JPS5936687A - 1,3-dithian, its preparation, insecticide and acaricide containing it as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R is lower alkyl, or aryl; R1 is lower alkyl; X and Y are H, or lower alkyl, X and Y are linked to form tetramethylene, or pentamethylene; Z is O, or S). EXAMPLE:O-Ethyl S-n-propyl S-(2,2-dimethyl-1,3-dithian-5-yl)dithiophosphoric ester. USE:An insecticide and an acaricide. PROCESS:A 5-halo-1,3-dithian(e.g., 5-chloro-2,2-dimethyl-1,3-dithian, etc.) shown by the formula II (Hal is halogen) is reacted with a dithiophosphate (e.g., potassium S-n-propyl O-ethylphosphorodithiophosphate, etc.) shown by the formula III (M is alkali metal) in a solvent such as acetone, etc. preferably at 20-50 deg.C for 1- 20hr.

Description

Detailed Description of the Invention The present invention is based on the general formula [1] (3) [wherein RiJ represents a lower alkyl group or an allyl group, R□ represents a lower alkyl group, X and Y are the same or different, Hydrogen atom, lower alkyl group or X and Y
Tetramethylene group also works with and represents a pentamethylene group, and Z is l! #Represents an elementary atom or a sulfur atom. ], 3-dithianes (hereinafter referred to as compounds of the present invention), their production methods, and insecticides and acaricides containing them as active ingredients.

The metal compound of the present invention having the general formula CI) in which 2 is an oxygen atom,
General formula (II) [wherein X and Y are the same or different, hydrogen atom,
A lower alkyl group or X and Y together represent a tetramethylene group or a pentamethylene group, and Ha-6 represents a halogen atom. [In the formula, M represents an alkali metal atom, R and R1
is as described above. ] The dithiophosphate represented by is mixed with a solvent that does not impair the progress of the reaction, such as ketones such as acetone, methyl ethyl ketone, and methyl butyl ketone, hydrocarbons such as n-hexane, benzene, and toluene, diethyl ether, tetrahydrofuran, In ethers such as dioxane, halogenated hydrocarbons such as chloroform, methylene chloride, or solvents such as acetonitrile, at θ~0°C,
Preferably, it can be produced by reacting for about 7 hours to 2θ hours at 7 to 2θ°C.

The compound of the present invention in which 2 is a sulfur atom in the general formula (1) is different from the compound of the present invention in which 2 is an oxygen atom in the general formula [1] and //2
This or a small excess of the general formula III) [wherein R2 represents a lower alkyl group, a thiophene group, a phenyl group, or a phenyl group substituted with a halogen atom or a lower alkoxyl group] / , 3-dithia-J, lI-diphosphetane-3.Gudisulfides and solvents such as hydrocarbons such as n-hexane, benzene, toluene, and xylene, diethyl ether, tetrahydrofuran, and dioxane, etc., which inhibit the progress of the reaction. In solvents such as ether, chloroform, methylene chloride, etc.
It can be produced by reacting for a while.

Next, production examples of the compounds of the present invention will be shown.

Production Example/Production of Compound (3) of the Present Invention j-chloro-,2,,2-dimethyl-/,3-dithiane/, 2y (0.01 mol) and S-n-propyl〇-ethylphosphoro Potassium dithiophosphate salt -, 5iy (
0,071 mol) was dissolved in 60 liters of acetone and stirred and refluxed for 3 hours. The reaction mixture was diluted with toluene/θθml and washed with water. After drying the toluene layer with anhydrous dilute acidic soda, it was concentrated under reduced pressure to leave a light brown oily residue.3. θθ was obtained. This product was subjected to silica gel column chromatography to obtain 3-dithian-j-yl)dithiophosphoric acid ester (3.3%). (F rate Otsu 9%) (as C11H230□ps4) Analysis value 38. D / Otsu, Otsu 3 Formulation Example - Production of the compound of the present invention (/S) 0-ethyl S-propyl S-(9,2-dimethyl-/
, 3-dithian-8-yl) phosphorodithiolate/,
73f (0°068 mol), 2, goubis(termethoxyphenyl)-/, 3-dithia-, 2, goudiphosphethane-, terdisulfide/. θy(θ, θθ, 2S
mol) and toluene 10θml/hour ntN
The mixture was stirred and refluxed. The reaction mixture was condensed under reduced pressure, and the resulting yellow oily residue was subjected to silica gel column chromatography [where X and Y are as described above]. It can be produced by halogenating the j-hydroxy-/,3-dithiane represented by the formula with a halogenating agent such as thionyl chloride, phosphorus oxychloride, or hydrogen bromide.

j-hydroxy-/ represented by the general formula [■].

A production example of 3-dithiane is shown below as a reference example.

Reference fAJ/ (,2-ethyl-j-hydroxy-7
, 3-dithiane production) 11 ethyl/, 3-dithiane-8-onet, 4tgy
(0.09 mol) was dissolved in 60 ml of methanol, and 6 g of thionyl chloride (θ, θ-1 mol) was added to the solution at 2θ~
The mixture was added in 7 portions while stirring at 3θ°C.

After addition, stir at room temperature for 7 hours to add a chloroform layer θ to the reaction solution.
θlI/ was added and washed with water. The chloroform layer dried over anhydrous sodium sulfate was concentrated under reduced pressure to give a pale yellow oil, nl,
7.3A10 2-ethyl-4-hydroxy/,
3-dithian j, θ/c/9, the Gorgitian class is -
Shown incl.

Chapter - Table general formula - An example of the production of dithianes is shown.

Reference Example 2 (Production method of S-chloro-2-ethyl-/,3-dithiane) 2-ethyl-3-hydroxy-7,3-dithiane y,
sy (0,027 mol) in chloroform 70 ml Il
C bath%, thionyl chloride 6.53F (0,0,3
8 mol)≠→Mite Park←≠≠ was added to room temperature l-1-rl-.

Nozo response mixture? After stirring I for 6 hours at room temperature, it was reduced under reduced pressure.
An oily residue of BIT color was obtained. This product was heated in n-hexane and subjected to decolorization treatment to reduce JIE and shrink to form a brown oily substance n D /, , 5! ; 3.2 gy of 5-chloro-ethyl/3-dithiane of gg was obtained.

The third layer shows j-halo/3-dithiane which can be produced by such a method.

(/3) general formula Monodithians j-hydroxy-/ represented by general formula (V).

General formula (Vl)b, which is the starting ah of 3-dithianes, [wherein, X and Y are as described above, and B represents a hydrogen atom or an ethoxycarbonyl group. ] S-keto/, 3-dithianes and V-ethoxycarbonyl-j-keto/, 3-dithianes are shown in Table 1.

Table q Thianes and q-ethoxycarbonyl=S-keto/,3-dithianes The compounds of the present invention can be mixed with solid carriers, liquid carriers, gaseous carriers, surfactants, and other formulation auxiliaries to form emulsions. It can be formulated into powders, granules, irrigation agents, oils, aerosols, etc., and used as insecticides and acaricides. Various of these preparations contain 0% by weight of the compound of the present invention as an active ingredient.
, 1 to 99%, preferably Ko to O to O.

Solid phase body-21. So, clays (e.g. kaolin, bentonite, acid clay, pyrophyllite, sericite)
, talc, and other inorganic minerals (such as hydrated silica, pumice, diatomaceous earth, sulfur powder, and activated carbon).

Liquid carriers include alcohols (e.g., methyl alcohol, ethyl alcohol), ketones (e.g., acetone, methyl ethyl ketone), ethers (e.g., diethyl ether, dioxane, methyl cellosolve, tetrahydrofuran), aromatic compounds. Hydrogens (e.g. benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. kerosene, kerosene), esters, nitriles, acid amides (e.g. methylformamide, dimethylacetamide), halogenated hydrocarbons kind (
Examples include dichloroethane, trichloroethylene, and carbon tetrachloride).

Gaseous carriers include chlorofluorocarbon gas, LPG, etc.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, and polyhydric alcohol esters. ) Formulation auxiliaries, such as fixing agents and dispersing agents, include casein, gelatin, starch, CMC.
(carboxymethyl cellulose), gum arabic, alginic acid, calcium or sodium lignin sulfonate, bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc. Stabilizers include pAp (isopropyl acid phosphate), TCP (tricresyl phosphate), etc. ),
Examples include tall oil, epoxidized oil, various surfactants, and various fatty acids or their esters.

Examples of formulations are shown below. The compounds of the present invention are shown by compound numbers in Table 7, and parts are parts by weight.

Formulation Example: 20 parts each of the compounds (1) to (/7) of the present invention, and 20 parts each of an emulsifier (a mixture of polyoxyethylene styrylphenyl ether, a polymer of polyoxyethylene styrylphenyl ether, and an alkylaryl sulfonate). , and 1210 parts of xylene were added and mixed with thorough stirring to obtain 20 emulsions of each.

Formulation Example 20 parts of each of the compounds (1) to (/7) of the present invention were thoroughly mixed with 5 parts of an emulsifier (sodium lauryl sulfate).1. ? 0
Add 75 seconds of 0-mesh diatomaceous earth and stir and mix thoroughly in a crusher to obtain each 2.0-chi hydrating powder.

Formulation Example 3 Dissolve 3 parts each of the compounds (1) to (/7) of the present invention in an appropriate amount of acetone, add 27 parts of 300 Metsstarck,
After thorough stirring and mixing in a mixing vessel, the acetone is removed by evaporation to obtain each of the three-chip powders.

Formulation Examples Compounds of the present invention (1) to (17) each have xyt in the o and i parts.
Add 121 parts of 10 ivy and dissolve in white kerosene to make a total of 10 parts to obtain each oil agent.

Formulation Example S 0 parts of the compound (3) of the present invention, 0 parts of an emulsifier (polyoxyethylene styrylphenyl ether, a mixture of polyoxyethylene styrylphenyl ether, a polymer of polyoxyethylene styrylphenyl ether, and an alkylaryl sulfonate), 0 parts of xy, 1 fufu
% emulsion is obtained by stirring and mixing them well.

A formulation example is the compound of the present invention (1) O, 2 parts, tetramethrin 0,
1 part, xylene 7 parts, deodorized kerosene 7.7 parts Total mixed solution % L
After filling the aerosol container and completely destroying the valve part, propellant (liquefied petroleum gas) gs is passed through the valve part.
An aerosol can be obtained by filling a portion under pressure.

Formulation Example 7 Add 5 parts of each of the compounds (1) and (S) of the present invention, 5 parts of lignin sulfonate, 90 parts of clay, and mix with sufficient stirring. Next, the mixture is mixed with a suitable spoon (9), mixed with stirring, and prepared using a granulator, and then dried with ventilation to obtain each granule.

The compounds of the present invention can be used to protect against lepidoptera such as planthoppers, leafhoppers, stink bugs, and cutworms that damage vegetables, fruit trees, wood, etc. in rice paddies, etc.
Orthoptera insects such as grasshoppers, and spider mites,
Pathogens such as insects, flies, cockroaches, ticks,
It is useful as an active ingredient in insecticides and acaricides against nits, lice, and grain storage pests.

When the compound-1 of the present invention is applied to paddy fields, fields, orchards, forests, etc., the application rate is 100g/ha to 1000g/ha.
ha is appropriate. In addition, when applying diluted emulsions and wettable powders with water, the application concentration is / OpI) m ~ 10
00 ppm.

Next, test examples will show that the compounds of the present invention are useful as active ingredients for insecticides and acaricides. The compound of the present invention is the first
Indicated by compound number in the table.

(20) Test Example 1 A filter paper tube of the same size was placed at the bottom of a polyethylene cup with a diameter of 3.5 mm. Formulation Example / A yoo-fold dilution of the emulsion of the compound of the present invention obtained in water (4oo ppm@this);
Drop onto 7m'tP paper and use sucrose as bait. OW'f
10 adult female houseflies were released into the container, the lid was closed, and after q and r hours, the mortality rate was determined by checking whether they were alive or dead (repeat).

The results are shown in Table S.

Table j Test Example - Formulation Example / Adding the emulsion of the compound of the present invention obtained by
2 ml of the 1100 times diluted solution was soaked into /&g of artificial food for Spodoptera spp. and placed in a polyethylene cup with a diameter of //-. I released 10 3rd instar Spodoptera larvae into it, and (, 2,?) *-: Almost no damage was observed.

If 9 days after sowing, potted green beans (initial leaf stage) are infested with 70~/Ai females of P. chinensis per leaf and left in a thermostatic chamber of Core C for a week, various Many stage spider mites have bred. At this time, a poo-fold dilution of the emulsion of the compound of the present invention and the control drug obtained in Formulation Example 1 with water (equivalent to j00 ppm) was sprayed on a turntable at 10-/pot, and spider mites of each plant were sprayed on a turntable. The damage was investigated. Result total 7th
Shown in the table.

(,2 da) +: Slight damage is observed.

廿: The same damage as in the untreated area is observed.

※※: Diluted with commercially available emulsion f jooppm of dicofol and used.

(Children)

Claims (1)

[Claims] (1) General formula [wherein R represents a lower alkyl group or an allyl group,
R1 represents a lower alkyl group, X and Y are the same or different, and represent a hydrogen atom, a lower alkyl group, or a tetramethylene group or a pentamethylene group together with X and Y, and 2 represents a #raw mackerel or a sulfur atom. . ] 7,3-dithian cyst shown. (Incorporated) General Formula [In the formula, X and Y are the same or different hydrogen atoms, lower alkyl groups, or X and Y together represent a tetramethylene group or a pentamethylene group, and Ha-13 represents a halogen atom. ] j-halo/. 3-dithianes and the general formula [wherein R represents a lower alkyl group or an allyl group,
Ro represents a lower alkyl group, and M represents an alkali metal atom. [In the formula, R+ R1* X and Y are as described above.] ] A method for producing /, 3-dithianes. (萄 General formula [wherein R represents a lower alkyl group or an allyl group,
Ro represents a lower alkyl group, and X and Y are the same or different and represent a hydrogen atom, a lower alkyl group, or X and Y together represent a tetramethylene group or a pentamethylene group. ] The 7,3-dithianes shown and the general formula [wherein R2 represents a lower alkyl group, a thiophene group, a phenyl group, a halogen atom, or a phenyl group substituted with a 1-class alkoxyl group. [In the formula, R, R1, X and Y are as described above. ] A method for producing /, 3-dithianes. (9) General formula [wherein R represents a lower furkyl group or an allyl group,
R□ represents a lower alkyl group, X and Y are the same or different and represent a hydrogen atom, a lower alkyl group, or X and Y together represent a tetramethylene group or a pentamethylene group, and 2 represents an oxygen atom or a sulfur atom. ] An insecticide and acaricide characterized by containing 3-dithiane as an active ingredient.