JPH029001B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of the group of alkylbenzyl pyrethroids, certain members of which are novel compounds, as soil insecticides. The prior art includes numerous patents and literature articles relating to pyrethroids (particularly for domestic and agricultural use). However, pyrethroids, which are currently popular in the agricultural field due to their high toxicity in foliar applications, generally do not exhibit practical insecticidal activity. There is therefore a need for pyrethroid soil insecticides with low mammalian toxicity properties. The present invention thus provides a method of protecting crops from attack by soil-dwelling insects and their larvae, which protects crops from the soil in which they are growing or in which they are to be grown. ,formula [In the formula, R ₁ represents a tetrahaloethyl or dihalovinyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms, n is 0, 1, 2, 3 or 4, and each X is n is greater than 1, they may be the same or different and independently represent an alkyl group having 1 to 4 carbon atoms or a fluorine, chlorine or bromine atom. ] Provides a crop protection method characterized by applying an insecticidal amount of alkylbenzylcyclopropane carboxylate. Examples of compounds within the scope of the invention include 2-(2,2
-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid, including the following esters: 3-methylbenzyl, 2-ethylbenzyl, 2-ethyl-
6-methylbenzyl, 4-n-propylbenzyl, 4-isopropylbenzyl, 3,4-dimethylbenzyl, 2,5-dimethylbenzyl, 2,3
-dimethylbenzyl, 3,5-dimethylbenzyl, 2,3,6-trimethylbenzyl, 2,3,
4-trimethylbenzyl, 2,3,5-trimethylbenzyl, 2,3,4,5-tetramethylbenzyl, 2-methyl-4-ethylbenzyl, 2,6
-dimethyl-4-ethylbenzyl, 2-chloro-
6-Methylbenzyl, 2-chloro-4,6-dimethylbenzyl, 2,4-dichloro-6-methylbenzyl, 2,6-dichloro-4-methylbenzyl, 2,6-dimethyl-4-chlorobenzyl, 2
-Methyl-6-fluorobenzyl, 2-methyl-
4-fluorobenzyl, 2-fluoro-4-methylbenzyl, 2,4-difluoro-6-methylbenzyl, 2,6-difluoro-4-methylbenzyl, 2,4-dimethyl-6-fluorobenzyl,
2,6-dimethyl-4-fluorobenzyl, 2-
Fluoro-4-ethylbenzyl, 2-chloro-4
-ethylbenzyl, 2-fluoro-6-ethylbenzyl, 2,6-difluoro-4-ethylbenzyl, and 2-(2,2-dibromovinyl)-
The corresponding esters of 3,3-dimethylcyclopropanecarboxylic acid and the like. The alkylbenzenecyclopropane carboxylates defined above are those in which the alkylbenzyl group is 2,6-dimethylbenzyl, 2-methylbenzyl, 2-bromo-3-methylbenzyl, 2-bromo-6-methylbenzyl and 3,5- dimethyl-
New except for the compound which is 4-chlorobenzyl. Suitable compounds are those in which R ₁ represents a dibromodichloroethyl, dichlorovinyl or dibromovinyl group. Preferably, R ₁ represents a 2,2-dichlorovinyl group, n is 0, 1 or 2, and the substituents R ₂ and X on the benzene ring are at the 2-position and/or the 4-position and/or the 6-position. Yes, especially R ₂
is a methyl or ethyl group, X is a methyl or ethyl group or a chlorine atom, more particularly R ₂ is methyl and X is methyl or chlorine. Thus, suitable alkylbenzyl groups include 2-methylbenzyl, 4-methylbenzyl, 4-ethylbenzyl, 2,6-dimethylbenzyl, 2,4-dimethylbenzyl, 2
-Methyl-4-chlorobenzyl, 2-methyl-6
-chlorobenzyl and 2,4,6-trimethylbenzyl. Because of the asymmetric carbon atom in the acid moiety, the active compounds may exist as optical isomers. The use of racemic mixtures of the possible isomers and mixtures of the various forms as well as single isomers such as the trans form, preferably the cis form, especially the (1R, cis) form of cyclopropanecarboxylic acid is within the scope of the invention, but When these forms are used substantially free of other stereoisomers, their purity is at least about 75%, preferably at least about 80%. Higher purities, such as at least 95%, are particularly useful. The active compound may be present in one or more carriers and/or
Or it is conveniently applied in the form of a composition which also contains a surfactant. The term "carrier" used herein
means a substance, which may be synthetic or natural, inorganic or organic, with which the active compound is mixed or formulated in order to facilitate its application to the soil or its storage, transport or handling. The carrier may be solid or liquid. Any of the materials commonly used in formulating insecticides, herbicides or fungicides can be used as a carrier. Suitable solid supports are natural and synthetic clays and silicates, such as diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as attapuljites and vermiculites;
Aluminum silicates such as kaolinites, montmorillonites and micas; calcium carbonates; silicates of calcium or aluminum; elements such as carbon and sulfur; natural and synthetic resins such as coumaron resins, polyvinyl chloride, styrene polymers and copolymers; solid polychlorophenols; bitiumen; waxes such as beeswax, paraffin wax and chlorinated mineral waxes; and solid fertilizers such as superphosphates. Suitable liquid carriers are water; alcohols such as isopropanol and glycols; 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; chlorine. Carbonized hydrocarbons such as carbon tetrachloride, perchloroethylene, trichloroethane; compounds that are normally vaporized and gaseous, but have been liquefied. Mixtures of different liquids are also often suitable. Surfactants can be emulsifiers, dispersants or wetting agents. It may be non-ionic or ionic. Any of the surfactants commonly used in formulating insecticides, herbicides or fungicides may be used. Examples of suitable surfactants are sodium or calcium salts of polyacrylic acids and ligninsulfonic acids; fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule and ethylene oxide and/or propylene oxide. condensation products; glycerol, sorbitan,
Fatty acid esters of sucrose or pentaerythritol; these and ethylene oxide and/or
or condensation products with propylene oxide; condensation products of fatty alcohols or alkylphenols such as p-octylphenol or p-octylcresol with ethylene oxide and/or propylene oxide; sulfates or sulfonates of these condensation products; Alkali metal or alkaline earth metal salts of sulfuric acid esters or sulfonic acid esters containing at least 10 carbon atoms, preferably sodium salts, such as sodium lauryl sulfate, sodium secondary alkyl sulfates, sulfonated castor oil and sodium alkylaryl sulfonates such as sodium dodecylbenzene sulfate; polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide. The compositions may be formulated as wettable powders, dusts, granules, solutions, emulsions, emulsions, suspension concentrates, and aerosols. Hydrating agents are 25, 50 and
Typically formulated to contain 75% toxic agent, in addition to the solid carrier, 3-10% w dispersant and if necessary 0-10% w stabilizer and/or other additives such as penetrants or Usually contains a fixing agent. Dusting agents are usually formulated as dust concentrates with a composition similar to that of wettable powders but without a dispersion medium, and are further diluted with a solid carrier at the site of use to reduce toxicity, typically between 1/2 and 10%w. Obtain a composition containing: There are 10 or more granules.
It is usually prepared to have a size of 100BS mesh (1.676-0.152mm) and can be manufactured by agglomeration or impregnation techniques. Generally, granules are 1/2 to 25%w
of poisonous agents, and 0-10% w of additives such as stabilizers,
It will contain a slow release modifier and a binder. Emulsions are usually made with 10 to 50
%w poison, 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 obtain stable, non-settling, flowable products and typically contain 10-75% w toxic agent, 0.5-15% w dispersant, 0.1
~10% w of suspending agents such as protective colloids and thixotropic agents, 0-10% w of suitable additives such as antifoams, corrosion inhibitors, stabilizers, penetrants and fixing agents,
and water or an organic liquid in which the toxic agent is substantially insoluble as a liquid carrier, and certain organic solids or inorganic salts are used as liquid carriers to aid in anti-settling or as antifreeze agents for water. can be dissolved in Also within the scope of the invention are aqueous dispersions and emulsions, such as compositions obtainable by diluting the wettable powders or concentrates according to the invention with water. The emulsion may be water-in-oil or oil-in-water and may have a thick "mayonnaise"-like consistency. The composition may also contain other ingredients, such as other compounds with insecticidal, herbicidal or fungicidal properties. The compounds are particularly useful for controlling various insects in soil that are damaging growing plants. The effectiveness of these substances as soil insecticides to protect growing plants is surprising in view of the low soil activity of other pyrethroids widely used as foliar insecticides. The substances of the invention are suitable for use in species of Diabrotica , such as Diabrotica virgifera Le Conti (western corn beetle),
Diabrotica longicornis sei (northern corn beetle)
longicornis say) and Diabrotica undecimupunctata howardei barbel (southern corn beetle) ( Diabrotica
undecimpunctata howardi Barber), especially for the control of their larval stages. Since the substance of the invention has exceptionally good larvicidal activity,
rootworms, cutworms and wireworms,
For example , Diabrotica (net beetle) Agrotis , Crymodes , Amathes, Euxoa , Peridroma , Lacinipolia , Nephelodes , Actebia , Fuerutia ( Feltia ), Loxagrotis
It can be advantageously used against the larvae of Agriotes , Lemonius , Horiatonotus , Ctenicera , Conoderus , and the like. Some of the relatively well-known larval species mentioned above are: Agrotis ipsilon Hufnagel (black neck beetle), Agriotes manx soi (Agrotis manx soi).
mancus Soy) (wheat click beetle), and especially the three species of Diabrotica mentioned above. The substances of the invention are applied to the soil at a rate of about 0.1 to about 11 Kg/ha. Good soil control to suppress insects is about 0.1 to about 5 Kg/ha, especially about 0.1
It is obtained at a rate of ~4Kg/ha. In the method according to the invention, the active ingredient may be conveniently formulated for use as granules or powders containing a solid diluent impregnated with the active ingredient. Such preparations usually contain about 1 to 50% by weight of active ingredient. More effective control may be provided if the preparation is physically mixed with the topsoil (e.g. by leveling with a harrow as a pre-treatment prior to sowing). The preparations may be applied as solutions, ie as solutions or dispersions of the active ingredient in non-phytotoxic (non-toxic to plants) solvents or liquid diluents, suitably water. Such drenches may be prepared by diluting a concentrate containing the active ingredient, an emulsifier and preferably an organic solvent such as toluene with water. Preparation is done by obi, ridge or side dress.
It can be applied as a soil and may or may not be incorporated into the soil. Active compounds are, for example, 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid or its reactive derivatives such as acid chlorides,
They may be obtained by treating suitably substituted alkylbenzyl alcohols or their reactive derivatives such as halides with salts or alkyl esters as in eg FR 2 290 415. The reaction is preferably carried out in the presence of a suitable base such as a tertiary amine such as triethylamine or an alkali metal carbonate such as potassium or sodium carbonate and in the presence of an inert solvent. Various acids and their reactive derivatives are
Collection Czechoslov.Chem.
Commun. pp. 2230-2236 (1958), U.S. Patent No.
No. 4,024,163, No. 4,179,575 and No. 4,257,978; alcohols are known from, for example, US Pat.
Known from the number. The invention is illustrated by the following examples describing the synthesis and testing of the materials of the invention. These examples are given for illustrative purposes only and should not be considered as limiting the invention. Product identity was confirmed by elemental, infrared (IR) and nuclear magnetic resonance spectroscopy (NMR) analysis as appropriate. Example 2,4,6-trimethylbenzylcis-2-
(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate 2.1 g of cis-2-(2,2-dichlorovinyl) in a stirred slurry of 1.5 g of potassium carbonate in 50 ml of acetonitrile. -3,3-dimethylcyclopropanecarboxylic acid, approximately 0.1 g of 18-
crown-6-ether and then 1.7 g of 2,
4,6-trimethylbenzyl chloride was added. The reaction mixture was heated to 60-65°C for 2 1/2 hours. The reaction mixture was cooled and partitioned between water and methylene chloride. The methylene chloride layer was dried over MgSO ₄ and evaporated to give 2.4 g of the desired product as a colorless solid. melting point
44-59℃. Example 2-chloro-6-methylbenzylcis-2-
(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate 0.75 g 2-chloro-6-methylbenzyl alcohol in 20 ml methylene chloride and 0.9 ml
of triethylamine and cooled in an ice bath was added 1.3 g of cis-triethylamine.
2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid chloride was added. The resulting mixture was washed three times with water, then separated and dried. The methylene chloride solution was concentrated, distilled and chromatographed to yield 0.9 g of the desired product. Example-XII Following a similar procedure to Example and, the esters as listed in the table below were prepared. [Table] Example 2-chloro-6-methylbenzyl(cis)-2
-(1,2-dibromo-2,2-dichloroethyl)-3,3-dimethylcyclopropanecarboxylate 4.4 g of 2-chloro-6 in 25 ml of carbon tetrachloride
-Methylbenzyl(cis)-2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate is stirred with 5
2.1 g of bromine in ml of carbon tetrachloride are added dropwise. The resulting mixture is irradiated with ultraviolet light for 7 hours. The solvent is evaporated from the resulting mixture and the residue is distilled to obtain the desired product. Following a procedure similar to the example above, 2,6-dimethylbenzyl (1R, cis)-2-(1,2-dibromo-2,2-dichloroethyl)-3,3-dimethylcyclopropanecarboxylate, 4- Methylbenzyl(cis)-2-(1,2-dibromo-
2,2-dichloroethyl)-3,3-dimethylcyclopropanecarboxylate and the like are produced. Examples Soil Activity Test compounds are dissolved in a solvent and fully incorporated into dry soil. After eliminating traces of solvent, water is added and thoroughly mixed to bring the soil moisture level to 9%. Half fill a 100ml wide-mouth bottle with 60g of moist soil. 15 in 0.2% sodium hypochlorite solution
Two sweet corn seeds, surface sterilized for minutes and washed with water, are pressed into the soil near the periphery of the jar. Drill small holes of approximately 2.5 cc into the soil surface and insert 20 Diabrotica undecimpunctata.
Eggs of the western snail beetle (undecimpunctata Mannerheim) are placed in the hole. They are immediately covered with finely ground zonolite or vermiculite and the covered material is moistened with approximately 1.3 cc of water. The bottle is then capped with a lid in which two 2 mm holes are punched for ventilation. The bottle is placed under a lamp and kept at 27°C. The eggs are generally two to four days old.
old). After one week, examine the contents of the jar for the presence of live larvae, record their number, and examine the sweet corn roots for growth damage.
Compounds that show control in the first week at a rate of 3 ppm or less are evaluated after several additional weeks. Several optical forms of alkylbenzyl (1R,
cis)-2-(2,2-dichlorovinyl)-3,3
- The test results for dimethylcyclopropane carboxylate are shown in the table below. In these studies, the results were evaluated and reported as follows. [Table] [Table]

Claims (1)

[Scope of Claims] 1. A method of protecting crops from attack by soil-dwelling insects and their larvae, which protects the soil in which such crops are growing or are to be grown. In the expression [In the formula, R ₁ represents a tetrahaloethyl or dihalovinyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms, n is 0, 1, 2, 3 or 4, and each X is n is greater than 1, they may be the same or different and independently represent an alkyl group having 1 to 4 carbon atoms or a fluorine, chlorine or bromine atom. ] A crop protection method comprising applying an insecticidal amount of alkylbenzylcyclopropane carboxylate. 2. A process according to claim ₁ , wherein R 1 represents a dibromodichloroethyl, dichlorovinyl or dibromovinyl group. 3 The resulting alkylbenzyl group is 4-methylbenzyl, 2,6-dimethylbenzyl, 2-methyl-
R ₂ , X and n are selected to be 6-chlorobenzyl or 2,4,6-trimethylbenzyl;
The method according to claim 2. 4. Physically mixing granules containing an alkylbenzyl carboxylate as defined in claims 1, 2 or 3 together with a solid carrier and a surfactant and soil.
Or the method described in Section 3. 5. The method according to claim 1, 2 or 3, wherein the alkyl benzyl carboxylate is formulated with a liquid carrier and applied to the soil as a solution at an application rate of 0.1 Kg/ha to 11 Kg/ha. 6. The method according to any one of claims 1 to 5, wherein the alkylbenzyl carboxylate has a cis configuration and is substantially free of other stereoisomers.