JPH07101968A - Amide-thiophosphoric ester derivative and insecticide, nematocide and acaricide containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain an amide-thiophosphoric ester derivative which has a specific chemical structure and has extremely excellent insecticidal, acaricidal and nematocidal actions against soil insects, soil nematodes giving damages to a variety of crop plants, flowers, lawns and the like. CONSTITUTION:A derivative of the formula I (R1 is methyl, ethyl; R2 is n-propyl, sec-butyl; R3 is 1-4 C alkoxy, 1-4 C thioalkoxy, phenyl, phenoxy; n is 1, 2), for example, 0-ethyl S-sec-butyl N-cyanomethyl-N- methoxcarbonylphosphoroamidethiodate. For example, it is preferred that the reaction of phosphoric chloride and a nitrile derivative of formula III in the presence of sodium hydride in a solvent such as diethyl ether gives the objective derivative.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amidothiophosphate derivative and an insecticidal, nematicidal and acaricidal agent containing the same as an active ingredient.

2. Description of the Related Art It is known that certain amide thiophosphoric acid ester derivatives have insecticidal, nematicidal and acaricidal activity. For example, Japanese Unexamined Patent Publication No. 59-108796 discloses a general formula 2

[Chemical 2] [In the formula, A is an n-propyl group, an isobutyl group or sec
Represents a butyl group, and R'represents a methyl group or an ethyl group. ] It is described that the amidothiophosphoric acid ester derivative represented by] has insecticidal, nematicidal and acaricidal activity.

However, the amidothiophosphoric acid ester derivative represented by the above general formula 2 has a relatively high acute toxicity to mammals. Therefore, it is an insecticide, nematicide, and acaricide. Could not be put to practical use as an active ingredient of.

[0002]

In view of such a situation, the inventors of the present invention have diligently studied to find out an excellent insecticide, nematicide, and acaricide, and as a result, the compound represented by the general formula

[Chemical 3] [In the formula, R ₁ represents a methyl group or an ethyl group, and R ₂
Represents an n-propyl group or a sec-butyl group, and R ₃
Represents a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ thioalkoxy group, a phenyl group or a phenoxy group, and n represents 1 or 2. It was found that the amidothiophosphate derivative represented by the formula (hereinafter referred to as the compound of the present invention) has excellent insecticidal, nematicidal and acaricidal efficacy and relatively low acute toxicity to mammals. Was completed. That is, the present invention provides an amidothiophosphate derivative represented by the general formula 3 and insecticides, nematicides and acaricides containing the same as an active ingredient. The compound of the present invention, for example, Nikameichu, lepidopteran pests such as Spodoptera litura, Culex pipiens, Diptera pests such as housefly, nematodes such as Sweet potato Nematode, mites such as Nematoda spp. It has insecticidal and acaricidal effects, but among them, it exhibits extremely excellent insecticidal and nematicidal effects against soil pests and nematodes that live in soil and feed various crops, flowers, lawns, etc. .

Examples of the compounds of the present invention are shown in Tables 1 to 7.
(The substituents of the compound represented by the general formula 3 are shown.)

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

The compound of the present invention can be produced, for example, by the following method. (Production method A) General formula 4

[Chemical 4] [In the formula, R ₁ and R ₂ have the same meanings as described above. ]
Phosphorus chloride represented by

Embedded image NC (CH ₂ ) _n NHCOR ₃ [wherein R ₃ and n have the same meanings as described above]. ] The method of reacting with the nitrile derivative shown by these in the presence of a base. The reaction is usually carried out in a solvent, and examples of the solvent used include ethers such as diethyl ether and tetrahydrofuran, and aromatic hydrocarbons such as benzene and toluene. Examples of the base used include alkali metal hydrides such as sodium hydride and potassium hydride. The reaction is usually -70
℃ ~ solvent reflux temperature or 100 ℃ temperature range, usually 1
Do for 10 hours. The amount ratio of the reagents used is 1 mol of the nitrile derivative represented by the general formula 5
The phosphoric acid chloride represented by is usually 1.0 to 1.2 mol, and the base is usually 1 to 1.2 mol. Phosphorous chloride represented by the general formula 4 is, for example, Houben-W
eyl, Methodender Organischen chemie, Band E2, 542
~ By the method described on page 543 (1982),
It can be manufactured. The nitrile derivative represented by the general formula 5 is described in, for example, Beilstein Handbuch, Volume 4, 363.
It can be manufactured by the method described on the page.

(Production Method B) General Formula 6

[Chemical 6] [In the formula, R ₁ , R ₂ and n have the same meanings as described above. ] And an amide thiophosphate compound represented by the following general formula:

[Chemical 7] [In the formula, R ₃ has the same meaning as described above. ] The method of making it react with the acid chloride shown by these in the presence of a base. The reaction is usually carried out in an organic solvent, and examples of the solvent used include ethers such as diethyl ether and tetrahydrofuran, and aromatic hydrocarbons such as benzene and toluene. Examples of the base used include alkali metal hydrides such as sodium hydride and potassium hydride. The reaction is usually carried out at a temperature of -70 ° C to the reflux temperature of the solvent or 100 ° C for 1 to 10 hours. The amount ratio of the reagents used is usually 1.0 to 1.2 mol of the acid chloride represented by the general formula 7 and 1 mol of the base represented by the general formula 6, relative to 1 mol of the amide thiophosphate compound represented by the general formula 6. It is a ratio of 1 to 1.2 mol. General formula
The amide thiophosphoric acid ester compound represented by the chemical formula 6 is obtained by reacting the phosphoric acid chloride represented by the general formula 4 with aminoacetonitrile [or a salt thereof (for example, an inorganic acid salt such as hydrochloride or sulfate)] or 2-aminopropiolate. It can be produced by reacting a nitrile [or a salt thereof (for example, an inorganic acid salt such as hydrochloride and sulfate)] in the presence of a base in an organic solvent, water or a mixed solvent of both. Examples of the organic solvent used include ethers such as diethyl ether and diisopropyl ether, halogenated hydrocarbons such as methylene chloride and chloroform, and aromatic hydrocarbons such as benzene and toluene. Examples of the base used include tertiary amines such as pyridine and triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. The amount ratio of the reagent used is usually 1.0 to 1 for the phosphoryl chloride represented by the general formula 4 with respect to 1 mol of aminoacetonitrile (or its salt) or 2-aminopropionitrile (or its salt). 0.2 mol, and the base is usually 1 to 1.2 mol. In the production method A and the production method B, the target compound can be isolated by subjecting it to usual post-treatments such as extraction with an organic solvent and concentration after completion of the reaction, but if necessary, column chromatography Further purification by distillation, etc. is also possible.

Examples of the pests, nematodes and harmful mites which the compound of the present invention has a controlling effect on include the following. Hemiptera Pests, Brown Planthopper ( Laodelphax striatellus ), Brown Planthopper ( Nilaparvata lugens ), White- tailed Planthopper ( So
gatella furcifera) planthoppers, such as green rice leafhopper (Nephotettix cincticeps), leafhoppers, such as Taiwan green rice leafhopper (Nephotettix virescens), aphids, stink bugs, whiteflies, scale insects, tingidae class, Lepidoptera rice stem borer, such as psyllid acids (Chilo suppressalis ), Kobunomeiga
( Cnaphalocrocis medinalis ), European corn borer ( Ostrinia nubilalis ), Shibattoga ( Pa
rapediasia teterrella ), Watanomaiga ( Notarcha )
derogata ), Pyrophora interpuncta ( Plodia interpunct)
Ella and other common moths , Spodoptera litura ( Spodoptera
litura), armyworm (Pseudaletia separata), cabbage armyworm (Mamestra brassicae), black cutworm (Agroti
s ipsilon ), Trichoprussia , Heliotis,
Long-tailed moths such as Helicopterpa and Pieris
rapae crucivora ) and other white butterflies, Adoxophyes spp., Grapholita molesta
), Codling moss ( Cydia pomonella ) and other leaf tortoises, Peach moth ( Carposina niponensis )
Shinkuiga such, Hamoguriga such as Rionetia genus Rimantoria genus, tussock such as user Proc-Eustis genus, such as diamondback moth (Plutella xylostella) Suga such as, pink bollworm (Pectinophora gossypiella) Kibaga such as, the United States white Arctiidae (Hyphantria cunea) Hydrangeas such as, Moth ( Tinea translucens ), Koga
(Tineola bisselliella) Hirozukoga such like Diptera Culex (Culex pipiens pallens), such as, Culex such as Culex (Culex tritaeniorhynchus), Aedes aegypti, Aedes spp such as Aedes albopictus, Anopheles spp such as Anopheles sinensis,
House flies such as chironomids , house flies ( Musca domestica ), house flies ( Muscina stabulans ), blow flies, flesh flies, house flies, sand flies ( De)
lia Platura ), onion fly ( Delia antigua ).
Western corn rootworm ( Diabrotica virgifer ) such as fruit flies, fruit flies, fruit flies, butterfly flies, gnats , flies, flies, leaf flies, etc.
a ) the Southern corn rootworm ( Diabrotica undeci
mpunctata ) and other corn rootworms, Rana bursa ( Anomala cuprea ), and Scutellaria ( Anomala )
chafers such as rufocuprea ), Maysweville
( Sitophilus zeamais ), rice weevil ( Lissorh
optrus oryzophilus ), alfalfa weevil ( Hypera pastica ), adzuki bean weevil ( Calosobruchy )
s chinensis) Weevil such as, chai loco Mei mealworm (Tenebrio molitor), mealworm such as red flour beetle (Tribolium castaneum), cucurbit leaf beetle (Aulacophora femoralis), Kisujinomihamushi (Phyllotreta striolata), beetles such as Colorado potato beetle (Leptinotarsa decemlineata) ,
Anemone beetle, Epilachna
Vigintioctopunctata) Epilachna such as, Hirata beetles such, Naga Shinkuimushi acids, Cerambycidae such, Aoba ants backlash Staphylinidae (Paederus fuscipes), etc. Orthoptera network Orthoptera pests German cockroach (Blattella germanica), black cockroach (Periplaneta fuliginosa), American cockroach (P
eriplaneta americana ), Black-tailed Cockroach ( Perip
laneta brunnea ), American cockroach ( Blatta ori
entalis) Thysanoptera South thrips such as (Thrips palmi), green onion thrips (Thrips tabaci), Hana thrips (Thrips
Hawaiiensis ), etc.Hymenoptera pests Ants, hornets, wasps, hornets such as Japanese wasps ( Athalia rosae ruficornis ), etc.Orthoptera pests Mera , grasshoppers etc.Heteroptera pests Human flea ( Purex irritans ) etc. Eye pest Pediculus humanus capitis , lice ( Phthirus
pubis ) and other termite pests Yamato termites ( Reticulitermes speratus ), house termites ( Coptotermes formosanus ) and other mites such as Tetranychus uriticae , Tetranychus cinnabarinus , and
( Tetranychus kanzawai ), mandarin orange mite ( Panonychu
s citri), Ringohadani (Panonychus ulmi), spider mites such as Origonikasu genus, tangerine rust mite (Aculop
s pelekassi ), Dermatophagoides farinae ( Calacarus cari )
natus) Fushidani such as, Chanohokoridani (Polyph
aqotarsonemus latus ) and other dust mites, sand spider mites, mosquito mites, ticks such as Boophilus microplus , mites, Pyroglyphidae, house dust mites such as Pyroglyphidae, spider mites, nematodes, and nematodes (Tylenchida) Pratylenchus coffeae Pratylenchus coffeae Pratylenchus penetrans Pratylenchus loosi Glycera elastroides a Heterodera e Hederadeae ( Globodera rostochien
sis ) Meloidogynidae Meloidogyne hapla Meloidogyne incognit
a )

When the compound of the present invention is used as an active ingredient for insecticides, nematicides and acaricides, it may be used as it is without adding any other ingredients, but it is usually a solid carrier, liquid carrier, Mix with a gaseous carrier, bait, etc., add surfactants and other formulation auxiliary agents if necessary, and prepare oils, emulsions,
Flowable agents such as wettable powders, water suspension agents and water emulsions, granules, powder agents, aerosols, self-combustion smoke agents, chemically reactive smoke agents, porous smoke smoke agents such as perforated ceramic plate smoke agents. Agent, UL
V formulation, poison bait, etc. are used. These formulations include
The compound of the present invention as an active ingredient is usually 0.01% by weight.
~ 95% content. Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (serisite, quartz, Sulfur, activated carbon, calcium carbonate,
Hydrated silica, etc., chemical fertilizers (ammonium sulfate, phosphorus ammonium, ammonium nitrate, urea,
Examples of the liquid carrier include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, benzene, etc.). Toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane,
Kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil, vegetable oils such as cottonseed oil, and the like, and a gaseous carrier, that is, a propellant, Examples thereof include CFC gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like. Examples of the surfactant include alkyl sulfate salts, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. can give. Examples of formulation adjuvants such as sticking agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol). , Polyvinylpyrrolidone, polyacrylic acids, etc., and examples of the stabilizer include PAP (isopropyl acid phosphate) and BH.
T (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , Surfactants, fatty acids or esters thereof, and the like. Examples of base materials for self-burning smoke agents include nitrates, nitrites, guanidine salts,
Combustion exothermic agents such as potassium chlorate, nitrocellulose, ethyl cellulose, wood powder, alkali metal salts, alkaline earth metal salts, pyrolysis stimulants such as dichromate and chromate, oxygen supply agents such as potassium nitrate, melamine , Wheat starch and other combustion-supporting agents, diatomaceous earth and other fillers, synthetic pastes and other binders and the like. As the base material of the chemically reactive smoke agent, for example, alkali metal sulfide, polysulfide,
Exothermic agents such as hydrosulfides, hydrous salts and calcium oxides, carbonaceous materials, catalysts such as iron carbide and activated clay, organic blowing agents such as azodicarbonamide, benzenesulfonylhydrazine, dinitrosopentamethylenetetramine, polystyrene and polyurethane. Examples include fillers such as natural fiber pieces and synthetic fiber pieces. As a base material for poison baits, for example, grain flour,
Vegetable essential oils, sugars, bait ingredients such as crystalline cellulose, antioxidants such as dibutylhydroxytoluene, nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, food intake preventives such as capsicum powder, cheese flavor, onion flavor, etc. Inviting fragrances, etc. Formulations of flowable agents (suspension in water or emulsions in water) generally comprise from 1 to 75% of the compound of the invention 0.5 to 15% dispersant, 0.1 to 10% suspension aid (eg. , Protective colloids and compounds that impart thixotropy), 0 to 10% of suitable auxiliary agents (for example, antifoaming agents, rust preventives, stabilizers, spreading agents, penetration aids, antifreezing agents, antibacterial agents) It is obtained by finely dispersing it in water containing an agent, an anti-smudge agent, etc. It is also possible to use an oil in which the compound is hardly dissolved in place of water to prepare a suspension in oil. As the protective colloid, for example, gelatin, casein, gums, cellulose ether, polyvinyl alcohol, etc. are used. Examples of the compound that imparts thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, polyacryl, and the like. The preparation thus obtained is used as it is or after diluted with water or the like. Also other pesticides,
It can be used simultaneously with or without mixing with nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers, animal feeds and the like.

Examples of the insecticide and / or acaricide and / or nematicide used include fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate] and phenthion [O, O-dimethyl O- (3-methyl-4- (methylthio) phenyl) phosphorothioate], diazinon [O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-ylphosphorothioate], chlorpyrifos [O, O -Diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate], acephate [O, S-dimethylacetylphosphoramidothioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo] -1,3,4-thiadiazole-3-
Ilmethyl O, O-dimethyl phosphorodithioate], disulfoton [O, O-diethyl S-2-ethylthioethyl phosphorothioate], DDVP [2,2
-Dichlorovinyl dimethyl phosphate], sulprophos [O-ethyl O-4- (methylthio) phenyl S
-Propyl phosphorodithioate], cyanophos [O-
4-cyanophenyl O, O-dimethyl phosphorothioate], dioxabenzophos [2-methoxy-4H-
1,3,2-benzodioxaphosphinin-2-sulfide], dimethoate [O, O-dimethyl-S- (N-
Methylcarbamoylmethyl) dithiophosphate], fentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2-trichloro- 1-hydroxyethylphosphonate], azinphos-methyl [S-3,4-dihydro-4-oxo-1,
2,3-benzotriazin-3-ylmethyl O, O-
Dimethyl phosphorodithioate], monocrotophos [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate], ethione [0,0,0 ′,
0'-Tetraethyl S, S'-methylenebis (phosphorodithioate)] phostiazate [N- (O-ethyl-S-sec-butyl) phosphorylthiazolidine-2-
On] and other organic phosphorus compounds, BPMC (2-sec-butylphenylmethylcarbamate), benfuracarb [ethyl N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio]] -N-isopropyl-B-alaninate],
Propoxur [2-isopropoxyphenyl N-methylcarbamate], carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo [b] furanyl N
-Dibutylaminothio-N-methylcarbamate], carbaryl [1-naphthyl-N-methylcarbamate],
Methomyl [S-methyl-N-[(methylcarbamoyl)
[Oxy] thioacetimidate], Ethiophenecarb [2- (ethylthiomethyl) phenylmethylcarbamate], Aldicarb [2-methyl-2- (methylthio)]
Propionaldehyde O-methylcarbamoyloxy], oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide], phenothiocarb [S-4-phenoxybutyl)
Carbamate compounds such as -N, N-dimethylthiocarbamate, etofenprox [2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether], fenvalerate [(RS) -α-cyano- 3-phenoxybenzyl (RS) -2- (4-chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenyl)] -3-Methylbutyrate], phenpropatrine [(RS) -α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS) -α-cyano -3-Phenoxybenzyl (1RS, 3RS)-(1RS, 3RS) -3- (2,
2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS, 3RS)-(1RS, 3RS) -3
-(2,2-Dichlorovinyl) -2,2-methylcyclopropanecarboxylate], cyhalothrin [(RS)
-Α-cyano-3-phenoxybenzyl (Z)-(1R
S, 3RS) -3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S) -α-cyano-m-phenoxybenzyl ( 1R, 3R) -3-
(2,2-Dibromovinyl) -2,2-dimethylcyclopropanecarboxylate], cycloprothrin [(R
S) -α-Cyano-3-phenoxybenzyl (RS)-
2,2-dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate], fulvalinate (α-
Cyano-3-phenoxybenzyl N- (2-chloro-
α, α, α-trifluoro-p-tolyl) -D-valinate), bifenthrin (2-methylbiphenyl-3-)
Ilmethyl) (Z)-(1RS) -cis-3- (2-chloro-3,3,3-trifluoroprop-1-enyl)
-2,2-dimethylcyclopropanecarboxylate,
Acrinathrin ([1R- {1α (S ^* ), 3α
(Z)}]-2,2-Dimethyl-3- [3-oxo-3
-(2,2,2-Trifluoro-1- (trifluoromethyl) ethoxy-1-propenyl] cyclopropanecarboxylic acid cyano (3-phenoxyphenyl) methyl ester), 2-methyl-2- (4-bromodifluoro) Methoxyphenyl) propyl (3-phenoxybenzyl) ether, tralomethrin [(1R, 3S) 3 [(1′R
S) (1 ', 2', 2 ', 2'-tetrabromoethyl)]-2,2-dimethylcyclopropanecarboxylic acid
(S) -α-cyano-3-phenoxybenzyl ester, silafluofene [4-ethoxyphenyl [3-
(4-Fluoro-3-phenoxyphenyl) propyl]
Pyrethroid compounds such as dimethylsilane, buprofezin (2-tert-butylimino-3-isopropyl-5-
Phenyl-1,3,5-triadiazin-4-one)
Thiadiazine derivatives such as imidacloprid [1- (6
-Chloro-3-pyridylmethyl) -N-nitroimidazolidine-2-indeneamine], nitroimidazolidine derivatives, cartap (S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate)], thiocyclam [N, N -Dimethyl-1,2,3-trithiane-
5-ylamine], benzultap [S, S′-2-dimethylaminotrimethylene di (benzenethiosulfonate)], and other nereistoxin derivatives, N-cyano-
N-cyanoamidine derivatives such as N'-methyl-N '-(6-chloro-3-pyridylmethyl) acetamidine, endosulfan [6,7,8,9,10,10-hexachloro-1,5,5a, 6,9,9a-hexahydro-
6,9-methano-2,4,3-benzodioxathiepine oxide], γ-BHC (1,2,3,4,5,6-
Hexachlorocyclohexane], 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol and other chlorinated hydrocarbon compounds, chlorfluazuron [1- (3,
5-dichloro-4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) phenyl) -3-
(2,6-Difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl)
Urea], flufenoxuron [1- (4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl)
Urea] and other benzoylphenylurea-based compounds, amitraz [N, N ′ [(methylimino) dimethylidine] di-2,4-xylidine], chlordimeform [N′-
Formamidine derivatives such as (4-chloro-2-methylphenyl) -N, N-dimethylmethinimidamide], diafenthiuron [N- (2,6-diisopropyl-4-phenoxyphenyl) -N'-tert. -Butylcarbodiimide] and other thiourea derivatives, fipronil [5-amino-
1- (2,6-dichloro-α, α, α-trifluoro-
p-tolyl) -4-trifluoromethylsulfinylpyrazole-3-carbonitrite], bromopropylate [isopropyl 4,4'-dibromobenzilate], tetradiphone [4-chlorophenyl 2,4,5-5-
Trichlorophenyl sulfone], quinomethionate [S, S-6-methylquinoxaline-2,3-diyldithiocarbonate], propargate [2- (4-tert.
-Butylphenoxy) cyclohexylprop-2-yl sulfite], fenbutatin oxide [bis [tris (2-methyl-2-phenylpropyl) tin] oxide], hexithiazox [(4RS, 5R
S) -5- (4-chlorophenyl) -N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidine-
3-carboxamide], clofentezine [3,6-bis (2-chlorophenyl) -1,2,4,5-tetrazine, pyridathiobene [2-tert-butyl-5- (4-te
rt-Butylbenzylthio) -4-chloropyridazine-3
(2H) -one], fenpyroximate [tert-butyl (E) -4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl) methyleneaminooxymethyl]
Benzoate], tebufenpyrad [N-4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide], polynactin complex [tetranactin, dinactin, trinactin], milbemectin, avermectin, ivermectin. , Azadirachtin [AZAD], pyrimidifen [5
-Chloro-N- [2- {4- (2-ethoxyethyl)-
2,3-dimethylphenoxy} ethyl] -6-ethylpyrimidin-4-amine and the like.

When the compound of the present invention is used as an agricultural insecticide, nematicide or acaricide, its application amount is usually 1 g to 1000 g, preferably 10 g to 100 g per 10 ares. When emulsions, wettable powders, flowable agents, etc. are diluted with water, the application concentration is usually 10 ppm.
It is ~ 1000ppm, and granules, powders, etc. are applied as they are without any dilution. When used as an insecticidal or acaricide for epidemic prevention, emulsions, wettable powders, flowable agents, etc. are usually diluted with water to 0.01 ppm to 10000 ppm and applied, and oil, aerosol, smoke agent, ULV agent are applied. , For bait, apply as it is. The application amount and application concentration depend on the type of formulation, application time, application site, application method, pest type, degree of damage, etc., and may be increased or decreased without regard to the above range. can do.

[0010]

The present invention will be described in more detail below with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. First, production examples of the compound of the present invention will be shown. Production Example 1 To a mixed solution of 271 mg of sodium hydride (60% W / W oil dispersion) in tetrahydrofuran (50 ml) was added 0.62 g of methyl N-cyanomethyl carbamate while stirring at room temperature. After the generation of hydrogen gas stopped, O-
A solution of 1.18 g of ethyl S-sec-butyl chlorophosphate in tetrahydrofuran (5 ml) was added, and the mixture was heated under reflux for 2 hours. Tetrahydrofuran was distilled off under reduced pressure, and the residue was extracted with chloroform. The chloroform layer was washed with water and then dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 475 mg of O-ethyl S-sec-butyl N-cyanomethyl N-methoxycarbonylphosphoramidothiolate (invention compound 9). Production Example 2 To a mixed solution of 220 mg of sodium hydride (60% W / W oil dispersion) in tetrahydrofuran (50 ml) was added 0.64 g of ethyl N-cyanomethylcarbamate under stirring at room temperature. After the generation of hydrogen gas stopped, O-
A solution of 1.01 g of ethyl S-n-propylchlorophosphate in tetrahydrofuran (5 ml) was added, and the mixture was heated under reflux for 2 hours. Tetrahydrofuran was distilled off under reduced pressure, and the residue was extracted with chloroform. The chloroform layer was washed with water and then dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 680 mg of O-ethyl S-n-propyl N-cyanomethyl N-ethoxycarbonylphosphoramidothiolate (the present compound 8). Production Example 3 A solution of sodium hydride (0.22 g, 60% W / W oil dispersion) in tetrahydrofuran (50 ml) was added,
With stirring at room temperature, 1.18 g of O-ethyl S-sec-butyl N-cyanomethyl phosphoroamide thiolate was added. After the generation of hydrogen gas stopped, phenylchlorocarbonate
0.78 g was added and the mixture was heated under reflux for 1 hour. Tetrahydrofuran was distilled off under reduced pressure, then treated in the same manner as in Production Example 1,
-Ethyl S-sec-Butyl N-Cyanomethyl N-
Phenoxycarbonyl phosphoramido thiolate 270
mg (invention compound 14) was obtained. Table 8 shows examples of the compound of the present invention. (The substituents of the compound represented by the general formula 3 are shown.)

[Table 8]

Next, formulation examples are shown. In addition, a part represents a weight part. Formulation Example 1 Emulsion 10 parts of each of the compounds 1 to 20 of the present invention were dissolved in 35 parts of xylene and 35 parts of dimethylformamide, 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate were added, and the mixture was stirred well. To obtain each 10% emulsion. Formulation Example 2 Wettable Powder 20 parts of each of the compounds 1 to 20 of the present invention are added to a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of diatomaceous earth. , Stir and mix with juice mixer, 2 each
0% wettable powder is obtained. Formulation Example 3 Granules To 5 parts of each of the compounds 1 to 20 of the present invention, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 60 parts of clay are added, and they are sufficiently stirred and mixed. Then, an appropriate amount of water is added to these mixtures, and the mixture is further stirred, granulated by a granulator, and dried by ventilation to obtain each 5% granule. Formulation Example 4 Dust agent 1 part of each of the compounds 1 to 20 of the present invention was dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder and PAP were added thereto.
0.3 parts and 93.7 parts of clay are added, and the mixture is stirred and mixed with a juice mixer, and acetone is removed by evaporation to obtain each 1% powder. Formulation Example 5 Flowable Agent (Emulsion in Water) 10 parts of each of the compounds 1 to 20 of the present invention is added to 40 parts of an aqueous solution containing 6 parts of polyvinyl alcohol, and stirred with a mixer to obtain a dispersant. To this, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate was added, and further 10 parts of propylene glycol was added thereto and gently mixed with stirring to obtain each 10% emulsifier in water. Formulation Example 6 Oil formulation 0.1 part of each of the compounds 1 to 20 of the present invention was dissolved in 5 parts of xylene and 5 parts of trichloroethane, and this was deodorized kerosene 8
Mix to 9.9 parts to obtain each 0.1% oil. Formulation Example 7 Oily aerosol 0.1 parts of each of the compounds 1 to 20 of the present invention, tetramethrin
0.2 part, d-phenothrin 0.1 part, trichloroethane 1
After mixing and dissolving 0 part and 59.6 parts of deodorized kerosene, filling the aerosol container and attaching the valve part, 30 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain each oil-based aerosol. . Formulation Example 8 Aqueous aerosol 0.2 parts of each of the compounds 1 to 20 of the present invention, d-allethrin
0.2 parts, 0.2 part of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorizing kerosene and 1 part of emulsifier {Atmos 300 (registered trade name of Atlas Chemical Co.)} were mixed and dissolved, and 50 parts of pure water. Fill the aerosol container with and, and attach the valve part, through the valve part the propellant (liquefied petroleum gas)
40 parts under pressure are filled to obtain each aqueous aerosol.

Next, Test Examples will show that the compound of the present invention is useful as an active ingredient of insecticides, nematicides and acaricides and has relatively low acute toxicity to mammals. The compounds of the present invention are shown by the compound numbers shown in Table 8, and the compounds used for comparison and control are shown by the compound symbols shown in Table 9.

[Table 9] Test Example 1 Insecticidal test against Larvae of Spodoptera litura L. 2 ml of a water-diluted solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 1 was soaked in 13 g of an artificial diet for Spodoptera litura that was prepared in a polyethylene cup having a diameter of 11 cm. Let Among them, Hasmonyoto 4th instar larva, 1
0 animals were released, and their life and death were investigated 6 days later, and the mortality rate was calculated. The results are shown in Table 10.

[0013]

[Table 10] Test Example 2 Insecticidal test against larvae of brown planthoppers Rice stalks (about 5 cm in length) were immersed for 1 minute in a solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 1 diluted with water. After air-drying, put rice stalks in a 5.5 cm diameter polyethylene cup lined with 5.5 cm diameter filter paper containing 1 ml of water, and release about 30 larvae of the brown planthopper into the cup. investigated. The effect criteria are A: No live insects are observed. B: Five or less live insects are recognized. C: 〃 6 or more are allowed. And The results are shown in Table 11.

[0014]

[Table 11] Test Example 3 Insecticidal test against German cockroaches A polyethylene cup having a diameter of 5.5 cm was covered with a filter paper of the same size, and the emulsion of the test compound obtained according to Formulation Example 1 was diluted with water (500 ppm) 0.7 ml. Was dropped on a filter paper, and about 30 mg of sucrose was uniformly added as a bait. Ten adult German cockroaches were released therein, the lid was put on, and one day later, the life and death thereof were investigated, and the mortality rate was calculated. The results are shown in Table 12.

[0015]

[Table 12] Test Example 4 Insecticidal test against housefly A polyethylene cup having a diameter of 5.5 cm is covered with a filter paper of the same size, and the emulsion of the test compound obtained according to Formulation Example 1 is diluted with water (500 ppm) 0.7 ml. Was dropped on a filter paper, and about 30 mg of sucrose was uniformly added as a bait. Ten adult houseflies were released in the flask, the lid was put on, and one day later, the life and death thereof were examined to determine the mortality rate. The results are shown in Table 13.

[0016]

[Table 13] Test Example 5 Insecticidal test against Southern corn rootworm larvae A polyethylene cup having a diameter of 5.5 cm was covered with a filter paper of the same size, and the emulsion of the test compound obtained according to Formulation Example 1 was diluted with water (50 ppm). ) 1 ml was dropped on the filter paper. Approximately 30 Southern corn rootworm eggs were placed on this filter paper, and 1 corn sprouting was put in as bait. After 8 days, the survival of dead larvae was investigated. The effect evaluation criteria were A: 100% mortality, B: 99-90% mortality, C: less than 90% mortality. The results are shown in Table 14.

[0017]

[Table 14] Test Example 6 Efficacy test against root-knot nematodes 1 ml of a diluted solution (500 ppm) of the emulsion of the test compound obtained according to Preparation Example 1 in water-root root-knot contaminated soil 1
The mixture was treated with 9 g, mixed, and stored at 27 ° C. for 24 hours (concentration of active ingredient in soil: 25 ppm). Then, the soil was placed on the root of a cup-planted tomato plant (about 2 weeks after germination) and lightly watered. After about 4 weeks, the root damage of tomato plants was investigated. The effect evaluation criteria are: -There is almost no root gall. +: Several to ten or more root knots are attached. ++: The root gall appears to be untreated. (More damage than +) The results are shown in Table 15.

[0018]

[Table 15] Test Example 7 Insecticidal test against Culex pipiens A test compound was made into an emulsion according to Formulation Example 1, diluted with water, and 0.7 ml of the solution was added to 100 ml of ion-exchanged water.
(Active ingredient concentration 3.5 ppm). 20 dead larvae of Culex pipiens were released in it, and the mortality rate after 1 day was investigated. The criteria for effect evaluation were as follows: A: 90% or more mortality rate B: 10% or more and less than 90% mortality rate C: Less than 10% mortality rate. The results are shown in Table 16.

[0019]

[Table 16] Test Example 8 Test against Red Mite (Acari: Pseudomonas aeruginosa) Two days after sowing, the potted vine, Green beans (primary leaf stage), were parasitized with 10 female adults of the Japanese red mite, 2 per leaf.
It was placed in a thermostatic chamber at 5 ° C. Six days later, the test compound was made into an emulsion according to Formulation Example 1, and a chemical solution diluted with water to an active ingredient of 500 ppm was sprayed on a turntable in an amount of 15 ml per pot, and 2 ml of the same solution was simultaneously irrigated with soil. After 8 days, the degree of damage of each plant due to spider mites was investigated. The criteria for effectiveness are: -No damage is observed. +: Some damage is recognized. ++: The same damage as the untreated area is recognized. And The results are shown in Table 17.

[0020]

[Table 17] Test Example 9 Mouse Oral Acute Toxicity Test Each of the test compounds was diluted to a predetermined concentration with corn oil,
About 20 ICR 6-week-old male mice (weight 24-31 g)
Diluted solution 0.1g per 10g body weight after fasting
Each ml was forcibly administered intragastrically. Four hours after the administration, food and water were given and the animals were kept in cages. Seven days after the administration, the life and death were investigated and the mortality rate was obtained (4 animals per group). The results are shown in Table 18.

[0021]

[Table 18]

[0022]

The compound of the present invention exhibits excellent insecticidal, nematicidal and acaricidal effects and relatively low acute toxicity to mammals.

Front page continuation (72) Inventor Mitsuru Sasaki 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd.

Claims (2)

[Claims] 1. A general formula: ## STR1 ## [In the formula, R ₁ represents a methyl group or an ethyl group, and R ₂
Represents an n-propyl group or a sec-butyl group, and R ₃
Represents a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ thioalkoxy group, a phenyl group or a phenoxy group, and n represents 1 or 2. ] The amide thiophosphoric acid ester derivative shown by these. 2. An insecticidal, nematicidal, and acaricidal agent containing the amidothiophosphate derivative according to claim 1 as an active ingredient.