JPS6340428B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides novel N-pyridylaniline derivatives,
The present invention relates to methods for producing them and pest control agents containing them. The present invention is based on the general formula () (In the formula, X is a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, or a trifluoromethyl group, Y is a hydrogen atom or a lower alkoxy group, and n is an integer of 0 to 4. However, When n is 0, 1 or 2, at least one of X and Y is a lower alkoxy group, and when n is 3 or 4, at least one of X is a lower alkyl group or a trifluoromethyl group. ) represented by N-
Pyridylaniline derivatives, methods for producing them, and pest control agents containing them. In the general formula (), the halogen atom represented by X is fluorine, chlorine, bromine, and iodine, and the alkyl moiety of the lower alkyl group and lower alkoxy group represented by Examples include propyl, isopropyl, n-butyl, and the like. Furthermore, when n is 2 to 4, the substituents represented by X may be the same or different. Specific examples of the N-pyridylaniline derivative represented by the general formula () and its analogous compounds include the following. Compound No. 1; N-(5-chloro-2-pyridyl)
-2,4-dinitro-6-trifluoromethylaniline
mp133～135℃ Compound No.2; N-(5-iodo-2-pyridyl)
-2,4-dinitro-6-trifluoromethylaniline
mp170～172℃ Compound No.3; N-(5-promo-2-pyridyl)
-2,4-dinitro-6-trifluoromethylaniline
mp137-140℃ Compound No. 4; N-(2-chloro-3-pyridyl)
-2,4-dinitro-6-trifluoromethylaniline
mp125-126℃ Compound No.5; N-(4-methyl-2-pyridyl)
-2,4-dinitro-6-trifluoromethylaniline
mp134-135℃ Compound No. 6; N-(5-trifluoromethyl-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline Oil Compound No. 7; N-(3-pyridyl)-2,4-dinitro-6-trifluoromethylaniline n ³⁰ _D 1.556 Compound No. 8; N-(4-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp44-45℃ Compound No. 9; N-(3,5-dichloro-2-pyridyl)-2,4-dinitro -6-
Trifluoromethylaniline
mp98～101℃ Compound No.10; N-(3,5-dibromo-2-pyridyl)-2,4-dinitro-6-
trifluoromethylaniline
mp161-164℃ Compound No.11; N-(3-bromo-5-chloro-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp106-108℃ Compound No.12; N-(3-chloro-5-bromo-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp89-91℃ Compound No.13; N-(3-bromo-5-methyl-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp123-125℃ Compound No. 14; N-(3-chloro-5-trifluoromethyl-2-pyridyl)-2,
4-dinitro-6-trifluoromethylaniline mp74-77℃ Compound No. 15; N-(2-chloro-5-trifluoromethyl-6-pyridyl)-2,
4-dinitro-6-trifluoromethylaniline mp129-131℃ Compound No.16; N-(5-iodo-6-ethyl-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp127-130℃ Compound No.17; N-(3-nitro-5-bromo-2
-Pirzil)-2,4-dinitro-6-trifluoromethylaniline mp186-189℃ Compound No.18; N-(3-nitro-5-methyl-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline n ³⁰ _D 1.579 Compound No. 19; N-(3,5-dichloro-6-methyl-2-pyridyl)-2,4-dinitro-6 -Trifluoromethylaniline mp72-75℃ Compound No.20; N-(5-chloro-6-methyl-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp167-168℃ Compound No.21; N-(5-trifluoromethyl-6
-Chloro-2-pyridyl)-2,
4-dinitro-6-trifluoromethylaniline mp195-196℃ Compound No.22; N-(4,6-dimethyl-2-pyridyl)-2,4-dinitro-6-
trifluoromethylaniline
mp146-147℃ Compound No.23; N-(5-nitro-2-pyridyl)
-2,4-dinitro-6-trifluoromethylaniline n ³⁰ _D 1.599 Compound No. 24; N-(3-chloro-6-nitro-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp146-147℃ Compound No.25; N-(4,6-dichloro-2-pyridyl)-2,4-dinitro-6-
trifluoromethylaniline
mp169～170℃ Compound No.26; N-(4-chloro-6-methyl-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp163-165℃ Compound No.27; N-(5-methoxy-2-pyridyl)-2,4-dinitro-6-trifluoromethylaniline m .
p.102～105℃ Compound No.28; N-(2,6-dichloro-3-pyridyl)-2,4-dinitro-6-
Trifluoromethylaniline
mp107～110℃ Compound No.29; N-(3-trifluoromethyl-6
-Chloro-2-pyridyl)-2,
4-dinitro-6-trifluoromethylaniline oil compound No. 30; N-(3,5-dichloro-4,6-
dimethyl-2-pyridyl)-2,
4-dinitro-6-trifluoromethylaniline mp131-133℃ Compound No. 31; N-(3,5-dichloro-4-methyl-2-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp166 ~169℃ Compound No. 32; N-(3,5-dichloro-4-pyridyl)-2,4-dinitro-6-
trifluoromethylaniline
mp141-142℃ Compound No.33; N-(3-bromo-5-trifluoromethyl-2-pyridyl)-2,
4-dinitro-6-trifluoromethylaniline Oil Compound No. 34; N-(3-bromo-5-nitro-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp118-120℃ Compound No.35; N-(3-trifluoromethyl-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp106-108℃ Compound No.36; N-(3-trifluoromethyl-5
-Bromo-6-chloro-2-pyridyl)-2,4-dinitro-6-
Trifluoromethylaniline Oil Compound No. 37; N-(3-trifluoromethyl-5
-Chloro-2-pyridyl)-2,
4-dinitro-6-trifluoromethylaniline mp120-122℃ Compound No.38; N-(3-trifluoromethyl-5
-bromo-2-pyridyl)-2,
4-dinitro-6-trifluoromethylaniline mp146-148℃ Compound No.39; N-(3-chloro-5-trifluoromethyl-2-pyridyl)-2,
4-dinitro-3-methoxy-6
-Trifluoromethylaniline
Oil compound No. 40; N-(3,5-dichloro-2-pyridyl)-2,4-dinitro-3-
Methoxy-6-trifluoromethylaniline Oil compound No. 41; N-(4-methyl-5-bromo-2
-pyridyl)-2,4-dinitro-6-trifluoromethylaniline mp58~60℃ The N-pyridylaniline derivative represented by the general formula () is usually represented by the general formula () (In the formula, Hal is a halogen atom, and Y is as described above.) and the general formula () (wherein, X and n are as described above) in the presence of an acid binder. The acid binder used in the above reaction is a basic substance, such as alkali metal hydroxide, carbonate,
Examples include hydrides, hydroxides and carbonates of alkaline earth metals, and preferably potassium hydroxide, sodium hydride, sodium hydrogen carbonate and the like. The above reaction is preferably carried out in the presence of a solvent. Examples of the solvent used include aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran, and sulfolane, with dimethylformamide being preferred.
The reaction temperature is generally -100°C to 200°C, and the reaction time is 0.5 to 24 hours, preferably 1 to 10 hours. Next, specific synthesis examples of the compounds of the present invention and analogous compounds thereof will be described. Synthesis example 1 (reference example) N-(3,5-dichloro-2-pyridyl)-
Synthesis of 2,4-dinitro-6-trifluoromethylalinine 2-amino-3,5-dichloropyridine 1.65g
was dissolved in 20 ml of dimethylformamide, and 1.0 g of powdered potassium hydroxide was gradually added while stirring. Thereafter, 2.7 g of 2,4-dinitro-6-trifluoromethylchlorobenzene was added over a period of 5 minutes while maintaining the temperature at 30°C, and the mixture was allowed to react for about 3 hours. The reaction solution was made acidic with concentrated hydrochloric acid and extracted with methylene chloride. The extract layer was washed with water, dried, and the solvent was distilled off. After separation using a silica gel column (eluent: toluene), the solvent was distilled off to obtain 2.5 g of the target product having a melting point of 98 to 101°C. Synthesis example 2 (reference example) N-(2-chloro-5-trifluoromethyl-
Synthesis of 6-pyridyl)-2,4-dinitro-6-trifluoromethylalinine Dissolve 1.8 g of 2-chloro-6-amino-5-trifluoromethylpyridine in 20 ml of dimethylformamide, and dissolve into powder while stirring. potassium hydroxide
1.0g was added gradually. Then, 2.7 g of 2,4-dinitro-6-trifluoromethylchlorobenzene
A 10 ml solution of dimethylformamide was gradually added dropwise at room temperature, and the mixture was allowed to react for about 3 hours. The reaction solution was acidified with concentrated hydrochloric acid, poured into water, the precipitate was filtered, and recrystallized with methanol to obtain 2.9 g of the target product with a melting point of 129-131°C.
I got it. Synthesis Example 3 N-(3,5-dichloro-4,6-dimethyl-
Synthesis of 2-pyridyl)-2,4-dinitro-6-trifluoromethylalinine 1.9 g of 2-amino-3,5-dichloro-4,6-dimethylpyridine was dissolved in 20 ml of dimethylformamide, and powdered with stirring. potassium hydroxide
0.7g was added gradually. There, 2.7 g of 2,4-dinitro-6-trifluoromethylchlorobenzene
A 10 ml solution of dimethylformamide was gradually added dropwise at room temperature, and the mixture was allowed to react for about 10 hours. The reaction product was treated in the same manner as in Synthesis Example 2 above to give a melting point of 131 to 133.
1.6 g of the target product was obtained at ℃. Synthesis example 4 N-(5-methoxy-2-pyridyl)-2,4
-Synthesis of dinitro-6-trifluoromethylalinine Using 1.2 g of 2-amino-5-methoxypyridine and 2.8 g of 2,4-dinitro-6-trifluoromethylchlorobenzene, the same procedure as in Synthesis Example 3 was carried out. The mixture was allowed to react for 5 hours. The reaction product was purified in the same manner as in Synthesis Example 1, and the melting point was 102°C.
1.2 g of the target product was obtained at ~105°C. Synthesis Example 5 N-(3-chloro-5-trifluoromethyl-
Synthesis of 2-pyridyl)-2,4-dinitro-3-methoxy-6-trifluoromethylaniline 1.9 g of 2-amino-3-chloro-5-trifluoromethylpyridine and 2,4-dinitro-3-methoxy- 6-trifluoromethylchlorobenzene
Using 2.8 g, the reaction was carried out in the same manner as in Synthesis Example 3 for 3 hours. The reaction product was purified in the same manner as in Synthesis Example 1 to obtain 1.4 g of the target product in the form of an oil. Further, the N-pyridylaniline derivative represented by the general formula () and its analogous compounds exhibit good effects when used as active ingredients of pest control agents. For example, as shown in the test examples below, the compound of the present invention exhibits high activity as an active ingredient of a pest control agent, and exhibits an excellent growth-inhibiting effect on insects, mites, and pathogenic bacteria that are particularly harmful to agriculture and horticulture. . For example, insects include diamondback moths, leafhoppers, aphids, etc., mites include two-spotted spider mites, false red spider mites, orange spider mites, etc., and pathogens include gray mold, rust, powdery mildew, downy mildew, etc.
It effectively controls pathogens such as green mold on citrus, scab on apples, rice blast, sheath blight, leaf blight, and canker. When using this product as an active ingredient in a pest control agent, it can be formulated into various forms such as emulsions, powders, wettable powders, liquids, etc. along with pesticide adjuvants, just as in the case of conventional pesticide formulations. . When these preparations are actually used, they can be used as they are, or they can be diluted to a predetermined concentration with a diluent such as water. The pesticide adjuvants mentioned here include solid carriers such as talc, kaolin, bentonite, diatomaceous earth, white carbon, clay, and starch, and liquid diluents such as water, xylene, toluene, chlorobenzene, cyclohexane, dimethyl sulfoxide, dimethylformamide, and alcohol. Agents, emulsifiers, dispersants, spreading agents, etc. can be mentioned. In addition, if necessary, it can be mixed or used in combination with other agricultural chemicals such as insecticides, acaricides, fungicides, plant growth regulators, etc. In this case, even better effects may be exhibited. The pest control agent of the present invention generally has an active ingredient of 1-
It is carried out at a concentration of 10,000 ppm, preferably 20 to 2,000 ppm. Test examples and formulation examples of pest control agents based on the compounds of the present invention and similar compounds thereof are described below, but the present invention is of course not limited to these descriptions. Test Example 1 Each test compound was dissolved in water and cabbage leaves were immersed in a chemical solution adjusted to a concentration of 800 ppm for about 10 seconds, taken out and air-dried. Wet paper was placed in a Petri dish (9 cm in diameter), and the leaf pieces were placed on top of it. Release the 2nd to 3rd instar diamondback moth larvae there, cover the lid, and
It was left in a lighted incubator at ℃. On the 8th day after the insects were released, whether they were alive or dead was determined, and the insecticidal rate was calculated using the following calculation formula, and the results shown in Table 1 were obtained. Insect killing rate (%) = Number of dead insects / Number of released insects x 100

[Table] Test Example 2 Dissolve each test compound in acetone to prepare a chemical solution with a predetermined concentration.
400 μg) was taken out to form a substantially uniform film on the inner bottom of a 9 cm Petri dish. After releasing 15 adult bean weevils into this Petri dish and keeping it in a thermostat at 25℃ for 24 hours with a lid, the insecticidal rate was determined in the same manner as in Test Example 1, and the results are shown in Table 2. Got the results.

[Table] Test Example 3 Each test compound was diluted in water to prepare a chemical solution with a specified concentration, and young rice seedlings (about 10 cm in length) were immersed in the solution for 10 seconds, air-dried, and then placed in a test tube with an inner diameter of 2 cm. Ta. 15 adult leafhoppers were released into this, and the test tube was kept in a lighted incubator at 28°C with the mouth of the tube covered with gauze. 24 hours after the insects were released, the insect killing rate was determined in the same manner as in Test Example 1, and the results shown in Table 3 were obtained.

[Table] Test Example 4 An emulsion containing 20 parts by weight of the test compound, 60 parts by weight of xylene and 20 parts by weight of Solpol 2806B (surfactant) was diluted with water to prepare a chemical solution of a predetermined concentration. Leave only one primary leaf of a young kidney bean seedling, cut off the other leaves, and transplant it into an ice cream cup.
Thirty insects were released and immersed in the chemical solution for 10 seconds. After air drying, it was placed in a constant temperature chamber with lighting at 28°C, and after 3 days, the insect killing rate was determined in the same manner as in Test Example 1, and the results shown in Table 4 were obtained.

[Table] Test example 5 Green beans in a 6cm diameter pot (variety: Edogawa)
6 to 8 days after germination, female adult spider mites (Tetranychus cinnabarinus) appear on the true leaves.
We released 10 animals and left them at 27℃ for about 48 hours to spawn.
Adults were removed. The true leaves were immersed for 10 seconds in a chemical solution in which each active ingredient compound was diluted in water and adjusted to a predetermined concentration, and this was kept in a constant temperature room at 27° C. for 10 days. We investigated the number of hatched and unhatched eggs in each treatment area,
Based on this, the unhatched rate is determined and the egg killing rate is determined.
Obtained the results in the table. Egg killing rate % (unhatched rate) = Number of unhatched eggs / Number of hatched eggs + Number of unhatched eggs × 100

[Table] Test Example 6 Paddy rice (variety: Chukyo Asahi) was cultivated in a clay pot with a diameter of 9 cm, and when it reached the 3-leaf stage, the active ingredient compound was applied.
A chemical solution adjusted to a concentration of 50 ppm was uniformly sprayed using a spray gun. After being left in a greenhouse at 24 to 25°C for a day and night, a spore suspension of rice blast fungus was spray inoculated. On the 5th day after inoculation, the number of lesions on the 3rd leaf was investigated, and the control value was determined by applying the following formula.
Obtained the results in the table. Control value (%) = (1 - number of lesions in treated area / number of lesions in untreated area) x
100

[Table] Test Example 7 Paddy rice (variety: Chukyo Asahi) was cultivated in a clay pot with a diameter of 9 cm, and when it reached the 5-leaf stage, the active ingredient compound was added.
A chemical solution adjusted to 100 ppm was uniformly sprayed using a spray gun. After being left in a greenhouse at 24 to 25°C overnight, rice leaves on which the rice sheath blight fungus had been cultured in advance were inoculated into the leaf sheaths by pinching them. After being left in an inoculation room at a temperature of 30°C and a humidity of 100% for 5 days, the lesion length of 5 stems per pot was investigated, and the control value was determined by applying the following formula, and the results shown in Table 7 were obtained. Control value (%) = (1 - total lesion length in treated area/total lesion length in untreated area) x 100

[Table] Formulation example 1 (reference example) (a) N-(3,5-dichloro-2-pyridyl)-
2,4-dinitro-6-trifluoromethylaniline 20 parts by weight (b) Siegrite 72 parts by weight (c) Sodium ligninsulfonate 8 parts by weight The above ingredients were mixed uniformly to prepare a wettable powder. Formulation example 2 (reference example) (a) N-(2-chloro-5-trifluoromethyl-3-pyridyl)-2,4-dinitro-6-trifluoromethylaniline 5 parts by weight (b) Talc 95 parts by weight The above ingredients were mixed uniformly to form a powder. Formulation example 3 (a) N-(3,5-dichloro-4,6-dimethyl-2-pyridyl)-2,4-dinitro-6-trifluoromethylaniline 20 parts by weight (b) Xylene 60 parts by weight (ha) ) Polyoxyethylene alkylaryl ether 20 parts by weight The above components were mixed and dissolved to form an emulsion. Formulation example 4 (reference example) (a) Siegrite 78 parts by weight (b) Lavelin S (trade name manufactured by Daiichi Kogyo Seiyaku)
2 parts by weight (c) Solpol 5039 (trade name manufactured by Toho Chemical Industries)
5 parts by weight (d) Carplex (trade name manufactured by Shionogi & Co., Ltd.)
15 parts by weight mixture of each of the above components and N-(3,5-dichloro-2-pyridyl)-2,4-dinitro-6-
and trifluoromethylaniline at a weight ratio of 4:1 to prepare a wettable powder.

Claims (1)

[Claims] 1. General formula (In the formula, X is a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, or a trifluoromethyl group, Y is a hydrogen atom or a lower alkoxy group, and n is an integer of 0 to 4. However, When n is 0, 1 or 2, at least one of X and Y is a lower alkoxy group, and when n is 3 or 4, at least one of X is a lower alkyl group or a trifluoromethyl group. ) represented by N-
Pyridylaniline derivative. 2 General formula (In the formula, X is a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, or a trifluoromethyl group, Y is a hydrogen atom or a lower alkoxy group, and n is an integer of 0 to 4. However, When n is 0, 1 or 2, at least one of X and Y is a lower alkoxy group, and when n is 3 or 4, at least one of X is a lower alkyl group or a trifluoromethyl group. ) represented by N-
A method for producing a pyridylaniline derivative, comprising: (In the formula, Hal is a halogen atom, and Y is as described above.) A compound represented by the general formula (wherein X and n are as described above) is reacted with a compound represented by the above in the presence of an acid binding agent. 3 General formula (In the formula, X is a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, or a trifluoromethyl group, Y is a hydrogen atom or a lower alkoxy group, and n is an integer of 0 to 4. However, When n is 0, 1 or 2, at least one of X and Y is a lower alkoxy group, and when n is 3 or 4, at least one of X is a lower alkyl group or a trifluoromethyl group. ) represented by N-
A pest control agent characterized by containing a pyridylaniline derivative as an active ingredient.