JPH026496A - Organic phosphoric acid amide compound, its production and harmful animal-controlling agent containing the same compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is H or halogen; R<1> and R<2> are alkoxy or alkylthio; Z is O or S; R<1> and R<2> are not alkoxy at the same time when X is H and Z is S) or its salt. EXAMPLE:3-(S-sec-butyl O-ethylthiophosphorylamino)-4-chlorobenzoisothiazole-1,1- dioxide. USE:A harmful animal-controlling agent. PREPARATION:The objective compound can be produced by reacting a compound of formula II (e.g., 3-amino-4-chlorobenzoisothiazole-1,1-dioxide) with a compound of formula III (Hal is halogen) (e.g., S-sec-butyl O- ethylthiophosphoric acid chloride) usually in the presence of an acid acceptor (e.g., sodium hydroxide) in a solvent (e.g., THF) preferably at 0-40 deg.C for 2-12hr.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is a novel organic phosphoric acid amide compound, which is an oxygen atom or a sulfur atom, R1 and R2 are an alkoxy group or an alkylthio group, and R1 and A specific organic phosphoric acid amide compound represented by the following general formula (1) in which R2 is not an alkoxy group is not disclosed, and this specific organic phosphoric acid amide compound is There is also no mention that it has a control effect against harmful animals.

(Disclosure of the Invention) The present inventors conducted various studies on organic phosphoric acid amide compounds, and found that benzisothiazole-
It has been found that 1,1-dioxide exhibits high activity as a pest control agent.

The present invention provides the following method: - formula (wherein, When X is a hydrogen atom and Z is a sulfur atom, R1
and R2 are not at the same time an alkoxy group).

These also include salts with basic substances.

In the above-mentioned ritual (1), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl moiety of an alkoxy group and an alkylthio group in which R1 and R2 are not represented include those having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. also includes structural isomers of linear or branched fatty chains.

The organic phosphoric acid amide compound represented by formula (1) has a tautomer represented by the following general formula (1'). The compound of the above-mentioned ritual (1) has the following general formula (
It may be in the form of its tautomer represented by 1'), and the tautomer is also included in the present invention.

(X, R', R" and Z are as described above) Also, the tautomerism such as the relationship between -ritual (1) and -ritual (I') above also applies to -ritual (II) below. exists in

The compound represented by the above-mentioned formula (1) can be produced by the following production method.

The reaction is usually carried out in a solvent in the presence of an acid acceptor, the reaction temperature is usually -30 to +60°C, preferably 0 to 40°C, and the reaction time is 2 to 12°C. It's time.

As acid acceptors, alkali metal hydrides such as sodium hydride and potassium hydride; n-butyllithium,
Organic compounds of lithium such as t-butyllithium nitriethylamine, 1,8-diazabicyclo-(5,4,
0) Organic bases such as -7-undecene and the like. Examples of solvents include ethers such as diethyl ether and tetrahydrofuran; aprotic polar solvents such as hexamethylphosphoric triamide and dimethylformamide; halogenated hydrocarbons such as methylene chloride and chloroform; ketones such as acetone and methyl ethyl ketone. etc., and each of them individually,
Alternatively, they can be used in combination.

Next, a specific production example of the compound represented by the above-mentioned formula (I) will be described.

Synthesis Example 13-(S-sec-butyl 〇-ethylthiophosphorylamino)-4-chlorobenziisothiazole-1,1-dioxide (compound number 2)
Synthesis of 3-amino-4-chlorobenziisothiazole-1,1
1 g of -dioxide was dissolved in a mixed solvent consisting of 50 mJ of tetrahydrofuran and 2 ml of hexamethylphosphoric triamide.

Next, sodium hydride (60% Nujol mixture) 0
．． After adding 2 g to this solution under water cooling, stirring was continued while gradually returning the liquid temperature to room temperature until hydrogen gas generation was completed.

Next, the solution was cooled on ice again, and 5 ml of a tetrahydrofuran solution containing 1.1 g of 5-sec-butyl, O-ethylthiophosphoric acid chloride was gradually added dropwise. After the dropwise addition, the solution temperature was gradually returned to room temperature and further Stirring was continued for 2 hours.

After the reaction was completed, the reaction solution was poured into 200 nl of ice water, and then extracted with ethyl acetate. The remaining organic layer was washed with saturated brine and dried over anhydrous sodium sulfate.

After distilling off the solvent under reduced pressure, the residue was subjected to silica gel column chromatography (eluent: methylene chloride/methanol = 3
0/1) to obtain the target product, which is an amorphous solid, 0.4
I got g.

Next, representative examples of the compounds represented by the above-mentioned formula (I.) will be described.

The compound of the present invention exhibits a control effect against harmful aJ substances,
For example, it exhibits excellent activity as an active ingredient in insecticides, acaricides, nematicides, and soil insecticides.

For example, two-spotted spider mite, false two-spotted spider mite, orange spider mite,
Plant-parasitic mites such as bed mites, diamondback moth, armyworm, fall armyworm, codling moth, ballworm, tobacco budworm, gypsy moth, Colorado potato beetle 1. Cucurbit beetles, poleweed beetles, aphids, planthoppers, leafhoppers, scale insects, stink bugs, woodlice, thrips, beetle beetles, wasp flies, scarab beetles, kumanaya moth, kaburaya moth, onion fly, ant I
Agricultural pests such as house dust mites, cockroaches, houseflies, Culex mosquitoes, grain storage pests such as dust moths, adzuki bean weevils, ground beetles, mealworms, etc., burrs, yellowtail beetles, termites, etc. It is effective against fleas, lice, flies, etc. that parasitize clothing, house pests, and other livestock, and it is also effective against cat nematodes, cyst nematodes, white nematodes, and rice nematodes. It is also effective against plant-parasitic mites such as the Chinese nematode, strawberry nematode, and pine nematode.

It is also effective against soil pests. Soil pests mentioned here include gastropods such as slugs and snails,
Examples include isopods such as pill bugs and woodlice. In addition, dicofol (product name: Narita Pharmaceutical Co., Ltd. Okiku)
It is also effective against pests such as plant-parasitic mites with low organophosphorus resistance, organophosphorus-resistant oilseeds, insects, and houseflies.

Furthermore, since the compound of the present invention has excellent systemic migration properties, the compound of the present invention can be applied to soil to eliminate soil harmful insects, mites, nematodes, gastropods, etc.
At the same time, it is possible to control pests on the stems and leaves.

When using the compound of the present invention as an active ingredient of a pest control agent, it can be used in combination with an agricultural chemical auxiliary, such as an emulsion, a powder, a granule, a wettable powder, a liquid, an aerosol, a paste, etc., as in the case of conventional pesticide formulations. It can be formulated into various forms such as suspensions. The mixing ratio of these is usually 0.5 of the accompanying component.
~90 parts by weight and 10 to 99.5 parts by weight of agricultural chemical adjuvant. When these preparations are actually used, they can be used as they are, or they can be diluted to a predetermined concentration with a diluent such as water.

The agrochemical auxiliary agents mentioned herein include carriers, emulsifiers, suspending agents, dispersants, spreading agents, penetrants, wetting agents, thickeners, stabilizers, etc., and may be added as appropriate if necessary. Carriers are divided into solid carriers and liquid nail bodies. Solid carriers include starch, activated carbon, soybean flour, wheat flour, wood flour, fish meal, animal and vegetable powders such as milk powder, talc, kaolin, bentonite, calcium carbonate, and zeolite. Examples of liquid carriers include water, alcohols such as methyl alcohol and ethylene glycol, ketones such as acetone and methyl ethyl ketone, dioxane,
Ethers such as tetrahydrofuran, aliphatic hydrocarbons such as kerosene and kerosene, aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane, and turben-1-naphtha, and halogenated hydrocarbons such as chloroform and chlorobenzene. , acid amides such as dimethylbormamide, esters such as ethyl acetate and glycerin ester of fatty acids, nitrites such as acetonitrile, and sulfur-containing compounds such as dimethyl sulfoxide.

In addition, other agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides,
It can be mixed or used in combination with plant growth regulators, etc., and may exhibit even better effects in this case.

For example, an insecticide, acaricide, or nematocide and Lt' are 0-(4-furomo-2-chlorophenyl)0-ethyl S
-7''ropylphosphorothioate-1,2゜2-dichlorovinyldimethylphosphate, ethyl 3-methyl-4-
(Methylthio)phenylisopropylphosphoroamide 1., 0.0-dimethyl 0-4-nitro-m, -1-lilbosphorothioe-1., 〇-ethyl 0-4-nitrophenylbosbothioate ,0,0-diethyl0-2-
Isopropyl-6-methylpyrimidin-4-yl phosphorothioate, 0.0-dimethyl O-(3,5,6-1
-lichloro-2-pyridyl) phosborothioate, 0.
S-dimethylacetyl phosphoramidothioate, 0-
Organic phosphate ester compounds such as (2,4-dichlorophenyl)0-ethyl S-7'ropyl phosphorodithioate; 2-(Methylthio)propionaldehyde○-methylcarbamoyloxime, 2,3-dihydro-2,2-dimethylbenzofuran-7-ylmethylcarbamate, dimethyl N,N'[thiobis[(methylimino)carbonyloxime]]bisethane imidothioate, S-methyl N-(methylcarbamoyloxy)thioacetimidate, N,N-dimethyl-2-methylcarbamoyloxyimino-2-(methylthio)acetamide, 2-(ethylthiomethyl)phenylmethyl- Carbamate compounds such as 1-12-dimethylamino-5,6-dimethylpyrimidin-4-yldimethylcarbamate, s,s'-2-dimethylaminotrimethylenebis(thiocarbament); 2.2. 2-) Organochlorine compounds such as dichloro-1,1-bis(4-chlorophenyl)ethanol and 4-chlorophenyl-2,4,5-trichlorophenylsulfone; organometallic compounds such as tricyclohexyltine hydroxide (RS)-α-cyano3-phenoxybenzyl(1?5)-2-(4-chlorophenyl)-3-methylbutyrate, 3-phenoxybenzyl(11?S)-cis, trans-3-(2
,2-dichlorovinyl) -2,2dimethylcyclopropane hydroxylate, (1?S)-α-cyano-3
-phenoxybenzyl (IR3) -cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, (S)-α-cyano-3-phenoxybenzyl (IR) -cis- 3-(2,
2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate, (R5)-α-cyano-3-phenoxybenzyl (11?S) -cis, trans-
3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate, 4-methyl-2,3,5,6-titrafluorobenzyl-3-(2-chloro -3,3,3-trifluoro-
Pyrethroid compounds such as 1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid; 1-
(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea, 1-(3,5-dichloro-4
-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-3-(2,6-difluorobenzoyl)urea, 1-(3+5-dichloro-2,4-difluorophenyl)-3-( Benzoylurea compounds such as 2,6-difluorobenzoyl)urea; 2-
tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-titrahydro 211-1.3
．． 5-thiadiazin-4-one, trans-(4-chlorophenyl)-Ncyclohexyl-4-methyl-2-oxothiazolidinone-3-carpoxamide, N-methylbis(2,4-xylyliminomethyl)amine Compounds like; isopropyl (2r!, 4E) -11-)
Juvenile hormone-like compounds such as t-xy-3,7,11-)dimethyl-2,4-dodecagenoate; other compounds include dinitro compounds, organic sulfur compounds, urea compounds, and triazine compounds. Examples include compounds. Furthermore, it can be mixed or used in combination with microbial pesticides such as BT agents and insect pathogenic virus agents.

For example, the fungicides include S-benzyl, 0. Organophosphorus compounds such as 〇-diisopropyl phosphorothioate, 〇-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen bosbonate,
Organochlorine compounds such as 4,5.6.7-titrachlorophthalide and tetrachloroisophthalonitrile; polymers of Manganese ethylene bis(dithiocarbamate);
Zinc ethylene bis(dithiocarbamate) polymer,
Dithiocarbame-1-based compounds such as complex compounds of zinc and maneb, polymers of didizinc bis(dimethyldithiocarbamate), ethylene bis(dithiocarbamate), and zinc propylene bis(dithiocarbamate); 3a;
4,7.7a-Tetrahydro-N=(+-lichloromethanesulfenyl)phthalimide, 3a.

4.7.7a-Tetrahydro-N-(1,1,2,2
-tetrachloroethanesulfenyl)phthalimide, N
-N-halogenothioalkyl compounds such as (trichloromethylsulfenyl)phthalimide; 3-(3,5
-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazuridine-l-carboxamide, (R5)
-3-(3,5-dichlorophenyl)-5-methyl-
Dicarboximide compounds such as 5-vinyl-1,3-oxazolidine-2,4-dione, N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide: Benzimidazole-based compounds such as methyl 1-(butylcarbamoyl)benzimidazole-2-ylbamate, dimethyl 4,4'-(0-phenylene)bis(3-thioallophanate); 1-(4-chlorophenoxy) -3,3-dimethyl-1-(Ill-1,2,4-triazol-1-yl)butanone, ■-(biphenyyl-4-yl-1; ,2,4-triazol-1-yl)butan-2-ol, 1-[N
-(4-chloro-2-trifluoromethylphenyl)-
2-propoxyace1-imidoylcoimidazole, l
-(2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylmethyl) -111
-1,2,4-1-riazole, 1-(2-(2゜4-
dichlorophenyl)-4-propyl-13-dioxolan-2-ylmethyl) -111-L2,4 triazole, 1-(2-(2,4-dichloro1:1 phenyl)pentyl) -111-12,4-1- Azole compounds such as lyazole; 2,4'-dichloro-α-(pyrimidin-5-yl)benzhydryl alcohol, (±)-
2,4′-difluoro-α-CIl! -1.2.4-1
-Carbinol compounds such as lyazol-1-ylmethyl)benzhydryl alcohol; benzanilide type compounds; acylalanine type compounds such as methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate; 3-chloro-N
-(3-chloro-2,6-sinitro-4-α, α, α-
trifluorotolyl)-5-trifluoromethyl-2-
Viridinamine compounds such as pyridinamine; other compounds include piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, urea compounds, antibiotics, etc. It will be done.

The pest control agent of the present invention is effective for controlling various harmful insects, harmful mites, harmful nematodes, harmful soil pests, etc., and the application amount is generally 1 to 20,000 ppm, preferably 2.
0-2. It is carried out at an active ingredient concentration of OOOppm. The concentration of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, time, location, pest outbreak situation, etc. For example, in the case of aquatic harmful insects, it is possible to control them by spraying a chemical solution in the above concentration range to the place where they occur.
The active ingredient concentration range in water is below. The application amount per unit area is about 0.1 to 5,000 g, preferably 10 to 1,000 g as the active ingredient compound per 103.
h is used.

However, in special cases it is also possible to depart from these ranges.

Various formulations containing the compound of the present invention or diluted products thereof can be applied by any of the commonly used application methods, such as scattering (e.g., scattering, spraying, misting, atomizing, powdering, water surface application, etc.). , soil application (mixing, irrigation, etc.)
It can be carried out by surface application (painting, powder coating, coating, etc.), immersion of poison bait, etc. Also, the so-called ultra-high-speed concentration small amount 1'+
It can also be applied heavily (100 tralow volumes). In this method, the active ingredient is
It is possible to contain 00%.

Sample 1 Sweet potato knot nematode 8″ line 1 sweet potato knot nematode contaminated soil 1/14.00
A drug solution adjusted to have an active ingredient of 808/a was irrigated. On the day after the treatment, the entire layer of treated soil was mixed, and tomato seedlings at the 3- to 4-leaf stage were transplanted. After 20 days from the chemical solution treatment, the degree of young clumps was investigated, and the extent of clump formation was determined according to the following criteria.

Evaluation criteria for the degree of young cat clumps: O No clump formation 1 〃Small 2〃〃Medium 3〃Large 4 - Very large The results were that the degree of clump formation was 0 for both Compound Shade 1 and 2.

Test Example 2 Onion fly insecticidal test Put 40 g of air-dried ±IB into an ice cream cup, pour 10 ml of the chemical solution adjusted to a concentration of 400 ppm,
Mixed evenly. After 24 hours of mixing, onion pieces were embedded in the soil as bait, and 10 third instar onion fly larvae were released into the soil and left in a thermostat with lighting at 26°C. Seven days after release, we investigated whether the insects were alive or dead, and calculated the mortality rate using the formula below.
Compound 2 showed a mortality rate of 80%.

Formulation Example 1 (a) Compound 1 20 parts by weight (b)
N,N'-dimethylborumamide 32 parts xylene 40 parts heavy oil (d) Polyoxyethylene alkylphenyl ether
8 parts or more are uniformly mixed and dissolved to form an emulsion.

Formulation Example 2 (a) Compound 1 5 parts by weight (b) Bentonite 45 parts by weight (c) Kaolin 50 parts by weight or more are kneaded with a small amount of water, extruded into granules, and dried to form granules. do.

Formulation Example 3 (a) Compound 2 0.50 parts by weight (
b) Polyoxyethylene octylphenyl ether
0.15 parts by weight (c) Polyoxyethylene phosphate ester 0.10 parts by weight (d) Finely divided silica 1.0 parts by weight (e) Granular calcium carbonate 98.25 parts by weight (a)
- (C) are uniformly mixed in advance, powdered with an appropriate amount of acetone, and then sprayed onto the mixture of (D) and (E) to remove acetone to form granules.

Formulation Example 4 (a) Compound 11k11 50 parts by weight (b) Finely divided silica 15 parts by weight (
c) 25 parts by weight of fine clay (d)
Sodium naphthalene sulfonate polymeric condensation 2 parts by weight (B) Dialkyl sulfosuccinate 3 parts by weight (B) Polyoxyethylene alkyl ether sulfate
5 parts by weight or more are uniformly ground and mixed to form a wettable powder.

Formulation Example 5 (a) Compound Toru 2 1 part by weight (b) Talc 99 parts by weight or more are mixed uniformly to form a powder.

Formulation Example 6 (a) Compound N112 50 parts by weight (b) Methyl cellosolve 30Iiffi
Part (c) Polyoxyethylene alkylphenyl ether 20 parts by weight or more are uniformly mixed and dissolved to form a liquid agent.

Claims (1)

[Claims] 1. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…(I) (In the formula, X is a hydrogen atom or a halogen atom, and R^1
and R^2 are each independently an alkoxy group or an alkylthio group, and Z is an oxygen atom or a sulfur atom, provided that when X is a hydrogen atom and Z is a sulfur atom,
(R^1 and R^2 are not both alkoxy groups) or a salt thereof. 2. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…(I) (In the formula, X is a hydrogen atom or a halogen atom, and R^1
and R^2 are each independently an alkoxy group or an alkylthio group, and Z is an oxygen atom or a sulfur atom, provided that when X is a hydrogen atom and Z is a sulfur atom,
R^1 and R^2 are not both alkoxy groups) A pest control agent containing an organic phosphoric acid amide compound or a salt thereof as an active ingredient. 3. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…(I) (In the formula, X is a hydrogen atom or a halogen atom, and R^1
and R^2 are each independently an alkoxy group or an alkylthio group, and Z is an oxygen atom or a sulfur atom, provided that when X is a hydrogen atom and Z is a sulfur atom,
In the method for producing an organic phosphoric acid amide compound represented by the general formula ▲ mathematical formula, chemical formula, table, etc. There are compounds represented by the general formula ▲ mathematical formulas, chemical formulas, tables, etc.
al. is a halogen atom).