Abstract:
Herbicidal bromo- or chloroacetamides of the formula: ##STR1## where R is alkyl or alkoxy of 1 to 4 carbon atoms; 
     X is chlorine or bromine; and 
     Y is S or N--CH 3 .

Description:
BACKGROUND OF THE INVENTION 
     Recently in U.S. Patent Nos. 3,769,301 and 3,907,544 herbicidal compounds of the general formula: ##STR2## where 
     X is halogen; 
     n is 1 or 2; 
     A is, among others, --N--(CO) m  --R 4  ; 
     where 
     m is 0, 1, or 2; and 
     R 3  and R 4  together can form a alkylene bridge or 2-5 carbons; and 
     Y is oxygen or sulfur, 
     Were disclosed. 
     The compounds taught within these patents are active herbicides; the need still exists, however, for herbicides which are more active. The presence of undesired vegetation is very damaging to useful crops such as rice. In the current world situation, wherein food shortages are acute, it is most important not to lose a significant portion of a valuable crop such as rice. The presence of such undesired vegetation results in the loss of a significant portion of such crop. Thus, a need exists for a particularly effective herbicide which will destroy as much of this unwanted vegetation as is possible without causing significant damage to the desired crops, e.g. rice. 
     According to the instant invention, herbicidal compounds have been discovered which are highly active herbicides and yet cause minimal damage to certain desired crops, e.g. rice. 
     DESCRIPTION OF THE INVENTION 
     This invention relates to the novel compounds of Formula I and to agricultural compositions containing them, and to the method of use of these compounds as selective, as well as general, herbicides having both pre- and post-emergence activity: ##STR3## where R is alkyl or alkoxy of 1 to 4 carbon atoms; 
     X is chlorine or bromine; and 
     Y is S or N--CH 3 . 
     Preferred, for reasons of economy and/or ease of synthesis and/or higher herbicidal activity, are the compounds of Formula I where, independently: 
     I. r is alkyl or alkoxy of 1 or 2 carbon atoms; 
     Or 
     Ii. x is chlorine. 
     More preferred for their outstanding biological activity are those compounds of Formula I wherein R is methyl or methoxy, X is chlorine, and Y is S. Specifically preferred are the compounds: 
     A. 2-chloro-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-methylphenyl)acetamide,m.p. 134°-137° C; 
     b. 2-chloro-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-methoxyphenyl)acetamide, m.p. 188°-191° C. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The novel compounds of this invention are prepared by haloacetylation of the corresponding anilines (II) in an aprotic solvent such as toluene, chloroform, benzene, and the like in the presence of an acid acceptor such as triethylamine, pyridine, etc., as shown by Equation A. 
     The reaction takes place at a temperature of about -30° to 80° C, preferably -10° to 5° C over a period of about 30 minutes to 5 hrs, preferably about 1 to 3 hrs. ##STR4## 
     The anilines (II) are prepared by the condensation of 2-substituted aniline, formaldehyde and the corresponding imide under the conditions of Mannich reaction [Kadin, J. Org. Chem. 38, 1348 (1973); Kononenko, et al., J. Org. Chem. USSR, 9, 59 (1973)], which is herein incorporated by reference, as given by Equation B. ##STR5## 
     The preparation of the novel compounds of the present invention is illustrated by the following examples. 
     EXAMPLE 1 
     2-chloro-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-methyl-phenyl)acetamide 
     A mixture of 10.7 g of o-toluidine, 3.3 g. of paraformaldehyde, and 11.7 g of 2,4-thiazolidinedione in 100 ml of absolute ethanol was refluxed 5 hrs under nitrogen. atmosphere. On cooling, the resulting precipitate was filtered off to give 22.1 g of N-(2-methylphenylaminomethyl)-2,4-thiazolidinedione, mp 109°-111° C; identified by IR and NMR. 
     A solution of 4.5 g of chloroacetyl chloride in 10 ml of toluene was added dropwise to a suspension of 7.8 g of N-(2-methylphenylaminomethyl)-2,4-thiazolidinedione and 3 g of pyridine in 80 ml of toluene at -5° C with stirring and kept on an ice bath for 3 hrs. The resulting precipitate was filtered and washed with water to give 2-chloro-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-methylphenyl)acetamide, mp 133°-136° C. The toluene filtrate was extracted with two 50 ml portions of 5% hydrochloric acid, 50 ml of water, dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated on a rotary evaporator to give the product which was crystallized from benzene-ether, mp 134°-137° C. The total yield was 6.0 g [M +  = 312 (molecular ion by mass spec.)]. 
     EXAMPLE 2 
     2-Chloro-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-methoxyphenyl)acetamide 
     A mixture of 13.3 g of 2,4-thiazolidinedione and 12.3 g of o-anisidine was dissolved in 100 ml of warm ethanol at 55° to 70° C. The solution was cooled to about 30° C, and 9.1 ml of 37% formaldehyde solution was added and stirred overnight. The resulting precipitate was filtered to give 22.5 g of N-(2-methoxyphenylaminomethyl)-2,4-thiazolidinedione, mp 88.5°-91° C; identified by IR and NMR. 
     A suspension of 7 g of anhydrous potassium carbonate, 7.3 g of N-(2-methoxyphenylaminomethyl)-2,4-thiazolidinedione, and 5.3 g of chloroacetyl chloride in 50 ml of chloroform was cooled in an ice bath and stirred at ambient temperature for 48 hrs. The resulting precipitate was filtered, washed with water and recrystallized from nitromethane-ethanol to give 5.6 g of 2-chloro-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-methoxyphenyl)acetamide; mp 188°-191° C; M +  = 328. 
     Cal&#39;d for C 13  H 13  ClN 2  O 4  S: C: 47.49; H: 3.99; Cl: 10.78; N: 8.52; S: 9.75; 
     Found: C: 47.8; H: 4.16; Cl: 11.55; N: 8.59; S: 9.73. 
     EXAMPLE 3 
     2-Chloro-N-(2,4-dioxo-1-methylimidazolidin-3-ylmethyl)-N-(2-methoxyphenyl)acetamide 
     A mixture of 12.3 g of o-anisidine, 3.3 g of paraformaldehyde, and 11.4 g of 1-methylhydantoin in 100 ml of absolute ethanol was refluxed for 8 hrs under nitrogen atmosphere. At the end of this time, the solution was cooled on a dry ice-acetone bath and the solvent was decanted to leave a viscous oil. The oil was dissolved in 800 ml of ether and the etheral solution was allowed to evaporate slowly at room temperature. The resulting precipitate was filtered to give 12 g of 1-methyl-3-(2-methoxyphenylaminomethyl)hydantoin, mp 93°-96.5° C, identified by IR and NMR. 
     A solution of 4.5 g of chloroacetyl chloride in 10 ml of toluene was added dropwise to a solution of 7 g of the 1-methyl-3-(2-methoxyphenylaminomethyl)hydantoin and 2.8 g of pyridine in 40 ml of toluene at -10° C. The suspension was stirred on an ice-bath for 1.5 hrs. The resulting precipitate was filtered and thoroughly washed with 5% hydrochloric acid, water, and recrystallized from chloroformether to give 6.0 g of N-(2,4-dioxo-1-methylimidazolidin-3-ylmethyl)-N-(2-methoxyphenyl)acetamide, mp 169°-172° C; M +  = 325. 
     The following compounds were also prepared by the general method set forth in the preceding examples. 
     
         ______________________________________Compounds             Physical Property______________________________________2-Chloro-N-(2,4-dioxothiazolidin-3-                 mp 124.5-125.5° C ylmethyl)-N-(2-ethoxyphenyl)- acetamide2-Chloro-N-(2,4-dioxothiazolidin-3-                 mp 151.5-152.5° C ylmethyl)-N-(2-ethylphenyl)- acetamide2-Chloro-N-(2,4-dioxothiazolidin-3-                 mp 141-143° C ylmethyl)-N-(2-isopropylphenyl)- acetamide2-Chloro-N-(2,4-dioxothiazolidin-3-                 oil ylmethyl)-N-(2-isopropoxyphenyl)- acetamide2-Chloro-N-(2,4-dioxothiazolidin-3-                 mp 120-123° C ylmethyl)N-(2-sec-butylphenyl)- acetamide2-Chloro-N-(2,4-dioxo-1-methyl-                 mp 126-127° C imidazolidin-3-ylmethyl)-N- (2-ethoxyphenyl)acetamide2-Chloro-N-(2,4-dioxo-1-methyl-                 mp 92-95° C imidazolidin-3-ylmethyl)-N- (2-ethylphenyl)acetamide2-Chloro-N-(2,4-dioxo-1-methyl-                 oil imidazolidin-3-ylmethyl)-N- (2-isopropylphenyl)acetamide2-Chloro-N-(2,4-dioxo-1-methyl-                 mp 84-92° C imidazolidin-3-ylmethyl)-N- (2-methylphenyl)acetamide2-Chloro-N-(2,4-dioxo-1-methyl-                 oil imidazolidin-3-ylmethyl)-N- (2-sec-butylphenyl)acetamide2-Chloro-N-(2,4-dioxo-1-methyl-                 oil imidazolidin-3-ylmethyl)-N- (2-isopropoxyphenyl)acetamide______________________________________ 
    
     Other compounds of this invention include the following: 
     2-Chloro-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-n-propoxyphenyl)acetamide 
     2-Chloro-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-n-butylphenyl)acetamide; 
     2-Chloro-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-n-butoxyphenyl)acetamide; 
     2-Bromo-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-methoxyphenyl)acetamide; 
     2-Bromo-N-(2,4-dioxothiazolidin-3-ylmethyl)-N-(2-methylphenyl)acetamide; 
     2-Bromo-N-(2,4-dioxo-1-methylimidazolidin-3-ylmethyl)-N-(2-n-propoxyphenyl)acetamide; 
     2-Chloro-N-(2,4-dioxo-1-methylimidazolidin-3-ylmethyl)-N-(2-n-butylphenyl)acetamide; 
     2-Chloro-N-(2,4-dioxo-1-methylimidazolidin-3-ylmethyl)-N-(2-n-butoxyphenyl)acetamide, 
     Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 1 to 99% by weight of active ingredient(s) and at least one of a) about 0.1 to 20% surfactant(s) and b) about 5 to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions: 
     
         ______________________________________        Percent by Weight        Active            Sur-        Ingredient                Diluent(s)                          factant(s)______________________________________Wettable Powders          20-90      0-74      1-10Oil Suspensions, Emulsions, Solutions (including Emulsifi- able Cocentrates)           5-50     40-95      0-15Aqueous Suspensions          10-50     40-84      1-20Dusts           1-25     70-99     0-5Granules and Pellets           1-95      5-99      0-15High Strength Compositions  90-99      0-10     0-2______________________________________ 
    
     Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing. 
     Typical solid diluents are described in Watkins, et al., &#34;Handbook of Insecticide Dust Diluents and Carriers,&#34; 2nd. Edn., Dorland Books, Caldwell, N.J. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, &#34;Solvents Guide,&#34; 2nd, Edn., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. &#34;McCutcheon&#39;s Detergents and Emulsifiers Annual&#34;, McCutcheon&#39;s Publ. Corp., Ridgewood, N.J., as well as Sisely and Wood, &#34;Encyclopedia of Surface Active Agents,&#34; Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended. 
     The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer-or fluid-energy-mill. Suspensions are prepared by wet-milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, &#34;Agglomeration&#34;, Chemical Engineering, Dec. 4, 1967, pp. 147ff. and &#34;Perry&#39;s Chemical Engineer&#39;s Handbook,&#34; 4th. Edn., McGraw-Hill, N.Y., 1963, pp. 8-59ff. 
     For further information regarding the art of formulation, see for example: 
     H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, Line 16 through Col. 7, Line 19 and Examples 10 through 41. 
     R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, March 14, 1967, Col. 5 Line 43 through Col. 7 Line 62 and Ex. 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, 169-182. 
     H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3 Line 66 through Col. 5 Line 17 and Examples 1-4. 
     G. C. Klingman, &#34;Weed Control as a Science,&#34; John Wiley &amp; Sons, Inc., New York, 1961 pp. 81-96. 
     J. D. Fryer and S. A. Evans, &#34;Weed Control Handbook&#34;, 5th Edn. Blackwell Scientific Publications, Oxford, 1968, pp. 101-103. 
     
                       EXAMPLE 4______________________________________Wettable Powder2-chloro-N-(2,4-dioxothiazolidin-3-yl-                       50% methyl)-N-(2-methylphenyl)acetamidesodium alkylnaphthalenesulfonate                        2%low viscosity methyl cellulose                        2%diatomaceous earth          46%______________________________________ 
    
     The ingredients are blended, coarsely hammer-milled and the air milled to produce particles of active essentially all below 10 microns in diameter. The product is reblended before packaging. 
     
                       EXAMPLE 5______________________________________Wettable Powder2-chloro-N-(2,4-dioxothiazolidin-3-                      80% ylmethyl)-N-(2-methoxyphenyl)ace- tamidesodium alkylnaphthalenesulfonate                       2%sodium ligninsulfonate      2%synthetic amorphous silica  3%kaolinite                  13%______________________________________ 
    
     These components are blended, micropulverized until the particles are essentially under 50 microns in size, and then reblended. 
     
                       EXAMPLE 6______________________________________Granulewettable powder of Example 5                     15%gypsum                    69%potassium sulfate         16%______________________________________ 
    
     The ingredients are blended in a rotating mixer and water is sprayed on to accomplish granulation. When most of the material has reached the desired range of 1.0 to 0.42 mm (U.S.S. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 12% active ingredient. 
     
                       EXAMPLE 7______________________________________Solution2-chloro-N-(2,4-dioxothiazolidin-3-yl-                       30% methyl)-N-(2-methylphenyl)acetamidedimethylformamide           70%______________________________________ 
    
     The ingredients are combined and stirred to produce a solution, which can be used for low volume applications. 
     
                       EXAMPLE 8______________________________________Aqueous Suspension2-chloro-N-(2,4-dioxothiazolidin-3-yl-                      25% methyl)-N-methoxyphenyl)acetamidehydrated attapulgite       3%crude calcium ligninsulfonate                      10%sodium dihydrogen phosphate                      0.5%water                      61.5%______________________________________ 
    
     The ingredients are ground together in a ball- or roller-mill until the solid particles have been reduced to diamters under 10 microns. 
     Utility 
     The compounds of Formula I are useful for the control of undesired vegetation in crops. More particularly, the compounds of the present invention control barnyardgrass (Echinochloa spp.) in rice cultures. 
     The compounds of the present invention are most effective against barnyardgrass when applied prior to emergence of barnyardgrass plants from the soil. They may be applied in upland (dry) cultures or in paddy (flooded) cultures. 
     The precise amount of the compounds of the present invention to be used will vary according to the cultural method employed, the soil type, weather, etc. However, broadly speaking, they are used at rates of about 0.12 kg to about 12 kg, preferably 0.25 to 6 kg, per hectare. The lower rates in this range will generally be selected on sandy soils low in organic matter content or in situations where maximum persistence is not necessary. 
     The compounds of the present invention may be applied singly or in admixtures with other herbicides, including but not restricted to: 1-(p-cumyl)-3,3-dimethylurea; 2,4,6-trichlorophenyl-4&#39;-nitrophenylether; 2-methylthio-4,6-bis(ethylamino)-s-triazine; ethyl hexahydrothiol-1-azepinecarboxylate. 
     The effectiveness of the compounds of Formula I against barnyardgrass in rice is illustrated by the following tests. 
     Procedure, Test 1 
     Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua). Cassia tora, morningglory (Ipomoea spp.), cocklebur (Xanthium sp.), sorghum, corn, soybean, rice, wheat and nutsedge tubers were planted in a growth medium and treated preemergence with the chemicals dissolved in a non-phytotoxic solvent. At the same time, cotton having five leaves (including cotyledonary ones), bush beans with the second trifoliate leaf expanding, crabgrass with two leaves, barnyardgrass with two leaves, wild oats with one leaf, cassia with three leaves (including cotyledonary ones), morningglory with four leaves (including the cotyledonary ones), cocklebur with four leaves (including the cotyledonary ones), sorghum with three leaves, corn with three leaves, soybean with two cotyledonary leaves, rice with two leaves, wheat with two leaves, and nutsedge with three-five leaves were sprayed. Treated plants and controls were maintained in a greenhouse for 16 days, then all species were compared to controls and visually rated for response to treatment. 
     Ratings for compounds tested by this procedure are recorded in Table 1. 
     
         Table 1  PLANT RESPONSE TEST 1 POST EMERGENCE   Bush Cot- Morning Cockle- Cass- Nut- Crab- Barnyard Wild   Soy-  Sor-  Compound Kg/Ha bean ton glory bur ia sedge grass grass Oats Wheat Corn bean Rice ghum  ##STR6##  2 0 0 2G 0 0 2G 6H 2C9H 0 0 0 0 3G 0  ##STR7##   2 0 0 0 0 0 0 2H 9H 0 0 0 0 0 0  PRE-EMERGENCE   Morning Cockle- Cass- N ut- Crab- Barnyard Wild   Soy-  Sor-  Compound Kg/Ha glory bur ia sedge grass grass Oats Wheat Corn bean Rice ghum  ##STR8##  2 0 2H 0 0 10E 10H 2G 0 0 9H 5E 0  ##STR9##  2 0 0 2G 0 7H 10H 0 0 0 0 0 0 
    
     The plant response ratings above are composed of a number and a letter. The number describes the extent of the response and ranges from zero to ten with zero representing no response, and ten representing 100% response. The letter describes the type of the response, with &#34;C&#34; representing chlorosis-necrosis, &#34;E&#34; representing emergence inhibited, &#34;G&#34; growth retarded, and &#34;H&#34; formative effect (malformation or hormone type). 
     Additional greenhouse tests have been conducted, as described below: 
     Procedure, Test 2 
     A medium-textured soil, fairly low in organic matter content, was planted to seeds of the species listed in the following table. Planting depth was about 0.5 cm except for corn and soybeans which were planted at a depth of 2.5 cm. The test compounds were dissolved/suspended in a nonphytotoxic solvent. Within a few hours of planting, the test solutions were applied to the soil surface. The rates of application for the test compounds are shown in the table. Immediately after treatment the soil surfaces were exposed to simulated rainfall at the rate of approximately 5 mm of water over a period of 180 minutes. From this point the plantings were maintained in the greenhouse and watered on a demand basis. Plant response ratings were made around 4 weeks after planting and treatment. 
     The same rating procedure and symbols as mentioned in Test 1 apply for Test 2. 
     
           PLANT RESPONSE TEST 2   Rate  Barnyard-  Wild Crab-  Johnson-  Compound Kg/Ha Rice grass Wheat Oats grass Sorghum grass    1/4 4H 8H 0 0 9H 0 0  0 3G 0 0 3G 0 0  ##STR10##Gaint Blue- Cheat-   Cock- Pig- Nut- Curly Morning-  Tea- Velvet- Jimson- Soy- Sugar- Compound Foxtail grass grass Corn Mustard lebur weed sedge indigo glory Cassia weed leaf weed bean beet    7H 0 2C 0 0 0 0 0 0 0 0 0 0 0 0 0  4G 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0  ##STR11## 
    
     Procedure, Test 3: 
     A medium-textured soil, fairly low in organic matter content, was planted with the species listed in the table below. The plantings were maintained in a moist condition for 2 to 3 weeks until most species were in the 2- to 4-leaf stage of development. The test compounds were dissolved/suspended in a non-phytotoxic solvent which was applied as overall soil/foliage treatments to the mixed stand of young crops and weeds at the rates given in the attached table. The plantings were then maintained in the greenhouse where they were watered on a demand basis. Plant response ratings were made around 2 weeks after treatment. 
     
         __________________________________________________________________________PLANT RESPONSE TEST 3                 Soy-    Cot-         Velvet-                                            Ses-Compound          Kg/ha                 bean                     Corn                         ton Rice                                 Wheat                                      leaf  bania                                                 Cassia__________________________________________________________________________             1/4 4B  2B  7B  0   0    9B    6B   3B                 2B  0   3B  0   0    2C    2B   2B ##STR12##__________________________________________________________________________             Morn-                Barn-             ing Al-                    Jimson-                         Cockle-                              Crab-                                  yard-                                      Giant                                          Wild    Nut-Compound          glory                 falfa                    weed bur  grass                                  grass                                      foxtail                                          oats                                             Sorghum                                                  sedge__________________________________________________________________________             2B  3B 8B   2B   0   2B  2C  0  3B   0             0   2C 2C   1B   0   0   2C  0  0    0 ##STR13##__________________________________________________________________________the same rating procedure and symbols as mentioned in Test 1 apply for Test 3. 
    
     Procedure, Test 4: 
     The test compound was applied in an overall spray in a nonphytotoxic solvent containing a wetting agent and a humectant to pots (pre-emergence) containing seeds of an intermediate (hydrid) rice, a japonica rice, barnyardgrass (Echinochloa sp.), curly indigo (Aeschynomene virginica), and wild morningglory Convolvulus arvensis), and was also applied to established (post-emergence) plantings of the same species. The treatments were maintained in a greenhouse for three weeks after which plant response ratings were taken. The same rating procedure and symbols as mentioned in Test 1 apply in the present test. 
     
         __________________________________________________________________________TEST 4                  PRE-EMERGENCE       POST-EMERGENCE                  Inter           Wild                                      Inter-          Wild                  med-                      Japo-                          Barn-   Morn-                                      med-                                          Japo-                                              Barn-   Morn-              Rate                  iate                      nica                          yard                              Curly                                  ing iate                                          nica                                              yard                                                  Curly                                                      ingCompound           Kg/Ha                  Rice                      Rice                          Grass                              Indigo                                  Glory                                      Rice                                          Rice                                              Grass                                                  Indigo                                                      Glory__________________________________________________________________________ ##STR14##         0 4G 10E 9E                  1/8 1/4 1/2 1                      0 0 0 0                          0 0 0 0                              0 0 0 0                                  0 0 0 0                                      0 0 0  --                                          0 0 0 0                                              0 0 0 0                                                  0 0 0 --                                                      0 0 0 0 ##STR15##         2G 9G 9G 10E                  1/8 1/4 1/2 1                      0 0 0 0                          0 0 0 0                              0 0 0 0                                  0 0 0 0                                      -- 0 0 0                                          0 0 0 0                                              0 0 0 0                                                  0 0 0 0                                                      0 0 0 0__________________________________________________________________________ 
    
     procedure, Test 5: 
     The test compound was applied to the water surface of a soil-containing tub (with seeds of barnyardgrass (Echinochloa sp.) mixed into the soil) designed to simulate a rice paddy. Two days later rice plants in the three leaf stage were transplanted into the tub. Final plant response ratings, presented below, were taken 21 days after transplanting: 
     
         __________________________________________________________________________                       Plant Response RatingsCompound             Rate, kg/Ha                       Rice                          Barnyardgrass__________________________________________________________________________                0.5    1G 9G ##STR16## ##STR17##__________________________________________________________________________                0.5    0  9Cthe same rating procedure and symbols as mentioned in Test 1 apply for Test 5. 
    
     It should be noted from the tests above that these compounds controlled barnyardgrass and other weeds with little effect on the crop (rice). The preemergence control was especially good.