JPS6032774A - Pyridazinone derivative, its preparation, insecticide, acaricide, nematocide, and fungicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R is alkyl; R<1> and R<2> are H, or lower alkyl; R<3> and R<4> are lower alkyl, halogen, lower haloalkyl, nitro, cyano, or alkoxycarbonyl; R<5> is halogen; X and Y are O, or S; m and n are 0- 3). EXAMPLE:2-t-Butyl-4-chloro-5-(p-phenoxy)benzyloxy-3(2H)-pyridazinone. USE:An agricultural and horticultural insecticide, acaricide, nematocide, and fungicide. An agricultural chemical having excellent insecticidal effect on sanitary insect pests such as Nephotettix cincticeps Uhlera, diamond moth, Culex pipiens pallens Coquillett, etc., effective for controlling acarids living in fruits and vegetables, and acarids living in animals, effective for controlling blights of fruits and vegetables such as downy mildew, etc. PREPARATION:For example, a compound shown by the formula II is reacted with a compound shown by the formula III (Hal is halogen) in a solvent in the presence of an absorbent for a hydrogen halide, to give a compound shown by the formula I .

Description

Detailed Description of the Invention The present invention is based on the general formula (■): Hiki (wherein R is an alkyl group, if and R2 are each independently a hydrogen atom or a lower alkyl group, and - and I are each a Independently lower alkyl group, halogen atom, lower haloalkyl group.

Nitro group, cyano group or alkoxycarbonyl group,
R51j/-t rogen atom, X and Yit each independently represent a VCeR elementary atom or a sulfur atom.

m represents 0 or an integer of 1 to 3, and when 0m is 2 or 6, R5 may be the same or different.

n represents 0 or an integer from 1 to 6, and n is 2 or ri5
In the case of , R4i may be the same or different. )
The present invention relates to a 5(21-pyridazinone derivative), its production method, and an insecticide, acaricide, nematocide, and fungicide containing one or more of the derivatives as an active ingredient.

Various 3(2H)-pyridazinone derivatives have been known to be useful as medicines and agricultural chemicals, but the compounds that have insecticidal activity and are in practical use have the structure of the following formula (to). Only pyridafenthion (trade name: Offnac) is expressed.

In addition, a compound represented by the following general formula (to) (West German Patent No. 2.752.101) and a compound represented by general formula (b) (Pesticide Science (Pe5)
tic1de Sci, vol. 34, p. 775 (1975
(1976) and Chemical Abstracts (Oaem, Abθtr,) 90
Volume 168656u (1979), Volume 92 41867
F (1980), vol. 93, 152452X (198
0), Volume 94, 84044u (1981)) is known to have insecticidal and acaricidal activity. However, in general formula (■), 1. ♂ represents a lower alkyl group, z is 0
Or represents 8. In the general formula (■, R5, Hl.

R represents an alkyl group, a halogen atom, an alkoxy group, A and B kto or 8;

(b) However, all of the above-mentioned known compounds belong to the group of organic phosphorus compounds, and fall under the category of organic phosphorus insecticides and acaricides in the field of agrochemicals.

On the other hand, Special Publication No. 58-7998, Special Publication No. 40-3798
No. 1 describes that the compounds represented by the general formulas 00 and 2 are useful as herbicides and plant growth regulators.

Furthermore, JP-A-58-85869 describes that Fi is useful as a fungicide for agriculture and horticulture.

(Shu (to) (2) However, in X) R1B alkyl group, phenyl residue R
2 represents hydrogen, an alkyl group substituted with methoxy or a dialkylamine group, an alkenyl group, a cycloalkyl group, a benzyl group, or an acetyl group. In @, R1 represents hydrogen, a phenyl residue, and u2 represents an alkyl group, a phenyl residue, or a carboxymethylene group. In (to), R1 is an alkyl group.

It represents an alkenyl group, a cycloalkyl group, or an optionally substituted phenyl group, u2 is a chlorine atom or a bromine atom, and R is a hydrogen atom or an alkyl group.

Represents a cycloalkyl group or a phenyl group which may be substituted, and represents xHso or ij SO2.

However, the remarkable insecticidal, acaricidal, and nematicidal effects found by the present inventors in the compounds of the above general formulas (X), @, and (6) are not known at all.

Therefore, the compound of the present invention is a new substance, and has a chemical structure different from that of (X), (XO, (2)), which has insecticidal and acaricidal effects. In other words, the compound of the present invention is not in the category of conventional organophosphorus insecticides and acaricides, but is a novel 5(2H)-pyridazinone compound, Among these pyridazinone compounds are weeding and planting control.

As mentioned above, some compounds with bactericidal activity were known, but none with insecticidal or acaricidal activity were known, and this was discovered for the first time by the present inventors.

Next, Table 1 shows nine examples of compounds according to the present invention. The compounds listed in Table 1 are for illustrative purposes only and are not intended to limit the scope of the present invention.

Note that the compound number will also be used in the following description.

The compounds of the present invention shown in Table 1 can be synthesized from reaction formulas (1), (2), and (alK).

Hiki (2) However, in the 9 reaction formula (11, tzL (3), R, R, R
.

R1, R', R5, X, Y and m, ni have the same meanings as above. Also, Ha mino-j halogen atom 9
M represents an alkali metal.

Reaction formula (1) is a compound represented by 2-alkyl-4-710geno-5-hydroxy (or mercapto)-5(2H)-pyridazinone (m) and the general formula (to), which absorbs hydrogen chloride in a solvent. This shows a reaction in which (I) is obtained by reacting in the presence of a solvent.

Lower alcohols (e.g. ethanol, butanol, etc.)
, aromatic hydrocarbons (benzene, toluene, etc.), ketones (acetone, methyl ethyl ketone, etc.), amides (N
, N-dimethylformamide, etc.) and dimethyl sulfoxide. As the hydrogen halide absorbent, an inorganic base (sodium carbonate, potassium carbonate, etc.) or an organic base (pyridine, triethylamine, etc.) can be used. The reaction temperature may range from room temperature to 150°C, but preferably 60 to 120°C. (II), 0
Although the molar ratio of 10 can be set arbitrarily, it is desirable to set it to around 1:1.

It is desirable that the ratio of the hydrogen halide absorbent to @) or (b) is set to 1 or more, preferably #''11.2 to 2.5.The reaction shown in reaction formula (1) in 9. It is also possible to use a modified method such as preparing a salt by reacting with a base such as IJium (preliminary hydrogenation), and adding (to) and reacting.

The reactions shown in reaction formula (2) and (a) are homogeneous reactions.

The reaction shown in reaction formula (1) can be carried out under the same conditions.

However, in the case of the reaction shown in reaction formula (2), a strong base such as hydrogenation (IJ) is required for the preparation of (g). The reactions of reaction formulas (2) and (8) are desirably carried out at as low a temperature as possible, for example by stirring at room temperature for a long time.

Next, the method for synthesizing the nine compounds of the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these.

Example L - tert-butyl-4-chloro-5-(p-phenoxy)
Benzyloxy-5(2H)-pyridazinone (compound) I
Synthesis of 2-t-butyl-4-chloro-5-hydroxy-5 (645)
2H)-pyridazinone 2. Of (10 mmol),
Anhydrous potassium carbonate 2.8 r (20 mmol), N,
20 g of N-dimethylformamide was mixed, 2.2 f (about 10 mmol) of p-phenoxybenzyl chloride was added, and the mixture was heated in an oil bath at 110 to 120° C. for 2 hours while stirring.

Free? 20 ml of H1 water was added and extracted twice with 50 ml of chloroform. The chloroform extracts were combined, washed with 50 g of water, and dried over anhydrous sodium sulfate. Distill the chloroform under reduced pressure.

A yellow oil 571 was obtained. Purification by silica gel chromatography (eluent: benzene: ethyl acetate = 4:1) gave 2.4 f of an almost colorless glassy substance (yield: 63
h) Confirm that the compound obtained by the above procedure is the desired compound.
Confirmed by H-NMR spectrum (CDC!, solution) δ [ppm] H ratio Assignment 5.25 (S) 2Hゝ0OH2- -4'-) IJ fluoromethyl)]] Synthesis of benzyloxy 5(2H)-pyridazinone (Compound Shop 48)
H)-pyridanone 2.29 (10 mmol) and 3-(
2'-chloro-47-trifluoromethyl)benzyl alcohol3. Or (10 mmol) was dissolved in dimethylformamide 20- and powdered potassium hydroxide 6
00 (10 mmol) was added and stirred overnight at room temperature. It was poured into 500 g of water and extracted twice with 50 g of Hensen each. The benzene extract was washed with water and dried over anhydrous sodium sulfate. Benzene was distilled off, and the residue was washed with n-hexane to obtain the desired product 3.11. The 'H-NM
Confirmed by R (ODOj!s solution) 21- δ[ppm1 H ratio Attribution 5.29 (S) /-chloro-4'-) IJ fluoromethyl)]]]benjaxy-52H)-pyridazinone (compound 44B) dehydrated N
, 10 mmol worth of sodium hydride paste was suspended in 30 d of N-dimethylformamide, 301 ml of 5-(2'chloro-4'-trifluoromethylphenoxy)benzyl alcohol was added at room temperature, and the mixture was stirred at room temperature for 30 minutes. . 2-t-butyl 4,5-dichloro-5 (2H
)-pyridazinone 2.2f (10 mmol) was added.

Thereafter, the same procedure as in Example 2 was carried out to obtain 2.7y of the target compound &48.

Example 1. The compounds shown in Table 2 were synthesized by the same operations as in Example 2 or Example 5. The structure of each compound was confirmed by 'H-NMR-spectrum.

Compounds A45 and A48 are also listed in Table 2.

Compounds shown in Table 2 The compounds of the present invention are used as insecticides, acaricides, nematicides, and fungicides for agriculture and horticulture [1. Generally, a suitable carrier 1
For example, solid carriers such as clay, talc, bentonite, diatomaceous earth, water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, It can be applied in combination with liquid carriers such as esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.), and optionally emulsifiers, dispersants, suspending agents, penetrating agents, spreading agents, and stabilizers. Addition of liquids, emulsions, hydrating agents, etc.
Powder.

It can be put to practical use in any dosage form such as granules. Further, if necessary, other types of herbicides, various insecticides, fungicides, plant growth regulators, synergists, etc. may be mixed and applied at the time of formulation or spraying. There are 3 types of herbicides to mix, for example, Farm Chemicals Handbook (Farm C
Chemicals Handbook), No. 69
(1985). The application scene of the medicine tij.

There are differences depending on the application period, application method, target pests, cultivated crops, etc., but in general, the appropriate amount of active ingredient is about 0.05 to 5 kg per hectare.

Next, some of the formulation examples of the present invention will be specifically listed.
It is not limited only to these.

In addition, "parts" in the following formulation examples mean parts by weight.

The above ingredients are completely mixed and dissolved to form an emulsion.

In use, the above emulsion is diluted with water to a factor of 500 to 20.00 Ω and sprayed.

Issai Ishiden” - Irrigation agent The above is uniformly mixed and pulverized to form a wettable powder.

When using, mix the above hydrating agent with water at a concentration of 500 to 20. D.

Dilute to 0 times and spray.

j [Crazy Jl oil agent Mix the above ingredients uniformly to make an oil agent.

Apply 1 tr of oil with the above composition to grooves and puddles? Hit 01-5
Apply 0 me or 10-100 me by aircraft.
Spray Go/10a.

Formulation example 4 Powder compound A50 compound ・・・・・・・・・・・・・・・
...6.0 parts Carplex (anti-caking agent) ・
・・・・・・・・・・・・・・・・・・ Part 05 (White Carbon: IAK Nogi Sputum Listing Product Name) Rishi - ・
・・Songs・Songs・・・・・・・・・・ 95 parts lisic acid diisozo “J Building”・・・・・・・・・・・・・・・・
・・・・・・ 1.5 parts or more is mixed uniformly to form a powder.

Powder of the above composition is 1 [per 1 are 0. Os~1
Spread 5KP.

The compounds of the present invention include Hemiptera pests such as black leafhopper, Lepidoptera pests such as diamondback moth, and Coleoptera pests.

It has excellent insecticidal power against sanitary pests such as Culex mosquito, and is also effective in controlling various mites that parasitize fruit trees and canola, as well as mites that parasitize animals. In addition to the above-mentioned insecticidal and acaricidal effects, the compounds of the present invention are also effective in controlling diseases such as downy mildew on fruit trees and canola. Therefore.

The compound of the present invention is an excellent agricultural chemical that has the property of controlling pests and diseases at the same time.

Next, the usefulness of the compounds of the present invention will be specifically explained by giving test examples.

11 cases of one trial] - Insecticidal test against adult house fly 1 riL of an acetone solution of the compound of the present invention at a concentration of 11,000 pp was dropped onto a No. 9 Petri dish so as to spread uniformly, and the acetone was completely evaporated at room temperature.

Ten adult houseflies were put in and covered with a perforated plastic lid. This petri dish was stored in a constant temperature room at 25℃, and
The number of dead insects after 4 hours was investigated, and the mortality rate was calculated using the following formula to obtain the results shown in Table 5.

The test was conducted in two sections.

Insecticidal test against Culex Culex larvae An aqueous solution of the compound of the present invention at a concentration of 10 ppm was placed in a waist-high petri dish with a diameter of 9 mm and a height of 6 mm, and then 10 adult Culex Culex larvae were conjugated.

This waist-high petri dish was stored in a constant temperature room at 25°C.

The number of dead insects after 96 hours was investigated, and the mortality rate was calculated using the same calculation formula as in Test Example 1.

The results are shown in Table 3.

The test was conducted in two sections.

Test Example 5 Contact Insecticidal Test against Diamondback Moth rc A leaf of Citrus Orchid was immersed in a water emulsion of the present compound at a concentration of 10,001) pm for about 10 seconds, air-dried, and then placed in a Petri dish. 10 insects were released at a time and housed in a constant temperature room at 25°C with a lid with holes.The number of dead insects was investigated after 96 hours, and the number of dead insects was calculated using the same calculation formula as in Test Example 1.
− I got the rate.

The results are shown in Table 3.

The test was conducted in two sections.

ffi Contact insecticidal test against Japanese lady beetle Tomato leaves were immersed in a water emulsion of the compound of the present invention at a concentration of 1000 ppm for about 10 seconds, air-dried, and then placed in a petri dish.
Into this, 10 second instar larvae of the Japanese ladybug were released per petri dish, and they were housed in a thermostatic chamber at 25°C with a perforated lid, and the number of dead insects was investigated after 96 hours. The mortality rate was calculated using a similar formula.

The results are shown in Table 3.

The test was conducted in two sections.

-Test M-Acaricidal efficacy test against spider mites A green bean leaf was cut into a circle with a diameter of t5 mm using a leaf punch, and placed on a damp F paper on a styrene cup with a diameter of 7 mm. This includes a collection of 910 Kanzawa spider mite larvae.
Head inoculated. Half a day after inoculation, a chemical solution prepared by diluting the emulsion of the compound of the present invention with a spreading agent to a concentration of 11,000 pp was sprayed using a rotary scattering tower at a rate of 2 drops per styrene cup, and the number of deaths after 96 hours was investigated. The mortality rate was calculated using the same formula.

The results are shown in Table 5.

The test was conducted in two sections.

1. Insecticidal test against black leafhopper Yellow leaves of rice are immersed in an emulsion of the compound of the present invention at a concentration of I n 00 ppm for about 1Ω second, and the yellow leaves are placed in a glass cylinder.
Adult leafhoppers that are resistant to organophosphorus insecticides were released and housed in a thermostatic chamber at 25°C with a perforated lid.
The number of deaths after 96 hours was investigated, and the mortality rate was calculated using the same formula as in Test Example 1.

The results are shown in Table 6.

The test was conducted in 1st and 2 sections.

Nematicidal efficacy test against Nematode nematode Contaminated soil of Nematode nematode was placed in a styrofoam cup with a diameter of 8. The emulsion of the compound of the present invention was diluted with water to 1000
A ppm concentration chemical solution was prepared, a spreading agent was added, and the soil was irrigated at 50 kg per styrofoam cup. After 48 hours, tomato seedlings of the indicator crop were transplanted. After 30 days of transplantation, the roots of the tomato plants were washed with water and examined for root gall parasitism.

The results are shown in Table 3.

Root gall parasitism index 0...No root galls observed 1...Slight Vcg observed 2...Moderately observed 3...Many observed 4...Very numerous observed Table 5 Insecticide , acaricidal, and nematocidal test results I. Potato soil Cucumber downy mildew control test Using cucumbers (variety: Sumo 33-hanshiro) grown in pots for 2 weeks, emulsions of 9 compounds of the present invention were injected at a predetermined concentration (1000
20 d of the chemical solution adjusted to (ppm) was sprinkled per pot.

The cucumbers were placed in a greenhouse for one day and infected with Pseudoperonospora ub-en.
Inoculation was carried out by spraying a spore suspension (150 spores) of 150 magnification (150 spores). Cucumbers inoculated with spores of the downy mildew fungus were placed in a room at 25°C and a relative humidity of 100°C for 24 hours, and then transferred to a greenhouse to wait for the onset of disease.

Seven days after inoculation, the degree of disease was investigated according to the following criteria.

The results are shown in Table 4.

0: No inoculated leaves develop disease 1: Less than 5% of inoculated leaves develop disease 2: 6-20% of inoculated leaves develop disease 3: 21-50qID of inoculated leaves develop disease 4: 51-90% of inoculated leaves develop disease 5: 90 or more of the inoculated leaves are infected. 4 Table 1 35 complete - Procedural amendment 1 Indication of the case 1982 Patent Application No. 138878 2 Name of the invention Pyridazinone derivatives, their manufacturing process, and insecticide, acaricide, and nematocide・Fungicide 3 Relationship with the case to be amended Patent applicant address 14-14, Kanda Nishiki-cho 3-chome, Chiyoda-ku, Tokyo 101
Date of amendment order 1-6 Contents of amendment (1) “R is j as rR” stated on page 9, line 11 of the specification.
Correct to ``ha''.

(2) "R stands for 1" in the first line of page 11 of the specification.
3 is corrected to ``.

(3) In the table for compound No. 47 in the table on page 24 of the specification, 'HJ' in the R'4 column is corrected to r4' -CF3J.

(4) “Hoto” written on page 30, line 9 of the specification is corrected to “Hoto J”.

(5) “No-rice” described in page 31, line 10 of the specification is “
Corrected to "Ni Ina".

Procedural amendment 1 Indication of the case 1982 Patent Application No. 138878 2 Name of the invention Pyridazinone derivatives, their manufacturing process, and insecticides, acaricides, nematicides, and fungicides 3 Person making the amendment/Relationship with the case Patent applicant address 101 3-7 Kanda Nishikicho, Chiyoda-ku, Tokyo &
Contents of the amendment (1) The following items are added following the line for compound A77 in the table on page 16 of the specification.

(2) Add the following item following line 550 of the compound shop in the table on page 24 of the specification.

(3) The following item is added following the line for compound 1655 in the table on page 53 of the specification.

" -ζ1ζ-

Claims (1)

[Claims] (1) General formula (1): (In formula 0, R is an alkyl group, R1 and zo each independently represent a hydrogen atom or a lower alkyl group, and RM and R4 each independently represent a lower alkyl group. group, halogen atom, lower haloalkyl group. Nitro group, cyano group or alkoxycarbonyl group.
US represents a halogen atom, and X and Y each independently represent an oxygen atom or a sulfur atom. m represents 0 or an integer from 1 to 5, and when 1m is 2 or 3, pi may be the same or different. n represents 0 or an integer of 1 to 5, and when n is 2 or 3, R may be the same or different. 5(2H)-pyridazinone derivative represented by ). (2) General formula (It)? With the compound represented by. A compound represented by general formula (b): is reacted in the presence of a hydrogen halide absorbent. General formula (1): A method for producing a compound represented by: (However, in the above formula, R represents an alkyl group, and R1 and R each independently represent a hydrogen atom or a lower alkyl group.
F and R'H each independently represent a lower alkyl group, halogen atom, lower haloalkyl group, nitro group, cyano group or fc nialkoxy carbonyl group, R'i a halogen atom, X and Yij each independently represent an oxygen atom or Represents a sulfur atom. m represents 0 or an integer from 1 to 6; When m is 2 or 3, 1jR3 may be the same or different. n represents 0 or an integer of 1 to 3. When n is 2 or 3, R4 may be the same or different. Hs, , 11 represents a tino-rogen atom. )(8) General formula (■): A compound represented by: By reacting with the compound represented by. General formula (1): A method for producing a compound represented by: (However, in the above formula, R represents a delkyl group as n (and R
2 each independently represents a hydrogen atom or a lower alkyl group
R3 and R'n each independently represent a lower alkyl group, halogen atom, lower haloalkyl group, nitro group, cyano group or alkoxycarbonyl group, R6 represents a halogen atom, and X and Y each independently represent an oxygen atom or a sulfur atom. represent m represents 0 or an integer of 1 to 5; When m is 2 or 3, FL5 may be the same or different. n ij represents O or an integer from 1 to 5. When n is 2 or 5, R4 may be the same or different. 1M of HaJu halogen atoms represents an alkali metal. ) (4) General formula (■): A compound represented by: by reacting the compound represented by n in the presence of a hydrogen chloride absorbent. General formula (1): A method for producing a compound represented by: (However, in the above formula, R represents an alkyl group, and nj and R
#''t Each independently a hydrogen atom or a lower alkyl group nH and R't'l each independently a lower alkyl group, a halogen atom, a lower haloalkyl group, a nitro group, a cyano group or an alkoxycarbonyl group US represents a halogen atom; .n represents the group or an integer from 1 to 3. When n is 2 or fC#i5, R4ij may be the same or different from each other.
) General formula (■): (In Formula 9, R is an alkyl group, ul and R2 are each independently a hydrogen atom or a lower alkyl group, R1 and I are each independently a lower alkyl group, a halogen atom, or a lower haloalkyl group) . Nitro group, cyano group or alkoxycarbonyl group,
R't;j represents a halogen atom, X and Y [each independently represents an oxygen atom or a sulfur atom; m represents an integer of 1 to 3, and when 1m is 2 or 5, R' may be the same or different. n represents 0 or an integer from 1 to 3, and n is 2 or 1-t
In the case of 6, R4 may be the same or different from each other. ) 5(1'!i of 2Hl-pyridazinone derivative
Agricultural and horticultural insecticide containing two or more types of 1 or 1 liter as active ingredients,
Acaricide, nematocide, fungicide.