AU646168B2 - New pyrethrinoid esters of 2,3-dihydro-4-methyl-2-oxo-3-(2-propynyl)-thiazol-5-yl methyl alcohol, their preparation process and their use as pesticides - Google Patents

Description

646168 P/00/01 ReguLation 3.2

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

TO BE COMPLETED BY APPLICANT 0 :.:::Actual Inventor(s): Marc BENOIT, Jacques DEMASSEY and Jean-Pierre DEMOUTE 0 o-Address for Service: CALLINAN LAWRIE, 278 High Street, Kew, 3101, Victoria, Australia Invention Title: "NEW PYRETHRIN OLD ESTERS OF 2,3 -DIHYDRO-4-METHYL-2-OXO-3- METHYL ALCOHOL, THEIR PREPARATION PROCESS AND THEIR USE AS PESTICIDES" The following statement is a full description of this invention, including the best method of performing it known to me:- New pyrethrinoid esters of 2,3-dihydro-4-methyl-2-oxo-3methyl alcohol, their preparation process and their use as pesticides.

The present invention relates to new pyrethrinoid esters of 2,3-dihydro-4-methyl-2-oxo-3-(2-propnyl)-thiazol-5-yl methyl alcohol, their preparation process and their use as pesticides.

A subject of the invention is the compounds of formula

CH

3

CH

3

F

3 C\ C CH CO 2

-CH

2 0

H

3 C CH, 2 C CH S* e in all their possible stereoisomer forms as well as their 20 mixtures.

A more particular subject of the invention is: the compounds of formula in which the cyclopropane copula is of 1Rcis structure, the compounds of formula in which the geometry of the double bond is Z.

Among the preferred compounds of the invention, there can be mentioned [1R[lalpha,3alpha(Z)]]-3-[(2-chloro-2trifluoromethyl)-ethenyl]-2,2-dimethyl cyclopropane carboxylate of [2,3-dihydro-4-methyl-2-oxo-3-(2-propynyl)- 30 The compounds of formula have useful properties which allow their use for combating parasites. It may be for example for combating parasites of premises, parasites of vegetation and parasites of warm-blooded animals. Thus it is that the products of the invention can be used to combat insects, nematodes and parasitic acaridae of vegetation and animals.

Therefore a subject of the invention is the use of 2 compounds of formula for combating parasites of premises, parasites of vegetation and parasites of warm-blooded animals.

The compounds of formula can be used for combating insects in premises, for combating in particular flies, mosquitoes and cockroaches.

The products of formula can also be used for combating insects in the agricultural domain, for combating, for example, aphides, the larvae of lepidoptera and coleoptera. They are used at doses comprised between 10 g and 300 g of active ingredient per hectare.

The compounds of formula have in particular a very good knock-down power.

It emerges from the results of the biological tests hereafter that the products of formula also possess a remarkable aphicide activity.

o. The products of formula can also be used to combat 6 parasitic acaridae of vegetation.

The compounds of formula can also be used for 20 combating parasitic nematodes of vegetation.

The compounds of formula can also be used for combating parasitic acaridae of animals, for combating for example ticks, and notably ticks of the Boophilus species, those of the Hyalomnia species, those of the Amblyomnia species and those of the Rhipicephalus species, or for combating all types of mites and notably the sarcoptic, psoroptic and chorioptic mite.

Therefore a subject of the invention is also the compositions intended for combating parasites of vegetation, 30 parasites of premises and parasites of warm-blooded animals, characterized in that they contain at least one of the products defined above.

The compositions according to the invention are prepared according to the usual processes of the agrochemical industry or the veterinary industry or the industry of products intended for animal fodder.

These compositions can be presented in the form of powders, granules, suspensions, emulsions, solutions, 3 solutions for aerosols, combustible bands, baits or other preparations usually employed for the use of these types of compounds.

In addition to the active ingredient, these compositions contain, in general, a vehicle and/or a surface active agent, non-ionic, ensuring, moreover, a uniform dispersion of the constitutive substances of the mixture. The vehicle used can be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, a mineral, animal or vegetable oil, a powder such as talc, clays, silicates, kieselguhr or a combustible solid.

In particular a subject of the invention is the insecticide compositions containing as active ingredient at least one of the products defined above, and more particularly the compositions containing as active ingredient the product of Fxample 1 The insecticide compositions according to the invention contain preferably 0.005% to 10% by weight of active ingredient.

20 According to an advantageous operating method, for use in premises, the compositions of the invention can be presented in the form of baits. The insecticide compositions according to the invention can also be used in the form of fumigant compositions.

The compositions according to the invention can then be advantageously constituted, for the non-active part, by a combustible insecticide coil, or also by an incombustible fibrous substrate. In the latter case, the fumigant obtained after incorporation of the active ingredient is placed on a 30 heating apparatus such as an electric vaporizer.

In the case where an insecticide coil is used, the inert support can be, for example, pyrethrum marc compound, Tabu powder (or Machilus Thumbergii leaf powder), pyrethrum stem powder, cedar leaf powder, sawdust (such as pine sawdust), starch and coconut shell powder. The dose of active ingredient can then be, for example, 0.03 to 1% by weight.

In the case where an incombustible fibrous support is used, the dose of active ingredient can then be, for example, 4 0.03 to 95% by weight.

The compositions according to the invention for use in premises can also be obtained by preparing a sprayable oil based on the active ingredient, this oil soaking the wick of a lamp and then being set alight.

The concentration of active ingredient incorporated in the oil is, preferably, 0.03 to 95% by weight.

Also a subject of the invention is the acaricide compositions containing as active ingredient at least one of the products of formula defined above.

Also a subject of the invention is the nematicide compositions containing as active ingredient at least one of the products of formula above.

The insecticide compositions according to the invention, as acaricide and nematicide compositions, can optionally have added to them one or more other pesticide agents. The acaricide and nematicide agents can be presented notably in the form of powder, granules, suspensions, emulsions, solutions.

20 For acaricide use, wettable powders, for foliar spraying containing 1 to 80% of active ingredient, or liquids for foliar spraying containing 1 to 500 g/litre of active ingredient are preferably used. Powders for foliar dusting o* containing 0.05 to 3% of active ingredient can also be used.

For nematicide use, liquids for soil treatment S. containing 300 to 500 g/litre of active ingredient are preferably used.

The acaricide and nematicide compounds according to the invention are preferably used at doses comprised between 1 30 and 100 g of active ingredient per hectare.

Also a subject of the invention is the acaricide compositions intended for combating parasitic acaridae of warm-blooded animals, notably ticks and mites, characterized in that they contain as active ingredient, at least one of the products of formula defined above.

When it concerns the combating of parasitic acaridae of animals, the products of the invention can be incorporated in food compositions in combination with a nutritional mixture 5 suitable for animal fodder. The nutritional mixture may vary according to the type of animal, it may contain cereals, sugars and grains, soya, peanut and sunflower cakes, flours of animal origin, for example fishmeal, synthetic amino acids, mineral salts, vitamins and anti-oxidants.

Therefore a subject of the invention is also the compositions intended for animal fodder, containing as active ingredient at least one of the products of formula as defined previously.

It can also be indicated that the products of the invention can be used as biocides or as growth regulators.

Also a subject of the invention is the combinations endowed with insecticide, acaricide or nematicide activity, characterized in that they contain as active ingredient, on the one hand at least one of the compounds of general formula and on the other hand at least one of the pyrethrinoid esters chosen from the group constituted by the esters of allethrolone, of 3,4,5,6-tetrahydrophthalimidomethyl alcohol, of 5-benzyl-3-furyl methyl alcohol, of 3-phenoxybenzyl 20 alcohol and of alpha-cyano-3-phenoxybenzyl alcohol with chrysanthemic acids, by the esters of 5-benzyl-3-furyl methyl alcohol with 2,2-dimethyl-3-(2-oxo-3,4,5,6-tetrahydrothiophenylidenemethyl)-cyclopropanecarboxylic acids, by the esters of 3-phenoxybenzyl alcohol and of alpha-cyano-3phenoxybenzyl alcohol with 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acids, by the esters of alphacyano-3-phenoxy-benzyl alcohol with 2,2-dimethyl-3-(2,2dibromovinyl)-cyclopropanecarboxylic acids, by the esters of C* 3-phenoxybenzyl alcohol with 2-parachlorophenyl-2-isopropyl 30 acetic acids, by the esters of allethrolone, of 3,4,5,6tetrahydrophthalimidomethyl alcohol, of 5-benzyl-3-furyl methyl alcohol, of 3-phenoxybenzyl alcohol, and of alphacyano-3-phenoxybenzyl alcohol with 2,2-dimethyl-3-(1,2,2,2tetrahaloethyl)-cyclopropanecarboxylic acids, in which "halo" represents a fluorine, chlorine or bromine atom, it being understood that the compounds can exist in all their possible stereoisomer forms, as well as the acid and alcohol copulas of the above pyrethrinoid esters.

6 The combinations according to the invention are particularly useful both in allowing, by the polyvalency of their action, the combating of a wider range of parasites, and in demonstrating, in some cases, a synergic effect.

To enhance the biological activity of the products of the invention, they can be added to the standard synergists used in such a case such as 1-(2,5,8-trioxadodecyl)-2-propylbenzene (or piperonyl butoxide) or N-(2ethyl-heptyl)-bicyclo-[2,2-1]-5-heptene-2,3-dicarboximide, or piperonyl-bis-2-(2'-n-butoxy-ethoxy) ethylacetal (or tropital).

Therefore a subject of the invention is the pesticide compositions defined previously, characterized in that they contain in addition a pyrethrinoid synergist.

Also a subject of the invention is a preparation process, characterized in that an acid of formula (II):

*C

CH CH 3 3 F, C C=H ,H

(II)

Cl

*S

or a functional derivative of this acid, is subjected to an alcohol of formula (III): HOH C- C0 30 (III) H3 CH C ECH or a functional derivative of this alcohol, in order to obtain the corresponding compound of formula The functional derivative of the acid used is preferably an acid chloride.

When the acid of formula (II) and the alcohol of formula 7 (III) are reacted, the operation is preferably carried out in the presence of dicyclohexyl carbodiimide.

The alcohol of formula (III) is described in the European Patent No. 0300898.

The following examples illustrate the invention without however limiting it.

EXAMPLE 1: [1R[lalpha,3alpha(Z)]-3-[2-(chloro-2-trifluoromethyl)- ethenyl]-2,2-dimethyl cyclopropanecarboxylate of [2,3-dihydro-4methyl-2-oxo-3-(2-propynyl)-thiazol-5-yl]methyl A mixture containing 1.70 g of dicyclohexylcarbodiimide, 100 mg of 4-dimethylaminopyridine and 20 cm 3 of methylene chloride is introduced at 0/5 0 C, into a mixture of 2 g of [1R[1alpha,3alpha(Z)]-3-[2-(chloro-2-trifluoromethyl)- -ethenyl]-2,2-dimethyl cyclopropanecarboxylic acid and 1.40 g e of 2,3-dihydro-4-methyl-3-(2-propynyl)-thiazol-5-yl methyl alcohol and 70 cm 3 of methylene chloride. The reaction S. medium is agitated for a quarter of an hour at 0°C, then left to return to 20 0 C and agitated for 2 hours. It is filtered 20 and concentrated under reduced pressure. 3.6 g of a product is obtained which is chromatographed on silica, eluting with a cyclohexane ethyl acetate mixture The solvent is evaporated off, and after drying 2.75 g of a product is obtained which is chromatographed on silica with a hexane ethyl acetate mixture Evaporation is carried out, followed by drying. In this way 2.35 g of the desired product is obtained.

[alpha]D +2705 1.50 (c 0.7% CHC1 3 EXAMPLE: Preparation of a fumigant composition 30 The following are homogeneously mixed: product of Example 1 0.25 g Tabu powder 25.00 g cedar leaf powder 40.00 g pine sawdust 33.75 g brilliant green 0.50 g p-Nitrophenol 0.50 g 8 BIOLOGICAL STUDY A Study of the knock-down effect on the housefly The test insects are 4-day old female houseflies. The operation is carried out by direct spraying at a concentration of 0.10 g/litre in a Kearns and March chamber using a mixture of acetone and Isopar L (petroleum solvent) as solvent (quantity of solvent used 2 cm 3 per second). insects per treatment are used. Checks are carried out every minute for 10 minutes, then after 15 minutes, and the KT 50 is determined by the usual methods.

The experimental results obtained are summarized in the following table, in relative power relative to bioallethrine.

9*

S.

S S S

S

S. S

S

S

S S

SSSS

5555

S..

S. COMPOUNDS RP EXAMPLE 1 6.65