NL7907498A - 2,6-DIHALOGENEBENZYL ESTERS AND THEIR USE AS PESTICIDES. - Google Patents

Description

* St Λ K 1462

Applicant: Shell Internationale Research Maatschappij B.V.,

Carel van Bylandtlaan 30, The Hague

Short designation: "2,6-Dihalogeribenzyl esters and their use as pesticides"

The present invention relates to 2,6-dihalo-benzyl esters, to their preparation and to compositions containing these esters and used as pesticides, in particular insecticides and acaricides.

5 The Belgian patent no. 862.10 $ (Bayer A.G) refers to a general group of compounds of the formula 5 3 CH * </ y ^ λ chco - o - αΚς-Μ sss

CHj H \ = V

P

n in which the R groups, which may or may not be the same, are selected from fluorine, chlorine and bromine, and when H is fluorine or bromine 10, m and n are 0-5 with the proviso that m and n are not both 0 stalls to be? when R is chlorine, m is 0-4 and n is 1-5? 79074 98 i * <f - 2 - when m is O and n 5, E can, in addition to the other groups mentioned, also represent a methyl group. This Belgian patent also shows that in the art similar ones. compounds exist in which the benzyl group is substituted only by 5 chlorine atoms.

It has now surprisingly been discovered that a new group of compounds, which belongs to the large group of compounds discussed above, has a particularly useful pesticide activity and, in addition to insecticidal activity, above all has a surprising miticidal activity.

The invention therefore relates to 2,6-dihalobenzyl esters of the formula I: B1

H C = C

\ / ^ fi2 Y1 X x- ~ \ CH? /-.-\^00 - 0 - CH2- / \ (I) CH3 H /

- - Y

1 2 in which B and B are independently selected from fluorine, chlorine and bromine, Y1 is chlorine and I2 is fluorine or chlorine, with the proviso that when B1 and B2 are both bromine, Y2 is fluorine, and 12 when neither B nor B is bromine at least one of these two components is the same as at least one of the components Y1 and Y2.

The compounds of formula I can exist as geometric and optical isomers, mixtures of isomers and racemates, since there are two asymmetric centers in the substituted cyclopropyl ring system, as will be apparent to those skilled in the art. Among the compounds of the invention, the cis compounds of formula I are preferred, most preferred being those commonly referred to as 1, E-cis compounds.

1 2

In the compounds of formula I, preferably B, B and 2 1 Y are fluorine or chlorine and Y is chlorine, while at least one of the components 7907498: * - 3 - 1 2 is the same as at least one of the 1 2 components Y and Y. The compounds in which at least two of the components E 2 and Y 2 are chlorine, while the other is fluorine or chlorine, are particularly preferred.

The 2,6-dihalobenzyl esters of the formula I can be prepared according to methods similar to those used for known compounds. A compound of formula II: E1 is left by a suitable method

X

H CH = C ^ Y x · 'Λ αχ) y \ ^ - CO2 react

CHj H

With a compound of formula III: Q-OH2-f 79074 98 12 1 2 wherein E, E, Y and Y have the above meanings, one of the components Q and Z is a halogen atom, preferably a chlorine or bromine atom and the other is a hydroxy group. The reaction is preferably carried out in the presence of a suitable base, for example a tertiary amine such as triethylamine or an alkali metal carbonate such as potassium or sodium carbonate, in the presence of an inert solvent. Z preferably represents a hydroxyl group and Q represents a chlorine or bromine atom.

The compounds of formula II above and their individual isomers are preferably prepared by a known method, for example as described in British Pat. 1,413,491 and 1,448,228.

The compounds of formula III above can be readily prepared from 2,6-dichlorotoluene and 2-chloro-6- -4-fluorotoluene, which are known compounds, using conventional halogenation techniques, eg reaction with N-bromosuccinimide and optional subsequent hydrolysis .

The 2,6-dihalobenzyl esters according to the invention are of interest as pesticides, in particular as insecticides and acaricides for household and agricultural applications. The invention therefore also relates to pesticidal compositions containing a carrier and / or a surfactant as well as a 2,6-dihalo-10-benzyl ester of the formula 1 as the active ingredient. The invention further relates to a method for controlling insects, ticks and / or acarides, in particular mites, which are located in a field, in which an amount of a 2,6-dihalo-benzyl ester suitable for pesticide purposes according to the invention or of a composition containing such a compound is applied to the field.

By the term "carrier" in this description is meant material which may be inorganic or organic and of synthetic or natural origin and with which the active compound is mixed in order to apply it to the crop, seed, soil or other object to be treated, or to facilitate the storage, transport or processing thereof. The carrier can be a solid or a liquid. Any substance commonly used in the formulation of pesticides, herbicides or fungicides can be used as a carrier.

Suitable solid carriers are natural and synthetic clays and silicates, for example natural silicas, such as diatomaceous earth, magnesium silicates, for example talc, magnesium aluminum silicates, for example attapu casting and vermiculites; aluminum silicates, for example kaolinites, montmorillinites and micas; calcium carbonates; calcium sulfate; synthetic hydrated silicon oxides and synthetic calcium or aluminum silicates; elements such as carbon and sulfur; natural and synthetic resins such as coumarone resins, polyvinyl chloride and ethyl polymers and copolymers solid polychlorophenols; bitumen; waxes such as beeswax, paraffin and chlorinated mineral paraffins, as well as solid fertilizers, for example, superphosphates.

Examples of 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 fractions, such as kerosene, light mineral oils; chlorinated hydrocarbons, such as carbon tetrachloride, perchlorethylene, trichloroethane, as well as liquefied, usually vaporous, gaseous compounds. Handles of different liquids are often suitable.

The surfactant can be an emulsifying agent, a dispersing agent or a wetting agent; the substance can be non-ionic or ionic. Any surfactant commonly used in formulating pesticides, herbicides or fungicides can be used. Examples of useful surfactants are the sodium or calcium salts of polyacrylic acids and lignin sulfonic acids; the condensation products of fatty acids or aliphatic amines or amides with at least 12 carbon atoms per molecule with ethylene oxide and / or propylene oxide; the fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol, condensates thereof with ethylene oxide and / or propylene oxide; condensation products of fatty alcohols or alkyl phenols, for example j-octylphenol or jv-octylcresol, with ethylene oxide and / or propylene oxide; sulfates or sulfonates of these condensation products; alkali or alkaline earth metal salts, preferably sodium salts of sulfuric or sulfonic acid esters containing at least 10 carbon atoms per molecule, for example sodium lauryl sulfate, secondary sodium alkyl sulfates, sodium salts of sulfonated castor oil and sodium alkylaryl sulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The preparations obtained according to the method according to 79074 98 i-'- - - - 6 - invention can be formulated in the form of spray powders »dusting powders, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Spray powders usually contain 25, 50 or 75 wt% active material and, in addition to solid carriers, usually 3-10 wt% of a dispersant, and sometimes 0-10 wt% of one or more stabilizers and / or other additives, such as penetrate agents or adhesives. Dusting powders are usually formulated in the form of a dusting powder concentrate with a composition similar to that of a wettable powder, but without dispersant, and are diluted on site with a further amount of solid carrier to a formulation usually 0.5-10 wt% active material. contains. Granules are usually prepared in a size of 1,676-0,152 mm using agglomeration and impregnation techniques. Granules generally contain 0.5-25% by weight of active material and 0-10% by weight of additives, such as stabilizers, slow release agents of the active material, and binders. Emulsifiable concentrates usually contain, in addition to the solvent and, if required, auxiliary solvent, 10-50% w / w active material, 2-20% w / v emulsifiers and 0-20% w / v suitable additives, such as stabilizers, penetrants and anti-corrosion materials. Suspension concentrates are formulated to provide a stable, non-sediment-forming, free-flowing product and usually contain 10-75 wt.% Active material, 0.5-15 wt.% Dispersants, 0.1-10 wt.% Suspending agents, such as protective colloids and thixotropic agents, 0-10% by weight of suitable additives, such as anti-foaming agents, anti-corrosion agents, stabilizers, penetrating agents and adhesives and as carrier water or an organic liquid in which the active material is practically insoluble; certain organic solids or inorganic salts can be dissolved in the carrier to help prevent sedimentation or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example preparations 790 74 98 - 7 - obtained by diluting a spray powder or a concentrate according to the invention with water are also within the scope of the present invention. The said emulsions may be of the water-in-oil or oil-in-water type and may have a thick "mayonnaise" -like consistency.

The preparations obtained according to the method according to the invention can also contain other ingredients, for example other compounds with pesticide, herbicidal or fungicidal properties.

The invention is further illustrated in the following examples ·

Example 1 Se preparation of 1.S-cis-2-chloro-6-fluorobenzyl 2- (2,2-dichlorovinyl) -5,5-dimethylcyclonropane carboxylate 15 (a) Se preparation of 2-chloro-6-fluorohenzyl bromide 2-chloro -6-Fluorotoluene (14 »45 s) and N-br om om sue c inimi de (19» *> g) were refluxed together with azo-bis-isobutyronitrile (0.1 g) in anhydrous carbon tetrachloride for 18 hours while the mixture was irradiated with an infrared lamp.

The solution obtained was cooled in ice, filtered and evaporated to give a light orange liquid which was distilled under reduced nitrogen pressure to give the desired product (20.1 g, 90%) with a boiling point of 74 ° C / 3. 00 mm Hg was rained.

(B) The preparation of 1, R-cis-2-chloro-6-fluorobenzyl 2- (2,2-dichlorovinyl) -5,5-dimethylcyclonronane arboxylate.

1, R-cis 2- (2,2-dichlorovinyl) -5 '5-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 portions of diethyl ether. The combined extracts were washed with an anhydrous sodium bicarbonate solution, dried over magnesium sulfate, evaporated and purified in a SiOg column, eluted with 35 toluene and evaporated to give 1.8 g (100%) of the 790 74 98-8 - desired product was obtained.

Refractive index = 1.5420 ^ 4 = -22.4 ° (C2, CHCl3).

Example 2 - Preparation of 1R-cis-2,6-dichlorobenzyl 2- (2,2-5 dichlorovinyl) -3. 5-dimethylcyclo'Dro-daancarboxylate 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 two hours, reaction mixture was treated as in Example 1, yielding 5 * 6 g (100%) of the desired product.

25

Refractive index n ^ = 1.5638 [<] b5 = -26.50 ° (C2, CHCl3)

Examples 5-11 The following compounds were prepared as described in Examples 1 and 2: cis-2,6-dichlorobenzyl 2- (2-chloro-2-fluorovinyl) -3,3-dimethyl-cyclopropanecarboxylate (yield 86% ) n ^ = 1,541 cis-2-chloro-6-fluorobenzyl 2- (2,2-dichlorovinyl) -3,3-dimethyl-20-cyclopropanecarboxylate (yield 98%) n ^ = 1.5401

B

trans-2-chloro-6-fluorobenzyl 2- (2,2-dichlorovinyl) 3 * 3-dimethyl-cyclopropanecarboxylate (yield 98%) = 1.5360 cis-2-chloro-6-fluorobenzyl 2- (2.2- dibromovinyl) -3 * 3-dimethyl-cyclopropanecarboxylate (yield 98%) s 1 * 5664 25-2,6-dichlorobenzyl 2- (2,2-dichlorovinyl) -3,3-dimethyl-cyclopropanecarboxylate (yield 87%), mp 91 -95 ° C cis-2-chloro-6-fluorobenzyl 2- (2-chloro-2-fluorovinyl) -3> 3 "dimethylcyclopropanecarboxylate (yield 72%) n = 1.521 1.R-ci8-2-chloro-6 -fluorobenzyl 2- (2,2-difluorovinyl) -3 »3-30 dimethylcyclopropanecarboxylate (yield 91%) = 1.4937» f << £ 4 = -9.50 ° (C 2 CHCl 3) 1, B-cis-2 -chloro-6-fluorobenzyl 2- (2,2-dibromovinyl) -3 »3-dimethyl- 790 74 98 - 9 - cyclopropane carboxylate (yield 63%) = 1.565» fc <] ^ = - 7.69 (C2 CHCl) -) / 1: 1-cis / trans-2,6-dichlorobenzyl 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylate (yield 70%) 5 Pesticide tolerance

The activity against insects and ticks of the compounds according to the invention has been established by tests on: Insects: Musea domestica (M.d.)

Spodoptera littoralis (S.l.) 10 Aphis fabae (A.f.)

Heliothis zea (ïï.z.)

Mites: Tetranvehus urticae (T.u.)

Sign: Boophilus microplus (B.m.)

The test methods used are described below: 15 (1) Home domestica (M.d.)

Sr, a 0.4 wt% solution in acetone of the compound to be tested was prepared and placed in a micrometer syringe.

Two to three day old adult female houseflies (Musea domestica) were anesthetized with carbon dioxide and 1 µl of the 20 test solution was streaked on the underside of each specimen. 20 flies were treated. Treated flies were kept in glass jars covered with tissue paper, which was held in place with elastic. Bones in dilute sugar solution 23 soaked cotton balls were placed on the tissue paper as food.

After 24 hours, the percentage of dead and dying flies was recorded. (2) Spodoptera littoralis (S.l.)

Tan broad bean plants were always two leaves removed and placed on filter paper in plastic Petri dishes. The leaves were sprayed on the underside with an aqueous formulation containing 20 wt.% Acetone, 0.05 wt. # TEITON X-100 (trade mark) as a wetting agent and 0.4% by weight of the compound to be tested. Varying concentrations were obtained by diluting the formulation. After spraying, 79074 98-10 was left to dry for half to an hour, after which 10 larvae of the Egyptian cotton leaf beetle (Spodoptera littoralis) were placed on each pair of leaves. After 24 hours, the percentage of dead and dying larvae was recorded.

5 (3) Aphis fabae (A.f.)

The same tests as for Spodoptera littoralls were carried out on adult aphids (Aphis fabae). as described under 2 above.

(4) Heliothis zea (H.z.) 10 The compounds to be tested were taken up in an aqueous solution containing 20 wt% Ace ton, 0.04 wt% Atlox 1045A (trademark) and 0.2 wt% of the test compound; for the dose-death curves, more solutions were prepared by diluting the 0.2% solution with an aqueous solution of 0.05 wt% Atlox 1045A. Cut Windsor broad bean plants were placed on a turntable and sprayed with 4 ml of the test solution. Immediately after spraying, 5 larvae of the corncob borer (Heliothis zea) were transferred to each plant which was placed in water through an opening in a test board, keeping the temperature and relative humidity of the environment at 27 ° C and 40 ° C respectively. 50% were kept. The number of dead larvae was determined after 44-46 hours.

(5) Tetranvchus urtioae (T.u.) 25 leaf bean plants cut from haricot plants were placed on filter paper which was kept moist by means of a strip of cotton wool dipped in water. Ten adult mites were placed on each disc and the discs were sprayed with a solution or suspension of the test compound in acetone-water (20:80) containing 0.05% TEITON X-100 (Trademark) as a wetting agent. After 24 war, the percentage of dead and dying mites was determined.

(6) Boophilus microplus (B.m.)

A 0.01 wt% solution of the test compound was prepared in acetone containing 10 wt% polyethylene glycol. By 790 74 98 - 11 dilution of this solution, different concentrations were obtained. 1 ml of the test solution was evenly applied to a filter paper contained in a Petri dish. When the filter paper was sufficiently dry, it was folded in half and partially pleated along the outer edge to form a package. About 80-100 of one animal two to three week old larvae ticks (Boophilus microplus) were transferred into the package »after which it was completely sealed. The package was then placed in an incubator and at a temperature of 27 ° C and a relative humidity of 80% After 24 hours the package was opened and the percentage of dead and dying larvae was determined The results are shown in Table I. The test species are indicated by the above initial letters and the activity of the compound is expressed in the form of a toxicity index (OI) calculated using the following formula *

Toxicity index (G.I.) - ™ ethylpergthion (etendaexdl pO of the test compound) The killing activity of the compounds of the invention was determined by the Keams-March chamber test using the housefly (Musea domestica) as a test insect.

The Keams-March chamber consists of a transparent glass cylinder of 2 z 1 foot into which flies can be brought at one end via a sliding panel. One 0.2 ml aliquot of a 20% ylQ1 / 80% Shellsol K solution containing active material was injected into the chamber at 10 psi for 1 1/2 seconds while air was supplied for another 2 seconds to allow the injected distribute the solution evenly. Approximately 70 flies were used in each treatment and 1, 2, 3 »4» 5 »7 and 10 minutes after spraying, the number of dead flies was counted. Based on the concentration of active ingredient required to reach a $ 0% death rate after 10 minutes, the compounds were divided into the following 6 groups: 7907498 - 12 -

Group Or 90% after 10 minutes at a concentration of 0.02-596

Group 1: 90% after 10 minutes at a concentration of 0.05%

Group 2: 90% after 10 minutes at a concentration of 0.1%

Group 3 · 90% after 10 minutes at a concentration of 0.2% 5 Group 4: 90% after 10 minutes at a concentration of 0.4% Group 5 '{90% after 10 minutes at a concentration of 0.4 % Group 6: no dead flies at a concentration of 0.4%.

The results of these tests are also listed in Table I.

10 TABLE I

Link of Group Toxicity Index

Example M.d. S.l. A.f. H.z. T.u. I B.m.

1 44 96 26 30 98 908 0 15 2 44 98 12 28 33 1110 1 3 13 44 5 + 34 1200 2 4 23 41 22 34 72 400 1 5 32 24 9 25 31 57 1 6 14 35 20 53 20 2 20 7 17 107 26 80 61 581 2 8 12 79 29 + 19 482 0 9 17 121 19 19 4 240 1 10 52 137 75 + 10 343 0 11 21 77 26 + 17 178 2

___I I

25 + not yet tested 790 74 98

Claims (6)

Esters according to claim 1, characterized in that R, R and 21 are each fluorine or chlorine, 7 is chlorine, and at least one of the components R and R is the same as at least one of the 1 2 components 7 and 7. Esters according to claim 1 or 2, characterized in that 1 2 is at least two of the components R, R and 7 chlorine, while the other 15 is chlorine or fluorine. Esters according to any one of claims 1-3 * in the form of their cis isomers. Esters according to any one of claims 1 to 3 in the form of their 1.R-cis isomer. 6. Process for the preparation of a 2,6-dihalobenzyl ester of the formula I as described in any one of claims 1 to 5, characterized in that a compound of the formula II is used: 7907498-14 - B1 / H CH = CV B2 (II) reacts C53, _ / - \ CO CO 2 CH 2 B with a compound of the formula III:. ch2-H Y2 12 12 wherein B, B, Y and Y have the same meaning as in claim 1, one of components Q and Z represents a halogen atom and the other represents a hydroxyl group. 2,6-dihalobenzyl esters, prepared by a process according to claim 6, 8 »Pesticide composition, characterized in that it contains a carrier 10 and / or a surfactant and as an active ingredient a 2,6-dihalobenzyl ester according to any one of claims 1-5 and 7 A method for controlling insects in a field, wherein a 2,6-dihalobenzyl ester according to any one of claims 15 1-5 and 7 or a composition according to claim 8 is applied thereon. 79074 98