DE2941332A1 - 2-BOMB CYLESTER, THEIR PRODUCTION AND THEIR USE AS A PEST CONTROL - Google Patents

Description

description

2-bromobenzyl esters, their preparation and their use as Pesticides

The invention relates to 2-bromobenzyl esters, their preparation and agents for controlling pests which use these compounds as active ingredients contain substance, especially insecticides and acaricides.

The 2-bromobenzyl esters according to the invention correspond to the general formula I my

,1

(ι)

in which R is a hydrogen, fluorine, chlorine, bromine or iodine atom

2
and R is a fluorine, chlorine, bromine, or iodine atom, X represents a hydrogen atom, a cyano, Äthinyl- or thioamido group, α is an integer of 1 to 4 and Y represents one or more substi- the tenten are each independently a hydrogen, fluorine, chlorine, bromine or iodine atom.

The compounds of the general formula I have 2 or 3 asymmetric centers, depending on the nature of the substituent X and, as the person skilled in the art can easily recognize, the compounds of the general formula I can be used as geometric and optical isomers,

030018/0745

1A-52 700 Ζ * Ö

2 9 Λ 1 3 3 2

Mixtures of isomers and racemates are present.

The preferred compounds of general formula I have one or more of the following characteristics

1 2

(i) R and R each represent a fluorine, chlorine or bromine atom

(ii) X is a hydrogen atom or a cyano group. (iii) X is a hydrogen atom
(iv) η is 1,

(v) Y is a hydrogen, fluorine, chlorine or bromine atom (vi) Y is a 6-fluorine or 6-chlorine or 6-bromine substituent

vzw. 6-fluorine or 6-chlorine,

1 2
(vii) the 2 (2-Rj 2-R -Vinyl) -3,3-dimethylcyclopropanecarboxylate]

has cis configuration,

(viii) the 2 (2-R ¹ , 2-R ² -vinyl) -3,3-dimethylcyclopropanecarboxyl part has 1R-cis configuration.

The 2-bromobenzyl esters of general formula I are with the help prepared by procedures analogous to those for known compounds. In a suitable procedure a connection of the general formula II

CH ₂ - / \ -COZ

(Π)

with a compound of the general formula III

030018/0745

1A-52 700 -> ^ Q -

(III)

1 2
implemented, in which R, R, X, Y and η are as defined above, one of the substituents Q and Z is a halogen atom, preferably a chlorine or bromine atom, and the other substituent is a hydroxyl group. The reaction is preferably carried out in the presence of a suitable base, for example in the presence of a tertiary amine such as triethylamine or an alkali metal carbonate such as potassium or sodium carbonate, in the presence of an inert solvent. Appropriately, Z stands for an OH group and Q for a chlorine or bromine atom.

The compounds of general formula II and their individual Isomers are expediently prepared in a manner known per se, for example as in GB-Psen 1,413,491 and 1,448 described.

The compounds of general formula III in which X is a hydrogen atom and Q is a halogen atom, are expedient prepared by halogenating corresponding halobromotoluenes.

The halobromotoluenes can be obtained by introducing the corresponding halogen under diazotization of the corresponding Halotoluidines. Halotoluidines are produced by reducing the corresponding halonitrotoluenes obtained with the aid of known processes, for example according to Entwistle et al, J.C.S. Perkin I, 1977, pages 443 and 444. Compounds of the general formula III,

Ü30Q 1 8/0745

/ 4

1A-52 700 z —Ί—

in which X is a hydrogen atom and Q is an OH group, can by Hydrolysis of the compounds in which Q is a halogen atom obtained will.

Compounds of the general formula III in which X is a cyano, ethynyl or thioamido group are known per se Made from compounds in which X is a hydrogen atom means via the corresponding aldehyde.

The 2-bromobenzyl esters according to the invention develop interesting ones Pest control effect, especially as insecticides and acaricides for use in the household and in agriculture. The invention therefore also relates to pesticides that have a Contain carrier and / or surface-active agent together with a 2-bromobenzyl ester of the general formula I as active ingredient. The invention also relates to a method of controlling insects, ticks and / or acarids in one location their occurrence by this place with a pesticidally effective amount of a 2-bromobenzyl ester according to the invention or with a Agent containing such a compound is treated.

/ 5

030018/0745

1A-52 7OO-s < "* ~ 29 /, 13 32

Carriers in the sense of the description are inorganic or organic substances of synthetic or natural origin, with which the active compound is mixed or prepared in order to apply it to the plant, the sowing, the soil or other objects which are to be treated or their storage, transport and handling to facilitate. The carrier can be solid or liquid. All substances customary for preparing pesticides, herbicides or fungicides can be used as carriers.

Suitable solid carriers are natural and synthetic clays and silicates, for example naturally occurring keel acids such as diatomaceous earth, magnesium silicates, for example talc, magnesium aluminum silicates such as attapulgites and vermiculites, aluminum silicates such as kaolinites, montmorillonites and mica, calcium carbonates, calcium sulfate, synthetic hydrated calcium oxides and synthetic hydrated silicon oxides and synthetic hydrated silicon oxides Aluminum silicates, elemental substances such as carbon and sulfur, natural and synthetic resins such as coumarone resins, polyvinyl chloride and styrene polymers, solid polychlorophenols, bitumen, waxes such as beeswax, paraffin wax and chlorinated mineral waxes and solid fertilizers such as superphosphates. _{+ and} copolymers

Suitable liquid carriers are water, alcohols such as isopropanol and glycols, ketones such as acetone, methyl ethyl ketone and cyclohexanone, Ether, aromatic hydrocarbons such as benzene, toluene, xylene, petroleum fractions such as kerosene and light mineral oils, chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene, Trichloroethane and liquefied, normal, vaporous, gaseous compounds. Often there are mixtures of different liquid compounds.

/ 6

030018/0745

The surfactant can be an emulsifier or a dispersant or a wetting agent as well as nonionic or ionic. All usually when preparing Used pesticides, herbicides or fungicides surface-active compounds can be used. Examples of suitable surfactants are Sodium or calcium salts of polyacrylic acid and ligininsulphonic acids, the condensation products of fatty acids, or aliphatic amines or amides, which have at least 12 carbon atoms in the molecule contain, with ethylene oxide and / or propylene oxide, fatty acid esters of glycerol, sorbitan, cane sugar or pentaerythritol, condensation products of these compounds with ethylene oxide and / or 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 or alkaline earth metal salts, preferably sodium salts or sulfuric acid esters or sulfonic acid esters of at least 10 Carbon atoms in the molecule contain, for example, sodium laury sulfate, Sodium sec.alkyl sulfates, sodium salts of sulfonated castor oil and sodium alkyl aryl sulfonates such as sodium dodecylbenzene sulfate as well as polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The agents according to the invention can be formulated as wettable powders, dusts, granulates, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 25, 50 or 75 fi agent and generally in addition to the solid support 31-0 wt. $ Of a dispersing agent and, where necessary, 0-10 wt.% Stabilizer (s) other additives such as penetrants or stickers. Dusts are usually prepared as a dust concentrate with a composition similar to that of the wettable powders, but without a dispersant. You will be stuck in the free field with more

030018/0745 / 7

700 * r -40- 29Al 332

Carrier diluted to a composition usually containing 0.5-10% by weight of active ingredient. The granules generally have a diameter of 1.676-0.152 mm and are produced using conventional agglomeration or impregnation processes. In general, they contain 0.5-25% by weight of active ingredient and 0-10% by weight of additives such as stabilizers, release retarders and binders. Emulsifiable concentrates usually contain, in addition to the solvent and optionally cosolvents, 10-50% by weight of active ingredient, 2-20% w / v. Emulsifier and 0-20 i "Gew./Vol. suitable additives such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are prepared in such a way that a stable, non-sedimented + product is obtained and usually contain 10-75 wt -10% by weight of additives such as antifoams, corrosion inhibitors, stabilizers, penetrants and adhesives and, as a carrier, water or an organic liquid in which the active ingredient is essentially insoluble. Certain organic solids or inorganic salts can be dissolved in the carrier in order to prevent sedimentation or as antifreeze agents for water. , _r -,. "" ..,.

+ flowable

Aqueous dispersion and emulsions! for example means that are obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the invention. These emulsions can be of water-in-oil or oil-in-water type and a thick mayonnaise-like type Have consistency.

The agents according to the invention can also contain other ingredients, for example other compounds with pesticidal, herbicidal, or fungicidal properties.

The following examples serve to explain the invention in more detail.

/ 8 0300 18/0745

1A-52 700

example 1

Preparation of 1: 1 cis / trans 2-bromo-6-chlorobenzyl 2- (2,2-dichlorovinyl) -3-3-dimethylclopropane carboxylate.

a) 2-Bromo-6-chlorobenzyl bromide.

2-Bromo-6-chlorotoluene (20.55 g) and N-bromosuccinimide (19.6 g) were irradiated with an IRr lamp together in carbon tetrachloride (100 ml) with stirring and under reflux for 22 hours. The resulting solution was cooled in ice, the whole filtered and the filtrate evaporated. The title product remained and was dissolved in petroleum ether (60-80). A portion crystallized in the form of pink needles (8.5 g); another portion was obtained as a dark orange solid (17.7 g) by evaporation of the solvent. The overall yield was 26.2 g or 92 %.

b) 1: 1 cis / trans 2-bromo-6-chlorobenzyl 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylate 1: 1 cis / trans 2- (2,2-dichlorovinyl) -3, 3-dimethylcyclopropane caronic acid (2.3 g), 2-bromo-6-chlorobenzyl bromide (2.85 g) and potassium carbonate (1.6 g) were stirred and refluxed in acetone (30 ml) for 6 hours. The reaction mixture was cooled, diluted with water and extracted three times with 50 ml of diethyl ether each time. The combined ether extracts were washed with water and three times with aqueous sodium bicarbonate solution, dried over magnesium sulfate and evaporated. Remained the orange title compound (4.1 g, 98%) with mp 61-67 ⁰ C.

030018/0745

1A-52 700 y

analysis

Calculated for

C ₁₅ H ₁₄ BrCl ₃ O ₂ : C 43.6 H 3.4 Br 19.4 Cl 25.9 Ji Found

: C 43.8 H 3.4 Br 19.1 Cl 25.4 %

Examples 2 to 11

The following compounds were prepared in a manner analogous to that in Example 1

l, R-cis-2 <bromo -6-chloro-benzyl 2- (2,2wUfluor-vinyl) -3,3-dimethyl-

cyclopropane earboxylate (76 #) iu ⁹ = 1.533, Mj? - -15.45

(C CH Cl) ^{D D}

1: 1 cis / trans-2-bromo-benzyl 2- (2,2-dichloF-vinyl) -3,3-dimethylcyclopropane carboxylate (8S #) O ^ - 1, 5606

cis-2-bromo ienzyl 2- (2,2- <lichlon-vinyl) -3,3-dimethylcyclopropane carboxylate (^ ⁵

trans-2-Bx> m -benzyl 2- (2,2-dichloro-v7-ynyl) -3,3-dimethylcyclopropanecarboxylate (82 ^) njp »3, 5600

-6-chloro-benzyl 2- (2,2-dichloro-vinyl) -3,3-dimethylcyclopropane-carboxylate t 9t *) n ^ ¹ = 1.5682 [* <ξ ⁵ = -26.8 (c2 CHCl ₃ )

cis -2-bromo-6-chloro-benzyl 2- (2,2-dibromo-vinyl) -3,3-dimethylcyclopropanecarboxylate . "($ 81) m.p. 101-3 ° C

cis-2 "Broni -6-fluoro-benzyl 2- (2-chloiO-2-fluoro-vinyl) -3.3 * diDiethylcyclopropancarboxylat (-65J6) mp 53-54 ⁰ C

cis -2-bromo -6-fluoro-benzyl 2- (2,2-dichloro-vinyl) -3,3-dimethylcyclopropane -carboxylate (66 ^) m.p. 68-69 ° C

l, R-cis-2-B ^ om -6-fluoro-benzyl 2- (2,2-dichloro-vinyl) -3,3-dimethylcyclopropane-carboxylate (8ljS) n? ¹ = 1.551, KE ⁵ = -21.9

CHCl ₅ ) '

cis-2-BOM -6-fluoro-benzyl 2- (2,2-dibromo-d.nyl) -3,3-d ± methylcyclopropane-carboxylate (c%), mp 66-67 ⁰ C

/ 10

Π300 18/0745

1A-52 700 KT

Attempts to work as a pesticide.

The insecticidal action of the compounds according to the invention and their activity against ticks has been studied and examined using the following pests.

Insect housefly

Egypt. Cotton leafworm black bean aphid grain beetle

Mites greenhouse spider mite ticks cattle tick

The examination methods for each pest species are given below.

a) House fly - Musca domestica (M.d.)

A 0.4% by weight solution of the test compound in acetone

30018/0745

1 / ;: 70 0 - \

- // ^ - 2 9 Λ 1? 3 2

was prepared and taken up in a micrometer syringe. 2 to 3 day old, adult female house flies were anesthetized with _{CO 2} and 1 / ul of the test solution was applied to the ventral side of the abdomen of each fly; a total of 20 flies were used for the experiment. The treated flies were kept in glasses which were covered with absorbent paper and tied. Cotton balls soaked with dilute sugar solution were placed on the paper cover as a food source. After 24 hours, the percentage of dead and dying flies was determined.

b) Egyptian cotton leafworm - Spodoptera littoralis

(S.l.)

Leaves were removed in pairs from broad bean plants and placed on filter paper in plastic Petri dishes. The leaves were sprayed on the underside with an aqueous agent containing 20% by weight acetone, 0.05% by weight TRITON X-100 as a wetting agent and 0.4% by weight compound, which should be checked. Different concentrations were obtained by diluting the batches at test connection. After spraying, the leaves were left Dry for 0.5 to 1 hour; then each pair of leaves became populated with 10 larvae of the Egyptian cotton leafworm (Spodoptera littoralis (S.l.) after 24 hours the percentage of dead and dying larvae was determined.

c) Black bean aphid - Aphis fabae (A.f.) The studies were carried out with adult bean aphids carried out analogously to the test procedure described under b).

d) Corn beetle - Heliothis zea (H.z.)

The test compounds were incorporated into aqueous solutions

030018/0745

1A-52 700

works, the 20 wt .-% acetone, 0.04 wt .- # Atlox 1 and 0.2% by weight of test compound. For the dose-mortality curves these solutions were further diluted with an aqueous solution containing 0.05 parts by weight of Atlox 1045A. Cut Vindsor broad bean plants were placed on a turntable and sprayed with 4 ml of test solution. Immediately after spraying, 5 grain beetle larvae were placed on each plant, which in turn a hole in a test board was stuck in water; the environment became more relative at 27 ° C and 40 to 50 Ji Kept moist. Mortality counts were made after 44 to 46 hours.

e) Greenhouse spider mite - Tetranychus urticae (T.u.) Discs were cut out of the leaves of green bean plants and placed on filter paper damp by a cotton plug that was dipped in water

Each disc was populated with 10 adult spider mites; The discs were then sprayed with a solution or a suspension of the test compound in acetone-water ( 20:80) containing 0.05% TRITON X-100 as a wetting agent. After 24 hours, the dead and dying mites were counted.

f) beef tick - Boophilus microplus (B.m.)

There was a 0.1 wt .-% solution of the test compound in acetone made containing 10 wt .- # polyethylene glycol. By diluting this solution, different concentrations were obtained of the test compounds obtained. In each case 1 ml of test solution was applied evenly to a filter paper in a Given to petri dish. Once the filter paper was sufficiently dry, it was folded in half and along the Curved on the outside to form a packet or a bag. Approximately 80 to 100 2 to 3 week old beef tick larvae (one-host cattle tick) were put in the pocket

030018/0745

1A-52 700 -

ben, which was then completely sealed. The bag was then kept in an incubator at 27 ° C. and 80 % relative humidity for 24 hours. The bag was then opened and the percentage of dead and dying larvae was determined.

The results are shown in Table 1 attached. The effectiveness of the compounds is expressed in terms of the Toxicity index (T.I.) indicated, which is calculated as follows

Toxicity index (TI) = LC ₅₀ ethyl parathion (standard) Test connection

The initial knockdown activity of the compounds according to the invention was determined using the housefly Determined with the help of the Kearns-March chamber test.

The Kearns-Narch chamber consists of a transparent 0.61 χ 0.305 m large glass cylinder into which the flies can be introduced with the help of a slide rail or slide wall at one end. 0.2 ml of a 20% MeCl _2/80 # Shellsol K solution containing the active ingredient, 1,5 seconds at 687 was mbar (10 psl) sprayed into the chamber and maintain the air supply for 2 seconds to the uniform distribution of the Support Spnys. Approximately 70 flies were used for each experiment and counts for immediate onset of action were taken at intervals of 1, 2, 3, 4, _7, 5, 7 and 10 minutes after spraying. The compounds were divided into 6 classes, depending on the active ingredient concentrate required for an initial 90 degree effect after 10 minutes! on. This results in the following scheme:

0300 18/0745

1Δ-52 70ο

Class 0 Class 1 Class 2 Class 3 Class 4 Class 5 Class 6

9056 10 minutes

9056 10 minutes

9056 10 minutes

9056 10 minutes

9056 10 minutes

9056 10 minutes

Concentration 0.025% Concentration 0.05 56 Concentration O ₉ 1 % Concentration 0.2 56 Concentration 0.4 56 Concentration 0.4 56

no initial effect

0.4 56

The results of these experiments are also in the listed in the following table

Table I.

Connect
application
example Toxicity index M.d. s.i. A. f. H. z. T. u. B.m. i Knock
down
Great 1 40 IhO 27 46 10 422 2 2 25th 134 33 ⁺ 7th 1240 0 3 4.5 9 6th 8.9 13th 8th 4th 4th 4.6 20th 7th 14th 21st 15th 4th 5 5.4 9 5 6.2 4th + 4th 6th 43 12th 78 63 594 1 7th 15th 75 14th 32 + 1 ^ 7 4th 8th 16 34 14th + 27 290 2 9 20th 35 9 + 24 238 1- 10 15th 44 19th + ' 14th 80 3 11 34 48 27 ⁺ 49! 481 2

+ not yet checked

72II49

0300 1 8/0745

ORIGINAL INSPECTED

Claims (11)

Claims in which R ^{1 is} a hydrogen, fluorine, chlorine, bromine or iodine atom and R is a fluorine, chlorine, bromine or iodine atom, X is a hydrogen atom, a cyano, ethynyl or thioamido group, η is a is an integer from 1 to 4 and Y stands for one or more substituents and each represents a hydrogen, fluorine, chlorine, bromine or iodine atom. 2. Ester according to claim 1, characterized in that 1 2 that R and R each represent a fluorine, chlorine or bromine atom stand 3. Esteri.nach claim 1 or 2, characterized in that that X stands for a hydrogen atom or a cyano group. 030018/0745 / 2 ORIGINAL INSPECTED 1A-52 700 -2- 4. Ester according to claim 3, characterized in that it rejects, that X stands for a hydrogen atom. 5 · Esters according to one of claims 1 to 4 «characterized in that that η means the number 1. 6. Ester according to one of claims 1 to 5, characterized in that that Y stands for a hydrogen, fluorine, chlorine or bromine atom. 7. ester according to any one of claims 1 to 5, characterized in that that Y is a fluorine, chlorine or bromine atom in each case in the 6-position. 8. Ester according to one of claims 1 to 6, characterized in that g e k e η n- 1 2 indicates that R and R independently of one another for a Fluorine, chlorine or bromine atom, X is a hydrogen atom, η is the number 1 and Y is a fluorine or chlorine atom in the 6-position means. 9. Ester according to one of claims 1 to 8, characterized in that the 2 (2-rJ 2-R ² -Vinyl) -3,3-dimethylcyclopropanecarboxyl part has ice configuration. 10.Ester according to one of claims 1 to 9, characterized in that the 2 (2-R ¹ , 2-R ² -Vinyl) -3,3-dimethylcycl propane carboxyl part has 1R-cis configuration. 11. Process for the preparation of a 2-bromobenzyl ester of the general Formula I according to one of Claims 1 to 10, characterized in that that a compound of the general formula II 0300 18/0745 / 3 ORIGINAL INSPECTED 1A-52 700 -3- (ID COZ with a compound of the general formula III Br 1 2
reacted, in which R, R, X, Y and η have the meaning given in claim 1, one of the substituents Q and Z is a halogen atom and the other substituent is an OH group. ■ ^ .Pesticides contain a carrier and / or a surfactant along with a 2-bromobenzyl ester according to any one of claims 1 to 10 as an active ingredient. 030018/0745