Abstract:
A novel compound for combatting insect, mite, fungus or bacterium is a pyridylaniline represented by the following formula (I) ##STR1## wherein X is a trifluoromethyl group, a halogen atom, a lower alkyl group or a lower alkoxy group; n is an integer of 0 to 4; R is a hydrogen atom or an acetyl group; Y is a hydrogen atom, a halogen atom a lower alkoxy group, a lower alkylthio group, a hydroxy group, an azido group or a phenoxy group of which the phenyl ring may be substituted by a hydroxy group; Z 1 , Z 2  and Z 3  are a trifluoromethyl group or a nitro group, provided that at least one of X is a trifluoromethyl group or a lower alkyl group when n is an integer of 3 or 4.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a novel pyridylaniline for combatting insect, mite, fungus or bacterium. 
     2. Description of the Prior Art 
     It has been known that certain pyridylanilines have activities for combatting noxious livings such as insects, mites, fungi, bacteria and rodents in the prior arts, for example, the compounds having rodenticidal activity are disclosed in U.S. Pat. No. 4,140,778 and the compounds having pesticidal activity are disclosed in U.S. Pat. No. 3,965,109 and U.S. Pat. No. 3,926,611. 
     It has not been known that pyridylanilines having the specific substituents on pyridyl ring according to the present invention have activities for combatting noxious insect, mite, fungus, and bacterium. 
     SUMMARY OF THE INVENTION 
     It is an object of the present invention to provide novel pyridylanilines which are effective for combatting noxious insect, mite, fungus and bacterium. 
     It is another object of the present invention to provide novel compositions which have insecticidal, acaricidal, fungicidal and bactericidal activities. 
     It is the other object of the present invention to provide a process for producing the novel pyridylaniline. 
     The foregoing and other objects of the present invention have been attained by providing a pyridylaniline represented by the following formula (I) ##STR2## wherein X is a trifluoromethyl group, a halogen atom, a lower alkyl group or a lower alkoxy group; n is an integer of 0 to 4; R is a hydrogen atom or an acetyl group; Y is a hydrogen atom, a halogen atom a lower alkoxy group, a lower alkylthio group, a hydroxy group, an azido group or a phenoxy group of which the phenyl ring may be substituted by a hydroxy group; Z 1 , Z 2  and Z 3  are a trifluoromethyl group or a nitro group, provided that at least one of X is a trifluoromethyl group or a lower alkyl group when n is an integer of 3 or 4. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The pyridylanilines of the present invention can be the compounds having the formula (I) wherein the halogen atom can be F, Cl, Br or I and the lower alkyl group for the lower alkyl group, the lower alkoxy group or the lower alkylthio group can be C 1  -C 4  alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl groups. 
     The optional compounds included in the pyridylanilines having the formula (I) are the compounds having the formula (III), (V) or (X). ##STR3## wherein X and n are defined above, and Y 1  represents hydrogen atom or a halogen atom; Y 2  represents hydrogen atom, a lower alkoxy group, a halogen atom, azido group, or phenoxy group which can be substituted by a hydroxyl group; Y 3  represents a lower alkoxy group, a lower alkylthio group, hydroxyl group, azido group or phenoxy group which can be substituted by a hydroxyl group; and m is an integer of 0 to 3. The most important pyridylanilines are the compounds having the formula (VII) ##STR4## wherein X 4  is a halogen atom; X 5  is a hydrogen atom or a halogen atom; Y 2  is defined above. 
     The pyridylanilines of the present invention can be produced by the following processes. 
     REACTION (I) 
     Pyridylanilines having the formula (I) wherein R is hydrogen atom and Y is hydrogen or halogen atom 
     The compounds are produced by the following reaction in the presence of a base. ##STR5## wherein X, Y 1 , Z 1 , Z 2 , Z 3  and n in the formulas (A), (B) and (VIII) are defined above and U and W in the formulas (A) and (B) are respectively a halogen atom or amino group and W is amino group in the case of U of a halogen atom; and W is a halogen atom in the case of U of amino group. 
     The starting compounds (A) are mostly known and disclosed in U.S. Pat. No. 3,681,369, and E.P.O. Publication No. 0000483 etc. 
     The starting compounds (B) are mostly known and disclosed in U.S. Pat. No. 4,117,167 and E.P.O. Publication No. 0000156, and No. 0004642. 
     In the industrial process, it is preferable to react the compound (A) wherein U is amino group with the compound (B) wherein W is a halogen atom. 
     The base used in the reaction can be alkali metal hydroxides, carbonates, hydrides, or alkaline earth metal hydroxides and carbonates, preferably potassium hydroxide, sodium hydroxide, sodium hydride and sodium bicarbonate. 
     The reaction is preferably carried out in the presence of a solvent. Suitable solvents include aprotonic polar solvents such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran, sulfolane and dioxane. It is preferable to use dimethylformamide or tetrahydrofuran. The reaction temperature is usually in a range of -100° C. to +200° C. preferably 0° to 200° C. and the reaction time is in a range of 0.5 to 24 hours especially 1 to 10 hours. 
     REACTION (II) 
     Pyridylanilines having the formula (I) wherein R is hydrogen atom and Y is hydroxyl group, a lower alkoxy group, a lower alkylthio group, azido group or phenoxy group which can be substituted by hydroxyl group 
     The compounds are produced by the following reaction in the presence of a base ##STR6## wherein X, Y 3  Z 1 , Z 2 , Z 3  and n in the formulas (X) and (XI) are defined above and Hal represents a halogen atom. In the formula (C), Y 4  represents hydrogen atom, a lower alkyl group or phenyl group which can be substituted by hydroxyl group; and Y 5  represents a lower alkyl group. The base used in the reaction is the same as the bases used in the former reaction (I). 
     The reaction is preferably performed in a solvent. The solvent can be the solvents used in the reaction (I) and alcohols such as methanol and ethanol, and halohydrocarbons such as carbon tetrachloride, chloroform and m-dichlorobenzene. The reaction temperature is usually in a range of -30° C. to +170° C. preferably 0° C. to 170° C. The reaction time is in a range of 0.5 to 20 hours. 
     In the reaction (II) using the starting compound having Y 4  of a hydroxy phenyl group, it is preferable to react them in nitrogen atmosphere. When the boiling point of the solvent is low, it is preferable to react them in a closed reactor. 
     REACTION (III) 
     Pyridylanilines having the formula (I) wherein R is acetyl group 
     The compounds are produced by the following reaction. ##STR7## wherein X, Y, Z 1 , Z 2 , Z 3  and n in the formulas (XII) and (XIII) are defined above. 
     The acetylating agents can be anhydride, halides and esters of acetic acid, such as acetic anhydride, acetyl chloride, and ethyl acetate. 
     The base can be the bases used in reaction (I) and organic bases such as pyridine and triethylamine preferably organic bases. The reaction temperature is in a range of 0° to 100° C. The reaction time is in a range of 1 to 10 hours. 
     Certain examples of syntheses will be illustrated. 
     PREPARATION 1 
     Preparation of N-(3,5-dichloro-2-pyridyl)-2,6-dinitro-4-trifluoromethylaniline 
     In 20 ml. of dimethylformamide, 1.65 g. of 2-amino-3,5-dichloropyridine was dissolved and 1.0 g. of powdery potassium hydroxide was gradually added with stirring. After the addition, 2.7 g. of 2,6-dinitro-4-trifluoromethylchlorobenzene was added at 30° C. during 5 minutes and the reaction was continued for about 3 hours. The reaction mixture was acidified with conc. HCl and the product was extracted with methylenechloride. The extracted layer was washed with water and dehydrated. The solvent was distilled off and the product was separated by a silica gel column with an eluent of toluene and the solvent was distilled off to obtain 2.8 g. of the object compound having the melting point of 85° to 87° C. 
     PREPARATION 2 
     Preparation of N-(3,5-dichloro-6-methyl-2-pyridyl)2,6-dinitro-3-chloro-4-trifluoromethylaniline 
     In 30 ml. of dimethylformamide, 1.8 g. of 2-amino-3,5-dichloro-6-methylpyridine was dissolved in 0.67 g. of powdery potassium hydroxide was gradually added with stirring. After the addition, a solution of 3.07 g. of 2,4-dichloro-3,5-dinitrobenzotrifluoride in 10 ml. of dimethylformamide was added dropwise at room temperature and the reaction was continued for about 3 hours. The reaction mixture was acidified with conc. HCl and was poured into water. The precipitate was filtered and recrystallized from methanol to obtain 2.96 g. of the object compound having a melting point of 128° to 130° C. 
     PREPARATION 3 
     Preparation of N-(3,5-dichloro-2-pyridyl)-2,6-dinitro-3-chloro-4-trifluoromethylaniline 
     In 20 ml. of dimethylformamide, 1.63 g. of 2-amino-3,5-dichloropyridine was dissolved and 0.73 g. of powdery potassium hydroxide was added with stirring. After the addition, 3.06 g. of 2,4-dichloro-3,5-dinitrobenzotrifluoride was added during 10 minutes. The reaction was continued for about 2 hours. After the reaction, the reaction mixture was poured into water and acidified with conc. HCl and the product was extracted with methylene chloride. The extracted layer was washed with water and dehydrated and the solvent was distilled off and the product was separated by a silica gel column with an eluent of toluene and then the solvent was distilled off to obtain 1.38 g. of the object compound having the melting point of 64° to 65° C. 
     PREPARATION 4 
     Preparation of N-(3-chloro-5-triluoromethyl-2-pyridyl)-2,6-dinitro-3-chloro-4-trifluoromethylaniline 
     METHOD A 
     In accordance with the process of Preparation 3 except using 1.97 g. of 2-amino-3-chloro-5-trifluoromethylpyridine instead of 1.63 g. of 2-amino-3,5-dichloropyridine and adding 0.62 g. of powdery potassium hydroxide instead of 0.73 g. of the same, the process was carried out to obtain 1.15 g. of the object compound having the melting point of 100° to 102° C. 
     METHOD B 
     In 60 ml. of tetrahydrofuran, 3.22 g. of 2-amino-3-chloro-5-trifluoromethylpyridine was dissolved and 2.0 g. of powdery potassium hydroxide was gradually added with stirring and the mixture was cooled at 0° C., and a solution of 5.0 g. of 2,4-dichloro-3,5-dinitrobenzotrifluoride in 40 ml. of tetrahydrofuran was added dropwise at the same temperature and the mixture was heated to react them at room temperature for 3 hours. The reaction mixture was poured into water and 150 ml. of ethyl acetate was added and the mixture was acidified with conc. HCl and the product was extracted. The extraction solution was washed twice with water and dehydrated over anhydrous sodium sulfate and concentrated. The product was separated by a silica gel column with an eluent of a mixture of n-hexane and ethyl acetate (10:1) and the solvent was distilled off to obtain 6.5 g. of the object compound having the melting point of 100° to 102° C. 
     2-Amino-3-chloro-5-trifluoromethylpyridine used in Preparation 4 can be produced by the following process. 
     In a 50 ml. autoclave, 6.5 g. of 2,3-dichloro-5-trifluoromethylpyridine and 20 ml. of 28% ammonia water were charged and stirred at 100° C. for 24 hours and heated at 125° C. for 5 hours to react them (pressure of about 2 atm.). After cooling the reaction mixture, the resulting crystal was washed with water and dehydrated to obtain 1.5 g. of 2-amino-3-chloro-5-trifluoromethylpyridine having the melting point of 90° to 92° C. 
     PREPARATION 5 
     Preparation of N-(3,5-dichloro-4-pyridyl)-2,6-dinitro-4-trifluoromethylaniline 
     In accordance with the process of Preparation No. 2 except using 1.63 g. of 3,5-dichloro-4-aminopyridine instead of 1.8 g. of 2-amino-3,5-dichloro-6-methylpyridine; and using 50 ml. of dimethylformamide instead of 30 ml. of the same and using 2.7 g. of 2,6-dinitro-4-trifluoromethylchlorobenzene instead of 3.07 g. of the same, the process was carried out to obtain 2.8 g. of the object compound having the melting point of 138° to 140° C. 
     PREPARATION 6 
     Preparation of N-(3,5-dichloro-2-pyridyl)-2,4-dinitro-6-trifluoromethylaniline 
     In 20 ml. of dimethylformamide, 1.65 g. of 2-amino-3,5-dichloropyridine was dissolved and 1.0 g. of powdery potassium hydroxide was gradually added with stirring. After the addition, 2.7 g. of 2,4-dinitro-6-trifluoromethylchlorobenzene was added at 30° C. during 5 minutes to react them for about 3 hours. The reaction mixture was acidified with conc. HCl and the product was extracted with methylenechloride. The extracted layer was washed with water and dehydrated and the solvent was distilled. The product was separated by a silica gel column with an eluent of toluene and the solvent was distilled off to obtain 2.5 g. of the object compound having the melting point of 98° to 101° C. 
     PREPARATION 7 
     Preparation of N-(2-chloro-5-trifluoromethyl-6-pyridyl)-2,4-dinitro-6-trifluoromethylaniline 
     In 20 ml. of dimethylformamide, 1.8 g. of 2-chloro-6-amino-5-trifluoromethylpyridine was dissolved and 1.0 g. of powdery potassium hydroxide was gradually added with stirring. After the addition, a solution of 2.7 g. of 2,4-dinitro-6-trifluoromethylchlorobenzene in 10 ml. of dimethylformamide was added dropwise at room temperature and the reaction was continued for about 3 hours. The reaction mixture was acidified with conc. HCl and was poured into water. The precipitate was filtered and recrystallized from methanol to obtain 2.9 g. of the object compound having the melting point of 129° to 131° C. 
     PREPARATION 8 
     Preparation of N-(3,5-dichloro-4,6-dimethyl-2-pyridyl)-2,4-dinitro-6-trifluoromethylaniline 
     In 20 ml. of dimethylformamide, 1.9 g. of 2-amino-3,5-dichloro-4,6-dimethylpyridine was dissolved and 0.7 g. of powdery potassium hydroxide was gradually added with stirring and a solution of 2.7 g. of 2,4-dinitro-6-trifluoromethylchlorobenzene in 10 ml. of dimethylformamide was added dropwise at room temperature to react them for about 10 hours. The reaction mixture was treated as the process of Preparation No. 7 to obtain 1.6 g. of the object compound having the melting point of 131° to 133° C. 
     PREPARATION 9 
     Preparation of N-(5-methoxy-2-pyridyl)-2,4-dinitro-6-trifluoromethylaniline 
     In accordance with the process of Preparation 8 except using 1.2 g. of 2-amino-5-methoxypyridine and 2.8 g. of 2,4-dinitro-6-trifluoromethylchlorobenzene, the reaction was carried out for 5 hours. The reaction mixture was treated as the process of Preparation 6 to obtain 1.2 g. of the object compound having the melting point of 102° to 105° C. 
     PREPARATION 10 
     Preparation of N-(3-chloro-5-trifluoromethyl-2-pyridyl)-2,4-dinitro-3-methoxy-6-trifluoromethylaniline 
     In accordance with the process of Preparation 8 except using 1.9 g. of 2-amino-3-chloro-5-trifluoromethylpyridine and 2.8 g. of 2,4-dinitro-3-methoxy-6-trifluoromethylchlorobenzene, the reaction was carried out for 3 hours. The reaction mixture was treated as the process of Preparation 6 to obtain 1.4 g. of the object oily compound. 
     PREPARATION 11 
     Preparation of N-(3-chloro-5-trifluoromethyl-2-pyridyl)-2,6-dinitro-3-ethoxy-4-trifluoromethylaniline 
     In 30 ml. of ethanol, 1.5 g. of sodium hydride was added with stirring and a solution of 7.0 g. of N-(3-chloro-5-trifluoromethyl-2-pyridyl)-2,6-dinitro-3-chloro-4-trifluoromethylaniline (obtained in Preparation 4) in 50 ml. of dimethylsulfoxide was added dropwise to react them at room temperature for 3 hours. The reaction mixture was poured into water and the product was extracted with methylene chloride. The extracted layer was washed with water and dehydrated and the solvent was distilled, the product was separated by a silica gel column with an eluent of a mixture of n-hexane and ethyl acetate (4:1) and the solvent was distilled off to obtain 4.0 g. of the object compound having the melting point of 106° to 108° C. 
     PREPARATION 12 
     Preparation of N-acetyl-N-(3-chloro-5-trifluoromethyl-2-pyridyl)-2,6-dinitro-3-chloro-4-trifluoromethylaniline 
     In 20 ml. of pyridine, 2.3 g. of N-(3-chloro-5-trifluoromethyl-2-pyridyl)-2,6-dinitro-3-chloro-4-trifluoromethylaniline (obtained in Preparation 4) was dissolved and a solution of 0.34 g. of acetylchloride in 10 ml. of pyridine was added dropwise to react them at 60° to 70° C. for 2 hours. Pyridine was distilled off from the reaction mixture and the product was separated by a silica gel column with an eluent of n-hexane and ethyl acetate (4:1) and the solvent was distilled off to obtain 0.8 g. of the object compound having the melting point of 75° to 77° C. 
     The typical pyridylanilines having the formula (III) are shown. 
     
         ______________________________________ ##STR8##                     (III)                 Position of   PropertyCompound              pyridine      meltingNo.     X.sub.n       ring      Y.sub.1                               point(°C.)______________________________________1       5-Cl          2         H   104-1062       3-Cl5-CF.sub.3                 2         H   104-1053       3,5-Cl.sub.2  2         H   85-874       3,5-Cl.sub.2  2         Cl  64-655       5-Cl          2         Cl  143-1446       4,6-Cl.sub.2  2         Cl  194-1967       3-Cl5-CF.sub.3                 2         Cl  100-1028       3,5-Cl.sub.26-CH.sub.3                 2         Cl  128-1309       3,5-Cl.sub.24,6-(CH.sub.3).sub.2                 2         H   184-18510      4-CH.sub.35-Br                 2         Cl  98-10011      3,5-Cl.sub.24,6-(CH.sub.3).sub.2                 2         Cl  146-14812      3,5-Cl.sub.24-CH.sub.3                 2         Cl  135-13713      3,5-Cl.sub.24-CH.sub.3                 2         H   116-11814      2,6-Cl.sub.2  3         Cl  166-16815      3,5-Cl.sub.2  4         H   138-14016      3,5-Cl.sub.2  4         Cl  129-13017      3,5-Br.sub.2  2         Cl  144-14718      3-Br5-Cl      2         Cl  131-13319      5-CF.sub.3    2         Cl  oily                               (n.sub.D.sup.25 1.571)20      3-Cl5-Br      2         Cl  119-12121      3-Br5-CF.sub.3                 2         Cl  89-9222      3-Br5-CF.sub.3                 2         H   112-11423      5-Br6-C.sub.2 H.sub.5                 2         Cl  137-13924      5-Br6-C.sub.2 H.sub.5                 2         H   146-14825      2,6-(OCH.sub.3).sub.2                 3         H   153-15526      3-CF.sub.35-Br6-Cl                 2         H   130-13227      3-CF.sub.35-Cl                 2         H   113-11528      3-CF.sub.35-Br                 2         H   104-10629      3-CF.sub.35-Cl                 2         Cl  138-14030      3-CF.sub.35-Br                 2         Cl  110-11231      3-CF.sub.35-Br6-Cl                 2         Cl  48-5232      3-Br5-CF.sub.36-Cl                 2         H   190-19233      3-Br5-CF.sub.36-Cl                 2         Cl  156-16034      3-Cl5-CF.sub.36-Cl                 2         H   150-15435      3-Cl5-CF.sub.36-Cl                 2         Cl  144-14536      3-CF.sub.3    2         Cl  oily37      3-CF.sub.3    2         H   81-8338      3-Cl5-CF.sub.3                 2         F   127-129______________________________________ 
    
     The typical pyridylanilines having the formula (X) are shown. 
     
         ______________________________________ ##STR9##                     (X)            Posi-            tion ofCom-             pyri-               Propertypound            dine                meltingNo.   X.sub.n    ring    Y.sub.3     point(°C.)______________________________________39    3-Cl5-CF.sub.3            2       OCH.sub.3   71-7340    &#34;          2       OC.sub.2 H.sub.5                                106-10841    &#34;          2       OC.sub.3 H.sub.7 (n)                                102-10442    &#34;          2       OC.sub.3 H.sub.7 (iso)                                138-13943    &#34;          2       OC.sub.4 H.sub.9 (n)                                109-11044    &#34;          2       OC.sub.4 H.sub.9 (iso)                                123-12445    &#34;          2       SCH.sub.3   138-13946    &#34;          2       SC.sub.2 H.sub.5                                oily47    &#34;          2       OH          183-18748    &#34;          2                     ##STR10##  178-18249    &#34;          2                     ##STR11##  162-16550    &#34;          2                     ##STR12##  78-8151    &#34;          2       N.sub.3     oily______________________________________ 
    
     The typical pyridylanilines having the formula (I) except the compounds (III) and (X) are shown. 
     
         __________________________________________________________________________ ##STR13##                                (I)         Position                PropertyComp.         of pyri-                meltingNo. X.sub.n   dine ring              R     Y   Z.sub.1                           Z.sub.2                              Z.sub.3                                 point(°C.)__________________________________________________________________________52  5-Cl      2    H     H   NO.sub.2                           NO.sub.2                              CF.sub.3                                 133-13553  5-I       2    &#34;     &#34;   &#34;  &#34;  &#34;  170-17254  5-Br      2    &#34;     &#34;   &#34;  &#34;  &#34;  137-14055  2-Cl      3    &#34;     &#34;   &#34;  &#34;  &#34;  125-12656  4-CH.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  134-13557  5-CF.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  oily58   --       3    &#34;     &#34;   &#34;  &#34;  &#34;  n.sub.D.sup.30 1.55659   --       4    &#34;     &#34;   &#34;  &#34;  &#34;  44-4560  3,5-Cl.sub.2         2    &#34;     &#34;   &#34;  &#34;  &#34;  98-10161  3,5-Br.sub.2         2    &#34;     &#34;   &#34;  &#34;  &#34;  161-16462  3-Br5-Cl  2    &#34;     &#34;   &#34;  &#34;  &#34;  106-10863  3-Cl5-Br  2    &#34;     &#34;   &#34;  &#34;  &#34;  89-9164  3-Br5-CH.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  123-12565  3-Cl5-CF.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  74-7766  2-Cl5-CF.sub.3         6    &#34;     &#34;   &#34;  &#34;  &#34;  129-13167  5-I6-C.sub.2 H.sub.5         2    &#34;     &#34;   &#34;  &#34;  &#34;  127-13068  3,5-Cl.sub.26-CH.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  72-7569  5-Cl6-CH.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  167-16870  5-CF.sub.36-Cl         2    &#34;     &#34;   &#34;  &#34;  &#34;  195-19671  4,6-(CH.sub.3).sub.2         2    &#34;     &#34;   &#34;  &#34;  &#34;  146-14772  4,6-Cl.sub.2         2    &#34;     &#34;   &#34;  &#34;  &#34;  169-17073  4-Cl6-CH.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  163-16574  5-OCH.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  102-10575  2,6-Cl.sub.2         3    &#34;     &#34;   &#34;  &#34;  &#34;  107-11076  3-CF.sub.36-Cl         2    &#34;     &#34;   &#34;  &#34;  &#34;  oily77  3,5-Cl.sub.24,6-         2    &#34;     &#34;   &#34;  &#34;  &#34;  131-133    (CH.sub.3).sub.278  3,5-Cl.sub.24-CH.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  166-16979  3,5-Cl.sub.2         4    &#34;     &#34;   &#34;  &#34;  &#34;  141-14280  3-Br5-CF.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  oily81  3-CF.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  106-10882  3-CF.sub. 35-Br6-Cl         2    &#34;     &#34;   &#34;  &#34;  &#34;  oily83  3-CF.sub.35-Cl         2    &#34;     &#34;   &#34;  &#34;  &#34;  120-12284  3-CF.sub.35-Br         2    &#34;     &#34;   &#34;  &#34;  &#34;  146-14885  3-Cl5-CF.sub.3         2    &#34;     OCH.sub.3                        &#34;  &#34;  &#34;  oily86  3,5-Cl.sub.2         2    &#34;     &#34;   &#34;  &#34;  &#34;  oily87  4-CH.sub.35-Br         2    &#34;     H   &#34;  &#34;  &#34;  58-6088  3-Cl5-CF.sub.3         2    COCH.sub.3                    Cl  &#34;  CF.sub.3                              NO.sub.2                                 75-7789  3-Cl5-CF.sub.3         2    H     H   CF.sub.3                           &#34;  &#34;  oily90  3,5-Cl.sub.2         2    &#34;     &#34;   &#34;  &#34;  &#34;  92-9491  3-CF.sub.35-Br6-Cl         2    &#34;     &#34;   &#34;  &#34;  &#34;  oily92  5-CF.sub.36-Cl         2    &#34;     &#34;   &#34;  &#34;  &#34;  142-14493  5-Cl      2    &#34;     &#34;   &#34;  &#34;  &#34;  oily94  3-CF.sub.36-Cl         2    &#34;     &#34;   &#34;  &#34;  &#34;  157-15995  3-Cl5-Cl6-CH.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  110-11196  4-CH.sub.35-Br         2    &#34;     &#34;   &#34;  &#34;  &#34;  oily97  3-Br5-Cl  2    &#34;     &#34;   &#34;  &#34;  &#34;  96-9898  3-Cl5-Br  2    &#34;     &#34;   &#34;  &#34;  &#34;  87-9099  3-CF.sub.36-Cl         2    &#34;     &#34;   &#34;  &#34;  &#34;  83-86100 5-CF.sub.36-Cl         2    &#34;     &#34;   &#34;  &#34;  &#34;  162-165101 3,5-Cl.sub.2         2    &#34;     &#34;   &#34;  &#34;  &#34;  73-75102 3-Cl5-CF.sub.3         2    &#34;     &#34;   &#34;  &#34;  &#34;  oily__________________________________________________________________________ 
    
     TEST 1 
     In each unglazed pot having a diameter of 9 cm, rice plant (Chukyo Asahi) was cultured. At 3 leaf stage of the rice seedlings, 10 ml. of each solution of each active ingredient having a concentration of 100 ppm was sprayed by a spray gun. After maintaining the pot in a green-house at 24° to 25° C. for one day, each spore suspension of Pyricularia orzae was sprayed. Five days after the inoculation, number of lesions on the third leaf of seedling was observed. The protective value was calculated by the following equation: ##EQU1## 
     The results are shown in Table 1. 
     
                       TABLE 1______________________________________Comp.  Protective            Comp.   Protective                            Comp. ProtectiveNo.    value (%) No.     value (%)                            No.   value (%)______________________________________1      91        18      100     35    952      100       19      100     36    1003      100       20      100     37    1004      100       21      100     38    1005      100       22      100     39    1007      100       23      93      40    1008      100       24      90      41    959      83        25      85      42    9510     86        26      100     43    9511     84        27      100     44    9512     100       28      100     45    10013     92        29      100     46    9514     100       30      100     47    9515     100       32      10016     100       33      10017     100       34      100______________________________________ 
    
     In accordance with the test, except using each solution of each active ingredient having a concentration of 50 ppm, each test was carried out. Compound Nos. 54, 60, 61, 64, 65, 67, 68, 69, 75, 76, 78, 80, 81, 82, 83, 84, 85, 86, 87, 92 and 100 were used. The protective values were respectively 100. 
     In the test, the concentration of the active ingredient was varied and Compound No. 7 was compared with N-(2,6-difluoro-3,5-dichloro-4-pyridyl)-N-(4-nitro-2-trifluoromethylphenyl)amine (hereinafter referring to as Reference Compound) disclosed in U.S. Pat. No. 3,965,109, No. 4,140,778 and No. 3,926,611. The results are shown in Table 2. 
     
                       TABLE 2______________________________________       Protective value (%)Compound No.  25 ppm       12.5 ppm______________________________________Comp. No. 7   100          98Reference      0            0compound______________________________________ 
    
     TEST 2 
     In each unglazed pot having a diameter of 9 cm, rice plant (Chukyo Asahi) was cultured. At 5 leaf stage of the rice seedlings, 20 ml. of each solution of each active ingredient having a concentration of 100 ppm was sprayed by a spray gun. After maintaining the pot in a green-house at 24° to 25° C. for one day, rice straw on which Rhizoctonia solani was cultured was held on sheath for inoculation. The pot was kept in an inoculation chamber at 30° C. and a humidity of 100% for 5 days. Each length of lesions of five stems per pot was measured. The protective value was calculated by the following equation: ##EQU2## The results are shown in Table 3. 
     
                       TABLE 3______________________________________Comp.  Preventive            Comp.   Preventive                            Comp. PreventiveNo.    value (%) No.     value (%)                            No.   value (%)______________________________________2      100       35      100     62    1003      100       36      92      63    1004      93        37      100     64    1006      100       39      100     65    1007      100       40      100     68    1008      90        41      95      72    10014     100       42      95      73    8715     100       43      95      74    9316     100       44      95      75    10018     100       45      100     76    10019     100       47      95      78    10026     100       48      100     79    9029     100       49      100     80    10030     95        50      100     85    10031     90        51      95      86    10032     100       54      90      87    10033     100       60      100     88    10034     100       61      100______________________________________ 
    
     TEST 3 
     In each unglazed pot having a diameter of 9 cm, cucumber plant (Suyo) was cultured. At one leaf stage, 10 ml. of each solution of each active ingredient having a concentration of 500 ppm was sprayed by a spray gun. After maintaining the pot in a green-house at 24° to 25° C. for one day, each spore suspension of Collectotrichum lagenarium was sprayed. Six days after the inoculation, number of lesions on the first leaf of seedling was observed. The protective value was calculated as Test 1. The results are shown in Table 4. 
     
                       TABLE 4______________________________________Compound No.    Protective value (%)______________________________________Comp.    3          100    4          100    7          100    8          100    12         75    14         100    26         90______________________________________ 
    
     TEST 4 
     In each unglazed pot having a diameter of 9 cm, cucumber plant (Suyo) was cultured. At one leaf stage, 10 ml. of each solution of each active ingredient having a concentration of 500 ppm was sprayed by a spray gun. After maintaining the pot in a green-house at 24° to 25° C. for one day, spores of Sphaerotheca fuliginea (obtained from the Sphaerotheca fuliginea seedlings) were inoculated. Ten days after the inoculation, number of lesions on the first leaf of seedling was measured. 
     The protective value was calculated as Test 1. The results are shown in Table 5. 
     
                       TABLE 5______________________________________Comp.  Protective            Comp.   Protective                            Comp. ProtectiveNo.    value (%) No.     value (%)                            No.   value (%)______________________________________3      100       16      100     31    1007      100       21      100     32    10014      95       22      100     33    10015     100       26      100     34    100                            51    100______________________________________ 
    
     When each solution having a concentration of 100 ppm was sprayed in the test, the protective values of Compound No. 62 and No. 66 were respectively 100. 
     TEST 5 
     A mixture of 9 ml. of a potato-glucose-agar medium (PDA medium) and 1 ml. of each active ingredient was poured into each Petri-dish to be solidified. An agar disc on which various fungi were cultured was put on the medium to keep it at the optimum temperature for the specific days, the growths of mycelia were observed to determine the minimum growth inhibition concentration of the active ingredient to these fungi. The following fungi were used. 
     A: Phytophthora infestans 
     B: Diaporthe citri 
     C: Alternaria solani 
     D: Venturia inaequalie. 
     The results are shown in Table 6. 
     
                       TABLE 6______________________________________Infestans  A          B        C      D______________________________________Comp. No.   3      100        100     10    &lt;1   4      &gt;100       100    100    &lt;1   7      100        &lt;1     &lt;1     &lt;1______________________________________ 
    
     TEST 6 
     Young seedling of kidney bean treated to cut off leaves except one primordial leaf was transplanted in a cup and about 30 of larvae and adults of Tetranychus telarius (L) were inoculated on the primordial leaf. This was dipped for 10 seconds in each solution obtained by diluting each wettable powder of Composition No. 5 containing each active ingredient with water at the concentration of 800 ppm and was dried in air and was kept in a constant temperature chamber with lighting at 28° C. Three days after the treatment, mortality was measured and each percent mortality was calculated as follows. ##EQU3## The results are shown in Table 7. 
     
                       TABLE 7______________________________________ Percent            Percent        PercentComp. mortality Comp.    mortality                            Comp.  mortalityNo.   (%)       No.      (%)     No.    (%)______________________________________ 3    100       37       100     101    10015    100       39       100     102    10022    100       40       100     Ref26    100       41       100     Comp.   4027    100       49       10028    100       89       10029    100       90       10034    100       100      100______________________________________ 
    
     TEST 7 
     Each active ingredient was dissolved in acetone to prepare each solution having the specific concentration. 1 Ml. of the solution (400 μg. of each active ingredient) was uniformly adhered on the inner bottom surface of Petri-dish having a diameter of 9 cm to form a film. In the dish, 15 of adults of Callosobruchus chinensis were charged and the dish was covered with a cap and kept in a constant temperature chamber at 25° C. for 24 hours. Each percent mortality was calculated as that of Test 6. The results are shown in Table 8. 
     
                       TABLE 8______________________________________     Percent                PercentComp.     mortality   Comp.      mortalityNo.       (%)         No.        (%)______________________________________ 2        100         62         100 3        100         63         10052        100         65         10054        100         70         10060        100         77         10061        100         81         100______________________________________ 
    
     TEST 8 
     Each minimum growth inhibition concentration (MIC) of Compound No. 16 to various microorganisms was measured by the agar dilution process. The results are shown in Table 9. In the cases of bacteria, the results were observed 24 hours after the inoculation and in the cases of fungi, the results were observed 1 week after the inoculation. 
     
                       TABLE 9______________________________________                          MICMicroorganism       Medium     (ppm)______________________________________Bacillus subtilis PC1219               Bouillon   &lt;0.2Staphylococcus aureus 209P               agar       &lt;0.2Escherichia coli    medium     12.5Salmonella typhimurium IFO 12529                          6.25Klebsiella pneumoniae IFO 3512 12.5Serratia marcescens IFO 12648  6.25Proteus morganii IFO 3848      6.25Pseudomonas aeruginosa         12.5Penicillium italicum               Sabouraud&#39;s                          3.12Penicillium chrysogeum IFO 4626               agar medium                          3.12Penicillium citrium IFO 6352   6.25Penicillium funiculosum IFO 6354                          6.25Aspergillum niger IFO 6341     3.12Aspergillum fumigatus IFO 4057 6.25Aspergillum flavus IFO 6343    6.25Aureobasidium pullulans IFO 6353                          6.25Chaetomium globosum IFO 6347   3.12Gliocladium virens IFO 9166    12.5Myrothecium verrucaria IFO 6133                          6.25Gibberella fujikuroi IFO 6349  12.5Trametes sanguinea             6.25______________________________________ 
    
     TEST 9 
     In each unglazed pot having a diameter of 9 cm, cucumber plant (Suyo) was cultured. At one leaf stage, 10 ml. of each solution of each active ingredient having a concentration of 250 ppm was sprayed by a spray gun. After maintaining the pot in a green-house at 24° to 25° C. for one day, a disc (punched agar disc) obtained by culturing Botrytis cinerea on a potato-glucose-agar medium (PDA medium) was put on the leaf of cucumber to inoculate them. Three days after the inoculation, lengths of lesions were measured and each protective value was calculated as Test 2. The results are shown in Table 10. 
     
                       TABLE 10______________________________________     Protective              ProtectiveComp. No. value (%)   Comp. No.   value (%)______________________________________ 7        100         48          10014        95          49          10016        100         50          10017        9218        10019        10021        10022        10023        8126        8529        10030        10033        10034        10035        10036        9637        93______________________________________ 
    
     In accordance with the test, except the concentration of the active ingredient was decreased, the comparative tests of Compound No. 7 and Reference compound were carried out. The results are shown in Table 11. 
     
                       TABLE 11______________________________________          Protective value (%)Compound       (62.5 ppm)______________________________________Compound No. 7 100Reference       0compound______________________________________ 
    
     TEST 10 
     In each unglazed pot having a diameter of 9 cm, cucumber plant (Suyo) was cultured. At two leaf stage, 20 ml. of each solution of each active ingredient having a concentration of 500 ppm was sprayed by a spray gun. After maintaining the pot in a green-house at 24° to 25° C. for one day, each spore suspension of Plasmopara viticola was sprayed. Six days after the inoculation, number of lesions on the first seedling was observed. The protective value was calculated as Test 1. The results are shown in Table 12. 
     
                       TABLE 12______________________________________Compound No.    Protective value (%)______________________________________4               1007               10020              10026              9333              8534              8351              10088              100______________________________________ 
    
     TEST 11 
     Each emulsifiable concentrate of each active ingredient as Composition No. 3 was dispersed in water at a concentration of 800 ppm. Each leaf of cabbage was dipped into each emulsion for about 10 seconds and taken up and dried in air. 
     A wet filter paper was put in each Petri dish (diameter of 9 cm), and each treated leaf was put on the filter paper. Larvae of Plutella xylostella at 2nd to 3rd instar were charged and the dish was covered with a cap and kept in a constant temperature chamber with lighting at 28° C. Eight days after the charge, mortality was measured and each percent mortality was calculated. The results are shown in Table 13. 
     
                       TABLE 13______________________________________ Percent            Percent        PercentComp. mortality Comp.    mortality                            Comp.  mortalityNo.   (%)       No.      (%)     No.    (%)______________________________________ 7    100       57       100     68     10015    100       58       100     70     10029    100       59       100     74     10040    100       60       100     77     10041    100       61       100     81     10042    100       62       100     83     10043    100       63       100     87     10052    100       64       100     Ref.    053    100       65       100     comp.55    100       66       10056    100       67       100______________________________________ 
    
     The pyridylanilines of the present invention impart excellent effect for combatting noxious livings such as insects, mites, fungi and bacteria, for example, excellent antifungal and antibacterial effect for controlling noxious fungi and bacteria multiplicating on industrial products, seeds and fruits in storage such as Aspergillus sp. Gibberella sp. and Penicillium sp. 
     The pyridylanilines are also effective for controlling noxious living grown on agricultural and horticultural crops and up-land, for example, insects such as Lepidoptera as Plutella Xylostella, Mamestra brassicae and Spodoptera litura; Hemiptera as Nephotettix cincticeps and Delphacodes striatella; Coleoptera as Callosobruchus chimensis and Epilachna vigintioctopunctata; and Diptera such as Musca domestica and Culexopipiens pallens; and mites such as Tetranychus urticae, Tetranychus telarius and Panonychus citri; and fungi and bacteria for plants such as Pyricularia oryzae, Rhizoctonia solani, Collectotrichum lagenarium, Pseudopernospora cubensis, Sphaerotheca fuliginea, Phytophthora infestans, Diaporthe citri, Alternaria solani, Venturia inaequalis, Plasmopara viticola, Botrytis cinerea, Puccinia recondita and Sclerotinia sclerotiorum. 
     The pyridylanilines impart excellent effect for controlling various noxious livings especially noxious fungi to agricultural and horticultural plants. 
     The compounds having the formula (V) or (VII) are especially effective for agricultural and horticultural fields since the compounds impart excellent effect for controlling Botrytis cinerea, Plasmopara viticola, Colletotrichum lagenarium, Sphaerotheca fuliginea, Pyricularia oryzae and Rhizoctonia solani etc. 
     A concentration of pyridylaniline for the application was depending upon object noxious livings, a method of application, a form of the composition and a dose of the active ingredient and is not critical and it is usually in a range of 1 to 10,000 ppm preferably 20 to 2,000 ppm. 
     When the compounds are used as active ingredients of the insecticidal, acaricidal, fungicidal or bactericidal composition, it is possible to prepare various forms of the compositions such as dust, wettable powder, emulsifiable concentrate, inert emulsion, oil solution, aerosol preparation, etc. with adjuvants as the cases of agricultural compositions. The composition can be applied with or without diluting them in suitable concentrations. 
     Suitable adjuvants include powdery carries such as talc, kaolin, bentonite, diatomaceous earth, silicon dioxide, clay and starch; liquid diluents such as water, xylene, toluene, dimethylsulfoxide, dimethylformamide, acetonitrile, and alcohol; emulsifiers dispersing agents, spreaders etc. 
     The concentration of the active ingredient in the insecticidal acaricidal, fungicidal or bactericidal 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, acaricides, plant growth regulators. Sometimes synergistic effects are found. The other agricultural ingredients include organic phosphoric acid ester type compounds, carbamate type compounds, dithio (or thiol) carbamate type compounds, organic chlorine type compounds, dinitro type compounds, organic sulfur or organometallic type compounds, antibiotics, substituted diphenyl ether type compounds, urea type compounds, triazine type compounds, benzoylurea type compounds, pyrethroid type compounds, imide type compounds and benzimidazole type compounds and more particularly, benzoylurea type insecticides such as N-(2,6-difluorobenzoyl)-N&#39;-(p-chlorophenyl)urea; pyrethroid type insecticides such as α-cyano-3-phenoxybenzyl-2-(4-chlorophenyl) isovalerate; imide type germicides such as N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide; benzimidazole type germicides such as methyl-1-(butylcarbamoyl)-2-benzimidazolecarbamate; thiocarbamate type germicides such as S-ethyl N-(3-dimethylaminopropyl)thiocarbamate hydrochloride; dithiocarbamate type germicides such as manganese ethylenebisdithiocarbamate; and urea type germicides such as 2-cyano-N-(ethylaminocarbonyl)-2-(methoxyimino)acetamide. 
     The agricultural fungicidal compositions are the typical compositions of the present invention. 
     The typical forms of the composition are the wettable powder and the emulsifiable concentrate. The typical compositions are as follows: 
     
         ______________________________________Agricultural fungicidal composition (concentrate):         Usual       Preferable______________________________________Active ingredient:           2-80 wt. %     5-80 wt. % Liquid or solid carrier: Surfactant:            ##STR14##     10-95 wt. %  1-20 wt. %Wettable powder:Active ingredient:             5-70 wt. %Solid carrier:                10-90 wt. %Surfactant:                    3-20 wt. %Emulsifiable concentrate:Active ingredient:             5-80 wt. %Liquid carrier:               10-95 wt. %Surfactant:                    3-20 wt. %______________________________________ 
    
     Suitable adjuvants include powdery carries such as talc, kaolin, bentonite, diatomaceous earth, silicon dioxide, clay and starch; liquid carriers such as water, xylene, toluene, dimethylsulfoxide, dimethylformamide, acetonitrile, and alcohol; and surfactants such as sodium alkyl benzene sulfonate, polyoxyethylene alkylaryl ether, sodium naphthalene sulfonate formaldehyde condensate, calcium ether sulfate, polyoxyethyleneglycol dodecylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene fatty acid ester, sodium alkylsulfate, sulfate of polyoxyethylene alkylaryl ether and di-alkylsulfosuccinate etc. 
     
         ______________________________________Composition No. 1:______________________________________Active ingredient:      20    wt. partsXylene:                 72    wt. partsPolyoxyethylene alkylphenyl ether:                   8     wt. parts______________________________________ 
    
     The components were uniformly mixed and dissolved to prepare an emulsifiable concentrate. 
     
         ______________________________________Composition No. 2:______________________________________Active ingredient:   5     wt. partsTalc:                95    wt. parts______________________________________ 
    
     The components were uniformly mixed to prepare a dust. 
     
         ______________________________________Composition No. 3:______________________________________Active ingredient:   20 wt. partsXylene:              60 wt. partsPolyoxyethylenealkylaryl ether:                20 wt. parts______________________________________ 
    
     The components were mixed and dissolved to prepare an emulsifiable concentrate. 
     
         ______________________________________Composition No. 4:______________________________________Jeeklite:              78    wt. partsSodium naphthalenesulfonate-                  2     wt. partsaldehyde condensate:Mixture of polyoxyethylenealkyl-                  5     wt. partsaryether sulfate and fine silicondioxide (50:50):Fine silicon dioxide   15    wt. parts______________________________________ 
    
     A mixture of these components was mixed with each active ingredient at a ratio of 4:1 by weight to prepare a wettable composition. 
     
         ______________________________________Compositon No. 5:______________________________________Active ingredient:    70 wt. partsJeeklite:             10 wt. partsMixture of polyoxyethylene alkylaryl                 20 wt. partsether sulfate and fine silica (50:50):______________________________________ 
    
     The components were uniformly mixed and pulverized to prepare a wettable powder. 
     
         ______________________________________Composition No. 6______________________________________Active ingredient:      30    wt. partsSodium laurylsulfate:   2     wt. partsSodium dinaphthylmethanesulfonate:                   3     wt. partsFine silicon dioxide (SiO.sub.2. nH.sub.2 O):                   20    wt. partsDiatomaceous earth:     45    wt. parts______________________________________ 
    
     The components were uniformly mixed to prepare a wettable powder. 
     
         ______________________________________Composition No. 7:______________________________________Active ingredient:      5     wt. partsXylene:                 91    wt. partsPolyoxyethylenealkylphenyl ether:                   4     wt. parts______________________________________ 
    
     The components were uniformly mixed to prepare an emulsifiable concentrate. 
     
         ______________________________________Composition No. 8:______________________________________Active ingredient:      5     wt. partsFine silicon dioxide:   10    wt. partsJeeklite:               80    wt. partsMixture of polyoxyethylenealkylaryl                   5     wt. partsethersulfate and fine silicon dioxide(50:50):______________________________________ 
    
     The components were uniformly mixed and pulverized to prepare a wettable powder.