LU81677A1 - NOVEL DERIVATIVES OF OXADIAZOLINE-1,3,4 ONE-5, THEIR PREPARATION AND THE INSECTICIDE COMPOSITIONS CONTAINING THEM - Google Patents

Description

I î »ï: r * /! The invention relates to new derivatives of oxa-diazoline -1, 3, 4 · one 5 corresponding to the following formula: y »-H-CH (O> CH (CH.) - R, \ / TV 1 3 I1 ... (R4) n (QN - ch - coo - c Nq / ^ o. 4 x r1 in which: - X represents a halogen atom '5 - Rj, 1 * 2 and R ^, identical or different each represents a hydrogen atom or an alkyl radical containing from 1 to 3 carbon atoms - R ^ represents a halogen atom, an alkyl radical containing from 1 to 3 carbon atoms or an alkyloxy containing

K

10 from 1 to 3 carbon atoms - n is an integer which can be equal toO, 1,2, 3 or 4 provided that, when n is equal to 2, 3 or 4, the substituents are the same or different.

The invention also relates to the preparation of the compounds according to formula I. It further relates to the insecticidal compositions containing as active ingredient at least one compound r according to formula I as well as the insecticidal treatments carried out using these compositions.

The invention relates more particularly to the compounds corresponding to the following formula:

t ** t **** m ~ m ±, --- V CH (CH *) 9 R9 N ---- N - CH. ^ f / 'v ·' ° · 'i' V— \ / · \ .ö / vö (Vn.

(ii) · 'in which x * R ^ and Rg, R ^ and n have the same significance as in formula I. In formula II, X represents- / j // I - · *'

V

*; i 2 preferably smells of chlorine. The compounds according to formulas I and II all have at least one asymmetrically substituted carbon atom. Each of these compounds therefore exists in several stereoisomeric forms which also form part of the invention.

Some oxadiazole derivatives have. already described in the literature for their insecticidal properties.

Thus, US Pat. No. 4,096,273 describes derivatives of 3-benzyl-4-chloro-phenyl) -2 methyl-3-butyryloxÿ-alcqyjj ^ oxadiazole - 1,2 ', 4 usable as insecticides and corresponding to the general formula î n S_ _CH, - (O> / 7Λ »Il II ^ x.

Cl - <W / '- CH - C - O - CH-v N

\ / i t \ / CH (CH3) 2 R * in which R 'represents a hydrogen atom or a. alkyl radical containing from 1 to 4 carbon atoms and 15 X 'represents a hydrogen or chlorine atom.

The compounds according to the invention are different from those described in this American patent and exhibit, with respect to them, a significantly higher insecticidal activity.

The compounds according to formula I can be pre- ”. trimmed according to a process comprising the following stages î A - Action of a derivative of an alkanoic acid on a derivative of benzylhydrazine, according to the reaction scheme: ^ 3 / - "v 25 Y“ C - CO - Y '+ NH2 - MH - CH-YQ, /) R2 (R4) n ;; Rj r3 —JY - C - CO - NH - NH - CII- / 0V + ΥΉ 30 R2 (R.) n /// (III) 4 U / in which : ' /,

t I

'1; 9 '3! . .

- R1 # R ^, R ^, R ^ and n have the same meaning as in formula I.

-Y and Y ’, identical or different, each represent a chlorine atony or a hydroxyl radical, with the proviso that, when Y represents a hydroxyl radical, Y ′ does not represent a chlorine atom. B - Cyclization of compound III resulting from the preceding step, by action of phosgene, according to the reaction scheme: „j -1? I — r ~ CB · @ compound III + C0C1 -— to Y - C -“ * D5. '* (R,) n + 2HC1 * »n ° 4. . R2.

(IV) 10 in which R ^, R £, R3, R4 and n have 3a m®rae meaning that, in the formula I- and Y has the same meaning as before. - C - Action of compound IV resulting from the previous step on a derivative of phenyl ~ 2-inethyl-3 butyric acid, of formula. * n îH (ch3> 2 UJ> - CH - CO - 2 X (V) in which X represents a halogen atom and Z, different from Y defined previously represents the hydroxyl radical or a · chlorine atom, depending on the reaction scheme: Π \ f {CH3, v>) £) ~ CH C0 2 + Y i * -v0 (R4) n X 2.

_ R3 / CH (CH 3) £ -.1¾ - CH - (T)) + HG1 // Æ) · .Λ-Λ. "* '$ I - - I.,, -... · ....

I.

4.

k in the presence of a base serving as an acceptor, of HCl such as, for example, triethylamine, N, N dimethylaniline or pyridine.

A preferred embodiment of the process described above consists in using / as starting material for the first step of the process, an ot -chloro-alkanoic acid, or a chloride of this acid, of formula - 'î * -

Cl - C - CO - Y '(VI) - v ’h - - · in which Rj and have the same meaning as in formula 1 and Y're represents a hydroxyl radical or a chlorine atom.

According to this preferred embodiment, step A is carried out in an inert organic solvent medium such as an aromatic or aliphatic hydrocarbon, at a temperature of between 10 and 50 ° C. approximately. When the compound V is an acid, the water formed during step A is removed by azeotropic distillation.

In the case where this compound VI is an acid chloride, the reaction is preferably carried out in the presence of an ary'sulfonic or alkyl sulfonic acid, such as methane sulfonic acid.

The cyclization according to step B of the compound thus obtained is carried out in an inert organic solvent medium, aromatic> 20 hydrocarbon for example, at a temperature between 20 and 110 ° C.

According to step C of the process, the (chioro-alcoyl) ~ 2 benzyl-4 oxadiazoline-1,3,4 one-5 resulting from step B is reacted. an acid of formui: 'Ç "CCK3) 2 /; f (À- CH - C00H.. (ΪΠ) V' · '- V ·> -.

Λ. · - ·.

in which X has the same meaning as in formula I, / 1/25 in roüiea inert organic solvent such as hydrocarbon aro - /// ^ nvkA 4 · / »nmnri qa ontro 1Π l Jf I J - ,.

; . r 5 and 140 ° C approximately.

According to another embodiment of the process described above, a starting material for step A is an -hydroxyalkanoic acid of formula s 5 "fl

HO - 0 - COOH (VIII) V

r2 'in which Rj and R2 have the same meaning as in formula ‘1 and this step A is carried out in an organic solvent medium, at a temperature between about SO and 150 ° C., removing the closed water by azeotropic distillation.

XO The cyclization according to step B of the process, of the compound thus obtained, is carried out in an aqueous medium, at a temperature between 10 and 30 ° C.

. According to step C of the process, the ′ (hydroxy-alkyl) -2 benzyl-4 oxadiazoline-1,3,4 one-5 resulting from step B, 15 is reacted with an acid chloride of formula :, 7 ~ \ 9 <CH3> 2 V y- ch - co - ci (ix), in which X has the same meaning as in formula I, in an inert organic solvent medium, such as acetone, · methylene chloride or hydrocarbons aromatic, at a temperature between 10 and 50 eC approximately. * 20 The acid according to ia formula VII is prepared according to the method described in Beilsiein 91, p. 216, for the preparation of 2-phenyl-3-methyl-butyric acid. (4-chlorine phenyl) -2 methyl-3-butyric acid is a compound known per se described in Chem. Abstr 55, 1016ο.

The acid chloride according to formula IX is obtained ,, / according to a process known per se, by the action of chloride / jy ί * i *! ι 6 i ".-’ thionyle on the acid according to formula VII.

According to a variant of the process described above, also forming part of the invention, the compounds according to formula I, for which R3 represents a hydrogen-S gene, can also be prepared according to a process comprising the following steps: D - Action of the hydrazide of an o <-hydroxy-alkanoic acid on a benzaldehyde derivative to give the hy-drazone of the preceding benzaldehyde, according to the reaction scheme:

Ri "i ho - c - oo - nh - m2 + \ Q no - c - co - nh -" =

"2 · / \ K

(R4) n + H20 in which R ^, R2, R4 and n have the same meaning as in formula I *. This reaction is carried out in a hydroalcoholic medium (water and ethanol for example) in the presence of acetic acid, at a temperature between approximately 20 and 40 ° C.

E - Hydrazine reduction of the hydrazone resulting from the previous step according to the reaction scheme:

Rj _ ^ + H2 ^ HO - C - CO - NH - N = aKOV "/ H0 - C" CO-ΝΉ-ΝΗ - CE, (Ç \)

Xzs, \ · 2ν ^ / ^ (Rjn • ‘. * * 2 <R4> n R, 4

This reduction is carried out in the presence of palladium on black, at a temperature of between 20 and 20 60 ° C. approximately.

F - Cyclization of the resulting compound. From the previous step, by action of phosgene to give a compound of formula: / V / R, 'H - N - CH, - (Q,) // .Ml M VI / mr ) „// ... 110 - c — UA 1 / R2 '/ 7 · ί il" »'

This cyclization is carried out according to the same reaction scheme and using the same reaction conditions as lice * 1‘step B of the process described above.

G - Action of the compound resulting from step 5 F on a derivative of 2-phenylmothy1-3 butyric acid from 'Γοτηΐηΐθ! CH (CHJ-n ~ \. 6 * {£)) - · CH - GO ~ Cl χΛίν. In which X has the same meaning as in the formula • I.

This reaction is carried out according to the same. 10 reaction scheme and using the same conditions as for step C of the method described above.

The new compounds according to general formula I exhibit remarkable insecticidal properties. They are particularly active by contact and ingestion. Particularly interesting results are obtained with these compounds in the case of Diptera, Coleoptera and Lepidoptera.

The following examples are given without implied limitation to illustrate the invention.

EXAMPLE 1 Preparation of (4-chioro-phenyl) -2-methyl-3-butyrate of (4-benzyl-oxadiazoline-1,3,4 one-5 yl-2) -methylc (compound No. 1).

To a solution of S, 2 g of 2-hydroxymethyl-4-benzyl-oxadiazoline ~ i, 3.4 one-5 and 4.04 g of triethyiamine in 100 ml of acetone, the solution is added dropwise in 10 minutes. 9.2 g solution of 4-chloro-phenyl) -2 methyl-3-butyric acid chloride in 100 ml of acetone. The mixture is left to stir for two hours at laboratory temperature. The precipitate formed is then separated by filtration on sintered glass and the organic solution is concentrated under reduced pressure.

The residue is taken up in 250 ml of isopropyl ether and the solution 30 washed successively with 200 ml of water, 100 ml of a 3.6% hydrochloric acid solution / aqueous poirls / volume, 100 ml of an aqueous solution of soda at 4% W / V and 100 king of water. fi // f. ' f.

8 ï. * --7 / -7- '· ":; ·:

After drying and concentration under reduced pressure, the residue obtained is purified by chromatography on a silica column to provide 12 g of (4-chlorine-phenyl) -2-3-methyl-butyrate of (4-henzyi-1,3-oxadiazoline, 4,4- 5 y 1-2) methyl melting at 70 ° C ”5 Elemental composition calculated · found • C% 62.92 · 62.76 H 90 5.28 5.29 O% 15.97 15.78 10 - N% . 6.99 7.03. . .

Cl% S, 84 9.0

Chloride of acid (4-chloro-phenyi) -2 methyl-.

3 butyric is obtained by the action of thiony chloride on the acid (chloro ~ 4 pheny]) - 2 methyl-3 butyric, melting at S5 °, itself prepared 15 according to the method described in Beilstein 9 I - p, 216 by the action of * isopropyl bromide on (4-chloro-phenyl) .- acetonitrile scde and hydrolysis with sulfuric acid of the product obtained.

2-Hydroxymethylbenzyl-4oxadiazoIin-1,3,4 one-5 is prepared as follows; 61 g of benzylhydrazine 20 are reacted with 53 g of glycolic acid dissolved in 200 ml of toluene at the reflux temperature.

After azeotropic distillation of the water formed, the reaction medium is taken up in 500 ml of water. The aqueous layer is decanted and washed with twice 250 ml of methylene chloride, then this aqueous layer is recharged in a flask and saturated with phosgene at 20 ° C. The reaction medium is taken up in 500 ml of methylene chloride, the the organic layer is decanted and washed successively with 500 ml of a 100 g / l potassium bicarbonate solution, then with 500 ml of distilled water. After drying over sodium sulphate and concentration under reduced pressure, 35 g of hydroxymethyl benzyl-oxadiazoline-1,3,4 one-5, melting at 54 ° C., are obtained.

EXAMPLE 2; ,

Preparation of (4-chloro-phenyl) -2-3-methyl-butyrate / of 4-benzyl oxadiazoline-1,3,4-one-5 yl-2} -l ethyl, in the form of /// 35 two diastereoisomeric compounds. : 1 fj / * ·.

": Ί - '9 * To a solution of 11 g of ihydroxy-l ethyl]) - 2 benzyl-. 4 cxadiazoline-1,3,4 one-5, Isomer L, in 50 ml of methylene chloride, the solution of 11.6 g of chloride of acid (chloro-k phenyl) -2 methyl-3 is rapidly added butyric in 10 ml of methylene chloride, 5 then drop by drop in 10 minutes 4 g of pyridine. The mixture is left to stir for 2 hours at laboratory temperature. The reaction medium is then taken up in 300 ml of an aqueous solution of hydrochloric acid 3.5% W / V. The organic coudra is decanted, washed successively with 300 ml of an aqueous solution of potassium bicarbonate at 10 10 -% W / V and 300 ml of water, and dried. ’·. ... ...

After filtration and concentration under pressure. ‘Reduced, I residue, weighing 22 g, 'is' purified on a column, da silica.

* The 17 g of oil obtained after chromatography gives after crushing with petroleum ether:.

15 -7 g of (4-chloro-phenyl) -2-methyl-3-butyrate of (4-benzyî oxadiazoline-1,3,4 one-5 yi-2) -l ethyl, stereoisomer A (compound No 2), melting at 102 ° C, [^ J 39.6 (c * 10, acetone), * - 9 g of (chloïo-k phenyl) ~ 2 methyl-3-butyrate of (benzyi-4 oxadlazoline- 1,3, k one-5 y 1-2) -1 ethyl, stereoisomer B (compound No 3) in the form of a pasty solid melting at 40-45 ° C ^ = - 21.3 ° (c = 10, acetone).

Calculated elementary composition found

Compound No 2 Compound No 3 C% 63.69 63.69 63.26 25 H%,. 5.59 5.71 5.94 0% 15.42 15.60 14.91 N% 6.75 7.01 6.17

Cl% 8.55 ’S, 45 8.85.

The hydroxy-1 ethyl (I) -2benzyl-4oxadiazoline-1,3,4 one-5, L-isomer is obtained, according to the method described in Example 1, by reacting 33 g of lactic acid, L-isomer, on 25 g of benzyihydrazine in toluene heated to reflux, then by cyclizing with phosgene,.

in an aqueous medium, the compound obtained. This gives 18 g of (hydroxy- / / 1 ethyl) -2 ben.zyl-4 oxadiazoüne-1,3,4 one-5, isomer L, melting at //

35 70 ° C, [cfj = - 19 ° (c = 10, acetone). / M

i * “* - 10 EXAMPLE 3;

By operating as in Example 2, on the same amounts of reagents from (hydroxy-ethyl 1) -2 benzyi-4 oxadiazoline-1,3,4 one-5, isomer D (prepared from acid lactic, isomer 5 D), melting at 70 ° C, fHl ?? "+ 19.7" (c "10, acetone), one obtains - 7 g of stereoisomer C (compound No 4) melting at J. G4aC" foy ^ = -: - 42 ° (c = 10, acetone), ' ·.

- 9 g of siéréoisornère D (compound No 5) in the form of oil, jpQj? ®. = + 22 ° (c = 10, acetone). / *

Elementary composition î · calculated found compound Mo 4 compound Ko 5 C% 03.09 69, 89 63.90 H% 5.59 5.68 6.0 15 0 90 15, ½ 15.26 15.40. + * N 96 6.75 6.93 6.16

Cl 9S 8.55 8.44 <9.31 r ‘: · 'EXAMPLE 4

Preparation of (4-chloro-phenyl) -2 methyl-3 20 butyrate of [(2-methylbenzyl} -4 oxadiazolinc ~ 1,3,4 one-5-yl-2 J methyl (Compound Wo 6).

To a solution of 19 g of (4-chloro-phenyl) -2-methyl-3-butyric acid and 11.7 ml of triethylamine in 175 ml of xylene heated to 110 ° C., the following are added over 20.25 minutes, · The solution of 13.3 g of 2-methyl (2-methylbenzyl) -4 oxadiazoline-1,3,4 pne-5 in 35 ml of xylene. It is heated for 4 hours at reflux. After cooling, the reaction medium is washed successively with 100 ml of water, 100 ml of a 3.5% aqueous solution of hydrochloric acid, 100 ml of a 4% aqueous solution of sodium hydroxide and 100 ml of water. After drying, discoloration on animal hoir and concentration under reduced pressure, the residue obtained is purified by chromatography on a silica column to provide 11.2 g of [4-jraêthy 1- (4-chloro-phenyl) -2-methyl butyrate 2 bsnzyl) -4 // 35 oxadiazoline-1,3,4. ane-5 - yl - 2 ^ methyl in the form of oil \ k / j 'r. .

11! .. .. · · j Compositior; calculated elementary found δ C & 3, f> 9 63.55% H 5.59 5.78 5% 0 15.42. '15, 44 "£ N 6.75; 6.88; i '% Cl 8.55. 9.12

Chlormethyl-2 (methylated benzyl) -4 oxa-di.asoline-1, 3,4 one 5 is prepared as follows: one proceeds.

10 react, 56.7 ml (d ** 1.42) of chloroacetyl chloride on 2-methyl banxhyärazine. (1GO a) in · solution in toluene (1000 ml), in the presence of metnanesulfonic acid (46.2 ml), at ordinary temperature, then the pho.sgene ('200'g) S-a temperature between 25 and 112eC. Concentrated and thus obtained in the form of oil / 13.3 g of 2-methylchlormethyl (2-methylbenzyl) -4 oxadiazoline-1,3,4 on 5. h EXAMPLE 5

Preparation of (4-chloro-phenyl) -2-3-methyl-buty- * rate of [(2-chloro-benzyl) -4 oxadiazoline-1,3,4 one-5 yl-2j 20 methyl (compound n ° 7).

By operating as in Example 1 from a solution of 16 g of 2-hydroxymethyl (2-chloro benzyl) -4 oxa-. diazoline-1,3,4 one 5 in 100 ml of acetone, and a solution of 17.8 g of (4-chloro-phenyl) -2-methyl-3-butyric acid in 50 ml of acetone, 26 g of [[((2-chloro-benzyl) -4-oxadiazoline-1,3,4 one 5 yl-2 ^ methyl) are obtained in the form of oil (4-chloro-phenyl) -2 methyl-3-butyrate.

. . Elementary composition. · Calculated found 30 SC 57.94, 58.61 £ H 4.63 4.68% O 14.70 13.94 5 K 6.44 6.15 V. Cl 16.29 16.31, / '"35 Hydroxyméi; hyl-2 (2-chloro-benzyl) -4 /// 4 · *.

>, 12 t '* I ‘cxadi a ^ oiine: -! , 3,4 ono-5 is obtained by the action of phosgene on a solution · of (cblorc-2 benzyl) -i glycolyl-2 hydrazin ·; (38 g) in 600 ni d'nmi A with a temperature between '20 and 30a.

On cin.:io »rc / ~>: üisi> after recri stall isation - '/ oroDvlious / / 5 in X'éther iso-it g &' hyàroxyméthyl-2 (chloro-2 benzyl) -4 oxadiazoline-1,3 , 4 one-5 melting at 6 ° C (R - 42%).

(2-chloroenzinX) ~ 1 glycolyl-2 hydrazine - * · · * is prepared by hydrogen reduction of glycolylhydra- zone of 2-chloro-benzaldehyde, (41.5 g), '' in solution in 10 415 ml. of dioxane, in the presence of palladium on black in autc * 2 clave, in hydrogen, under a pressure of 15 kg / cm, at a temperature between 20 and 60 ° C. After filtration and concentration, 38 g of 2-hydroxymethyl (chloro-i benzyl) -4 oxadiazoline-1,3,4 on 5 are obtained.

15 The glycolylhydrazone of 2-chloro-benzaldefc-hyde (41.5 g) melting at 166 ° C is itself obtained by the action of glycolylhydrazine (18 g) on 2-chloro-benzaldehyde (30.9 g) solution in a mixture of water (20 ml), acetic acid (10 ml) and ethanol (60 ml), at a temperature between 20 and 40 ° C.

After precipitation and cooling, it is filtered, washed with water and alcohol and dried. 41.5 g of (4-chloro-phenyl) -2-methyl-3-butyrate are thus obtained. * · £ (2-chloro-benzyl) -4 1,3,4-oxadiazoline one-5 yl-2] methyl • 25 EXAMPLE 6

By operating according to the method described in example * 4 starting from suitable raw materials, the following compounds were prepared: .....

‘T 4 *.

/, -.

/ ''! · / '-. . 13 _ CH (CH3) 2 Rj j} - »- ch2- / §> cl ~ \ 0) - ch - coo - c-1 ^ 0. “Vn S2 5 Compound Rj 1¾ ^ pgnt Composition Sl & rentai re_

No (R ^> n Calculated fusion found 8 H H - / 0) -Ci oil J. C%. 57.94 I 58.54 d H% 4.63 4.85 10 O% 14.70 '14.86. Cl% 16.29 15.80 ______'___ N-% 6.44 6.29 9 CH3 CH3 Jr} \ 85 ° CC% 64.41 63.86 H% 5.87 5.87 "15 0% 14.92 -14.91 t

Cl% 8.27 8.98 N 5 6.53 6.04 10HH oil C% 61.32 62.90 ^ H% 5.38. 5.65 20 3 0% 18.57 18.17

Cl% 8.23 7.70 _____3________________N% 6.50 __-__ 5.90 ___ 11 Iï H - (0) -Œ3 oil C% 63'69 63.22. * H% 5.99 '5.48! 25 0% 15.42 14.81

Cl% 8.55 9.25 N% 6.75 7.18 12 H H oil C% 63.69 62.50 • CH3 H% 5.59 .. 5.40 30 0% 15.42 15.02

Cl 5 8.55 10.02 .RS 6.75 7.70 13 H H / p) Ci oil 61.32 61.76 -0CB i r P -, c r. / 35 ί O Z 18.57 38.0 // i ί * ”" 14 _ '* * .. _ „/ T \ Point Elementary composition composes R, <Q> âe

KB Calculated merge found

Ci% 8.23 6.50 U% 6.50 6.0 5 _____________ — ___ 14 H H / ρλ oil C% 57.94 58.20 H% 4.63 4.64

Cl 0% 14.70 14.12

Cl% 16.29 16.70 * 10 ’NS 6.44 6.28 EXAMPLE 7

Insecticide activity by contact (fly, tribo-lium). 1 ml of an acetic tonic solution or suspension of the product to be studied, at a given concentration, is introduced into a 120 ml glass jar and four pots are thus prepared for each concentration of product to be studied. When the solvent has evaporated, either 5 flies (Musca domestica) or 10 triboliums (Tribolium 20 confusum) are placed in each pot. For each concentration of product to be studied, two pots are used per insect species. The pots are covered with a metallic cloth and the number of dead insects is counted after 24 hours of contact in the case of flies, and after 3 days in the case of tribo-25 liums. The concentration which causes the death of 90% of the insects is thus determined, hereinafter designated C19Q. The results observed are indicated in the table below, in which the Clgg are expressed in micrograms per milliliter, taking as comparison product the compound No. 1 of the US patent 4096273. / ί m · · 15.

Compound No. Tribolium Fly

C190C19Q

1 10 100 3 30 300 5 5 100 - '_ 6 100 _ 11 200 _ 12 100 13 1000 _ 10 Comparison compound 30 1000 EXAMPLE I

Insecticide activity by contact-ingestion (foliage treated by soaking - caterpillars of Piutella maculipennis and caterpillars of Pieris brassicae).

15 An emulsifiable solution is prepared having the following composition: - active material to be tested .................................. ...... 250 g - emulsifier (mixture of calcium phenylsulfonate and oxyethylene nonylphenol) ................. 90 g 20 - surfactant (monolaur ate of sorbitan ô ^ ethylene ............................. 20 g - solvent (mixture of 2 volumes of acetophenone for 3 volumes of toluene). .................. qs ........ I 000 ml • The solution thus obtained is then diluted with 25 of distilled water containing 0.02% of the same surfactant, so as to obtain several solutions of determined concentration.

Young broccoli (Brassica oleracea) leaves in the four-leaf stage are soaked for 10 seconds in the solutions to be studied. The cabbage leaves are allowed to dry and, when they are dry, they are distributed in cylindrical plastic boxes. In each box, 10 caterpillars (3rd stage) of Piutella maculipeniÿs or Pieris brassicae are placed. For each / species of caterpillar, two boxes are used per material concentration / active L. / li 16 •

After 3 days, there are live caterpillars and dead caterpillars for each concentration of active ingredient and the concentration which causes 50% mortality of the caterpillars (C15Q) is determined. The results observed are indicated in the table below, in which the ICs are expressed in micrograms per milliliter:

Compound n ° Plutella Pieris <cl50> (C150> 10 1 20 100 2 1000 1000 3 100 300 5 1000 - 8 1000 15 10 2000 2000 11 2000 12 1000 2000 13 300 1000

Product of 20 Comparison 300 500

For their use in practice, the compounds according to the invention are rarely used alone. Most often, they are part of compositions which generally comprise eB plus of the active material according to the invention, a support and / or a surfactant. In these compositions, the content of active material can vary from 0.05% by weight to 95% by weight.

The term "support" within the meaning of the present description designates a material, organic or mineral, natural or synthetic, with which the active material is associated to facilitate its application to the plant, to seeds or to the soil, or to its transport. , or its handling. The support can be solid (clays, natural or synthetic silicates, calcined magnesia, kieselguhr, tricalcium phosphate, /? / * 17 cork powder, absorbent black, resins, waxes, solid fertilizers ... ) or fluid (water, alcohols, ketones, petroleum fraction, chlorinated hydrocarbons, liquefied gases).

The surfactant can be an emulsifying, dispersing or wetting agent which can be ionic or non-ionic. Mention may be made, for example, of salts of polyacrylic acids, of ligninsulfonic acids, of sulforicino-leatates, of quaternary ammonium salts, of condensates of ethylene oxide on fatty alcohols, fatty acids or amines 10 fatty and in particular products based on ethylene oxide condensates such as ethylene oxide condensates with octylphenol, or esters of fatty acids of anhydro-sorbitols which have been dissolved by etherification of the radicals free hydroxyls by condensation with ethylene oxide. It is preferable to use agents of the nonionic type, since they are not sensitive to electrolytes.

The compositions according to the invention can be prepared in the form of wettable powders, dusting powders, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.

The wettable powders according to the invention can be prepared so that they contain from 20 to 95% by weight of active ingredient and they usually contain from 3 to 10% by weight of a dispersing agent, and, when it is necessary, from 0 to 10% by weight of one or more stabilizers and / or other additives # such as penetration agents, adhesives or anti-caking agents, dyes, etc.

By way of example, here is the composition 30 of a wetted powder, the percentages being expressed by weight: - active material (compound No 6) ................... .50 g - calcium lignosulfonate (deflocculant) .......... 5% - isopropylnaphthalene sulfonate (wetting) ---------- 1%.

35 - anti-clumping silica ...................-.......... 5% / /; / "NVï a vno fVarvInirO Si / / 18 ** *" ..... '' The powders for dusting are usually prepared in the form of a dust concentrate having a composition similar to '· ··' a wettable powder, but without dispersing agent: and they can be diluted at the place of use with the aid of an additional quantity of fluid support so as to obtain a composition which can conveniently coat the grains to be treated and containing usually 0.5 to 10% by weight of active ingredient.

As an example, here is composition 10 of a -powder for dusting ..: - active material (compound No 6) .................... .50% - anionic wetting agent ......................... 1% - anti-clumping silica ............. .................. 6%

- kaolin (charge) ................................... 43 S

The granules, intended to be placed on the ground, are usually prepared so that they have dimensions between 0.1 and 2 mm and they can be manufactured by agglomeration or impregnation. In. generally, the granules will contain from 0.5 to 25% active ingredient, from 2 to 20% w / v of suitable additives, such as stabilizers, slow release modifiers, binders and solvents.

The emulsifiable concentrates applicable in spraying usually contain, in addition to the solvent and, when necessary, a co-solvent, from 10 to 50 ζ by weight / volume of active ingredient, from 2 to 20% by weight / volume of suitable additives, such as stabilizers, penetrating agents, corrosion inhibitors, and dyes and adhesives.

30 As an example, here is the composition of an emulsifiable concentrate, the quantities being expressed in g / liter: - active ingredient (compound No 6) ................. 400 g / 1 - dodecylbenzene sulfonate ....................... 24 g / 1 day

35 - nonylphenol oxyethylated with 10 molecules ..... 16 g / l / VJ

- cyclohexanone ..................-................ 200 g / 1 / y - aromatic solvent .... ................ gsp ... 1 liter * 19 '»

Aqueous dispersions and emulsions, for example compositions obtained by diluting with water; a wettable powder or an emulsifiable concentrate according to the invention, are included in the general framework of the present invention. These emulsions can be of the water-in-oil type or of the oil-in-water type and they can have a thick consistency like that of a "mayonnaise".

For an application known as "1 very low 10 volume" with a spray in very fine droplets, solutions in organic solvents containing from 70 to 99% of active material are prepared.

The compositions according to the invention can contain other ingredients, for example, protective colloids, adhesives or thickeners as well as other known active ingredients with pesticidal properties, in particular insecticides or fungicides. / ÿ f

V

Claims (12)

5 CH (CH-). R ~ N — N - @ - "- 030 - Ç - n ^ Wq ^ - ^ (R4, n X R1 in which s. X represents a halogen atom, 10. R1 # R2 and R3, identical or different, each represents one. hydrogen atom or an alkyl radical containing from 1 to 3 carbon atoms, • · R ^ represents a halogen atom or an alkyl radical containing from 1 to 3 carbon atoms, or alkyloxy “* · * * r • * · 15 containing from 1 to 3 carbon atoms, .... "·. · N represents an integer equal to 0,1,2, 3 or 4, provided that, when n is equal to 2, -3 or 4, the suk'sti- 'killants are identical'or - different. - '7 - 20 2. Compound according to claim 1, characterized in that this compound corresponds to the following formula: “3. CH (CH3) 2 R2 n —h - CH -Zq \ 25 x- (0) -ch: -coo-cJ ^ 0J ^ E1 in which X, R2 "R3, R4 and n have the same meaning as in claim 1. 3. Compound according to claim 2, - 30 characterized in that X represents a chlorine atom. 4. Process for the preparation of the compound according to claim 1, characterized in that it comprises the following sequence of steps: t / A - Action of an alkanoic acid derivative ^ A 35 âe formula: / "/ a / .- · / '* .-. T: / * mf 21 Y - C - CO - Y' * 2 in which R ^ and R2 have the same meaning as in claim 1 and Y and Y ', identical or different, each represents a chlorine atom or a hydroxyl radical, provided that when Y represents the hydroxyl radical, Y ′ does not represent a chlorine atom, on a benzylhydrazine derivative, of formula: 10 * 3 / in which R3, R ^ and n have the same meaning as in claim 1, to give a compound of formula: * ί1 Γ3 y_v 'Γ VI / ^ ÎRjn. R2 B - Cyclization of the compound resulting from the previous step, by action of phosgene, to give a compound of formula: _ R NN - CH - <θ \ γ „έ_Ι! l 'c /' - o R2 25 in which R, R2, R ^, R4 and n have the same meaning as in the claim ion 1 and Y has the same meaning as in step A of claim 4. C - Action of the compound resulting from the previous step on a derivative of phenyl-2-methyl-3-buty-30 rique, formula: CH (CH) JS) ~ CH - CO - ZX in which X has the same meaning as in that claim 35 cation i and Z represents the hydroxyl radical or an atom ce) chlorine, provided that Z is different from Y as defined / sfr, ·> - a »* 22 in step B of claim 4, in the presence of a base. 5. Method according to claim 4, characterized in that the base used for step C is tri-thylamine, N, N dimethylaniline or pyridine. 6. Method for preparing a compound according to claim 1, characterized in that it comprises the following sequence of steps: D - Action of the hydrazide of an rt-hydro-xyalkanoic acid, of formula: 10 HO - C - CO - NH - NH- f. - Λ * 2 in which R ^ and R2 have the same meaning as in claim 1, on a benzaldehyde derivative, of formula: ch0 (E4) n in which R ^ and n have the same meaning as in claim 20 1, to give the compound of formula: H, HO - C - CO - NH - N = CH-YoN; 2. - E - Reduction by hydrogen of the compound 25 resulting from the previous step, to give a compound of formula: HO - C - CO - NH - NH - CH2- / q \ R2 ^ -> TR4) n in which R1 # R2, R ^ and n have the same meaning as in the previous step. F - Cyclization of the compound resulting from the previous step, by action of phosgene, to give a / compound of formula ï R, N - N - CH0 - / (y \ / Y HO-C1 - Il L 2 35 k2 (/ r23 in which R ^, R2, R ^ and n have the same meaning as in claim 1. G - Action of the compound resulting from the preceding step on a derivative of 2-phenyl-3-methyl-butyri-5 acid as , of formula: ch (ch3) 2 XÆ> - CH - COC1 in which X has the same meaning as in claim 10 tion 5. 7. As means intended for the implementation of the methods according to claims 4 and 6, compound of formula: R1 R3 Y - C - CO - NH - NH - CH - (Γ) Λ 'V ^ ySR,) n R2 2 4; in which R ^, R2, R ^ f R ^ and n have the same meaning as in claim 4 and Y represents a chlorine atom or a hydroxyl radical. 8. As a means for carrying out the methods according to claims 4 and 6, compound of formula: R, N — N - CH- \ Ç \\ Y - C - -4. "3", * 25 wherein R ^, R2, R3 # R ^, n and Y have the same meaning as in claim 7. 9. Insecticidal composition, characterized in that it contains as active material at least one compound according to claim 1, in combination with a supporl and / or a surfactant usable in agriculture and compatible with said active material. 10. Composition according to claim 8, characterized in that it contains from 0.05 to 95% by weight of active material. iS (Ki ^ V <Urd <Λ P ** A, .- ”SP“ · ** A évMÙfXtm, t * <U XtMrt \ clvÂAXC * m% ”λ ûJtaug:“ YuAAi / ft '& ikiiu'i ,.. JLl J λ * tJuahjrr $ J? IJk / »