DE2936726A1 - DERIVATIVES OF 1.3.4-OXADIAZOLINE-5-ONS, THEIR PRODUCTION AND USE AS INSECTICIDES - Google Patents

Description

PHILAGRO

14-20, rue Pierre Baizet

69009 - Lyon (France)

Derivatives of 1.3 »4-oxadiazolin-5-one, their production and use as insecticides

The invention relates to new derivatives of 1.5.4 — Oxadi azolin-5-ones of the general formula I.

R ₃

DCH (CH ^) ₂ Rp NN -CH-

_ CH COO - C -

^R 1

in which:

X is a halogen atom,

R _x ,, Rp and R, simultaneously or independently hydrogen or C, - to C _7. -Alkyl,

503.1- (PH 1578 ETR) -SF / Nu

030012/0917

R _{4 is} hydrogen, C ₁ - to CU-alkyl or

C ₁ - to C ₅

and

η 0 £ η 4 =. 4 (integer), where the sub-

tuenten R _{4 are} identical or different when η is 2, 3 or 4-.

The invention also relates to the preparation of the compounds of the formula I and insecticidal compositions, which contain at least one compound of the formula I as active ingredient, and their use for the treatment of insecticides.

The invention relates in particular to compounds of the formula II

CH (CH ₅ ).
- CH 'COO - C -I' / L ^^^ (R ^ n (II)

with X, R ₁ , Ro, R ₄ and η as in formula I. In formula II, X preferably denotes a p-chlorine atom.

The compounds of the formulas I and II all have at least an asymmetrically substituted carbon atom. Each of these compounds can thus be in several stereoisomers There are forms which are also encompassed by the invention.

Certain oxadiazole derivatives have already been described as insecticidally active substances in the literature.

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US Pat. No. 4,096,273 describes derivatives of 3-benzyl-2,4-chlorophenyl-3-methylbutyryloxyalkyl-i.3.4-oxadiazoles which can be used as insecticides and which have the general formula

0 N _ιΓ - CH ₀ -

// 'Λ \ "Il" ²

Cl - <()> - CH - C - 0 - CH J N

CH (CH,) ₂ R ¹ 0

correspond, in which R ^{1 is} hydrogen or C ^ - to C ^ -alkyl and X ^{1 is} hydrogen or chlorine.

The compounds according to the invention differ structurally from the compounds described in US Pat. No. 4,096,273 and have a significantly higher insecticidal activity compared to these.

The compounds of the formula I can be prepared by a process with the following stages:

(A) Reaction of an alkanearboxylic acid derivative with a benzylhydrazine derivative according to:

YC-CO-Y ¹ + NH ₂ - NH - CH

R ₁

YC-CO-NH-NH-CH- ^ i j) + Y ¹ H

R ₂

(III),

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where mean:
R ₁ , Ro, Rt, R ^ and η the same as in formula I.

Y and Y ¹ simultaneously or independently Cl

or OH, where Y 'is not Cl when Y is OH;

(B) Cyclization of the compound III obtained by reaction with phosgene according to:

R ₁ NN -CH-

COCl ₂ > YCI! I ^^ '^ MRjJn + 2 HCl

² (IV)

with R ^ J, Rp, Rz, R ^ and η as in formula I and Y as above;

(C) Reaction of the compound IV obtained with a derivative of 2-phenyl-3-methyl-butteric acid of the formula

CH (CH ₅ ) ₂

- CH CO-Z (V),

IT

in which:
X is a halogen atom,
Y same as above
and

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2935726

Z different from Y OH or Cl

after:

CH (CH ₃ ) ₂

CH CO - Z + Y

R ₁ NN -

ι ³

CH

R,) n

CH (CH ₃
CH

CO-O-C - "

N -CH-

+ HCl

in the presence of a base such as triethylamine, N, N-dimethylaniline or pyridine as the HCl acceptor.

According to a preferred embodiment of the above according to the invention Process is an α-chloroalkanecarboxylic acid or as the starting material in the first process stage a corresponding acid chloride of the formula VI

Cl - C - CO - Y ¹

(VI)

with R ₁ and R ₂ as in formula I and Y '= OH or Cl

used.

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293S726

According to this preferred embodiment, the process step (A) in an inert organic solvent medium such as an aromatic or aliphatic hydrocarbon is carried out at a temperature between about 10 and 50 ⁰ C.

When the compound VI is an acid, the water formed in step (A) is separated off by azeotropic distillation .

If an acid chloride is used as compound VI, the reaction is preferably carried out in the presence of an aryl or alkyl sulfonic acid such as methanesulfonic acid carried out.

The cyclization of the compound thus obtained in stage (B) takes place in an inert organic solvent medium, for example in an aromatic hydrocarbon, at a temperature between 20 and 110 ^° C.

In process stage (C), the 2-chloroalkyl-4-benzyl-1.3.4-oxadiazolin-5-one resulting from stage (B) is used with an acid of the formula VII

CH (CH ₃ ) ₂
- CH COOH (VII)

with X as in formula I.

in an inert organic solvent medium such as an aromatic or aliphatic hydrocarbon at a temperature between about 10 and 140 ⁰ C.

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2536726

implemented.

According to another way of carrying out the process explained above, the starting substance for step (A) is a iX-Hydroxyalkanecarboxylic acid of the formula VIII

?
HO-C- COOH (VIII)

with It] and Rp as in formula I.

used, the reaction in this stage (A) being carried out in an organic solvent medium at a temperature between about 80 and 150 ^° C. and the water formed being separated off by azeotropic distillation.

The cyclization of the compound thus obtained in process step (B) takes place in an aqueous medium at a temperature between 10 and 50 ^° C.

Process stage (C) is the result of stage (B) 2-Hydroxyalkyl-4-benzyl-1.3.4-oxadiazolin-5-one with an acid chloride of the formula IX

CH (CH ₃ ) ₂
- CH CO - Cl (IX)

with X as in formula I.
in an inert organic solvent medium,

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ORIGINAL INSPECTED

for example in acetone, methylene chloride or aromatic hydrocarbons, at a temperature between about 10 and 50 ⁰ C implemented.

The acid of the formula VII is used according to that described in Beilstein 9 I, p. 216, for the preparation of 2-phenyl-3-methyl-butyric acid procedure described. 2.4-chlorophenyl-3-methyl-butyric acid is a compound known per se, which is described in Chem. Abstr. 59 »1016e.

The acid chloride of the formula IX is by a process known per se by reacting thionyl chloride with accessible to the acid of formula VII.

According to another embodiment of the process explained above, the compounds of the formula I, in which R, represents a hydrogen atom, also according to the invention be produced by a process with the following stages:

(D) Conversion of the hydrazide of a QL-hydroxyalkanecarboxylic acid with a benzaldehyde derivative to the corresponding hydrazone according to:

HO - C - CO - NH - NH ₂ + (f j \ - CHO>

² (HJn

»HO - C - CO - NH - N = CH -

² (HJn

0S0012 / 0917

293 ^ 726

with R ^, Ro, R ^ and η as in formula I,

the reaction being carried out in an aqueous-alcoholic medium (for example using water and ethanol) in the presence of acetic acid at a temperature between about 20 and 40 ^° C .;

(E) Reduction of the hydrazone obtained from the previous stage with hydrogen according to:

^H 2 HO - C - CO - NH - N = CH --Γ

^ KlUn

HO - C - CO - NH - NH -

in the presence of palladium-carbon at a temperature between about 20 and 60 ⁰ C;

(F) Cyclization of the compound obtained from (E) by reaction with phosgene to give a compound of the formula

HO-C

-'I

R ₂

according to the same reaction scheme and using the same reaction conditions as in step (B) of the

030012/0917 ORIGINAL INSPECTED

2 η ■ ">' π ο;" * ΰ ο ■ :: · / ... ο

procedure explained above
and

(G) Reaction of the compound obtained in step (P) with a derivative of 2-phenyl-3-methyl-butyric acid of formula

CH (CH ₃ ) ₂
- CH CO - Cl

with X as in formula I.

This reaction takes place according to the same reaction scheme and using the same reaction conditions as in step (C) of the procedure outlined above.

The compounds of general formula I according to the invention have remarkable insecticidal properties and are particularly effective as contact and food poisons. Particularly interesting results can be obtained with the inventive Achieve connections in Diptera, Coleoptera and Lepidoptera.

The invention is explained in more detail below with reference to exemplary embodiments, which are not restrictive.

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ORIGINAL INSPECTED

9 3

Example 1

Preparation of 2- (4-chlorophenyl) -3-methylbutyric acid (4-benzyl-1.3 «4-oxadiazolin-5-on-2-yl) methyl ester (Connection 1)

To a solution of 8.2 g of 2-hydroxymethyl-4-benzyl-1.5.4-oxadiazolin-5-one and 4.04 g of triethylamine in 100 ml of acetone a solution of 9.2 g of 2- (4- chlorophenyl) -3-methylbutyric acid chloride in 100 ml of acetone is added dropwise in 10 min added, whereupon the mixture is stirred at room temperature for 2 h. The precipitate formed is then filtered with a glass frit filtered off and the organic solution is evaporated under reduced pressure. The residue is in 250 ml of isopropyl ether reabsorbed; the solution obtained is successively with 200 ml of water, 100 ml of an aqueous, 3.6% (w / v) hydrochloric acid solution, 100 ml of one aqueous, 4% (w / v) NaOH solution and with 100 ml of water washed.

After drying and evaporation under reduced pressure, the residue obtained is purified by chromatography on a silica column, after which 12 g of 2- (4-chlorophenyl) -3-methylbutyric acid- (4-benzyl-1,3.4-oxadiazolin-5-one-2 -yl) methyl esters are obtained; F. 70 ⁰ C.

Elemental analysis * % H % O % N % Cl % C. 5, 28 15th , 97 6, 99 8th , 84 ber .: 62, 92 5, 29 15th , 78 7, 03 9 , 0 found: 62, 76

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ORIGINAL INSPECTED

233Ü7 / 6

The acid chloride of 2- (4-chlorophenyl) -; 5-methylbutyric acid is obtained by reacting thionyl chloride with 2- (4-chlorophenyl) -3-methyl butyric acid (m.p. 85 ⁰ G) I, p. 216, the method described is accessible by reacting isopropyl bromide with phenylacetonitrile-Na and hydrolysis of the product obtained with sulfuric acid.

The 2- hydroxymethyl-4-benzyl-1.?.'i-oxadiazolin-5-one is by reacting 61 g of benzyl hydrazine with 53 g of glycolic acid in solution in 200 ml of toluene at / reflux temperature manufactured.

After the water formed has been separated off by azeotropic distillation, the reaction medium is taken up in 500 ml of water. The aqueous phase is decanted, washed twice with 250 ml of methylene chloride, then placed in a flask and saturated at 20 ⁰ G with phosgene. The reaction mixture is taken up in 500 ml of methylene chloride, whereupon the organic phase is decanted and washed successively with 500 ml of a potassium hydrogen carbonate solution (100 g / l) and with 500 ml of distilled water. After drying over sodium sulfate and evaporation under reduced pressure, 35 g of 2-hydroxymethyl-4-benzyl-1,3.4-oxadiazolin-5-one are obtained; F. 54 ⁰ C.

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ORIGINAL INSPECTED

Example 2

Preparation of 2- (4-chlorophenyl) -3-methylbutyric acid-1- (4-benzyl-1.3 · ^ - oxadiazolin - ^ - on - ^ - yl) -ethyl ester (in the form of two diastereomeric compounds)

To a solution of 11 g of 2- (1-hydroxyethyl) -4-benzyl-1.3.4-oxadiazolin-5-one (L-isomer) in 50 ml of methylene chloride quickly becomes a solution of 11.6 g of 2- (4-chlorophenyl) -3-methylbutyric acid chloride added in 100 ml of methylene chloride, whereupon 4 g of pyridine are added dropwise over 10 minutes. Then 2 h at room temperature touched.

The reaction mixture is then taken up in 300 ml of an aqueous, 3.5% strength (GA) hydrochloric acid solution. The organic layer is decanted off, one after the other with 300 ml of an aqueous, 10% strength (GA) potassium hydrogen carbonate solution and washed with 300 ml of water and then dried.

After filtration and evaporation under reduced pressure, the residue obtained in an amount of 22 g is obtained purified by column chromatography on silica. Do 1? g of an oil from which, after rubbing with Petroleum ether the following compounds can be obtained:

7 g of 2- (4-chlorophenyl) -3-methylbutyric acid 1- (4-benzyl-1.3.4-oxadiazolin-5-on-2-yl) ethyl ester (stereoisomer A) (compound 2), m.p. 102 ⁰ C, Μψ = -39.6 ° (c = 10, acetone)

OS0012 / 091?

9 g of 2- (4-chlorophenyl) -3-methylbutyric acid 1- (4-benzyl-1,3.4-oxadiazolin-5-on-2-yl) ethyl ester (stereoisomer B) (compound 3) in the form of a pasty solid ; F. 40 to 4-5 ⁰ C, TolJ ^ ⁰ = 21.3 ° (c = 10, acetone).

Elemental analysis:

% C% H % 0% N% C1

calc .: 63.69 5.59 15.4-2 6.75 8.55

found (Compound 2): 63.69 5.71 15.60 7.01 8.4-5

found (Compound 3): 63.26 5.94-14, 91 6.17 8.85

The L-isomer of 2- (1-hydroxyethyl) -4-benzyl-1.3.4-oxadiazolin-5-one is prepared according to the method described in Example 1 by reacting 33 g of L-lactic acid with 25 g of benzylhydrazine in toluene at reflux temperature and subsequent cyclization of the compound obtained with phosgene in an aqueous medium. In this way, 18 g of L-2- (1-hydroxyethyl) -4-benzyl-1.3.4-oxadiazolin-5-one are obtained; M.p. 70 ⁰ C, foLJ ^ ⁰ = -19 ° (c = 10, acetone).

Example 3

The procedure is as in Example 2 using the same amounts of ßeaktanten, starting with 2- (1-hydroxyethyl) -4-benzyl-1.3.4-oxadiazolin-5-one (D isomer) (prepared from D- Lactic acid), ^{m.p. 70 0} C, ^ ⁰ + 19.7 ° (c = 10, acetone).

It will be received

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7 g of stereoisomer C (compound 4); F. 104 ⁰ C, ToLJp ⁰ = +42 ⁰ Cc = 10, acetone)

and

9 g of stereoisomer D (compound 5) in the form of an oil; ° ^{= +22} ° ^{(c = 10} »

Elemental analysis:

% C% E% O% N% Cl

calc .: 63.69 5.59 15.42 6.75 8.55

found (Compound 4): 63.89 5.68 15.26 6.93 8.44

found (Compound 5): 63.90 6.0 15.40 6.16 9.31

Example 4

Production of 2- (4-chlorophenyl) -3-methylbutyric acid- / 4-

(2-methylbenzyl) -1.3.4-oxadiazolin-5-on-2-yl} methyl ester (Compound 6)

To a heated at 110 ⁰ C solution of 19 g of 2- (4-chlorophenyl) -3-niethy butyric acid and 11.7 ml of triethylamine in 175 ml of xylene is within 20 min a solution of 13.3 g of 2-chloromethyl-4! - (2-methylbenzyl) -1.3.4-oxadiazolin-5-one in 35 ml of xylene was added, whereupon the mixture was refluxed for 4 h.

After cooling, the reaction mixture is successively with 100 ml of water, 100 ml of an aqueous 3.5 # strength Hydrochloric acid solution, 100 ml of an aqueous, 4% NaOH

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ORIGINAL INSPECTED

Solution and 100 ml of water. After drying, Decolorization with activated charcoal and evaporation under reduced pressure, the residue obtained is by column chromatography Purified on silica, whereupon 11.2 g of 2- (4- chlorophenyl) -3-methyl-butyric acid- [4- (2-methylbenzy 1) 1.3.4-oxadiazolin-5-on-2-yl] methyl ester occur in the form of an oil.

Elemental analysis:

% C % H % 0% N% Cl

calc .: 63.69 5.59 15.42 6.75 8.55

found: 63.55 5.78 15.44 6.88 9.12

2-chloromethyl-4- (2-methylbenzyl) -1.3.4-oxadiazolin-5-one is made as follows:

56.7 ml of chloroacetyl chloride (f = 1.42 g / ml, corresponding to 80.5 g) are reacted with 100 g of 2-methylbenzhydrazine in solution in toluene (1000 ml) in the presence of methanesulfonic acid (46.2 ml) at room temperature, whereupon at a temperature zi
is directed.

Temperature between 25 and 112 ⁰ C phosgene (200 g)

After evaporation, 13.3 g of 2-chloromethyl-4- (2-methylbenzyl) -1.3.4-oxadiazolin-5-one are obtained obtained in the form of an oil.

0300 1 2/09

Example 5

Preparation of 2- (4-chlorophenyl) -3-methylbutyric acid- (4- (2-chlorobenzyl) -1.3 «4-- oxadiszolin-5-on-2-yl) methyl ester (Compound 7)

The procedure is as in Example 1, except that a solution of 16 g of 2-hydroxymethyl-4- (2-chlorobenzyl) -1.3 «4-oxadiazolin-5-one in 100 ml of acetone and a solution of 17.8 g of 2- (4-chlorophenyl) -3-methylbutyric acid in 50 ml Acetone is assumed; 26 g of 2- (4-chlorophenyl) -3-methylbutyric acid (4- (2-chlorobenzyl) -1.3 · 4-oxadiazolin-5-on-2-yl) methyl ester are obtained obtained in the form of an oil.

Elemental analysis:

% C% H % 0% N% C1

calc .: 57.94 4.63 14.70 6.44 16.29

found: 58.61 4.68 13.94-6.15 16.31

The 2-hydroxymethyl-4- (2-chlorobenzyl) -1.3 «4-oxadiazolin-5-one is obtained by reacting phosgene with a solution of 1- (2-chlorobenzyl) -2-glycolylhydrazine (38 g) in 600 ml of water accessible at 20 to 30 ^{° C.}

In this way, after recrystallization from isopropyl ether, 16 g of 2-hydroxymethyl-4- (2-chlorobenzyl) -1.3.4-oxadiazolin-5-one are obtained; M.p. 67 ^° C., yield 42 %.

The 1- (2-chlorobenzyl) -2-glycolylhydrazine is produced by means of induction of the glycolylhydrazone of 2-chlorobenzaldehyde (41.5 g)

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with hydrogen in solution in 415 ml of dioxane and in the presence of palladium-carbon in an autoclave at a hydrogen pressure of 15 kg / cm and 20 to 60 ^° C. After filtration and concentration, 38 g of 2-hydroxymethyl-4- (2-chlorobenzyl) -1.3.4-oxadiazolin-5-one are obtained.

The 2-chlorobenzaldehyde glycolylhydrazone (4-1> 5 g) (ϊ ¹ · 166 ⁰ G) used for this purpose is in turn obtained by reacting glycolylhydrazine (18 g) with 2-chlorobenzaldehyde (30.9 g) in solution in a mixture of Water (20 ml), acetic acid (10 ml) and ethanol (60 ml) at 20 to 40 ⁰ C produced.

After precipitation and cooling, it is filtered, washed with water and alcohol and dried. Be that way 41.5 g of 2- (4-chlorophenyl) -3-methylbutyric acid 4- (2-chlorobenzyl) -1.3 «4-oxadiazolin-5-one-2-y]} methyl ester obtain.

Example 6

Following the procedure of Example 4, using the following compounds are synthesized according to suitable starting materials:

0012/0917

egg -

- CH

COO

-ϊ \

Ver
bia-
manure
No. R ₁ R ₂ Ό TR) n F.
( ⁰ C) r \
\ j
H Elemental analysis , 94
, 63 found 8th H H ) -Cl oil 0 calculated , 70 58.54
4.85 Cl 57
4th , 29 14.80 N 14th , 44 15.80 r \
\ J 16 , 41 6.29 9 CH ₃ CH ₃ 85 H 6th , 87 63.86 f 0 64 92 5.87 Cl 5, 27 14.91 N 14, 53 8.98 8th, 32 6.04 10 H H oil H 6, 38 62.90 } 0 61, 57 5.65 OCH ₃ Cl 5, 23 18.17 N 18 50 7.70 8th, 5.90 6,

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Elemental analysis calculated

C G 3.69 H 5.99 O 15.42 Cl 8.55 N 6.75

found (%)

63.22

9.25 7.18

C 63.69 H 5.59 O 15.42 Cl 8.55 N 6.75

62.50

5.40

15.02

10.02

7.70

C 61.32 H 5.38 0 18.57 Cl 8.23 N 6.50

61.76 5.37

18.0 6.50 6.0

Cl

C 57.94 H 4.63 0 14.70 Cl 16.29 N 6.44

58.20 4.64

14.12

16.70

6.28

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- do -

Example 7

Insecticidal contact effect (fly, tribolium)

1 ml of a solution or suspension of the to be examined Compound in acetone at a given concentration is placed in each case in a 120 ml glass vessel; in this way four vessels are prepared for each concentration of the compound to be tested. After evaporation of the solvent 5 flies (Musca domestica) or 10 tribolia (Tribolium confusum) are used.

For each concentration of the product to be examined, two vessels are used per insect species. The vessels are covered with a metal mesh, whereupon the number of dead insects is determined after 24 h in the case of the flies or after 3 days in the case of the tribolia. In this way the concentration is determined which leads to death in 90% of the insects »this concentration is referred to below as CL _Q q.

The results obtained are shown in the table below, in which the CLq ₀ values are given in ng / ml.

As a comparative compound, compound No. 1 was used U.S. Patent No. 4-096,273 is used.

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(Link
Ρ ^Γ · Fly
Cl ₉₀ i, ug / ml) Tribolium
CL ₉₀ (yug / rnl) 1 10 100 3 30th 300 5 100 - 6th 100 - 11 200 - 12th 100 - 13th 1000 - Comparative
link 30th 1000

Example 8

Insecticidal effectiveness as a contact and hot poison

The studies were carried out using soaking treated leaves on larvae of Plutella maculipennis and made by Pieris brassicae.

Procedure:

It becomes an emulsifiable solution with the following composition manufactured:

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Active ingredient to be investigated 250 g

Emulsifier (mixture of calcium phenyl sulfonate and ethoxylated Nonylphenol) 90 g

surface-active agent (ethoxylated Sorbitan monolaurate) 20 g

Solvent (mixture of 2 parts by volume of acetophenoa and 3 parts by volume Toluene) to 1000 ml

The solution thus obtained is then treated with distilled water containing 0.02% of the same surfactant Diluted by means in such a way that several solutions of a certain concentration are obtained.

Young leaves of broccoli (Brassica oleracea) in the four-leaf stage are 10 s in the to be examined Solutions immersed. After allowing to dry, the leaves are spread on cylindrical plastic trays. In 10 larvae (3rd stage) of Plutella maculipennis or Fieris brassicae are given to each dish. For every type of larva two dishes are used per concentration of the active ingredient.

After 3 days, the number of surviving and dead larvae is determined for each active ingredient concentration, and from this the concentration which leads to 50% mortality of the larvae is determined (CL ₅₀ ).

The results obtained are shown in the table below, in which the CL ^ Q values are given in ng / ml are:

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link
No. Plutella maculipennis
CL ₅₀ (^ ig / ml) Pieris brassicae
CL ₅₀ (yug / ml) 1
2
3
5
8th
10
11
12th
15th 20th
1000
100
1000
1000
2000
2000
1000
500 100
1000
500
2000
2000
1000 Comparison
link 500 ' 500

The compounds of the present invention are seldom used alone for practical use. They are mostly in Compositions before which in general, in addition to the active ingredient according to the invention, a carrier and / or a surface-active Funds included. The active ingredient content in these compositions can be between 0.05 and 95% by weight.

According to the invention, a carrier is an organic or inorganic, natural or synthetic substance understood to which the active ingredient to facilitate its application to plants, seeds or soil as well as for the better Transport or tied for easier handling.

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The carrier can be solid (clays, natural or synthetic Silicates, calcined magnesium oxide, kieselguhr, tricalcium phosphate, cork flour, activated carbon, resins, Waxes, solid fertilizers etc.) or be liquid (water, alcohols, ketones, petroleum fractions, chlorinated hydrocarbons, Liquefied gases and the like).

The surfactant can be an emulsifier, a dispersant or be a wetting agent and possess ionic or nonionic properties. These include, for example Salts of polyacrylic acids, lignin sulfonic acids, SuIforieinöleates, quaternary ammonium salts, condensation products of ethylene oxide with fatty alcohols, fatty acids or fatty amines and especially products on the Basis of condensation products of ethylene oxide such as condensation products of ethylene oxide with octylphenol or Fatty acid esters of anhydrosorbites produced by etherification the free hydroxyl groups have been made soluble by condensation with ethylene oxide. The use of non-ionic Surfactants are preferred according to the invention because they are not sensitive to electrolytes.

The compositions according to the invention can be in the form of wettable powders or wettable powders, powders for dusting, Granules, solutions, emulsifiable concentrates, emulsions, concentrates in suspension and in the form of Aerosols are produced.

The wettable powders of the invention can be prepared to contain 20 to 95% by weight of active ingredient and usually 3 to 10% by weight of a dispersant and, if necessary, 0 to 10% by weight of one or more

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ORIGINAL INSPECTED

Stabilizers and / or other additives such as penetrants, Contains adhesives or anti-clumping agents, colorants and the like.

A powder that can be wetted according to the invention has, for example the following composition:

Active ingredient (compound 6) 50 g

Deflocculant (calcium lignosulphate) 5% by weight

Wetting agent (isopropyl naphthalene sulfonate) 1% by weight

Anti-clumping agent (silica) 5% by weight

Filler (kaolin) 39% by weight

The powders for dusting are usually in the form of a dust concentrate with a similar composition to that of wettable powder, but produced without a dispersant; they can be used at the application site with a corresponding Amount of liquid carrier can be diluted so as to obtain a composition which is convenient to coat of the seeds to be treated and usually contains 0.5 to 10% by weight of active ingredient.

Such a powder according to the invention for dusting has the following composition, for example:

Active ingredient (compound 6) 50% by weight

anionic wetting agent 1 "

Anti-clumping agent (silica) 6 "

Filler (kaolin) 43

Granules intended for soil treatment are usually

030012/0917

INSPECTED

wisely made so that their grain size is between 0.1 and 2 mm; they can be produced by agglomeration or impregnation. Such granules generally contain 0.5 to 25% active ingredient and 2 to 20 % (GA) suitable additives such as stabilizers, modifiers to achieve a slow release of the active ingredient, binders, solvents and the like.

Emulsifiable concentrates which can be used for spraying usually contain, in addition to the solvent and, if necessary, a cosolvent, 10 to 50 % (GA), 2 to 20 % (GA) suitable additives such as stabilizers, penetrants, corrosion inhibitors and the like, as well as colorants and adhesives.

Has an emulsifiable concentrate according to the invention for example the following composition:

Active ingredient (compound 6) dodecylbenzenesulfonate

Nonylphenol ethoxylated with 10 molecules of ethylene oxide

Cyclohexanone

aromatic solvent ad

Aqueous dispersions and emulsions, for example compositions by diluting a wettable powder or emulsifiable concentrate according to the invention with Water are accessible are also encompassed by the invention. The emulsions of the invention can from Water-in-oil or oil-in-water type and one thick consistency like mayonnaise.

400 g / l 24 g / i 16 g / l 200 g / l 1 1

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ORIGINAL INSPECTED

For use in very small volumes for atomization in very fine droplets, solutions are prepared in organic solvents that contain 70 to 99% active ingredient.

The compositions according to the invention can also contain other constituents, for example protective colloids, adhesives or thickeners and others known active ingredients with pesticidal properties, in particular insecticides or fungicides.

030012/0917

Claims (10)

Expectations a halogen atom, and Ε-, simultaneously or independently, hydrogen or C ₁ - to C, -alkyl, Halogen, C ₁ -C 4 -alkyl or C ₁ -C 4 -alkoxy and 0ίηί4 (integer), where the substituents R ^, can be the same or different when η is 2, 3 or 4-. 503.1- (PH 1578 ETR) -SP / Nu 030012/0917 293S726 2. Derivatives of 1,3.4-oxadiazolin-5-one according to Claim 1 with X = p-Cl. 3. Derivatives of 1.3. 4-Oxadiazolin-5-ones according to Claim 1 or 2 with R ₃ = H. ^L v. Process for the preparation of the compounds according to any one of claims 1 to, marked by (A) Reaction of an alkanearboxylic acid derivative of the formula γ _ C - CO - Y ¹ _t
R ₂ in which] L · and R _{2 have} the meaning of claim 1 and Y and Y ^{1 are} identical or different and are Cl or OH,
where Y ^{1 is} not Cl, when Y is OH, with a benzylhydrazine derivative of the formula 30012 / Π91t
ORIGINAL INSPECTED NH ₂ - NH - CH - with R ^, Ry ₊ and η as in claim to a compound of the formula Y_C_CO-NH-NH-CH -f \ H, Y ^ (R;,) n; (B) Cyclization of the compound from (A) with phosgene to give a compound of the formula with R ^ j, Rp »R ^, R ^ and η as in claim 1 and Y as above in (A) and (C) Reaction of the compound from (B) with a derivative of 2-phenyl-3-methyl-butyric acid formula CH (CH ₅ ) _? -CH-CO-Z with X as in claim 1, Y as above and 030012/081 * ORIGINAL INSPECTED 2935726 Z is OH or Cl, where Z is different from Y, in the presence of a base. 5. The method according to claim 4, characterized in that as base in stage (C) triethylamine, Ν, Ν-dimethylaniline or fyridine is used. 6. A method for the preparation of the compounds according to any one of claims 1 to 3 » marked by (A ¹ ) Conversion of the hydrazide of an Oc-hydroxyalkanecarboxylic acid of the formula fl HO - C - CO - NH - NH ₀ I <- R ₂ with R ^ and R ₂ as in claim 1 with a benzaldehyde derivative of the formula - CHO with R ^ and η as in claim 1 to a compound of the formula 030012/0017 ORIGINAL INSPECTED 2933726 HO - C - CO - NH - N - CH - R ^ ( ^ßl ) Reduction of the compound from (A ¹ ) with hydrogen to a compound of the formula R ₁
HO - C - CO - NH - NH - CH ₉ - R ₂ (V with R ₁ , R ₂ , R ^ and η as in (D); ( ^c ') Cyclization of the compound from (B ¹ ) by reaction with phosgene to give a compound of the formula R ₁ NN-CH ₀ ho - c- Il I with R ^, R ₂ , R ^ and η as in claim 1 and Reaction of the compound from (C ¹ ) with a derivative of 2-phenyl-3-methyl-butyric acid of the formula -ch- coci 030012/0917 ORIGINAL INSPECTED 2933726 with X as in claim 7. Compounds of the formula Y-C-CO-NH-NH-CH with R ^, Ro, Rz »R ^. and η as in claim 4- and Y is Cl or OH as intermediate products of the process according to any one of claims 4 to 6. 8. Compounds of the formula R "N N -CH γ - έ -J _n ι L • o ^{/ x} o ^ R ₂ with R ^, R ₂ , R ^ _1, R ^, η and Y as in claim as intermediate products of the process according to one of claims 4 to 6. 9. Insecticidal compositions, characterized by at least one compound according to any one of claims to 3 as an active ingredient together with a carrier and / or surface-active agent which is suitable for use in agriculture and is compatible with the active ingredient. 030012/0917 ORIGINAL INSPECTED 10. Composition according to claim 9, characterized with an active ingredient content of 0.05 to 95% by weight. 030012/0917 ORIGINAL INSPECTED