Abstract:
N-benzoyl N&#39;-pyridyloxy phenyl urea having the formula ##STR1## wherein X 1  represents a halogen atom or methyl group; X 2  represents hydrogen or halogen atom; X 3  and X 4  respectively represent hydrogen or halogen atom; X 5  represents hydrogen or halogen atom; and X 6  represents a halogen atom or nitro or trifluoromethyl group are novel compounds. The compositions containing the compound as the active ingredient are effective as the insecticide for extinction of injurious insects with high safety in agricultural, forestry and hygienic applications.

Description:
This application is a continuation-in-part of Ser. No. 844,174, filed Oct. 21, 1977. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention: 
     The present invention relates to novel N-benzoyl N&#39;-pyridyloxy phenyl ureas and the process for producing the same and the insecticidal composition containing the same. 
     2. Description of the Prior Arts 
     Almost of the conventional insecticides impart neurotoxicity and contact toxicity to all kinds of insects. 
     And, it has been required to find selective insecticidal compounds without toxicity to useful insects, N-benzoyl N&#39;-phenyl ureas disclosed in U.S. Pat. No. 3,748,356 and N-benzoyl N&#39;-phenoxyphenyl ureas (no pyridyloxy group) disclosed in U.S. Pat. No. 4,005,223 have such insecticidal properties. 
     The N-benzoyl N&#39;-pyridyloxyphenyl ureas according to the present invention have a substantially better action than the above described known compounds. 
     SUMMARY OF THE INVENTION 
     It is an object of the present invention to provide novel N-benzoyl N&#39;-pyridyloxy phenyl ureas. 
     It is another object of the present invention to provide a process for producing N-benzoyl N&#39;-pyridyloxy phenyl ureas. 
     It is the other objects of the present invention to provide selective insecticidal compositions which are remarkably effective to certain injurious insects without affecting useful insects in remarkably low toxicity to animals. 
     The novel compounds of the present invention are N-benzoyl N&#39;-pyridyloxy phenyl ureas having the formula ##STR2## wherein X 1  represents a halogen atom or methyl group; X 2  represents hydrogen or halogen atom; X 3  and X 4  respectively represent hydrogen or halogen atom; X 5  represents hydrogen or halogen atom; and X 6  represents a halogen atom or nitro or trifluoromethyl group. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     
         __________________________________________________________________________CompoundNo.   Suitable compounds having the formula (I) include:__________________________________________________________________________1     N-(2-chlorobenzoyl)N&#39;-[3-chloro-4-(5-bromopyridyl-2-oxy)phenyl]urea 7 m.p. 196° to 199° C.2     N-(2-chlorobenzoyl)N&#39;-[3-chloro-4-(5-nitropyridyl-2-oxy)phenyl]urea 1 m.p. 209° to 212° C.3     N-(2-chlorobenzoyl)N&#39;-[4-(3,5-dibromopyridyl-2-oxy)phenyl]urea m.p. 185° to 188° C.4     N-(2-chlorobenzoyl)N&#39;-[3-chloro-4-(3,5-dibromopyridyl-2-oxy)phenyl] 4 urea m.p. 223° to 224° C.5     N-(2-chlorobenzoyl)N&#39;-[4-(3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 216° to 218° C.6     N-(2-chlorobenzoyl)N&#39;-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl] . urea m.p. 225° to 228° C.7     N-(2-chlorobenzoyl)N&#39;-[3,5-dichloro-4-(3,5-dichloropyridyl-2-oxy) phenyl]urea m.p. 221° to 223° C.8     N-(2-chlorobenzoyl)N&#39;-[4-(5-bromopyridyl-2-oxy)phenyl]urea m.p. 179° to 180° C.9     N-(2-chlorobenzoyl)N&#39;-[3-chloro-4-(5-chlorpyridyl-2-oxy)phenyl]urea 7 m.p. 198° to 200° C.10    N-(2-chlorobenzoyl)N&#39;-[3,5-dichloro-4-(5-chloropyridyl-2-oxy)phenyl] 2 urea m.p. 147° to 148° C.11    N-(2-chlorobenzoyl)N&#39;-[4-(5-trifluoromethylpyridyl-2-oxy)phenyl]urea N m.p. 149° to 151° C.12    N-(2-chlorobenzoyl)N&#39;-[3-chloro-4-(5-trifluoromethylpyridyl-2-oxy) phenyl]urea m.p. 182° to 185° C.13    N-(2-chlorobenzoyl)N&#39;-[4-(3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl]urea m.p. 186° to 187° C.14    N-(2-chlorobenzoyl)N&#39;-[3,5-dichloro-4-(5-trifluoromethylpyridyl-2-ox y) phenyl]urea m.p. 206° to 208° C.15    N-(2-chlorobenzoyl)N&#39;-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl- pyridyl-2-oxy)phenyl]urea m.p. 140° to 144° C.16    N-(2-chlorobenzoyl)N&#39;-[3-chloro-4-(3-chloro-5-trifluoromethylpyridyl - 2-oxy)phenyl]urea m.p. 224° to 226° C.17    N-(2,6-dichlorobenzoyl)N&#39;-[4-(3,5-dichloropyridyl-2-oxy)phenyl]urea O m.p. 228° to 230° C.18    N-(2,6-dichlorobenzoyl)N&#39;-[3-chloro-4-dichloropyridyl-2-oxy) phenyl]urea m.p. 214° to 216° C.19    N-(2,6-dichlorobenzoyl)N&#39;-[3,5-dichloro-4-(3,5-dichloropyridyl-2-oxy ) phenyl]urea m.p. 273° to 275° C.20    N-(2,6-difluorobenzoyl)N&#39;-[4-(3,5-dichloropyridyl-2-oxy)phenyl]urea O m.p. 184° to 185° C.21    N-(2,6-difluorobenzoyl)N&#39;-[3-chloro-4-(3,5-dichloropyridyl-2-oxy) phenyl]urea m.p. 230° to 231° C.22    N-(2,6-difluorobenzoyl)N&#39;-[3-chloro-4-(5-chloropyridyl-2-oxy)phenyl] A urea m.p. 210° to 212° C.23    N-(2,6-difluorobenzoyl)N&#39;-[4-(5-trifluoromethylpyridyl-2-oxy)phenyl] B urea m.p. 185° to 188° C.24    N-(2,6-difluorobenzoyl)N&#39;-[4-(3-chloro-5-trifluoromethylpyridyl-2-ox y) phenyl]urea m.p. 190° to 192° C.25    N-(2,6-difluorobenzoyl)N&#39;-[3-chloro-4-(5-trifluoromethylpyridyl-2-ox y) phenyl]urea m.p. 195° to 198° C.26    N-(2,6-difluorobenzoyl)N&#39;-[3,5-dichloro-4-(5-trifluoromethylpyridyl- 0 2-oxy)phenyl]urea m.p. 209° to 212° C.27    N-(2,6-difluorobenzoyl)N&#39;-[3,5-dichloro-4-(3-chloro-5-trifluoro- methylpyridyl-2-oxy)phenyl]urea m.p. 203° to 205° C.28    N-(2,6-difluorobenzoyl)N&#39;-[3-chloro-4-(3-chloro-5-trifluoromethyl- pyridyl-2-oxy)phenyl]urea m.p. 187° to 190° C.29    N-(2-methylbenzoyl)N&#39;-[4-(5-chloropyridyl-2-oxy)phenyl]urea m.p. 198° to 200° C.30    N-(2-methylbenzoyl)N&#39;-[4-(5-bromopyridyl-2-oxy)phenyl]urea m.p. 188° to 191° C.31    N-(2-methylbenzoyl)N&#39;-[4-(5-trifluoromethylpyridyl-2-oxy)phenyl]urea 1 m.p. 140° to 142° C.32    N-(2-methylbenzoyl)N&#39;-[3-chloro-4-(5-bromopyridyl-2-oxy)phenyl]urea N m.p. 207° to 209° C.33    N-(2-methylbenzoyl)N&#39;-[3-chloro-4-(5-trifluoromethylpyridyl-2-oxy) phenyl]urea m.p. 188° to 191° C.34    N-(2-methylbenzoyl)N&#39;-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl] O urea m.p. 213° to 215° C.35    N-(2-methylbenzoyl)N&#39;-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl- pyridyl-2-oxy)phenyl]urea m.p. 214° to 217° C.36    N-(2-methylbenzoyl)N&#39;-[3-bromo-4-(3,5-dichloropyridyl-2-oxy)phenyl] 5 urea m.p. 222° to 224° C.37    N-(2-methylbenzoyl)N&#39;-[4-(3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 216° to 219° C.38    N-(2-methylbenzoyl)N&#39;-[4-(3,5-dibromopyridyl-2-oxy)phenyl]urea m.p. 219° to 221° C.39    N-(2-methylbenzoyl)N&#39;-[4-(3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl]urea m.p. 171° to 173° C.40    N-(2-methylbenzoyl)N&#39;-[3,5-dichloro-4-(5-trifluoromethylpyridyl-2-ox y) phenyl]urea m.p. 219° to 221° C.41    N-(2-methylbenzoyl)N&#39;-[3-chloro-4-(3-chloro-5-trifluoromethylpyridyl - 2-oxy)phenyl]urea m.p. 156° to 159° C.__________________________________________________________________________ 
    
     The N-benzoyl N&#39;-pyridyloxy phenyl ureas having the formula (I) are produced by reacting a compound having the formula ##STR3## wherein X 1  represents a halogen atom or methyl group; X 2  represents hydrogen or halogen atom; R 1  represents amino or isocyanate group with a compound having the formula ##STR4## wherein X 3  and X 4  are the same and different and respectively represent hydrogen or halogen atom; X 5  represents hydrogen or halogen atom; X 6  represents halogen atom or nitro or trifluoromethyl group; and R 2  represents an amino or isocyanate group and R 2  is amino group in the case that R 1  is isocyanate group, R 2  is isocyanate group in the case that R 1  is amino group. 
     More particularly, the compounds having the formula (I) can be produced by the following processes (1) and (2). 
     (1) The reaction of benzoyl isocyanate having the formula ##STR5## with pyridyloxy aniline having the formula ##STR6## (wherein X 1 ,X 2 ,X 3 ,X 4 ,X 5  and X 6  are defined above) 
     (2) The reaction of benzamide having the formula ##STR7## with pyridyloxy phenyl isocyanate having the formula ##STR8## (wherein X 1 , X 2 ,X 3 , X 4 , X 5 , and X 6  are defined above). 
     The reaction is preferably carried out in the presence of a solvent. Suitable solvents include benzene, toluene, xylene, pyridine etc. 
     The reaction temperature is usually in a range of 0° to 120° C. and the reaction time is usually in a range of 0.1 to 24 hours. The reaction is preferably carried out at the temperature from 50° C. to a refluxing temperature for 1 to 5 hours. 
     Certain examples of preparations of the compounds of the present invention will be described. 
     EXAMPLE 1 
     Preparation of N-(2-chlorobenzoyl)N&#39;-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl]urea 
     A solution prepared by dissolving 2.9 g of 3-chloro-4-(3,5-dichloro-pyridyl-2-oxy) aniline in 50 ml of toluene was heated at 80° C. A solution prepared by dissolving 1.8 g of 2-chlorobenzoyl isocyanate in 20 ml of toluene was added dropwise to the former solution under stirring it and the reaction was carried out for 1 hour. After the reaction, the reaction mixture was cooled and the precipitate was filtered and washed with toluene and then with petroleum ether and dried to obtain 3.2 g of N-(2-chlorobenzoyl)N&#39;-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl]urea (m.p. 225° to 228° C.). 
     EXAMPLE 2 
     Preparation of N-(2,6-dichlorobenzoyl)N&#39;-[4-(3,5-dichloropyridyl-2-oxy)phenyl]urea 
     In accordance with the process of Example 1, except using 2.5 g of 4-(3,5-dichloropyridyl-2-oxy)aniline instead of 3-chloro-4-(3,5-dichloropyridyl-2-oxy)aniline and using 2.4 g of 2,6-dichlorobenzoyl isocyanate instead of 2-chlorobenzoyl isocyanate and reacting at 30° C. for 8 hours instead of 80° C. for 1 hour, the process was repeated to obtain 3.8 g of N-(2,6-dichlorobenzoyl)N&#39;-[4-(3,5-dichloropyridyl-2-oxy)phenyl]urea (m.p. 228° to 230° C.). 
     The compounds of the present invention impart excellent selective insecticidal effect as clearly understood from the following experiments. 
     EXAMPLE 3 
     Preparation of N-(2,6-difluorobenzoyl)N&#39;-[4-(3-chloro-5-trifluoromethylpyridyl-2-oxy)phenyl]urea 
     In accordance with the process of Example 1, except using 1.0 g of 4-(3-chloro-5-trifluoromethylpyridyl-2-oxy)anilin instead of 3-chloro-4-(3,5-dichloropyridyl-2-oxy)aniline and using 0.64 g of 2,6-difluorobenzoyl isocyanate instead of 2-chlorobenzoyl isocyanate and reacting at room temperature for 3 hours instead of 80° C. for 1 hour, the process was repeated to obtain 0.5 g of N-(2,6-difluorobenzoyl) N&#39;-[4-(3-chloro-5-trifluoromethylpyridyl-2-oxy)phenyl]urea (m.p. 190° to 192° C.). 
     EXAMPLE 4 
     Preparation of N-(2-methylbenzoyl)N&#39;-[4-(5-trifluoromethylpyridyl-2-oxy)phenyl]urea 
     A solution was prepared by dissolving 0.5 g of 4-(5-trifluoromethylpyridyl-2-oxy)aniline in 20 ml of toluene. A solution prepared by dissolving 0.32 g of 2-methylbenzoyl isocyanate in 20 ml of toluene was added dropwise to the former solution under stirring it and the reaction was carried out at room temperature for 1 hour. 
     After the reaction, the reaction mixture was cooled and the precipitate was filtered and washed with hexane and then recrystallized from ethanol to obtain 0.3 g of N-(2-methylbenzoyl)N&#39;-[4-(5-trifluoromethylpyridyl-2-oxy)phenyl]urea (m.p. 140° to 142° C.). 
     Most of the conventional insecticides impart quick effect and neurotoxicity and contact toxicity. However, the compounds of the present invention impart the delayed effect that the compounds affect to molting (ecdysis) and metamorphosis of specific insects which orally take the compound with feeds or water whereby the death of the specific insects is caused. 
     The compounds of the present invention impart remarkable insecticidal effect to larvae of Lepidoptera, Coleoptera, Hymenoptera and Diptera, for example, larvae of the following insects: 
     diamondback moth (Plutella xylostella), common white (Pieris rapae crucivora), cabbage armyworm (Mamesta brassicae), cabbage looper (Plusia nigrisigma), tobacco cutworm (Prodenia litura), smoller citrus dog (Papilio xuthus), small blackish cochlid (Seopelodes contracta), fall webworm (Hyphantria cunea), gypsy moth (Lymantria dispar), rice stem borer (Chilo suppressalis), bollworm (Heliothis zea), tobacco budworm (Heliothis virescens), bollweevil (Anthonomus grandis), confused flour beetle (Tribolium confusum), colorado potato beetle (Leptinotarsa decemlineata), sawfly (Neurotoma irdescens), Culex mosquito (Culex pipiens pallens), mosquito (Culex pipiens molestus). 
     The compounds of the present invention do not substantially impart insecticidal effect to adults and are ineffective to natural enemies as predatory insects and impart low toxicity to animals. 
     When the compounds are used as active ingredients of the insecticidal composition, it is possible to prepare various forms of the compositions such as dust, wettable powder, emulsifiable concentrate, invert emulsion, oil solution, aerosol preparation, etc. with adjuvants as the cases of agricultural compositions. The compositions can be applied with or without diluting them in suitable concentrations. 
     Suitable adjuvants include powdery carriers such as talc, kaolin, bentonite, diatomaceous earth, silicon dioxide, clay and starch; liquid diluents such as water, xylene, toluene, dimethylsulfoxide, dimethyl formamide, acetonitrile, and alcohol; emulsifiers dispersing agents spreaders etc. 
     The concentration of the active ingredient in the selective insecticidal composition is usually 5 to 80 wt. % in the case of the oily concentrate; and 0.5 to 30 wt. % in the case of dust; 5 to 60 wt. % in the case of wettable powder. 
     It is also possible to combine with the other agricultural ingredients such as the other insecticides, miticides, plant growth regulators. Sometimes synergetic effects are found. 
     The selective insecticides of the present invention are effective for inhibiting various injurious insects and they are usually applied at a concentration of the active ingredients of 5 to 10,000 ppm preferably 20 to 2,000 ppm. 
     When the active ingredient of the present invention is applied to noxious insects in water the composition having said concentration can be applied to inhibit them, whereby the concentration of the active ingredient in water can be lower than said concentration. 
     EXPERIMENT 1 
     The active ingredients were respectively dispersed in water to prepare dispersions having specified concentrations. Leaves of cabbage were dipped into the dispersions for about 10 seconds and taken out and dried under passing air. 
     A piece of moistened filter paper was put on each Petri dish (diameter 9 cm) and the dried leaves of cabbage were put on the filter paper and larvae of diamondback moth in 2nd or 3rd instar were fed on them and the Petri dishes were covered and kept in constant temperature at 28° C. with lightening. After 8 days from the treatment with the dispersion, the dead larvae were measured and the mortality rates were calculated by the following equation: ##EQU1## 
     
                       Table 1______________________________________Com-   Mortality rate (%)      Mortality rate (%)pound  (concentration)                Compound  (concentration)No.    200 ppm  100 ppm  No.     200 ppm                                   100 ppm______________________________________1      100      100      20      100    1002      100      100      21      100    1003      100      100      22      100    1004      100      100      23      100    1005      100      100      24      100    1006      100      100      25      100    1007      100       80      26      100    1008      100      100      27      100    1009      100      100      28      100    10010     100       60      31      100    10011     100       80      33      100    10012     100      100      34      100    10013     100      100      35      100    10014     100      100      36      100    10015     100      100      38      100    10016     100      100      39      100    10017     100      100      40      100    10018     100      100      41      100    10019      80       60______________________________________ 
    
     EXPERIMENT 2 
     On radish young seedlings grown in unglazed pots, adults of diamondback moth were fed and kept for 24 hours to blow ova. One day later, aqueous dispersions of the active ingredients (500 ppm) were respectively sprayed on the young seedlings to fall drops of the dispersion and dried and kept in glass greenhouse. After 10 days from the treatment with the dispersion, the mortal larvae were measured and the mortality rates were calculated by the equation ##EQU2## 
     The results are shown in Table 2. 
     
                       Table 2:______________________________________Compound No.       Mortality rate (%)______________________________________2                   804                  1006                  100______________________________________ 
    
     EXPERIMENT 3 
     About 20 cc of germinated rice seeds were put into cups (diameter: 9 cm, height: 3 cm) to grow them. When they grew to seedlings having a height of 1 to 2 cm, the aqueous dispersions at specified concentrations were respectively sprayed at a ratio of 2 cc per 1 cup and dried, and larvae of rice stem borer (just hatched) were fed and the cups were covered. After 10 days from the treatment with the dispersion, the dead larvae were measured and the mortality rates were calculated by the equation of Experiment 1. The results are shown in Table 3. 
     
                       Table 3:______________________________________        Mortality rate (%)Compound     (concentration)No.          200 ppm       100 ppm______________________________________ 1           100           100 2           100           100 4           100           100 6           100           10011           100           10012           100           10023           100           10024           100           100______________________________________ 
    
     EXPERIMENT 4 
     In a cup (diameter of 9 cm; height of 3 cm), about 20 cc of emerged rice seeds were bred to grow to young seedlings having height of 1.5 to 2 cm and then, 2 cc of each composition having 400 ppm a concentration of each active ingredient was sprayed per 1 cup, and dried, and larvae of rice stem borer in 3rd instar were fed on them and Petri dish was covered. After 10 days from the treatment, the dead larvae were measured and the mortality rates were calculated in accordance with the method of Experiment 1. The results are shown in Table 4. 
     
                       Table 4:______________________________________               Mortality rateCompound No.        (%)______________________________________31                  10033                  10034                  10036                  10037                  10038                  10039                  100______________________________________ 
    
     EXPERIMENT 5 
     N-(2-chlorobenzoyl)N&#39;-[4-(3,5-dibromopyridyl-2-oxy) phenyl]urea (Compound No. 3) was used to prepare the aqueous dispersions at specified concentrations. The effects of the dispersions to various insects were tested. The mortality rates after 10 days from the treatments were obtained in accordance with the process of Experiment 1. 
     The results are shown in Table 5. 
     
                       Table 5:______________________________________                    Concen-                    tration   MortalityInsects      Treatment   (ppm)     rate______________________________________cabbage armyworm:        cabbage leaf                     50       1002nd instar larvae        dipping(Lepidoptera)confused flour beetle:        wheat flour2nd larval instar        blending    200       100larvae (Coleoptera)1 sp. of sawfly        cherry branch3rd instar larvae        spraying    250       100(Hymenoptera)______________________________________ 
    
     EXPERIMENT 6 
     Leaves of azalea were dipped in an aqueous solution of each active ingredient (50 ppm) for 10 seconds, and they were dried in air and charged in a wide mouth glass bottle, and larvae of gypsy moth in 2nd instar were fed on them. The mouth of the bottle was covered with a gauze and was kept in a thermostat constant temperature bath with light at 28° C. After 6 days from the treatment, the dead larvae were measured and the mortality rates were calculated in accordance with the method of Experiment 1. The results are shown in Table 6. 
     
                       Table 6:______________________________________               Mortality rateCompound No.        (%)______________________________________ 3                  10013                  10015                  10012                  10020                  10011                  10023                  10024                  10025                  10027                  10028                  10035                  10041                  100______________________________________ 
    
     EXPERIMENT 7 
     Leaves of cabbage were dipped in an aqueous solution of each active ingredient (50 ppm) for 10 seconds, and they were dried in air. A wet filter paper was disposed in each Petri dish (diameter of 9 cm) and each leaf was put on it and larvae of tabacco cutworm in 2nd or 3rd instar were fed and the Petri dish was covered and was kept in a thermostat constant temperature bath with light at 28° C. After 7 days from the treatment, the dead larvae were measured and the mortality rates were calculated in accordance with the method of Experiment 1. The results are shown in Table 7. 
     
                       Table 7:______________________________________               Mortality rateCompound No.        (%)______________________________________ 3                  100 4                  10013                  10014                  10015                  10012                  10020                  10021                  10024                  10025                  10026                  10033                  10035                  10039                  100______________________________________ 
    
     EXPERIMENT 8 
     In each cup (diameter of 9 cm), about 250 ml of an aqueous solution of each active ingredient (100 ppb) was charged, larvae of mosquito (Culex pipiens molestus) in 3rd instar were charged and the cup was covered and was kept in a thermostat constant temperature bath with light at 28° C. After 10 days from the treatment, the dead larvae were measured and the mortality rates were calculated in accordance with the method of Experiment 1. The results are shown in Table 8. 
     
                       Table 8:______________________________________               Mortality rateCompound No.        (%)______________________________________ 3                  100 8                  10011                  10012                  10013                  10015                  10020                  10021                  10023                  10024                  10025                  10027                  10028                  10039                  100______________________________________ 
    
     Composition 1: 
     
         ______________________________________(a)   N-(2-chlorobenzoyl)N&#39;-[3-chloro-4-(3,5-dichloropyridyl- 2-oxy)phenyl]urea                        20 wt. parts(b)   Dimethyl sulfoxide     70 wt. parts(c)   Polyoxyethylenealkylphenyl ether                        10 wt. parts______________________________________ 
    
     The components were uniformly blended to dissolve the ingredient to prepare an emulsifiable concentrate. 
     Composition 2: 
     
         ______________________________________(a) N-(2-chlorobenzoyl)N&#39;-[4-(3,5-dichloropyridyl-2-oxy)phenyl]    urea                    5 wt. parts(b) Talc                   92 wt. parts(c) Sodium naphthalene sulfonate    formaldehyde condensate                       3 wt. parts______________________________________ 
    
     The mixture was pulverized to uniformly mix them to prepare a dust. 
     Composition 3: 
     
         ______________________________________(a) N-(2,6-dichlorobenzoyl)N&#39;-[4-(3,5-dichloropyridyl-2-oxy)    phenyl]urea                     50 wt. parts(b) Jeeklite (fine divided clay)                     45 wt. parts(c) Sodium ligninsulfonate                      5 wt. parts______________________________________ 
    
     The components were pulverized to uniformly mix them to prepare a wettable powder. 
     Composition 4: 
     
         ______________________________________(a) N-(2,6-difluorobenzoyl)N&#39;-[4-(3-chloro-5-tri-    fluoromethylpyridyl-2-oxy) phenyl] urea                          20 wt. parts(b) N,N-dimethylformamide      70 wt. parts(c) Polyoxyethylenealkylphenyl ether                          10 wt. parts______________________________________ 
    
     The components were uniformly blended to dissolve the ingredient to prepare an emulsifiable concentrate. 
     Composition 5: 
     
         ______________________________________(a) N-(2-chlorobenzoyl)N&#39;-[3,5-dichloro-4-(-3-chloro-5-trifluoromethylpyridyl-2-oxy)phenyl]urea5 wt. parts(b) Talc                       95 wt. parts______________________________________ 
    
     The mixture was pulverized to uniformly mix them to prepare a dust. 
     Composition 6: 
     
         ______________________________________(a) N-(2-methylbenzoyl)N&#39;-[3-chloro-4-(3-chloro-5-trifluoromethylpyridyl-2-oxy)phenyl]urea    5 wt. parts(b) Talc                       95 wt.parts______________________________________ 
    
     The mixture was pulverized to uniformly mix them to prepare a dust.