NL7907497A - 2-BOMBENZYL ESTERS AND THEIR USE AS PESTICIDES. - Google Patents

Description

* g 1463

Applicant: Shell Internationale Besearch Maatschappij B.V.,

Carel van Byiandtlaan 30, * The Hague

Eorte designation: "2-33 cream benzyl ester B and their application of all pesticides" o 0

The present invention relates to 2-brobenzy 1 esters, to their preparation and to compositions containing these esters and used as pesticides, in particular as insecticides and acaricides.

The invention therefore relates to 2-bromobenzyl esters of the formula I: Λ B1 H CS-C 1 y Xf 12 CH, -.1- CO-O-CH. _ // \ (x) 5 CH, H \ —μ- / 3 <«a 1 2 where B is hydrogen, fluorine, chlorine, bromine or iodine, B is fluorine, chlorine, bromine or iodine, X is hydrogen, a cyan -, ethynyl or 10-thioamide group, n is an integer from 1 to 4 and T or 790 74 97 k'-2 - each Y is independently selected from hydrogen, fluorine, chlorine, bromine or iodine.

It should be noted that, depending on the nature of the substituent X, the compounds of the formula I have two or five three asymmetric centers. As will be known to those skilled in the art, the compounds of the formula I can exist as geometric and optical isomers, mixtures of isomers and racemates.

Preferred compounds of the formula I have one or more of the following characteristics: 12 (1) S and S are independently selected from fluorine, chlorine and bromine.

(2) X is hydrogen or a cyano group.

(3) X is hydrogen (4) n is 1 15 (5) Y is selected from hydrogen, fluorine, chlorine or bromine (6) Y is a 6-fluoro, 6-chloro or 6-bromo substituent, preferably 6-fluoro or 6-chlorine.

1 2 (7) the 2 (2-E-2-B-vinyl) -3f3-dimethylcyclopropanecarboxyl group has a cis-structure 20 (θ) the 2 (2-5 -2-E-vinyl) -3 »3 -dimethylcyclopropanecarboxyl group has a 15-cis structure.

The 2-bromobenzyl esters of the formula I can be prepared by the same methods as known compounds. According to a suitable method, a compound of the formula II: 11 a ce »<j /“ Yv (, I> CS A CO 2 is reacted CH 3 h with a compound of the formula III: 790 7497 r) - 3 -

Br a - ^ (m) <E> n 12 in which R, Η, X, Y and η 'have the above meanings, one of the components Q and Z is a halogen atom, preferably a chlorine or bromine atom and the other a hydroxyl group is. 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 is a chlorine or bromine atom.

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

The above compounds of formula III, wherein X 15 is hydrogen and Q is halogen, are preferably prepared by halogenation of the corresponding halobromol toluenes. The halobromotoluenes can be prepared by incorporation of the appropriate halogen via diazotization of the appropriate halotoluidine. Halo toluidines can be prepared by reducing the corresponding halonitrotoluene by known methods, for example, according to Entwistle et al, J.C.S. Perkin I, 1977, pages 443 and 444. Compounds of formula III, wherein X is hydrogen and Q is a hydroxyl group, can be prepared by hydrolysis of the compounds wherein Q is halogen.

Compounds of the formula III, wherein X is a cyano, ethynyl or thioamide group, may be prepared from compounds in which X is hydrogen by a known method via the corresponding aldehyde.

790 74 97 '- 4 -

The 2-bromobenzyl 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-bromobenzyl ester of the formula I as the active ingredient. The invention further relates to a method for controlling insects, ticks and / or acarides in a field, in which an amount of a 2-bromobenzyl ester according to the invention or of a composition suitable for pesticide purposes, comprising such a compound contains.

The term "carrier" in this specification is understood to mean 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, or to facilitate the storage, transport or processing thereof. The carrier can be a solid or a liquid. Any substance commonly used in formulating pesticides, herbicides or fungicides can be used as a carrier.

Suitable solid carriers are natural and synthetic clays and silicates, eg natural silicas, such as diatomaceous earth, magnesium silicates, eg talc, magnesium aluminum silicates, eg attapulgites 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 styrene polymers and copolymers solid polychlorophenols; bitumen; waxes such as beeswax, paraffin and chlorinated mineral paraffins, as well as solid fertilizers, for example, superphosphates.

790 7 497 • * * - 5 -

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. Mixtures 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 pesticide, herbicide or fungicide application 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 pentaeryrythritol; condensates thereof with ethylene oxide and / or propylene oxide; condensation products of fatty alcohols or alkyl phenols, for example, oct-octyl phenol or octyl cresol, 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 alkyl aryl sulfonate; and polymers of ethylene oxide and copolymers of 50 ethylene oxide and propylene oxide *

The preparations obtained according to the method according to the invention can be formulated in the form of spray powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Spray powders 35 usually contain 25, 50 or 75 wt% active material and 79074 97-6 - except 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 penetrants or adhesives. Dusting powders are usually formulated in the form of a 3 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 form a composition 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 wt% active material and 0-10 wt% 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 wt% active material, 2-20 w / v% emulsifiers and 0-20 w / v%! suitable additives such as stabilizers, penetrants and anti-corrosion agents. Suspension concentrates are formulated to provide a stable, non-sediment-forming free-flowing product and usually contain 10-75% by weight active material, 0.5-15% by weight dispersants, 0.1-10% by weight 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 anti-freeze agents for water.

Aqueous dispersions and emulsions, for example, preparations obtained by diluting a spray powder or a concentrate according to the invention with water also fall 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 790 7 497-7 thick "mayonnaise" -like consistency.

The preparations obtained according to the method according to the invention may 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 - The preparation of 1: 1 cis / trans 2-bromo-6-chloro-benzyl 2- (2,2-dichlorovinyl) -3,3-dimethylvvclo-10-prouanecarboxylate (a) The preparation of 2-bromo-6-chlorobenzyl bromide 2-Bromo-6-chlorotoluene (20.55 g) and N-bromosuccinimide (19.6 g) were refluxed together in carbon tetrachloride (100 ml) for 22 hours while the mixture was irradiated with an infrared lamp. The resulting solution was cooled in ice, filtered and evaporated to give the desired product, which was dissolved in petroleum ether (60-80). A portion was recrystallized therefrom in the form of pink needles (8.5 g) and a portion was obtained by evaporation in the form of a dark orange solid (17.7 g) (total yield 26.2 g, 92% ), (b) Preparation of 1: 1 cis / trans 2-bromo-6-chlorobenzyl 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylate 1: 1 cis / trans 2- (2,2-dichlorovinyl) 5.3-methyl-cyclo-25-propanecarboxylic acid (2.3 g) 2-bromo-6-chlorobenzyl bromide (2.85 g) and potassium carbonate (1.6 g) were refluxed together in acetone for 6 hours ( 30 ml) stirred. The reaction mixture was cooled, diluted with water and extracted three times with 50 ml portions of diethyl ether. The combined ether-50 extracts were washed with water and with an aqueous sodium bicarbonate solution (three times), dried over magnesium sulfate and evaporated to give the desired orange product (4.1 g, 9 &%), mp 61-67 ° C was obtained.

Analysis 35 Calc'd C 2 H BrCl 3: C 43.6; H 3.4; Br 19.4; Cl 25.9 Found: C 43.8; H 3.4; Br 19.1; Cl 25.4 7907497 - 8 -

Examples 2-11

The following compounds were prepared according to the methods described in Example 1: 1, R-Cl-2-bromo-6-chlorobenzyl 2- (2,2-difluorovinyl) -3,3-5 dimethylcyclopropane carboxylate (yield 76%) n ^ = 1,533 »[o (] j5 * -15,45 (02OHOlj) 1 -1 cis / trans-2-bromobenzyl 2- (2,2-dichlorovinyl) -3» 3-dimethyl-cyclopropanecarboxylate (yield 89%) n ^ = 1 »5606 cis-2-bromobenzyl 2- (2,2-dichlorovinyl) -3,3" dimethylcyclo-10-propanecarboxylate (yield 80 $) n = 1.5614 trans-2-bromobenzyl 2- (2.2 -dichlorovinyl) -3,3-dimethylcyclo-propanecarboxylate (yield 82%) n ^ = 1, R-cig-2-bromo-6-chlorobenzyl 2- (2,2-dichlorovinyl) -3 »3-dimethyl-cyclopropanecarboxylate ( yield 30%) n ^ 1 = 1.5682 ^ 5 = -26.8 15 (C2 CHCl3) cis-2-bromo-6-chlorobenzyl 2- (2,2-dibromovinyl) -3,3-dimethylcyclopropane carboxylate ( yield 84%), melting point 101-3 ° C. ciB-2-bromo-6-fluorobenzyl 2- (2-chloro-2-fluorovinyl) -3 »3-diinethyl-eyclopropanecarboxylate (yield 65%)» melting point 53 “54 ° C 20 cis-2-bromo-6-fluorobenzyl 2- (2,2-dichlorovinyl) - 3 »3-dimethylcyclopropane carboxylate (yield 66%), melting point 68-69 ° C 1, R-cis-2-bromo-6-fluorobenzyl 2- (2,2-dichlorovinyl) —3» 3-dimethyl cyclopropane carboxylate (yield 81%) n ^ = 1 »551» 9 (C2 CHCl ^) 25 cis-2-bromo-6-fluorobenzyl 2- (2,2-dibromovinyl) -5 »3-dimethylcyclopropanecarboxylate (yield 74%)» melting point 66-67 ° C Pesticide efficacy

The efficacy against insects and ticks of the compounds of the invention was determined by tests on: 30 Insects: Musea domestica (M. d.)

Spodoptera littoralis (S.l.)

Aphis fabae (A.f.)

Heliothis zea (H.z.)

Mi.it and: Tetranyehus urticae (T.u.) 35 Sign: Boophilus microplus (B.m.) 7907497 r - - 9 -

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

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 test solution was streaked on the underside of each specimen. 20 flies were treated. The treated flies were stored in glass jars covered with blotting paper, which was held in place with elastic. Cotton wool soaked in dilute sugar solution was placed on the tissue paper as food.

After 24 hours, the percentage of dead and dying flies was recorded.

(2) Spodoutera littoralis (S.l.) 15 fava bean plants, two leaves were removed each time and placed on filter paper in plastic Petri dishes. The leaves were sprayed on the underside with an aqueous formulation containing 20% by weight acetone, 0.05%,% 10 X-100 (trademark) 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, the leaves were allowed 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.

(3) Aphis fabae (A.f.)

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

30 (4) Heliothis zea (ïï.z.)

The compounds to be tested were taken up in an aqueous solution containing 20 wt% acetone, 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 79074 97-10 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 placed 5 in water through an opening in a test board, keeping the temperature and relative humidity of the environment at 27 ° C and 40-50 respectively % were maintained. The number of dead larvae was determined after 44-46 hours.

(5) Tetranyohus urticae (T.u.) 10 Leaf discs 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-15 water (20:80) containing 0.05% TRITON X-100 (Trademark) as a humectant. After 24 hours, the percentage of dead and dying mites was determined.

(6) Boouhilus micro-plus (B.m.)

A 0.01 wt% solution of the test compound was prepared in acetone containing 10 wt% polyethylene glycol. Different concentrations were obtained by diluting this solution. 1 ml of the test solution was evenly applied to a filter paper contained on 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. Approximately 80-100 two to three week old animal larva ticks (Boophilus microplus) were transferred into the package and sealed. The package was then placed in an incubator and kept 50 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 animal species being tested are indicated by the above initial letters 35 and the activity of the compound is expressed in the form 790 7 4 97 f - 11 - of a toxicity index (GI) which was calculated using the following Tommie: τ-

Toxicity Index (G.I.) - «sthylparathlor. (standard) ° 50 of the test compound 5 The killing activity of the compounds according to the invention was determined by means of the Kearns-March chamber test using the housefly {Musea domestica) as a test insect.

The Kearns-March chamber consists of a 2x1 foot transparent glass 10 cylinder into which flies can be placed at one end via a sliding panel. 0.2 ml aliquot of a 20% MeClg / SO 2 Shellsol K solution containing active material was injected into the chamber at 10 psi for 1 second while air was supplied for 2 more seconds to inject the injected solution. distribute evenly. Approximately 70 flies were used in each treatment and 1, 2, 5, 4, 5, 7 and 10 minutes after spraying, the number of dead flies was counted. Based on the concentration of active ingredient needed to reach 90% mortality after 20 minutes, the compounds were divided into the following 6 groups:

Group 0: 90% after 10 minutes at a concentration of 0.025%

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 5: 90% after 10 minutes at a concentration of 0.2%

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.

79074 97 -12 -

TABLE I

Vending I ClftleheldslnAex I ^

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

5 1 40 140 '27 46 10 422 2 2 25 134 33 + 7 1240 0 3 4.5 9 6 8.9 13 8 4 4 4.6 20 7 14 21 15 4 5 5.4 9 5 6.2 4 +4 10 6 43 144 12 78 63 594 1 7 15 75 14 32 + 147 4 8 16 34 14 + 27 290 2 9 20 35 9 + 24 238 1 10 15 44 19 + 14 80 3 15 11 34 48 27 + 49 481 2 + not yet tested 7907497

Claims (6)

Esters according to claim 1, characterized in that R and R are independently selected from fluorine, chlorine and bromine. • jO 3 · Esters according to claim 1 or 2, characterized in that X is hydrogen or a cyano group. Esters according to claim 3, characterized in that X is hydrogen. Esters according to any one of claims 1 to 4, characterized in that n is 1. Esters according to any one of claims 1 to 5, characterized in that Y is selected from hydrogen, fluorine, chlorine or bromine. Esters according to any one of claims 1 to 5, characterized in that Y is an é-fluoro, 6-chloro or 6-bromo substituent. Esters according to any one of claims 1 to 6, characterized in that 1 2 20. and R are independently selected from fluorine, chlorine and bromine, X is hydrogen, n is 1 and Y is a 6-fluoro or 6-chloro- substituent. Esters according to any one of claims 1 to 8, characterized in that the 2 (2-R 2 -R-vinyl) -3,3-dimethylcyclopropanecarboxyl group has a cis structure. Ester according to any one of claims 1 to 9, characterized in that the 2 (2-R -2-R-vinyl) -5,5-dimethylcyclopropanecarboxyl group has a 1R-cis structure. 79074 97 - 14 - II. Process for the preparation of 2-bromobenzyl esters of the formula I, as described in any one of claims 1-10, characterized in that a compound of the formula II: R1 / H CH = C is used. Y V Y \ (n) CHj / \ coz reacts ch5 H5 with a compound of the formula Ills Br. Q - CH - ^ (III) (T) '; n 12 wherein S, R, X, Y and n have the meaning defined in claim 1, one of the designations Q and Z represents a halogen atom and the other represents a hydroxyl group. 12. 2-Bromobenzyl esters prepared by a process according to claim 11. IJ. Pesticidal composition, characterized in that it contains a carrier and / or surfactant and as active ingredient a 2-bromobenzyl ester according to any one of claims 1-10 and 12. 14. Method for controlling insects on a field, characterized in that a 2-bromobenzyl ester according to any one of claims 1-10 and 12 or a composition according to claim 13 is applied thereon. 790 7 4 97