JPS58189192A - Organic phosphoric ester derivative, its preparation, and agent to destory noxious organism containing it - Google Patents

Abstract

NEW MATERIAL:An organic phosphoric ester derivative shown by the formula I [R<1> is H, lower alkyl, cycloalkyl, or arylalkyl; R<2> is H, alkanoyl, alkoxycarbonyl, or (thio)carbamoyl; X is halogen, lower alkyl (thio), lower alkoxyl, or nitro; n is 0-2]. EXAMPLE:O-Ethyl-S-n-propyl-O-(4-methoxycarbonylhydrazonomethyl)phenylp hosphorothiolate. USE:An agent to destory noxious organisms. Having low toxicity to mammals, fishes and shellfishes. PROCESS:For example, phosphoric chloride shown by the formula II is reacted with a phenolic derivative shown by the formula III in the presence of an acid acceptor such as pyridine, NaOH, etc. preferably in an inert solvent, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organophosphorus ester enzyme represented by the general formula (1) (hereinafter abbreviated as the present invention), Mix it with fresh Wi9i agent.

The compound of the present invention is a result of the Kurarashi Chemical Society, which has not been published in any literature.

As a #H-agent for southern livestock insects, agricultural hawks**, forest insects, and storage insects, and as an #H agent for agricultural insects, agricultural hawks 1F4 SOhI
It is a temple of M as Janggang.

The role of the agricultural sector in improving the productivity of agriculture has been largely due to the control of insects, weeds, etc., which has contributed to the preservation of crop yields and trade. It is also desired to develop a cultivating mulberry agent having the following properties.

This development - Ministry and others aim to develop a new fii insecticide
) While conducting research on the red book activity of the fine ester llI4, we obtained the knowledge that the compound 1 of the present invention exhibits excellent vJ gap properties. Although these are representative examples of the compounds of the present invention, they are not intended to be construed as such.

In addition, the compound of the present invention is a-mm. .

Compound 9111 of the present invention is reacted with the phosphorus chloride substituted by formula (1) 0′-Σant-kai [violet] C1 in the presence of the pheno-kiII receptor represented by the general formula (4) and the pheno-kiIII receptor. This allows the production of seeds. The above reaction can be carried out using inert substances such as jliI-spun verticalized water-bulk chain, aromatic expansion-verticalized water-bulk chain, salt-bulkified hydrocarbon chain, ether chain, ester chain, etc.
It is preferable to carry out the reaction in a medium, and as a #receptor, a base such as pyridine ore, trinium chloride, etc., is used, as is a base such as sodium hydroxide, natriwaum, or a free base of Karik Gojo. In general, it becomes permeable in IIL minutes to several tens of hours under the conditions of 150°C and straight from 0C.

After the completion of the 15L reaction, tin salt was applied to the organophosphorus ester #1 according to the 5JIil method, in which electricity was applied to the organic phosphorus ester #1.
You can get 9qst.

The compound of the present invention has the general formula I] [wherein h1. χ and mouth are #kiniokaji. ] and the general formula (VJ8, NNH♂
EV) [The B'' in the formula is the same as Ichii.] Hydrazine represented by , Shiotoshi if necessary.

#Add tlI insects such as spears and heat from 0℃ to 150℃
am
-r-can do.

j! The compound of the present invention is a hydrazone #4 compound represented by the general formula [former R', R'' in the formula, ”
The chloride represented by Cm is strictly prohibited.

It can be considered by being in the presence and responding to the yushugaya body.

In addition, for the compounds of the present invention in which the male in the general formula -1 (D) is a (Dentetsu) carbamoyl group or (II!Il + thiocarbamoyl), Shikien Y2C2h-it'
(4) It is possible to heat the incyanato to be raised at 1C in a mass, preferably in the presence of a triethylamine rope, at around 841 m or as required.

The method for producing the compound of the present invention will be described in detail in the following synthesis section.

廿lft1l 〇-Ethyl 6-Loglobi-〇-
(4-Methoxycarbonylhydrazonomethylphenylphosphorothiolate 4-(methoxycarbonylhydrazonomethyl))phenol iar and triethylamine 4.0V in 1 trahydro7 run solution 100-x f k - S-n-1
0 virchloride phosphorothiole) IL 1 ft. was lowered at room temperature. - At the end of the test, the mixture was heated under reflux for 15 minutes in the dark.

After cooling the triethylamine salt tlt field, add 500Mtk of ethyl acetate to the residue obtained by removing the reaction bath aj trohydrofuran under reduced pressure, and wash with water and 1-fJ sodium water bath solution. Subsequently, the mixture was washed with water and dried to obtain #mL yellow grips.

This column chromatography (silica gel).

From benzene-ethyl acetate system fllttl&)VC? l
Prepared title compound 171F (#yellow oil, 111τ-1
5587n.

t- got it.

Chemistry * structure is #I embroidered by WK watki resonance absorption spectrum and dish spectrum.

Even in the following combination examples, the structure of the compound is different.
This was carried out using the Ideki resonance absorption spectrum and the purchase spectrum, and when necessary, the infrared absorption spectrum was also used as a reference.

Synthetic image 2 0-ethyl-B -u -7'ropyru0-
(2-(ethoxycarbonylhydrazonomethylphenylphosphorothiolate) 2-(ethoxycarbonyl hydra l)1fk)pheno-
12,1? and 1.5 t of triethylamine, 2.6 ft'1ll of KQ-ethyl-8-n-globyl chloride phosphorothiolate in 120-liter of tetrahydro72
(IkKTeIi4下し1'L.m下*rAfter*(Cts threshold heating was taken into account.

Reaction generation wisdom is dedicated to the method of joint thievery, and a tank of tin salt is poured into a tank of 5m.
Monochemical *<Yellow grip, N3-t5545) 2.5
ft14).

In-laws cases 3-13 The following compound was synthesized using the method of compound kIi, v@↓.

Compound-A2 (Lee 1.5532)' AM
(# 1.5912n' !+3 (Half-integrated) I Jk16 (Station Yellow Garden) # 423 (M'1;=1-bso 1)I
A24 (I t5290)' 427
(' 1.5512)I island 62 (11,
5665) ' Aa42 (' 1.5420) # 4
50 (# 1.5578) 1 Muro 1 (Yellow-
14-) Kanari fi14o-ethyl-B-rI-norovir: 0
-[2-methyl-4-ethoxycarbonylhydrazine (
1'-Methyl-)methyl] phenyl phosyl hydrideolate 0-ethyl-B-n-7' lobi-(2-methyl-4-acetyl) phenyl phosphorothiolate 52 and cycarbonyl hydrono/ t2t (D ethanol)
1112.5-ml of vinegar was added to the Am solution and heated in a pot for 1 hour.

Cooling imitation ethanol [To the residue obtained by distillation under reduced pressure, add 100 alt of chloroform, add water, and add 1-f of caustic soda to the residue.
The product was washed with water, dried, and solidified to obtain yellow oily Wt.

This crude product was purified by column chromatography to obtain the title compound (pale yellow oil-*"U = t5475).
I prayed for t924.

Dog bX, dog 15 0-ethyl-8-n-norovir-〇-
(2,6-cypromo4-ethoxylponylhydronezonomethyl)phenylphosphorodeoleate U-ethyl-5
-n-Norobyl-〇-(Z,6-dipromo-4-formyl)phenylphosphorothio-late and ethoxycarbonylhydrazine in the presence of vinegar acupuncture 1 in ethanol, reaction according to the power paper of 14 And, after treatment with a wire, 1 (yellow 1 stick) was obtained.

Zeng 9 戊 vs 41 b~23 The following compound was synthesized according to the method of sweet acid ν1114.

8Mk7 (*'414 color fm shape @)l
No&L 9 (heart=1.5760)l
Nok 17 (# 1.595 b)
)l ノ＾λ 2(J (11,b485
)l mu25 (11,5501) I noh51 (# 1.b77
2) l M45 (# 1.5599) # A6
2 (yellow solid) Combined *N24 0-Ether-B-n-propyl-O-(M
-Methylcarbamoyl methyl) 7; Nylphosphorothiolate 0-ethyl-B-Q-Norobi-(4-hydrazomethyl)phenyl phosphorothiolate 5ft Benzene 5
0adK-EsumikageshitaMethi^isocyana-)t5#l was strictly applied. - VIIl11 by column chromatography using benzene under pressure at night! The compound was a yellowish brown oily substance.

The compound of the present invention has a water ring and a sewage ring.

**, 41. It is an extremely useful compound as a deterrent for various types of stag beetles, lint bugs, rice pot worms, etc.

Next, we will show the common use of the compound of the present invention, but of course it is limited only to the following Wffl, so it is not enough.

Southern houseflies, mosquitoes, and cockroaches (2) Water pails with insects; Japanese snail moth, Japanese flycatcher, white-spotted beetle, black-and-white leafhopper, black leafhopper [cannabis] fall armyworm, Japanese armyworm, Japanese aphid, Japanese aphid, and diamondback moth.

Ninoyutsuyaboshitentokumushi [Kokakumonhamaki] Kokakumonhamaki, Kuwakona Power Iga 2mushi, Ringono.
Ticks, tangerine spider mites, two-spotted spider mites, false red spider mites Book @ Minghwagu-ri Comparing with Zeng Ji, it has the power of tS insects and the timeliness of the river, and it is a response to #FJK or Its effect was discovered in the city of Ikuo Sanchiku, and it is also praised for its efficacy.

In addition, the compound W of the present invention can be cut into a sweet potato pattern and used for pest control 51jJ.

Furthermore, the compound of the present invention is also resistant to lactobacillus and copper, and is preferable in terms of safety 11I.

Compound of the present invention *t-insecticidal steel, acaricide, insecticide or #'
When used as an i-cide, -* should be used as a carrier such as clay, silica, bentonite, etc., or water, alcohol (methanol, ethanol, etc.), ketone, etc. , ether copper, m aliphatic hydrocarbon-1 aromatic Mizuki @ (ben(n, toluene, medium silane group),
Ken Ariiso, Kenamides (dimethylformamidesaki)
, silver for beauty salons, 2) ljk-kaku, which has a common affinity with tatami mats, and emulsified steel if desired.

Dispersants, m11a agents, detergent agents, permeation agents, stabilizers, etc.
- & addition, emulsion, oil, water su'M, 5 powders, 5 powders, paste, 70g, aerosol.

Practical use in any medicine such as anticancer agent, mosquito repellent, electric mosquito racket, etc.
can do.

In addition, depending on your needs, use of Xiongshin insecticidal steel,
Apply pesticides, herbicides, weeds, fertilizers, and fertilizers or simultaneously.

It has been a long time since I have seen a fan with a formulation example using the compound of the present invention as an insecticide, acaricide, insecticide M or coppercide, but the present invention is not limited to these alone. .

Here, F, [sJ are all Arashiryo Zheng].

Combination! Of these, 1. Milk, the compound of the present invention, 2.
・・・・・・・・・・・・・・・ 25 Chung Kiji Roll
・・・・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 26 BQ in 60 Sorbo
(Tadabe Kagaku - Product name) 15 parts or more The high-strength emulsion was diluted with water to a volume of 50 ffl to give a 1#I/toothness of 25 to 50-1. Or 1000
- Distributed to 2000 ~ 100~1 soz per U10a
i to make a blastocyst.

Combination i1! l112 Hydrating powder book 4 #ii:, & 7-mu 2 ro・
・・・・・・・・・−・・・・・・・・・・・・
・50 Noodle Dairy Seekuphyto (#1 Product Name 9...
・・・・・・・・・・・・・・・・・・ 40 Stirring Ball 5059 (Toho Chemical - Product Name P... 5*〃-
Grexna 80 ・・・・・・・・・・・・－・・・・
・ 5-ligninsulfonic acid no da --・・・・
−・・・・・・・・・・・・・・・・−・ Two or more galleries are mixed and pulverized uniformly to make an irrigation agent. For each Km of use, water use agent with the above composition [diluted 500 to 2000 times with water and 50
~50 A/10A meeting.

Compounding Shin 3 Powder Honpatsu Chemical Chim 38 ・・・・・・・・・・・・・・・・・・
・－・・・・・・・・・－・5 Art Creation −
・・・・－１－・・・・・・・・・・・・・・・
......--...-... 97 s or more is uniformly j1+ and made into a powder. 1 per t1 powder of the above composition
5F or Fi10a roaring spray from 3 to 4 o'clock.

Combination of 4 grains Compound of the present invention 55・・・・・・・・・・・・・・・・・・
−・・・・・・・・・・ 10s bentonite ・
−・・・・・・・・・・・・・・・・・・・・・・・・
〜・・・・・・50 Ikuta, Ruri
・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 59 Sodium lignin sulfonate ・・・・・・・・・・・・・・・・・・
1S Grind the above ingredients uniformly and combine them, add a small amount of water and stir thoroughly. Extrusion method i! Granulate with L granule machine.

This is t-amed to produce annealed copper.

The resulting working calyx is 10 am long and has 3 to 4 female calyxes.

The usefulness of the present invention will now be fully explained in the following sections. 7 In addition, as a control bar steel, a combination compound was used.

Pirate conversion formula 1 + c mountain U), P -Q 4J5-CH=NNHCO
oC,H.

Relative softening knowledge 2 (SU, HISU, B -o -C) -U) 4 ri廂 UQ 萅H5 ratio softening @A3 (L] #3P4.i 422 distribution compound cutting) □ Supplement Part 1: Insecticidal test against adult houseflies by tactile injection. Place the acetone # solution ICC ￥t9exs on a toppln directly on the main and control steel strips evenly in a petri dish so that the traps are absorbed, and heat at an appropriate temperature. After complete evaporation, 10 adult house flies were placed in a perforated glass attenuator. This petri dish was placed in a greenhouse at 25°C and inspected 24 hours a day to determine the death rate of dead insects (tn*).

The results for 1 ward will be determined using the 2 ward system.

Results [Show to the 4th group.

JIK4 Publication II 4 Ga 2 Insecticidal test against adult house fly
rJ11 Kawaho) Book@Useful proboscis and Yosho Ik agent t acetone Kll understanding,
The acetone bath solution was applied to the thorax and dorsum of house flies using a microsyringe, and the ta value was 91. In addition, houseflies treated with tin salt as described above were placed in a 6ts styrene cup along with water-impregnated absorbent cotton, and a J sterol cup tP was placed.
It was kept at a constant temperature of 25℃ (C24) for #f.
A to the simple needle nose 2? ) 95's8 Death Qin kk (LDea
) 'Calculate Friend.

In addition, 1III& tried 910 keels in the 1st ward, and became bamboo in the 2nd ward. The results are shown in t-5.

5 Contact insecticidal test against Japanese butterfly flycatcher 9. Stir the uninvented compound and control compound in a 100 ppm water emulsion for about 10 dollars, air dry, then put in a petri dish. 175 larvae [
Release 1 o per petri dish for a long time, make a hole *tt, te 2
The animals were housed in a stable room at 5°C, and dead insects at 48:08 were examined.

Results t--show in Table 6.

i6JM test h4 Residual effect test rate % for Hasmonyotoku #!
Aits Zeng Ji and Naishu ◆ Copper 500 ppm Certification Ceremony 1
L enemy [to 1/1 of the 5th to 4th period. . Ga bond woodcutter (C mowing, displacing and spraying to get wet enough, and invaded the stormy dredge.

I was worried about the 7th drug in a petri dish at 4110 days ago.

This +J has seven yo-) '172 Rei Mfflt petri dish teeth 1υI#tj'') & also Iikura and 25℃ fun-
I ate 4 meals of Kufu and a half at 48 o'clock.

By the way, tA, what happened in practice #1 and 2 section?

Seven results 1 The compound of the present invention@mu55 eliminated more than 90 dead insects.

iK performance control b Penetration transfer note for Hassanayoto 9 1 and anti-oboro drug I Q ppm 6-4 concentration of Kanranzono root 1 (24 o'clock IMJ &
Repair friend. Transfer this Karlan sono to Nyare and release 2nd instar larvae of Hesmonyotowa into this at a rate of 10 per petri dish.
The dead insects were then stored in a thermostatic oven at 25°C for 48 hours.

Note that test 1111 [was conducted in the 2nd section.

The ending is shown in the 7th group.

7 Insecticidal test conducted in '7 (51) Potato slices were immersed in a 100 ppm water emulsion containing the compound of the present invention for about 10 seconds, placed in a pot, and placed in the water. Release 10 pieces of 72nd instar larvae into a petri dish and make the holes open 2 times.
Housed in a constant temperature storm at 5℃.

72iiNkl carpet JI! I ate 4 dead insect ridges.

In addition, the assessment kjL was conducted using a two-district system.

As a result, Compound 1 of the present invention had a mortality rate of 9011+ or higher.

tankN'7 Kaede kaede is effective in preventing rice blast disease*! 19 e
12 seedlings were grown in 4-season pots of x (using variety Nipponbare 9, 2 compounds of the present invention and 50% of copper in Karihigami #).
Using a spray gun, I sprinkled 0 ppm of the chemical solution on 3 bottles and 4 o's, and on the 1st I evenly sprayed the spore solution of the rice blast disease, and maintained mmK overnight. The disease was caused by the rear glass guide.

Control was calculated by counting the number of lesions observed for one week.

Tie it down to 1 d structure.

No. 8#1t j5 % Calculation Hoto Hito Kagaku Kogyo IIa Formula Your Company 1 Procedural Sleeve Book June 1981 to [J Indication of the Case of Mr. Kazuo Wakasugi, Commissioner of the Office of Special Correction 1988 Patent Application No. 67645-) Name of the invention: autophosphoric acid ester derivatives, methods for producing the same, and A'
Relationship with Auto 46 White Pest Control Agent Sleeve 11 4.6 J 'lt $ Ino 1 Patent Applicant (i: lsu I t+ 1 Tokyo Chiyo Lf 1 Ward Kami "U Nishikicho 3-7-1 Name (, l', Ii old t-1
An autogenous nisdel phosphate derivative represented by the general formula (1) C.

(2) The general formula [[]' (represented by Method for producing autologous phosphate ester derivatives.

'a) Reacting the carbonyl compound represented by the general formula (IV) with the hydrazine derivative represented by the general formula [VJ 11□NN[+h'' (V) or its inorganic acid salt or inorganic acid salt] Characteristic general formula [
I] Production method of the expressed organic phosphate ester derivative.

(4) A hydrazine derivative represented by the general formula (Vl) and the general A (VfB) or the general formula [■]
A method for producing an organic phosphoric acid ester derivative represented by the general formula (1), which comprises reacting an isocyanate represented by R' (■).

(5) A self-harming agent characterized by containing an autophosphoric acid ester derivative represented by general formula (1) C as an active ingredient.

Claims (1)

[Claims] (i) An organic phosphorus ester represented by the general formula [1] Yr+ #exclusively. (2) Phosphorus enemy chloride represented by the formula Lu' 0,8,0〉〓-at [frog] C, H, 8 and the general formula [rut jλ phenol #gravel body and ta & receiver V + A process for producing a #4 rod of isosulfonic acid ester represented by the general formula [1], in which a carbonyl compound represented by the formula I and - JkALV] H, li 肚a" t-v] 1 □ Hydrazine #conductor or its 1411 coating or Fi uncoated cough salt and t centering to t% mold [1] C Next 4 Noa JL6 Self-made sales Estelle Kinjin body JJi
T paper, (4 no. &Shikimon" atL 金人') RUN 纏宏 dedication and \l -. Tahiro general formula (Yll-h'
Lm is the iso-7 anato and ta is centered on the t-axis, which is the rice ceremony (1). (1) Organic phosphorus ester #S4 is contained as an effective component of 44-grade steel.