New esters ß- (B-naphtyl) - isovaleric, their preparation and their application to the fight against the parasites.

The present invention relates to novel esters has - (w-naphth-L ^) isovaleric, process for their preparation and Leu: -.' application to pest control.

The esters of the invention have the formula

THE CD

wherein is hydrogen or cyano or ethinyl®

The compounds of formula I are prepared according to methods known per se, for example retort follows?

acid acceptor ^ "

D. ¹ ^ acid

I->

I in the formulae III and V, has the meaning given for formula I,

Dajqs formula III and IV, X is a halogen atom, in particular chlorine or bromine and, in the

5 formula VI * ee represents a. in to c ^ alkyl group, especially a methyl or ethyl group. As acid acceptors for the methods 1 and 2, it is in particular tertiary amines, such as pyridine and trialcoylamines, or hydroxides, oxides, carbonates and bicarbonates metals Al ' îq hugs - and alkaline earth, as well as alkali metal alcoholates such as for example the T-butoxide and sodium methoxide. As a fixing water for the method 5, may be employed for example dicyclohexylcarbodiimide. The methods 1 to 4 are performed at a temperature popcorn 'll -10 and engagement between 100 °c, most of the time between 20 and 80 °0, at normal pressure or higher and preferably in a solvent or an inert solvent, suitable diluents or solvents are for example ethers and ether type compounds, such as. diethyl ether, the sulfophenylxanthine ether, dioxane, the diméthoxyétha -20 ne and tetrahydrofuran; amides as carboxamides disubstituted nitrogen; aliphatic or aromatic hydrocarbons optionally halogenated, in particular benzene, toluene, xylene, chloroform and chlorobenzene;

nitriles as 1' acetonitrile; dimethylsulfoxide and

>5 ketones such as acetone and methyl ethyl ketone. The method 2 can also be effected in aqueous solution.

The starting materials of formulae II to VI are known or can be prepared by analogy to substan. these known. A method for obtaining the compound of formula 50 II is described in the example 1,

The compound of formula I is in the form of a mixture of various optically active isomers when, in the repair, not only of emplcde. unit optically-active starting materials. The various mixtures of isomers can be separated into the individual isomers 55 by known methods.

In the compound of formula I is meant both the individual isomers, mixtures thereof.

The compounds of formula I are suitable for combating animal pests and plants of various types.

This is how they can be implemented for combating phytopathogenic representatives mite species Tetranychus and Panomychus and against ticks of the families Ixodidae and dermanyssidés. They are particularly well suited however for insect control for example following families 9.ï Tettigoniidae, gryllidés, gryllotalpidés, blattidés, reduviidés, pyrrhoooridés, eimicidés, delphacidés, aphididéc, diaspididés, pseuaococcidés, searabéidés, Dermestidae, coccinellidés, Tenebrionidae, Chrysomelidae, bruchidés, tinéidés, Noctuidae, lymantriidés, pyralidés, Culicidae, tipulidés, stomoxydés, trypétidés, Muscidae, blowfly and pulicidés *

The compounds of formula I are suitable especially for combating plant pests ., particularly insect rodents, in ornamental plants and the useful plants, in particular in cotton cultures (e.g. against Spodoptera littoralis Boddie virescens) and vegetable crops (e.g. against LeptinotarsadecemlineataMyzus and Myzus persicae).

The active substances of formula I also show activity against very favorable mouch.es, for example parasitizing Musca domestica and mosquito larvae.

The insecticidal or acaricidal activity can be considerably enlarged by the addition of other insecticides and/or acaricidal s and adapted to certain environments. Suitable additives are for example organic phosphorus compounds, nitrophenols and derivatives, formamidines of, ureas, other compounds such as pyrethrum, and carbamates and chlorinated hydrocarbons.

Is associated with a particular advantage of the compounds of formula I with substances which exert an action of synergy or reinforcement with the pyréthroîdes. Examples of such compounds are inter alia piperonyl butoxide, the propinyléther, the propinyloxirae, carbamate propinyl and phosphate propinyl, 2 - (3.4 to-méthylènedioxyphénoxy) -3.6₃ 9 tri oxaundé stick (or SesamexSesoxane), the phosphorotrithioate of s, e, s tributyl, the 1.2 to-méthylènedioxy~4-a 7/2 - (octylsulfonyl) propyl7-benzene.

The compounds of formula I can be implemented

=5 alone or together with carriers and/or additives. Suitable additives may be solid or liquid and correspond to the substances usually used in the technique of the formulation, such as the substances_G natural or regenerated, solvents, dispersants, wetting the 3, adhesives, thickeners, binders and/or fertilizers. -

The preparation of^{the R} the present invention seloô agent is implemented in a manner known per se, by intimately mixing and/or grinding the active substances of the formula I with the appropriate supports, 5 possibly adding inert solvents or dispersants

to the related active substances. The active ingredients may be present and be used under the following forms:

Solid Pormes: agents for dusting and spreading, granules (BPM -

nulés coated, impregnated granules and granules

O-homogeneous);

Pormes liquids:

a) concentrates of active water dispersible: powders for spraying (wettable powders), pastes, emulsions;

5 b.) solution '.

The active substance content in the agents disclosed above is between 0.1 and 95 $, it should, however, mention that when applying the substance by aircraft or other suitable device, could carry out of merger, 0 levels as up to $99 * 5 or even employ the pure active substance.

The active substances of formula I according to the invention can be formulated for example as follows:

Dusting - powder : to prepare a powder dusting has 55) to 5 $and b) to 2 $, employed the following substances s) 5 parts of active substance

95 parts of talc;

b) 2 parts of active substance

1 part of finely divided silica,

97 parts of talc;

The active substances are mixed with the carriers and ground and may be employed. in this form.

Granule : 5% to prepare a granule is employed the following substances:

5 parts of active substance

0.25 part d¹ epichlorohydrin

0.25 part cétylpolyglycol ether

3.50 parts of polyethylene glycol

91 parts of kaolin (grain size and 0.3 and 0.8 millimeters).

The active substances are mixed with epichlorohydrin and dissolved in 6 parts of acetone and then added ether of polyethylene glycol and cétylpolyglycol. The solution thus obtained is sprayed onto kaolin and acetone is then evaporated under vacuum.

Spray powder : to prepare a spray powder to) to 40%, and b) and c) to 25% and d) to 10% is employed the following constituents:

a) 40 parts of active substance

5 parts of sodium salt of lignin sulfonic acid

1 part of sodium salt of 1' mpthalènesulfonique acid

54 parts of silicic acid;

25 parts of active substance

4.5 parts of calcium lignosulfonate

1.9 parts of mixture chalk champagne-hydroxyethyl cellulose (1:1)

1.5 parts of dibutyl naphthalene sulfonate sodium 19.5 parts of silicic acid,

19.5 parts chalk champagne,

'the, '! parts of kaolin;

c) 25 parts of active substance

2.5 parts of isooctylphénoxy-to-polyoxyéthylèneéthanol

1.7 parts of mixture chalk champagne-hydroxyethyl cellulose (1:1)

8.3 parts of silicate and aluminum scdium 15, 5 parts of kieselgur,

4 - 6 parts of kaolin;

d) 10 parts of active substance

3 parts of mixture of sodium salts of alcohol sulfates, fatty saturated,

5 parts of naphthalenesulfonic acid/formaldehyde condensate

82 parts of kaolin.

The active ingredients are intimately mixed and ground in suitable mixers on mills and corresponding cylinders. Powders are obtained for spraying excellent wettability and suspensibility which can be diluted with water to give suspensions of any desired concentrations and employed in particular for the application on the sheets.

Emulsifiable concentrates : to obtain an emulsifiable concentrate has) to 10%, and b) to 25% and c) to 50%, there is employed the following substances:

a) 10 parts of active substance,

3, 4 - parts of epoxidized vegetable oil,

3, 4 - parts of an emulsifier composite consisting of a fatty alcohol polyglycol ether and calcium salt of an alkyl aryl sulfonate,

40 parts of dimethylformamide,

43.2 parts of xylene;

b) 25 parts of active substance,

2.5 parts of epoxidized vegetable oil,

10 parts of a mixture of alkyl and aryl sulfonate fatty alcohol polyglycol ether,

5 diméthylformanide parts,

57 5 parts of xylene;

c) 50 parts of active substance,

4.2 parts polyglycol ether tributylphénol■, 5.8 parts of calcium dodecylbenzenesulfonate, 20 parts of cyclohexanone,

20 parts of xylene.

WITH from such concentrates, obtainable, by dilution with water, emulsions of any desired concentration.

1 - - EXAMPLE

Preparation of the compound of formula

' ^ - ^ HCV COOCH VOS -

C

VBE1 / C. ^HM

HM

2 g of the acid chloride (~P-naphthyl) - - 1.8 g of the nitrile and isovaleric acid 3 a-phénoxymandélique, in 50:1 toluene, are added to the ambient temperature of 0.7 g of pyridine derivatives.

The mixture is stirred for 15 hours at room temperature. After washing to neutrality, drying and evaporation of the solvent, to give the compound of formula

6<

Eyelash-to-COOCH-R. γ θ ^

CH-NC

as 3aune clear viscous oil having a refractive index of 1 ·, 595 ο

Is obtained analogously jetproof following compounds! ^HM 3^HR "^HM 3

HAS) Insecticidal activity by ingestion

The feet of the tobacco and of potato minitubers are sprayed with an emulsion to 0, 05 c/o active substance (prepared from an emulsifiable concentrate to 10 c/o).

After drying the tobacco plants and of potato minitubers are infested with caterpillars of Spodoptera littoralis Boddie virescens ^ L-stage at all.

The experiment is conducted at 24 °c and with a relative air humidity of 60 the j ^.

The compounds of the example 1 showed in the test above good insecticidal activity by ingestion against Spodoptera littoralis caterpillars of Boddie virescens.

B.) Insecticidal activity by contact

One day before application of the active substance is infected beans (is Vicia faba) potted with about 200 pushed aphids (USDA APHIS fabae). Applying a slurry at a concentration of 1000 ppm (slurry prepared from a wettable powder to 25%) is performed with a syringe to compressed air leaves infested with aphids.

Observing the results 24 hours after application.

The compounds of the example 1 showed in the test above good activity by contact against USDA APHIS fabae