IL45624A - 1,2,3-triazolyl derivatives of phosphoric acids their preparation and their use as insecticides acaricides and nematicides - Google Patents

Description

45624/2 Novel 1,2,3^ rias The said 1 , 2 , 3-triazolyl compounds correspond to the formula wherein represents ethyl, methoxy, ethoxy, n-propylthio, meth lamino or dimethylamino , R-2 , represents methoxy, ethoxy or dimethylamino, R-β represents unsubstituted phenyl, or phenyl mono- or disubstituted by fluorine, chlorine and/or bromine or monosubstituted by methyl, methoxy or trifluoromethyl , Y represents hydrogen, chlorine or bromine, n represents the numbers 0 or 1, and X represents oxygen or sulphur.

Especially preferred compounds of formula I are those wherein represents methoxy, ethoxy or n-propylthio, R2 represents methoxy or ethoxy, represents unsubstituted phenyl, or phenyl mono- or di substituted by fluorine, chlorine and/or bromine or monosubstituted by methyl, methoxy or trifluoromethyl , Y represents hydrogen, chlorine or bromine, n represents the numbers 0 or 1, and X represents sulphur. 45624/2 The compounds of formula I can be prepared by the following metho la) X In formulae II to VIII, the symbols to R^, X, Y ^ and n have the meanings given for formula I, Hal stands for. fluorine, chlorine, bromine or iodine, particularly, however, for fluorine, chlorine or bromine, R^ stands for alkoxy or alkylthio, and Me denotes a monovalent metal, preferably an alkali metal, especially sodium or potassium. Suitable acid-binding agents are, for example, the following bases: tertiary amines such as triethylaraine, dimethylaniline and pyridine, inorganic bases such as hydroxides and carbonates of alkali metals and alkaline-earth metals, preferably sodium and potassium carbonate. The reactions la, lb, 2a and 2b are performed under normal pressure, at a temperature of 0 - 150°C, and preferably in solvents or diluents which are inert to the reactants. Suitable solvents or diluents are, for example: aromatic hydrocarbons such as benzene, toluene and ligroins; halogenated hydrocarbons such as chlorobenzene, polychloro-benzenes and bromobenzene ; chlorinated alkanes having 1 to 3 carbon atoms; ethers such as dioxane and tetrahydro-furan; esters such as acetic acid ethyl ester; ketones such as methyl ethyl ketone and diethyl ketone; and nitriles, etc Of the compounds of formula III or IV to be used as starting materials, only 2-phenyl-4-hydroxy-l , 2 , 3-triazole is known. This is prepared by firstly converting glyoxal, by reaction with phenylhydrazine, into glyoxal-diphenylhydrazone, and condensing this in the presence of copper sulphate to 2-phenyl-l , 2 , 3-triazole (see J.L. Riebsomer, J. Org. Chem. 13, (1948), 815). This ^ is then converted with fluorosulphonic acid methyl ester into 2-phenyl-3-methyl-l,2,3-triazolium fluorosulphonate , which yields, by treatment with N-bromosuccinimide and sodium hydroxide solution, 2-phenyl-3-methyl-l , 2 , 3- triazolin- 4-one (see M. Begtrup et al, Acta Chem. Scand, 25_, (1971) 2097) . The last-mentioned compound is subsequently converted by reaction with benzoyl chloride into 2-phenyl- 4-benzoyloxy-l , 2 , 3-triazole , which yields, with alkaline hydrolysis, 2-phenyl-4-hydroxy-l , 2, 3-triazole (see M.

Begtrup, Acta Chem. Scand. 26, (1972), 715). By an analogous process, it is possible to prepare further compounds of formula III, which are substituted in the phenyl radical according to the above definition for the radical ^, starting with correspondingly substituted phenylhydrazines.

The compounds thus obtained can be chlorinated or brominated ' in the 4- position. The introduction of chlorine or bromine in the 4-position is effected by the action of elementary chlorine or bromine in solvents inert to these agents, such as halogenated hydrocarbons. Furthermore, N-chloro- succinimide and N-bromosuccinimide are suitable for the introduction of chlorine and bromine, respectively. With the use of these halogenating agents, the procedure is carried out in the aforementioned halogenated hydrocarbons, particularly in carbon tetrachloride. in which n is 0 The compounds of formula Ill/obtained in this manner can in addition be converted in the usual manner by the action of hydrogen peroxide or organic peroxy acids, such as peroxyben^oic acid or m-chloroperoxybenzoic acid, in glacial acetic acid sKo the corresponding 1-oxides* The starting compounds of the general formula III in which n = 1 and Y «* hydrogen can also be advantageously prepared by heating an oxime-hydrazone of the formula ΗΟ-ΙΜΤ( 3(ΕΓ02)«Ν-ΗΗ-Ε5 (Ilia) in the presence of a lower aliphatic carboxylic acid at temperatures of between 15 and 100°C.

The compounds of ormula I have a broad blocidal action, and can be used for the control of various animal and plant p^ests.

They are particularly aaitable for the control of insects of the families: Acrldidae, Blattidae, Sryllldae, Gryllotalpidae, Tettigoniidae, Clmicidae, Fhrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Ghryeomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermes-tidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Iymantriidae, Pyralidae, Galleridae, Culicldae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, rypetidae and Pulicidae; as well as acarids of the familiess Ixodidae, Argasidae, Tetrany-chidae and Dermanyssidae. Especially advantageous is their use against leaf-eating insects. Some compounds of formula I are also suitable for the control of phytopathogenic nematodes.

The insecticidal and acaricidal action can be appreciab-lybroadened and adapted to suit given circumstances by the addition of other insecticides and/or acaricides. Suitable additives are, for example, organic phosphorus compounds, nitro-phenols and derivatives thereof, formamidines, ureas, pyrethrin- The compounds of formula I can be used on their own or together with suitable carriers and/or additives.

Suitable carriers and additives may be solid or liquid, and they correspond to the substances common in formulation practice, such as, for example, natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of formula I can be processed into the form of dusts, emulsion concentrates, granulates, dispersions, sprays or solutions, the formulation of these preparations being effected in a manner commonly known in practice.

The agents according to the invention are prepared in a manner known per se by the intimate mixing and/or grinding of active substances of formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances The active substances can be obtained and used in the following forms : solid preparations:- dusts, scattering agents, granulates, coated granulates , impregnated granulates and homogeneous granulates; liquid preparations : - a) water-dispersible active-substance concentrates: wettable pov7ders, pastes or emulsions; b) solutions.

The content of active substance in the described agents is between 0.1 and 95 " .

The active substances of formula I can be formulat for example, as follows: Dus s : The following substances are used in the preparation of a) a 57o dust, 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 dispersed silicic acid, 97 parts of talcum.

The active substances are mixed and ground with the carriers .

Granulate : The following substances are used to prepare a 5% granulate: 5 parts of active substance, 0.25 part of epichlorohydrin, 0.25 part 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 solution thus obtained is sprayed onto kaolin, and the acetone subsequently evaporated off 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, 5 parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic 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 silicic 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, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives, and the mixture is subsequently ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.

Emulsifiable concentrates: The following substances are used to prepare a) a 10%, and b) a 2570 emulsifiable concentrate: a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts of a combination ernulsifier of fatty alcohol polyglycol ether sulphonate calcium salt, • . AO parts of dimethylformamide, 43.2 parts of xylene; b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulphonate/fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene.

From these concentrates it is possible to prepare, by dilution with water, emulsions of any desired concentration.

S ray: The following constituents are used to prepare a 57o spray: 5 parts of active substance, 1 part of epichlorhydrin, 94 parts of ligroin (boiling limits 160 - 190°C) .

Agent for the ultra low volume spraying technique 95 parts of active substance, 5 parts of epichlorohydrin .

Example 1 -4^ A) Preparation of 0,0-diethyl-O- [2-p-chlorophenyl-l,2,3- triazox- (2) -yl- (4) ] -thiophosphate 12 ml of triethylamine is added dropwise to a solution of 21.1 g of 2-p-chlorophenyl-4-hydroxy-l,2,3-triazole-l-oxide and 19.0 g of diethylthiophosphoric acid chloride in 300 ml of acetonitrile . After 6 hours' refluxing, the reaction mixture is cooled to room temperature, and the formed triethylamine hydrochloride is filtered off. The filtrate is concentrated in vacuo, and subsequently extracted by shaking with ether/water. The ether phase is separated, and dried with sodium sulphate. After removal of the drying agent, the ether is distilled off. The residue is purified through silica gel with 5% of methanol in chloroform as the eluant .

The eluant is distilled off to obtain the compound of the formula S II 0~P(OC„H ) 2 5 2 0 in the form of oil having a refractive index 20 ¾ = 1.5728.

B) Preparation of 0,0-diethyl-O- [2-phenyl-l,2,3-triazolyl- (4) ] -thiophos hate 16.1 g of 2-phenyl-4-hydroxy-l, 2,3-triazole and 18.9 g of diethylthiophos horic acid chloride are refluxed with 13.8 ml of triethylamine in 300 ml of acetonitrile for 5 hours . The reaction mixture is cooled to room temperature and triethylamine hydrochloride is filtered off. The filtrate is concentrated in vacuo, and subsequently extracted with ether/water. The ether phase is separated, and dried with sodium sulphate. After removal of the drying agent, the ether is distilled off. The residue is purified through silica gel with chloroform as the eluant.

The eluant is distilled off to obtain the compound of the formula g II CH C-0-P(0C H(,) - II II " 5 2 in the form of yellow oil having a refractive index of n^° = 1.5480.

The following compounds are prepared in an analog manne : ^ ( Example 2 Insecticidal stomach poison action Cotton and potato plants were sprayed with a 0.05% aqueous active-substance emulsion (obtained from a 10%> emulsifiable concentrate) .

After the drying of the resulting coating, Spodoptera littoralis or Heliothis virescens larvae were placed onto the cotton plants, and Colorada beetle larvae (Leptinotarsa decemlineata) onto the potato plants . The test was carried out at 24°C with 60% relative humidity.

The compounds according to Example 1 exhibited in the above test a good insecticidal stomach poison action against Spodoptera littoralis, Heliothis virescens and Leptinotarsa decemlineata larvae.

Example 3 Action against Chilo suppressalis Rice plants of the type Caloro were planted, 6 plants per pot, in plastic pots having a top diameter of 17 cm, and grown to a height of about 60 cm. Infestation with Chilo suppressalis larvae (L^; 3-4 mm long) was carried out 2 days after application of the active substance in granular form (amount applied = 8 kg of active substance per hectare) to the paddy water. The evaluation of the insecticidal action was made 10 days after application of the granules .

The compounds according to Example 1 were effective against Chilo suppressalis in the above test.

Example 4 Action against ticks A) Rhipicephalus bursa In each case, 5 adult ticks or 50 tick larvae were placed into a small glass test tube, and subsequently immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, 1 and 0.1 ppm of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that the active-substance emulsion could be absorbed by the cotton wool .

An evaluation in the case of the adults was made after 2 weeks, and in the case of the larvae after 2 days.

There were two repeats for each test.

B) Boophilus microplus (larvae) With a dilution series analogous to that in Test A, tests were carried out with 20 sensitive larvae and OP-resistant larvae, respectively (resistance is with respect to diazinon compatibility) .

Compounds according to Example 1 were effective in these tests against adults and larvae of Rhipicephalus bursa and against sensitive and OP-resistant larvae, respectively, of Boophilus microplus.

Example 5 Acaricidal action Phaseolus vulgaris (plants) were infested, 12 hours before the test for acaricidal action, with an infested piece of leaf from a mass culture of Tetranychus urticae.

The transferred mobile stages were sprayed with the emulsified test preparations from a chromatography-sprayer in a manner ensuring no running-off of the spray liquor.

An assessment was made after 2 to 7 days, by examination under a binocular, of the living and of the dead larvae, adults and eggs, and the results were expressed as percentages. The treated plants were kept during the "holding time" in greenhouse compartments at 25°C.

The compounds according to Example 1 were effective in the above test against adults, larvae and eggs of Tetranychus urticae.

Example 6 Action against soil nematodes In order to test the action against soil nematodes, the active substances were added, in the concentration stated in each case, to soil infested with root-gall-nematodes (Meloidogyne arenaria) the whole was then intimately mixed. In the one test series, tomato seedlings were planted immediately after preparation of the soil in this manner, and in the other test series tomatoes were planted after a waiting time of 8 days.

For an assessment of the nematocidal action, the galls present on the roots were counted 28 days after planting and sowing, respectively.

Some active substances according to Example 1 exhibited in this test a_good action against Meloidogyne arenaria.

The results of the activity of some compounds of the present invention against the various pests mentioned in Examples 1 to 6 are given in the table below.

The results of the activity of some compounds of the present against the various pests mentioned in Examples 1 to are given in the table below.

Claims (2)

1. 45624/2 WHAT WE CLAIM IS: 1. · A compound of the formula wherein R^ represents ethyl, methoxy, ethoxy, n-propylthio, methyl- amino or dimethylamino, R2 represents methoxy, ethoxy or dimethylamino, represents unsubstituted phenyl, or phenyl mono- or disubstituted by fluorine, chlorine and/or bromine, or monosubstituted by methyl, methoxy or trifluoromethyl , Y represents hydrogen, chlorine or bromine, n represents the number 0 or 1, and X represents oxygen or sulphur.

2. A compound according to Claim 1 wherein R^ represents methoxy, ethoxy or n-propylthio, R2 represents methoxy or ethoxy, R^ represents unsubstituted phenyl, or phenyl mono- or disubstituted by fluorine, chlorine and/or bromine, or monosubstituted by methyl, methoxy or trifluoromethyl , Y represents hydrogen, chlorine or bromine, n represents the numbers 0 or 1, and X represents sulphur. - 24 - 45624/2 Compound according to Claim 2 of the formula S" (OC H(.) > Compound according to Claim 2 of the formula Compound according to Claim 2 of the formula S II 45624/2 Compound according to Claim 1 of the ormula 0 Compound according to Claim 2 of the formula Compound according to Claim 2 of the formula - 26 " 45624/2 Compound according to Claim 2 of the formula Compound according to Claim 2 of the formula - O - Ρ(00 Η,-) 2 5 0 Compound according to Claim 2 of the formula 45624/2 Compound according to Claim 2 of the formu Compound according to Claim 2 of the formula O - P(OCH3)2 14. Compoun formula - 28 - 45624/2 Compound according to Claim 2 of the for - 0 - P(0C HC) 2 5 Compound according to Claim 2 of the formula formula 45624/2 Compound according to Claim 2 of the formula 19. Compound according to Claim 2 of the formula 20. Compound according to Claim 2 of the formula -30 - 45624/2 Compound according to Claim 2 of the formula - O - ΡίΟΟ-,Η.)·, · 2 0 < Compound according to Claim 1 of the formula Compound according to Claim 2 of the '.' S CH C - 0 - P (OC H,.) II II 45624/2 Compound according to Claim 1 of the formula Compound according to Claim 2 of the formula Compound formula 45624/2 Compound according to Claim 1 of the formula Compound according to Claim l of the fo , Proces unds accord Claim l he formula - 33 - 45624/2 is reacted with a compound of the formula in the presence of an acid-binding agent, or with a compound of the formula wherein to R^, X, Y and n have the meanings given in Claim 1, Hal stands for fluorine, chlorine, bromine or iodine, and Me stands for a monovalent metal. 30. Pest-control agents containing as active component a compound according to Clain 1 together with suitable carriers and/or other additives-. 34 - 45624/2 4 31. A method of combatting various animal and plant pests at a locus, which method comprises applying to the locus a W compound as claimed in claim 1. 32. A method according to claim 31 wherein the pests are of the class Insecta ■· or of the order Acarina. 33. A method according to claim 31 wherein the pests are of the class Nematoda.