LU83780A1 - NEW ORGANOPHOSPHONOTHIOIC DERIVATIVES - Google Patents

Description

I ~ K

* i

The present invention relates to new O-alkyl derivatives and ^ JL = âjryl-S- (tertio-alkyl) alkyl phospbonothioates, their preparation, their use as active ingredients of insecticide and * nematicide compositions, in particular for the protection of plants as well as intermediates of these derivatives.

Some insecticides O-alkyl and O-aryl-phospbonothioates are known, in particular in the American patent 3,209,020. However, none of the compounds described in this patent contains in its formula S-tertioalkyl group.

We have now discovered that compounds of formula: / -0Ri R - P. (I) Γ-,

O

in which: - R is an alkyl radical containing from 1 to 8 carbon atoms, baloalkyl containing from 1 to 8 carbon atoms, alkenyl containing from 2 to 8 carbon atoms, haloalkenyl containing from 2 to 8 carbon atoms, alkynyl containing from 2 to 8 carbon atoms or haloalkynyl containing from 2 to 8 carbon atoms, - is an alkyl radical containing from 1 to 8 carbon atoms or an aryl radical, and - R ^ is a tertiary alkyl radical containing from 4 to 8 carbon atoms, have a broad spectrum of insecticide and - nematicide activity. They are particularly interesting for the fight against Diabrotica sp because of their excellent / effectiveness and their residual persistence in the soil «/ * - *,‘ 1 bis #

A group of preferred compounds has the general formula I in which: - R is an alkyl radical containing from 1 to 4 carbon atoms, preferably methyl or ethyl, - is an alkyl radical containing from 1 to 4 carbon atoms, the radical phenyl or the phenyl radical substituted by at least (and preferably one) a member chosen from the group comprising an alkyl radical containing from 1 to 4 carbon atoms (preferably methyl), alkoxy containing from 1 to 4 carbon atoms (from preferably methoxy), alkylthio containing from 1 to 4 carbon atoms, alkylsulfinyl containing from 1 to 4 carbon atoms, alkylsulfonyl containing from 1 to 4 carbon atoms or a chlorine, bromine or fluorine atom or a nitro or cyano group or a nitro or cyano or trifluoromethyl group, - R2 is a tert-butyl or tert-amyl radical.

The compounds according to the invention can be prepared according to methods known per se in this field.

Preferably, these compounds are prepared from a halide of S- (alkyl) alkoylpbospbonothioic acid, by action of the halide of S- (tertioalkyl) alkylphospbonotbioic acid on an alcohol in the presence of a base, according to the scheme. following preferred reaction:.

- 2

* K

* i

__ ^ OR

· + Ri0H b ^ -> R-PC 1 + base. HX

ô \ sr · ° \ SR2 SR2 in which: - R, R ^ and R2 have the meanings indicated above, - X is a halogen atom, preferably chlorine.

The reaction is preferably carried out at a temperature of about 0 ° C. to 100 ° C., in an organic solvent, in the presence of a tertiary amine or an aqueous base, such as aqueous sodium hydroxide, or, when it is desired to obtain alkali alcoholate or phenate, of alkali metal salts such as sodium.

As suitable organic solvents, there may be mentioned, for example, benzene, toluene, cyclobexane and butanone-2 or the alcohol itself.

As suitable tertiary amines, mention may be made of trimethylamine, triethylamine, dimethylaniline, diethylaniline and pyridine.

The intermediate compounds of formula:

X

* - k: I! ss2 o in which R, R2 and X have the meanings indicated above and which form part of the present invention, can be prepared according to a simple process by direct addition of thiols to alkylphosphonic dihalides.

The synthesis of S-alkyl alkylphosphonothioic acid halides is usually carried out by methods different from the direct addition of thiols to alkylphosphonic halides because this reaction is accompanied by an undesirable side reaction, in which the two atoms of halogens are substituted with alkylthiol. The side reaction poses a particular problem when using alkylthiols. /

It has now been discovered that the tertiary alkylthiols react gently with the alkyl phosphonic dichlorides to give the addition of a thiol in good yields, according to the scheme:

solvent ^ X

R - + HSR "+ base ................ R - + base HX

in which: - R is an alkyl radical containing from 1 to 8 carbon atoms, haloalkyl containing from 1 to 8 carbon atoms, alkenyl containing from 2 to 8 carbon atoms, haloalkenyl containing from 2 to 8 carbon atoms, alkynyl containing from 2 to 8 carbon atoms or balogenoalkynyl containing from 2 to 8 carbon atoms,

Preferably, R is an alkyl radical of 1 to 4 carbon atoms, in particular methyl or ethyl.

- is a tertiary alkyl radical containing from 4 to 8 carbon atoms, preferably the tert-butyl and tertioamyl radicals, and - X is a halogen atom, preferably chlorine.

As solvents suitable for the reaction, mention may be made of water and organic solvents. In the case of water, the base is advantageously mineral, like sodium hydroxide. In the case of organic solvents, the base is advantageously a tertiary amine such as trimethylamine, triethylamine, pyridine, dimethylaniline or dietbylaniline.

As suitable organic solvents, mention may be made of benzene, toluene, cyclohexane, acetone and butanone-2.

Generally, the reaction is carried out at a temperature between about 20 ° C and 100 ° C; in fact the temperature is not critical provided that it is sufficient for the reaction to proceed with a reasonable yield and is not excessive. It is preferable to add the tertiary amine to the other reactants at a temperature of approximately 20 to 30 ° C. and then to heat the entire reaction medium to a temperature of approximately 70 to 80 ° C. to complete the reaction. /

This is normally carried out using a / 4 alkylphosphonic acid, thiol and base. However, about a 10-20% excess of alkylphosphonic acid halide over other reagents can be used. On the other hand, a slight excess (5-10%) of thiol and of the base with respect to the alkylphosphonic acid dihalide does not significantly modify the yield.

The following examples illustrate the preparation of the intermediates of the compounds according to the invention of the compounds themselves as well as the insecticidal properties of the latter. It is clear that all the compounds described in this application can be prepared by methods analogous to those described below.

Example 1: S-tert-butyl ethylphosphonothioic acid chloride.

’C H -P

2 5 "C CH

0 \ ÇB3. S-C-CH.

I J

Cli3 To a solution of 32.0 g (or 0.22 mole) of ethylphosphonic acid dichloride in 300 ml of toluene, l & g (or 0.2 mole) of 2-methyl-2-propan-2 thiol are added.

22 g (ie 0.22 mole) of triethylamine are added with stirring and drop by drop, the reaction temperature being maintained at 30-35 ° C during the addition of the amine, the mixture is kept stirring until next day, at room temperature. The amine hydrochloride is filtered and the toluene solution concentrated in vacuo. 0 "adds 200ml of hexane and the solution is again filtered.

The solvents are removed by stripping under vacuum and the distilled residual liquid, the product (25g, ie with a yield of 72.5%) is distilled at 72-73 ° C under 0.7 mm of mercury. The structure indicated below is confirmed by proton NMR spectrography in CDCl 4 with tetramethylsilane as reference.

Example 2 Preparation of O-ethyl S-tertiobuty1 ethylphosphonothioate / A solution of 8.0 g (or 0.048 mole) of λ / “/ f • * - 5 obtained in Example 1, in 50 ml of toluene, add a solution of sodium ethylate (0.04 mole) in 40ml of ethanol. The addition is carried out dropwise and with stirring, the reaction being maintained under nitrogen. Stirring is continued overnight at room temperature, then approximately 80% of the solvents are removed under vacuum. 100 ml of toluene are added and the sodium chloride formed by the reaction is filtered. The toluene is stripped in vacuo and the residual liquid distilled. The product (5.8 g, ie with a yield of 69.6%) is distilled at 69-72 ° C under 0.2 mm of mercury.

Analysis by proton NMR of this compound confirms the structure indicated above.

Examples 3 to 6: * The procedure is analogous to Example 2 by preparing the following compounds of formula: X "l - R’ P \ SR2

VS

the meaning of the radicals and the boiling point are listed in the table below:

Boiling point

Example R JR ^ ° C / mm Hq 3 CH CH tert-buty1 64-67 / 0.7

m O O

4 C_H_ C_H tert-butyl 61-63 / 0.05 <2 5 3 7 5 C „H_ (CH) CH tert-butyl 42-43 / 0.05 3 5 3 3 6 CjHg C2H5 tert-amyl 56-58 / 0.07 "

Example 7 Preparation of O-phenyl S-tertiobutyl ethylphosphonothioate In a solution of 5.0 g, ie 0.025 mole, of chloride of S-tertiobutyl ethylphosphonothioic acid obtained in Example 1 and of 2.35 g ( or 0.025 mol) of phenol in 20 ml of acetone, 2.5 g (or 0.025 mol) of triethylamine are added in one piece. The mixture is kept under nitrogen, with stirring and at room temperature.

-The reaction mixture is diluted with 100 ml 'of / toluene and washed once with a hydroxide solution dd \ jl,'. * 6 sodium 5% and twice with water, The solution is dried over anhydrous sodium sulfate and the solvent removed by stripping in vacuo. The residual liquid is subjected to a large vacuum (0.2 mm Hg) at 60 ° C for 15 minutes. The desired product is obtained, the structure of which is confirmed by proton R.M.N spectrography in CDCl 4 with, as reference, tetramethylsilane.

Examples 8 to 15:

The procedure is analogous to Example 7 for the preparation of the following compounds of formula: / ° Rl • "-

It “” ____o _____ 'whose meaning the radicals as well as the. boiling point are listed in the table below:

Example R J *! Rg 8 C2H5 o-metbyl-phenyl tert-butyl 9 C2H5 p-chloro-phenyl tert-butyl 10 C2H5 phenyl tert-amyl 11 ^ 2Η5 m-trifluoromethyl tert-amyl phenyl 12 ^ 2H5 P “fluoro-phenyl tert-amyl 13 ^ 2 ^ 5 Prchlorophenyl tert-amyl 14 C2H5 o-chloro-phenyl tert-amyl 15 C_H_ phenyl tert-amyl ___ _______ 5 _____, ___________________-__ „__________

Example 16

4.6 g of metacresol are dissolved in 100 ml of acetone and potassium carbonate is added. The mixture is kept under stirring at temperature for 30 minutes, then added with 7.5 g of S-tert-butyl methylphosphonothioic acid chloride. Stirring is continued overnight, the medium is filtered and the solvent evaporated. / 7 / f 6 bis

After adding 100 ml of water, the medium is subjected to extraction with ether (100 ml). The extract is washed with 5% potassium hydroxide then with water and finally dried and evaporated to dryness to give 4.0 g of 0-3 tolyl-S-tert-butyl mehtylphosphonothioate. The product is identified by R.M.N. Its purity is greater than 90%.

Example 17; Intrinsic efficiency test on Diabrotica (Corn rootworm) and beech looper (Southern armyworm) A) Intrinsic efficiency on Diabrotica (CRW)

The test compound is dissolved in 1% in acetone or ethanol. The stock solution is then diluted with an aqueous solution of Tween-20 at the desired concentration (i.e.: 100, · 10, 1, 0.1, 0.005 ppm). Two milliliters of this solution are pipetted into a 9cm Petri dish containing two layers of filter paper.

Second stage larvae are introduced into the box which is then closed. After 2 days (48 hours) of exposure, the dead and dying larvae are counted ^^ / y 'y / y 7 The insecticidal activity is primarily a contact and vapor action and very little by ingestion. The results are reported in Table 1.

B) Intrinsic efficiency on beech looper (Spodoptera eridania) (SAW)

A 1% stock solution of the test compound is prepared in acetone and then diluted to the desired concentration with an aqueous solution containing 500 ppn of Tween-20. Lima bean leaves are soaked in the solution and transferred to Petri dishes (100x15mm) containing two filter papers moistened with 2 ml of water. Each Petri dish contains a leaf and is left open so that the solution dries on the leaf. Five larvae in the third stage of beech looper (Spodoptera Eridania) are placed on the leaf and the Petri dish finally closed.

The insects are kept for 72 hours at 25 ° C, after which the mortality count is carried out.

The results are reported in Table 1.

TABLE 1

% OF MORTALITY

C R W SAW

^^ v ^ Dose in ppm 1 0.1 0.05 500 100

Example # 2 100 95 75 100 100 3 100 100 100 100 90 4 100 70 - 100 15 5 80 45 80 15 6 100 95 100 100 50 7 100 100 90 100 95 8 100 100 15 100 100 9 100 35 40 100 95 10 100 100 70 * 100 80

11 100 100 85 100 80 U

12 100 100 90 100 60 'Il ·' 8 13 100 85 55 100 75 14 95 95 15 100 80 16 100 100 - - · These results show the excellent insecticidal activity of the compounds according to the invention which can be used to control against many types of plant parasitic insects such as beetles (especially Diabrotica sp), and lepidoptera (especially beech looper). Furthermore, in these tests, no pbytotoxicity was observed on the treated plants.

For their use in practice, the compounds according to the invention are not used alone. Most often, they are part of compositions, included in the context of the present invention, which generally comprise, in addition to the active material according to the invention, a support and / or a surfactant compatible with the active material.

In general, these compositions usually contain from 0.001% to 95% by weight of active material. Their surfactant content is generally between 0.1 and 20% by weight.

The term "support" within the meaning of the present description designates a material, organic or mineral, natural or synthetic, with which the active material is associated to facilitate its application or its transport, or its handling. This support must therefore be inert and acceptable in agriculture. The support can be solid (for example clays, natural or synthetic silicates, calcium or magnesium carbonates, calcium sulphate) or liquid (for example water, alcohols, ketones, ethers-oxides, esters, aromatic or paraffinic hydrocarbons, halogenated hydrocarbons , petroleum fractions, liquefied gases ftc ...).

When the support is water or a usual organic solvent, the composition preferably comprises, in addition to the active material, another compound such as, for example a surfactant, a pesticide (for example an insecticide or fungicide). / The surfactant (or surfactant), p; usable in the compositions according to the invention, can J tin 9 be a wetting agent, dispersing or emulsifying, being able to be ionic or nonionic. Mention may be made, for example, of nonionics, such as ethylene oxide condensates with fatty alcohols or with fatty acids, or with fatty amides or amines, alkylphenols, fatty acid esters and sorbitol. , derivatives of sucrose, anionics, such as the salts of lignosulfonic acids, alkylarylsulfonic acids, alkylsulfosuccinates and sulfosuccinamates, amino acid derivatives, cationics such as alkylaraine or imidazoline acetates, amphoterics such as alkylbetaines or sulfobetaines.

In addition to the active material, the support and the surfactant, the compositions according to the invention may contain other additives such as non-surfactant dispersing agents, peptizers, protective colloids, thickeners, adhesives increasing the resistance to rain, stabilizers, preservatives, corrosion inhibitors, dyes, sequestrants, anti-foam, anti-caking, anti-freeze etc ...

The compositions according to the invention can be prepared in the form of wettable powders, dusting powders, granules, solutions, emulsifiable concentrates, emulsions, suspensions, concentrated or not, and aerosols.

Wettable powders usually contain 10 to 95% by weight of active material and they usually contain, in addition to the active material and an inert carrier, 0 to 5% by weight of a wetting agent, 3 to 10 % by weight of a dispersing agent, and, if necessary, from 0 to 10% by weight of one or more stabilizers and / or other additives such as penetrating agents, adhesives, anti-caking agents or dyes.

They are usually prepared by premixing the active ingredient with a solid support and agents. wetting and dispersing agents. This premix is then ground,. / Either in a grinder, for example a pin equipped with a ju / 10 powder selector, or in an "Air Jet" grinder, the latter being preferred for active ingredients with low Fusion point.

By way of example, here is the weight composition of a wettable powder according to the invention: - active material (compound No 1) ...................... 30% - calcium lignosulfonate (deflocculant) ............. 5% - isopropylnapbtalene sodium sulfonate (wetting). 1% - anti-clumping silica ................................ 30% · - kaolin ........ ..................................... 34%

The powders for dusting can be prepared like wettable powders but without the surfactants, dispersants, protective colloids unnecessary in these formulations. In this case, the solid support is chosen ’specially to facilitate grinding, to absorb if the active material is liquid and to guarantee fluence.

The granules and micro-granules, generally with a low active ingredient content, can be pre-manufactured and then impregnated or mass-produced, for example by atomization or by extrusion. In the latter case, they require the addition of binders and hygroscopic products to ensure their rapid disintegration on the ground.

They generally contain from 0.5 to 25% by weight of active material, from 0 to 10% by weight of additives such as stabilizers, slow-release modifiers, binders and solvents.

The emulsifiable concentrates contain the active material dissolved in a solvent (generally an aromatic hydrocarbon) and in addition, when necessary, an auxiliary or cosolvent solvent which may be a ketone, an ester, an ether-oxide, etc. generally, they contain from 5 to 60% by weight / volume of * active materials, from 2 to 20% by weight / volume of emulsifying agent and can be prepared, for example, by dissolution of active material, in the solvent or in the mixture of solvents and emulsifier, in a tank equipped with good agitation and a circulation of fluid for heating or cooling. As an example, here is the composition of an emulsifiable / concentrate, the quantities being expressed in /// 11 g / 1: - active material (compound No 1) ............ ...... 400 g / i - alkaline dodecylbenzene sulfonate ............... 24 g / 1 - nonylphenol oxyéfchylé with 10 molecules of ethylene oxide ..... ...................... 16 g / 1 - cyclohexanone ...................... ............. 200 g / 1 - aromatic hydrocarbons ................ qsp.l liter

The concentrated suspensions called "flowable", also applicable as a spray after dilution in water, are prepared so as to obtain a fluid, stable product, which does not deposit. They usually contain from 10 to 50% by weight of active material, from 0.5 to 15% by weight of surfactants, from 0.5 to 10% by weight of protective colloids or anti-sediment agents, from 0 to 10% of miscellaneous additives, such as defoamers, thickeners, stabilizers, adhesives, anti-gels and as a support for water or an organic liquid in which the active ingredient is insoluble or a mixture of the two.

Certain organic solids or mineral salts can be dissolved in the support to delay sedimentation or as an anti-freeze for water.

These concentrated suspensions can be prepared, for example, by dispersing the pre-ground active material in a liquid carrier which may be water, a vegetable oil or a mineral oil or the emulsified mixture of the two containing the auxiliary ingredients such as the viscosity, preservative and antifreeze, then grinding of the dispersion in a ball mill.

Aqueous dispersions and emulsions, for example compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included within the general scope of the present invention. These emulsions can be of the water-in-oil type or of the oil-in-water type, and they can have a thick consistency like that of a "mayonnaise". For a so-called "very low volume" application, with spraying into very fine droplets, solutions are prepared in organic solvents, / containing from 70% to 99% of active material. λ!

In addition to the compounds corresponding to formula (I), of / 1 /

Claims (17)

1. New organophospbon derivatives of formula ^ ORl R - P (I) ih sr2 0 in which: - R is an alkyl radical containing from 1 to .8 carbon atoms, haloalkyl containing from 1 to 8 carbon atoms, alkenyl containing from 2 to 8 carbon atoms, haloalkenyl containing 2 to 8 carbon, alkynyl containing 2 to 8 carbon atoms or haloalkynyl containing 2 to 8 carbon atoms - R ^ is an alkyl radical containing 1 to 8 carbon atoms or an aryl radical, and / - R ^ is a tertiary alkyl radical containing from 4 to 8 / V, carbon atoms. / i / 13 2. Compound according to claim 1), characterized in that, in the formula, R is an alkyl radical containing from 1 to 4 carbon atoms. 3. Compound according to one of claims 1 and 2, characterized in that, in the formula, is an alkyl radical containing from 1 to 4 carbon atoms. 4. Compound according to claim 1), characterized in that, in the formula, R ^ is a phenyl or phenyl radical substituted by at least one substituent, identical or different, chosen from the group comprising an alkyl radical containing from 1 to 4 carbon atoms, alkoxy containing from 1 to 4 carbon atoms, alkyl sulfinyl containing from 1 to 4 carbon atoms, alkyl sulfonyl containing from 1 to 4 carbon atoms, or a "chlorine, bromine or fluorine atom , a nitro, cyano or trifluoromethyl group. 5. Compound according to one of claims 1 to 3), characterized in that in the formula, is a tert-butyl or tert-amyl radical. 6. Compound according to one of claims 1, 2 and 5), characterized in that in the formula, R is the radical> ethyl, R ^ is an alkyl radical containing from 1 to 3 carbon atoms and R2 is the radical tertiobutyl or tertioamyl. 7. Compound according to one of claims 1, 2 and 4, characterized in that, in the formula, R is the methyl or ethyl radical, is a phenyl or phenyl radical substituted by a chlorine or fluorine atom, or by a methyl radical Tou ^ r ^ Pfiforomethyl and R is the radical tert-butyl or tert-amyl. 8. Process for the preparation of a compound according to one of claims 1 to 7), characterized in that a balide of alkylphosphonothioic acid is reacted with an alcohol or phenol according to the scheme: _ ^ X ^ OR, / + R, OH base x RP ^^ 1 + hase. HX / X * X tv j ° SR2 sr2 ni / 14 in which X is a halogen atom and the radicals R, R ^ and R2 have the above meanings. 9. Method according to claim 9), characterized in that reacts an alkylphosphonothioic acid chloride. 10. Method according to one of claims 8 and 9), characterized in that it operates between 0 and 100 ° C, in an organic solvent, in the presence of a tertiary amine or a mineral base. 11. Composition insecticide and / or nematicide, characterized in that it contains as active material, at least one compound according to one of claims 1 to 7). 12. A method for protecting plants against insects characterized in that a composition according to claim 11 is used. 12 the preparation of these compounds and insecticide and / or nematicide compositions containing them, the present patent application relates to a method of combating insects, characterized in that it consists in bringing the insects into contact with an effective amount of a compound corresponding to formula (I), This insecticidal treatment can, if desired, be carried out as a preventive measure, that is to say ♦ before there is presence of insects, by applying the compound according to invention on the aerial parts of the plants to be protected or on the soil, or by incorporating the product into the soil. The dose of active ingredient to be used may however vary depending on the compound used and the insect to be controlled. „In general, doses of active ingredient ranging from 4 -2 3 from 10 to 10 g / cm are very suitable. When the compounds are used as nematicides, they are effective at doses of 0.5-5 kg / hectare. Of course, in difficult cases, higher doses can be used. 13. New organopbosphonated derivatives of formula: R - R / X Il SR * _____________O_____ in which s - R is an alkyl radical containing from 1 to 8 carbon atoms, haloalkyl containing from 1 to 8 carbon atoms, alkenyl containing from 2 to 8 carbon atoms, haloalkenyl containing from 2 to 8 carbon atoms, alkynyl containing from 2 to 8 carbon atoms or haloalkynyl containing from 2 to 8 carbon atoms, - R2 is a tertiary alkyl radical containing from 4 to 8 carbon atoms , - X is a halogen atom. 14. Compound according to claim 13), characterized in that, in the formula, X is a chlorine atom. 15. Compound according to one of claims 13 and 14), characterized in that, in the formula, R is the tert-butyl or tert-amyl radical. 16. Compound according to one of claims 13 to 15), characterized in that, in the formula, R is a J · alkyl radical containing from 1 to 4 carbon atoms. ' / u 17. Process for the preparation of a compound according to ///