IL38543A - A triazolyl-thiophosphoric acid ester,its manufacture and pesticidal compositions containing it - Google Patents

Description

38543/2 ,n»HDOiDi. n- »¾iTK'nB nxainn *?v TOOK mis o» aan D»P B ''it p o»*i*i_ m rnaan A triazolyl-thlophoephorlo aold ester, ite manufacture and peetloldal oomposltlone containing It CIBA-GEIGY A.G. 2 38543/2 The present invention relates to 0,0-diethyl-O-1-(4-chlorophenyl)-5-methyl-1 , 2 ,4-triazolyl-( 3)-thiophosphate of the formula I its manufacture and its use in pest control.

The compound according to the invention of the formula I may be manufactured by reacting 1-(4-chlorophenyl)-3-hydroxy-5-methyl-l,2,4-triazole of the formula II: -3- 38543/2 or a salt thereof with an 0,0-diethyl-thiophosphonic acid halide of the formula III S !! X - P - 0 - C Kc (III) I OC2H5 wherei X represents a chlorine or bromine atom, the reaction being conducted, when the free triazole of the. formula II is employed, in the presence of an acid binding agent; As salts of the hydroxytriazole of the formula II which are suitable for the process according to the invention there may be used, for example, salts of monovalent metals, in particular the alkali metal salts; besides these, however, there may be used other salts, for example those of monovalent heavy metals.

As acid binding agents the following bases may for example be used: tertiary amines, such as triethylamine, di-. methyl aniline, pyridine bases, inorganic bases, for example hydroxides and' carbonates of alkali and alkaline earth metals, preferably sodium and potassium carbonate.

The reaction, may be carried out preferably in sol- - - vents or diluents which are inert towards the reactants. The following, for example, are suitable for this purpose:- aromatic hydrocarbons, such as benzene, toluene, gasolines, halogenated hydrocarbons, chlorobenzene , polychlorobenzenes, bromobenzene , chlorinated alkanes containing 1 to 3 carbon atoms ethers, such as dioxan, tetrahydrofuran; esters, for example ethyl acetate; ketones, for example methyl ethyl ketone, diethyl ketone, nitriles etc.

The starting material of the formula II is a new compound (m.p. 208-212°C) which can be manufactured according to methods which are known per se. This compound is obtained for example by reacting a correspondingly substituted semi-carbazide with ortho-carboxylic acid ethyl ester, or by firstly acylating a correspondingly substituted semi-carbazide and subsequently effecting cyclisation under alkaline conditions (cf. for example J.B. Chem. Ber. £6, 1797).

In particular, the compound- of the formula I possesses insecticidal and acaricidal properties and may be used against all development stages such, for example, as eggs, larvae, pupae, nymphs and adults of insects and representatives of the order acarina, for example against insects of the families : Telti onidae Tenebrionidae Gryllidae Chrysomelidae Gryllotalpidae Bruchidae Blattidae Tineidae Peduviidae Noctindae Phyrrhocoriae Lymatriidae Cimicidae Pyralidae Delphacidae Culicidae Aphididae . Tipulidae Diaspididae Stomoxydae Pseudococcidae Trypetidae Scarabaeidae Musc dae > Dermestidae Calliphoridae and Coccinellidae Pulicidae Acarida of the families: Ixodidae Argasidae Tetranychidae -6- 38543/2 The insecticidal or acaricidal action can be sub- stabtially broadened and adapted to the particular circum-. stances by the addition of other insecticides and/or acari- cides.

Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formu¬ lation technique such, for example, as solvents dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers .

The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding the active substance, of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substance-may be available and can be used in the following forms: Solid forms Dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules.

Liquid forms : a) active substances which are dispersible in water: wettable powders, pastes, emulsions; b) solutions.

To manufacture solid forms (dusts, tracking agents), is the active substances aro mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used alone or in admixture with one another.

Granules can be very easily manufactured by dissolving the aft active substance of the formula I-a- in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, SIC^, granicalcium, bentonite ets* and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the active substance^? of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/ ormaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substance^ and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/ formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorp- tion/desorption ratio, with the active substance^, for example its in the form of 'their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/ litre to 600 g/litre can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.

It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product.

To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose) , hydroxyethyl glycol ethers of mono-alkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulfonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes) , fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones , polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.

The water-dispers ible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substance and anti-foam agents and, optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding the active substance with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Carriers are, for example, those mentuoned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulfonic acid, in addition, alkylaryl sulfonates, alkali and alkaline earth metal salt¾ of dibutyl naphthalene sulfonic acid, fatty alcohol sulfates such as .salts of sulfated hexadecanols , heptadecanols , octadecanols , and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salt of oleoyl methyl tauride, ditertiary acetylene glycols, dialkyl dilaxiryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substance^ are mixed, ground, sieved and strained with the additives mentioned above that, in wettable powder, the solid particle size of from 0.02 to 0.04 and in pasts, of 0.03 is not exceeded. To produce emul- sifiable concentrates and pastes, dispersing agents such as those cited above, organic solvents and water are used.

Examples of suitable solvents are the following: alcohols, benzene, xylenes, toluene, dimethyl sulfoxide, and mineral oil fractions boiling between 120 and 350° C. The solvents must be practically odorless, not phytotoxic, inert to the active substances and not readily inflammable.

Furthermore, the agent^ according to the invention can be applied in the form of solutions. For this purpose the active substance or oovoral active- oubotanooo of the is general formula I are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalene and mineral oils alone or mixed with .each other, can be used as organic solvents.

The content of active substance in the above described agents is between 0.1% to 95%, in which connection it should be mentioned that in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.

The active substance^ of the formula la* can, for example, be formulated as follows: Dusts The following substances are used to manufacture a) a 5% and b) a 2 dust: a) 5 parts of active substance 95 parts of talcum b) 2 parts of active substance 1 part of highly disperse silica 97 parts of talcum.

The active substances are mixed with the carriers and ground. Granules The following substances are used to produce 5% granules: parts of active substance, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3 - 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on to kaolin, and the acetone subsequently evaporated in vacuo.

Wettable powder: The following constituents are used for the preparation of a) a 40%, b) and c) a 25 %, and d) a 10% wettable powder: a) 40 parts of active substance, parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silica acid. b) 25 parts of active substance, 4.5 parts of calcium lignin sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silica acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin. c) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1,7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin. d) 10 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/ formaldehyde condensate, 82 parts of kaolin. is The active substances- ira intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powder are obtained which can be diluted with water to give suspensions of any desired concentration.

Emulsifiable concentrates: The following substances are used to produce a) a 10% and b) a 257o emulsifiable concentrate: a) 10 parts of active substance, 3 .4 parts of epoxidised vegetable oil, 13. 4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkyl- arylsulphonate calcium salt, 40 parts of dimeth lformamide, 43. 2 parts of xylene. b) 25 parts of active substance, 2. 5 parts of epoxidised vegetable oil, parts of an alkylarylsulphonate/ fatty alcohol- polyglycol ether mixture parts of dimethylformamide, 57 . 5 parts of xylene.

From these concentrates it is possible to produce, by dilution with water, emulsion of any desired concentration Spray: The following constituents are used to prepare a 5% spray: parts of active substance, 1 part of epichlorohydrin, 94 parts of benzine (boiling limits, 160° - 190° C) . -14- 38543/2 Example 1 0,0-Diethyl-O-l- (4-chlorophenyl) -5-methyl-1,2 ,4-triazolyl- (3) -thiophosphate ^^^^^^^^^^^^^^^^^^^^^^^^^^^.^. a) 18.65' Grams (0.1 M) of 1- (4-chlorophenyl) semicarbazide and 16.2 g (=18.2 ml) of ortho-acetic triethyl ester are heated together with 40 ml of glycol monomethyl ether, in the process of which a clear yellow solution is obtained. The ethanol which forms in continually distilled off at an internal temperature of 120°C. The residue is cooled after 4¾ hours and treated with 200 ml of ether, yielding l-(4- chlorophenyl)-3-hydroxy-5-methyl-l,2,4-triazole (m.p.: 255- 60°C. b) 36 Grams (0.172 M) of 1- (4-chlorophenyl) -3-hydroxy-5-methyl 1,2,4-triazole and 23.6 g (0.172 M) of potassium carbonate are heated together with copper powder (from the tip of • spatula) in 400 ml of methyl ethyl ketone and the mixture is boiled fo 1 hour under reflux. Then 32.3 g (0.17.2 M) of 0,0-diethylthiophosphoric chloride are added dropwise at 50°C. The reaction- mixture is .refluxed for 3 hours and the solvent then evaporated in vacuo. The residue (59 g) is taken up in 500 ml of ehter and washed successively with water, 0.5N HC1, saturated bicarbonate solution and sodium chloride solution. After drying the ether solution over sodium sulphate. The ether is evaporated in vacuo, leaving as residue 43.8 g of crude product. This product is filtered over 800 g of silica gel using methylene chloride as solvent, to yield 0,O-Diethyl-0-1- (4-chloro- - e - 2 - azol l- 3 -thio hosh ate Example 2 Action against ticks A) Rhicephalus bursa In each of two test series 5 adult ticks and 50 tick larvae are counted into a glass tube and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from an amulsion series each containing 100, 10, 1 and 0.1 ppm of test substance.

The tube is then sealed with a standardised cotton wool plug and placed on its head, so that the active substance emulsion can be adsorbed by the cotton wool.

In the case of the adults evaluation takes place after 2 weeks, and in that of the larvae after.2 days. Each test is repeated twice.

The compound^ according to Example 1 acts in the above test against adults and larvae of Rhicephalus bursa.

B Boophilus microplus (larvae) Tests are carried out in each case with 20 OP-sen-sitive larvae using an analogous dilution series as in the case of test A.

The compound^ according to Example 1 ac & in the above test against sensitive larvae of Boophilus microplus.

Example 3 Acaracidal action Phaseolus vulgaris (dwarf beans) have an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test for the acaricidal action. The occupying mobile stages are sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth- does not run off. The number of living and dead larvae, adults and eggs are evaluated after 7 days under a stereoscopic microscope and the result expressed in percentages. During the "interim", the treated plants are kept in greenhouse compartments at 25° C. is The compound^ according to Example 1 e¾?e active in the above test against eggs, larvae and adults of Tetranchus urticae.

Example 4 A) Insectical Ingest poison action Tobacco and potato plants are sprayed with a 0.05% aqueous emulsion (obtained from a 10% emulsifiable concentrate) After the coating has dried, Egyptian cotton leaf worms (Spodoptera literalis) are settled on the tobacco plants and Colarado potato beetle larvae (Leptinotarsa decemlineata) on the potato plants. The test is carried out at 24° C and 60% relative humidity. s The compound^ according to Example 1 have an ingest poison action against Spodoptera litoralis and Leptinotarsa decemlineata.

B) Systemic insecticidal action To determine the systemic action, rooted bean plants (Vicia fabae) are put into a 0.01% aqueous active substance solution (obtained from a 10% emulsifiable concentrate) . After 24 hours, aphids (Aphis fabae) are placed on the parts of the Xjlant above the soil. The aphids are protected from contact and gas action by means of a special device. The test is carried out at 24° C and 70% relative humidity. In the above s test the compound^? according to Example I have a systemic action against Aphis fabae.

Example 5 Fungicidal action a) Action against Botrytis cinerea on Vicia faba Fully developed, uniformly large leaves of Vicia faba, which have been sprayed dripping wet from a spraying device with a broth (0.05%> content of active substance) prepared from «¾■ the active substance formulated as a 10% wettable powder, were placed three at a time in Petri dishes in which filter paper has been laid. When the leaves were dry again, they were infected with a freshly prepared, standardised spore suspension of the fungus (concentration: 100Ό00 spores/ml) and kept for 48 hours in a humid atmosphere at 20°C. After this time, the leaves displayed black, initially dot-shaped specks which rapidly spread. The number and size of the infected areas served as a yardstick for determining the effectiveness of the test substance. b) Action against Erysiphe cichoracearum on Cucu is sativus Young Cucumis sativus plants were sprayed with a spo.re suspension after they had been sprayed with a 0.05% suspension of the active substance formulated as wettable powder and after the spray coating had dried. The degree of attack (extent of the leaf surface coated with the mycel coating) on the infected, treated leaves was assessed after 8 days in a greenhouse at approx. 23° C in comparison with untreated, infected controls. c) Action against Uromyces appendiculates on Phaseolus vulgaris Phaseolus vulgaris plants in the 2-leaf stage were sprayed until dripping wet with a suspension of the active substance formulated as wettable powder (concentration = 0.05% of active substance) . After the spray coating had dried, the plants were infected with a fresh spore suspension of bean rust and then kept for 1 day in a humid chamber, then for 12 days in a greenhouse at 20-22°C.

The number and size of the rust pustules served as a yardstick for assessing the effectiveness of the active substances. d) Action against Phytophthora infestans on Solanum Lycopers icum S. Lycopersicum plants of the same variety and in the same development stage were treated with a broth of 0.05% active substance (prepared from the active substance formulated as a wettable powder) . After the coating layer had dried, the dry plants were sprayed dripping wet with a zoospore suspension of Ph. Infestans. They were then kept for 6 days in a greenhouse at 18-20°C and high humidity (95-100%), after which time they displayed typical leaf specks. The evaluation of the tested substance was based on their number and size.

The compound^ according to Example 1 displayed good fungicidal action in the above tests a) to d) .

Example 6 Action against soil nematodes To test the action against soil nematodes, the active -19- 38543/2 substance ( in a concentration of 50 ppm) is applied to and intimately mixed with soil infected with root gall nematodes (Meloidgyne Avenaria) . Immediately afterwards, tomato cuttings are planted in the thus prepared soil in a series of tests and after a waiting time of 8 days tomato seeds are sown in a- nother test series.

In order to assess the nematocidal action, the galls present on the roots are counted 28 days. after planting and sowing respectively. The compound, according to Example 1 displayaa nematocidal action in the above test. .' Example 7 · - - 1 Comparative Test A ■ ■■ ··' ·'· · ' ■ .·■■·■··'.

Test compounds: The compound of the present invention The compound according to U.S.Patent No.3 686 200, Claim 7 Test animals Dermestes frischii Larvae Test preparation parts of active ingredient 95 parts of talc · " Test The test preparation was applied to filter paper in a con- - 38543/2 A Comparative Test B Test compounds; of the ntion B ccording to nt Specificatio Test animals ·' .

II .

Aedes aegypti adults Test preparation Acetonic solutions of the active ingredients A and B.

Test Coatings of the acetonic solution of test substances were pipetted into Petri dishes to give a concentration of 1 mg of test substance per dish.

After one hour 20 A¾des aegypti adults were placed in the dishes and the time evaluated efter which all insects were lying on their Results Comparative Test c Test compounds: . " The compound of the present invention B The compound according to (OC 2H5)2 US Patent No.3 686 200 , Claim 3 Test animals Heliothis zea larvae Test preparation parts of active substance, 3 . 4 parts of epoxidised vegetable oil., 13 . 4 parts of a combihation emulsifier consisting of fatty alcohol polyglycol ether and alkyl-arylsulphonate calcium salt, 40 parts of dim th lformamide , 43. 2 parts of xylene.

Test Cotton plants were sprayed with a 0.05% aqueous emulsion --'(obtained from a 10% emulsifiable concentrate). After the coating had dried 10 Heliothis zea larvae were settled o each of the cotton plants.- The test was carried out at 24°C and 60% relative humidity .

Comparative Test D Test compounds: A The compound of the (OC2H5)2 present invention B The compound according t (0¾Η5)2 US Patent No. 3 686 200, Claim 3 Test animals Rhipicephalus bursa adults and larvae Test preparation parts of active substance, 3.4 parts of epoxidised vegetable oil, 13.4 parts of a combination emulsifier consisting of fatty alcohol, polyglycol ether and alkyl-arylsulphonate calcium salt, 40 parts of dimethylformamide, 43.2 parts of xylene* Test Groups of adults and 50 tick larvae were dipped into an emulsion containing 0.1 ppm active ingredient. Evaluation took place 3 days after application for larvae and 2 weeks after application for adults.

Results % mortality after % mortality after 3 days for 2 weeks for Test compounds Rhipicephalus . Rhipisephalus bursa larvae bursa adults A 100 100 B 0 0 -24- 58543/2

Claims (16)

1. The compound 0,0-diethyl-O-l- (4-chlorophenyl)-5-methyl« 1,2,4-triazolyl- (3)-thiophosphate of the formula I

2. Process for the production of 0,0-diethylrO-l- (4-chloro-phenyl)-5-methyl-l,2,4-triazolyl- (3)-thiophosphate of the formula I as illustrated in claim 1 which comprises reacting 1- (4-chlorophenyl)-3-hydroxy-5-methyl-l,2,4-triazole of the formula II or a salt 'thereof with an 0 ,0-diethyl-thiophosphonic acid halide of the formula III S II X - P - 0 - C-H,. (HI) I OC2H5 wherei X represents a chlorine or bromine atom, the reaction being conducted, when the free triazole of the formula II is employed, in the presence of an acid binding agent;

3. Process according to claim 2 substantially as hereinbefore described in example 1.

4. A pesticidal composition which comprises (i) the compound of claim 1 in intimate admixture with at least one of the following (ii) a solid extender; (iii) a surfactant; or (iv) an aeresol' propellant . ' : '

5. A solid composition according to claim 4 which comprises one or both of (ii) and (iii).

6. A composition according to claim 5 in the form of a granulate or pellets .

7. A composition according to claim 6 wherein the granules or pellets are coated or impregnated with (i) .

8. A liquid composition according to claim 4 which comprises one or both of (iii) or (iv) .

9. A composition according to claim 8, comprising (iii) and a hydrocarbon which boils at a temperature above 130°C.

10. A composition according to claim 1 comprising, as (iv) , a polyhalogenated hydrocarbon.

11. A method of combatting pests at a locus which comprises applying to said locus the compound claimed in claim 1 or a -26- 38543/2 ^

12. A method as claimed in claim 11 wherein the pests ate of the class Insecta or Acarina.

13. A method as claimed in claim 12 wherein the pests are of the species Dermestes frischii, Aedes aegypti, Heliothis Zea or Rhipicephalus bursa.

14. A method as claimed in claim 11 or 12 wherein the locus comprises agricultural or horticultural plants, crops or produce or stored goods of organic material.

15. Agricultural or horticultural plants, crops or produce or stored goods or organic material whenever treated by a method as claimed in claim 14.

16. The compound claimed in claim 1 or a composition as claimed in any one of claims 4 to 10 in a container bearing instructions teaching the use of said compound or composition for a method as claimed in any one of claims 11 to 14. ' ND:ed