JPS6054370A - Pyridazinone derivative, its preparation and insecticidal, miticidal and nematocidal agent - Google Patents

Abstract

NEW MATERIAL:The compound of 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 is O or S; m and n are integer of 0-3). EXAMPLE:2-t-Butyl-4-chloro-5-(p-benzoylbenzyloxy)-3(2H)-pyridazinone. USE:Agricultural and horticultural insecticide, miticide and nematocide. PREPARATION:The compound of formula I can be produced by reacting the compound of formula II with the compound of formula III at 60-120 deg.C in the presence of a hydrogen halide acceptor (e.g. sodium carbonate, pyridine, etc.).

Description

Detailed Description of the Invention The present invention is based on the general formula (i): 5 (wherein R is an alkyl group, R1 and R2 are each independently a hydrogen atom or a lower alkyl group, RK and R'lt1. independently a lower argyl group, a halogen atom, a lower/-roalkyl group;

Nitro group, cyano group or tahaalkoxy group
US represents a halogen atom, and X represents an oxygen atom or a sulfur atom. m represents 0 or an integer from 1 to 3, and when 1m is 2 or 3, R3 may be the same or different. nId
, n or an integer from 1 to 5, and when n is 2 or 5, R4 may be the same or different from each other. The present invention relates to a 3(21()-pyridazinone derivative represented by ), its production method, and an agricultural and horticultural insecticide, acaricide, and nematicide containing one or more of the derivatives as an active ingredient.

Conventional 5 (2H)-pyridazinone derivatives include pharmaceuticals,
Various compounds are known to be useful as pesticides and (-), but the only compound that has insecticidal activity and is in practical use is pyridafention (trade name: Offnac), which is represented by the structure of the following formula (b). Compounds represented by the following general formula (to) (Pesticide German Patent No. 2.752.101) and compounds represented by general formula (b) (Pesticide SC1, Vol. 4, 775)
(1975) Vol. 7, pp. 97 and 107 (1976)
) and Chemical Abstracts (0aen4 Ab
str, ) Volume 90, 168656u (1979),
Volume 92, 41867F (1980), Volume 95, 13
2452M (1980), Volume 94, 84044u (1
981)) is known to have insecticidal and acaricidal activity. However, in general formula (4), R' , , R'
represents a lower alkyl group, and represents 200 or S. General formula (in ~, R5, R', R' is an alkyl group,
R'fl halogen atom, alkoxy group.

A and B represent 0 or S.

9- However, all of the above-mentioned known compounds belong to the group of organic phosphorus-based compounds, and fall under the category of organic phosphorus-based insecticides and acaricides in the field of agricultural chemicals.

On the other hand, Special Publication No. 5B-7998 9% Publication No. 40-5798
It is described in the above issue that compounds represented by the general formulas (1) and (2) are useful as herbicides and plant growth regulators.

Further, JP-A-58-85869 describes that ilt@ is useful as a fungicide for agriculture and horticulture.

However, R11lt is an alkyl group and a phenyl residue.

R2ha hydrogen, an alkyl group, an alkenyl group, a cycloalkyl group substituted with a methoxy or dialkylamino group,
Represents a benzyl group or an acetyl group.

In (b), R1 is hydrogen, phenyl residue, 12ilt
Represents an alkyl group, phenyl residue or carboxymethylene group. In (to), R1 represents an alkyl group, an alkenyl group, a cycloalkyl group, or an optionally substituted phenyl group, and R2r, ? A chlorine atom or a bromine atom, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an optionally substituted phenyl group, and X is so or ill:SO2
represents.

However, the compounds of general formulas (X)', @, (2) have remarkable insecticidal and acaricidal properties as found by the present inventors.
Its nematicidal bactericidal action is completely unknown.

Therefore, the compound of the present invention is a novel substance. It has a chemical structure that is different from the compounds listed in (1), (2), and (2), which have insecticidal and acaricidal effects, and also has a different physiological action from (3), @, and (2). Specifically, the compound ilf of the present invention is not in the category of conventional organophosphorus-based insecticides and acaricides, but is a novel 6(2a)-pyridazinone-based compound, and among such pyridazinone-based compounds, it is effective in killing weeds and Planting style.

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.

Table 1 Basin A compound represented by

Compound of the present invention #-, [Reaction formula (1), (2), (8
The color can be synthesized by 1.

n (u) Offi (ff) (To) (IV) Bean) R'' (1) However, 1 reaction formula (1) m (2) , (S) K OiteR, R', R2゜R' * R' @R5*
X* Y and m, nij have the same meanings as above. Further, Ha represents an alkali metal containing 9M halogen atoms.

Reaction formula (1) ij 2-Alkyl-4-halogeno-5-hydroxy (or mercapto)-3(2n)-pyritazinone CI [) and a compound represented by general formula (b) are mixed in a solvent with a hydrogen halide absorbent. React in the presence of (I)
The reaction that yields is shown. As a solvent.

Lower alcohols (e.g. ethanol, butanol, etc.)
, aromatic hydrocarbons (benzene, toluene, etc.), ketones (acetone, methyl ethyl ketone, etc.), amides (L
(N-dimethylformamide, etc.), dimethyl sulfoxide, etc. can be used. As a hydrogen halide absorbent, inorganic bases (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. The molar ratio of @) and (b) can be set arbitrarily, but it is preferable to set it around 1:1. stomach.

(9) The ratio of the hydrogen halide absorbent to Fi (b) is preferably set to 1 or more, preferably 1.2 to 2.5 K. Incidentally, the reaction shown in the equation (1) can be carried out in a modified manner, such as by reacting the compound (TO) with a base such as sodium hydride in advance to prepare a salt, and then adding [O] to react.

The reactions shown in reaction formulas (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 (IJium) is required for the preparation of (V). It is desirable for the reactions of reaction formulas (2) and (8) to be carried out at as low a temperature as possible, for example by stirring for a long time at room temperature.

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

Example 12-t-butyl-4-chloro-5-(P-benzoylbenzyloxy)-5(2H)-pyridazinone (
Synthesis of compound &44) 2-tert-butyl-4-chloro-5-hydroxy-5(2H)-pyridazinone 1.
51 with N,N-dimethylformamide 10. 1.59 g of anhydrous potassium carbonate and 2.5 f of 4-bromomethylbenzophenone were added, and while stirring
Heated in an oil bath at 20°C for 3 hours. The mixture was cooled to room temperature, 100 ml of water was added, and the precipitated solid was collected, washed with water, and dried. This was recrystallized from ethanol/dioxane, m,
The target compound (compound A44) was obtained as pale brown granular crystals with a temperature of 144 to 146°C (yield: 639 ml).

The 'H-NMR spectrum of the compound obtained by the above procedure was measured in deuterated chloroform, and the following results were obtained.

From the above data, it was confirmed that the compound obtained in Example 1 was the desired compound g1. Ta.

Example 2 Synthesis of 2-t-butyl-4-chloro-5-(P-benzoylbenzyloxy)-5(21i)-pyridazinone (compound A44) 2-t-butyl-4,5-dichloro-5( 2a) - Pyridazinone 2.21 and P-benzoylbenzyl alcohol 2.1 fwoN, N -Dissolved in N-silylformamide 20-, powdered and added with 600 g of potassium hydroxide,
Stir overnight at room temperature.

The mixture was poured into 500ml of water and extracted twice with 5O1Rt of benzene each time. The benzene extract was washed with water and dried over anhydrous sodium sulfate. Distill off benzene.

Hereinafter, the target product, compound A44, was obtained by the same operation as in Example 1.
I got it. (Yield 8t2t).

Example 3 Synthesis of 2-t-butyl-4-chloro-5-(P-benzoylbenzyloxy)-s(2H)-pyridazinone (Compound A44).

0 10 m/30 m of dehydrated N,N-dimethylformamide
Suspend mmol equivalent of sodium hydride paste and add P-benzoylbenzyl alcohol 2,1 at room temperature.
2 was added and stirred at room temperature for 30 minutes. 2-t-butyl-
4,5-dichloro-5(2H)-pyridazinone 2.27
and the same procedure as in Example 2 to obtain the target compound A.
I got 44. (Yield: 561 cm) Example 4 2-t-butyl-4-chloro-5-[4-(
1)-chlorobenzoyl)-benzylthio]-5(2H
)-Synthesis of pyridazinone (compound black 51) 2-ter
t-Butyl-4-chloro-5-mercaptoly(2H)
- Viridashi/71.0f-jzN, dissolved in 10d of N-dimethylformamide, powdered anhydrous sodium carbonate 0
．． 77 and 1.4 F of 4-bromomethyl-4'-chloro-benzophenone were added and heated in an oil bath at 60-70° C. for 6 hours with stirring. Thereafter, the same operation as in Example 1 was carried out to obtain the target compound (Compound 51)'f: as yellow needle-like crystals having a tsum, p, of 177 to 180°C. (Yield 615
H-NMR (ODC!),) Example 1. Example 2. Example 5. Alternatively, the compounds shown in Table 2 were synthesized by the same operation as in Example 4. The structure of each compound was confirmed by rj' H-NMR-spectrum.

Compounds 44 and &51 are also listed in Table 2.

In Table 2, when the compound of the present invention is used as an agricultural and horticultural insecticide, acaricide, or nematicide-sharpening agent, a suitable partner 1 such as clay, talc, Solids such as bentonite and diatomaceous earth 4
(1 body water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), It can be applied by mixing with a liquid carrier such as 11I amides (dimethylformamide, etc.), and if desired, an emulsifier 1 dispersant, suspending agent, penetrating agent, spreading agent, stabilizer, etc. can be added to form a liquid or emulsion. , hydrating agents, powders.

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. The type of herbicide to be mixed is 0. For example, Farm Chemicals Handbook (Farnj
O)+err+4. ca1. sHF1. -ndboo
K), 69th edition (1985), and the like. The amount of drug applied depends on the application situation.

Although there are differences depending on the application period, application method, target pests, cultivated crops, etc., the amount of active ingredient is generally F per hectare.
l, 0, [ ] 5 to 5 is appropriate.

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

In the following formulation examples, "part" means 1 part by weight.

”Self-control: row j-emulsion The above ingredients are completely mixed and dissolved to form an emulsion.

When using, add 500 to 20,0 flO of the above emulsion with water.
Dilute and spray.

I Ball I Yu Hydrating Agent "Compound A46..."
...... 25 parts or more are mixed and pulverized uniformly to make an irrigation agent.

When used, the above irrigation agent is diluted 500 to 20.00 times with water and sprayed.

Compound of mouth oil compound A47・・・・・・・・・・・・・・・
・・・・・・50 parts (methyl cellosolve ・・・・・・・・・・・・・・・・
... 50 parts or more are mixed uniformly to make an oil agent.

Apply 1 tr of oil with the above composition to grooves and puddles? Hit 0゜1～
50-application or by aircraft at 10-10 rows/10a.

Formulation example 4 Powder Mix the above ingredients uniformly to make a powder.

The powder having the above composition is sprayed at 005 to 15 xp per 10 ares.

The compound of the present invention is used for Hemiptera pests such as 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.

Next, the usefulness Vc of the compound of the present invention will be specifically explained with reference to test examples.

ULMLiLL Insecticidal test against adult house flies 11000pp of the compound of the present invention 8 degrees acetone solution 1-9
Drop the mixture onto a glass plate so that it spreads evenly, and allow the acetone to evaporate completely at room temperature.

Ten adult houseflies were placed in the hole and a plastic lid was placed over the hole. 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 6.

The test was conducted in two sections.

] 11 Salmon main Insecticidal test against Culex Culex larvae An aqueous solution of the compound of the present invention with a concentration of 10 ppm was placed in a 9 m diameter, high q60
After placing 200 people in an 11 L petri dish, 10 adult Culex Culex larvae were formed.

1 Store this waist-high petri dish 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 formula as in Test Example 1.

The results are shown in Table 5.

The test was conducted in two sections.

Test Example 3 Contact Insecticidal Test against Diamondback Moth A leaf of Citrus Orchid was immersed in a water emulsion containing 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. The insects were released head by head, placed in a thermostatic chamber at 25° C. with a lid with holes, and the number of dead insects was counted after 96 hours, and the mortality rate was calculated using the same formula as in Test Example 1.

The results are shown in Table 3.

The test was conducted in two sections.

(Test J side A) Contact insecticidal test against Japanese lady beetle 7. Tomato leaves were immersed in a water emulsion of the compound of the present invention at a concentration of 11,100 ppm for about 10 seconds, air-dried, placed in a petri dish, and in which the Japanese lady beetle was placed. Release 10 2nd instar larvae per petri dish, cover with a perforated lid, and cook for 25 hours.
The insects were housed in a constant temperature room at 0.degree. C., and the number of dead insects was investigated after 96 hours, and the mortality rate was calculated using the same formula as in Test Example 1.

The results are shown in Table 5.

Please note that the exam will be conducted in two sections.

Test JIJ Yu Akira Acaricidal Efficacy Test against Kanzawa Spider Mite Cut green bean leaves into a circle with a diameter of 1.5a using a leaf punch, and place it in a damp F on a styrene cup with a diameter of 7.
I put it on paper. This was inoculated with 10 Kanzawa spider mite larvae per leaf. 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 1000 pprn M degree was sprayed using a rotary scattering tower at a rate of 2 drops per styrene cup.
The number of dead insects after 6 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 6.

The test was conducted in two sections.

Test Example 6 Insecticidal test against black leafhopper A yellow rice leaf was immersed in an emulsion containing the compound of the present invention at a concentration of 1000 ppm for about 10 seconds, and the yellow leaf was placed in a glass cylinder to kill adult black leafhopper, which is resistant to organophosphorus insecticides. Release, store the perforated lid in a temperature controlled room at 1 to 25℃, and keep it at 96℃.
The number of dead insects after a certain period of time 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 7: Nematicidal efficacy test against Nematode nematode The soil contaminated with Nematode nematode was placed in a styrofoam cup with a diameter of 8 mm. The emulsion of the compound of the present invention is diluted with water and
A chemical solution with a concentration of 0.00 ppm was prepared, a spreading agent was added, and 50 ml per styrene cup was irrigated onto the soil. After 48 hours, tomato seedlings of the indicator crop were transplanted. 50 days after transplanting, wash tomato roots with water 1. The plant was inspected for root knot parasitism.

The results are shown in Table 3.

Root gall parasitism index: No root galls observed 1... Slightly observed 2... Moderately observed 3... Many observed 4... Extremely many observed Table 3 Insecticide , acaricide, nematocidal test results patent applicant Nissan Chemical Industries, Ltd. Procedural Amendment 111: October 1980 Light statement 1 Description of the case 1981 Patent Application No. 1G30113 2 Name of the invention Pyridazinone derivatives, their manufacturing process and insecticidal・Acaricide/Nematicide 3 Relationship with the case of the person making the amendment Patent applicant address 14-117, 3-chome Nishikicho, Kami ITI, Chiyoda-ku, Tokyo 101 Area weight of amendment order Voluntary amendment 5 Details of the invention in the specification to be amended Explanation 6 Contents of amendment (1) Third line from the bottom of specification No. 29T'r (7) r
'30 parts-l wo, 13 parts'.

(2) r 15 ft++- on the 2nd line of the 30th summer of the specification
Correct 1 to ``1°5 copies.''

Proceedings Amendment Store February 1980 Q Patent Office H Officer Kazuo Wakasugi 1 Indication of the Case 1982 Patent Application No. 163003 2 Name of the Invention Pyridazinone Derivatives, Their Manufacturing Process and Insecticides, Acaricides, and Nematicides 3 Amendment Relationship with the case of a person who does the following Patent applicant address: 3-7 Kanda Nishiki-cho, 1 Daita-ku, Tokyo I4, 101
Date of amendment order (2) 6 Contents of amendment (1) In the row for compound tooth 14 in Table 3 of the Specification No. 35TT, 'IJ' in the column for Nematode Nematode is corrected to "0".

2- Procedural amendment December 9, 1982 Patent Application No. 163003 2 Name of the invention Pyridazinone derivative, its manufacturing method, and insecticide, acaricide, and nematicide 3 Relationship with the case of the person making the amendment Patent application Address 101 3-7 Kanda Nishiki-cho, Chiyoda-ku, Tokyo Name (398) Nissan Chemical Industries, Ltd. 4 Date of amendment voluntary amendment 6 Supplementary city contents 1 Contents (1) Last line of table on page 16 with details After that, add the next complimentary page.

(2) Add the following $ field following the last line of the table on page 26 of the specification.

578- (3) Add the following following the last line of the table on page 35 of Mei 1'8I.

8- 10- 9-

Claims (1)

[Scope of Claims] (1) General formula (1): (However, in formula 1, RFi alkyl group, R1 and R2 each independently represent a hydrogen atom or a lower alkyl group, RB
and R'tli, each independently a lower alkyl group, a halogen atom, or a lower haloalkyl group. Nitro group, cyan group or alkoxycarbonyl group,
R5 represents a halogen atom, an oxygen atom, or a sulfur atom. m represents 0 or an integer of 1 to 5, and when 9m is 2 or 3, R3 may be the same or different. 1-n represents 0 or an integer from 1 to 3, and when n is 2 and 5, R4 may be the same or different. 5 (2H)-pyridazinone derivative represented by ). (2) A compound represented by the general formula (of: ) is reacted with a compound represented by the following in the presence of a hydrogen halide absorbent. To produce a compound represented by the general formula (T): Method. (However, in the above formula, Rtlj alkyl group, R1 and R2u each independently represent a hydrogen atom or a lower alkyl group, R5 and R't'l each independently represent a lower alkyl group, a halogen atom, a lower haloalkyl group, A nitro group, cyano group or alkoxycarbonyl group, R'
ii A halogen atom is represented by X [represents an oxygen atom or a sulfur atom. m represents an integer of 1 to 3, and when 9m is 2 or 5, R5 may be the same or different. n is Ot
represents an integer from 1 to 3, and if n is 2 or 5, R
4 may be the same or different from each other. Ha) represents a halogen atom. ) (8) General formula (■): A compound represented by: By reacting with the compound represented by. A method for producing the compound represented by (However, in the above formula, Rij alkyl group, R1 and R2u each independently represent a hydrogen atom or a lower alkyl group, R1 and R4 each independently represent a lower alkyl group,
A halogen atom, lower haloalkyl group, nitro group, cyano group or alkoxycarbonyl group *R"t'i represents a halogen atom, x represents an oxygen atom or a sulfur atom. m is 0
Or it represents an integer of 1 to 5, and when 1m is 2 or if5, R3 may be the same or different. n represents an integer from 1 to 3, and when n is 2 or 5, iR'i is the same [6Ha, JltTt, which may be the same or different, represents a halogen atom; 2M represents an alkali metal; ) 4- (4) General formula (■): A compound represented by: by reacting the compound represented by in the presence of a hydrogen halide absorbent. General formula (■): A method for producing a compound represented by: (However, in the above formula, 'lR [alkyl group, R1 and t each independently represent a hydrogen atom or lower alkyl group, R5 and R' ri each independently represent a lower alkyl group, halogen atom, lower haloalkyl group, nitro group, cyano group or alkoxycarbonyl group 'c@'' represents a halogen atom, and X represents an oxygen atom or a sulfur atom.m
ij represents O or an integer from 1 to 3, and 9m is 2 or 5
15 may be the same or different, n represents 0 or an integer from 1 to 3, and 1] is 2 or 3, tit
R4 may be the same or different from each other. Haj represents a halogen atom) (5) General formula (I): (However, in the formula 0, RFi alkyl group is if and R2
each independently represents a hydrogen atom or a lower alkyl group m
m and R' ij are each independently a lower alkyl group, a halogen atom, or a lower haloalkyl group. Nitro group, cyano group or alkoxycarbonyl group,
R5 represents a halogen atom, and xh represents an oxygen atom or a sulfur atom. m ij O also represents an integer from F'i1 to 5, 1m
When is 2 or 3, R3 may be the same or different. n represents 0 or an integer of 1 to 5, and when n is 2 or 3, one or two 5(2H)-pyridazinone derivatives represented by R4 (,1 may be the same or different from each other).
Insecticide, acaricide, and nematocide for agricultural and horticultural use that contains seeds or more as an active ingredient.