JPS6244542B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to 2,6-dihalobenzyl esters, processes for their preparation, and insecticidal and acaricidal compositions. Belgian patent No. 862109 (Bayer AG) uses the general formula (In this formula, the R parts may be the same or different and are selected from fluorine, chlorine, and bromine, and when R is fluorine or bromine, m is 0 to 5 and n is 0 to 5, but m and n are never 0, and when R is chlorine, m is 0 to 4 and n is 1 to 5,
When m is 0 and n is 5, R may be a methyl group in addition to the above atoms. This Belgian patent also generally states that in the prior art there are similar compounds in which the benzyl moiety is replaced exclusively with chlorine atoms. Surprisingly, it has been found that a new class of compounds falling within the broad class of compounds mentioned above have, in addition to their insecticidal activity, a particularly useful toxic pesticide activity, and in particular a surprising acaricidal activity. Ta. According to the present invention, the following formula (In this formula, R ¹ and R ² are each independently fluorine,
selected from chlorine and bromine, Y ¹ is chlorine;
Y ² is fluorine or chlorine, provided that R ¹ and R ²
If both are bromine, then Y ² is fluorine, and if both R ¹ and R ² are not bromine, then R ¹ and
When at least one of R ² is the same as at least one of Y ¹ and Y ² and all of R ¹ , R ² , Y ¹ and Y ² are chlorine, the ester is a cis-isomer. 2,6-dihalobenzyl esters of the form ) are provided. The compounds of formula have geometric and optical isomers,
It may exist as a mixture of isomers and racemates, and there are two asymmetric centers in the substituted cyclopropyl moiety, as will be readily apparent to those skilled in the art. Preferred compounds of the invention are cis-form compounds of the formula:
1. Those commonly designated as R-cis-compounds are most preferred. Advantageously in compounds of formula R ¹ , R ² and Y ² are each fluorine or chlorine, Y ¹ is chlorine and at least one of R ¹ and R ² is Y ¹ and Y ²
The same as at least one of the following. R ₁ , R ² and
Particularly preferred are compounds in which at least two of Y ² are chlorine and the others are fluorine or chlorine. 2,6-dihalobenzyl esters of the formula can be prepared by methods analogous to those used for known compounds. A convenient manufacturing method is the formula The compound represented by the formula (In these formulas, R ¹ , R ² , Y ¹ and Y ² are as defined above, and one of Q and Z represents a halogen atom, preferably a chlorine atom or a bromine atom, and the others represent a hydroxyl group. ). The reaction is preferably carried out in the presence of an inert solvent, a suitable base, for example a tertiary amine such as triethylamine or an alkali metal carbonate such as potassium carbonate or sodium carbonate.
Conveniently Z represents a hydroxyl group and Q represents a chlorine or bromine atom. Compounds of the above formula and their individual isomers are disclosed, for example, in British Patent No. 1413491 and British Patent No.
Conveniently manufactured by known methods as described in US Pat. No. 1,448,228. The compound of the above formula is a known compound 2,6
-dichlorotoluene and 2-chloro-6-fluorotoluene by conventional halogenation techniques such as reaction with N-bromo-succinimide followed by optional hydrolysis. The 2,6-dihalobenzyl esters of the present invention are of interest as insecticides and acaricides for domestic and agricultural markets. Accordingly, the present invention includes within its scope insecticidal and acaricidal compositions comprising a 2,6-dihalogen benzyl ester of the formula as an active ingredient as well as a carrier and/or a surfactant. The present invention also provides methods for inhabiting insects and tick and/or red mite pests in a habitat comprising applying to the habitat an effective amount of a toxic pesticide of a composition comprising the 2,6-dihalobenzyl ester of the present invention or a composition as described above. It also includes methods of eradication on land. The term "carrier" as used herein refers to the term "carrier" with which the active compound is mixed or used to facilitate its application to crops, seeds, soil or other materials to be treated, or to facilitate its storage, transport or handling. It means a substance that is prepared, inorganic or organic, and which may be of synthetic or natural origin. The carrier may be solid or liquid. Any material commonly used in formulating insecticides, herbicides or fungicides can be used as a carrier. Suitable solid carriers are naturally occurring and synthetic clays and silicates, such as natural silicas such as diatomaceous earth, magnesium silicates such as talc, magnesium aluminum silicates such as attapulgite and permiculite, kaolinite, montmorillonite and mica. such as aluminum silicates, calcium carbonate, calcium sulfate, synthetic hydrous silicon oxides and synthetic calcium or aluminum silicates, elements such as carbon and sulfur, naturally occurring and synthetic resins such as coumaron resins, polyvinyl chloride and styrene polymers, solids. Solid fertilizers such as polychlorophenols, bitiumen, waxes such as beeswax, paraffin wax and chlorinated mineral waxes, and superphosphates. Suitable liquid carriers are water, ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethers, aromatic hydrocarbons such as benzene, toluene and xylene, petroleum distillates such as kerosene and light mineral oils, carbon tetrachloride, perchlorethylene. , chlorinated hydrocarbons such as trichloroethane, and liquefied, usually vaporous, gaseous compounds. Mixtures of dissimilar liquids are often suitable. Surfactants may be emulsifiers or dispersants or wetting agents and may be nonionic or ionic. Any surfactant used in the formulation of insecticides, herbicides or fungicides may be used. Suitable surfactants are, for example, sodium or calcium salts of polyacrylic acids and ligninsulfonic acids, condensations of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide. products, fatty acid esters of glycerin, sorbitan, sucrose or pentaerythritol, together with ethylene oxide and/or
or condensates with propylene oxide, aliphatic alcohols or p-octylphenol or p-
- Condensation products of alkylphenols such as octyl cresol with ethylene oxide and/or propylene oxide, sulfates or sulfonates of these condensation products, alkalis or alkaline earths containing at least 10 carbon atoms in the molecule. Metal salts preferably sodium salts or sulfuric esters or sulfonic esters such as sodium lauryl sulfate, sodium secondary alkyl sulfate,
Sodium salts of sulfonated castor oil, and sodium alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide. The compositions of the invention can be formulated as wettable powders, powders, granules, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 25%, 50% and 75% of the toxic agent and usually contain, in addition to the solid carrier, 31-0% by weight of dispersant and optionally stabilizers and/or other additions such as penetrants or adhesives. The formulation contains 0-10% by weight of the agent. Powders are formulated as powder concentrates with a composition similar to that of wettable powders, but without dispersants, and are further diluted with a solid carrier at the site of application, usually to a composition containing 1/2 to 10% by weight of the toxic agent. Get things. Granules are 10-100 British standard mesh (1.676-0.152mm)
and can be manufactured by agglomeration or impregnation techniques. Generally, granules contain 1/2-25% by weight of toxic substances.
Zero additives such as stabilizers, slow-acting modifiers and binders
- Contains 10% by weight. In addition to the usual solvent, emulsifying concentrates contain co-solvents, 10-50% by weight of toxic substances,
It contains 2-20% w/v emulsifier and 0-20% w/v of suitable additives such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are formulated to provide stable, non-settling fluid products and are usually free of toxic substances.
10-75% by weight, dispersants 0.5-15%, suspending agents such as protective colloids and thixotropic agents 0.1-
10% by weight, 0-10% by weight of suitable additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and adhesives and water or an organic liquid in which the poison is substantially insoluble as carrier; Certain organic solids or inorganic salts can be dissolved in the carrier to help prevent settling or as antifreeze agents for water. Also included within the scope of the invention are aqueous dispersions and emulsions, such as wettable powders or compositions obtained by diluting the concentrates of the invention with water. The emulsions may be water-in-oil or oil-in-water and can have a thick "mayonnaise-like" consistency. The compositions of the invention may also contain other ingredients, such as other compounds with insecticidal, herbicidal or fungicidal properties. Next, in order to explain the present invention more specifically,
Examples are shown below. Example 1 2-(2,2-dichlorovinyl)-3,3-dimethyl-cyclopropanecarboxylic acid 1,R-cis-2-chloro-6-fluorobenzyl ester (a) 2-chloro-6-fluoro bromide Production of benzyl 2-chloro-6-fluorotoluene (14.45
g) and N-bromosuccinimide (19.6 g) were stirred together with azo-bis-isobutyronitrile (0.1 g) in anhydrous carbon tetrachloride under reflux while irradiated with an infrared lamp for 18 hours. The resulting solution was cooled in ice, filtered and evaporated to give a light orange liquid, which was distilled under reduced pressure of nitrogen to give the title product (20.1 g, 90%), bp 74℃／3.00mmH
g. (b) 2-(2,2-dichlorovinyl)-3,3-
Dimethylcyclopropanecarboxylic acid 1,R-cis-2-chloro-6-fluorobenzyl ester 1.R-cis-2-(2,2-dichlorovinyl)
-3,3-dimethylcyclopropanecarboxylic acid (1.1 g), 2-chloro-6-fluorobenzyl bromide (1.1 g) and anhydrous potassium carbonate (0.7 g) were stirred together in acetone under reflux for 2 hours. . The reaction mixture was cooled, diluted with water and extracted three times with 50 ml each time of diethyl ether. The combined extracts were washed with aqueous sodium bicarbonate, dried over magnesium sulfate, evaporated, purified on a SiO ₂ column, eluted with toluene and evaporated to give 1.8 g (100 g) of the title product.
%) was obtained. Refractive index n ¹⁹ _D = 1.5420 [α] ²⁴ _D = -22.4° (C2, CHCl ₃ ) Example 2 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid 1,R-cis- 2,6-dichlorobenzyl ester 1,R-cis-2(2,2-dichlorovinyl)
-3,3-dimethylcyclopropanecarboxylic acid (3,5 g), 2,6-dichlorobenzyl chloride (3.0 g), potassium iodide (0.5 g) and potassium carbonate (2.3 g) were refluxed together in acetone for 2 hours. The mixture was stirred while stirring. The reaction mixture was worked up as described in Example 1 to give 5.6 g (100%) of the title product. Refractive index n ²³ _D = 1.5638 [α] ²⁵ _D = -26.50° (C2, CHCl ₃ ) Example 3 - Example 11 The following compounds were prepared analogously to the methods of Examples 1 and 2. 2-(2-chloro-2-fluorovinyl)-
3,3-dimethylcyclopropanecarboxylic acid cis-2,6-dichlorobenzyl ester (yield: 86
%) n ¹⁸ _D = 1.541 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid cis-2-chloro-6-fluorobenzyl ester (yield 98%)
n ¹⁹ _D = 1.5401 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid trans-2-
Chloro-6-fluorobenzyl ester (yield 98
%) n ¹⁹ _D = 1.5360 2-(2,2-dibromovinyl)-3,3-dimethylcyclopropanecarboxylic acid cis-2-chloro-6-fluorobenzyl ester (yield 98%)
n ²³ _D = 1.5664 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid cis-2,6-
Dichlorobenzyl ester (yield 87%) Melting point 91-
95℃ 2-(2-chloro-2-fluorovinyl)-
3,3-dimethylcyclopropanecarboxylic acid cis-2-chloro-6-fluorobenzyl ester (yield 72%) n ¹⁹ _D = 1.521 2-(2,2-difluorovinyl)-3,3-
Dimethylcyclopropanecarboxylic acid 1,R-cis-2-chloro-6-fluorobenzyl ester (yield 91%) n ²² _D = 1.4987 [α] ²⁴ _D = -9.50° (C2 CHCl ₃ ) 2-(2,2 -dibromovinyl)-3,3-dimethylcyclopropanecarboxylic acid 1,R-cis-
2-chloro-6-fluorobenzyl ester (yield 63%) n ¹⁹ _D = 1.565 [α] ²⁵ _D = -7.69° (C2 CHCl ³ ) 2-(2,2-dichlorovinyl)-3,3-dimethylcyclo Propanecarboxylic acid 1:1-cis/
Trans-2,6-dichlorobenzyl ester (yield 70%) (Reference example) Insecticidal test The insecticidal and acaricidal activities of the compounds of the present invention were evaluated using the following insect pests. Insects: House fly (Md) Egyptian potato beetle (Spodoptera)
littoralis) (Sl) Aphis fabae (Af) Corn moth (Heliothis zea) (Hz
) Mites: Two-spotted mites (Tu) Tick mites: Red mites (Bm) The test methods used for various genera are as follows. (i) Musca domestica (Md) A solution of the test compound dissolved in acetone at a concentration of 0.4% by weight was prepared and collected in a micrometer syringe. Female house flies (Musca domestica), 2 to 3 days old, were anesthetized with carbon dioxide.
20 flies were tested by applying 1μ of the test solution to the inside of each fly's abdomen. The treated flies were placed in a glass container covered with tissue paper secured with a rubber band. Pads of yellowweed soaked in a dilute solution of sugar were placed on top of tissue paper as food. The percentage of dead or dying flies after 24 hours was recorded. (ii) Spodoptera
littoralis) (Sl) Two leaves were taken from a broad bean seedling, placed on paper and placed in a plastic Petri dish. The underside of the leaves was sprayed with an aqueous preparation containing 20% by weight of acetone, 0.05% by weight of TRITON X-100™ as a wetting agent and 0.4% by weight of the test compound. Dilution of this preparation resulted in varying concentrations. After the leaves were sprayed, they were left to dry for 1/2 to 1 hour, and then each pair of leaves was infected with 10 larvae of the Egyptian potato beetle (Spodoptera littoralis). The percentage of dead or dying larvae after 24 hours was recorded. (iii) Aphis fabae (Af) Egyptian potato beetle (Spodoptera) mentioned in (ii) above.
Tests were carried out on adult aphids (Aphis fabae) using methods similar to those used for Aphis fabae. (iv) Corn moth (Heliothis zea) (Hz) The test compound was used in the form of an aqueous solution containing 20% by weight of acetone, 0.04% by weight of Atlox 1045A™ and 0.2% by weight of the test compound, and the dosage For a further diluted solution to obtain a volume-kill curve, add a 0.2% solution to Atrox 1045A0.05.
It was prepared by diluting it with % by weight of water. A cut Windsor broad bean seedling was placed on a rotary table and 4 ml of the test solution was sprayed onto it. Immediately after spraying, five adult corn moths (Heliothis zea) were individually transferred to seedlings placed in water through a hole in the test stand, maintaining the environment at a temperature of 27°C and a relative humidity of 40-50%. Ta. Mortality was counted after 44-46 hours. (v) Tetranychus urticae (Tu) A bean leaf was cut into disks and placed on paper kept moist with cotton wool wicks soaked in water. Each disk-shaped leaf was infected with 10 adult mites, and then the test compound was dissolved in an acetone-water (20:80) mixture containing 0.05% TRITON X-100™ as a wetting agent. The suspension was sprayed onto the disc. (vi) Boophilus microplus (B.
m.) A 0.1% by weight solution was prepared by dissolving the test compound in acetone containing 10% by weight of polyethylene glycol. This solution was diluted to obtain different concentrations. 1 ml of the test solution was applied evenly to the paper inside the Petri dish. When it is sufficiently dry,
The paper was folded in half and pleated along its outer edge to form a packet. Approximately 80 larvae of Boophilus microplus, 2 to 3 weeks old.
One hundred animals were transplanted into the packet, which was then completely sealed. The packet was then placed in an incubator at 27°C and relative humidity of 80%. After 24 hours, the packets were opened and the percentage of dead or dying larvae was calculated. The test results are shown in Table 1, in which the test species are indicated by the initial letters above, and the activity of the compound is expressed in the form of a toxicity index (TI) calculated from the following formula. Toxicity index (TI) = LC ₅₀ of ethyl parathion (standard) / LC ₅₀ of test compound
activty) is Kearns March (Kearns)
March) chamber test using the common house fly (Musca domestica). The Kearns-March chamber consists of a clear glass cylinder measuring 2 feet by 1 foot into which flies can be introduced through a sliding plate at one end. Contains active substances
20% MeCl ₂ /80% Shellsol K solution
Spray 0.2ml into the room for 1 1/2 seconds at 10psi pressure,
Air was introduced for an additional 2 seconds to help further distribute the spray evenly. Approximately 70 flies were used for one treatment, and 1 minute, 2 minutes, 3 minutes, and 4 minutes after spraying were used.
The number of deaths was counted at minutes, 5 minutes, 7 minutes and 10 minutes.
Compounds were graded 6 according to the concentration of toxicant required to achieve 90% eradication after 10 minutes. In other words, Class 0: The concentration that can eliminate 90% in 10 minutes is 0.025%. Possible concentration
0.4% Grade 6 Not killed at 0.4% The results of these tests are also shown in the table.

[Table] Various dichlorobenzyl esters of 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid were tested according to the insecticidal test method described above. The results are shown in Table 1. In this table, the toxicity indices are as described above except for grades B and C. Grades B and C were tested using a single application rate of the compound, 0.2% wt. Grades B and C represent the percentage of dead mites or insects, so grade B is 30-80% and grade C is less than 20%. All compounds for which numerical toxicity data were given achieved a grade A (grade A indicates greater than 90% mite or insect killing).

【table】

Claims (1)

[Claims] Linear formula (In this formula, R ¹ and R ² are independently fluorine,
selected from chlorine and bromine, Y ¹ is chlorine;
Y ² is fluorine or chlorine, provided that R ¹ and R ²
are both bromine, then Y ² is fluorine, and when R ¹ and R ² are both bromine, then R ¹
and at least one of R ² is at least one of Y ¹ and Y ²
2,6 characterized in that it is the same as the species, and when R ¹ , R ² , Y ¹ and Y ² are all chlorine, the present ester is in the cis-isomer form). -Dihalobenzyl ester. 2 R ¹ , R ² and Y ² are each fluorine or chlorine, Y ¹ is chlorine, and at least one of R ¹ and R ² is the same as at least one of Y ¹ and Y ² . An ester according to claim 1, characterized in: 3. The ester according to claim 1 or 2, wherein at least two of R ¹ , R ² and Y ² are chlorine, and the other group is chlorine or fluorine. 4. Ester according to any one of claims 1 to 3, characterized in that it is in the form of a cis-isomer. 5. Ester according to any one of claims 1 to 3, characterized in that it is in the form of the 1,R-cis-isomer. 6th order equation (In this formula, R ¹ and R ² are independently fluorine,
selected from chlorine and bromine, Y ¹ is chlorine;
Y ² is fluorine or chlorine, provided that R ¹ and R ²
are both bromine, then Y ² is fluorine, and when R ¹ and R ² are both bromine, then R ¹
and at least one of R ² is at least one of Y ¹ and Y ²
and if R ¹ , R ² , Y ¹ and Y ² are all chlorine, the ester is in the cis-isomer form) In the manufacturing method of The compound represented by and the formula (In the formula and formula, R ¹ , R ² Y ¹ and Y ² are as described above, one of Q and Z represents a halogen atom, and the other one represents a hydroxyl group) The above-mentioned production method is characterized by reacting the compound with a compound that is 7 The following formula as the active ingredient (In this formula, R ¹ and R ² are independently fluorine,
selected from chlorine and bromine, Y ¹ is chlorine;
Y ² is fluorine or chlorine, provided that R ¹ and R ²
are both bromine, then Y ² is fluorine, and when R ¹ and R ² are both bromine, then R ¹
and at least one of R ² is at least one of Y ¹ and Y ²
and if R ¹ , R ² , Y ¹ and Y ² are all chlorine, the ester is in the cis-isomer form) An insecticidal and acaricidal composition characterized in that it also contains a carrier and/or a surfactant.