Patent Document

This application has been filed under 35 USC 371 as the national stage application of PCT/RU93/00210, filed Sep. 2, 1993. 
     FIELD OF UTILITY 
     The instant application is related to agriculture, specifically to chemical agents for plant protection and eradication of undesired vegetation. 
     BACKGROUND OF THE INVENTION 
     Derivatives of sulfonylurea are known to possess herbicidal activity. 
     Specific action of all preparations of sulfonylurea series is related to inhibition of the early stage in amino acid biosynthesis by suppression of enzyme acetolactate synthetase (ALS) activity. A relationship between the herbicidal activity of sulfonylurea derivatives and their ability to inhibit ALS has been established. 
     The ALS in most of the higher plants is highly sensitive to herbicides of the sulfonylurea series. Nevertheless, the endurance of some plants to said compounds, pointing to unspecific sensitivity to ALS, is connected to inactivation or detoxication of the sulfonylurea derivative. These processes proceed at with different rates in various plants and that results both in high selectivity of herbicidal compositions towards various agricultural species and in resistance developed in weeds. The sulfonylurea derivatives of the instant invention are for use in cereals--e.g., corn, barley, rye and oats. 
     Most of the known derivatives of the sulfonylurea series are slowly decomposed in soil and overdosage of said herbicides results in detrimental effects in crop rotation as well as to serious phytotoxicity in certain agricultural species, e.g., corn, soybean etc. 
     All known herbicidal compositions based on sulfonylurea are wettable powders or microgranules. The absence of water-soluble preparations in this series is explainable by low water-solubility of sulfonylureas and their relatively high hydrolysis rate (C. Smith, Sulfonylurea herbicides, 1991, PJB Publication Ltd., pp. 51, 67, 99, and 107). 
     To counteract said shortcomings a herbicidal composition had to be developed with lower application dosage, wider activity spectrum on weeds and absence of phytotoxicity towards cultivated species. 
     A herbicidal composition with wide spectrum of activity has been disclosed (EP application #236273) consisting of two sulfonylureas A and B: ##STR1## with the addition of a surfactant, an organic solvent and water. 
     A method for the control of undesired vegetation using said herbicidal composition involves treating the vegetation or soil with said herbicidal composition in the form of an emulsion or suspension in dosage up to 3 kg/ha. The disclosed herbicidal composition displays undesirable phytotoxic effects on such crops as corn, soybean etc. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The instant invention discloses a herbicidal composition, comprising a mixture of benzenesulfonylurea derivative (I) in the form of its ammonium salt ##STR2## with a benzenesulfonylurea derivative (II) In the form of its ammonium salt ##STR3## wherein R 1  is hydrogen or methyl and R 2  is chloro, methoxycarbonyl or 2-chloroethoxy; a surfactant, an organic solvent--triethyleneglycol and water In the following mass percentage: 
     
         ______________________________________compound of the formula (I)              1,5-30%compound of the formula (II)              1,5-30%surfactant         1,0-5,0%triethyleneglycol  20-40%water              up to 100%______________________________________ 
    
     As a surfactant an agent selected from the following group is applicable: bis-polyoxyethylated alkylamine, sodium bis(2-ethylhexyl)succinate sulfonate, polyethyleneglycol monoalkyl ethers or alkylaryl ethers of polyethyleneglycol or polypropyleneglycol. 
     Compound I and its use are described in the following two publications, which are incorporated herein by reference in their entirety: 
     (1) Author&#39;s Certificate No. SU 1782974 (Inventor: Mr. V. Sorokin), published in the Official Russian Gazette (&#34;Izobretenija i . . . &#34;) on Dec. 23, 1992, No. 47/1992; and 
     (2) N. N. Melnikov, Pesticides and Growth Regulators, Moscow, Khimija, 576 pages, published in 1995, wherein the compound and its preparation are described on pages 504-505 under the title &#34;Chlorsulfoxim&#34; (Krug). 
     The combination of the two sulfonylureas (I) and (II) in the form of their ammonium salts results in unexpected synergism as evidenced by the results of biological testing. 
     Herbicidal compositions containing a single sulfonylurea (I) or (II) in the form of its ammonium-salt display a different spectrum of effects on plants. The composition based on sulfonylurea (I) mainly stimulates the growth of crops (wheat, corn, soybean, cotton) and suppresses the growth of weeds (cocklebur, lambsquarters, wild mustard) while the composition based on sulfonylurea (II) is strongly herbicidal to all species except wheat. 
     The synergism of the mixture consisting of ammonium salts of sulfonylureas (I) and (II) can result both in an increase of the herbicidal action--(+)-synergism and in a decrease of the herbicidal action--(-)-synergism, i.e., antagonism. In the cases where (I) displays the stimulating effect on the growth of plants, e.g., corn, soybean, cotton, the addition of (II) (displaying a pronounced phytotoxicity itself) within limits of (I)&gt;(II), results in (-)-synergism (antagonism). The addition of (I) to (II), i.e., when (I)&lt;(II), results in (+)-synergism. 
     The quantitative effect of synergism can be calculated by the equation: 
     
         E=E.sub.o -E.sub.c 
    
     wherein 
     E o  --observed % of plants destroyed by the mixture of compounds; 
     E c  --% of destroyed plants calculated according to Colby: 
     
         E.sub.c =X+Y-(X+Y)/100 
    
     wherein 
     X--the % of destroyed by (I). 
     Y--the % of plants destroyed by (II). 
     For example: 
     on corn, (I)/(IIA)=2/1, E=-58%; (I)/(IIA)=1/2, E=+12%; on cocklebur, (I)/(IIA)=13/1, E=+46%; (I)/(IIA)=1/13, E=+22%. 
     An analogical effect is displayed in all tests. Thus, application of ammonium salts of the sulfonylureas (I) and (II) makes possible effective control of undesired vegetation while substantially lowering the dosage of each component and reliably protecting such crops as wheat, corn, soybean etc. 
    
    
     The invention is further illustrated by the following examples. 
     EXAMPLE 1 
     Diethylethanolammonium Salt of 1-(2-chlorobenzenesulfonyl)-3-(4-isopropylydeniminoxy-6-dimethylamino-1,3,5-triazin-2-yl)urea 
     The reaction vessel was charged with 427 g (1 Mole) of 1-(2-chlorobenzene sulfonyl)-3-(4-isopropylydeniminoxy-6-dimethylamino-1,3,5-triazin-2-yl)urea (I), 117 g (1 Mole) of diethylaminoethanol and 10 L of water and the suspension stirred until solution was complete. The solvent was evaporated on rotary vacuum evaporator and the diethylethanolammonium salt of the sulfonylurea (I) collected in quantitative yield. 
     By the method described in Example 1 the diethylethanolammonium salts of the benzenesulfonylurea (II) were also prepared. Elemental analyses and physico-chemical data for the diethylethanolammonium salts of the sulfonylureas (I) and (II) are presented in Table 1. 
     EXAMPLE 2 
     Herbicidal Composition 
     The reaction vessel was charged with calculated amounts of the diethylethanolammonium salts of sulfonylureas (I) and (II), calculated amounts of water, triethyleneglycol and surfactant. The mixture was stirred at 20° C. for one hour. 
     Examples of herbicidal compositions with different quantities of constituents are presented in Table 2. 
     EXAMPLE 3 
     Test of Herbicidal Action 
     Test of herbicidal composition 1.1 (Example 1 from Table 1) was carried out under laboratory conditions applying 100 g/ha of the composition with concentration of ammonium salts of sulfonylureas ranging from 1.5 to 30% of the mass of composition. 
     As the test crops and weeds the following plants were used: 
     monocotyledonous--wheat, corn; 
     dicotyledonous--lambsquarters, soybean, flax, cotton, cocklebur wild mustard. 
     Treatment of the vegetation was carried out: 
     for cereals--at the third leaf phase; 
     for soybean--at the tripple leaf phase; 
     for other species--at the second true leaf phase. 
     Soil humidity was kept at 60-70% of saturation by daily watering. 
     The effectivity of the herbicidal compositions was established by comparing plants treated with test compositions and with etalon herbicides and controls on 14th day after treatment. 
     The results of testing are summarized in Tables 3-6. 
     The disclosed combination of the sulfonylurea derivative (I) and derivatives of substituted benzenesulfonamide (II) results in an unexpected synergism as evidenced by the results of biological testing. Herbicides containing an ammonium salt of sulfonylurea (I) or an ammonium salt of substituted benzenesulfonamide derivatives (II) display different effects on plants. Thus, sulfonylurea (I) (the top row of data in each of Tables 3-6) mainly stimulates the growth of crops (wheat, corn, soybeans, cotton), but suppresses the growth of weeds (cocklebur, lambsquarters, wild mustard). The derivatives of substituted benzenesulfonamide (II) (the far left column data in each of Tables 3-6) are strongly herbicidal to all plant species except wheat. 
     The data in Tables 3-6 show that for crops there is a wide range of concentrations of herbicidal compositions that either stimulate the growth of crops or do not significantly influence their growth. In the same ranges there are specific compositions that selectively inhibit the growth of certain weeds. These data show that there is not a linear additivity of the effects of the components of the composition, but that new and unexpected biological effects take place, thus making the disclosed compositions advantageous as compared with the single components. 
     An analogical effect is displayed in all tests. Thus, the application of herbicidal compositions on the basis of mixtures containing ammonium salts of sulfonylurea (I) and derivatives of substituted benzenesulfonamides (II) makes possible the effective control of undesired vegetation while substantially lowering the dosage of each component and reliable protection of the such crops as wheat, corn, soybeans, and the like. 
     
                                           TABLE 1__________________________________________________________________________Elemental analyses and physico-chemical data ofdiethylethanolammonium salts of (I) and (II)Structural                  Summary Elemental analysis                                          M.p.formula                     formula calcul.                                    found °C.                                              cm.sup.-1                                                 nm__________________________________________________________________________ ##STR4##                   C.sub.21 H.sub.33 ClN.sub.8 O.sub.5 S                               C H N                                 46.3  6.1 20.6                                    46.5  6.1 20.7                                       46.4  6.0 20.6                                          125-7                                              1650                                                 240 ##STR5##                   C.sub.18 H.sub.27 ClN.sub.6 O.sub.3 S                               C H N                                 45.6  5.7 17.7                                    45.7  5.5 17.9                                       45.6  5.6 18.0                                          142-6                                              1651                                                 234 ##STR6##                   C.sub.20 H.sub.30 N.sub.6 O.sub.7 S                               C H N                                 48.2  6.0 16.2                                    48.3  6.1 16.7                                       48.4  5.9 16.6                                          123-5                                              1642                                                 238 ##STR7##                   C.sub.20 H.sub.31 ClN.sub.6 O.sub.6 S                               C H N                                 46.3  6.0 16.2                                    46.5  6.0 16.0                                       46.4  5.9 16.3                                          154-8                                              1655                                                 238 ##STR8##                   C.sub.21 H.sub.32 N.sub.6 O.sub.7 S                               C H N                                 49.2  6.3 16.4                                    49.1  6.2 16.4                                       49.3  6.1 16.2                                          120-7                                              1645                                                 241__________________________________________________________________________ 
    
     
                       TABLE 2______________________________________Herbicidal        Percentage ofcomposition       components______________________________________1.1 Diethylethanolammonium                 1.5    1.5  10   30   30    salt of (I)    Diethylethanolammonium salt                 1.5    30   10   1.5  30    of (II) (IIA, IIB, IIC, IID)    Surfactant        1      2.5   2   2.5   5    Triethyleneglycol 40     30   35   30   20    Water             56     365  43   36   15______________________________________ 
    
     
                                           TABLE 3__________________________________________________________________________Herbicidal activity of composition 1.1 {compound(I) + compound(IIA)}__________________________________________________________________________Wheat                LambsquartersIIA\I   0  1,5    5  10 20 30 IIA\I                   0  1,5                         5  10 20 300     +5 +15       +18          +8 +12                0     18 25 48 70 811,5   +2 +5 +6 +32          +6 +8 1,5                   46 72 71 72 78 885  +6 +3 +8 +7 0  +13                5  85 88 88 82 83 10010 0  0  +4 0  +3 +9 10 100                      100                         100                            100                               94 9620 13 14 3  6  2  +14                20 100                      100                         100                            100                               100                                  10030 21 27 14 12 7  0  30 100                      100                         100                            100                               100                                  100Corn                 CottonIIA\I   0  1,5    5  10 20 30 IIA\I                   0  1,5                         5  10 20 300     +4 +8 +15          +12             2  0     +8 +12                            +23                               +11                                  81,5   27 +2 +4 +6 +4 0  1,5                   12 +6 +5 +2 +18                                  +125  35 42 0  +9 +4 +8 5  23 0  +2 +4 +2 +1310 48 54 51 5  +16             8  10 41 23 38 0  +12                                  +820 72 83 79 68 51 42 20 67 58 66 42 21 +430 81 91 93 96 79 63 30 72 86 88 81 64 34Soybean              FlaxIIA\I   0  1,5    5  10 20 30 IIA\I                   0  1,5                         5  10 20 300     +8 +12       +17          +9 +12                0     0  +2 +8 +3 51,5   28 15 7  +15          +33             +13                1,5                   11 17 12 9  8  05  47 58 47 +16          +13             18 5  20 16 12 9  5  210 87 81 89 58 +13             9  10 26 23 18 14 9  420 97 98 100       100          66 13 20 20 21 20 18 16 1130 100 100    100       100          100             77 30 28 29 26 18 19 13Cocklebur            Wild mustardIIA\I   0  1,5    5  10 20 30 IIA\I                   0  1,5                         5  10 20 300     0  0  12 12 17 0     13 31 43 58 651,5   10 57 54 70 70 79 1,5                   58 49 48 72 82 835  17 66 76 73 73 81 5  76 58 61 69 83 8610 61 72 84 64 64 73 10 89 81 74 89 81 9220 71 86 93 78 78 86 20 100                      93 90 94 100                                  8730 77 91 97 100          100             91 30 100                      100                         98 99 100                                  100__________________________________________________________________________ 
    
     
                                           TABLE 4__________________________________________________________________________Herbicidal activity of composition 1.1 {compound(I) + compound(IIB)}__________________________________________________________________________Wheat                LambsquartersIIB\I   0  1,5    5  10 20 30 IIB\I                   0  1,5                         5  10 20 300     +5 +15       +18          +8 +12                0     18 25 48 70 811,5   0  0  +2 +8 +8 +8 1,5                   63 82 84 80 79 915  0  4  8  +4 +4 6  5  88 93 92 91 92 8910 8  11 13 8  4  4  10 100                      100                         96 91 9  8820 16 21 19 17 17 10 20 100                      100                         100                            98 100                                  9630 24 29 30 21 22 18 30 100                      100                         100                            100                               100                                  100Corn                 CottonIIB\I   0  1,5    5  10 20 30 IIB\I                   0  1,5                         5  10 20 300     +4 +8 +15          +2 2  0     +8 +12                            +23                               +11                                  81,5   21 +6 +7 +11          5  11 1,5                   9  +1 +14                            +27                               +37                                  +145  27 +33    6  +3 1  14 5  16 13 +8 +7 +6 +1710 52 64 65 7  +2 9  10 57 32 22 +4 +16                                  +1120 68 69 73 68 19 6  20 69 48 53 42 4  +3030 74 83 79 81 79 25 30 81 63 59 67 72 19Soybean              FlaxIIB\I   0  1,5    5  10 20 30 IIB\I                   0  1,5                         5  10 20 300     +8 +12       +17          +9 +12                0     0  +2 +8 +3 51,5   21 6  +7 +11          5  +15                1,5                   13 16 13 10 +11                                  05  38 39 21 +3 1  14 5  14 13 22 7  12 +210 48 49 59 40 +2 9  10 23 22 20 17 17 620 81 76 69 72 78 6  20 33 21 24 15 28 2730 100 100    100       100          100             77 30 28 29 26 18 27 34Cocklebur            Wild mustardIIB\I   0  1,5    5  10 20 30 IIB\I                   0  1,5                         5  10 20 300     0  0  +2 12 17 0     13 31 43 58 651,5   33 74 52 72 66 74 1,5                   61 73 77 86 82 745  42 58 79 70 78 80 5  83 87 86 89 96 8910 68 74 81 86 78 86 10 100                      94 96 100                               92 9620 83 88 91 93 95 87 20 100                      100                         100                            100                               100                                  10030 100 100    100       100          100             96 30 100                      100                         100                            100                               100                                  100__________________________________________________________________________ 
    
     
                                           TABLE 5__________________________________________________________________________Herbicidal activity of composition 1.1 {compound(I) + compound(IIC)}__________________________________________________________________________Wheat                LambsquartersIIC\I   0  1,5    5  10 20 30 IIC\I                   0  1,5                         5  10 20 300     +5 +15       +18          +8 +12                0     18 25 48 70 811,5   0  +2 0  +17          +18             0  1,5                   71 97 92 79 82 775  0  0  2  +4 +4 6  5  92 100                         100                            91 82 7910 0  0  0  +4 +4 7  10 95 100                         100                            100                               96 8620 8  0  4  0  0  +2 20 100                      100                         100                            100                               100                                  10030 6  5  2  3  7  17 30 100                      100                         100                            100                               100                                  100Corn                 CottonIIC\I   0  1,5    5  10 20 30 IIC\I                   0  1,5                         5  10 20 300     +4 +8 +15          +12             2  0     +8 +12                            +23                               +11                                  81,5   48 12 +6 +8 +13             8  1,5                   0  7  6  +5 +13                                  +55  64 38 17 0  +14             14 5  8  10 8  4  0  +410 72 48 38 31 +13             0  10 14 8  10 12 12 1220 86 63 59 42 28 27 20 48 32 26 20 18 830 88 72 69 55 48 46 30 62 54 48 29 42 37Soybean              FlaxIIC\I   0  1,5    5  10 20 30 IIC\I                   0  1,5                         5  10 20 300     +8 +12       +17          +9 +12                0     0  +2 +8 +3 51,5   33 27 12 +17          +11             +6 1,5                   16 16 12 8  4  75  41 38 22 17 +12             6  5  24 19 24 11 8  610 62 39 47 48 24 +3 10 18 16 19 17 8  920 87 64 58 55 57 17 20 31 27 22 21 19 830 74 82 76 78 66 62 30 33 23 26 18 21 26Cocklebur            Wild mustardIIC\I   0  1,5    5  10 20 30 IIC\I                   0  1,5                         5  10 20 300     0  0  +2 12 17 0     24 33 43 58 651,5   33 46 42 58 55 62 1,5                   61 68 72 72 82 895  47 56 69 73 69 73 5  87 88 71 68 69 8610 58 62 78 81 77 78 10 92 84 82 86 78 8020 74 79 80 83 78 88 20 88 89 87 90 92 8230 83 85 83 89 90 94 30 100                      96 94 96 100                                  96__________________________________________________________________________ 
    
     
                                           TABLE 6__________________________________________________________________________Herbicidal activity of composition 1.1 {compound(I) + compound(IID)}__________________________________________________________________________Wheat                LambsquartersIID\I   0  1,5    5  10 20 30 IID\I                   0  1,5                         5  10 20 300     +5 +15       +18          +8 +12                0     18 25 48 70 811,5   0  +2 +4 +6 +10             +8 1,5                   72 86 90 91 89 935  6  4  0  +4 +6 +11                5  94 96 93 98 98 9310 14 12 8  4  +2 0  10 100                      100                         100                            100                               100                                  10020 23 26 18 12 8  2  20 100                      100                         100                            100                               100                                  10030 31 36 24 31 34 18 30 100                      100                         100                            100                               100                                  100Corn                 CottonIID\I   0  1,5    5  10 20 30 IID\I                   0  1,5                         5  10 20 300     +4 +8 +15          +12             2  0     +8 +12                            +23                               +11                                  81,5   38 12 0  +4 +11             +10                1,5                   23 8  4  0  +4 +25  54 36 24 12 +14             +8 5  41 36 16 11 2  610 72 56 48 14 +2 +6 10 64 58 55 14 6  +120 82 79 81 76 16 2  20 72 78 68 74 24 1430 86 88 93 88 93 28 30 86 82 92 83 78 68Soybean              FlaxIID\I   0  1,5    5  10 20 30 IID\I                   0  1,5                         5  10 20 300     +8 +12       +17          +9 +12                0     0  +2 +8 +3 51,5   36 21 8  +1 +2 +4 1,5                   12 17 8  12 5  35  52 33 18 21 +6 2  5  19 14 13 4  +3 +810 67 66 55 48 +8 4  10 26 23 18 16 13 620 83 88 78 61 60 31 20 33 42 37 28 27 1030 96 100    91 100          83 92 30 30 41 24 33 32 18Cocklebur            Wild mustardIID\I   0  1,5    5  10 20 30 IID\I                   0  1,5                         5  10 20 300     0  0  +2 12 17 0     13 31 43 58 651,5   44 56 52 64 66 58 1,5                   67 83 81 88 82 945  56 69 66 71 69 74 5  85 88 92 84 88 9610 74 77 83 74 83 88 10 100                      96 98 100                               94 10020 88 94 96 87 93 92 20 100                      100                         100                            100                               100                                  10030 96 100    100       100          100             98 30 100                      100                         100                            100                               100                                  100__________________________________________________________________________

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