JPH02121996A - Phosphoric acid ester derivative and insecticidal and miticidal agent containing the same - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> to R<3> represent lower alkyl; X<1> and X<2> represent H or halogen; Y represents O or S). EXAMPLE:O-Ethyl S-n-propyl O-[4-(alpha-trichloromethyl-alpha-methoxy)methyl]phenylphosphoro thioate expressed by formula IV. USE:An insecticidal and miticidal agent. PREPARATION:A phenol derivative expressed by formula II [example; 4-(alpha- trichloromethyl-alpha-methoxy)methylphenol] is reacted with a phosphoric acid chloride expressed by formula III (example; O-ehtyl S-n-prophylphosphoric acid chloride) in the presence of an acid finding agent (example; triethylamine) nor mally in an organic solvent such as THF or in a two phase system of the organic solvent and water preferably at 0-50 deg.C for 1-5hr.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel phosphoric acid ester derivative and an insecticide and acaricide containing the derivative.

(Prior Art) Many compounds having insecticidal and acaricidal activities are known among the conventionally known afi 17 acid ester derivatives. It is short-lived and highly toxic to warm-blooded animals.

Therefore, among the conventionally known organic phosphate ester derivatives, there is still no known compound that has low residual efficacy and low toxicity to warm-blooded animals and has been put to practical use as an insecticide or acaricide.

(Problems to be Solved by the Invention) The object of the present invention is to provide a novel phosphate ester derivative that has strong insecticidal and acaricidal activity, has a long residual effect, and has low toxicity to warm-blooded animals. It is in.

(Means for Solving the Problems) The present invention relates to a compound of the general formula [wherein R', R2 and R3 represent a lower alkyl group]. X' and X2 are the same or different and represent a hydrogen atom or a halogen atom. Y represents fIll'Jt, an atom, or a sulfur atom. The present invention relates to a phosphoric acid ester derivative represented by the following formula and an insecticide or insecticide containing the derivative as an active ingredient.

The compound of the present invention also maintains strong activity against organophosphorus-resistant insects and mites.

The phosphoric acid ester derivative of the present invention is a novel compound that has not been described in any literature, and is represented by the following general formula (1).

[In the formula, R', R2 and R3 represent a lower alkyl group.

X1 and X2 are the same or different and represent a hydrogen atom or a halogen atom. Y represents an oxygen atom or a sulfur atom.] In the present invention, each group represented by R1, R2, Rco, ν, and X2 is specifically as follows.

Examples of lower alkyl groups include methyl, ethyl, rhopropyl, isopropyl, 11-butyl, isobutyl,! 1i
Examples include ee-butyl, amyl, and hexyl groups.

Examples of the halogen atom include a chlorine atom and a bromine atom.

The phosphoric acid ester derivative represented by the above general formula (1) can be produced by various methods, and a typical method is, for example, one method shown in Reaction Formula 1 below.

Reaction formula 1 % formula % (1) [In the formula, R1, R2H", X', It is produced by reacting phosphoric acid chloride represented by (Ill) in the presence of an acid binder.

The above reaction is carried out in an organic solvent or in a two-phase system of an organic solvent and water. Examples of organic solvents used include ethyl ether, butyl ether, tetofhydrofuran,
Ethers such as nooxane, nitriles such as acetonitrile and propionitrile, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane, dichloromethane, chloroform, and carbon tetrachloride. Examples include m.

Phenol derivatives represented by general formula (n) and general formula (
The ratio of the phosphoric acid chloride represented by II) to be used is not particularly limited and can be appropriately selected from a wide range, but usually the latter is about 0.5 to 2 times the former by mole, preferably 1 to 1 mole. It is preferable to set it to about .5 times the mole. In addition, as the acid binder, a wide variety of conventionally known ones can be used, and specifically, tJ & tertiary amines such as triethylamine and pyridine, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydroxide, potassium hydroxide, etc. Examples include alkali metal hydroxides such as alkali metal hydroxides, sodium hydride, potassium hydride, and the like. The amount of such acid binder to be used is usually 1 to 2 to
The amount is preferably about twice the molar amount, preferably about 1 to 1.2 times the molar amount. The reaction normally proceeds suitably at 0 to 50°C and is generally completed in about 1 to 5 hours.

In Reaction Formula 1 above, the compound (I[l) used as a starting material is a known compound and can be easily obtained industrially. Compound (II), which is the other starting material, can also be easily produced, for example, according to the known methods shown in Reaction Formula 2 and Reaction Formula 3 below.

Reaction formula 2 Reaction formula 3 The reaction of reaction formula 2 is carried out in the presence of a base using, for example, potassium carbonate.
It is disclosed in the publication No.

The reaction of Reaction Formula 3 is carried out in the presence of a suitable condensing agent, such as sulfuric acid, and the details are given in Org, Syn, eCoi.
1, Vol. 4, 72 (1963).

The compound of the present invention obtained by the above method can be easily isolated and purified from the reaction mixture by conventional separation methods such as solvent extraction, solvent dilution, distillation, recrystallization, column chromatography, etc. According to the above production method, the compound of the present invention is produced with high yield and high purity.

Representative examples of the compounds of the present invention are shown below.

・0-Ethyl 5-n-propyl 0-(4-(ff-)lichloromethyl-a-methoxy)methyl]phenylphosphorothioate (Compound 1) ・0-ethyl 5-n-
Propyl 0-(4-(a-trichloromethyl-α-methoxy)methyl]phenyldithiophos 72-) (
Compound 2) O-methyl 5-iso-butyl 0-(4-
(α-Trichloromethyl-a-methoxy)methyl]phenylphosphorothioate (Compound 3) 0-ethylSn-propyl 0-[4-'(α-trichloromethyl-〇-methoxy)methyl-2-chloro]phenylphosphorothioate (Compound 4) ・0-ethyl 5-iso-butyl 0-(4-(α-trichloromethyl-a-methoxy)methyl-2-chlorologophenyl phosphorothioate (Compound 5) ・0-ethyl 5-see-butyl 0 -(4-(α-trichloromethyl-a-methoxy)methyl-2-chlorophenyl phosphorothioate (compound 6) ・0-methyl 5-iso-butyl 0-(4-(α-trichloromethyl-α-methoxy) Methyl-2-chloro]phenylphosphorothioate (Compound 7) ・0-EthylSn-propyl 0-(4-(α-trichloromethyl-a-methoxy)methyl-2,6-dichlorophenylphosphorothioate (Compound 8) 0-Methyl 5-iso-butyl 0-(4-(α-trichloromethyl-a-methoxy)methyl-2,6-nochloro]phenylphosphorothioate (compound 9) ・0-ethyl 5-n-propyl 0-(4 -(a-)lichloromethyl-α-nitoxy)methyl-2-chloro]phenylphosphorothioate (compound 10) ・0-methyls 1so-butyl 0-(4-(Q-to17 chloromethyl-a-ethoxy)methyl -2-Chlorophenyl phosphorothioate (Compound 11) ・〇-Ethyl 5-iso-butyl 0-(4-(a-)lichloromethyl-a-nitoxy)methyl-2-chlorologophenyl phosphorothioate (Compound 12) ・0- Ethyl Sn-propyl 0-(4-(α-trichloromethyl-a-ethoxy)methyl) phenylphosphorothioate (compound 17+3)・0-ethyl Sn-propyl 0-(4-(α-trichloromethyl-a-ethoxy)methyl -2,6-dichlorologophenyl phosphorothioate (compound 14) ・O-methyl 5-iso-butyl 0-(4-(α-trichloromethyl-a-ethoxy)methyl-2,6-dichlorologophenyl phosphorothioate (compound 15) ) ・0-ethyl 5-n-propyl 0-(4-(α-trichloromethyl-〇-11-propoxy)methyl-2-90
0ro] Phenyl phosphorothioate compound 16) ・0-ethyl 5-iso-butyl 0-(4-(a-)lichloromethyl-an-propoxy)methyl = 2-90
[b] Phenylphosphorothioate (compound 17) -0-methyl S-; so-butyl 0-(4-(α-trichloromethyl-α-n-propoxy)methyl-2-90
phenylphosphorothioate (compound 18) -0-dityl 5-n-propyl 0-(4-(ff-)lichloromethyl-an-butoxy)methyl]7enylphosphorothioate (compound 19) 0- Dithyl Sn-propyl 0-(4-((7-dolichloroamethyl-α-+1-butoxy)methyl-2-900ro) phenyl phosphorothioate compound 20) ・0-ethyl 5-iso-butyl 0-(4- <ff-)
Lichloromethyl-an-butoxy)methyl-2-chloro]phenyl phosphorothioate (compound 21) ・0-methyl 5-iso-butyl 0-(4-(ff-)
Lichloromethyl-an-butoxy)methyl-2-rio
o) Phenyl phosphorothioate (Compound 22) - 0-ethyl 5-n-propyl 0-(4-(α-trichloromethyl-α-n-p)oxy)methyl-2,6-nochloro]phenyl phosphorothioate (Compound 23)・0-ethyl 5-n-propyl o-(4-(cr-)dichloromethyl-α-ethoxy)methyl-2-chloro]phenylphosphorodithioate (compound 24) ・0-ethyl Sn-propyl 0-( :4-(α-trichloromethyl-a-n-butoxy)methyl-2-chloro]
Phenylphosphoronotioate (Compound 25) - 〇-Ethyl 5-n-propyl 0-(4-(α-trichloromethyl-a-methoxy)methyl-2-bromo]phenylphosphoronotioate (Compound 26) The compound of the present invention is Not only does it have excellent insecticidal activity, but also
It has strong acaricidal activity.

Moreover, compared to conventional organic phosphorus agents, the residual activity is longer.
Since it is also highly effective against organophosphorus-resistant mites, it is effectively used as a pest control agent for vegetables such as spinach and fruit.

When using the compound of the present invention as an insecticide or acaricide, emulsions, aqueous agents, suspensions, fine granules, powders, wettable powders, liniments, 7-ohm spray preparations, microcapsule preparations, aerosol preparations, It is used in various forms such as preparations for impregnating natural or synthetic substances, preparations for fumigation, and preparations for spraying in concentrated small quantities. In preparing these formulations, emulsification,
Various surfactants can be used for dispersion, suspension, and foaming. As the surfactant, for example, polyoxyethylene alyl ether as a nonionic surfactant,
Polyoxyethylene alkyl ester, polyoxyethylene sorbicun furkyl ester, sorbitan alkyl ester, etc. are used as anionic surfactants such as alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, and polyoxyethylene alkyl sulfate 7.
Examples include diate, allyl sulfonate, and lignin sulfite. Further, as the solubilizing agent, diluent, and carrier, various organic solvents, various aerosol propellants, various natural minerals and plants, as well as various synthetic compounds, etc. can be used. Among the organic solvents, particularly preferred are benzene, toluene, xylene, ethylbenzene, albenzene, alkylnaphthalene xane, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, dimethylformamide, dimethyl sulfoxide,
Examples include acetonitrile and mineral oil fractions.

Examples of aerosol propellants include propane, butane, halogenated hydrocarbons, nitrogen, carbon dioxide, and the like. Examples of minerals include kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, chalk, calcite, pumice, sepiolite, and dolomite. Examples of plants include walnut grains, tobacco stalks, and sawdust. Examples of synthetic compounds include alumina, silicates, sugar polymers, and the like. Examples of the adhesive include carboxymethylcellulose, gum arabic, polyvinylfurfur, and polyvinyl acetate. Also, these preparations include
It is also possible to color the material using a dye or a black iso dye.

In the present invention, when producing the above-mentioned various preparations, the compound of the present invention is contained in an amount of about 0.1 to 95% by weight, preferably about 0.0% by weight.
The formulation may be formulated to contain 5 to 90% by weight.

The illlgI preparation can be used as it is or after being diluted with a carrier or water, but it may be diluted with about 0.000 dilution depending on the purpose.
It can be freely diluted within the range of 0.01 to 100% by weight, preferably about 0.0001 to 10% by weight of the compound of the present invention. The amount of spraying depends on the occurrence of insects and mites, the weather, etc. 4
Although it cannot be said in general, the amount of the compound of the present invention per hectare is generally 0.1 to 10, preferably 0.1.
~lk.

(Example) The present invention will be further clarified by giving production examples and test examples below.

Production example 1 4-(a-trichloromethyl-a-methoxy)methyl 7
2.03 g of O-ethyl 5-n-propyl phosphoric acid chloride was added to 201 g of methylene chloride with stirring and water cooling. was dripped. After the dropwise addition, the reaction solution was stirred at room temperature for 1 hour, washed with a 5% aqueous hydrochloric acid solution, then with a 5% aqueous sodium bicarbonate solution, and finally with a saturated saline solution, and then dried over anhydrous magnesium sulfate. When the solvent was distilled off under reduced pressure, a pale yellow oil was obtained.
3.85 g of ethyl S n-propyl 0-(4-(α-trichloromethoxy)methyl]phenylphosphorothiony) was obtained.

Summer R (Neat): 1260cm
-' (P=O)NMRCCDCl, ): δ(p
pm) 0.8-1.80 (a+, 8F-[5a
lkyl), 2.56-3.10(m, 2!(
,CH25)-3,40(s=3HtCH30)
-3,90-4,50(m, 2 H9CH20L
4.54 (s-111, CH), 7.10-7
．． 60 (mt 4 H, aromatic-H) or higher, it was confirmed that the obtained compound was.

Production Example 2 2.21 g of 4-(a-)lichloromethyl-a-methoxy)methylphenol and 1.38 g of anhydrous potassium carbonate were placed in 30 d of a7tonitrile, and heated at 40 to 45° C. for 1 hour while stirring. Then, 2.18 g of 0-ethyl 5-n-probylnotiophosphoric acid chloride was added dropwise.

After the dropwise addition, the reaction mixture was stirred at 55 to 60°C for 5 hours, and then the salt was filtered out and the furnace liquid was concentrated. The residue was purified on a silica sol column (benzene-ethyl acetate = 10:1) to give a yellow oily 0-ethyl 5-n-propyl 0-(4-
(a-) Lichloromethyl-a-methoxy)methyl] phenylnotiophos 7ate 4, Q5. I got it.

I R (N eat): 66L 790cm
-' (P=S)NMR(CD C1s)
; δ (ppm) O, 7 to 1.90 (my 8
H.

alkyl)=2.60-3.12(+In 20
．． Cl42S)-3,42(!I3H9CH
iO)-3,90-4.46(m-2H-CH20),
4.54(s, IH-CH)-7,10-
7,6Q (mt 4 Hearomatic-H) From the above results, it was confirmed that the compound obtained was .

Production Examples 3 to 26 The compounds listed in Table 1 were obtained in the same manner as in Production Example 1 or 2 above. Table tjS1 also shows the physical properties and spectroscopic data of the compounds. In addition, in the table, Me, Et, P
r and Bu mean methyl, ethyl, propyl and butyl groups, respectively.

Test Example 1 (Namihagni test) 2 parts by weight of the compound of the present invention was dissolved in 77 tons (98 parts by weight). This is diluted to a predetermined concentration using an aqueous solution containing 0.04% spreading agent (using Nihon Nohyaku's New 9 No), and the solution is made into iW.
Manufactured. The green beans planted in pots were inoculated with adult A. chinensis, and then the solution prepared as described above was sprayed until it dripped. The mortality rate was measured after 3 days and the results are shown in Table 2.

fJ% 2 Table A; Eikarol (comparative compound) Test Example 2 (Spodoptera trifoliata test) 2 parts by weight of a given test compound are dissolved in 77 tons (98 parts by weight). This is diluted to a predetermined concentration using an aqueous solution containing 0.04% spreading agent (Shinsuno). The prepared solvent was sprayed on the cabbage leaves until it dripped, and after air-drying, 3rd instar larvae of Spodoptera were inoculated, and the mortality rate was measured after 2 days.
The results are shown in Table 3.

Table 3 B: Rannate (comparative compound) Test Example 3 (Peach 7 aphid test 9) Peach 7 aphid adults were released in each pot, 10 adults per pot, on cabbage leaves in plastic pots planted in Harasu. 10 of each sample solution prepared to a predetermined concentration! II to 10-1/3
After 24 hours of spraying on the pots, the mortality rate was measured and the results are shown in Table 4.

Table 4 C; Toquotine (comparison compound) Test example 4 (resistant Namihagni test) Two parts by weight of the test compound were dissolved in 77 tons and 98 parts by weight.

This was diluted to a predetermined concentration using an aqueous solution containing 0.04% spreading agent (Shinsuno) to prepare a liquid preparation.

Inden plants planted in pots were inoculated with organic phosphorus agent-resistant two-adult insects, and then the solution prepared as described above was sprayed until the indens dripped. The mortality rate after 3 days was measured and the results are shown in Table 5.

Table 5 D; Tumetoate (comparison compound) (Hereafter Up)

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1, R^2 and R^3 represent lower alkyl groups. X^1 and X^2 are the same or different and represent a hydrogen atom or a halogen atom. Y represents an oxygen atom or a sulfur atom. ] A phosphate ester derivative represented by (2) An insecticide or acaricide containing the phosphoric acid ester derivative according to claim 1 as an active ingredient.