SE427553B - ESTERS OF 3-HALOGEN-2, 2-DIMETHYLYCYLOPROPYL CARBOXYLIC ACID FOR USE AS INSECTICIDE - Google Patents

Description

The substituent Hal is preferably a chlorine, bromine or fluorine atom. Effective results in terms of achieved insecticidal activity have been obtained as Hal is a chlorine atom.

The substituents R 1 and R 2 are preferably both methyl groups.

The cyclopropyl carboxylates according to the invention can be prepared by conventional methods, e.g. esterification of a suitable acid with a suitable alcohol. Two generally preferred methods involve either reacting the acid chloride with the alcohol in the presence of a base (eg an amine such as triethylamine) or reacting the acid with a suitable alkyl halide in the presence of a base (eg an alkali metal salt such as potassium carbonate). Thus, a process for the preparation of the compounds of the invention comprises reacting a cyclopropyl compound of formula II: I - H Hal 31 I coz (II) R 2 with a substituted alkyl compound of formula III: "3 Y - ÄH - R 3 (III) ) (where one of the substituents Y and Z is an OH group and the other a halide (preferably a chloride) and Hal, R 1, R 2, R 3 and R 4 have the meanings given above) in the presence of a hydrogen halide acceptor, for example a base such as an organic or inorganic has. The reaction suitably takes place in an inert solvent and can be carried out at ambient temperature, e.g. a temperature in the range s-50 ° C.

In the preparation of the cyclopropyl carboxylates of the invention, the starting materials are essentially a substituted cyclopropyl carboxylic acid or a single derivative thereof (eg a compound of formula II) and an alkyl alcohol or a single derivative thereof (eg a compound of formula III) . The alcohols and the simple derivatives thereof are known compounds but the cyclopropyl acid and its derivatives are new compounds. The new compounds can be prepared by a process which essentially consists in a dehalogenation of the corresponding di-halo-cyclopropylcarboxylic acid in the presence of a dehalogenating agent, e.g. zinc and a lower alkanoic acid such as acetic or propionic acid.

The cyclopropyl carboxylates of the invention are of interest as pesticides, especially insecticides and acaricides in agriculture and for domestic use. Furthermore, they have shown a surprising activity as an exterminator for poultry such as Musca I domestica and thus have great value as insecticides in homes.

The invention therefore also comprises an insecticidal composition comprising a carrier and / or a surfactant and, as an active ingredient, a cyclopropylcarboxylate of the formula I. The invention also comprises a method for controlling insects within a field. and / or mites, which method is characterized in that a pesticidally effective amount of a cyclopropyl carboxylate according to the invention or a composition containing such a compound is introduced into the area. The term "carrier" here refers to a material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound is mixed or combined to facilitate the application to the plant, seed, soil or any other object which is to be treated, or its storage, transport or handling¿ The carrier can be a solid or a liquid. Any of the materials commonly used in the composition of pesticides, herbicides or fungicides can be used as carriers. Suitable solid carriers are natural or synthetic clays and silicates, for example natural silicas such as diatomaceous earth; magnesium silicates such as talc; magnesium aluminosilicates such as attapulgites and vermiculites; aluminosilicates such as kaolinites, montmorillonites and mica species; calcium carbonates; calcium sulfate; synthetic hydrated silica and synthetic calcium or aluminosilicates; elements such as carbon and sulfur; natural and synthetic resins such as coumaron resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorophenols; bitumen; 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; etrar; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as kerosene and light mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene, trichloroethane; and normally gaseously transferred liquid gaseous compounds. Mixtures of different liquids are often suitable.

The surfactant may be an emulsifier or dispersant or a wetting agent. It can be nonionic or ionic. Any of the surfactants commonly used in the manufacture of pesticides, herbicides or fungicides can be used. Examples of suitable surfactants are the sodium or calcium salts of polyacrylic acids and lignin sulfonic acids, condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and / or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; condensates thereof with ethylene oxide and / or propylene oxide; condensation products of fatty alcohols or alkylphenols, for example 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, of sulfuric acid or sulfonic acid esters containing at least 10 carbon atoms in the molecule, for example sodium lauryl sulphate, sodium sec-alkyl sulphates, sodium salts of sulphonated castor oil and sodium alkylaryl sulphonate sulphonylates; 7805561-5 and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide. The compositions of the invention may be used in the form of wettable powders, dusts, granules, solutions, emulsifiable concentrates and aerosols. Wettable powders usually have such a composition that they contain 25.50 and 75% of the toxic compound, and the solid carrier is usually 31-0% by weight of a dispersant and, when required, 8-10% by weight. % of one or more stabilizers and / or other additives such as penetrants or tackifiers. Dust is usually used in the form of concentrates with similar composition to the wettable powder but without any dispersant and diluted at the site of use with additional solid carrier to give a composition which usually contains 1/2 to 10% by weight of toxic compound. Granules are generally produced with a grain size between 1,676 and 0.152 mm and can be obtained by agglomeration or impregnation methods.

In general, granules contain 1 / 2-25% by weight of toxic compound and 0-10% by weight of additives such as stabilizers, modifiers to achieve slower release and binders. Emulsifiable concentrates usually contain, in addition to the solvent and, where required, the co-solvent 10-50% by weight of toxic compound, 2-20% w / v of emulsifiers and 0-20% w / v of suitable additives such as stabilizers, penetrants and corrosion inhibitors. The suspension concentrate is formulated to give a stable, non-sedimenting liquid product and usually contains 10-75% by weight of toxic compound, 0.5-15% by weight of dispersant, 0.1-10% by weight of suspending agent such as protective colloids and thixotropic agent. 10% by weight of suitable additives such as antifoams, corrosion inhibitors, stabilizers, penetrants and tackifiers, and as carriers water or an organic liquid in which the toxic compound is substantially insoluble. Certain organic solids and organic salts may be dissolved in the carrier to aid in the prevention of sedimentation or as antifreeze for water.

Dispersions and emulsions in water, for example compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, are also within the scope of the invention. Said emulsions may be of the water-in-oil or oil-in-water type and may have a thick, mayonnaise-like sauce. consistency.

The compositions of the invention may also contain other ingredients, for example other compounds having pesticidal, herbicidal or fungicidal properties. The invention is further elucidated by the following examples.

Example 1 - Preparation of alpha-cyano-3-phenoxybenzyl-3-chloro-2Z-dimethylcyclopropyl carboxylate. 3-Chloro-2,2-dimethylcyclopropanecarboxylic acid (0.75 g, 5.0 mm) and alpha-cyano-3-phenoxybenzyl bromide (1.45 g, 5.0 mm) were stirred together in acetone (30 nd) at room temperature for 4 hours. The reaction mixture was diluted with water and extracted with ether. The ether extracts were washed with sodium bicarbonate (x4) and dried over magnesium sulfate. Upon removal of the solvent, a yellow oil was obtained which was purified by elution from a silica gel column using 3% acetone / hexane; refractive index nD20l.5623.

Analysis: Calculated for C 26 H 18 NO 3 Cl: C 67.6; H 5.1; N 3.9 Found: I "C 67.7; H 5.1; N 3.ö Example 2 - Preparation of 5-hensyl-3-furylmethyl-3-chloro-2,2-dimethylcyclopropylcarboxylate. 3-chloro-2,2-dimethylcyclopropanecarboxylic acid (0.7 g, 4.7 mm) in toluene (20 ml) was heated under reflux for 45 minutes with an excess of thionyl chloride, the solvent was removed and the crude 3-chloro-2,2-dimethylcyclopropanoic acid chloride in toluene (20 ml) was added to 5-benzyl chloride. 3-Hydroxymethylfuran (11 g, 5.8 mm) and triethylamine (1.0 g) in toluene at room temperature The mixture was stirred overnight, diluted with water and extracted with diethyl ether.The ether extracts were washed with sodium bicarbonate (x2) and On removal of the solvent, an orange oil was obtained which was purified by elution from a silica gel column using toluene; refractive index nD2l l.54l4.

Analysis: Calculated for C 18 H 19 O 3 Cl: C 67.8; H 6.0% Found: a C 67.8; H 6.1% 78Û3561 ~ 5 Examples 3-5 Further examples of the compounds according to the invention were prepared by methods similar to those described in the previous examples. These compounds and their physical data are shown in Table I amvwee H mx. wmwm fl wbm w fi w fi äwßmml wbwwwm UH wbmmx we w w m w ß w mlnw fifi wl wwemomwwwwswmo: uwïiwïe www. än oämwmzoknw "omger 93 z» år anamma aware; .få z kb * _ _ .am .fmmso fi mmsww su fi fmawa .wß fi ma ... nämäoece "namb" Fm »Hüd fi n fi U Omw.o¶ m.æw w åmom wåmsoïmmswe so fi fi www n fi mäownï aik ”P3 W fi bbmd u OÉLH" m.mw 7803561-5 Exemgel 6 The insecticidal activity of the compounds according to the invention was tested on the following insects: ~ 0 The insects: Musca domestica (M. d.) 4 Phaedon cochleariae (P. c.) Spodoptera litteralis (S. l.) Aphis fabae (A. f.) g The test methods used for the different insect species were as follows: '(1) Musca domestica (Md) A 0.4% (wt%) solution in acetone of the compound to be tested was prepared and taken up in a micrometer siphon. 2-3 day old adult houseflies (Musca domestica) of the female were anesthetized with carbon dioxide and llul »of the test solution was placed on the abdominal side of each fly's hind body. 20 flies were tested. The treated flies were kept in glass beakers covered with paper cloth which was held in place by an elastic band. Cotton swabs soaked in dilute sugar solution were placed on top of the paper cloth as nourishment. After 24 hours, the percentage of 'dead and dying flies' was noted. (2) Phaedon cochleariae (P.c.). The compounds are used in the form of solutions or suspensions in water containing 20% by weight of acetone and 0.05% by weight of Triton X-100 as wetting agent. The formulations contained 0.4% by weight of the compound to be tested. Predatory bean seedlings trimmed to a single remaining leaf were sprayed on the underside of the leaf with the said preparation. The spraying was done with a spraying machine that emitted 340 liters per hectare, and the plants were carried under the spray jet on a conveyor belt. After spraying, the plants were allowed to dry for 1 / 2-1 hour and then enclosed in a 450 ml bottle from which the bottom was removed. 10 adult, 2-3 week old mustard beetles (Phaedon cochleariae) were placed on the sprayed leaves of each predatory plant. The open bottle ends were then sealed with square pieces of paper held in place by elastic bands. Mortality was noted after 24 hours. (3) Spodogtera litteralis (S. p.). Pairs of leaves were removed from broad bean seedlings and placed on filux paper in plastic petri dishes. The leaves were sprayed in the same manner as in 7803561-5 under (2) using the same concentrations. After spraying, the leaves were allowed to dry for 1 / 2-1 hour, after which 10 larvae of the Egyptian cotton leaf worm (Spodoptera litteralis) were applied to them. After 24 hours, the percentage of dead and dying larvae was noted. _. (4) Aghis fabae (A.f.). Pairs of leaves were removed from the farm bean plants and placed upside down on filter paper in a 9 cm petri dish. 10-20 adult, 5-7 day old aphids were transferred to a filter paper in a 5 cm petri dish covered with a lid of metal fabric. The leaves and aphids were sprayed in parallel with a 0.2% solution or suspension of the compound in 20% acetone in water containing 0.05% Triton X-100. After spraying, the aphids were transferred to the sprayed leaves and the percentage of dead and dying individuals was counted after 24 hours.

The results of these experiments are summarized in Table II, where the insects are designated with their initials above and A means complete extinction, B partial extinction and C no dead insects.

Table II Insecticidal activity according to M.d. P.c. S.l. A.f. 1 A A A B 3 C A B B 4 A A A A A 5 A A A A 2 A B A A Example 7 The acaricidal activity of the compounds of the invention was tested on the mite Tetranychus urticae (T.u.).

The test method used was as follows: On slices cut from the leaves of cut bean plants, 10 T.u. mites were applied 1 hour after drying in the same manner as described in Example 6 for the insect Phaedon cochleariae. Mortality determinations were performed after 24 hours. The results of these are shown in Table III, where the mite is designated in the same way as in the previous example.

Table III Acaricidal activity I I Compound acc. T.u.

Example 8 The eradication activity of the compounds of the invention on the common housefly (Musca domestica) was determined using the Kearn-March chamber test.

The Kearn-March chamber consists of a transparent glass cylinder with the dimensions 9x3 dm, in which flies can be let in through a sliding wall at one end. 0.2 ml of a 20% MeCl 2/80% _SheIlsol K solution containing active material was injected for 1 1/2 seconds into the chamber at a pressure of 0.7 kg / cm 2 and the air supply was maintained for a further 2 seconds to - easy even distribution of the spray jet. About 70 flies were used in each treatment and eradication counts were made 1, 2, 3, -4, 5, 7 and 10 minutes after each injection. The compounds were graded using six classes depending on the concentration of the toxic compound required to achieve 90% eradication after 10 minutes, i.e.

Class 0 90% after 10 minutes concentration 0.025% Class 1 90% after 10 minutes = concentration 0.05% Class 2 90% after 10 minutes = concentration 0.1% Class 3 90% after 10 minutes = concentration 0.2% Class 4 90% after 10 minutes = concentration 0.4% Class 5 90% after 10 minutes = concentration 0.4% Class 6 No extinction at 0.4% 7803561-5 11 The results of these experiments are shown in Table IV.

Table IV Extinction activity Association according to Class Example 1 0 2 0 3 1 4 0 5 0 COMPARATIVE EXPERIMENTS Representative compounds of the present invention and the most closely related compounds of Swedish patents 376,604 (patent A) and 414,304 (patent B) were evaluated for eradication activity with respect to Musca domestica according to the procedure of Kearns-March described in detail in Example 8 of the specification. The results are given in the table below, where the compounds tested are identified by reference to the substituents of the following formula: x coo - from H

Claims (2)

780356145 12 Test compound Extermination 1. A B X Source activity H Cl H Exawxn 4 acc. 0 fi næl.ans. _ Ücl cl n Patent A 3 H Cl CÉCH Etxenpel 5 enl. förel.ans. Cl Cl CECH Patent B CH3 CH3> CECH. Bc Claim 71. Cyclopropylcarboxylates for use as insecticides, characterized in that they have the general formula H _Hal 33 (I) 31 CO - O - GH - RÄ 122 H _ wherein Hal is a fluorine. , chlorine or bronze atom, R 1 and R 2 are each an alkyl group having 1-6 carbon atoms, R 3 is a hydrogen atom or a cyano or ethynyl group and R 4 is a phenoxyphenylph, benzylfuryl or tetrahydrophthalimido group. 2. Compounds according to claim 1, characterized in that Hal is a chlorine atom and R1 and R2 are each a methyl-9ruPP-