WO1994024114A1

WO1994024114A1 - Novel oxadiazole derivative

Info

Publication number: WO1994024114A1
Application number: PCT/JP1994/000624
Authority: WO
Inventors: Takashi Kishimoto; Kaoru Noda; Yasushi Shibata; Michihiko Matsuda; Renpei Hatano; Makio Yano; Takao Iwasa
Original assignee: Nippon Soda Co., Ltd.
Priority date: 1993-04-15
Filing date: 1994-04-14
Publication date: 1994-10-27

Abstract

A compound having excellent insecticidal and acaricidal effects and represented by general formula (I), wherein z represents oxygen, sulfur, -CH2- or (a), r3 representing C1 - C3 alkyl; r1 and r2 represent each independently hydrogen, C1 - C3 alkyl, hydroxy, halogen, thiocarbamoyl which may be substituted by C1 - C3 alkyl, C1 - C3 alkoxy, -S(O)mr4 (m representing an integer of 0 to 20, and r4 representing C1 - C3 alkyl), amino which may be substituted by C1 - C3 alkyl, or C1 - C3 alkylcarbonyloxy, or alternatively r1 and r2 may be combined together to represent oxo, hydroxyimino, C1 - C3 alkoxyimino or methylene; A represents halogen, C1 - C3 alkyl or C1 - C3 alkoxy; and n represents an integer of 0 to 4, provided when n is 2 or above, then A's may be the same or different from each other.

Description

Specification

New oxadiazole derivatives

Technical field:

The present invention relates to a novel oxadiazole derivative and an insecticide and acaricide. Background technology:

Many insecticides and acaricides have been used in the past, but their efficacy was insufficient, their use was limited due to drug resistance problems, and phytotoxicity and contamination of plants occurred. However, because of their high toxicity to humans and fishes, many of them are not necessarily satisfactory control agents. Therefore, there is a demand for the development of a drug that can be used safely with few such disadvantages.

EP 2753354 is a compound that has acaricidal activity and is related to the compound of the present invention. For example, the following compounds are described.

However, there is no description of the insecticidal activity in this specification.

DISCLOSURE OF THE INVENTION:

An object of the present invention is to provide an insecticide and acaricide that is effective and can be used safely.

As a result of various studies, the present inventors have found that the ortho-position of the phenyl group directly bonded to the oxaziazole ring is substituted with a chlorine atom, and that the phenyl group bonded to the oxaziazole ring via a carbon atom. In the para position of the formula, Ζ—C ₄ H g ⁴ (wherein, Z represents oxygen, sulfur, one CH ₂ — or —CH r ³ — (where r ³ represents a d-3 alkyl group).) It has been found that a compound having the formula (1) exhibits high activity not only in the susceptible ticks but also in the resistant ticks, and furthermore exhibits excellent insecticidal activity, thereby completing the present invention. That is, the present invention provides a compound represented by the general formula (I):

r

I

[In the formula, Z represents oxygen, sulfur, —CH ₂ — or —CH— (r represents a d alkyl group),

r! , r are each independently a hydrogen atom, d alkyl group, hydroxy group, halogen atom, thiocarbamoyl group optionally substituted by C! _-3 alkyl, C alkoxy group, — S (0) _m r ( In the formula, m represents an integer of 0 to 2, r ₄ represents a C _-3 alkyl group), an amino group optionally substituted with ₃ alkyl, or a C! _-3 alkylcarbonyloxy group, properly is, r!, r is together in a go-between Okiso group, human Dorokishii Mi amino group, _C]-3 Arukokishii Mi amino group, or a methylene group

A represents a halogen atom, a C, _-3 alkyl group or an alkoxy group, which may be different;

n represents an integer of 0 to 4. When n is 2 or more, A may be the same or different. ], A production method thereof, and an insecticide and acaricide.

The production method of the compound of the present invention is as follows.

Manufacturing method 1

In the formula, B represents a hydroxyl group or a halogen, and r,, r2, A, n, and Z have the same meaning as described above. The reaction is carried out in an organic solvent, if necessary, in the presence of a dehydrating agent and a base, for 1 hour to several 10 hours, from −20 ° C. to the boiling point of the solvent used. As the solvent, DMF, acetonitril, THF, benzene, chloroform, dioxane and the like can be used. '' Dehydrating agents include carbonyldiimidazole and 1,3-dicyclohexylcarpoimide, and bases include pyridine, triethylamine, DBU, sodium hydride, sodium hydroxide, Carbonate streams can be used.

, R ₂ , A, n, and Z have the same meaning as described above. The reaction is carried out in an organic solvent from 50 to the boiling point of the solvent used, for 1 hour to several 10 hours. As the solvent, DMF, toluene, xylene, dichlorobenzene and the like can be used.

Manufacturing method 2

, R ₂ , A, n, and Z have the same meaning as described above. The reaction is carried out in an organic solvent in the presence of a catalyst, if desired, from 100 ° C to the boiling point of the solvent used, from one hour to several Performed for 0 hours. As the solvent, dichloromethane, DMF, acetonitril, THF, chloroform can be used. As the catalyst, trifluoromethanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, hydrochloric acid and the like can be used.

Manufacturing method 3

Further, the compound of the present invention can also be produced by appropriately selecting a reaction similar to the following reaction formula or a known reaction depending on the type of the substituent.

a)

_{, R 2, A, n,} Z are as defined above, _c R is a lower alkyl group b)

A, n, and Z have the same meanings as described above, and 'indicates a d alkyl group. C)

A, n and Z have the same meaning as described above.

Even after the completion of the reaction if the reaction was performed in either method can be obtain an ordinary post-treatment ¹ Ri target compound by the be performed.

The structure of the compound of the present invention was determined from IR, NMR, MS and the like.

BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described in more detail by way of examples.

Example 1

1.4 g of N-hydroxy-1,6-dichlorobenzamidine was added to 50 ml of ethanol solution previously dissolved with 0.2 g of sodium metal and dissolved, and then methyl 4-t- 1.5 g of butoxyphenyl acetate was added, and the mixture was refluxed for 12 hours. After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and then ethyl acetate was distilled off under reduced pressure. The resulting residue is separated and purified by a silica gel column to give the desired 5- (4-t-butanol). 1.0 g of (xybenzyl) -13- (2,6-dichlorophenyl) -11,2,4-oxadiazole (Compound No. 1) was obtained. mp 6 0 _ 6 2 ° C

Example 2

1.04 g of N-hydroxy2,6-dichlorobenzamidine was added to 3 ml of a methanol solution in which 0.08 g of sodium metal was previously dissolved, and dissolved. 0.8 g of (4-t-butoxyphenyl) propionate was added, and the mixture was heated under reflux for 3 hours. After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and filtered, and then ethyl acetate was distilled off under reduced pressure. The obtained residue is separated and purified by a silica gel column, and the desired 5- (α-methyl-14_t-butoxybenzyl) -13- (2,6-dichlorophenyl) —1,2,4-oxadiazole ( Compound No. 2) 0.6 g was obtained.

ⁿ _D 2Ι · ⁰ 1.5468

Example 3

0.8 g of 5- (4-t-butoxybenzyl) -3- (2,6-dichlorophenyl) 1-1,2,4-oxadiazol was dissolved in 50 ml of acetic acid, and added at room temperature. Under ice cooling, 0.5 g of chromic anhydride was added and reacted at room temperature. After 2 hours, the reaction solution is The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate, washed with water, dried over magnesium sulfate, filtered, and the ethyl acetate was distilled off under reduced pressure. The resulting residue is separated and purified on a silica gel column, and the desired 5_ (4-t-butoxybenzoyl) — 3 -— (2,6-dichlorophenyl) —1,2,4-oxaziazole (compound No. 5) 0.4 g was obtained. mp 7 8—8 0

Table 1 shows typical examples of the compounds of the present invention including the above Examples.

Table 1

Compound number rir 2 An Z ^¾ Bu Physical constant n = 0 O'Bu mp 60-62. C

21.0

Me n _D 1.5468

OH

OH Me

= 0 rap 78-80 ° C

: CH ₂

= N0H shelf t

-CSNHMe (Continued

Compound number rir 2 An Z ^l Bu Physical constant

1 1 -OCOMe H n = 0 O'Bu

1 2 SMe 〃〃〃

1 3 SO e 〃〃

1 4 S0 ₂ Me 〃〃

1 5 -NHMe 〃〃〃

1 6 F 〃〃

1 7 CI 〃

1 8 H 〃〃 S'Bu

1 9 Me 〃〃

2 0 = 0 〃

2 1 H H 〃 NH'Bu

2 2 Me 〃〃〃

2 3 = 0 〃〃 Table 1 (continued)

Table 1 (continued)

Compound number r 1 r 2 An Z'Bu Physical constant

3 6 H H 2-OMe O'Bu

3 7 〃〃 3-OMe 〃

3 8 〃〃 2-OEt 〃

3 9 〃〃 3-OEt 〃

4 0 〃〃 2, 3-F ₂ 〃

4 1 〃 3, 5-F ₂ 〃

4 2 〃〃 2, 5-F2 〃

4 3 〃〃 2, 3-Ch 〃

4 4 〃〃 3, 5-C 〃

4 5 〃〃 2, 5- C The compound of the present invention can be used for controlling agricultural pests, sanitary pests, grain storage pests, clothing pests, house pests, and the like.

Lepidopteran pests, for example, Hasmonyoto, Totoga, Tamanayaga, Aomushi, Tamanaginba, Konaga, Jyanokokakumonhamaki, Chiyamahamaki, Momoshinguiga, Nashihimeshingui, Mikanhamoguriga, Chiyanhosoga, Kigahogama, Kigahogama Hemiptera pests, such as peaches, such as Kobu nomeiga, Yochi bite Pian corn borer, American squirrels, Spodoptera litura, Heliotis, Helicobelpa, Aggrotis, Iga, Kodlinga, Petakamimi, etc. Aphid, Aphid aphid, Aphid aphid, Wheat viper aphid, Elephant's bug, Elephant's bug, Anemone aphid, Cucumber aphid, Onycium aphid, Tobacco whitefly Coleopteran pests such as pear lice, pear grub beetles, stabbed beetle, brown beetle power, brown squirrel power, sagebill plant, maggot beetle, etc. Bark beetle, pine beetle, pine beetle, agliotis, agliotis , Rice leaf fly, key mouth drosophila, sand flies, koga squid force, anetsima force, shinakamadaka, etc. Hymenopteran pests, Pterocarpus thisrane, etc., Hymenopteran pests, for example, Diplomatidae, Japanese hornet wasps, Power brackenes, etc., Orthopterous pests, for example, Japanese cockroaches, Black cockroaches, Black cockroaches, Tonosamabata, etc. Pests, for example, house termites, mountain termites, etc., Lepidopteran pests, for example, rodents, lice, pests, for example, human lice, ticks, for example, Namihadani, Nisenamihadani, Kanzahahadani, Citrus red mite, Lingo spider mite, Lycopodium mite, Lingo savidenii, Dermatophagoides mite, Brevipalpas, Jote tranicas, Robinne mite, Scarab mite, Dermatophagoides farinae Plant-parasitic nematodes such as tick mites, swelling ticks and the like, for example, sweet potato nematodes, negusarecentiyu, soybean cistosiyu, rice singaresenchu, matsunoza centiyu, and the like.

In recent years, many insect pests and mites, such as moth, pest, leafhopper and aphid, have developed resistance to organic phosphorus agents, carbamates, and acaricides, and have caused a problem of insufficient efficacy of these agents. There is a need for drugs that are effective against sexual pests and mites. The compound of the present invention is an agent having an excellent insecticidal and acaricidal effect against not only susceptible strains but also pests and mites of organic phosphorus agents, carbamates, pyrethroids, and acaricide-resistant strains.

The pesticidal agent of the present invention contains the compound represented by the formula [I] as an active ingredient, and can be used as it is as a pure product of the active ingredient compound. That is, they are used in the form of wettable powders, aqueous solvents, powders, emulsions, granules, flowables, and the like. Additives and carriers include solid powders such as vegetable powders such as soybean flour and flour; diatomaceous earth, apatite, gypsum, talc, bentonite, clay, etc .; and benzoic acid. Organic and inorganic compounds such as soda, urea, and sodium sulfate are used.

For liquid dosage forms, vegetable oils, mineral oils, petroleum fractions such as kerosene, xylene and solvent naphtha, sikglohexane, siquiloxaxanone, dimethylformamide, dimethylsulfoxide, trichloroethylene Use methyl isobutyl ketone, water, etc. as the solvent. In these preparations, a surfactant can be added if necessary to obtain a uniform and stable form. The wettable powders, emulsions, aqueous solutions and flowables obtained in this way are diluted to a certain concentration with water and used as suspensions or emulsions. Is done.

It goes without saying that the compound of the present invention is effective alone, but it can also be used in combination with various insecticides, acaricides, nematicides, fungicides and synergists. Representative examples of insecticides and acaricides that can be used by mixing with the compound of the present invention are shown below.

Organophosphorus and carbamate insecticides:

Fenthion, Phinitrothion, Diazinone, Chlorpyrifos, ESP, Pamidothion, Phentoate, Dimethoate, Formothion, Marathon, Trichlorfon, Thiomethon, Hosmet, Dichlorvos, Acephate, EPBP, Methylparathine , Oxidimethonmethyl, Ethione, Salithion, Cyanophos, Isoxathion, Pyridafantion, Hosalon, Methidathion, Sulprophos, Chlorphanvinphos, Tetrachlorvinphos, Dimethylvinphos, Propaphos, Isofenphos, Etylthiophomethon, Monopyraphos Clotofos, Azinphos-methyl, Aldicarb, Methomil, Zodicalp, Carbofuran, Carbosulfan, Benfracarb, F Chiokarupu, Purobokisuru, B P M C, M T M C, M I P C, force Rubariru, pyrimidone mosquitoes one blanking, Echiofen Chikararu blanking, Fuenokishikarupu, cartap, thiocyclam, Bensuruta-up and the like.

Pyrethroid insecticides:

Permethrin, Cypermethrin, Delta Meslin, Fuemberate, Fenproha. Trin, pyrethrin, allesulin, tetramethrin, resmethrin, dimeslin, propasulin, phenothrin, protoline, full variate, siflutrin, cyhalothrin , Fullcitrine, ethopronx, cyclin protolin, tralomethrin, silafluofen, brofenprox, acrinatrin, etc.

Benzoylurea and other insecticides: ·

Difluvenzuron, chlorfluazuron, hexaflumuron, triflumuron, tefluvenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzepin, diafentiuron, imimi Dacloprid, fipronil, nicotine sulfate, rotenone, methyl aldehyde, machine oil, microbial pesticides such as BT and insect pathogenic viruses. Nematicide:

Fenamiphos, phosthiazetate, etc.

Acaricide:

Chlorbenzilate, phenylisobromolate, dicophor, amitraz, BPPS, benzomate, hexithiax, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradihon, avermectin, milbemectin. Hexatin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifene, phenothocalp, dienochlor and the like.

Fungicide:

Thiophanate methyl, benomyl, carbendazole, thiabendazole, phorpet, thiuram, ziram, zineb, maneb, polycarbamate, IBP, EDDP, fusaride, probenazole, isoprothiolane, TPN, capitan, Polyoxin, Blastosidine S, Kasugamycin, Streptomycin, Validamycin, Tricyclazol, Pyroquilon, Phanadoxide, Mepronil, Flutolanil, Pencyclon, Iprodione, Himexazol, Metalaxyl, Trirefrinolizol, Trifolone , Triazimefone, Vitelenol, finalimol, propiconazole, simoxanil, prochloraz, perfrazone, hexaconazole, microclobutanil, diclomedine, tech Oral phthalam, probeneb, dithianon, fosetyl, vinclozolin, procymidone, oxadixil, guazatine, propamocarp hydrochloride, fluazinam, oxolinic acid, hydroxyisoxazole, etc.

Next, examples of the preparation are shown, but the carrier, surfactant and the like to be added are not limited to these examples.

Example 4 Emulsion

Compound of the present invention 10 parts

Alkylphenylpolyoxyethylene 5 parts

Dimethylformamide 50 parts Xylene 3 5 parts

Mix and dissolve the above, dilute with water before use and spray as an emulsion.

Example 5 wettable powder

Compound of the present invention 10 parts

Higher alcohol sulfate 5 parts

Diatomaceous earth 80 parts

Silica 5 parts

Combine the above, pulverize into fine powder, dilute with water before use and spray as a suspension, Example 6

5 parts of the compound of the present invention

Talc 9 4.7 parts

0.3 parts of silica

Mix and grind the above and spray as it is when using.

Example 7 granules

5 parts of the compound of the present invention

Cray 7 3 copies

Vento Night 20

Dioctyl sulfosuccinate sodium salt 1 part

1 part of sodium phosphate

Granulate the above and apply as it is when used.

Industrial applicability:

Test Example 1 Efficacy against tabular beetle

10 days after germination, seedlings sown in three-size bowls were inoculated with adult Aphid aphids. One day later, the adults were removed, and the cucumber parasitized by the produced nymphs was diluted with water to a compound concentration of 125 ppm according to the emulsion formulation shown in Example 4 of the drug. The chemical was sprayed. Place in a constant temperature room with a temperature of 25 ° C and a humidity of 65%,

6 He later investigated the insecticidal rate. The results are shown in Table 2 below. 2 Compound No. Insecticidation after 6 days (%)

2 7 1 0 0 Control compound A 6 Control compound A: Pyrimicab

Test Example 2 Efficacy against Citrus red mites

After inoculating 10 adult female mites, acaricide-resistant mites, on the leaves of the mites in a petri dish, the compound concentration was adjusted according to the formulation of the emulsion described in Example 4 of the drug. A drug solution diluted with water to 31 ppm was sprayed on a rotary spray tower. After placing in a constant temperature room at a temperature of 25 and a humidity of 65%, the adults were removed 3 days after spraying, and on the 1st day, eggs that were laid during these 3 days were checked to see if they could develop into adults. Investigated and determined the effectiveness of killing. The results are shown in Table 3 below.

Compound number * Acaricidal effectiveness (%)

1 1 0 0 Control compound B 4 0

Control compound C 1 Control compound B

(Compound described in EP 2 7 3 5 3 4) Control compound C

(Compound described in EP 2 7 3 5 3 4) T e + T 1 C e + C 1

T e + T L C e + C L

* Acaricidal effectiveness (%) = X 100

C e + C 1

C e + C L

T e: Number of dead eggs in the treatment area

T 1: Number of dead larvae in the treated area

TL: Number of larvae in the treatment area

C e: Number of dead eggs in untreated area

C 1: Number of dead larvae in untreated area

C L: Number of larvae in untreated area

Claims

The scope of the claims

1. General formula [I]

r 3

[Wherein, Z represents oxygen, sulfur, —CH ₂ — or one CH— (r 3 represents a d- ₃ alkyl group);

r 1 and r 2 each independently represent a hydrogen atom, an alkyl group, a hydroxy group, a halogen atom, a thiocarbamoyl group optionally substituted with Ci-3 alkyl,

C 1-3 alkoxy group, — S (0) _m r 4 (m represents an integer of 0 to 2, and r ₄ is

C! -3 alkyl group), an amino group which may be substituted with alkyl, or a d- ₃ alkylcarbonyloxy group, or an oxo group, a hydroxyl group, or amino group, C -! ₃ Arukokishii Mi amino group, or a methylene group and a is a halogen atom, CI_ ₃ alkyl group, a d-3 alkoxy group,

n represents an integer of 0 to 4. When n is 2 or more, A may be the same or different. ]

A compound represented by the formula:

2. Formula [II]

Z'Bu (II)

_{_{Wherein, τ ri, r 2, A}} , n are as defined above. A compound represented by the formula (I)

[Where Z, r! r ₂ , A and n represent the same meaning as described above. ] The manufacturing method of the compound represented by these.

3. Formula [III]

ZH (III)

[In the formula, Z, r, .r ₂ , Α, and η represent the same meaning as described above. Wherein the compound represented by the formula (I) is reacted with isobutene:

[Wherein, Z, r, sr ₂ , A, and n represent the same meaning as described above. ] The manufacturing method of the compound represented by these.

4. Equation [I]

[Wherein, Z,, r ₂ , A, and n represent the same meaning as described above. ] An insecticide and acaricide, comprising one or more of the compounds represented by the formula (1) as an active ingredient.