JPS6011683B2 - Composition for killing mites - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method that can be applied directly to mites (acarj), their eggs or the areas where mites breed, especially plants.
The present invention relates to a composition for exterminating mites including spider mites (m-ship).

A large number of phosphorus compounds have been proposed as effective tick exterminators.

For example, U.S. Pat. No. 2,754,242 describes the two-star spider mite
The use of alkyl bis(halophenyl)phosphinates to control However, many of these phosphorus compounds have relatively high concentrations (5
00p. p. m or more), it is ineffective without its presence and therefore cannot be practically used as a commercial insecticide. That is, the use of these known compounds is expensive, and therefore these compounds cannot be used in large quantities. The inventors have now discovered that certain tertiary bis(halophenyl)phosphines, phosphine oxides, and phosphine sulfides are known to have similar chemical structures, including the compounds described in the aforementioned U.S. Pat. No. 2,754,242. It has been found to be a highly effective acaricide that can be used at lower concentrations than when using other substances.

According to the invention, therefore, an inert solid or liquid carrier and an effective amount of the formula: or and a phosphorus compound represented by a halogen atom selected from the group consisting of bromine, bromine and iodine, and Z represents oxygen or sulfur. things are provided.

The acaricides used in the present invention are tertiary bis(p-halophenyl)phosphine, phosphine oxide and phosphine sulfide.

These compounds are effective against mites, including spider mites, at significantly lower concentrations than when using known compounds with similar chemical structures described in the chemical and patent literature, such as the bis(halophenyl)phosphinates mentioned above. can be exterminated. A comparison of the effects of the mite agent of the present invention and the relationship between the effects and the types of substituents on the phenyl group and the phosphorus atom are shown in the Examples below. The miticide of the present invention not only kills larvae and adults of mites, but also prevents the eggs of mites from aging.
Although many known acaricides are effective when applied to the leaves of plants where mites are breeding, the acaricide of the present invention is effective when the acaricide is applied to the soil around the plant roots and It is unique in that it can also be transferred through the body to the leaves, where it kills mites and their eggs. Many of the tertiary bis(halophenyl)phosphines of the present invention have been described in the chemical literature.

This phosphine is a suitable halophenyl magnesium,
It is conveniently prepared by reacting a halide with dichloroorganophosphine. Dichloroorganophosphines are commercially available and can be prepared using known methods, such as
For example, John Wileyand SOnS. , I.M. Published by G. M. It can also be produced according to the method described in "Biroko nophosphor female Compo skin ship" written by Kosolapoff. The bis(halophenyl)organophosphines obtained by the above method are easily converted to the corresponding phosphine oxides or phosphine sulfides by reacting the phosphine with hydrogen peroxide or elemental sulfur, respectively. . Alternatively, phosphine oxides can be prepared directly from the halides described above by reacting halofenylmagnesium halides with organophosphonic acid dichlorides of the appropriate formula.

Specific production examples for producing the phosphorus compound of the present invention are shown below. In the production examples, parts and percentages are by weight. Preparation Example 1 Bis(p-chlorophenyl)methylphosphine oxide A solution of 1.143 mol of p-chlorophenylmagnesium bromide dissolved in tetrahydrofuran 900
7 dissolved in 400 cc of tetrahydrofuran
3 (0.55 mol) of dimethylphosphonate.

Ride was added.

The addition was carried out for 2 hours, during which time the reaction mixture was stirred and 30
The temperature was maintained between -4 and 0.

After the addition was complete, the reaction mixture was heated at the boiling point for 1 hour and then, after cooling, was heated for 2 hours. Extraction was performed with form. The chloroform layer was dried using anhydrous magnesium sulfate and the solvent was removed under reduced pressure. The solid residue was recrystallized once from benzene to give 90% of a white solid with a melting point of 167-169 quarts. Analysis of this recrystallized product revealed that the phosphorus content was 10.9% and the chlorine content was 22.3%. The theoretical values for the phosphorus content and chlorine content of bis(p-chlorophenyl)methylphosphine oxide are 10.
9 and 24.9%. Its chemical structure was confirmed by nuclear magnetic resonance method. Production Example 2 0.789 mol of p-chlorophenylmagnesium bromide was added to a solution containing 699 (0.39 mol) of bis(p-chlorophenyl)chloromethylphosphine oxide in chloromethylphosphonic acid dichloride and 400 cc of tetrahydrofuran. 285 cc of a tetrahydrofuran solution was added.

The above tetrahydrofuran solution was added dropwise over a period of 2 hours.
During this time the reaction mixture was maintained at a temperature of 30°C. After the addition was complete, the reaction mixture was incubated for 2 hours while maintaining the temperature at 60°C. After cooling the reaction mixture to ambient temperature, 400 c.
C of water was added gradually followed by 1200 cc of methylene chloride. The organic layer was separated, dried using anhydrous magnesium sulfate, and the methylene chloride was removed under reduced pressure. The residual bamboo thus obtained was passed through neutral alumina using ethyl acetate as a dissolving agent. The eluent was removed and the residue was recrystallized once from benzene to a melting point of 114~
A white solid of 1170% was obtained over 90 minutes. The analytical values of this product were as follows. Chlorine content 32.8%, phosphorus content 9.89%. The theoretical chlorine and phosphorus contents of bis(p-chlorophenyl)chloromethylphosphine oxide are 33.3% and 9.70%, respectively. The nuclear magnetic resonance spectrum of the product obtained above was consistent with the desired structure. Production example 3 Bis(p-chlorophenyl)methylphosphine 12.6
A solution containing 96 ml (0.50 mol) of p-chloroprobenzene and 180 cc of tetrahydrofuran was slowly added to the magnesium shavings.

During the above additions, the reaction mixture was kept under a nitrogen atmosphere and the reaction mixture was heated at reflux temperature for 2 hours. After cooling the reaction mixture, a solution of methyldichlorophosphine (29.3 min, 0.25 mol) in 25 cc of tetrahydrofuran was slowly added. After the addition was complete, the reaction mixture was heated at reflux temperature for 2 hours. After cooling the reaction mixture, 500cc
The mixture was slowly poured into cold water and the pH was brought to 5 by adding aqueous hydrochloric acid. The aqueous solution thus obtained was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and the chloroform was removed under reduced pressure. The chloroform was removed to obtain a residue of 649, which was then distilled to 0.
A fraction with a boiling point of 155-16,000 at 5-side Hg was obtained. The distillate converted to a white solid upon cooling. 34 mol of solid product was obtained and its analysis was as follows: Preparation Example 4 Bis(p-chlorophenyl)propylphosphine sulfide 0.2 mol of propyldichlorophosphine and 0.4 mol of propyldichlorophosphine
Bis(p-chlorphenyl)propylphosphine was produced by reacting mol of p-chlorophenylmagnesium furomide.

The product was isolated by extraction with chloroform and distillation as described above. Crabs with a boiling point of 160 to 16yo at 200 g were collected.

The analytical value was consistent with the theoretical value for bis(p-chlorphenyl)propylphosphine. The phosphine obtained above (
0.061 mol) was dissolved in 150 cc of benzene, and 2.1 hours (0.065 mol) of sulfur was added.

The reaction mixture was allowed to stand for 1 hour and the solvent was removed under reduced pressure. The residue was recrystallized once from diethyl ether to give a solid product, melting point 102-1070. The phosphorus and chlorine and sulfur contents of this product are:
They were 9.21%, 22.2% and 8.33%, respectively. The theoretical values of phosphorus content, chlorine content and sulfur content of bis(p-chlorophenyl)propylphosphine sulfide are 9.42%, 21.6% and 9.73%, respectively. When exterminating mites, especially spider mites, the phosphiso, phosphine oxide, and phosphine sulfide of the present invention can be applied directly to the mites, to plants where mites are breeding, or to plants where mites are likely to breed or Can be applied to other media.

Because the acaricides of the invention are characterized by long residual activity and low toxicity, these compounds can be applied to plants several days, and in some cases weeks, before mites appear on the plants. I can do it. The phosphorus compounds of the invention may be applied to plants in the form of liquid sprays, solid powders or wettable powders according to conventional methods.

Compositions suitable for spraying typically contain 1% of the active toxic ingredient.
Prepared by diluting liquid concentrates or wettable powders containing 0-90%.

To avoid the expense of transporting formulations containing large amounts of inert diluent, dilution of the composition is usually carried out at the site of spraying. The concentration of toxic components in sprays that should be applied to plants outdoors is between 10 and 100%.
p. m preferably 100 to 50 sails. p. It is m. Solid powder compositions, which are usually applied in relatively narrow bands, contain from 1 to 5% by weight of toxic components, preferably from 1 to 1% by weight.

The concentration of toxic ingredients required for a given formulation depends on the method of application,
That is, it will vary depending on a number of parameters, including the method of application, whether applied on the ground or sprayed from an airplane, the activity of the particular toxic ingredient against mites, and the weather in the area being treated.

In preparing powder compositions or wettable powders,
The miticide of the present invention can be applied to a number of commonly used finely divided solid carriers such as fuller, attapulgite, bentonite, pyrophyllite, vermiculite, diatomite, talc, dung, gypsum, and wood. Can be mixed into powder etc.

The finely divided carrier can be ground or mixed with the acaricide or moistened with a dispersion of the toxic component in a volatile liquid. Depending on the concentration of the ingredients, these compositions can be used as concentrates with subsequent addition of solid carriers to obtain formulations containing the desired amount of active ingredient. Also,
Such concentrated powder compositions may also be intimately mixed with surface-active dispersants such as ionic or non-ionic emulsifiers or dispersants to obtain fogging concentrates. Such concentrates can be readily dispersed in a liquid carrier to form spray compositions or liquid formulations containing any desired amount of the active ingredient. The type of surfactant and the amount used is determined by the surfactant's ability to disperse the concentrate in the liquid carrier and form the desired liquid composition. Suitable liquid carriers are water, methanol, ethanol, isof. Ro/gunol, methyl ethyl ketone, acetone, methylene dichloride,
Includes chlorobenzene, toluene, xylene and petroleum distillates. Most petroleum distillates have a boiling point of 205°C under atmospheric pressure and a flash point of about 30°C.
It is preferable that it is equal to or higher than qo. Alternatively, the acaricide is mixed with a suitable water-immiscible solvent and a surface-active dispersant to form an emulsifiable concentrate, which is further diluted with water and oil in the form of an oil-in-water emulsion. A sprayable composition can be formed. In such compositions, the carrier consists of an aqueous emulsion, ie, a water-immiscible solvent, an emulsifier, and water. Preferred dispersants for use in these compositions are oleaginous fractions and condensation products of alkylene oxides with phenols and organic or inorganic acids, polyoxyethylene derivatives of sorbitan esters, alkylaryl sulfonates. complex, etheralcohol rust
ols), mahogany soap, etc. Suitable organic liquids for use in the above compositions include petroleum distillates, hexanols, liquid chlorinated hydrocarbons and synthetic organic oils. The amount of surface-active dispersant used in liquid dispersions and aqueous emulsions is usually from about 1 to about 2 percent by weight of the total weight of the dispersant and active ingredient. The following examples demonstrate the effectiveness of the phosphorus compounds of the present invention as acaricides.

The formulation was prepared by the following method: the test compound was dissolved in a mixture of acetone and a liquid alkyl-aryl polyether alcohol type surfactant (Triton x-155, Triton is a registered trademark). The resulting composition was mixed with 10% acetone in the final formulation. p
．． m of surfactant by dilution using a water-acetone mixture. Two-star spider mite (Tetranychu)
The activity of a given compound as a contact acaricide against S. suicae) was investigated by infesting the leaves of Sievalimabean plants with adults and larvae of spider mites.

20 hours after infesting leaves with mites, two test compounds were applied.
0 blood. p. The leaves were either soaked in the formulation containing M or the leaves were soaked in the formulation. The test compound is a systemic acaricid and ovicide.
When investigating the effect as an andovicide, the active compound was used in combination with 52 others. p. Formulation 21c containing m
c was injected into the rocks around the plants where mites were infested.
Nine to 12 days after application of the formulation, the hollyhocks of all plants were examined microscopically to determine the number of dead mites and their eggs.

The following compounds have a rating of 20 in that they kill at least 70% of adult mites, larvae and/or eggs. p
．． It was confirmed that this is an effective contact-type miticide at a concentration of 1.0 m.

Bis(p-chlorphenyl)ethylphosphine oxide, bis(p-chlorphenyl)ethylphosphine, bis(p-chlorphenyl)methylphosphine oxide, bis(p-chlorphenyl)chloromethylphosphine oxide, bis(p-chlorphenyl)propylphosphine oxide, bis(p-chlorophenyl)methylphosphine sulfide, bis(p-chlorphenyl)methylphosphine, bis(p-chlorophenyl)propylphosphine, bis(p-bromphenyl)methylphosphine oxide, bis(p-fluor (orphenyl) methylphosphine oxide The following compound having a chemical structure similar to the acaricide of the present invention is 20 blood. p. It was not effective in killing spider mites and their eggs even at a concentration of 3.
Less than 0% of spider mites and their eggs were killed.

diphenylmethylphosphine oxide, diphenylchloromethylphosphine oxide, bis(p
-chlorphenyl)trichloromethylphosphine oxide, bis(m-chlorphenyl)methylphosphine oxide, tris(p-chlorophenyl)phosphine oxide, bis(p-chloro-m-nitrophenyl)methylphosphine oxide, bis(p-tolyl)methyl Phosphine oxide, bis(mop-dichlorophenyl)methylphosphine oxide, pis(p-chlorophenyl)hydroxymethylphosphine oxide, bis(p-chloro-o-methylphenyl)methylphosphine oxide, the following two most effective miticides: agent, i.e. bis(p
- Chlorphenyl) methylphosphine oxide ■ and bis(p-chlorophenyl) chloromethylphosphine oxide legs, the lowest concentrations at which these compounds are effective were further investigated, and the results of tests on these compounds and those used commercially. N′(
The test results for 4-chloro-o-tolyl)N.N-dimethylformamidine (Galecron: registered trademark) are shown in the table below.

In this test, leaves were examined 12 days after misting the test formulation. Compound Minato PPM Hemorrhoid Mass production rate Minato A 400 100 525100 68
545 25 53 - B 400 100 605 100 90 670 Galecron ■ 25 94 - (Control example) 400 65 135100 0
-25 0 - Bis(p-chlorophenyl)chloromethylphosphine oxide at 10 liters. p. The formulation containing M was injected into the soil around the roots of sea varietal beans that were infested with spider mites and their eggs.

Claims (1)

[Claims] 1 Inert solid or liquid carrier and effective amount formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is the number of carbon atoms 1 to 3 alkyl groups and chloroalkyl groups, X represents a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine, and Z represents oxygen or sulfur) A composition for exterminating mites and their eggs, characterized in that the composition consists of: 2 liquid or solid diluent and 1 to about 500 p.p. p. The composition according to claim 1, comprising a phosphorus compound of m. 3. The composition according to claim 1, containing a phosphorus compound in which X is chlorine. 4. The composition according to claim 1, which contains a phosphorus compound in which R is a methyl group, a chloromethyl group, an ethyl group, or a propyl group.