Abstract:
A herbicidal composition comprises a bipyridylium salt and a thiocarbamate having the formula ##STR1## wherein R and R 1  each represent a lower alkyl group which in combination with each other can form a heterocyclic ring with the N atom; R 2  represents ##STR2## AND X represents a halogen atom or a lower alkyl group; and n represents 0, 1 or 2.

Description:
This application is a continuation of application Ser. No. 609,725, filed Sept. 2, 1975, now U.S. Pat. No. 4,028,091. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a new herbicidal composition which is effective for both foliage treatment and soil treatment in agricultural areas such as orchards, upland fields, paddy fields and the like, and also in non-agricultural areas. 
     2. Description of the Prior Art 
     In general, it takes relatively less time to cultivate an orchard as compared with the time required for cultivation in other agricultural areas. However, in many cases, the orchard is developed adjacent to a forest and/or a wasteland. In these situations, many weeds are extended from the forest and/or wasteland into the orchard. Accordingly, various weeds, such as annual weeds, e.g., Manna-grass, Barnyard grass, Smartweed, and the like; perennial weeds, e.g., Field horsetail, Culy dock, Cayratia Japonica, Bindweed, and the like, and coppice appear. Some of these weeds grow very high and/or in high multiplication. Some weeds appear in the areas immediately surrounding the trees. The following problems, associated with the yield of the fruit and the control and tending of the operation, are caused by the presence of these weeds: 
     (1) The control and tending operations are disturbed. 
     (2) The effects of the wind and sunlight are diminished. 
     (3) Disease and insect damage are caused and promoted. 
     (4) The nutritional value of fertilizer is lost. 
     (5) Water in the soil is used up, causing drought injury. 
     In the conventional methods of inhibition of the weeds, it has been known to apply foliage-treatment type herbicides such as 1,1&#39;-dimethyl-4,4&#39;-bypyridylium dichloride or a mixture of 3,4-dichloropropionanilide and α-naphthyl N-methylcarbamate in the growing period of the weeds, or to apply soil-treatment type herbicides such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea or 2,4-bis(iso-propylamino)-6-methylthio-1,3,5-triazine, and the like before the weed seedlings appear. When the soil-treatment type herbicides are applied, the active ingredient is translocated in the soil and is absorbed by the roots of the trees, causing phytotoxicity. Also, the herbicidal effect is disadvantageously varied by changing said conditions, such as the water content of the soil. On the other hand, when the foliage-treatment type herbicides are applied, the herbicidal effect is relatively stable and confirmation of its efficacy can easily be made. Retreatments can then be made accordingly. As a result, foliage-treatment type herbicides such as 1,1&#39;-dimethyl-4,4&#39;-bipyridylium dichloride and a mixture of 3,4-dichloropropionanilide and α-naphthyl N-methylcarbamate have been used primarily. However, when 1,1&#39;-dimethyl-4,4&#39;-bipyridylium dichloride is used, the herbicidal effect against grown weeds is inferior. It is considered that this defect is caused by small translocation of the active ingredient into the bodies of the plants. Only the cells of the weeds in the immediate vicinity of the point of contact of the active ingredient are damaged under conditions of intense irradiation. The translocation of the active ingredient in the weeds is quite slow, causing an inferior effect. The herbicidal effect is also disadvantageously decreased by rain-fall after the application. In such cases, the regrowth of the weeds is rapid, whereby the purpose of the application of the herbicide cannot be attained. Accordingly, sequential applications of the herbicides are necessitated. Consequently, a need continues to exist for an effective herbicide especially for use in an orchard against grown weeds. 
     SUMMARY OF THE INVENTION 
     Accordingly, it is an object of the present invention to provide a herbicidal composition which is effective for inhibiting the growth of weeds in the growth stage as well as weeds in other stages in both agricultural and non-agricultural areas, especially in orchards. 
     Briefly, this and other objects of this invention, as will hereinafter become clear from the ensuing discussion, have been attained by providing a herbicidal composition which comprises a bipyridylium salt of 1,1&#39;-dimethyl-4,4&#39;-bipyridylium or 1,1&#39;-ethylene-2,2&#39;-bipyridylium and a thiocarbamate having the formula ##STR3## wherein R and R 1  each represent a lower alkyl group having 1 - 7 carbon atoms which in combination with each other can form a heterocyclic ring with the N atom; R 2  represents ##STR4## wherein X represents a halogen atom such as F, Cl, Br or I, or a lower alkyl group, having 1 - 7 carbon atoms and n represents 0, 1 or 2. 
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The thiocarbamates used in this invention have a relatively low herbicidal effect in foliage treatment when used alone. Accordingly, heretofore, it has been considered nearly impossible to improve the herbicidal effect in foliage treatment by combination with other herbicides. The present invention has been attained by the discovery of a special synergistic effect resulting from the combination of the specific bypyridylium salts and the specific thiocarbamates mentioned above. The surprising synergistic effects imparted by the combination of these ingredients are as follows: 
     (1) The herbicidal drought effect of the specific bipyridylium salt when used alone is remarkably improved. Effective results can be attained by using an amount of the specific bipyridylium salt which is only 1/2 - 1/4 of the amount required when the salt is used alone. 
     (2) The herbicidal effect against weeds in the grown stage is remarkably improved. The weed-growth inhibiting period is prolonged by prevention of the regrowth of the weeds. 
     (3) The herbicidal effect is improved, even when it is applied under intense irradiation. 
     (4) The decrease in the herbicidal effect caused by rainfall after application is negligible. 
     It is considered that the above-mentioned effects are effected by promoting the absorption and translocation of the specific bipyridylium salt into the body of plants by synergistic action with the specific thiocarbamate, and also by promoting the herbicidal effect of the specific bipyridylium salt in the body of the plant. The specific thiocarbamate itself imparts a herbicidal effect in soil-treatment in addition to the above-mentioned synergistic effects to control the growth of weeds in the soil. Accordingly, the herbicidal composition of this invention is an ideal herbicidal composition for both foliage and soil-treatment. Among other things, the synergistic effects could not be expected because the specific thiocarbamate is a soil-treating agent and the herbicidal effect is produced by inhibition of protein production in plants. 
     In the herbicidal composition of this invention, the ratio of the bipyridylium salt to the thiocarbamate should be 1 : 1 ˜ 100, preferably 5 ˜ 30. In foliage treatment, the amount of the bipyridylium salt should be 5 - 500 g/10 ares, preferably 10 - 50 g/10 ares, and the amount of the thiocarbamate should be 20 - 500 g/10 ares, preferably 100-300 g/10 ares. In soil treatment, the amount of the pyridylium salt should be 5 - 500 g/10 ares, preferably 10 - 50 g/10 ares, and the amount of the thiocarbamate should be 50 -1000 g/10 ares, preferably 200-600 g/10 ares. 
     Suitable bipyridylium salts include the dichloride and dibromide of 1,1&#39;-dimethyl-4,4&#39;-bipyridylium or 1,1&#39;-ethylene-2,2&#39;-bipyridylium; that is, 
     Compound A: 
     1,1&#39;-dimethyl-4,4&#39;-bipyridylium dichloride ##STR5## Compound B: 1,1&#39;-dimethyl-4,4&#39;-bipyridylium dibromide 
     Compound C: 
     1,1&#39;-ethylene-2,2&#39;-bipyridylium dichloride ##STR6## Compound D: 1,1&#39;-ethylene-2,2&#39;-bipyridylium dibromide. 
     Suitable thiocarbamates include the following: 
     Compound 1: 
     S-benzyl-N,N-di-n-propylthiolcarbamate 
     b.p. 123°-125° C./0.015 mm Hg 
     Compound 2: 
     S-(4-methylbenzyl)-N,N-diethylthiolcarbamate 
     b.p. 107°-115° C./0.002 mm Hg 
     Compound 3: 
     S-(4-chlorobenzyl)-N-hexamethyleneiminocarbothiolate 
     m.p. 53°-55° C. 
     Compound 4: 
     S-(2-chlorobenzyl)-N,N-diethylthiolcarbamate 
     b.p. 136°-140° C./0.04-0.05 mm Hg 
     Compound 5: 
     S-(2.5-dimethylbenzyl)-N,N-dimethylthiolcarbamate 
     b.p. 130°-140° C./0.012 mm Hg 
     Compound 6: 
     S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate 
     b.p. 127°-131° C./0.012 mm Hg 
     The herbicidal compositions of this invention impart excellent herbicidal effects when applied to gramineous weeds, broadleaf weeds, perennial weeds and the like on agricultural areas such as upland fields, paddy fields, as well as orchards, and on non-agricultural areas. In applying the two active ingredients, it is also possible to prepare two compositions each containing one of the active ingredients of the bipyridylium salt and the thiocarbamate. The two compositions can then be combined in the application so as to produce a mixture in the above-mentioned ratio. The active ingredients can be applied using conventional techniques such as by adding a solid or liquid diluent or a surfactant and diluting with water. 
    
    
     Having now generally described the invention, a further understanding can be obtained by reference to certain specific Examples and Experiments, which are provided herein for purposes of illustration only and are not intended to be limiting in any manner unless otherwise specified. 
     PREPARATION OF COMPOSITION 1 
     Wettable Powder 
     40 wt. parts of Compound 1, 10 wt. parts of Compound B, 2 wt. parts of polyoxyethylenealkylarylether, 2 wt. parts of polyvinyl alcohol, 25 wt. parts of silicon dioxide and 21 wt. parts of diatomaceous earth were uniformly mixed and crushed to yield a wettable powder. 
     Preparation of Composition 2 
     Emulsion 
     40 wt. parts of Compound 2, 10 wt. parts of Compound A, 10 wt. parts of polyoxyethylenealkyl phenol and 40 wt. parts of methanol were mixed and diluted with water to yield an emulsion. 
     Preparation of Composition 3 
     Wettable Powder 
     25 wt. parts of compound 3, 25 wt. parts of Compound C, 2 wt. parts of polyoxyethylenealkylarylether, 2 wt. parts of polyvinyl alcohol and 46 wt. parts of diatomaceous earth were uniformly mixed and crushed to yield a wettable powder. 
     Preparation of Composition 4 
     Wettable Powder 
     30 wt. parts of Compound 4, 15 wt. parts of Compound D, 2 wt. parts of sodium alkylacrylsulfonate, 2 wt. parts of polyvinyl alcohol, 10 wt. parts of silicon dioxide and 41 wt. parts of diatomaceous earth were uniformly mixed and crushed to yield a wettable powder. 
     Preparation of Composition 5 
     Emulsion 
     40 wt. parts of Compound 5, 5 wt. parts of Compound A, 7 wt. parts of polyoxyethylenealkylarylether, 3 wt. parts of calcium alkylbenzene sulfonate and 45 wt. parts of methanol were mixed and diluted with water to yield an emulsion. 
     The effect of the herbicidal compositions of this invention will be illustrated by certain experiments, which are not intended to be limiting unless otherwise specified. 
     EXPERIMENT 1 
     Manna-grass (height of 25 - 30 cm) and Pig weed (height of 25 - 30 cm) grown in pots of 100 cm 2  area were used for the experiments. The herbicidal compositions containing the amounts of the active ingredients specified in Table 1 were diluted with water. The diluted compositions were uniformly sprayed by a microsprayer at a rate of 100 liter/10 ares. The tests were performed twice in a greenhouse. After 15 days following the application, the weeds above the earth were cut, dried and weighed. The percentage of the weight of the dried weeds in the treated fields to that of the non-treated fields was calculated. Compositions prepared by mixing Compound A (an emulsion containing 24% of the active ingredient) or Compound D (an emulsion containing 30% of the active ingredient) and each of several thiocarbamates (an emulsion containing 50% of the active ingredient) in a tank were used. The applications of the compositions were conducted from 3:00 to 4:00 p.m. under an irradiation intensity of 30,000 Lux. The treating compositions and results are shown in Table 1. 
     
                       Table 1______________________________________                     Manna-    Pig-Active     Amount of      grass     weedingredient emulsions      (%)       (%)______________________________________      A              5Compound A 200cc   +      400cc 2       5      100     +      200   19      24+           50     +      100   38      46Compound 5  25     +       50   50      59      A              1Compound A 200cc   +      400cc 0       0      100     +      200   5       8+           50     +      100   18      21Compound 1  25     +      100   33      46      A              2Compound A 200cc   +      400cc 0       0      100     +      200   0       3+           50     +      100   3       16Compound 2  25     +      100   31      38      A              3Compound A 200cc   +      400cc 0       0      100     +      200   0       8+           50     +      100   6       21Compound 3  25     +       50   42      47      A              4Compound A 200cc   +      400cc 0       0      100     +      200   0       4+           50     +      100   11      17Compound 4  25     +       50   36      51      A              5Compound A 200cc   +      400cc 0       0      100     +      200   0       0+           50     +      100   3       11Compound 5  25     +       50   18      30      A              6Compound A 200cc   +      400cc 0       0      100     +      200   0       0+           50     +      100   5       8Compound 6  25     +       50   12      16      D              1Compound D 200cc   +      400cc 0       0      100     +      200   0       0+           50     +      100   3       14Compound 1  25     +       50   24      29      D              3Compound D 200cc   +      400cc 0       0      100     +      200   0       1+           50     +      100   5       15Compound 3  25     +       50   29      26      D              6Compound D 200cc   +      400cc 0       0      100     +      200   0       0+           50     +      100   2       0Compound 6  25     +        50  10      6      800            92        100Compound 1 400            100       100      200            100       100      100            100       100      800            88        96Compound 2 400            97        100      200            100       100      100            100       100      800            93        97Compound 3 400            98        100      200            100       100      100            100       100      800            98        100Compound 400      400            100       100      200            100       100      100            100       100      800            89        90Compound 5 400            97        96      200            100       100      100            100       100      800            90        95Compound 6 400            100       100      200            100       100      200            23        52Compound A 100            40        67       50            81        93       25            100       100      200            46        41Compound D 100            63        56       50            98        91       25            100       100Non-treatment      --             100       100______________________________________ 
    
     EXPERIMENT 2 
     Synergistic Effect (10 days following the application) 
     An orange orchard wherein various test weeds were uniformly grown was divided into blocks of dimension 2 m × 4 m. The herbicidal compositions containing amounts of the active ingredients as specified in Table 2 were diluted with water. The diluted compositions were sprayed at a rate of 100 liter/10 ares. After 10 days following the application, the herbicidal effects were observed. The weeds were Manna-grass (height of 40-50 cm); Smartweed (height of 50-70 cm); Hedge bindweed (height of 80-100 cm); and Cagratia japonice (height of 80-120 cm). The herbicidal effects are indicated using the following scale: 
     0: Number and height of the weeds is the same as that of the non-treated block. 
     1: 80% of the number or height of the weeds as compared with the non-treated block. 
     2: 60% of the number or height of the weeds as compared with the non-treated block. 
     3: 40% of the number or height of the weeds as compared with the non-treated block. 
     4: 20% of the number or height of the weeds as compared with the non-treated block. 
     5: weeds were completely dead. 
     The results are shown in Table 2. 
     
                       Table 2______________________________________Concentration ofactive ingredients       Manna-   Smart-  Hedge   Cagratia(ppm)       grass    weed    bindweed                                japonice______________________________________Compound A    720    3.0      2.5   3.0     3.0    360    1.5      1.0   1.5     2.0    180    0        0     0.5     0.5     90    0        0     0       0Compound ACompound CA            6400  +       1600   5      5     5       5200  +        800   5      5     5       5100  +        400   5      5     5       5 50  +        200   4.5    5     5       5Compound 6    4000   0.5      0.5   0       0    2000   0        0     0       0    1000   0        0     0       0     500   0        0     0       0Non-treated block       0        0       0       0______________________________________ 
    
     EXPERIMENT 3 
     Regrowth Inhibition of Manna-grass 
     Manna-grass (height of 30 - 35 cm) grown in pots of 100 cm 2  was used for the experiment. The herbicidal compositions containing the amounts of the active ingredients shown in Table 3 were diluted with water. The diluted compositions were uniformly sprayed by a microsprayer at a rate of 100 liter / 10 ares during the evening and the treated pots were kept in a greenhouse. Watering was conducted by sucking water from the bottom of each pot. The herbicidal effects were observed and are indicated as in Experiment 2. 
     The results are shown in Table 3. 
     
                       Table 3______________________________________            1 day   5 days  10 days                                  20 daysConcentration of after   after   after afteractive ingredients            appli-  appli-  appli-                                  appli-(ppm)            cation  cation  cation                                  cation______________________________________Compound A     360        3.5     3.5   1     0     180        2       2     0     0      90        1.5     1.5   0     0      45        0.5     0     0     0Compound A     A  6+         400 + 800  5       5     5     5Compound 6     200 + 400  5       5     5     5     100 + 200  5       5     5     4.5      50 + 100  5       5     4.5   3.0Compound 6     4000       0.5     0.5   0     0     2000       0       0     0     0     1000       0       0     0     0______________________________________ 
    
     EXPERIMENT 4 
     Effect of Rain 
     The test of Experiment 2 was repeated except for the application of artificial rain at a rate of 200 mm/hr. after 15 minutes following the application of the herbicidal compositions. The next day, the herbicidal effects were observed. 
     The results are shown in Table 4. 
     
                       Table 4______________________________________            Manna-      Manna-Concentration of grass       grassactive ingredients            non-rain    artificial(ppm)            block       rain block______________________________________Compound A     720        4.5         3     360        4           2     180        3.5         1Compound A     A   6     600 + 2400 5           5+         300 + 1200 5           5     150 +  600 5           5Compound 6      75 +  300 5           4.5Compound 6     4000       1.0         1.0     2000       0           0     1000       0           0______________________________________ 
    
     EXPERIMENT 5 
     Comparison of the effects of application at daytime versus those at evening 
     Manna-grass (height of 30-40 cm) grown in pots of 100 cm 2  was used for the experiment. The herbicidal compositions containing the amounts of the active ingredients specified in Table 5 were diluted with water. The diluted compositions were sprayed uniformly by a microsprayer at a rate of 10 liter/10 ares. The applications were conducted under an irradiation intensity of 50,000 lux of sunlight at daytime and a 2,500 lux at evening. After 5 days following the application, the herbicidal effects were observed and are indicated as in Experiment 2. 
     The results are shown in Table 5. 
     
                       Table 5______________________________________Concentration of 50,000 lux  2,500 luxactive ingredients            irradiation irradiation(ppm)            Manna-grass Manna-grass______________________________________Compound A     720        4           4.5     620        3           4     180        1.5         3.5Compound A     A    6     400 + 1600 5           5+         200 +  800 5           5     100 +  400 5           5Compound 6      50 +  200 5           5______________________________________ 
    
     Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.