NL7906754A - NEW INSECTICIDES AND PREPARATIONS CONTAINING THEM. - Google Patents

Description

; * w PHiLAGRO, Soeiêtê Anonyme according to Eran's law. in Lion, France. - '

New insecticides and preparations containing them.

This invention relates to new derivatives of the 1,3,4-oxadiazolinone of the general formula 1, wherein X represents a halogen atom,

Rj, Rj and Rg are independently a hydrogen atom or an alkyl-5 group with 1 to 3 carbon atoms, Rj is a halogen atom or an alkyl or alkoxy group with 1 to 3 carbon atoms, and n 0.1 , 2, 3 or 4, where in the case n is 2, 3 or 4, the groups R ^ may be the same or different from one another.

More particularly, this invention relates to compounds of formula 1, wherein X is a p substituent and Rg is hydrogen. Preferably X is a chlorine atom. All these compounds have at least one asymmetric carbon atom, so that they can exist in multiple stereoisomeric forms, all of which are included in the invention.

Some oxadiazole derivatives have already been described in the literature. For example, from U.S. Pat. No. 4,096,273, derivatives of the 3-benzyl-5- (2- (p-chlorophenyl) -4-methylbutyryloxyalkyl] -1,2,4-oxadiazole of Formula 2 wherein Rj is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms and hydrogen or chlorine, known, which would be useful as insecticides.

The compounds of the present invention differ from those previously known compounds and act much more as insecticides.

The invention also relates to a process for the preparation of the compounds of the formula 1, insecticidal preparations containing these compounds, and a process for the preparation of those preparations, as well as the use of these compounds and preparations.

The compounds of general formula 1 can be prepared in a manner known per se for analogous compounds, and in particular as indicated in the accompanying reaction scheme.

Typically, an acid of formula 3 or derivative thereof, wherein R 1 and R 2 have the meanings given previously 5 and Y and Y 'are independently chlorine or hydroxy (with the limitation that if Y is hydroxy, Y' cannot be chlorine ) reacting with a benzyl hydrazine of formula 4 wherein R 1, R 2 and n have the meanings given previously. Phosgene is allowed to act on the acid hydrazium of formula 8 thus obtained, whereby cyclization occurs to form a compound according to formula 9, in which R1, R2, R1, R1, Y and n have the meanings given previously. The 1,3,4-oxadiazolone of formula 9 thus obtained is then reacted in the presence of an acid scavenger with an acid or derivative thereof of formula 10 wherein X represents a chlorine atom and Z is chlorine or hydroxy but other than Y, whereby the -15 long compound according to formula 1 is formed.

In a preferred embodiment of this preparation method, a compound of formula 3 is taken as an α-chloro-fatty acid or its acid chloride, and then the reaction of this compound with the benzylhydrazin of formula 4 is preferably carried out in an inert organic solvent such as aliphatic or aromatic hydrocarbons at a temperature between 10 ° and 50 ° C. When the compound of formula III is an α-chloro fatty acid, the water formed in the reaction is removed by azeotropic distillation. However, if the compound of formula 3 is an acid chloride, the reaction preferably takes place in the presence of an aryl or alkyl sulfonic acid, for example with methanesulfonic acid.

The ring closure in the second stage then takes place in an inert, organic solvent, for example aromatic hydrocarbons, at a temperature between 20 ° and 100 ° C. The acylation after the cyclization then takes place with an acid according to formula 10, in which Z

hydroxy, and preferably in an inert organic solvent such as aliphatic or aromatic hydrocarbons, at a temperature between 10 ° and 140 ° C.

In another embodiment of the preparation method according to the invention, one starts from an α-hydroxy acid according to formula 3, in which Y and Y 'are both OH, and the reaction thereof with the 7906754 w 3 benzylhydrazine then preferably takes place in a organic solvent at a temperature between 80 ° and 150 ° C, the resulting water being removed by azeotropic distillation. The ring closure in the second stage then takes place in an aqueous medium at a temperature between 10 ° and 50 ° C. The acylation afterwards then takes place with an acid chloride according to formula 10 in which Z is chlorine, and preferably in an inert organic solvent such as acetone, methylene chloride or aromatic hydrocarbons, at a temperature between 10 ° and 50 ° C.

The acid of formula 10 can be prepared as described in Beilstein's Handbuch Volume 9, Supplement 1, p.

216 for the 2-phenyl-3-methylbutyric acid. The 2- (p-chlorophenyl) -3-methyl-butyric acid is mentioned in Chemical Abstracts 59_ (1965) 1016e. The acid chloride according to formula 10 can be easily obtained from the acid by allowing thionyl chloride to act on it.

For the preparation of compounds of formula 1 in which hydrogen is, a variant in the preparation method is possible, starting with an acid hydrazide of formula 5 and a benzaldehyde of formula 6, wherein R 1, R 2, R 1 and n are given previously have meanings. This reaction proceeds in dilute alcohol (eg a mixture of water and ethanol) in the presence of acetic acid, at a temperature between 20 ° and 40 ° C. The resulting hydrazone is then reduced with hydrogen, for example under the influence of palladium on carbon at a temperature between 20 ° and 60 ° C. The cyclization and the subsequent acylation proceed as indicated for the second embodiment.

The compounds of formula 1 are remarkable insecticides, which act both as a contact poison and as a stomach poison. Particularly interesting results have thus been obtained in the control of bivalves, turtle-backed and scale-winged birds (flies and mosquitoes, 30 beetles and butterflies).

Example I

Preparation of the (4-benzyl-5-oxo-1,3,4-oxadiazolyl) methyl ester of the 2- (4-chlorophenyl) -3-methylbutyric acid (compound No. 1).

To a solution of 8.2 g of 4-benzyl-2-hydroxy-35 methyl-1,3,4-oxadiazolinone-5 and 4.04 g of triethylamine in 100 ml of acetone, a solution of 9.2 g was added dropwise over 10 minutes. 2- (p-chloro- 79 0 6 7 S 4 'i.

4 phenyl) -3-methylbutyric acid chloride in 100 ml acetone. After standing at room temperature for 2 hours, the resulting precipitate was filtered over sintered glass and the organic solution was evaporated under reduced pressure. The residue was taken up in 250 ml of isopropyl ether and this solution was washed successively with 200 ml of water, 100 ml of 3.6% hydrochloric acid, 100 ml of 4% soda and again 100 ml of water. After drying and evaporation under reduced pressure, the residue was purified by chromatography on a column of silicic acid, whereby 12 g of the desired ester, m.p. 70 ° C, were obtained.

10 Elemental analysis e

Calculated Found G% 62.92 62.76 H% 5.28 5.29 0% 15.97 15.78 15 N% 6.99 7.03

Cl% 8.84 9.0

The 2- (p-chlorophenyl) -3-methylbutyric acid was prepared in accordance with Beilstein Part 9, Supplement 1, p. 216 by allowing isopropyl bromide to act on the sodium derivative of p-chloro-20-phenylacetonitrile followed by hydrolysis with sulfuric acid. The acid chloride was made by the action of thionyl chloride thereon.

For the preparation of the 4-benzyl-2-hydroxymethyl-

1,3,4-oxadiazolinone-5 was reacted 61 g of benzylhydrazine in 200 ml of toluene with 53 g of glycolic acid by reflux. After the expected amount of water was removed by azeotropic distillation, the reaction mixture was evaporated to dryness and the residue was taken up in 500 ml of water. The water layer was decanted and washed with 2 x 250 ml of methylene chloride. This water layer was then saturated with phosgene in a round bottom flask at 20 ° C. The reaction mixture was taken up in 500 ml of methylene chloride and the organic layer decanted and washed successively with 500 ml of 10% KHCO 2 solution and with 500 ml of distilled water. After drying over Na2SO4 and evaporating to dryness under vacuum, 35 g of 4-benzyl-2-hydroxymethyl-1,3,4-oxadiazolinone-5 with m.p. 54 ° C. Example II

Preparation of the a- (4-benzyl-5-oxo-1,3,4-oxadiazolyl) ethyl ester of the 2- (4-chlorophenyl) -3-methylbutyric acid, in the form of two diastereoisomers.

7906754 5

To a solution of 11 g of L-isomer of 4-benzyl-2- (α-hydroxyethyl) -1,3,4-oxadiazolinone-5 in 50 ml of methylene chloride was quickly dissolved 11.6 g of 2- (p-chlorophenyl -3-methylbutyric acid in 100 ml of methylene chloride was added and 4 g of pyridine was then added dropwise over 5 minutes. After standing at room temperature for 2 hours, the reaction mixture was evaporated to dryness and the residue was taken up in 300 ml of 3.5% aqueous hydrochloric acid. The organic layer was decanted and washed successively with 300 ml of 10% KHCO 2 solution and 300 ml of water, and dried. After drying and evaporation to dryness under reduced pressure, 22 g of residue were obtained, which was purified by chromatography on a column of silicic acid. This gave 17 g of oil, which after stirring with petroleum ether gave two portions of a- (4-benzyl-5-oxo-1,3,4-oxadiazolyl) ethyl ester of 2- (4-chlorophenyl) -3- methylbutyric acid, namely 7 g of isomer A (compound no. 2) with m.p. 102 ° C, / α7D * -39.6 ° (c = 15 in acetone), and 9 g of isomer B (compound No. 3), a rigid paste with mp. 40-45 ° C [δ = -21.3 ° (c = 10 in acetone).

Elemental Analysis Calculated Found 20 Compound No. 2 Compound No. 3 C% 63.69 63.69 63.26 H% 5.59 5.71 5.94 0% 15.42 15.60 14.91 N% 6.75 7.01 6.17 25 Cl% 8.55 8.45 8.85

The L-isomer of the 4-benzyl-2- (α-hydroxyethyl) -1,3,4-oxadiazolinone-5 was prepared according to Example I by reacting 33 g of L-lactic acid in boiling toluene with 25 g of benzylhydrazine and the resulting allow benzylhydrazine to act on phosgene in an aqueous medium. This gave 18 g of L-isomer of 4-benzyl-2- (α-hydroxyethyl) -20

1.3.4-oxadiazolinone-5 with m.p. 70 C, / α_7ρ = ~ 19 ° (c s 10 in acetone). Example III

According to example II, starting from the same amounts, but now the D-isomer of the 4-benzyl-2- (α-hydroxy-35 ethyl) -1,3,4-oxadiazolinone-5 (prepared from the D-lactic acid) with smp. 70 ° C and / = + 19.7 ° (c = 10 in acetone) 7906754 6 7 g of isomer C (compound no. 4) with mp. 104 ° C = + 42 ° (c = 10 in acetone) and 9 g of isomer D (compound No. 5) as oil, α_7ρ ^ = + 22 ° (c = 10 in acetone).

5 Elemental analysis e

Calculated Found

Compound No. 4 Compound No. 5 C% 63.69 63.89 63.90 HZ 5.59 5.68 6.0 10 0% 15.42 15.26 15.40 N% 6.75 6.93 6 , 16

Cl% 8.55 8.44 9.31

Example IV

Preparation of the 4- (o-methylbenzyl) 5-oxo-1,3,4-oxodiazolinyl ester of 2- (4-chlorophenyl) -3-methylbutyric acid (Compound No. 6)

To a solution of 19 g of 2- (p-chlorophenyl) -3-methylbutyric acid and 11.7 ml of triethylamine in 175 ml of xylene, a solution of 13.3 g of 2-chloromethyl-4- (o) was added over 20 minutes at 110 ° C. -methyl-benzyl) -1,3,4-oxadiazolinone-5 in 35 ml of xylene. After refluxing for 4 hours, it was allowed to cool and the reaction mixture was washed successively with 100 ml water, 100 ml 3.5% hydrochloric acid, 100 ml 4% Na 2 CO 2 solution and 100 ml water. After drying, decolorization with activated carbon and evaporation under reduced pressure, the residue was purified by chromatography on a column of silica. This gave 11.2 g of the elongated ester as an oil.

Elemental analysis Calculated Found C% 63.69 63.55 Η Z 5.59 5.78 30 0 Z 15.42 15.44 N Z 6.75 6.88

Cl Z 8.55 9.12

The 2-chloromethyl-4- (o-methylbenzyl) -1,3,4-oxa-diazolinone-5 was prepared as follows: 56.7 ml of chloroacetyl chloride were added in 1 liter of toluene in the presence of 46.2 ml of methanesulfonic acid react with 100 g o-methylbenzylhydrazine at room temperature. Then, 7906754 5 7 was introduced at temperatures between 25 ° and 112 ° C. 200 g of phosgene. Then the reaction mixture was evaporated, giving 13.3 g of the intended compound as oil.

Example V

Preparation of the β- (o-chlorobenzyl) -5-oxo-1,3,4-oxadiazolylmethyl ester of the 2- (p-chlorophenyl) -3-methylbutyric acid.

According to Example I, starting from 16 g of 4- (o-chlorobenzyl) -2-hydroxymethyl-1,3,4-oxadiazolinone-5 in 100 ml of acetone and a solution of 17.8 g of 2- (p-chlorophenyl) -3 -methylbutyric acid 10 in 50 ml of acetone 26 g of the ester just mentioned are obtained in the form of an oil.

Elemental analysis

Calculated Found C% 57.94 58.61 15 H% 4.63 4.68 0% 14.70 13.94 N% 6.44 6.15

Cl% 16.29 16.31

The 4- (o-chlorobenzyl-2-hydroxymethyl-1,3,4-oxa-20 diazolinone was obtained by allowing phosgene to act at a temperature of between 20 ° and 30 ° C on a solution of 38 g of 1- (o- chlorobenzyl) -2-glycolylhydrazine in 600 ml of water After recrystallization from isopropyl ether, this gave 16 g (42% yield) of the intended compound of formula 8.

The 1- (o-chlorobenzyl) -2-glycolyl hydrazine was prepared by reducing 41.5 g glycolyl hydrazone of o-chlorobenzaldehyde in 415 ml dioxane at temperatures between 20 ° and 60 ° C with 15 kg / cm2 of hydrogen under the influence of palladium on cabbage. After filtration and concentration, 38 g of the intended compound according to formula 7 were obtained. The glycolyl hydrazone of o-chlorobenzaldehyde, m.p. 166 ° C, was itself obtained by mixing in a mixture of 20 ml of water,

10 ml of acetic acid and 60 ml of ethanol at temperatures between 20 ° and 40 ° C react 18 g of glycolylhydrazine with 30.9 g of o-chlorobenzaldehyde. Example VI

In accordance with Example IV, the following compounds of formula 1 7906754 8 were prepared from the appropriate starting materials. Of these, compound No. 9 (with no substituent in the benzyl group) had a melting point of 85 ° C; the rest were oils.

Compounds of formula 1,

X = p-Cl and R3 = H

5 Compound R2 R ^ Element analysis' no · ......... Calculated _ Found 8 8 H 4-C1 C% 57.94 58.54 H% 4.63 4.85 0% 14.70 14.80 10 Cl% 16.29 15.80 _._ N% 6.44_6.29 9 CH3 CH3 HC% 64.41 63.86 H% 5.87 5.87 0% 14.92 14.91 15 Cl % 8.27 8.98 _N% 6.53_6.04 10 Η H 2-0CH3 C% 61.32 62.90 H% 5.38 5.65 0% 18.57 18.17 20 Cl% 8.23 7.70 _N% 6.50 _5.90 11 Η H 4-CH 3 C% 63.69, 63.22 H% 5.99 5.48 0% 15.42 14.81 25 Cl% 8.55 9. 25 _N% 6.75 7.18 12 Η H 3-CH 3 C% 63.69 62.50 H% 5.59 '' 5.40 0% 15.42 .15.02 30 Cl% 8.55 10. 02 _N% 6.75_7.70 13 Η H 3-0CH3 C% 61.32 61.76 H% 5.38 5.37.

0% 18.57 18.0 35 Cl% 8.23 6.50 _N% 6.50_6.0 7906754 9

Compound R1 R »R, Element analysis mg no. _Calculated_Found 14 Η H 3-C1 C Z 57.94 58.20 H% 4.63 4.64 5 0 Z 14.70 14.12

Cl Z 16.29 16.70, N Z 6.44, 6.28

Example VII

Insecticidal effect as contact poison.

1 ml portions of solutions or suspensions of the compounds to be tested in acetone, at certain concentrations, were placed in a 120 ml glass jar. After the acetone had evaporated, either 5 house flies (Musea domestica) or 10 meal beetles (Tribolium confusum) were placed in each pot. For each dose to be studied, 15 pots (ie 2 pots per insect species) were used. They were covered with a metal mesh and after 24 hours the number of dead flies and after 3 days the number of dead mealworms were counted. From the results, intrapolation calculated the concentrations at which 90 Z of the insects died, hereinafter referred to as the LC ^ q. For comparison, the LC ^ q was also determined from compound No. 1 of U.S. Pat. No. 4,096,273.

Connection no. Museums Tribolium _ LC90 LC90 1 10 100 3 30 300 25 5 100 6 100 11 200 12 100 13 1000 30 No. 1 out of 30 1000

Am.o.s. 4,096,273

Example VIII

Insecticidal effect as a stomach poison (on moistened leaves against the caterpillars of Plutella maculipennis and Pieris brassicae).

A self-emulsifying solution of the following composition was prepared: 7906754

JO

Active substance to be tested 250 g

Emulsifier (mixture of Ca nonyl sulfonate and oxyethylated nonyl phenol) 90 g

Surfactant (monolaurate of 5-ethylethylated sorbitan) 20 g

Solvent (toluene / acetophenone 3: 2) to 1000 ml

The solution thus obtained was diluted just before use with distilled water diluting 0.02% surfactant such that one had different concentrations of active substance.

Young broccoli leaves (from Brassica oleracea) at the stage of four leaves were moistened with one of the solutions thus prepared for 10 seconds. The cabbage leaves were then allowed to dry and placed in cylindrical plastic boxes. 10 caterpillars of the third stage of Plutella maculipennis or of Pieris 15 brassicae were placed in each box. Four boxes were used for each dose (ie two per butterfly type).

After 3 days the live and dead caterpillars were counted in all boxes and the results were calculated from the results by interpolation to determine the concentrations at which 50% of the caterpillars died (the LC ^ q) · This was additionally determined for compound no. 1 of the American U.S. Patent 4,096,273.

Compound no. Plutella Piéris _ LC50 LC50 25 1 20 100 2 1000 1000 3 100 300 5 1000 8 1000 30 10 2000 2000 11 2000 12 1000 2000 13 300 1000 no. 1 of the 35 Am.o.s 4.096.273 300 500

The compounds of the invention will rarely be used alone in practice. Usually, the 7906754 11 active substance is combined with a carrier and / or a surfactant. In such preparations, the active compound content can range from 0.05% to 95% by weight.

By "carrier" here are meant organic and inorganic, natural and synthetic substances with which the active substance is combined in order to facilitate its distribution over plants, seeds or building land and also the transport and handling thereof. The carrier can be solid (clay, natural and synthetic silicates, MgO, kieselguhr, Ca ^ CPO ^) ^, ground cork, activated carbon, synthetic resins, waxes, solid fats) or liquid (water, alcohols, ketones, petr leunr fractions, chlorinated hydrocarbons and liquid gases).

The surfactant can be an emulsifying, dispersing and / or wetting agent and may or may not be ionic. Among others, one can mention the salts of polyacrylic acids, lignin sulfonic acids and sulforicinoleic acid, and the quaternary ammonium salts, the condensation products of ethylene oxide with fatty alcohols, fatty acids and fatty amines (in particular oxyethylated octylphenol and the fatty acid esters of anhydro-sorbitan) i.e. . It is preferable to use non-ionic substances because they are insensitive to electrolytes.

The compositions of the invention can be wettable powders, dusts, granules, solutions, self-emulsifying concentrates, emulsions, suspension concentrates and aerosols.

The wettable powders according to the invention may be formulated to contain from 20 to 95% by weight of the active agent and additionally from 3 to 10% by weight of the dispersant and, if necessary, up to 10% of the stabilizer and / or other additives (adhesion aids, anti-penetration aids, -moths, dyes, etc.).

As an example, the composition of a wettable powder, in% by weight:

Active substance (compound no. 6) 50 g

Ca-lignin sulfonate (anti-flocculation) 5% isopropylnaphthalene sulfonate (humectant) 1%

Silica (against the moth) 5% 35 Filler (kaolin) 39%

Powder formulations usually have about the same composition as the wettable powders, but now without dispersant. On the spot they can be diluted with water in a known manner so that a liquid is obtained with which one can coat seeds to be treated; they usually contain 0.5 to 10% active substance. Such a 5 powder can, for example, have the following composition:

Active substance (compound no. 6) 50%

Anionic humidifier 1 Z

Silica (against the moth) 6%

Kaolin 43 Z.

Granules intended to be sprinkled on the ground are usually sized between 0.1 and 2 mm and made by agglomeration and watering. In general, such granules contain 0.5 to 25 Z of active substance and 2 to 20 Z of suitable additives such as stabilizers, sustained release auxiliaries, binders and solvents.

The self-emulsifying concentrates often contain, in addition to the ordinary solvent, a solubility, increasing auxiliary agent, 10 to 50% active agent and 2 to 20 Z suitable auxiliary agents such as stabilizers, corrosion inhibitors, dyes and adhesives. As an example, a self-emulsifying concentrate can have the following composition:

Active substance (compound no. 6) 400 g / 1

Dodecylbenzene sulfonate 24 g / l ethoxylated nonylphenol (10 oxyethylene- 16 g / 1 25 units per mole)

Cyclohexanone 200 g / 1

Aromatic solvent up to 1 liter

Aqueous dispersions and emulsions, for example, obtained by diluting wettable powders or self-emulsifying concentrates according to the invention with water are also within the scope of this invention. The emulsions can be either water-in-oil type or oil-in-water type, and they can have, for example, a consistency such as mayonnaise.

For a so-called "application with a minimum volume of 35", in which spraying into very fine droplets, solutions in organic "solvents containing 70-99 Z active substance are prepared. 7906754 13.

The compositions according to the invention may also contain other auxiliary substances, such as colloidal protectors, adhesives and thickeners, as well as other substances with pesticidal properties, in particular known insecticides and / or fungicides.

7906754

Claims (3)

Novel derivatives of the 1,3,4-oxadiazolinone-5, characterized in that they are compounds of the general formula 1, wherein 5 represents a halogen atom, R 1, R 1 and R 9 independently of each other are hydrogen and alkyl groups can be 1 to 3 carbon atoms, R 1 is a halogen atom or an alkyl or an alkoxy group of 1 to 3 carbon atoms, and 10 n can be 0, 1, 2, 3 or 4, where n 2, 3 or 4, the groups R ^ may be the same or different from one another. Compounds according to claim 1, characterized in that they are compounds of formula 1 wherein X is in the para position of the phenyl group. 3. A compound according to claim 2, characterized in that X represents a chlorine atom. 4. Process for the preparation of a 1,3,4-oxa-diazolinone-5, characterized in that a compound according to formula 1 is prepared in a manner known per se for analogous compounds, in which 20 X, Rj, R £, R3, R4 and n have the meanings given previously. Process according to claim 4, characterized in that a compound according to formula 3, wherein R 1 and R 2 have the meanings given previously and Y and Y 'are independently of each other hydroxy or chlorine (with the limitation that if Y is hydroxy Y (which cannot be chlorine) is reacted with a compound of the formula IV in which R 1, R 1 and n have the meanings given previously to allow phosgene to act on the compound of the formula 8 thus obtained, after which the compound thus obtained is Formula 9 reacts in the presence of a base with a compound of Formula 10, wherein X has the meaning previously given and Z represents hydroxy or chlorine, with the limitation that Z is other than Y, 6. Process according to claim 4, characterized in that a compound according to formula 5 in which R 1 and R 2 have the previously given meanings is reacted with a benzaldehyde according to formula 6 wherein R 1 and n have the previously given meanings. the hydrazone of formula 7 with hydrogen thus obtained reduces 7906754 to one. compound of formula 8 wherein Y is hydroxy, phosgene is allowed to act on this compound of formula 8, and the compound of formula 9 thus obtained in which Y is hydroxy is reacted with an acid chloride of formula 10 wherein X is the previously giving has meaning and Z represents chlorine. The new compound of formula 8 to be used in the processes according to claims 5 or 6, wherein Y, R 1, R 1, R 1, R 1, R 1 and n have the meanings given previously. The new compound of the formula 9 to be used in the process according to claim 5 or 6, wherein Y, Rj, a Rg, Rl and n have the meanings given previously. Insecticidal composition, characterized in that it contains one or more compounds according to formula 1. 10. A composition according to claim 9, characterized in that it contains 0.05 to 95% by weight of the compound of formula 1. 7906754 R, ·, _ ^ ο R, Rt γ 'Ri / p ^ \? L ^ ΝΗΝΗ, H / * \ Yc <+ η, ν-νη-ch ^ Q) ho-c / S * o' \ ^ (R) R 0 \ - ^ (R) "R," V " 3 I 5 6 & ✓κ-Β - '"- ®) * ι Λν =" ^ 3> Ycc Η H VT-A (R 1 HO-CC X — J ^ r ^ R, 0 g R- 7 Xcopi, μΛ0Α0 R1 9 CH-CH, NV 9, —v CH 0. 0- ™ - <z 'x 10 \' "d." · b, - / R \, © -4 ": <fi> ^ RU 1 7906754 'TJtrTT Aoon ολλ ·? Ω + · ο ΔτίΓιηνηΐί »mainly upns French law in Lyon France