JPS5859993A - Thiophosphoramidate, its preparation and insecticide, acaricide and nematocide consisting of said compound - Google Patents

Abstract

NEW MATERIAL:A compound of formulaI(R is H or methyl). EXAMPLE:1-[O-Methyl S-(n)-propylphosphoryl]ethylenenimine. USE:An insecticide, acaricide and nematocide. PROCESS:A halogen compound of formula III (Hal is halogen), e.g. O-methyl S-n- propylphosphorochloridothionate, is condensed with ethyleneimine or propyleneimine of formula IV in the presence of a deacidifying agent, e.g. triethylamine, at -10-+50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel thiophosphoramidate, a method for producing the same, and a compound containing the compound as an active ingredient.
More specifically, the present invention (1) relates to insecticides, acaricides, and nematicides having the following general formula (f) [
In particular, R is a thiophosphoric acid amidate represented by e which weakens a hydrogen atom or a methyl group.Invention 42
) is the general formula [■ ] In manufacturing the compound of the present invention, a halogen compound represented by the general formula [-] and an ethylene phosphide compound represented by the general formula [-] are used. or propylene imine 7
1) Ketones such as carbon, methyl isobutyl ketone, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as carbon tetrachloride and chloroform, 7m) In the presence of or using a solvent such as nitrile. Without A stone, #
# Triethyl f as an agent! To obtain #tea to be added by stirring for a short time from around -7θ°C to 50°C with a reaction temperature of 11 V using a diluted base such as L, pyridine, or an inorganic base such as caustic soda or I# acid soda.・To complete the reaction, the target product can be isolated by carrying out a usual assisted treatment. ・The present invention 0 contains a dilin-ester represented by the general formula (1) as an active ingredient. Insecticide characterized by
It is a miticide and nematocide.

The compound represented by the general formula [1] exhibits excellent insecticidal, acaricidal, and nematicidal effects, such as the planthopper, brown planthopper, black-bottomed planthopper, and black-bottomed planthopper. l
Kubai, peach 7 and 7 brums, cotton buds, radish aphids (more than half! I eyes), tea tree hemlock, kinmon book hemlock, t-kan leafminer moth, = Naga, kokaku tatami hemaki, chabamaki, Nikamaichi, Tsu, Kobuno borer moth, foxtail borer moth, pine borer moth, 7-walled moth, Hasmon mithu,
Swallowtail (Lepidoptera).

Japanese radish beetle, Japanese radish beetle, rice beetle, rice weevil, and adzuki bean weevil.

C Ugane Buibui, and Mekogane (Coleoptera).

Neck Ishima force, Hemadara force, Culex mosquito, House fly,
Onion fly, Golden fly, Chinchon fly, Rice fly (Diptera), Kobanei locust (Ordinary order), German cockroach, Japanese cockroach, Ri Q
Cockroaches (Ordinoptera), Nisenae spider mites, Suden spider mites, Sugitsu spider mites, Nisakakashi spider mites, Apple spider mites, Ixodes spp., Pisces ticks (Acarinae), Northern spider mites, Walnut spider mites, ttX Negusares centi, One, Dice cyst centimeter, Potato cyst centi crystal, Kitanekup dragon, Sweet potato cat centimeter, Ja9 Nekopu centi, Tametsu, 7 Lenari 7
Paddy fields, fields, such as Nekobutanchi-otsu, Inesingara-senchi-otsu, and Pine-nosed nematode
It is highly effective in controlling calliflora, sanitary pests, and house pests that occur on fruit trees, satsatsuna, forests, and wood.

Compound K11 of the present invention (thiophosphoramidate having a U structure exhibits insecticidal, acaricidal, and especially nematocidal activity)
i Tokukai Showaday! Although RK was known in Publication No. 1141, the present inventors investigated compounds of thiophosphoric acid 7midate and found that the alkyl of 〇-alkyl is methyl,
When 8-alkyl is alkyl or normal propyl.

It was discovered that when the alkyl in 0-alkyl is ethyl, it has extremely superior insecticidal, acaricidal, and nematocidal effects. 1. The present invention was completed. The compound of the present invention represented by the general formula (1) is (1) The compound of the present invention is a liquid or a solid.

Depending on the case, it may be mixed with a gaseous carrier, and if superimposed, various auxiliary agents may be added.
Formulated into oils, emulsions, irrigation tablets, microgranules, or powders and used in the usual manner; and of course other insecticides, acaricides, nematicides, fungicides, or seeds. It can be mixed with a disinfectant, fertilizer, or soil freshener and applied at the same time.In addition, an insecticide containing the compound of the present invention as an active ingredient.

It is preferable that the acaricide and nematocide contain the compound of the present invention in an amount of θ, /~lθ. It is particularly important to contain θ.
Next, the present invention will be explained in more detail with reference to Examples and Formulation Examples.

Example/(Synthesis example of compound number (1))
Ethyleneimine-06f and triethylamine 6, θ! The mixed solution was cooled so that the internal temperature of the reaction solution was /j-10°C, added dropwise with stirring, and then stirred in the room for 3θ minutes. After completion, water was added, the five layers of QQ wood were separated, dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to leave a brown oily residue, yielding 3P. This was column chromatographed using silica gel. Refine using the graph method.
7-(〇-Methyl B-(n)-propylphosyl)ethyleneimine J,J was obtained as a colorless oil and having a refractive index of nD/-44111.

Elemental analysis value analysis* sb, yb 4. Tsu & 7. θI
/jJ7 Example-(Synthesis example of compound number-) Colorless oily, refractive index Dfll・O was prepared in the same manner as in Example/.
/, 4#27 of 7-(0-methyl B-?)-propylcarsphoryl)-1-methylethylene idenone was obtained.

Elemental analysis value (as 07H, 6No, Pg) Analysis value 3ri, 9j 7. &t 4. n/4
1.7j Next, the excellent insecticidal, moldicidal, and nematicidal effects of the compounds of the present invention will be explained in detail by the following examples. In the following examples, the following known compounds were prepared into formulations obtained by the same procedure as used in each example and served as a control.

Compound Structure Ortolan Bap (D) BrOH20BBr att2oz
The compound of the present invention prepared according to the procedure shown in Example J of Irregular Axillary Nematicide Formulation Example/
Dilute the @ emulsion with water to the specified #tK.
, spray 2 pots.

After air-drying, Spodoptera japonica (5pQdOputOra 1
itura) da instar larvae/theta larvae were released, and the plants were covered with cages. Life and death of larvae after 30 days and feeding damage by larvae s1
*) I ate the sea bream *) Degree of feeding damage - Feeding damage ±... Feeding damage only K feet 10... Feeding damage feet... Large feeding damage example Mix 000 of the diluted medicine with water/θθPE) into sandy loam 5oty P.Pour half of the treated soil into a polyethylene cup with diameter/2 diameter and height T, and add directly @J 51% rhinoceros OJ Place 3 small pieces of carrot cut into 1 piece! -1 Add the remaining treated soil. Dogane Bui Bui (Muno group 1a oup
r.a) J-instar larva heads were released into the treated soil, and 7 days later, the survival of the larvae and the damage caused by feeding on carrots (8 tons*) were examined. Repetitions were carried out j times each. *) Degree of feeding damage -...No book±...Feeding damage slightly Toshi+...Feeding damage 廿...Mostly feeding damage Example j Formulation example/ An emulsion of the compound of the present invention prepared according to the procedure shown was diluted to 100.10.21.12.1211m with water, and a chemical solution θ, 7oo was dropped onto a piece of paper placed in a polyethylene cup with a diameter of 5 mm. Sugar J0111
! F and house fly (hats aaIII・-ti
6a) Female adults IO'a were released.

- Investigate the death of the first year of the year, dead insect car, Chuo Kenshinou II
(L050 ppm) was determined.Example 6 7-leaf A9 S! III's fake l/%dami τ*tranyah
uacinnabarinus) parasitize female adults,
After 06 days of storage at -6°C, an emulsion of the compound of the present invention prepared from JIIK as shown in Formulation Example was added to Sθθ with water.
(ppm diluted chemical solution on a turntable/in a pot)
The number of female adult spider mites on the trees was counted on the 10th day after spraying for /θ generations. Effectiveness*) Criteria for determining the effectiveness of false red spider mites... 711 KjlIIll Insects or θ ~ Tsuyori parasitism.

B...7 leaves are parasitized by female adults from 7θ to 371N.
C.../*KfH! There are more than J/It parasitic adults.

Example 7 Compound of the present invention (prepared according to the procedure shown in Formulation Example)
1) Soak the rice seedlings in a drug prepared by diluting each emulsion of (a) to SOθppm of each active ingredient for 7 minutes and air dry.Place the treated rice and Nikamaichi seeds (ahtxo auppr) in a plastic cup with diameter!, icm. @5saxis
) After 0/θ days of inserting J-instar larvae/θ condyles, the larvae can be killed by 70θ in both cases.
An example! Compound (1) of the present invention prepared by the procedure shown in Formulation Example q in rice planted in 9 Gunerbot at 900 min/R.
, (,!3 powders were sprayed at a ratio of /θR ATASHIJKP, and the plants were covered with wire mesh cages. In each cage, there was a
us) Female adult insects/1m were released*, 2411 hours - In the case of a lag time, 4 adults could be killed by /θθ. The compound of the present invention (
The emulsion in 1) is diluted with water to form an active ingredient SaOppm solution.

/1081 Plastic cup sowing/1 month of rice is sprayed with /ICM3/-1 cup on a turntable.

Air dry, cover each plant with a wire mesh cage, and find drug-resistant blacktip sharks in the cage! Hubai (Nephotettix)
ainctlcsps ) (middle phase W production) female adult/!
*Release in the wild. - Adult insects can be killed by /θθ at 9 hours and 11 hours.90 Examples/θ Effect of controlling Meloidgyne nematodes by application during tomato piloerection on Meloidgyne EW (Meloidgyne EW) contaminated soil! θθ
Mix f with an equal amount of non-contaminated soil, place it in a Wagnerbot with lj, θθθ, and plant 6 tomato seedlings at the 3rd to 4th leaf stage. Once the tomato seedlings are fully established, add IOd/pot (
After 1 day from the day of the chemical treatment, I noticed the extent of catfish growth on the ridge. Observations were made using seedlings planted in non-contaminated soil and contaminated soil in pots that were not treated with the chemical M as controls, and records were made according to the following criteria.

(Nekobu epiphyte degree) Display Nekobu epiphyte state θ
In the upper γ-boost U < cat 1 spitting - K clearly compared to the book Kub Ruhaku Ishuo Hoifun J sang ben 掬 Yu small is connected to the leaves H genus 6 (nearly the multi-species cat is whorled Da and - hemorrhoids or even more Many examples // Soybean rest nematode (°B@f@rod@ra glyc
in@s) Contaminated ±81001 was mixed with an equal volume of uncontaminated soil.

4.Put in S, θ〃R Wagner pot, Formulation Example 7
The emulsion of the compound of the present invention (C) prepared according to (2) was diluted with water, and the drug discovery solution was separately injected into lICl0 bottlings, mixed uniformly with the soil in the subsurface layer, and then mixed with soybean. /θ grains were sown, and the adhesion S degree of rest was observed on Jθ daily plants from the day of drug treatment. - Observation results are listed in accordance with Example IOK 〇 Example Negusare nematode control effect by no-seeding application Negusare Nematode (Pratylsnchusi SF,)
Mix the contaminated elutriate t with an equal amount of uncontaminated soil, //i,
Powders of the compounds of the present invention (/) and (to) prepared according to Formulation Example q were placed in a 0(X)R Wagner pot and applied separately to θ, -P/pot (/IF/R). .

After uniformly mixing with the soil below the surface layer/j-.

Five seeds of Elm 92f were sown.

The degree of development of Negusare nematodes was observed 6θ days after the drug treatment. The observation results were recorded in accordance with Example 10.
A plastic board is used to cover a field that is roaring from contaminated soil.mX/m
Section mK shall be the test section. The oil solutions of the compounds (1) and (b) of the present invention prepared according to Part J of Formulation Example were added separately to a depth of 75 mm at intervals of 20 mm on the soil surface.
approximately st bar).

Tomato seedlings were collected on the 6th day of the transplant, and their growth status was observed on the 11th floor.The results showed that they were comparable to those in any of the non-contaminated soil areas. On the other hand, the growth of tomato seedlings in the polluted soil section, which was treated with chemicals and was in danger, was poor in both plant height and root length, and a large number of clumps were attached. I saw life.

Formulation Example/90 parts each of the compounds (1), (a) of the present invention were added to xylene S.
Dissolve in part O, add 76 parts of emulsifier Tsurupol BM-Jθ (registered trademark of Toho Chemical, a mixture of anionic surfactant and nonionic surfactant), and stir and mix thoroughly to obtain an emulsion of DAθ. @Formulation Example Add 73 parts of Tulpol I [1M-100 (above mentioned) to each of the EO portions of the compounds (1) and (2) of the present invention, mix well, and add Carplex #lθ (Giotsugi Pharmaceutical Co., Ltd.) Title 1
Synthetic hydrated silicon oxide fine powder) part.

By sequentially adding ±3s parts of 3θθ mesh diatoms and stirring and mixing in a commercially available juice mixer, a wettable powder of 0 qb each is obtained.

Formulation Example 3 Tomilignin 0T (lllll Spindokama trade name, lignin sulfur umbrella acid salt) is added to the j part of each of the compounds (1) and (2) of the present invention.
J-bu and 08M clay (Sieglite Konegyo registered trade name) 9
Add 0 parts and thoroughly stir and mix in a grinder. Next, water is added in an amount of 7μ/Jb of these mixtures, further stirred, granulated using a granulator, and dried through ventilation to obtain respective granules. 7 setsonko ρ for each 5 parts of
3 parts of Carflex #lθ (described above), PA
0.3 part of P (isopropyl 7-hydro-sulfate) and 7 parts of Jθθmelle 1 talc def were added sequentially, and
After stirring and mixing in a mixer, the adenton was removed by evaporation to obtain 5% powder.

Formulation Example S 20 parts each of the compounds (1) and - of the present invention were dissolved in kerosene,
If the total amount is 700 parts, each will yield a 20% oil solution.

Claims (1)

[Scope of Claims] A thiophosphoric acid amidate represented by the following formula: [wherein R is a hydrogen atom or a methyl group]. (to) General formula [in the formula,! 4111 describes the condensation reaction of a halogen compound represented by 0] where Ial represents a halogen atom and ethyleneimine represented by the general formula [0] where R represents a hydrogen atom or a methyl group, and propyleneimine. The general formula is [wherein R is as described above]. ] Method for producing dithiophosphoric acid amidate represented by (3) General formula [wherein R represents a hydrogen atom or a methyl group. ] Insecticides, acaricides, nematicides and