GB1597487A

GB1597487A - Pesticidal cyclopropane carboxylates

Info

Publication number: GB1597487A
Application number: GB13621/77A
Authority: GB
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 1977-03-31
Filing date: 1977-03-31
Publication date: 1981-09-09
Also published as: CA1093563A; JPS53121744A; ES468309A1; BE865430A; ZA781796B; EG13297A; SE7803561L; IL54381A0; IT1096165B; DK139378A; DE2813552A1; AU3453478A; CH636072A5; FR2385678B1; IT7821740A0; NL7803355A; IL54381A; SE427553B; AU515078B2; BR7801928A

Abstract

New cyclopropanecarboxylates of the formula <IMAGE> in which X denotes a halogen atom, R<1> denotes a hydrogen atom or an alkyl group, R<2> denotes an alkyl group, or R<1> and R<2> together denote an alkylene chain, R<3> denotes a hydrogen atom or a cyano, ethinyl or thioamide group, and R denotes a phenoxyphenyl, benzylphenyl, phenylthiophenyl, benzylfuryl, halophenyl, phthalimido, tetrahydrophthalimido or halophenoxyphenyl group, are used as pesticide, in particular as insecticide and acaricide.

Description

(54) PESTICIDAL CYCLOPROPANE CARBOXYLATES (71) We, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V., a company organised under the laws of The Netherlands, of 30 Carel van Bylandtlaan, The Hague, The Netherlands, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to cyclopropane carboxylates to a method for their pre paration and to pesticidal compositions containing them.

The present invention provides cyclopropane carboxylates having the following general fonnula:--

wherein X is a halogen atom; R1 is a hydrogen atom or an alkyl group; R2 is an alkyl group; or R1 and R2 together represent an alkylene chain; RS is a hydrogen atom, a cyano, ethynyl or thioamido group; and R is a phenoxyphenyl, benzylphenyl, phenylthiophenyl, benzylfuryi, halophenyl, phthalimido, tetrahydrophthalimido, or halophenoxyphenyl group.

Preferred compounds according to the invention are those having general formula I wherein X is a halogen atom; R1 is a hydrogen atom or an alkyl group of 1 to 6 carbon atoms; R2 is an alkyl group of 1 to 6 carbon atoms or Rl and R2 together represent an alkylene chain of up to 5 carbon atoms; R3 is a hydrogen atom or a cyano or ethynyl group; and R is a phenoxyphenyl, benzylfuryl, phthalimido or tetrahydrophthalimido group.

The substituent X is a halogen atom in the compounds according to the invention and it is preferably a chlorine, bromine or fluorine atom; effective results in terms of the resulting pesticidal activity have been obtained when X is a chlorine atom.

The substituents R1 and R2 are preferably both methyl groups or R2 is a methyl group and R1 a hydrogen atom.

The cyclopropyl carboxylates according to the invention may be prepared by conventional methods e.g. the esterilication of the appropriate acid by the appropriate alcohol. Two generally preferred methods involve either reaction of the acid chloride with the alcohol in the presence of base (e.g. an amine such as triethylamine), or, the reaction of the acid with the appropriate substituted alkyl halide in the presence of a base (e.g. an alkali metal salt such as potassium carbonate). Thus a process for preparing the the compounds according to the invention comprises reacting a cyclopropyl compound of formula II:

with a substituted alkyl compound of formula III:

(wherein one of the substituents Y and Z represent an -OH group and the other represents halogen atom (suitably a chlorine atom), and X, R1, R2, R3 and R have the meanings hereinbefore specified) in the presence of a hydrogen halide acceptor, for example a base such as an organic or inorganic base. The reaction is suitably carried out in an inert solvent and may be effected at ambient temperature, e.g. a temperature in the range 5 to 50 C.

In the preparation of the cyclopropane carboxylates according to the invention the starting materials are essentially a substituted cyclopropane carboxylic acid or a simple derivative thereof (e.g. a compound of formula II) and an alkyl alcohol or a simple derivative thereof (e.g. a compound of formula III). The alcohols and simple derivatives thereof are known compounds but the cyclopropane acid and derivatives are novel compounds; the novel compounds and a process for their preparation are dis closed in copending application UK 3164/77 (Serial No. 1 594 224); this process essentially consists of dehalogenating the corresponding di-halo-cyclopropyl carboxylic acid in the presence of a dehalogenating agent, e.g. zinc and a lower alkanoic acid such as acetic or propioffic acid.

The cyclopropyl carboxylates according to the invention are of interest as pesticides, in particular as insecticides and acaricides for agricultural and domestic outlets.

Moreover they have shown surprising activity as knockdown agents for flying pests such as Musca domestica and thus are potentially useful for domestic insecticidal uses. The invention therefore includes within its scope a pesticidal composition comprising a carrier and/or a surface-active agent together with, as active ingredient, a cyclopropyl carboxylate of formula I. The invention also includes a method of combating insect and/or acarid pests at a locus which comprises applying to the locus a pesticidally effective amount of a cyclopropyl carboxylate according to the invention or composition containing such a compound.

The term ' carrier' as used herein means a material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated, or its storage, transport or handling. The carrier may be a solid or a liquid.

Any of the materials usually applied in formulating pesticides, herbicides, or fungicides may be used as the carrier.

Suitable solid carriers are natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earths; magnesium silicates, for example, talc; magnesium aluminium silicates, for example, attapulgites and vermiculites; aluminium silicates, for example, kaolinites, montmorillinites and micas; calcium carbonates; calcium sulphate, synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates; elements for example, carbon and sulphur; natural and synthetic resins such as, for example coumarone resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorophenols; bitumen; waxes such as for example, beeswax, paraffin wax, and chlorinated mineral waxes; and solid fertilisers, for example superphosphates.

Suitable liquid carriers are water, alcohols, for example, isopropanol and glycols; ketones for example, acetone, methyl ethyl ketone, and cyclohexanone; ethers; aromatic hydrocarbons, for example, benzene, toluene and xylene; petroleum fractions, for example, kerosine and light mineral oils; chlorinated hydrocarbons, for example, carbon tetrachdoride, perchloroethylene, trichloroethane; and liquefied normally vaporous, gaseous compounds. Mixtures of different liquids are often suitable.

The surface-active agent may be an emulsifying agent or a dispersing agent or a wetting agent; it may be nonionic or ionic. Any of the surface-active agents usually applied in formulating pesticides herbicides or fungicides, may be used. Examples of suitable surface-active agents are the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or anides 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; con densates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohols or alkyl phenols for example p-octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or alkaline earth metal salts, preferably sodium salts, or sulphuric or sulphonic acid esters containing at least 10 carbon atoms in the molecule, for example, sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alEylaryl sulphonates such as sodium dodecylbenzene sulphate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The compositions of the invention may be formulated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders are usually compounded to contain 25, 50 and 75% of toxicant and usually contain, in addition, to solid carrier, 3-10% w of a dispersing agent and, where necessary, 0-10% w of stabiliser(s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of wettable powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing ~ 10% w of toxicant. Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676-0.152 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 2 25% w toxicant and 010% w of additives such as stabilisers, slow release modifiers and binding agents.

Emulsifiable concentrates usually contain, in addition to the solvent and, when neces sary, co-solvent, 10-50% w toxicant, 2.20% w/v emulsifiers and 0-20% w/v of appropriate additives such as stabilisers, penetrans and corrosion inhibitors. Suspension concentrates are compounded so as to obtain a stable, non-sedimenting flowable product and usually contain 1075% w toxicant, 0.515% w of dispersing agents, 0.1 10% w of suspending agents such as protective coloids and thixotropic agents, 0-10% w of appropriate additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and as carrier, water or an organic liquid in which the toxicant is substantially insoluble; certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example, compositions obtained by dilut ing a wettable powder or a concentrate according to the invention with water, also lie within the scope of the present invention. The said emulsions may be of the water-in-oil or of the oil-in-water type ,and may have a thick ' mayonnaise '-like consistency.

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

The invention is further illustrated in the following examples.

Example 1.

Preparation of alpha-cyano-3-phenoxybenzyl 3 -chioro-2,2 dimethylcyclopropane 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 ml) 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 ( x 4) and dried over magnesium sulphate. Removal of solvent gave a yellow oil which was purified by eluting from a silica gel.- column using 3% acetone/hexane, R.I. nD20 1.5623.

Analysis Calculated for C20H18NO3Cl: C 67.6; H 5.1; N 3.9% Found: C 67.7; H 5.1; N 3.8% Example 2.

Preparation of 5-benzyl-3 -furylmethyl 3-chloro-2,2-dimethylcyclopropane carboxylate 3-Chloro-2,2-dimethylcyclopropanecarboxylic acid (0.7 g, 4.7 mm) in toluene (20 ml) was refluxed with excess thionyl chloride for 45 minutes. The solvent was removed and the crude 3-chloro-2,2-dimethylcyclopropane acid chloride in toluene (20 ml) added to 5-benzyl-3-hydroxymethylfuran (1.1 g, 5.8 mm) and triethylamine (1.0 g) in toluene (20 ml )at room temperature. The mixture was stirred overnight, diluted with water and extracted with diethyl ether. The ether extracts were washed with sodium bicarbonate ( x 2) and dried over magnesium sulphate. Removal of solvent gave an orange oil which was purified by eluting from a silica gel column using toluene, R.I. nU21 1.5414.

Analysis Calculated for C18H19O3Cl: C 67.8; H 6.0% Found: C 67.8; H 6.1% Examples 3-3.

Further examples of the compounds according to the invention were prepared by methods similar to those described in the preceding Examples. These compounds and their physical data are presented in Table I.

TABLE I

COMPOUND Example No. R R R.I. Analysis 3 H 3,4,5,6-tetrahydrophthalimido nD211.5270 Calculated for C15H18NO4Cl C 57.8; H 5.8; N 4.5% Found C57.2; H 5.1; N 4.2% 4 H 3-phenoxyphenyl nD211.5627 Calculated for C19H19O3Cl C 68.9; H 5.8% Found C 69.0; H 5.8% 5 -C#CH 3-phenoxyphenyl nD211.5642 Calculated for C21H19O3Cl C 71.1; H 5.4% Found C 71.1; H 5.5% Example 6.

The insecticidal activity of the compounds according to the present invention was assessed employing the following pests: Insects: Musca domestica (M.d.) Phaedon cochleariae (P.c.) Spodotera littoralis (S.l.) Aphis fabae (A.f.) The test methods employed for each species appear below: (i) Musca domestica (M.d). A 0.4% by weight solution in acetone of the compound to be tested was prepared and taken up in a micro-meter syringe. Two to three day old adult female houseflies (Musca domestica) were anaesthetised with carbon dioxide, and 1 l of the test solution was applied to the ventral side of the abdomen of each fly, 20 flies being tested. The treated flies were held in glass jars covered with paper tissue held by an elastic band. Cotton-wool pads soaked in dilute sugar solution were placed on top of the tissue as food. After 24 hours the percentage of dead and moribund flies were recorded.

(ii) Phaedon cochleariae (P.c.). The compounds were formulated as solutions or sus pensions in water containing 20% by weight of acetone and 0.05 c/ by weight of Triton X-100 (" TRITON " is a registered Trade Mark) as wetting agent. The formulations contained 0.4% by weight of the compound to be tested. Turnip and broad bean plants, trimmed to one leaf each, were sprayed on the undersurface of the leaf with the above formulation. Spraying was effected with a spraying machine, delivering 340 litres per hectare, the plants passing under the spray on a moving beltt. After spraying, the plants were left for B--1 hour drying period and then each plant was enclosed within a 450 ml bottle from which the bottom had been removed. Ten adult 2-3 week old mustard beetles (Phaedon cochleariae) were placed on the sprayed leaf of each turnip plant. The open ends of the bottle were then closed with squares of paper tissue held with elastic bands. Mortality counts were made after 24 hours.

(iii) Spodoptera littoralis (S.l.). Pairs of leaves were removed from broad bean plants and placed on filter paper inside plastic petri dishes. The leaves were sprayed as in (ii), using the same concentrations. After spraying the leaves were left for --1 hour drying period and then each leaf pair was infested with ten larvae of the Egyptian cotton leafworm (Spodoptera littoralis). After 24 hours the percentage of dead and moribund larvae were recorded.

(iv) Aphis fabae (A.f.). Pairs of leaves are removed from broad bean plants and placed ventral side uppermost on filter paper inside a 9 cm petri dish. Ten to twenty 5-7 day old adult aphids were transferred onto a filter paper inside a 5 cm petri dish and covered with a wire-mesh lid. 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 (" TRITON " is a registered Trade Mark). After spraying the aphids are transferred to the sprayed leaves and the percentage dead and moribund individuals recorded after 24 hours.

The results of those tests are shown in Table II in which the test species are identified by the initials noted above and A denotes complete kill, B some kill and C no kill of the test species.

TABLE II INSECTICIDAL ACTIVITY

Compound of Example No. M.d. P.c. S.l. A.f.

1 A A A B 3 C A B A 4 A A A A 5 A A A A 2 A B A A Example 7.

The acaricidal activity of the compounds according to the invention was assessed employing the following pest: Tetranychus urticae (T.u.) The test method employed was as follows. Leaf discs cut from French bean plants were inoculated with 10 red spider mites in the manner described in Example 6 for the insects Phaedon cochleariae 1 hour after drying. Mortality counts were made 24 hours after inoculation. The results of these tests are shown in Table III employing the same notation as used in the previous example.

TABLE III ACARICIDAL ACTIVITY

Compound of Example No. T.u.

1 A Example 8.

The knockdown activity of the compounds according to the invention was assessed employing the common housefly (Musca domestica) by means of the Kearns-March chamber test.

The Kearns-March chamber consists of a 2 foot x 1 foot transparent glass cylinder into which flies can be introduced through a sliding panel at one end. 0.2 ml of a 20% MeCl2/80% Shellsol K solution ("SHELLSOL" is a registered Trade Mark) containing active material was sprayed for 1 seconds into the chamber at 10 psi and the air supply kept on for a further two seconds to facilitate even distribution of the spray.

About 70 flies were used in each treatment and knockdown counts made at 1, 2, 3, 4, 5, 7 and 10 minutes after spraying. Compounds are graded into six classes according to the concentration of toxicant required to achieve 90% knockdown after ten minutes, that is to say Class 0 90% at 10 minutes = concentration 0.025% Class 1 90% at 10 minutes = concentration 0.05% CXlass 2 90% at 10 minutes = concentration 0.1% Class 3 90% at 10 minutes = concentration 0.2% Class 4 90% at 10 minutes = concentration 0.4% Class 5 l < 90% at 10 minutes = concentration 0.4% Class 6 No knockdown at 0.4% The results of these tests are shown in Table IV.

TABLE IV KNOCKDOWN ACTIVITY

Compound of Example No. Knockdown Grading 1 Class 0 2 Class 0 3 Class 1 4 Class 0 5 Class 0

Claims

WHAT WE CLAIM IS:1. Cyclopropane carboxylates having the following general formulae:-

X is a halogen atom; R1 is a hydrogen atom or an alkyl group; R2 is an alkyl group; or R1 and R2 together represent an alkylene chain; R3 is a hydrogen atom, a cyano, ethynyl or thioamide group; and R is a phenoxyphenyl, benzylphenyl, phenylthiophenyl, benzylfuryl, halophenyl, phthalimido, tetrahydrophthalimido, or halophenoxyphenyl group.
2. Compounds according to claim 1 wherein: X is a halogen atom; R1 is a hydrogen atom or an alkyl group of 1 to 6 carbon atoms; R2 is an alkyl group of 1 to 6 carbon atoms or R1 and R2 together represent an alkylene chain of up to 5 carbon atoms; R3 is a hydrogen atom or a cyano or ethynyl group; and R is a phenoxyphenyl, benzylfuryl, phthalimido or tetrahydrophthalimido group.
3. Compounds according to claim 1 or 2 wherein X is a chlorine, bromine or fluorine atom.
4. Compounds according to claim 1, 2 or 3 wherein R1 and R2 are both methyl groups or R2 is a methyl group and R1 a hydrogen atom.
5. Compounds according to claim 1 specifically named herein.
6. A process for the preparation of compounds according to any one of the preced ing claims, which comprises reacting a cyclopropyl compound of formula II:

with a substituted alkyl compound of formula III:

(wherein one of the substituents Y and Z represent an -OH group and the other represents a halogen atom, and X, R1, R2, R3 and R have the meanings hereinbefore specified) in the presence of a hydrogen halide acceptor.
7. A process according to claim 6 substantially as hereinbefore described and with reference to any one of Examples 1 to 5.
8. Compounds when prepared by a process claimed in claim 6 or 7.
9. Pesticidal composition comprising a carrier and/or a surface-active agent together with, as active ingredient, a cyclopropyl carboxylate according to any one of claims 1 to 5 or 8.
10. Composition according to claim 9 substantially as hereinbefore described and with reference to any one of Examples 6 to 8.
11. A method of combating insect and/or acarid pests at a locus which comprises applying to the locus a pesticidally effective amount of a cyclopropyl carboxylate according to any one of claims 1 to 5 or 8 or a composition containing such a comound according to claim 9 or 10.