DE2450815A1 - NEW THIADIAZOL DERIVATIVES, METHODS FOR THEIR PRODUCTION AND PESTICIDE COMPOSITIONS - Google Patents

Description

Pr, F. Zumstein sen. * Pr, fc £, Pr, R, Koenjgs |? Erger ■ * Plpl.-Phys. R. Hptebeiyi ^ r - Pr. Jr. £ flip Jun.

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KTQ.-NO. 397997, §LZ 70,030600

1618 D.

, Paris, France

New ThiadiazQl * -] perivate, process for their preparation un4 pesticide compositions

The invention relates to new thiadiozole derivatives of the formula X.

OR

where R. is A, 1-ethyl radical with 1 to 3 carbon atoms, "f represents an oxygen or sulfur atom, X an oxygen or sulfur atom or a nitrogen atom, a hydrogen atom or an alkyl radical with 1 to 3 carbon atoms carries, represents, η represents an integer from 1 to, R ^{1 is} a hydrogen atom, a cyano group, an alkoxycarbonyl group, an alkoxy radical having 1 to 3 carbon atoms, an alkenyl radical having 2 to 4 carbon atoms or a

Phenyl radical, which is optionally replaced by a halogen atom, a Monosubstituted alkyl or alkoxy radical with 1 to 3 carbon atoms or can be disubstituted by halogen atoms or alkyl or alkoxy radicals having 1 to 3 carbon atoms.

If R represents an alkyl radical, this can be a propyl, isopropyl or, preferably, be an ethyl or methyl radical.

When X represents a nitrogen atom, the latter R can be a hydrogen atom, carry a propyl, isopropyl, ethyl or preferably methyl radical.

If R ^{1 represents} an alkoxycarbonyl radical, the alkoxy radical can be a propyloxy, isopropyloxy, methoxy or, preferably, ethoxy radical.

If R ^{1 represents} an alkoxy radical, this can be a propyloxy, isopropyloxy, methoxy, or preferably ethoxy radical.

If R ^{1 represents} an alkenyl radical, this can be 2-methyl-1-propenylr »1-methyl-1-propenyl, 2-methyl-2-propenyl7,1-methyl-2-propenylr _f 1-butenyl?, 2-butenylr> 3-butenylr »allyl · = -, isopropenyl, 2-methylvinyl or, preferably, vinyl radical.

When R 'represents a monosubstituted phenyl radical, can the substituent may be in the o-, m- or, preferably, p-position and an isopropyloxy, propyloxy, ethoxy, methoxy, isopropyl, propyl, ethyl, methyl radical or an iodine, bromine, fluorine or preferably be chlorine atom.

If the radical R 'is a disubstituted phenyl radical, can the substituents independently of one another isopropyloxy, propyloxy, Ethoxy, methoxy, isopropyl, propyl, ethyl, methyl radicals or iodine, bromine or fluorine or preferably chlorine atoms

SÖS818 / 1229

be.:

The invention relates in particular to compounds of the above formula I, in which R represents an ethyl or methyl radical, X represents an oxygen or sulfur atom or a nitrogen atom substituted by a methyl radical, η represents the number ^1, 2 or 4 and R 1 represents a hydrogen atom, a p-chlorophenyl, phenyl, vinyl, p-tolyl or ο, ρ-dichlorophenyl group.

The compounds according to the invention possess insecticides and nematocidal properties which make them suitable for use in controlling insects and nematodes.

The insecticidal properties of these compounds can in particular by tests on Prodenia litura, Drosophila melanogaster, Blatella germanica, Sitophilus granarius> and Tribolium confusum be detected.

The nematocidal properties can be determined by testing on Panagrellus Silusiae and Ditylenchus miceliophagus can be detected. These Tests are described below in the experimental section.

The invention also relates to a method of manufacture of the compounds of the formula I, which is characterized in that a compound of the formula IV :.

N-

wherein R ¹ , X and η have the above meanings and A represents a cyano or alkoxycarbony1 group and M represents a hydrogen atom or an alkali metal, a cyclization in

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Presence of an oxidizing agent, if A represents a cyano group, or in the presence of ammonia and an alkali hypohalite, when A represents an alkoxycarbonyl group, subjects and then the compound of formula II

(H) j

thus obtained with a compound of formula III

OR

γ-ρζ - (in)

condensed, in which formulas, R, R ', X, ¥ and η the above have given meanings and Y stands for a halogen atom.

The oxidizing agent used is preferably hydrogen peroxide, however, bromine in the aqueous medium or an organic peracid such as peracetic acid, monoperphthalic acid can also be used or use perbenzoic acid.

The alkali hypohalite used is preferably sodium hypochlorite '·, however, one can also use potassium hypochlorite and Use sodium or potassium hypobromite.

The condensation of the compound of formula II with the compound of formula III can be carried out in a solvent such as e.g. Acetone or acetonitrile, in the presence of a base such as triethylamine or an alkali metal carbonate.

The starting compounds of the process according to the invention If they are not known, the compounds of the formula IV used can be prepared by one of the following processes which are determined by examples in the experimental part

5038 18/1 229

to be purified:

a) when X represents a sulfur atom, by reaction of a compound of the formula

wherein M and A are as defined above, with a compound of the formula

R '- (CH ₂ ) _n -Z

wherein R ¹ and η have the above meaning and Z represents an electronegative group such as a halogen atom or a radical of the formula R ^l - (CH _{2) n} -S0 _Zt;

b) when X represents an oxygen atom, by reaction of a compound of the general formula A-NH ₂ , in which A has the above meaning, with a xanthogen ester of the formula R '- (CH _O ) -OCS-alc, in which R ¹ and η are the above meaning

d. JX "

have ο and alc an alkyl radical with 1 to 3 carbon atoms represents, followed by the action of an alkali alcoholate to obtain the compound of formula IV ^ ';

c) when X represents a nitrogen atom, by reaction of a compound of the formula S = C = N = A, in which A represents an alkoxycarbonyl radical, with an amine of the formula R ¹ - (CH ₂ ) -NH-ale ^, in which R ^! and η are as defined above, and alc ,, represents an alkyl radical having 1 to 3 carbon atoms.

The invention also relates to insecticidal or nematocidal compositions or preparations which contain at least one compound of the formula I as “active ingredient”

These compositions can be in the form of powders, granules,

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Suspensions, emulsions, solutions containing the active substance, e.g. in admixture with a vehicle and / or an anionic, cationic or non-ionic surface-active Means, among other things, a "uniform dispersion of the Components of the composition ensures that they are present. The vehicle or carrier used can be a liquid such as water, alcohol, hydrocarbons or other organic solvents, an animal, vegetable or mineral oil or a powder such as talc, clays, silicates and diatomaceous earth *

The insecticidal liquids or powders for foliar spraying preferably contain 10 to 80% by weight of active ingredient.

An emulsifiable one, for example, is used as the insecticidal composition Concentrate containing, based on weight, 15% 3- (diethoxythiophosphoryloxy) -5- (p-chlorobenzylthio.) - i, 2,4-thiadiazole, 6.4% Atlox 4851 (combined with a sulfonate oxyethylene triglyceride, acid number: 1.5), 3.2% Atlox 4855 (oxyethylene triglyceride combined with a sulfonate, Acid number: 3) and 75.4% xylene.

The following examples illustrate the invention without restricting it.

Example 1 : 3- (Diethoxvthiophosphorvloxy) -5-methethio-1,2.4-

thiadiazole
a) 3-Hydroxy-5-iae.thylthio-1,2,4-thadiazole

80 g of dipotassium N-cyandithioimidocarbonate are dissolved in 500 cnr of water and introduced 50.4 g of dimethyl sulfate. The mixture is left to react for 2 hours at room temperature, filtered and added dropwise to Filtrate 44 cm of 30% hydrogen peroxide. You then acidify with the help of 40 cm of concentrated hydrochloric acid and cool in an ice bath. The crystals obtained in this way are filtered off, washed with water and dried so 36 g of 3 ~ hydroxy-5-methylthio-1,2,4-thiadiazole from F. =

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160 ° C. .

b) 3- (diethoxythiophosphorylox) -5-methylthio-1,2,4-thiadiazole

Man "mixed 7.6 g of the compound obtained above, 9.5 g Diäthylchlorthiophosphat and 7 g of potassium carbonate in 50 cm of acetone and stirred overnight at room temperature. The reaction mixture is filtered and the filtrate is Λμτ ^ ΛΓ evaporation concentrated under reduced pressure, and then chromatographed on a silica column using a benzene-ethyl acetate (9: 1) mixture as eluant. Rf value ~ 0.4; n _D ²⁰ = 1.5534.

Example 2: 3- (Dimethoxythiophosphorvloxy) - ^ - methylthio-1 »2,4-thiadiazole

In the same way as described above in example 1 under ^, but using dimethyl chlorothiophosphate the 3- (dimethoxythiophosphoryloxy) -5-methylthio-1,2,4-thiadiazole is obtained from the F. = 45 ° C

Example 3: 3- (Diethoxythiophoryloxy) -5-ethylthio-1,2,4-thiadiazole

In the same way as under a) of Example 1, but using diethyl sulfate and acetic acid instead of Hydrochloric acid gives 3-hydroxy-5-ethylthio-1,2,4-thiadiazole from the F. = 129 ° C

In the same way as under b) of Example 1, but using the compound obtained in the preceding paragraph, chromatography in benzene gives 3- (diethoxythiophosphoryloxy) -5-ethylthio-1,2,4-thiadiazole. Rf value = 0.35; n _D ²⁰ = 1.5325.

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Example 4; 3- (diethoxythiophosphoryloxy) -5 ~ p-chloropenzylthio ~ 1,2,4-thiadiazole

A mixture of 80 g dipotassium N-cyanodithioimidocarbonate, 64.9 g of p-chlorobenzyl chloride, 400 cm of methanol and 400 cm of water water is stirred for 5 hours. The solvents are evaporated and the residue is recrystallized from ethanol. You get so the S-p-chlorobenzyl and potassium N-cyanodithioimidocarbonate with a melting point of 250 ° C (decomp.).

k) 3-HydroxY-5-2z2i} i2E ^ ®S5llii} i2: li.2 _ii 4-thiadiazole

144 g of S-p-chlorobenzyl and potassium N-cyanodithioimidocarbonate are added to i 1 of water and 48 cm. of 30% hydrogen peroxide brought in. The mixture is heated to 65 ° C. and left Cool again to room temperature and filter the solution.

The filtrate is treated with 40 ml of concentrated hydrochloric acid acidified. The crystals obtained are filtered, washed with water and dried. This gives 90 g of 3-hydroxy-5- (p-chlorobenzylthio) -1,2,4-thiadiazole, which can be recrystallized from ethyl acetate. M.p. = 138 ° C.

thiadiazole

In the same way as under b) of Example 1, but starting from the product obtained in paragraph b) above, after chromatography with a cyclohexane-ethyl acetate mixture (9: 1) the 3- (diethoxythiophosphoryloxy) -5-p-chlorobenzylthio- 1,2,4-thiadiazole.
Rf value = 0.4; n ^ ^u = 1.590.

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Example 5 : 3- (Dimethoxythiophosphoryloxy) -5-P -chlorobenzene thio 1,2,4-thiadiazole

In the same way as under c) of Example 4, but under Use of dimethylchlorothiophosphate gives the 3- (dimethoxythiophosphoryloxy) -5-p-chlorobenzylthio-1,2,4- thiadiazole.

Rf-Fourth = 0.35? n _D ²⁰ = 1.605.

Example 6 ; 3- (Dimethoxythiophsophryloxv) -5-dimethylamino-1,2,4-thiadiazole

To a solution of 40 g of ethoxycarbonyl isothiocyanate in 200 cnr benzene is added 180 cnr ^{5 of} a 10% strength dimethylamine solution in ether. The temperature of the reaction mixture is maintained at 20-25 ° C and the excess solvent and dimethylamine are evaporated after stirring for 15 minutes. The remaining oil crystallizes. M.p. = 66 ° C; Rf value = 0.25 (silica / benzene acetate: ethyl acetate (9: 1)).

¹⁰ ) 2 :: 3 ^ν £ ϊ2ϊΥ.Ι 5-dimethylamino-1 _x 2 _Z 4-thiadiazole

In 450 cm ^ concentrated ammonia are at the same time with a temperature between 0 and 5 ° C containing a solution 43 g N, N-dimethyl-N'-ethoxycarbonylthiourea, '25 cm' Sodium hydroxide solution and 250 cnr water and a one molar sodium hypochlorite solution ■ poured.

The reaction mixture is stirred for 2 hours at 0 to 5 ° C. and then for 3 hours at room temperature and then by evaporation concentrated until mass formation. This residue is with the help of concentrated hydrochloric acid pH adjusted to 4. The solution thus obtained is extracted with chloroform, and the organic phase is dried over magnesium sulfate dried and then evaporated to dryness. the

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Crystals obtained are washed with petroleum ether (boiling point 40-75 ° C.). Are thus obtained 11 g of 3-hydroxy-5-d.imethylamino 1,2,4-thiadiazole, m.p. = 142 ⁰ C.
Rf. value (acetone: CHCl ₃ = 1: 1) = 0.2.

A mixture of 0.366 g of the compound obtained above, 0.3 cm- ⁵ dimethylchlorothiophosphate and 0.35 g of potassium carbonate in 10 cnr acetone for 16 hours. Stirred at room temperature.

The reaction mixture is then filtered and the filtrate is removed is concentrated by evaporation. It is then chromatographed on a silica column, using a Ethyl acetate / cyclohexanine mixture (6: 4) is eluted.

This gives 3- (dimethoxythiophosphoryloxy) -5-dimethylamino-1,2,4-thiadiazole.

Rf.value = 0.45.

Example 7 - 3- (Diethoxythiophosphoryloxy) -5-dimethvlamino-1,2,4-thiadiazole

In the same manner as under c of Example 6, but using diethyl chlorothiophosphate, the 3- (diethoxythiophosphoryloxy) -5-dimethylamino-1,2,4-thiadiazole is obtained after chromatography with a benzene-ethyl acetate mixture (8: 2) F. = 48 ° C.
Rf.value = 0.55.

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Example 8 : 3- (Diathoxythiophosphoryloxy) -5-ethoxy-1,2,4γ thiadiazole

200 g of 0-ethyl- and potassium-N-cyanothioimidocarbonate are added to 800 cm of water brought in.

Subsequently, 30% hydrogen peroxide is added in proportions of 10 cm. 130 cm admitted. It is brought to room temperature and then 30 g of sodium bicarbonate are added. The Solution with 500 cnr ethyl acetate and adjust the pH to 3 with the help of concentrated hydrochloric acid. One extracts with ethyl acetate and the organic phase is dried over sodium sulfate and then evaporated to dryness.

The. 85 g of the oil thus obtained are crystallized in 200 cm of ether, and the crystals are recrystallized from benzene. You get so. 28 g of 3-hydroxy-5-athoxy-1,2,4-thiadiazole vom M.p. = 98 ° C.

1 _Α 2 _Λ 4 ₌ thiadiazole

A mixture of 14.6 g of the compound obtained above, 19 g of diethyl chlorothiophosphate and 14 g of potassium carbonate in 200 cm of acetonitrile are stirred for 40 hours at room temperature.

The reaction mixture is then filtered and the filtrate is concentrated by evaporation. It is then chromatographed on a silica column, eluting with benzene (Rf.-Viert = 0.3). 19 g of 3- (diethoxythiophosphoryloxy) -5-ethoxy-1,2,4-thiadiazole are thus obtained; n _D = 1.503.

Example 9 ; 3 - (Dimethoxvphosphorvloxv) -5-Ethylthio-1,2,4-thiadiazole

In the same way as described in b) of Example 3, but using diinethylchlorothiophosphate, is obtained

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after chromatography in benzene, 3- (dimethoxythiophosphoryloxy) ~ 5-ethylthio-1,2,4-thiadiazole. Rf value = 0.5; n _D ²⁰ = 1.559. . ''

Example 10: 5- (Dimethoxvphosphorvloxv) -5-ethhvlthio-1, 2,4-thiadiazole

In the same way as described in bj of Example 3, however using Ο, Ο-dimethyl chlorophosphate one obtains the expected connection ... .Rf value = 0.2 (silicon dioxide-cyclohexane: Ethyl acetate = 4: 6).

Example 11: 3- (IUmethoxvphosphorvloxy) -5p -chlorobenzylthio-1,2,4-thiadiazole

In the same way as described in c) of Example 4, however using 0,0-dimethyl chlorophosphate one obtains the

20th

expected connection, n-p = 1.588p.

Example 12: 3- (diethoxvthiophsoporyloxy) -5-benzylthio-1,2,4-

thiadiazole Stage A: 3-Hydroxy-5-benzylthio-1,2,4-thiadiazole

A mixture of 194.4 g of dipotassium N-cyanodithioimidocarbonate, 150 cnr water, 1 liter of methanol and 126.7 g of benzyl chloride is stirred for 1 hour at room temperature. Then it is filtered, the methanol is evaporated, gives 2.5 1 water to the residue, and then slowly 110 cm ^"5 3O? Oiges hydrogen peroxide added. It is 1/2 hr. At 40 ⁰ C and then 15 hrs. At 20 ⁰ C stirred, acidified with hydrochloric acid, filtered off with suction and the precipitate recrystallized from toluene, giving 80 g of the expected product with an F ₀ = 125 ^° C.

Grade B: 3- (diethoxythiophsphoryloxy) -5-benzylo: cy-1,2,4-thiadiazole

In the same way as described in b) of Example 1, proceeding of 22.4 g of the composition obtained in the previous step

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bond and by working in acetonitrile, 10.5 g of the expected compound of F. <^ 50 ⁰ C.

Example 15: 3- (Diähtoxvthiophos-phoryloxv) - 5-allvlthio-1,2.4-

thiadiazole Level A; 3-Hydroxv> -5-allylthio-1,2,4-thiadiazole

The procedure is as described in Stage A of Example 12, starting out of 195 g of potassium N-cyanodithioimidocarbonate and 77 g Allyl chloride and by adding 30% hydrogen peroxide with 100 cm oxidized. 63 g of the expected compound with a mp = 84 ° C. are obtained.

Level B: 5- (diethoxythiophosphoryloxy) -5-allvlthio-1,2,4- • thiadiazole

Starting from 8.7 g of the compound obtained in the previous stage, the procedure described in Stage B of Example 12 is followed. 13 g of the expected compound are obtained. n _D ²⁰ = 1.5525.

Example 14: 3- (diethoxythiophosphoryloxy) -5 * ^a p-methylben2vl-

thio-1,2,4-thiadiazole Level A; 3-Hydroxy-5-p-methylbenzylthio-1,2 * 4-thiadiazole

The procedure described in 'Step A of Example 12 is repeated Procedure, starting from 58.2 g of potassium N-cyanodithioimidocarbonate and 42 g of p-methylbenzyl chloride followed by Oxidation with 35 cnr 30% hydrogen peroxide. You get 26 g of the expected compound of m.p. = 144 ° C.

Level B; 3- (Diathoxvthiophosphorvloxv) -5-P-methylbenzylthio-1,2,4-thiadiazole

The procedure described in Stage B of Example 12 is followed, starting with 23.8 g of that in the previous one Step compound obtained and using 10.1 g

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Triethylamine as base. 10.5 g of the expected compound from F. <40 ° C.

Example 15: 3- (Diethoxythiophosphorvloxy) -5-P-chlorobenzyl-

OXV-J1,2,4-thiadiazole Level A; Sodium O-p -chlorobenzyl dithiocarbonate

142 g of p-chlorobenzyl alcohol and 1200 cnr of tetrahydrofuran are mixed, 50 g of sodium hydride (50% in mineral oil) are added over the course of half an hour, the mixture is refluxed for 2 hours, filtered and 76 g of carbon disulfide are added to the filtrate. The mixture is stirred for 1/2 hour at 20 ^° C. and evaporated to dryness. The residue is taken up with ether, filtered off with suction and 205 g of the expected compound of F. = 250 ^° C. are obtained.

Stage B: methyl O-p -chlorobenzyl dithiocarbonate

A mixture of 205 g of the compound obtained in step A, 500 cm ^{3 of} benzene and 500 cm ^{3 of} methyl iodide is refluxed for 2 1/2 hours. Filter and concentrate the filtrate to dryness. 196 g of the expected compound are obtained.

Stage C; ; Potassium and Op-chlorobenzyl-N-cyanothioimido -

carbonate

60 g of potassium ethylate and 700 cm of ethanol are mixed, 34 g of cyanamide are added and, after dissolution, 200 g of the compound obtained in stage B are added. The mixture is stirred for 17 hours at 20 ^° C., the crystals obtained are filtered off with suction, washed with ether and 126 g of the expected compound with a melting point of 240 ^° C. are obtained.

Step D: 5-Hydroxy-5-P-chlorobenzyloxy-1,2,4-thiadiazole

The procedure described in stage A of Example 12 is followed using 13 g of that in the preceding one Stage obtained compound and 6 cm 3O? Oige hydrogen peroxide. After recrystallization from ethyl

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acetate. 2.4 g of the expected compound with a temperature of 170 ° C.

Level E; 3- (Dietfaoxythiophosphorvloxv) -5-P-chloroT3enz-yloxy-1,2,4-thiadiazole

The procedure is analogous to the procedure described in stage B of Example 12, starting from 2.5 g of the compound obtained in the previous stage, and 1.3 g of the expected compound is obtained. n _D ²⁰ = 1.5045.

Example 16: 3- (DiathoxvthiophsophOryloxv) -5-n-butoxy-1,2, 4-

thiadiazole Level Ai '. Potassium 0-n-butyl dithiocarbonate

280 g of potassium hydroxide biscuits and 2.5 l of butanol are mixed and 380 g of carbon disulfide ^{are then added at from 20 to 30 ° C.} It is stirred for 2 hours, suctioned off, the was washed. ' ^ Precipitation with butanol and then with ether and receives 640g of the expected compound from the F. ~ 260 ⁰ C (dec.)

Level B; Methyl-0-n-butyl dithiocarbonate

A mixture of 190 g of the compound obtained in the previous step, 1 liter of benzene and 500 cm of methyl iodide is refluxed for 10 hours, the filtrate is filtered off with suction and the filtrate is evaporated to dryness. The residue is rectified and 156 g of the expected connection of Kp _n , - = 74 ° C.

Stage C; Sodium and O-n-butyl-N-cvanothioimidocarbonate

To a solution of 55 g of sodium methylate in 36Ο cm of methanol and 36Ο cnr ethanol are added at 20 ⁰ C, 42 g of cyanamide are added and then 164 g of the compound obtained in the preceding stage and the mixture is stirred for 17 hours 'at 20 ⁰ C ₀ is evaporated off to' Dry, wash the residue with ether and obtain 120 g of the expected compound from F. = 240 ⁰ C.

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Level Df 3-Hvdroxv - ^ - n-butvloxv-1,2,4-thiadiazole

At 80 to 85 ° C 80 cnr 30% hydrogen peroxide are added a mixture of 72 g of those obtained in the previous step Compound, 200 cm of water and 500 mg of phenolphthalein added, keeps the pH value alkaline by adding caustic soda, cools and sucks off the sodium salt of the expected compound.

This salt is suspended in 100 cnr water, with hydrochloric acid-acidified, extracted with ethyl acetate to obtain 58 g of the expected compound, mp = 62 ⁰ C are obtained.

Level E; 3- (Diethoxythiophosporyloxy) -5-n-butoxy-1,2,4-thiadiazole

The procedure described in step B of Example 12 is followed, starting from 8.8 g of the compound obtained in the previous step, and 12 g of the expected compound are obtained; n ^ ⁶ = 1.4960.

Example 17: 3 ~ (Dläthoxvthi ophosphoryloxy) -5 ~ (2 4-dichloro _T, -benzylthio) -1,2,4-thiadiazol

Level A; 3-hydroxy-5- (2,4-dichlorobenzylthio) -1,2,4-thiadiazole

69.9 g of dipotassium N-cyanodithioimidocarbonate are mixed,

• 5 3

50 cm of water and 300 cm of methanol, are then at 30 ⁰ C, 72 g of 2,4-dichlorobenzyl chloride added, then stirred for 30 minutes at 30 ⁰ C, the methanol removed under reduced pressure gives 900 ecr water are added and slowly added 40 cm 30 ; Aiges hydrogen peroxide added. A basic pH value is maintained by adding potash, the mixture is stirred for 17 hours, washed with ethyl acetate, acidified by adding hydrochloric acid, the precipitate is filtered off with suction and recrystallized from toluene. 32 g of the expected compound with a melting point of 134 ° C. are obtained.

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Level Br 5- (diethoxvthf apho sphoryloxv) -5- (Z + 4-dicfhlor-

benzylthio) -1 '♦ 2,4-thi adlazol

In an analogous manner, the procedure of Step B of Example 14, starting from 29 ₁ 3 g of the compound obtained in the preceding stage, and receives 20 g of the expected compound; n-ß = T _r 5930.

Example 18 ; 3- (diethoxythiophosphoryloxy) -5-methoxy - 1 »2,4-

thiadiazole step A: 5-Hydroxv-5-inethoxv-1,2,4-thiadiaz.ol

46> 2 g of Q-methyl carbonate and potassium M-cyanothioimidocarbonate (obtained analogously to the procedure described in Example 15 in stage C, starting from dimethyl dithiocarbonate - described in BElLSTEHf - 3 _f 20S _t . 185, II 151 -) are mixed and added slowly at 70 ⁰ C 60 cm 3O5iiges ¥ asserstoffperox.yd added while the pH is maintained by addition of potassium carbonate at 8.4 to & _ti. 6 It is then washed with ether, acidified and the precipitate sucks off. -1: 8 g of the expected compound of: M. = 1.46 ° C. is obtained.

Level B: 3- (D ethoxythlophosphoryloxv) -5-methox-y - T »2,4-thiadazole

The procedure is analogous to that described in Step B of Example 1, starting from 6 _r ,, 6 g of Yerbindung obtained in the above Step A and 10 g of 0,0-DiäthylchIorthiaphosphat and obtained 4.2 g of the expected compound? ²³

Example 19: 3- (Diethoxythiopho sphoryloxy) -5-n-propvloxy-

i, 2 _T 4-thiadiazole level Ar potassium 0-n-propyldlthiocarbonate

280 g of potash are dissolved in 2 liters of propanol, ^{380 g of carbon disulfide are added at 20 °} C. and the mixture is then stirred for 2 hours.

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The precipitate formed is suctioned off and 624 g of the is obtained expected connection from F. =

Stage B: methyl ~ Q-n-propyldithio carbonate

429 g of the compound obtained in the preceding step are dissolved in 1 l of water and 369 g of dimethyl sulfate are added at a temperature below 50.degree. The mixture is stirred for 17 hours, the organic phase is decanted and 338 g of the expected

on

Connection of bp ₁ = 60 ° C; n _D = 1.5385.

Stage C; ITodium and O-n-propyl-K-cyano thioimido carbonate

51.7 g of sodium are dissolved in 2 l of propanol and 94.6 g are added Add cyanainide, then stir for 15 minutes and give 338 g the compound obtained in step B is added. It will be at 24 hours 35 ° C below one. Stirred inert gas stream. One concentrates on Dry to obtain 416 g of the expected compound.

Stage D; 3-Hydroxy-5-n-propyloxy-1 _T 2 _r 4-thiadiazole

The compound obtained in Step C is dissolved in 1 1 of water, and at 80 ⁰ C within 2 h. 450 cm ^ ⁵ 30 sodium Vfasserstoffperoxyd added while the pH is kept alkaline by adding sodium hydroxide. The mixture is stirred for a further 24 hours and then cooled. It is washed with ethyl acetate, acidified by adding hydrochloric acid and the precipitate is filtered off with suction, washed with water and dried. 200 g of the expected compound are obtained from F = 92 ° C.

Level E ; 3- (Dlethoxythlophosphoryloxy) -5-n-propvl-1 , 2,4-thiadiazole

The procedure described in Stage 3 of Example 12 is followed, starting with 24 g of that obtained in Stage D. Compound and 28.3 g of 0,0-diethylchlorothiophasphate and is obtained

26 5 17.5 g of the expected compound ; n ^ * = 1.5000.

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Investigation of the inseticidal activity of the compounds of Examples 4,9 ', 11,13 and 16

A) Test on the grain worm (Sitophilus granarius):

0.2 μΐ of the acetone solution of the compound to be tested is given on the central Taorax of an insect's eye. The concentrations of the active ingredient are 5000 and 500 ppm. 50 insects are used per concentration. The test insects are kept at 20 ⁰ C, and the evaluation is carried out for 4 h., 24 h., 48 hrs., 5 days and 6 days after treatment.

Those obtained with the compounds of Examples 9, 11, 13 and 16 experimental results and expressed as percent mortality are summarized in the table below:

percent
tuale
Morta
lity 'Vtf-ikstoff-
'kcunzentra-
clone in
rag / 1 9 5,000 100 16 I. j 500 11 13th 16 Connections ^:
d.Examples 11 100 100 1 9
\ '85 100: * no. 4 sti. - 100 100 100 i ' 85 50 100, ■ tr-2 / Γ-π 100 100 100 1 82 "48" »". 100 \ 80 ... 85 58 100 ^: ", 5 days). 100 100 i '"6".'. I ^:

B) Test on Tribolium confusum:

The test is analogous to that used for Sitophilus granarius (tropical application). The evaluation takes place 24 hours, 48 hours. and 5 days after treatment.

509 8 18/1229

The experimental results obtained with the compound of Example 9, expressed as percent mortality, are summarized in the table below:

Concentrations in
ppm. 5,000 2,500 500 Percentage of mortality
after 24 hours 92.3 58.8 8th Percentage of mortality
after 48 hours 98.1 62.7 10 Percentage of mortality
after 5 days; 96.2 60.8 8th

C) Test on Drosophila (Drosophila melanogaster):

This test measures steam activity. It consists in that the insects are placed in a Petri dish, covered over a tergal cloth with a crystallization vessel of the same diameter is connected, in which the compound to be tested is given as an acetone solution, which is prepared before the insects are introduced evaporates. There are three experiments per concentration with 25 individuals per concentration (adults not older than 48 hours). carried out. The results are expressed as percent mortality 1 hour, 2 hours, 4 hours, 6 hours and then 24 hours thereafter expressed in terms of non-treated comparison insets.

The results obtained with the compounds of Examples 9, 11, 13 and 16 are summarized in the table below.

509818/1229

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D) Test on the moth (ingestion)

Prodenia litura caterpillars are used. Round disks with a diameter of 8 mm cut from lettuce leaves are placed in closed plastic boxes. 4 μl of the acetone solution of the compound to be tested are placed on each leaf disc. 15 caterpillars are used per treatment (caterpillars averaging 10 days old). The animals are kept at 20 ⁰ C in natural light and at a relative humidity of 50 ^. The animals are fed after the treated disc has been consumed. The evaluation takes place 1 hour, 24 hours and 48 hours after the treatment.

The experimental results obtained with the compounds of Examples 4 and 16 Results, expressed as percent mortalities, are summarized in the table below:

Material concentration
tion in ppm 500 4th 0 16 0 250 4th 0 16 125 0 Connections of
Examples 80 20th 60 0 4th 0 1 H. 100 100 100 30th * 0 30th 24 hours 70 * 60 48 hours 80

* 10O ^ 'o Mortality after 4 days of contact time

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E) test on cockroach (male Blatella germanica)

This test is done through microcontact. The male Germanica cockroaches receive a microdroplet of the acetone solution between the second and third pair of legs. After treatment, the test insects in the shade at 20 ⁰ C are maintained. The assessment is made 24 hours, 48 hours and then 5 days after the treatment.

The experimental results obtained with the compounds of Examples 4, 11, 13 and 16, expressed as a percentage Mortality are summarized in the table below:

509818/1229

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P) Test on Panagrellus Silusiae

In a 10 cm ^ of the aqueous insecticidal solution to be tested containing pill board are given 0.5 cm of water with about 2000 nematodes. The mortality is determined with the magnifying glass 24 hours after the treatment and with three repetitions, each time 1 cnr solution is taken.

the soldering to be tested

The experimental results obtained with the compound of Example 4 are summarized in the table below, where the results are expressed as percent mortality:

Concentration in g / l 1 0.10 percent mortality
after 24 hours 100 100

G) Test on Ditylenchus Mvceliophagus

One works in the same way as with Panagrellus Silusiae. The experimental obtained with the compound of Example 4 Results are summarized in the table below as percent mortality:

Active ingredient concentration in p.p.m 1000 100 percentage mortality according to
24 hours 99 84

H) Test on Musca domestica:

This test is carried out under tropical application. The flies receive a drop of the acetone solution of the ' testing compound on the dorsal thorax after using

509818/122 3

Ether were put to sleep. The insects are at 20 ⁰ C and 50. % . relative humidity kept. They are fed with milk and water. The evaluation takes place 1 hour and then 24 hours after the treatment.

Those obtained with the compounds of Examples 11, 13 and 16 experimental results, expressed as percent mortality, are summarized in the table below:

percent hortality

Act .... conc. In p.p.m.

5,000

2,500

500

ICC

Verbid. Beiso '

11

16 J 11

IG

after 1 hour

100

96

62

26th

after 24 hours

100

100

100

100

100l 74

i 81

I) Test on Aphis fabae:

It becomes an experiment through contact ingestion on a bean plant (Vicia Faba). After spraying the solution of the compound to be examined, with complete wetting the plant is assured is infested with 20 wingless individuals per bean plant. The bean plants v / earth surrounded by a gauze to prevent the aphids from escaping. Take a count of the living and dead individuals depending on the time before. The results are taken into account as Abbott's percent effectiveness expressed by comparative tests.

The results obtained were as follows:

509 818/1229

percent
tuale. '■ ■
Mortali
activity Active ingredient con _T
centering
in ppm t
100 11 13th 16 I.
}. 9
10 J 1 16 • 16 0 after 2 hours links
d.Examples 0 90 27 I. 13th 0 0 after 24 hours 23 100 100 0 0 6th after 48 hours 29 100 100 | 17th 8th 18th

J) Test with Musca domestica larvae

This test is done by making contact. He "consists in that you add 2 ml of the acetone solution of the compound to be tested to 1 g of bran, which is on a watch glass that Lets the solvent evaporate and then the treated Put bran in a plastic box, add 2 ml of milk and after mixing with 20 Musca domestica larvae aged 3 to 4 days contaminated.

There are performed three trials per concentration, .the larvae are stored at relative 2O ⁰ C and 30% humidity.

The evaluation takes place 48 hours and 8 days after the treatment.

The experimental results obtained, expressed as percent mortality are summarized in the table below:

509 8 18/1229

percent
tuale
Morta- ^:
lity ■ Wirkstqf ^ conf .
centering in | 5 OOO
p «pm _ g 11 13 I 16 I.
92
i 500 11 '13 IG after
48'hour · ' Links !
d.Examples! 82 41 41 38 59 after
8 days I.
t
t
i l 90 90 I *
100 j 491 77 . 90

5098 18/12 2

Claims (1)

Claims 1.) Thiadiazole derivatives of the formula I: OR E-ZJpOR (I) where R represents an alkyl radical having 1 to 3 carbon atoms, ¥ represents an oxygen or sulfur atom, X represents an oxygen or sulfur atom or a nitrogen atom bearing a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms, η an integer of 1 to 4 and R ^{1 represents} a hydrogen atom, a cyano group, an alkoxycarbonyl group, an alkoxy radical having 1 to 3 carbon atoms, an alkenyl radical having 2 to 4 carbon atoms or one optionally monosubstituted by a halogen atom, an alkyl or alkoxy radical having 1 to 3 carbon atoms or by Represents halogen atoms or alkyl or alkoxy radicals with 1 to 3 carbon atoms disubstituted phenyl radical. 2, compounds of the formula I according to claim 1, wherein R is an ethyl or methyl radical, X is oxygen or Represents sulfur atom or a nitrogen atom substituted by a methyl radical, η denotes the number 1 or 2 and R is a hydrogen atom, a p-chlorophenyl radical, a phenyl radical, a vinyl radical, a p-tolyl radical or represents an ο, ρ-dichlorophenyl radical. 509818/1229 3. 3- (Diethoxythiophosphoryloxy) ~ 5-niethylthio-1,2,4-thiadiazole. 4. 3- (Dimethoxythiophosphoryloxy) - '5-Raethylthio-1,2,4-thiadiazole. 5. 3 ~ (diethoxythiophosphoryloxy) -5-ethylthio-1,2,4-thiadiazole. 6. 3- (Diethoxythiophosporyloxy) -5-p -chlorobenzylthio-1,2,4-thiadiazole. 7. 3- (Dimethoxythiophosphoryloxy) -5-p -chlorobenzylthio-1,2,4-thiadiazole. 8. 3- (Dimethoxythiophosphoryloxy) -5-dimethylainino-1,2,4-thiadiazole. 9. 3- (Diethoxythiophosphoryloxy) -5-dimethylamino-1,2,4-thiadiazole. 10. 3- (Diethoxythiophosphoryloxy) -5-ethoxy-1,2,4-thiadiazole. 11. 3 ~ (Dimethoxythiophosphoryloxy) -5-ethylthio-1,2,4-thiadiazole. 12. 3- (Dimethoxyphosphoryloxy) ~ 5-ethylthio-1,2,4-thiadiazole. 13. 3- (Dimethoxyphosphoryloxy) 5-p -chlorobenzylthio-1,2,4-thiadiazole. 14. 3- (Diethoxythiophosphoryloxy) -5-benzylthio-1,2,4-thiadiazole. 15. 3- (Diethoxythiophosphoryloxy) -5-allylthio-i, 2,4-thiadiazole. 16. 3- (Diethoxythiophosphoryloxy) -5-p-methylbenzylthio-1,2,4-thiadiazole. 17. 3- (Diethoxythiophosphoryloxy) -5-p-chlorobenzyloxy-1,2,4-thiadiazole. 18. 3- (Diethoxythiophosphorylqxy) -5-n-butoxy-1,2,4-thiadiazole. 19. 3- (diethoxythiophosphoryloxy) -5- (2,4-dichlorobenzylthio) -1,2,4-thiadiazole, 20. 3- (Diethoxythiophosphoryloxy) -5-methoxy-1,2,4-thiadiazole. 21. 3- (Diethoxythiophosphoryloxy) -5-n-propyloxy-1,2,4-thiadiazole. 22. Process for the preparation of the compounds according to claim 1, characterized in that a compound of the formula IV: S-M 5 0 3 8 18/1229 wherein R ', X and η have the meanings given above and A represents a cyano or alkoxycarbonyl group and M represents a hydrogen atom or an alkali metal a cyclization in the presence of an oxidizing agent, if A. is a cyno group, or in the presence of ammonia and an alkali metal hypohalite, if A represents an alkoxycarbonyl group, subjects, and then the compound of formula II thus obtained: OH with a compound of the formula III: ^Y - ^p C (in) condensed, in which formula R, R ¹ , X, W and η have the meanings given above and Y represents a halogen atom. 23 “Insecticidal or nematocidal compounds, thereby characterized in that they contain at least one of the compounds according to claim 1 as active ingredient. 24o insecticidal or nematocidal compositions, thereby, characterized in that they contain at least one of the compounds according to claim 2 as active ingredient 25. Insecticidal or nematocidal compositions, characterized in that they contain at least one active ingredient the compounds according to any one of claims 3 to 21 contained 509818/1 229