial surfactant. The thiolcarbamate stock solution for an application rate of 1.0 lb/A was prepared by dissolving 31 mg of an emulsifiable concentrate, containing 71.3 weight percent thiolcarbamate, in 20 ml of water. Granular thiolcarbamate formulations were used in some of the tests in place of the emulsifiable concentrates, at appropriate dilutions. Stock solutions for other application rates were made by using fractions or multiples of the above. Combinations were achieved by pipeting 5.0 ml from each of the appropriately selected stock solutions. 
     The tubs were allowed to stand for three weeks after the application of the test compounds and water was added as needed to maintain the water level. At the end of 3 weeks, the species were rated visually as percent control from 0 to 100%, where 0% represents no injury and 100% represents complete kill when compared to an untreated check tub. The percent control was based on the total injury to the plants due to all factors. 
     
                       TABLE II                                                    
______________________________________                                    
Post Flood Application                                                    
      Application                                                         
Cmpd. Rate                                                                
No.   (lb/A)    WG     AMG   SESB  YNS  RC   AVG                          
______________________________________                                    
3     2.00      80     75     80   0    20   80                           
      4.00      90     75    100   0    50   90                           
______________________________________                                    
 
    
     METHODS OF APPLICATION 
     The herbicidal compositions of the present invention are useful in controlling the growth of undesirable vegetation by preemergence or post-emergence application to the locus where control is desired, including pre-plant and post-plant soil incorporation as well as surface application. The compositions are generally embodied in formulations suitable for convenient application. Typical formulations contain additional ingredients or diluent carriers which are either inert or active. Examples of such ingredients or carriers are water, organic solvents, dust carriers, granular carriers, surface active agents, oil and water, water-oil emulsions, wetting agents, dispersing agents, and emulsifying agents. The herbicidal formulations generally take the form of dusts, emulsifiable concentrates, granules and pellets, or microcapsules. 
     A. DUSTS 
     Dusts are dense powder compositions which are intended for application in dry form. Dusts are characterized by their free-flowing and rapid settling properties so that they are not readily windborne to areas where their presence is not desired. They contain primarily an active material and a dense, free-flowing, solid carrier. 
     Their performance is sometimes aided by the inclusion of a wetting agent, and convenience in manufacture frequently demands the inclusion of an inert, absorptive grinding aid. For the dust compositions of this invention, the inert carrier may be either of vegetable or mineral origin, the wetting agent is preferably anionic or nonionic, and suitable absorptive grinding aids are of mineral origin. 
     Suitable classes of inert solid carriers for use in the dust compositions are those organic or inorganic powders which possess high bulk density and are very free-flowing. They are also characterized by low surface area and poor liquid absorptivity. Suitable grinding aids are natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica or silicate. Among ionic and nonionic wetting agents, the most suitable are the members of the group known to the art as wetting agents and emulsifiers. Although solid agents are preferred because of ease of incorporation, some liquid nonionic agents are also suitable in the dust formulations. 
     Preferred dust carriers and micaceous talcs, pyrophyllite, dense kaolin clays, tobacco dust and ground calcium phosphate rock. 
     Preferred grinding aids are attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic calcium and magnesium silicates. 
     Most preferred wetting agents are alkylbenzene and alkyl-naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, and ditertiary acetylenic glycols. Preferred dispersants are methyl cellulose, polyvinyl alcohol, lignin sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate, and sodium-N-methyl-N-(long chain acid) taurates. 
     The inert solid carriers in the dusts of this invention are usually present in concentrations of from about 30 to 90 weight percent of the total composition. The grinding aid will usually constitute 5 to 50 weight percent of the compositions, and the wetting agent will constitute from about 0 to 1.0 weight percent of the composition. Dust compositions can also contain other surfactants such as dispersing agents in concentrations of up to about 0.5 weight percent, and minor amounts of anticaking and antistatic agents. The particle size of the carrier is usually in the range of 30 to 50 microns. 
     B. EMULSIFIABLE CONCENTRATES 
     Emulsifiable concentrates are usually solutions of the active materials in nonwater-miscible solvents together with an emulsifying agent. Prior to use, the concentrate is diluted with water to form a suspended emulsion of solvent droplets. 
     Typical solvents for use in emulsifiable concentrates include weed oils, chlorinated hydrocarbons, and nonwater-miscible ethers, esters, and ketones. 
     Typical emulsifying agents are anionic or nonionic surfactants, or mixtures of the two. Examples include long-chain alkyl or mercaptan polyethoxy alcohols, alkylaryl polyethoxy alcohols, sorbitan fatty acid esters, polyoxyethylene ethers with sorbitan fatty acid esters, polyoxyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, calcium and amine salts of fatty alcohol sulfates, oil soluble petroleum sulfonates, or preferably mixtures of these emulsifying agents. Such emulsifying agents will comprise from about 1 to 10 weight percent of the total composition. 
     Thus, emulsifiable concentrates of the present invention will consist of from about 15 to about 50 weight percent active material, about 40 to 82 weight percent solvent, and about 1 to 10 weight percent emulsifier. Other additives such as spreading agents and stickers can also be included. 
     C. GRANULES AND PELLETS 
     Granules and pellets are physically stable, particulate compositions containing the active ingredients adhering to or distributed through a basic matrix of a coherent, inert carrier with microscopic dimensions. A typical particle is about 1 to 2 millimeters in diameter. Surfactants are often present to aid in leaching of the active ingredient from the granule or pellet. 
     The carrier is preferably of mineral origin, and generally falls within one of two types. The first are porous, absorptive, preformed granules, such as preformed and screened granular attapulgite or heat expanded, granular, screened vermiculite. On either of these, a solution of the active agent can be sprayed and will be absorbed at concentrations up to 25 weight percent of the total weight. The second, which are also suitable for pellets, are initially powdered kaolin clays, hydrated attapulgite, or bentonite clays in the form of sodium, calcium, or magnesium bentonites. Water-soluble salts, such as sodium salts, may also be present to aid in the disintegration of granules or pellets in the presence of moisture. These ingredients are blended with the active components to give mixtures that are granulated or pelleted, followed by drying, to yield formulations with the active component distributed uniformly throughout the mass. Such granules and pellets can also be made with 25 to 30 weight percent active component, but more frequently a concentration of about 10 weight percent is desired for optimum distribution. The granular compositions of this invention are most useful in a size range of  15-30 mesh. 
     The surfactant is generally a common wetting agent of anionic or nonionic character. The most suitable wetting agents depend upon the type of granule used. When preformed granules are sprayed with active material in liquid form the most suitable wetting agents are nonionic, liquid wetters miscible with the solvent. These are compounds most generally known in the art as emulsifiers, and comprise alkylaryl polyether alcohols, alkyl polyether alcohols, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, oil solution petroleum or vegetable oil sulfonates, or mixtures of these. Such agents will usually comprise up to about 5 weight percent of the total composition. 
     When the active ingredient is first mixed with a powdered carrier and subsequently granulated, or pelleted, liquid nonionic wetters can still be used, but it is usually preferable to incorporate at the mixing stage one of the solid, powdered anionic wetting agents such as those previously listed for the wettable powders. Such agents will comprise from about 0 to 2 weight percent of the total composition. 
     Thus, the preferred granular or pelleted formulations of this invention comprise about 5 to 30 percent by weight active material, about 0 to 5 weight percent wetting agent, and about 65 to 95 weight percent inert material carrier, as these terms are used herein. 
     D. MICROCAPSULES 
     Microcapsules consist of fully enclosed droplets or granules containing the active materials, in which the enclosing material is an inert porous membrane, arranged to allow escape of the enclosed materials to the surrounding medium at controlled rates over a specified period. Encapsulated droplets are typically about 1 to 50 microns in diameter. 
     The enclosed liquid typically constitutes about 50 to 95% of the weight of the entire capsule, and may contain a small amount of solvent in addition to the active materials. 
     Encapsulated granules are characterized by porous membranes sealing the openings of the granule carrier pores, trapping the liquid containing the active components inside for controlled release. A typical granule size ranges from 1 millimeter to 1 centimeter in diameter. In agricultural useage, the granule size is generally about 1 to 2 ml in diameter. Granules formed by extrusion, agglomeration, or prilling are useful in the present invention as well as materials in their naturally occurring form. Examples of such carriers are vermiculite, sintered clay granules, kaolin, attapulgite clay, sawdust, and granular carbon. 
     Useful encapsulating materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyurethanes, and starch xanthates. 
     E. IN GENERAL 
     Each of the above formulations can be prepared as a package containing the herbicide together with the other ingredients of the formulation (diluents, emulsifiers, surfactants, etc.). The formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site. 
     In general, any conventional method of application can be used. The locus of application can be soil, seeds, seedlings, or the actual plants, as well as flooded fields. Pre-emergent application is preferred. Dusts and liquid compositions can be applied by the use of powder dusters, boom and hand sprayers, and spray dusters. The compositions can also be applied from airplanes as dusts and sprays because they are effective in very low dosages. In order to modify or control the growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least one-half inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles. Instead, these compositions can be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. 
     The herbicide compositions can also be applied to the soil through irrigation systems. According to this technique, the compositions are added directly to irrigation water immediately prior to irrigation of the field. This technique is applicable in all geographical areas regardless of rainfall, since it permits supplementation of the natural rainfall at critical stages of plant growth. In a typical application, the concentration of the herbicide composition in the irrigation water will range from about 10 to 150 parts per million by weight. The irrigation water can be applied by the use of sprinkler systems, surface furrows or flooding. Such application is most effectively done before the weeds germinate, either early in the spring prior to germination or within two days after cultivation of the field. 
     The amount of the present composition which constitutes a herbicidally effective amount depends upon the nature of the seeds or 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 depending on the overall cost and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosage than more active compounds for the same degree of control.