JPH07206880A - Amidothiophosphoric acid ester derivative and insecticide, nematicide and acaricide containing the same derivative as active ingredient - Google Patents

Abstract

PURPOSE:To obtain a new amidothiophosphoric acid ester derivative for exterminating insect pests damaging various kinds of crops, petals, lawns, etc., being an amidothiophosphoric acid ester, excellent in insecticidal, nematicidal and acaricidal effect and useful as an active ingredient for insecticides, nematicides and acaricides. CONSTITUTION:An amidothiophosphoric acid ester derivative (e.g. O-methyl-S- sec-butyl-N-methyl-N-cyanomethylphosphoroamidothiolate) expressed by formula I (R1 is methyl or ethyl 1; R2 is n-propyl or sec-butyl), being a new compound, exhibiting excellent insecticidal, nematicidal and acaricidal effects and useful as an active ingredient for insecticides, nematicides and acaricides. This compound is obtained by reacting phosphoric acid chloride expressed by formula II with methylamino-acetonitrile or its salt in the presence of a base.

Description

Detailed Description of the Invention

[0001]

OBJECT 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.

DETAILED DESCRIPTION OF THE INVENTION As a result of intensive investigations by the present inventors to find out excellent insecticides, nematicides, and acaricides, the general formula 2

[Chemical 2] [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. ]
It was found that the amidothiophosphoric acid ester derivative (hereinafter referred to as the compound of the present invention) represented by the formula (3) has excellent insecticidal, nematicidal, and acaricidal effects, and has reached the present invention. That is,
The present invention provides an amidothiophosphoric acid ester derivative represented by the general formula 2 and insecticides and nematicides containing the derivative as an active ingredient.
Provide acaricide. 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 others, it exhibits extremely excellent insecticidal and nematicidal effects against soil pests and nematodes that live in soil and eat various crops, petals, lawns, etc. .

The compounds of the present invention have, for example, the general formula

[Chemical 3] [In the formula, R ₁ and R ₂ have the same meanings as described above. ]
It can be produced by reacting the phosphoric acid chloride represented by the above with methylaminoacetonitrile or a salt thereof (for example, an inorganic acid salt such as hydrochloride and sulfate) in the presence of a base. The reaction is usually carried out in an organic solvent. Examples of the organic solvent used include ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran, halogenated hydrocarbons such as methylene chloride and chloroform, aromatic hydrocarbons such as benzene and toluene. Examples thereof include hydrogens. As the base used, for example,
Examples thereof include tertiary amines such as pyridine and triethylamine, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, carbonates of alkali metals such as sodium carbonate and potassium carbonate. The amount ratio of reagents used is
Phosphorous chloride represented by the general formula 3 is usually used for 1 mol of methylaminoacetonitrile (or a salt thereof).
The ratio is 0.8 to 1.2 mol, and the base is usually 1 to 1.2 mol. The reaction is usually performed in the temperature range of -70 ° C to 100 ° C for usually 1 to 10 hours. The phosphoric acid chloride represented by the general formula 3 is, for example, Houben-Weyl, Methoden de
r Organishen chemie, Band E2, pages 542-543 (1982
Year). After completion of the reaction, the target compound can be isolated by subjecting it to usual post-treatments such as extraction with an organic solvent and concentration, but if necessary, it may be further purified by column chromatography, distillation or the like. It is 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, Little brown planthopper ( Laodelphax striatellus) , Northern 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 chienensis) weevils such as, chai loco Meno 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 brunnca ), American cockroach ( Blatta ori
entalis) Thysanoptera South thrips such as (Thrips palmi), green onion thrips (Thrips tabaci), Hana thrips (Thrips
hawaiiensis), etc. Hymenoptera ants, wasps, Arigatabachi acids, Nihon turnip drumstick (Athalia rosae ruficornis) sawflies such like Orthoptera pests eclipse such as, grasshoppers, etc. Siphonaptera pests human flea (Purex irritans) like lice Eye pest Pediculus humanus capitis , lice ( Phthirus
pubis ) and other termite insect pests Yamatic termites ( Reticulitermes speratus ), house termites ( Coptotermesformosanus) and other mites Tetranychus uriticae , Tetranychus cinnabarinus , Kanzawadani
( 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 of 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, rice cake, etc., and add surfactants and other formulation auxiliaries if necessary to add 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 liquid carriers 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 oil, sugar, bait ingredients such as crystalline cellulose, antioxidants such as dibutylhydroxytoluene, nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, antifeeding agents such as capsicum powder, cheese flavors, onion flavors, etc. Examples include attractive fragrances. Formulations of flowable agents (suspension in water or emulsions in water) generally contain from 1 to 75% of the compound of the invention.
0.5 to 15% dispersant, 0.1 to 10% suspension aid (for example, a compound that imparts a protective colloid or thixotropy), 0 to 10% suitable adjuvant (for example, a defoaming agent) ,
It is obtained by finely dispersing in water containing a rust preventive, a stabilizer, a spreading agent, a penetration aid, an antifreezing agent, an antibacterial agent, a smokeproofing 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, it may be mixed with or mixed with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feeds, etc. It is also possible to use them at the same time.

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 [O, O, O ′,
O'-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-isopurupyl-β-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], fluvalinate (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], tebufenozide [N-tert-butyl-N ′-(4-ethylbenzoyl) -3,5-dimethylbenzohydrazide], 4-bromo- 2- (4-chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile, bromopropylate [isopropyl 4,4'-dibromobenzilate], tetradiphone [4-chlorophenyl 2,4,5] -Trichlorophenyl sulfone], quinomethionate [S, S-6-methylquinoxaline-
2,3-diyldithiocarbonate], propalgate [2- (4-tert-butylphenoxy) cyclohexylprop-2-ylsulfite], fenbutatin oxide [bis [tris (2-methyl-2-phenylpropyl)] Tin] oxide], hexithiazox [(4RS, 5RS) -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-tert-butylbenzylthio) -4-chloropyridazin-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 [AZA
D], pyrimidiphene [5-chloro-N- [2- {4-
(2-Ethoxyethyl) -2,3-dimethylphenoxy} ethyl] -6-ethylpyrimidin-4-amine, pymetrozine [2,3,4,5-tetrahydro-3-oxo-4-[(pyridine-3- Ill) -methyleneamino]
-6-methyl-1,2,4-triazine and the like can be mentioned.

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.

[0007]

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 To a mixed solution of 0.95 g of methylaminoacetonitrile hydrochloride and 1.7 g of triethylamine in dichloromethane (90 ml) was added a solution of 1.7 g of O-methyl S-sec-butylchlorophosphate in dichloromethane (9 ml) with stirring at room temperature, and 2
Stir at room temperature for hours. The reaction solution was washed with water and then dried over anhydrous magnesium sulfate. Magnesium sulfate is filtered off,
The filtrate was concentrated. The residue was subjected to silica gel column chromatography, and O-methyl S-sec-butyl N-
Methyl N-cyanomethylphosphoramide thiolate 0.
25 g (compound 2) was obtained. ¹ H-NMR (CDCl _{3 /} TMS), δ (ppm): 1.02 (3H, t, J = 6.6
H _Z ), 1.45 (3H, dd, J = 2.4H _Z , 7.2H _Z ), 1.57-1.88 (2H,
m,), 2.86 (3H, d, J = 9.6H _Z ), 3.10-3.51 (1H, m), 3.77 (3H,
_{d, J = 12H Z),} 4.09 (2H, d, examples of J = 10.8H _Z) present compound shown in Table 1. (The substituents of the compound represented by the general formula 2 are shown.)

[0008]

[Table 1]

[0009] 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 4 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 dodecylbenzene sulfonate 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 4 of the present invention were 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, and juice. Stir and mix with a mixer for each 20
% Wettable powder is obtained. Formulation Example 3 Granules To 5 parts of each of the compounds 1 to 4 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 Powder 1 part of each of the compounds 1 to 4 of the present invention is dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder, PAP0.
3 parts of clay and 93.7 parts of clay were added, and the mixture was stirred and mixed with a juice mixer, and acetone was removed by evaporation to obtain a 1% powder of each. Formulation Example 5 Flowable Agent (Emulsion in Water) 10 parts of each of the compounds 1 to 4 of the present invention are 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 1 part of propylene glycol was added.
Add 0 parts and mix gently with stirring to obtain each 10% emulsion in water. Formulation Example 6 Oil agent 0.1 parts of each of the compounds 1 to 4 of the present invention was dissolved in 5 parts of xylene and 5 parts of trichloroethane, and this was deodorized kerosene 89.9
Mix 1 part to give each 0.1% oil. Formulation Example 7 Oily aerosol 0.1 parts of each of the compounds 1 to 4 of the present invention, tetramethrin 0.1.
2 parts, d-phenothrin 0.1 part, trichloroethane 10
Parts and 59.6 parts of deodorized kerosene are mixed and dissolved, filled into an aerosol container, a valve portion is attached, and then 30 parts of a propellant (liquefied petroleum gas) is pressure filled through the valve portion to obtain each oil-based aerosol. Formulation Example 8 Aqueous aerosol 0.2 parts of each of the compounds 1 to 4 of the present invention, d-allethrin 0.2.
2 parts, 0.2 part of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorizing kerosene and 1 part of an emulsifier {Atmos 300 (registered trade name of Atlas Chemical Co.)} were mixed and dissolved, and 50 parts of pure water were added. Fill the aerosol container, attach the valve portion, and through the valve portion, propellant (liquefied petroleum gas) 4
0 parts are pressure filled to obtain each aqueous aerosol. Formulation Example 9 Poison bait 10 mg of each of the present compounds 1 to 4 was dissolved in 0.5 ml of acetone, and this solution was used as a solid feed powder for animals (solid feed powder for breeding and breeding CE-2, trade name of CLEA Japan, Inc.). Process to 5 g and mix evenly. Then, it is air-dried with acetone to obtain each 0.5% poison bait.

Next, it will be shown by test examples that the compound of the present invention is useful as an active ingredient of insecticides, nematicides and acaricides. The compounds of the present invention are represented by the compound numbers shown in Table 1 and used as comparative controls to clarify the features of the present invention (these are novel compounds, but are synthesized in the same manner as the compounds of the present invention. Is indicated by the compound symbol shown in Table 2.

[Table 2]

Test Example 1 Insecticidal test against Larvae of Spodoptera litura L. 13 g of artificial emulsion for Spodoptera litura that was prepared by diluting 2 ml of a water-diluted solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 1 in a polyethylene cup with a diameter of 11 cm. Soaked in the feed. 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. As a result, the compounds 1 to 4 showed a mortality rate of 100%, while the compounds A to E showed a mortality rate of 0%. The untreated plot showed a mortality of 0%. Test Example 2 Egg-killing and larvicidal test for diamondback moth Emulsion of the test compound according to Preparation Example 1 was diluted with water (50 ppm) to lay 100-150 diamondback moth eggs, and 5 after seeding Soak 2 radish sprouts on 6th day and 2 radish sprouts for laying eggs in total for 30 seconds, let them air dry, and put them in a polyethylene cup with a diameter of 5.5 cm.
After the day, the presence or absence of hatching and the mortality of larvae were investigated, and the ovicidal rate and the larvicidal rate were calculated. The criteria for judgment are as follows. a: 100% ovicidal or larvicidal rate b: 90% or more and less than 99% ovicidal or larvicidal rate c: 90% or less ovicidal or larvicidal rate As a result, compounds 1, 2 and 4 Indicated. In addition, the untreated section shows c. Test Example 3 Insecticidal test against larvae of brown planthoppers Rice stalks (about 5 cm in length) were immersed for 1 minute in a diluted solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 1 in 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 criteria for effect evaluation are: a: No live insects are observed. b: Five or less surviving insects are recognized. c: Six or more live insects are recognized. And As a result, compounds 2 to 4 showed a. In addition, the untreated section shows c. Test Example 4 Insecticidal test against German cockroaches 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 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. As a result, compound 1
~ 4 showed 100% mortality, whereas compounds AE
Showed 0% mortality. The untreated plot showed a mortality of 0%. Test Example 5 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. As a result, the compounds 1 to 4 showed a mortality rate of 100%, while the compounds A to E showed a mortality rate of 0%. The untreated plot had a mortality of 0%.

Test Example 6 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. 1 ml of the liquid (50 ppm) 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 criteria for effect evaluation were as follows: a: 100% mortality rate b: 99-90% mortality rate c: less than 90% mortality rate. As a result, the compounds 1 to 4 showed a, while the compounds A to E showed c. In addition, the untreated section shows c. 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). Twenty larvae of the Culex pipiens larvae were released into the larvae, and the larvae were fed and fed for 8 days to investigate the mortality. The criteria for effect evaluation are as follows: a: mortality rate of 90% or more b: mortality rate of 10% or more and less than 90% c: mortality rate of less than 10%. As a result, the compounds 1 to 4 showed a, while the compounds A to E showed c. In addition, the untreated section shows c. Test Example 8 Insecticidal test against cotton aphid Cotton plants (cotyledon stage) inoculated with cotton aphid larvae were
A sufficient amount of a diluted solution (50 ppm) of water of the emulsion of the test compound obtained according to Formulation Example 1 was sprayed, and at the same time, 5 ml of the strain was irrigated. After air-drying, count the number of insects on the plant,
After 3 days and 7 days, the control value (%) was determined by counting the number of surviving insects. As a result, compounds 2 and 4 had a control value of 100%.
showed that. Test Example 9 Efficacy test against sweet potato root-knot nematode 1 ml of a diluted solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 1 was treated with 19 g of sweet potato root-knot nematode contaminated soil, and the mixture was stored at 27 ° C for 24 hours. (Concentration of active ingredient in soil was 25 ppm). Then, the soil was put 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. ++: A root gall is seen like an untreated area. (More damage than +) As a result, compounds 1 to 4 showed-. Test Example 10 Test Against Red Mite (Acari: Pseudomonas aeruginosa) 10 days after seeding, a potted vine, Green Bean (primary leaf stage), was infested with 10 female adults of the Japanese red mite, 2 per 1 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 As a result, while Compounds 1 to 4 showed −, Compound A showed + to ++ and Compounds B to E showed ++.

[0013]

The compound of the present invention exhibits excellent insecticidal, nematicidal and acaricidal effects.

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. ]
An amide thiophosphoric acid ester derivative represented by. 2. An insecticidal, nematicidal, and acaricidal agent containing the amidothiophosphate derivative according to claim 1 as an active ingredient.