GB2035301A

GB2035301A - 2-Bromobenzyl esters of alkenyl cycloproprane carboxylic acids and their use as pesticides

Info

Publication number: GB2035301A
Application number: GB7932152A
Authority: GB
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 1978-10-13
Filing date: 1979-09-17
Publication date: 1980-06-18
Also published as: NL7907497A; FR2438645B1; CH643230A5; DE2941332C2; BE879142A; GB2035301B; LU81778A1; IT7926436A0; FR2438645A1; DE2941332A1; IT1124604B

Abstract

2-Bromobenzyl esters of formula I <IMAGE> where R<1> is hydrogen, fluorine, chlorine, bromine or iodine, R<2> is fluorine, chlorine, bromine or iodine, X is hydrogen, cyano, ethynyl or thioamido, n is an integer from 1 to 4 and the or each Y is independently selected from hydrogen, fluorine, chlorine, bromine or iodine exhibit pesticidal, e.g., insecticidal and acaricidal, activity. They may be obtained by conventional ester formation reactions. Pesticidal compositions and their use as pesticides are also described.

Description

SPECIFICATION 2-Bromobenzyl esters and their use as pesticides This invention relates to 2-bromobenzyl esters, to their preparation, and to compositions containing them for use as pesticides, especially as insecticides and acaricides.

According to the invention there are provided 2-bromobenzyl esters of formula I:

where R1 is hydrogen, fluorine, chlorine, bromine or iodine, R2 is fluorine, chlorine, bromine or iodine, Xis hydrogen, cyano, ethynyl or thioamido, n is an integer from 1 to 4 and the or each Y is independently selected from hydrogen, fluorine, chlorine, bromine or iodine.

It should be noted that the compounds of formula I possess two or three centres of asymmetry, depending on the nature of the substituent X. As will be appreciated by those skilled in the art, the compounds of formula I may exist as geometrical and optical isomers, mixtures of isomers and racemates.

Preferred compounds of formula I have one or more of the following features: (i) R1 and R2 are independently selected from fluorine, chlorine and bromine, (ii) Xis hydrogen or cyano, (iii) Xis hydrogen, (iv) nisi, (v) Y is selected from hydrogen, fluorine, chlorine or bromine, (vi) Y is a 6-fluoro, 6-chloro or 6-brnmo substituent, preferably 6-fluoro or 6-chloro, (vii) the 2(2-R1-2-R2-vinyl)-3,3-dimethylcyclopropane carboxyl moiety has cis-configuration, (viii) the 2(2-R1-2-R2-vinyl)-3,3-dimethylcyclopropane carboxyl moiety has 1 R-cis-configuration.

The 2-bromobenzyl esters of formula I may be prepared by analogous methods to those used for known compounds. A convenient process comprises reaction of a compound of formula ll:

with a compound of formula III:

where R1, R2, X, Y and n are as defined above, one of Q and Z represents a halogen atom, preferably a chlorine or bromine atom, and the other represents a hydroxy group. 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. Conveniently Z represents a hydroxy group and Q represents a chlorine or bromine atom.

The compounds of formula II above and their individual isomers are conveniently prepared in known manner, for example as described in U.K. Patent Specifications Nos. 1,413,491 and 1,448,228.

The compounds of formula Ill above where Xis hydrogen and Q is halogen are conveniently prepared by halogenation of corresponding halobromotoluenes. The halobromotoluenes are obtainable by introduction of the appropriate halogen via diazotisation of the appropriate halotoluidine. Halotoluidines may be prepared by reduction of the corresponding halonitrotoluene by known methods e.g. Entwistle metal, J.C.S.

Perkin 1, 1977 Pages 443 and 444. Compounds of formula III where Xis hydrogen and 0 is hydroxy may be prepared by hydrolysis of the compounds where 0 is halogen.

Compounds of formula III where Xis cyano, ethynyl orthioamido may be prepared in known manner from those where X is hydrogen via the corresponding aldehyde.

The 2-bromobenzyl esters according to the invention are of interest as pesticides especially as insecticides and acaricides for domestic and agricultural outlets. The invention therefore includes within its scope pesticidal compositions comprising a carrier and/or a surface-active agent together with, as active ingredient, a 2-bromobenzyl ester of formula I. The invention also includes a method of combating insect, tick and/or acarid pests at a locus which comprises applying to the locus a pesticidally effective amount of a 2-bromobenzyl ester of the invention or composition containing such a compound.

The term "carrier" as used herein means a materiai, 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, talcs; 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 tetrachloride, 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 amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, su rcrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohols or alkyl phenols for examplep-octylphenol orp-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or alkaline earther 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 alkylaryl 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 a wettable powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing 1/2-10% 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 1/2-25% w toxicant and 0-10% w of additives such as stabilisers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w toxicant, 2-20% w/v emulsifiers and 0-20% w/v of appropriate additives such as stabilisers, penetrants and corrosion inhibitors.Suspension concentrates are compounded so as to obtain a stable, non-sedimenting flowable product and usually contain 10-75% w toxicant, 0.5-15% w of dispersing agents, 0.1-10% w of suspending agents such as protective colloids and thixotropic agents, 0-10% w of appropriate additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and as a carrier, water or an organic liquid in which the toxicant is substantialy 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 diluting 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 will be better understood from the following Examples.

Example 1 - Preparation of 1:1 cisitrans 2-bromo-6-chlorobenzyl2-(2,2-dichlorovinyl)-3,3- dimethylcyclopropane carboxylate (a) Preparation of 2-bromo-6-chlorobenzylbromide 2-bromo-6-chlorotoluene (20.559) and N-bromosuccinimide (19.6g) were stirred together in carbon tetrachloride (100 ml) under reflux for 22 hours exposure to radiation from an infra-red lamp. The resulting solution was cooled in ice, filtered and evaporated to yield the title product which was dissolved in petroleum ether (60-80). Part was recrystallised therefrom as pink needles (8.59) and part was recovered by evaporation as a dark orange solid (17.79) (total yield 26.29.92%).

(b) Preparation of 1:1 cis/trans 2-bromo-6-chlorobenzyl 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropane carboxylate 1:1 cisitrans 2-(2,2-dichlorovi nyl )-3,3-dimethylcyclopropane carboxylic acid (2.3g), 2-bromo-6- chlorobenzylbromide (2.859) and potassium carbonate (1.6g) were stirred together in acetone (30 ml) under reflux for 6 hours. The reaction mixture was cooled, diluted with water, and extracted three times with 50 ml portions of diethyl ether. The combined ether extracts were washed with water and with aqueous sodium bicarbonate solution (three times), dried over magnesium sulphate and evaporated to give the orange title product (4.19,98%) m.p. 61-670C.

Analysis CalculatedC15H14BrCi302: C43.6; H3.4; Br19.4; CI 25.9 Found : C43.8; H3.4; Br19.1; Cl25.4 Examples 2 to ii By similar methods to that employed in Example 1, there were also prepared the following compounds: 1 ,R-cis-2-bromo-6-chlorobenzyl 2-(2,2-difluorovinyl)-3,3-dimethylcyclopropane ca rboxylate (yield 76%) n1g = 1.533, [a]2D= -15.45 (C2CHCI3) 1::1 cis/trans-2-bromobenzyl 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropane carboxylate (yield 89%) n2D3 = 1.5606 cis-2-bromobenzyl 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropane carboxylate (yield 80%) n2D = 1.5614 trans-2-bromobenzyl 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropane carboxylate (yield 82%) n2D = 1.5600 1 ,R-cis-2-bromo-6-ch Iorobenzyl 2-(2,2-dich lorovi nyl )-3,3-dimethylcyclopropane carboxylate (yield 90%) nD21 = 1.5682 [a]2D -26.8(C2 CHCl3) cis-2-bromo-6-chlorobenzyl 2-(2,2-dibromovinyl)-3,3-dimethylcyclopropane carboxylate. (yield 84%) m.p.

101-3"C cis-2-bromo-6-fluorobenzyl 2-(2-chloro-2-fluorovinyl)-3,3-dimethylcyclopropane carboxylate (yield 65%) m.p.53-54 C cis-2-bromo-6-fluorobenzyl 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropane carboxylate (yield 66%) m.p.

68-69"C 1,R-cis-2-bromo-6-fluorobenzyl 2-(2,2-dichlorovinyl )-3,3-di methylcyclopropane carboxylate (yield 81%) n = 1.551 [α]D25 -21.9(C2CHCI3) cis-2-bromo-6-fluorobenzyl 2-(2,2-dibromovinyl)-3,3-dimethylcyclopropane carboxylate (yield 74%) m.p.

66-67 C Pesticidal tests The insecticidal and tickicidal activity of the compounds according to the present invention was assessed employing the following pests: Insects: Musca domestica (M.d.) Spodoptera littoralis (S.l.) Aphis fabae (A.F.) Heliothis zea (H.z.) Mites: Tetranychus urticae (T.u.) Ticks: Boophilius microplus (B.m.) 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 micrometer syringe. Two to three day old adult female houseflies (Musca domestica) were anaesthetized with carbon dioxide, and 1 I 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) 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 on the undersurface with an aqueous formulation containing 20% by weight of acetone, 0.05% by weight of TRITON X-100 (Trade Mark) as 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 left to 1/2-1 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.

(iii) Aphis fabae (A.f.) Tests were carried out on adult aphids (Aphis fabae) by similar methods to that used for Spodoptera littoralis in (ii) above.

(iv) Heliothiszea (H.z) The compounds to be tested were incorporated in aqueous solutions containing 20% by weight of acetone, 0.04% by weight of Atlox 1 045A (Trade Mark) and 0.2% by weight of the test compound, more dilute solutions for dosage-mortality curves being made by diluting the 0.2% solution with an aqueous solution of 0.05% by weight of Atlox 1 045A. Cut Windsor broad bean plants were placed on a turntable and sprayed with 4 ml of test solution. Immediately after spraying, Scorn earworm larvae (Heliothis zea) were transferred to each plant which was inserted into water through a hole in a test board and the environment was maintained at a temperature of 27"C and 40-50% relative humidity. Mortality was assessed after 44 to 46 hours.

(v) Tetranychus urticae (T.u.) Discs were cut from the leaves of French bean plants and were placed on filter paper kept moist by a cotton-wool wick dipping into water. Each disc was infested with ten adults mites, and the discs were then sprayed with a solution or suspension of the test compound in acetone-water (20:80) containing 0.05% of TRITON X-100 (Trade Mark) as wetting agent. After 24 hours the percentage of dead and moribund mites was assessed.

(vi) Boophilus microplus (B.m.) A 0.1% by weight solution of the compound to be tested was prepared in acetone containing 10% by weight of polyethylene glycol. Varying concentrations were obtained by diluting this solution. 1 ml of test solution was applied evenly to a filter paper inside a petri dish. When sufficiently dry, the filter paper was folded in half and crimped along part of its outer edge to form a packet. About 80-100 two to three week old one-host cattle tick larvae (Boophilus microplus) were transferred into the packet, which was then completed sealed. The packet was then placed in an incubator at 27"C and 80% relative humidity. After 24 hours the packet was opened and the percentage of dead and moribund larvae was assessed.

The results are shown in Table I in which the test species are identified by the intials noted above and the activity of the compound is expressed in the form of its Toxicity Index (T.l.) which is calculated from the following equation: Toxicity Index (to.) = LC50 of ethyl parathion (standard) LC50oftestcompound 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% MeCI2/80% Shellsol K solution containing active material was sprayed for 11/2 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 3 concentration 0.025% Class 1 90% at 10 minutes = concentration 0.05% Class 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 < 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 Knockof down Example M.d. S.l. A.f. H.z. T.u. B.m. Class 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 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 11 34 48 27 + 49 481 2 + not yet tested.

Claims

1. A 2-bromobenzyl esterofformulal:

where R1 is hydrogen, fluorine, chlorine, bromine or iodine, R2 is fluorine, chlorine, bromine or iodine, X is hydrogen, cyano, ethylnyl or thioamido, n is an integer from 1 to 4 and the or each Y is independently selected from hydrogen, fluorine, chlorine, bromine or iodine.

2. An ester according to Claim 1 wherein R1 and R2 are independently selected from fluorine, chlorine and bromine.

3. An ester according to Claim 1 or 2 wherein X is hydrogen or cyano.

4. An ester according to Claim 3 wherein X is hydrogen.

5. An ester according to any one of Claims 1 to 4 wherein n is 1.

6. An ester according to any one of Claims 1 to 5 wherein Y is selected from hydrogen, fluorine, chlorine or bromine.

7. An ester according to any one of Claims 1 to 5 wherein Y is a 6-fluoro,6-chloro or 6-bromo substituent.

8. An ester according to any one of Claims 1 to 6 wherein Ri and R2 are independently selected from fluorine, chlorine and bromine, X is hydrogen, n is I and Y is a 6-fluoro or 6-chloro substituent.

9. An ester according to any one of Claims 1 to 8 wherein the 2(2-R1-2-R2-vinyl)-3,3dimethylcyclopropane carboxyl moiety has cis-configuration.

10. An ester according to any one of Claims 1 to 9 wherein the 2(2-R1-2-R2-vinyl)-3,3dimethylcyclopropane carboxyl moiety has IR-cis-configuration.

11. An ester according to Claim 1 substantially as hereinbefore described in any one of Examples 1 to 11.

12. A process for preparing a 2-bromobenzyl ester of formula I as defined in any one of Claims 1 to 11 which comprises reaction of a compound of formula II:

with a compound of formula Ill:

where R1, R2, X, Y and n are as defined in Claim 1, one of Q and Z represents a halogen atom, and the other represents a hydroxy group.

13. A process according to Claim 12 substantially as hereinbefore described in Example 1.

14. A 2-bromobenzyl ester prepared by a process according to Claim 12 or 13.

15. A pesticidal composition which comprises a carrier and/or a surface-active agent together with, as active ingredient a 2-bromobenzyl ester according to any one of Claims 1 to 11 and 14.

16. A method of combating pests at a locus which comprises applying to the locus a 2-bromobenzyl ester according to any one of Claims 1 to 11 and 14 or a composition according to Claim 15.