JPS5926603B2 - Satsukiyu Satsudanizai - Google Patents

Description

Detailed Description of the Invention] (In the formula, R^1 and R^2 represent a halogen atom or a lower alkyl group, R^3 and R^4 represent a halogen atom, and R^5 represents a hydrogen atom or a cyano group. ) is the active ingredient.

In the present specification, the term "halogen" means fluorine, chlorine or bromine, and the term "lower alkyl group" means an alkyl group containing up to 4 carbon atoms. This invention relates to an insecticide and acaricide containing a novel ester compound as an active ingredient.

The insecticide and acaricide according to the present invention has the following formula I H(R^5)ρ (1) 0CH=CR^3R^4 shall be.

Preferred compounds of formula I are those in which R^1 and R^2 are both methyl, chlorine or bromine; particularly preferred compounds are those in which R^1, R^2, R^3 and R^4 are all salts.
It is an elemental compound.

It will be readily understood that compounds of Formula I are described without regard to their stereochemistry.

That is, the above formula does not distinguish between cis and trans geometric isomers, which are thought to be based on the substitution around the cyclopropane ring, nor does it distinguish between the various stereoisomers that may exist. However, all such geometric isomers and optical stereoisomers are included within the scope of the present invention. Accordingly, "compound" as used herein for esters of formula 1 describes isolated individual isomers and mixtures of isomers thereof, e.g. racemates, diastereomeric mixtures.Formula 1 Representative examples of compounds are shown below.

3(2,2-dichlorovinyloxy)penzyl(±
) cis/trans-chrysanthemate (hereinafter referred to as compound 1), 3(2,2-dichlorovinyloxy)benzyl (±)cis/trans-2(2,2-dichlorovinyl)3,3-dimethyl cyclopropanecarboxy rate (hereinafter referred to as compound 2), 3 (2,2-dichloro
vinyloxy)benzyl(±)cis-2(2,2-dichlorovinyl)3,3-dimethyl cyclopropane carboxylate (hereinafter referred to as compound 3), 3(2.
2-dichlorovinyloxy)benzyl(±)trans-2(2,2-dichlorovinyl)-3,3-dimethyl cyclopropanecarboxylate (hereinafter compound 4
), (±)α-cyano-3(2,2-dichloro
vinyl oxy)benzyl(±)cis/trans-2(
2,2-dichlorovinyl)3,3-dimethylcyclo
Propane carboxylate (hereinafter referred to as compound 5),
(±)α-cyano-3(2,2-dichlorovinyloxy)benzyl(10)cis-2(2,2dichlorovinyl)3,3-dimethyl cyclopropane carboxylate, (-)α-cyano-3(2・2-dichlorovinyloxy)benzyl(±)cis-2(2.2dichloro
vinyl) 3,3-dimethyl cyclopropane, carboxylate, 3(2,2-dichlorovinyloxy)benzyl(±)cis/trans-2(2,2-dibromo
vinyl) 3,3-dimethyl cyclopropane carboxylate, 3(2,2-dibromo vinyloxy)
Benzyl (±) cis/trans-chrysanthemate, 3
(2,2-dibromo vinyloxy)benzyl (±)
cis/trans-2(2,2-dichlorovinyl)3.
3-dimethyl cyclopropane carboxylate,
(±)α-cyano-3(2,2-dichlorovinyloxy)benzyl (±)cis/trans chrysanthemate, (±)α-cyano-3(2,2-dichlorovinyloxy)benzyl
oxy)benzyl (±) cis/trans 2(2,2-dibromo vinyl)3,3-dimethylcyclopropane
Carboxylates, compounds of formula 1, can be prepared in several different ways.

For example, a compound of the formula: or a metal salt thereof: (In the above formula, X represents... rogen, preferably a chlorine or bromine atom, and R1, R2, R3, R4 and R5 have the above meanings) It can be produced by reacting with a compound of

Alternatively, a compound of the formula: (wherein Y represents a halogen, preferably a chlorine atom)
T) 1T) 2D3D4] 4A quality P5l temple aisome ρn)→
It can also be produced by reacting with a compound (having a similar appearance).

Alternatively, the ester of the formula may be prepared by preparing a mixture of a simple ester of the acid of the formula (e.g. a lower alkyl ester such as a methyl or ethyl ester) and an alcohol of the formula in a solvent or diluent, preferably a base (e.g.
It can also be obtained by a transesterification reaction method by heating in the presence of lower alkoxides such as sodium methoxide or ethoxide.

Although these methods can in some cases be carried out by heating the reactants together in the absence of a diluent and/or base, the presence of a solvent or diluent and a base is preferred.

Suitable solvents are, for example, aliphatic ketones (e.g. acetone),
Non-hydroxyl materials such as dimethylformamide, dimethylsulfoxide, sulfolane, acetonitrile and tetrahydrofuran.

Particularly preferred are aliphatic ketones such as acetone.
In some cases hydroxylated solvents, e.g. methanol
and ethanol can also be used as long as the presence of hydroxyl groups does not prevent the reaction from proceeding. Suitable bases are sodium hydride (unsuitable if hydroxylated solvents or diluents are used), alkali metal carbonates such as potassium carbonate, and alkali metal hydroxides such as potassium hydroxide. The reaction temperature depends on the choice of reactants, solvent or diluent and base. When using acetone and potassium carbonate, the reaction generally occurs at room temperature. Higher temperatures up to 100° C. can be used when other bases are used. A typical method consists of dissolving or suspending the reactants in a solvent in the presence of a base. After the reaction has been carried out for a period of time, the product can be isolated by filtration to remove insoluble material and evaporation of the sap. The product can then be purified by vacuum distillation or by suitable chromatographic methods. If it is desired to produce a single geometric isomer of an ester of formula 1, this can be done by using pure cis or trans acids or derivatives thereof of formula or, or by using cis/trans mixtures thereof. This can be achieved by separating the desired isomer from a mixture of esters obtained by, for example, chromatography. The compounds of formula and formula v used for the preparation of esters of formula 1 are themselves novel compounds and can be prepared by the method described below.

For example, a compound in which R5 is hydrogen is a compound of the formula: (wherein Z is halogen, preferably the same as R3 and R4...
It can be prepared by electrochemical reductive dehydrohalogenation of a compound of the formula (which is a halogen) to give a compound of the formula: and then halogenation of the methyl group of the formula to produce the desired compound of the formula.

Enjoy the ceremony - 8Pr9, Chemiel3l6(
2), [Fold-8 Ichimakori? σ▼? Analogously to the method described, it can be prepared by reacting anhydrous chloral or promal with m-cresol in the presence of an acyl halide.

The aforementioned electrochemical reduction method uses an organic solvent, e.g. a lower alcohol such as methanol or ethanol, a cyclic ether such as dioxane or tetrahydrofuran, an aliphatic ketone such as acetone or cyclohexanone, or these solvents and water or a hydrous inorganic strong acid, e.g. It can be carried out in a mixture with sulfuric acid, hydrochloric acid or phosphoric acid.

This reduction is believed to occur primarily at cathodes with high hydrogen overpotentials, such as mercury, lead amalgam or lead cathodes.

The reduction can be conveniently carried out in an electrolytic cell equipped with a ceramic or glass frit diaphragm, a stirrer, a working electrode and a reference electrode. This process can be adapted to produce the desired product continuously using a solvent system from which the reaction product can be extracted, such as methylene chloride. Metal reductive dehydrohalogenation can be carried out using zinc powder and a suitable reducing medium such as acetic acid.

The halogenation of compounds of formula includes positive halogen sources, e.g.
This can be conveniently carried out in the presence of an N-haloimide such as bromosuccinimide or N-chlorosuccinimide.

Compounds of formula v in which R5 is hydrogen can be prepared from corresponding compounds of formula, for example by treatment with an alkali metal hydroxide, or alternatively by converting such compounds into a corresponding tonrate (
p-toluene sulfonate) and hydrolysis of this tonerate. R
Compounds of formula in which 5 is hydrogen can be prepared by treating the compound with a source of cyanide ions, e.g. an alkali metal cyanide such as sodium cyanide, and then further halogenating the resulting compound of formula R' can be converted into the corresponding compound where is a cyano group.

The reaction with cyanide may be conveniently carried out in a polar aprotic solvent such as dimethylformamide at elevated temperatures in the range of 50-100°C. The halogenation step may be conveniently carried out in a manner analogous to the preparation of compounds of formula where R° is hydrogen. Compounds of formula V in which R5 is cyano may be prepared from compounds of formula V in which R5 is cyano by methods analogous to those described for the corresponding compounds in which R° is hydrogen. However, a preferred method for preparing compounds of formula v in which R5 is a cyano group is to selectively oxidize a compound of formula to obtain a compound of formula and then reacting this compound with hydrogen cyanide or preferably is based on an alternative process consisting of converting the bisulfate compound to the cyanohydrin by reaction with cyanide ions (eg sodium cyanide).

An alternative method for preparing compounds of formula involves oxidizing a compound of formula v, where R5 is hydrogen, using aluminum isopropoxide and acetone under Otzpenauer reaction conditions.

Compounds of formulas, v, and are useful as intermediates for the preparation of compounds of formula I of the present invention, and therefore, in accordance with the present invention, processes for the preparation of these compounds are also provided.

As noted above, the compounds of Formula I are useful as insecticides and acaricides, which may most conveniently be formulated and used in the form of compositions.

The compounds of formula I according to the invention can therefore be used as insecticidal and acaricidal compositions in combination with agriculturally and horticulturally acceptable diluents or carrier substances. In preparing this composition, the active ingredient is a compound of formula I as defined above, in particular 1 to 1 as defined above.
selected from 5 compounds.

Such compositions are used in the agricultural and horticultural fields, and in each case the form of the composition used will depend on the particular application to be used.

The compositions may be in the form of granules or powders consisting of the active ingredient and a solid diluent or carrier.

The composition may also be a liquid formulation, usually an aqueous dispersion or emulsion, for use as a dip or spray. Compositions to be used as propellants may also be in the form of an aerosol, in which the liquid formulation is contained in a container under pressure in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoromethane.

For use in agriculture and horticulture, the active ingredient
Aqueous formulations containing from 0.001% to 1.0% by weight are used.

In addition to the compounds of formula I, the insecticidal and acaricidal compositions of the invention may, if desired, also contain at least one biologically active ingredient, such as an insecticide or a fungicide.

This composition also includes Pyrethroid (PyrethrOid).
It may contain synergists of the type useful for synergizing the activity of type s) insecticides.

When using the insecticide and acaricide of the present invention to control pests, it can be used in a variety of ways.

For example, the pest itself or the place where the pest is occurring, that is, the habitat of the pest, is treated with the insecticide and acaricide of the present invention. By treating the plant or its seeds, corms, scales, tubers, rhizomes or other growing parts of the plant or the medium on which the plant is growing with the insecticide and acaricide of the present invention, It can reduce damage to the site by pests.

The insecticide and acaricide of the present invention is toxic to various insects and other spineless pests such as: red spider mite (Tetranyhuste1arius), black spider mite (Aphis fabae), green spider mite (Tetranyhuste1arius); Oil bug (Megouravic)
eae)] yellow fever vector mosquito [Aedes aegyptii (Ae
desaeqypti)] Gogglefish (Blatel Germanica); House fly (Musca domestica)
)] Pierisbrassicae (Pierisbrassicae) Diamond-crested moth (Plutella macripenis)
acu11pennis)] Next, production examples of the active compound of the present invention and its raw material compound will be shown.

Manufacturing example 1 This example describes the production of Compound Black 1.

dl monochrylic acid (cis:trans ratio 50:50:132y)
, 3(2,2-dichlorovinyloxy)benzyl bromide (2.O7), anhydrous potassium carbonate (1.07) and acetone (25 mO) at room temperature (approximately 18-22°C).
) for 18 hours. The insoluble parts were removed by filtration and the solution was evaporated under reduced pressure to give a residual oil which was dissolved in chloroform and washed with saturated sodium bicarbonate solution and then with water. After drying the chloroform solution over anhydrous magnesium sulfate, the solvent was removed under reduced pressure and the residual oil was dissolved in chloroform (10% v/v).
and petroleum ether (boiling range 40-60°C, 90v
/v %) mixture was processed by preparative thin layer chromatography (TLC) as eluent. The desired product was identified by infrared absorption and nuclear magnetic resonance spectroscopy. Production Example 2 This example describes the production of Compound Black 2.

dl-3(2,2-dichlorovinyl)2,2-dimethylcyclopropanecarboxylic acid (trans:cis ratio 80:2
A mixture of 0,0.75y), 3(2,2-dichlorovinyloxy)benzyl bromide (1.07), anhydrous potassium carbonate (0.57) and acetone (25mO) was stirred at room temperature for 18 hours. Same method as used in Preparation Example 1, but using diethyl ether instead of chloroform as solvent and 20 v/v as TLC eluent.
% chloroform and 80 v/v % petroleum ether (boiling range 40-606C). Manufacturing example
3 This example is (±) α-cyano-3(2,2-dichlorovinyloxy)benzyl(10) cis/trans 2(2,2-
dichlorovinyl) 3,3-dimethylcyclopropane carboxylate (compound black 5, i.e. R in formula 1)
1, R2, R3, and R4 are chlorine, and R5 is a cyano group).

2(2,2-dichlorovinyl)3,3-dimethylcyclopropanecarboxylic acid (cis:trans ratio 40:60:1
．． 29y) was added to thionyl chloride (5.0y) and the mixture was heated at 100° C. (steam bath) for 1 hour, after which excess thionyl chloride was removed by azeotropic distillation with toluene.

The acid chloride thus obtained as a residue was mixed with n-hexane (
3, oml) and the resulting solution was dissolved in a solution of 3(2,2-dichlorovinyloxy)benzaldehyde cyanohydrin (1.5 V) in a mixture of n-hexane (7.0 mO and pyridine (0.5 mO)). was added dropwise at room temperature. After the addition was complete, the mixture was stirred at room temperature for 2 hours. The solid precipitate that formed was then removed by filtration and the solution was washed with water (10 ml x 2) and poured over anhydrous magnesium sulfate. and concentrated by evaporating the solvent under reduced pressure. The residual oil was eluted with a mixture of chloroform (2 parts by volume) and petroleum ether (boiling range 60-80°C: 3 parts by volume). Substantially pure (±)α-cyano-3(2,2-dichlorovinyloxy)benzyl, consisting of 40% cis isomer and 60% trans isomer, was prepared by thin layer chromatography using silica plates. (±
) cis/trans-2(2,2-dichlorovinyl)3.
3-dimethylcyclopropanecarboxylate was obtained.
Production Example 4 In this example, compound Fl. 3 and X). This explains the production of 4 and 10.

The product obtained by the method of Production Example 2 (250Tf1
9) with 35v/v% chloroform and 65v/v
% petroleum ether (boiling range 60 DEG -80 DEG C.) as eluent using a silica-coated plate.

The desired products were identified as Compound Black 3 (70 my: (±) cis isomer) and Compound Black 4 (100 η; (±) trans isomer) by infrared absorption and nuclear magnetic resonance spectroscopy. Production Example 5 In this example, 3(2,2-dichlorovinyloxy)benzyl
This explains the production of bromide.

(a) Production of 1(3-tolyloxy)-2,2,2-trichloroethyl acetate. Anhydrous ether 25 (1
Metacresol (27.0 V) was added to a solution of anhydrous chloral (37.07) in 25 mO and the mixture was stirred at room temperature for 20 minutes, then cooled to 10°C and triethylamine (25.0 V) in anhydrous ether (100 mO) was added.
30 solutions of 25y) were gradually added. Acetyl chloride (20.07) was then carefully added to the stirring mixture and stirring continued for an additional hour. Insoluble material was removed by filtration and the solution ▲ was dried over anhydrous magnesium sulfate. After the ether was removed by evaporation under reduced pressure of 35%, the residual oil was distilled under high vacuum to a boiling point of
A fraction of 32-134°C/0.5mmHg was collected. As a result of infrared absorption and nuclear magnetic resonance spectroscopy, this product was found to be 1(3-tolyloxy)2,2,2-trichloro.
40 ethyl acetate. (b)
Production of 3-tolyl-2,2-dichlorovinyl ether (1) Dehydrohalogenation method 1 by metal reduction method (3
-tolyloxy)-2,2,2-trichloroethyl acetate (14.27) was dissolved in glacial acetic acid (40ml) and zinc powder (3.6y) was slowly added to this solution with stirring at room temperature.

The temperature rose to 60°C due to the exothermic reaction that occurred. The mixture was then heated to 50-60°C for 4 hours. The mixture was filtered and the filtrate was poured into excess water and extracted with chloroform. The extract was washed twice with water, then with saturated sodium bicarbonate solution and finally with water. After drying this chloroform extract over anhydrous magnesium sulfate,
The solvent was removed by evaporation under reduced pressure and the residual oil was distilled to collect the crude 3-tolyl 2,2-dichloropynylether as a fraction boiling at 92-95°C/0.3 mmHg, which was redistilled. A fraction with a boiling point of 84° C./0.2 mmHg was obtained. (4) Dehydrogenation method using electrochemical reduction method 1-(3-tolyloxy)-2.2.2 Trichloroethyl acetate (15.87), concentrated sulfuric acid (
98 w/v %: 9.8y) and methanol (220
m1) was charged into the electrolytic cell.

The cell is maintained at a temperature of approximately 15° C. by a surrounding cooling bath and is equipped with a cylindrical diaphragm, a stirrer, a reference electrode (SCE) and a working electrode. The cathode is a lead plate (surface area approximately 40 crii). 5~10mA
This reaction was carried out using a current density of -1100 to 17
The test was carried out at a voltage of 00 m (SCE).

When the reduction is complete, the catholyte is neutralized with caustic soda and extracted with methylene chloride, the extract is dried over anhydrous sodium sulfate, and then evaporated to give the crude 3-tolyl-2.
2-dichlorovinyl ether was obtained as a residue. → ３
Production of (2,2-dichlorovinyloxy)benzyl bromide 3-tolyl 2●2-dichlorovinyl ether (1
2.27) in carbon tetrachloride (75 mO and N-
Bromosuccinimide (12.0 t) and a trace amount of wet benzoyl peroxide were added and the mixture was refluxed for 3 hours.

After filtration, the solvent was evaporated from the solution and the residue was dissolved in ether and extracted with 1% w/v sodium hydroxide solution. The ether solution was dried over anhydrous magnesium sulfate, the solvent was removed by evaporation under reduced pressure and the residual oil was distilled to give a fraction boiling at 150° C./0.5 mm Hg). As a result of NMR analysis, this fraction contained approximately 65% of the desired product.
It was found to contain about 30% unreacted starting material and a small amount of dibromomethyl compound remaining. Preparation Example 6 This example illustrates the preparation of 3(2,2-dichlorovinyloxy)benzyl alcohol.

3(2,2-dichloropynyloxy)benzyl bromide (2.87), sodium p-toluenesulfonate (
2.0y) and methanol (20ml).
Warm to 0°C for 1 hour, then add water (20Tn1) with stirring.
) and toluene (207TL0) were added.

The toluene layer was separated, washed with water and concentrated by evaporating the solvent under reduced pressure. The concentrate was then added dropwise to a 15% w/v aqueous solution of potassium hydroxide (100 mO) and the mixture was warmed to 60°C for 1 h, cooled to room temperature and extracted with a mixture of toluene (10 mO) and methyl isobutyl ketone (10 mO). , the extract was dried over anhydrous magnesium sulfate and the solvent was removed by evaporation under reduced pressure.
(2,2-dichlorovinyloxy)benzyl alcohol was obtained as a residual pale yellow oil. Preparation Example 7 This example illustrates the conversion of 3(2,2-dichlorovinyloxy)benzaldehyde to its cyanohydrin via its bisulfite compound.

To a stirred solution of sodium metabisulfite (3.27) in a mixture of water (5.2 m0 and methanol (5.2 m0) was added 3(2,2-dichlorovinyloxy)benzaldehyde (2,07) at room temperature. Added.

After 30 minutes, the white precipitate formed was collected by filtering, washed with cold methanol and dried (3(2,2-dichlorovinyloxy)benzaldehyde bisulfite compound (2.57)). Obtained.

This was suspended in water (5 m0) and this suspension was added to water (
A solution of sodium cyanide (0.47) in 5m0 was added at room temperature. The mixture was stirred for 2 hours and then extracted with diethyl ether (10ml x 2). Collect the extract,
Washing with water (10ml x 2), drying over anhydrous magnesium sulfate and evaporation under reduced pressure gave the cyanohydrin of 3(2,2-dichlorovinyloxy)benzaldehyde as a yellow oil. Production Example 8 This example illustrates the production of 3(2,2-dichlorovinyloxy)benzaldehyde.

3(2.2-dichlorovinyloxy)benzyl bromide (2,57) was carefully added to a stirred solution of hexamethylenetetramine (2.17) in carbon tetrachloride (20 mO) at room temperature.

After 5 minutes the precipitate was collected by filtration and washed with acetone.

The solid thus obtained was added to 16 mO of aqueous acetic acid (50% by weight) and the mixture was refluxed for 1 h.
A mixture of m0 and concentrated hydrochloric acid (4.5 m0) was added and the mixture was refluxed for a further 15 min. After cooling, the mixture was extracted with chloroform, the extract was washed with water (twice) and dried over anhydrous magnesium sulfate. The solvent was then evaporated under reduced pressure to yield substantially pure 3(2,2-dichlorovinyloxy)benzaldehyde as a residue, the identity of which was confirmed by infrared absorption and nuclear magnetic resonance spectroscopy. Next, specific formulation examples and activity test examples of the insecticide and acaricide of the present invention will be shown as examples.

EXAMPLE 1 This example is a formulation of a removal powder that can be applied directly to plants or other surfaces.

Example 2 The following ingredients were mixed in a suitable mixer in the proportions indicated to produce an emulsion concentrate which, when mixed with water, would give an emulsion suitable for agricultural use.

EXAMPLE A concentrate was obtained which, when mixed, gave an aqueous dispersion suitable as a spray for the control of pests.

(Note) 7 Risapol 9 is a condensate of 1 mol of nonilf J enol and 8 mol of ethylene oxide.

Example 4 Various active compounds of the invention were tested for activity against various insects and other vertebrate pests.

The test compound J was used in the form of a liquid preparation containing 0.1% by weight of the compound (however, in the test against Aedesaegyhpti, it was used in the form of a liquid preparation containing 0.01% by weight of the compound). These formulations contain each test compound in acetone 4
1 volume of diacetone alcohol and 1 volume of diacetone alcohol, and then this solution was mixed with 2"
It was prepared by diluting with water containing 0.01% by weight of a wetting agent sold under the trademark NX until the desired compound concentration was obtained. The test method employed for each pest is essentially the same, which involves supporting a large number of pests on a medium that is usually the pest's parasitic plant or the pest's food, and providing either the pest or the medium, or both. It consisted of treatment with a test formulation. Mortality of the pests was then assessed after a period of time, usually 1 to 3 days after treatment.
The test results are shown in Table 1.

In the table, the first column indicates the name of the pest species, and the following columns sequentially indicate the parasitic plant or medium that supported the pest, the number of days elapsed after treatment before evaluation of pest mortality, and each of the compounds numbered above. The results obtained are shown below. The evaluation is expressed as a numerical value of O to 3 based on the following criteria. Datsushi (-) in the table
indicates that no test was conducted.

In the table, 7 contact test 7 indicates that both pests and the medium were treated, and 7 residual effect test 2 indicates that only the medium was treated before being attacked by pests.

Claims (1)

[Claims] Primary formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 represent a halogen atom or a lower alkyl group, and R^3 and R^4 represent a halogen An insecticide and acaricide containing, as an active ingredient, a compound in which R^5 represents a hydrogen atom or a cyano group.