DK159261B - 2-CHLOR-6-HALOGENBENZYL-2- (2,2-DIHALOGENVINYL) -3,3-DIMETHYL-CYCLOPROPANCARBOXYLATES, PROCEDURES FOR PREPARING THEREOF, PESTICIDE PREPARATION COMPOSITIONS CONTAINING COMPONENTS OR CONNECTING COMPONENTS CONNECTING CONNECTIONS - Google Patents

Description

DK 159261B

The present invention relates to 2-chloro-6-halogeribenzyl-2- (2,2-di-halo vinyl) -3,3-dimethyl-cyclopropane carboxylates, processes for their preparation and compositions containing them for use as pesticides, in particular as insecticides and acaricides.

Belgian Patent Specification No. 862,109 describes a general class of compounds of the formula

/ R

H CH = C ^ CH] ιΛ, CO - O - CH 2 - CH 3 \ Fn 10 where the symbols R, which may be the same or different, denote fluorine, chlorine or bromine and, when R denotes fluorine or bromine, m is 0- 5, and n is 0-5, provided that m and n are not both 0; when R is chlorine, m is 0-4, and n is 1-5, and when m is 0 and n is 5, R may also be methyl. This Belgian patent also mentions in general the existence of similar known compounds in which the benzyl moiety is only substituted with chlorine.

It has now surprisingly been found that a novel class of compounds falling under the broad group of the compounds described above has particularly useful pesticidal action, especially 20 surprising miticidal action in addition to insecticidal action.

The present invention therefore relates to 2-chloro-6-halo-benzyl-2- (2,2-dihalo-vinyl) -3,3-dimethyl-cyclopropane carboxylates of the general formula I

2

DK 15926 1 B

/ r1

H HC = C

y v k ch3 J - \ - co - o - ch2-P y CH-, H /

Y

wherein at least two of R 2 and Y represent chlorine and the last one represents 5 chlorine or fluorine in the form of at least one of its cis isomers.

Preferred among the compounds of the present invention are those compounds of formula I, conventionally referred to as 1,1 R-cis compounds.

The compounds of formula I can be prepared by analogy to methods known per se. In a suitable process, a compound of general formula II is reacted

/ R

H CH = C

Y ^ coz ch3 h

DK 159261 B

3

with a compound of the general formula III

Cl Q - ch 2 -5 where R 1 and Y have the meaning given above and one of the symbols Q and Z represents halogen, preferably chlorine or bromine, and the other represents hydroxy. The reaction is carried out, preferably 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 vicinity of an inert solvent. Z is suitably hydroxy and Q is chlorine or bromine.

The compounds of formula II and the individual isomers thereof are conveniently prepared in known manner, for example as described in GB 1,413,491 and 1,448,228.

The compounds of formula III are readily prepared from 2,6-dichloro-toluene and 2-chloro-6-fluorotoluene, which are known compounds, by conventional halogenation techniques, e.g. reaction with N-bromosuccinimide and, if desired, subsequent hydrolysis.

The compounds of the present invention are of interest as pesticides, especially as insecticides and acaricides for the household and agricultural fields. Thus, the present invention comprises pesticidal compositions containing a carrier and / or a surfactant together with a 2,6-dihalo benzyl ester of formula I as active ingredient. The invention also relates to a method for controlling insects, blood mites and / or acarides, especially mites, at a site wherein a pesticide effective amount of a 2,6-dihalo benzyl ester of the present invention or composition is applied to the site. containing such a compound.

DK 159261 B

4

The term "carrier" as used herein refers to a material which may be inorganic or organic and of synthetic or natural origin by which the active ingredient is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated. read, or its storage, transport or handling. The carrier may be solid or liquid. Any material commonly used to formulate pesticides, herbicides or fungicides can be used as a carrier.

Suitable solid carriers are natural and synthetic clays and silicates, e.g. or aluminum silicates, elements such as carbon or sulfur, natural or synthetic resins such as cumaroh resins, polyvinyl chloride or styrene polymers, solid polychlorophenols, bitumen, waxes such as beeswax, paraffin waxes or chlorinated mineral waxes or solid fertilizers such as superphosphates.

Suitable liquid carriers are water, alcohols such as isopropanol or glycols; ketones, for example acetone, methyl ethyl ketone or cyclohexanone; ethers, aromatic hydrocarbons such as benzene, toluene or xylene, petroleum fractions, e.g., petroleum or light mineral oils, chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene or trichloroethane or condensed, usually vaporous gaseous compounds. Mixtures of different liquids are often suitable.

The surfactant may be an emulsifier, a dispersant, or a wetting agent; it can be non-ionic or ionic. Any of the surfactants commonly used to formulate pesticides, herbicides or fungicides may be used. Examples of suitable 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 having at least 12 carbon atoms in the molecule 35 with ethylene oxide and / or propylene oxide, fatty acid esters of glycerol,

DK 159261 B

5 sorbitan, sucrose or pentaerythritol, condensates thereof with ethylene oxide and / or propylene oxide, condensation products of fatty alcohols or alkyl phenols, e.g. p-octylphenol or p-octylcresol, with ethylene oxide and / or propylene oxide, preferably sodium salts, or sulfuric acid or sulfonic acid esters having at least 10 carbon atoms in the molecule, e.g.

The compositions of the present invention may be formulated as wettable powders, powders, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates or aerosols.

Wettable powders are usually formulated to contain 25, 50 or 75% toxicant and usually contain, in addition to solid carrier, 31-0% by weight of a dispersant and, if necessary, 0-10% by weight of stabilizer (s) and / or other additives such as penetrants or adhesives. Powders are usually formulated as a powder concentrate having a similar composition to a wettable powder, but without a dispersant, and diluted by use with additional solid support to form a composition which usually contains 1 / 2-10% by weight of toxicant.

The granules are usually prepared with a size of between 10 and 25,100 BS mesh (1,676-0,152 mm) and can be prepared by agglomeration or impregnation techniques. Granules generally contain 0.5-25% by weight of toxicant and 0-10% by weight of additives such as stabilizers, slow release modifiers and binders. Emulsifiable concentrates usually contain in addition to the solvent and, if necessary, co-solvent, 10-50% by weight toxicant, 2-20% w / v emulsifiers and 0-20% w / v suitable additives such as stabilizers, penetrants or corrosion inhibitors. Suspension concentrates are formulated to provide a stable, non-sedimenting liquid product and usually contain 10-75 wt% toxicant, 0.5-15 wt% dispersants, 0.1-10 wt% suspending agents such as protective colloids or thixotropy agents, 0-10 wt%

DK 159261 B

6 suitable additives such as anti-foaming agents, corrosion inhibitors, stabilizers, penetrating agents and adhesives and carrying water or an organic liquid wherein the toxicant is substantially insoluble; certain organic solids or inorganic salts may be dissolved in the carrier to help prevent sedimentation or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example, compositions prepared by diluting a wettable powder or concentrate of the present invention with water, also fall within the scope of the present invention. The emulsions may be water-in-oil or oil-in-water type and have a thick "mayonnaise" -like texture.

The compositions of the present invention may also contain other ingredients, for example, other compounds having pesticidal, herbicidal or fungicidal properties.

The present invention is further illustrated by the following Examples: EXAMPLE 1

Preparation of 1,1-cis-2-chloro-6-fluorobenzyl 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylate.

a) Preparation of 2-chloro-6-fluorobenzyl bromide.

14.45 g of 2-chloro-6-fluorotoluene and 19.6 g of N-bromosuccinimide are stirred together with 0.1 g of azo-bis- (isobutyronitrile in anhydrous carbon tetrachloride under reflux for 18 hours exposure to radiation from an infrared lamp The resulting solution is cooled in ice, filtered and evaporated to give a pale orange liquid which is distilled off under reduced nitrogen pressure to give 20.1 g (90% of theory) of the title compound, boiling point 74 ° C. 3.00 mm Hg.

b) Preparation of 1,1-cis-2-chloro-6-fluorobenzyl 2- (2,2-dichloro-vinyl) -3,3-dimethylcyclopropane carboxylate.

DK 159261 B

7 1.1 g of 1, R-cis-2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylic acid, 1.1 g of 2-chloro-6-fluorobenzyl bromide and 0.7 g of anhydrous potassium carbonate are stirred. together in acetone under reflux for 2 hours. The reaction mixture is cooled, diluted with water and extracted three times with 50 ml portions of diethyl ether. The combined extracts are washed with aqueous sodium bicarbonate solution, dried over magnesium sulfate, evaporated and purified on a silica column, eluting with toluene, and evaporated to give 1.8 g (100% of theory) of the title compound.

Refractive index n + = 1.5420 [α] D54 = -22.4 ° (C2, CHCl3).

EXAMPLE 2

Preparation of 1,1-cis-2,6-dichlorobenzyl 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylate.

3.5 g, R-cis-2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylic acid, 3.0 g of 2,6-dichlorobenzyl chloride, 0.5 g of potassium iodide and 2.3 g of potassium carbonate are stirred. together in acetone under reflux for 2 hours. The reaction mixture is treated as described in Example 1 to give 5.6 g (100% of theory) of the title compound.

Refractive index njp = 1.5638 [ce] g5 = -26.50 ° (C2, CHCl3).

DK 159261 B

8 EXAMPLES 3-5

The following compounds are prepared in a similar manner as described in Examples 1 and 2: cis-2,6-dichlorobenzyl 2- (2-chloro-2-fluorovinyl) -3,3-dimethylcyclo-propane carboxylate (yield 86% of theory) = 1,541 (Example 3), cis-2-chloro-6-fluorobenzyl 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylate (yield 98% of theory), n 5401 (Example 4) cis-2,6-dichlorobenzyl 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylate (yield 87% of theory), m.p. 91-95 ° C (Example 5).

Pesticide tests

The insecticidal and tickicidal effect of the compounds of this invention are assessed using the following harmful organisms:

Insects: Musca domes tica (M.d.)

Spodoptera littoralis (S. L.)

Aphis Fåbae (A.f.)

Heliothis zea (H.z.) 20 Mites: Tetranychus urticae (T.u.)

Blood mites: Boophilus microplus (B.m.).

The test methods used for each species are listed below: i) Musca domes tica (M.d.).

A 0.4% by weight solution in acetone of the compound to be tested is prepared and taken up in a micrometer syringe. 2 to 3 day old adult female flies (Musca domestica) are anesthetized with carbon dioxide and 1 µl of the test solution is placed on the ventral side of the abdomen on each fly. 20 flies are being tested. The treated flies are held in glass jars, covered with tissue paper, which is held with a

DK 159261B

9 elastic. Cotton sticks soaked with dilute sugar solution are placed on top of the tissue paper as a lining. After 24 hours, the percentage of dead and dying flies is noted.

ii) Spodoptera littoralis (S.I.).

5 Leaf pairs are removed from horse bean plants and placed on filter paper inside plastic Petri dishes. The leaves are sprayed on the underside with an aqueous formulation containing 20 wt.% Acetone, 0.05 wt.% "TRITON" ® X-100 as wetting agent and 0.4 wt.% Of the compound to be tested. After spraying, the leaves are allowed to dry for 0.5-1 hour and then each pair of leaves is infected with 10 larvae of the Egyptian cotton worm (Spodoptera littoralis) and after 24 hours the percentage of dead and dying larvae is noted.

iii) Aphis fabae (A.f.).

Tests on adult aphids (Aphis fabae) are performed by similar procedures to those used for Spodoptera littoralis in section ii) above.

iv) Heliothis zea (H.z.).

The compounds to be tested are incorporated in aqueous solutions containing 20% by weight acetone, 0.04% by weight "Atlox" ® 1045A and 0.2% by weight of the test compound; more dilute solutions for dose-mortality curves are prepared by diluting a 0.2% solution with an aqueous solution of 0.05% by weight "Atlox" ® 1045A. Cut Windsor horse beans on a turntable and sprayed with 4 ml of test solution. Immediately after spraying, 5 Heliothis zea larvae are transferred to each plant, which is immersed in water through a hole in the test table, and the environment is maintained at a temperature of 27 ° C and 40-50% relative humidity. Mortality is assessed after 44-46 hours.

V) Tetranychus urticae (T.u.)

DK 159261 B

10

Slices are cut from the leaves of Phaseolus vulgaris plants and placed on filter paper, which is kept moist by a cotton swab dipped in water. Each slice is infected with 10 adult mites, and the slices are then sprayed with a solution or suspension of the test compound ice in acetone water (20:80) containing 0.05% "TRITON" ® X-100 as wetting agent.

vi) Boophilus microplus (B.m.)

A 0.1% by weight solution of the compound to be tested is prepared in acetone which contains 10% by weight of polyethylene glycol. Different concentrations are obtained by diluting this solution. 1 ml of the test solution is uniformly placed on a filter paper in a Petri dish. When the filter paper is sufficiently dry, it is folded once and folded along a portion of its outer edge to form a package. Ca. 80-100 2-3-week-old one-host cattle larvae (Boophilus microplus) are transferred to the package, which is then completely closed. The package is placed in an incubator at 27 ° C and 80% relative humidity. After 24 hours, the package is opened and the percentage of dead and dying larvae is assessed.

The results are given in Table I, in which the test species are identified at the initials listed above and the activity of the compound is expressed in terms of its toxicity index, which is calculated from the following equation: LC50 value for ethyl parathion (standard)

Toxicity Index (T.I.) - - 25 LC5o value for test compound

The knockdown activity of the compounds of this invention is assessed using room flies (Musca domestics) in the Kearns-March chamber test.

The Kearns-March chamber consists of a ca. 61 x 30.5 cm transparent 30 glass cylinder to which flies can be passed through a slider at one end. 0.2 ml of a solution in 20% methylene chloride / 80% "Shell Shell" of the active material is sprayed for 1.5 seconds in the chamber at ca.

DK 159261B

11 0.7 kg / cm 2 and the air supply is maintained for an additional 2 seconds to facilitate uniform distribution of the spray. Approx. 70 flies in each treatment and knockdown counts are performed 1, 2, 3, 4, 5, 7 and 10 minutes after the spraying. The compounds are ranked in six classes according to the toxicant concentration required to achieve 90% knockdown after 10 minutes, ie.

class 0 90% at 10 minutes = concentration 0.025% class 1 90% at 10 minutes - concentration 0.05% class 2 90% at 10 minutes = concentration 0.1% 10 class 3 90% at 10 minutes = concentration 0.2 %.

class 4 90% at 10 minutes = concentration 0.4% class 5 <90% at 10 minutes = concentration 0.4% class 6 no knockdown at 0.4%.

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

Table I

Compound Toxicity Index Knock-down- from eczema classes pel no. Md. S.l. Of. H.Z. T.u. B. M.

20 _ 1 44 96 26 30 98 908 0 2 44 98 12 28 33 1110 1 3 13 44 5 + 34 1200 2 4 23 41 22 34 72 400 1 25 5 17 107 26 80 61 381 2 + not tested

Furthermore, to detect the surprising and unpredictable nature of the present invention, pesticide testing of a variety of dichlorobenzyl esters of 2- (2,2-dichlorovinyl) -3,3-dimethyl-cyclopropane carboxylic acids by the above invention was performed. methods described. The results are shown in Table II below, in which toxicity indices are as described above with the exception of grades B and C.

DK 159261 B

12 ut from tests using a single compound dose of 0.2% by weight. Grades B and C indicate percentages of mites killed, with grade B being 30-80% and grade C less than 20%. The compounds for which numeric toxicity data are given all obtained the grade A, which represents a kill rate of over 90%.

TABLE II

Position of chlorine substitution- Index of toxicity (parathion - 100) enter on benzyl moiety (isomer ___ 10 form of ester) H.d. S.l. Of. T.u 2.6 (cis) 17 107 26 61 2.6 (cis / trans) 21 77 26 17

2.3 (cis / trans) 8 29 12 B

2.4 (cis / trans) 6 23 6 C

2.5 (cis / trans) .3 17 3 C

3.4 (cis / trans) 2 19 2 C

3.5 (cis / trans) 2 10 C C

The results for the mites Tetranychus urticae clearly show the surprising and unpredictable effect of the present invention.

Finally, closely related compounds were made and tested known from Danish Patent Application No. 4893/77. These 25 compounds and the results obtained (similar in all respects to the methods used for Tables I and II) are shown in Table III below.

Claims (5)

Compound R Y Isomers Toxicity Index (parathion == 100) M.d. S.l. Of. T.u. 10 (i) F Cl cis / trans 16 56 11 5 (ii) Br Cl cis 19 48 8 4 (iii) Cl F cis 13 34 14 22 (iv) Cl F trans 19 41 9 10 Table III shows that the results obtained for mites (Tetranychus urticae) in Table I are extremely surprising and could not have been predicted by the prior art. 1. 2-Chloro-6-halogeribenzyl-2- (2,2-dihalovinyl) -3,3-dimethylcyclopropane carboxylate of the general formula I R 1 H HC = Cl 2 / N 2 Cl Y y ~ \ CH 3 Wherein at least two of rA, R4 and Y represent chlorine and the latter represents chlorine or fluorine in the form of at least one of its cis isomers. The ester according to claim 1, characterized in that it is in the form of its R-cis isomer. Process for the preparation of a 2-chloro-6-halo-benzyl-2- (2,2-dihalo-vinyl) -3,3-dimethyl-cyclopropane carboxylate of the general formula I according to claim 1 or 2, characterized in that a compound with the general formula II \ / v 10 \ / II ch3 / \ em ch3 h is reacted with a compound of the general formula III Cl y ~~ \ 0-¾- <y ih Y 15 wherein R 1, R 2 and Y have it as defined in claim 1 and one of the symbols Z and Q is halogen and the other is hydroxy. A pesticide composition, characterized in that it contains a carrier and / or a surfactant together with a 2-chloro-6-halo-benzyl-2- (2,2-dihalo-vinyl) -3,3-dimethyl-cyclopropane carboxylate according to claim 1 or 2 as active ingredient. DK 15926 1 B Process for controlling harmful organisms at a site, characterized in that a 2-chloro-6-halo-benzyl-2- (2,2-dihalo-vinyl) -3,3-dimethyl-cyclopropane-carboxylate according to the site is applied at the site. claim 1 or 2 or a composition according to claim 4.