DD202167A5 - PROCESS FOR THE PREPARATION OF NEW ORGANOTHIOPHOSPHONESEURED DERIVATIVES - Google Patents

Abstract

The invention relates to novel organo-thiophosphonsaeurederivate. They correspond to the formula I in which R is a (C deep 1-C deep 8) - (halo) alkyl, (C deep 2-C deep 8) - (halo) alkenyl or (C deep 2-C deep 8) - (halo) alkynyl, R is a deep 1 (C deep 1-C deep 8) alkyl or aryl, and R 2 is a (C deep 4-C deep 8) tert-alkyl. These products are useful as an active material of insecticidal or nematicidal agricultural compositions.

Description

, * _ AP C 07 P / 235 018/4

235018 4 ^60128/11

Process for the preparation of novel organothioic acid derivatives

Field of application of the invention

The present invention relates to a process for the preparation of novel derivatives of O-alkyl- and O-aryl-S- (tertiary-alkyl) -alkyl-thiophosphonates and their use as active materials of insecticides and nematicidal compositions, in particular for the protection of plants. as well as the intermediates of these derivatives,

Characteristic of the known technical solutions

Certain insecticidal O-alkyl and O-aryl thiophosphonates are known, especially from US Pat. No. 3,209,020. However, none of the compounds described in this patent in the formula carry the S-tert.-alkyl group.

Object of the invention

The object of the invention is to provide novel organophosphorus derivatives which can be used as insecticides in the soil and have an increased residence time with respect to the known active organophosphorus derivatives.

Explanation of the essence of the invention

The invention has for its object to find organophosphorus derivatives having the desired properties and processes for their preparation.

It has now been found that compounds of the formula:

" ""- ^ - CTD ' fT \

Il ^ 2 ^(I)

11.MAI1982 * ÜO8957

235018 h

R is an alkyl radical having 1 to 8 carbon atoms, a haloalkyl radical having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, haloalkenyl having 2 to 8 carbon atoms, alkynyl having 2 to 8 carbon atoms or haloalkynyl having 2 to 8 carbon atoms,

R 1 is an alkyl radical having 1 to 8 carbon atoms or an aryl radical and

R _{2 is} a tertiary alkyl radical having 4 to 8 carbon atoms,

have a broad insecticidal and nematicidal activity spectrum. They are of particular interest for the control of Diabrotica sp. due to their excellent effectiveness and residual remanence in the soil.

A group of preferred compounds has the general formula I wherein:

R is an alkyl radical having 1 to 4 carbon atoms, preferably methyl or ethyl,

R 1 is an alkyl radical having 1 to 4 carbon atoms, a phenyl radical or a phenyl radical substituted by at least (and preferably one) a member selected from the group consisting of an alkyl radical having 1 to 4 carbon atoms (preferably methyl), alkoxy having 1 to 4 carbon atoms (preferably methoxy), alkylthio having 1 to 4 carbon atoms, alkylsulfinyl having 1 to 4 carbon atoms, alkylsulfonyl having 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,

R _{2 is} a tert-butyl or tert-amyl radical.

The compounds of this invention can be prepared by methods known per se in the art. Preferably, these compounds are prepared starting from an S- (alkyl) -alkyl-thiophosphonic acid halide by the action of S- (tertiary-alkyl) -alkyl-thiophosphonic acid halide on an alcohol in the presence of a

235018 A

Base according to the following preferred reaction scheme:

^ - ° R + R ₁ OH Base _> RP ^ 1 ₊ Base. HX

O\

^SR 2

wherein:

R, R ^, and R _{2 have} the meanings given above and X is a halogen atom, preferably chlorine.

The reaction is preferably carried out at a temperature of about 0 to 100 C in an organic solvent in the presence of a tertiary amine or aqueous base such as aqueous sodium hydroxide or, if the alkali alcoholate or alkali phenolate is to be obtained, alkali metal salts such as sodium.

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

As suitable tertiary amines can be mentioned trimethylamine, triethylamine, dimethylaniline, diethylaniline and pyridine.

The Zwxschenverbxndungen the formula:

^ X

SX ₂

wherein R, R ₂ and X have the meanings given above, and which are part of the present invention can be prepared by a simple method by direct addition of thiols to alkylphosphonic acid dihalides.

The synthesis of the S-alkyl-alkylthiophosphonic acid halides is usually carried out by methods which are based on the direct addition of the thiols to the alkylphosphonic acid halides.

235018

caused by this reaction is accompanied by an undesirable side reaction, wherein the two halogen atoms are substituted by the alkylthiol. The side reaction presents a particular problem when using alkylthiols.

It has now been found that the tert-alkylthiols react mildly with the alkylphosphonic acid dichlorides and give the addition of a thiol in good yields according to the scheme:

_γ solution

RP ^ + HSR ₂ + base ^miItex ) RP ^ + base HX

R represents an alkyl radical of 1 to 8 carbon atoms, haloalkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, haloalkenyl of 2 to 8 carbon atoms, alkynyl of 2 to 8 carbon atoms or haloalkynyl of 2 to 8 carbon atoms; preferably R is an alkyl radical having 1 to 4 carbon atoms, especially methyl or ethyl; ;

R 1 is a tertiary alkyl radical having 4 to 8 carbon atoms, preferably tert-butyl and tert-amyl, and

X is a halogen atom, preferably chlorine.

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

Suitable organic solvents may be mentioned benzene, toluene, cyclohexane, acetone and butanone-2.

4 - 5 -

AP C 07 F / 235 018/4 60 128/11

Generally, the reaction is carried out at a temperature between about 20 and 10O ⁰ 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 too stormy. It is preferred the ter-tiäre amine to the other reactants at a temperature of about 20 to 3O ⁰ C to admit and then to heat the whole of the reaction medium to a temperature of about 70 to 8O ⁰ C, to complete the reaction.

This is normally carried out using a molar ratio substantially equal to alkylphosphonic acid halide, thiol and base, however, an excess of about 10 to 20% alkylphosphonic acid halide can be used relative to the remaining reactants. In contrast, a slight excess (5 to 10%) of thiol and base relative to alkylphosphonic dihalide does not significantly alter the yield.

embodiment

The invention is explained below by means of some examples _(in more detail.

The following examples illustrate the preparation of the intermediates of the compounds of the invention and of the compounds themselves and the insecticidal properties of the latter. It will be understood that all compounds described herein can also be prepared by methods analogous to those described below.

example 1 S-tert-butyl-ethyl-thiophosphonsäurechlorid

SC-CH ₃ CH ₃

ΑΛΙ-Λ4 Q / - 5a - AP C 07 1/235 018/4 Z O Ό UI ö 4 60 128/11

To a solution of 32.0 g (0.22 mol) of ethylphosphonic dichloride in 300 ml of toluene are added 18 g (0.2 mol) of 2-methyl-2-propan-thiol. 22 g (0.22 mol) of triethylamine are added while stirring and dropwise, the temperature of the reaction

235018 A

is kept at 30 to 35 ° C during the addition of the amine. The mixture is kept at ambient temperature with stirring until the next day. The amine hydrochloride is filtered off and the toluene solution is concentrated in vacuo. 200 ml of hexane are added and the solution is filtered again.

The solvents are removed by stripping in vacuo and the remaining liquid distilled, the product (25 g = 72.5% yield) is distilled at 72 to 73 ° C under 0.7 mm Hg. The above structure is confirmed by NMR proton spectrogrology in CDCl with tetramethylsilane as reference.

Example 2 Preparation of O-ethyl-S-tert-butylethyl thiophosphonate

To a solution of 8.0 g (0.048 mol) of the obtained according to Example 1 S-tert-butyl-1-ethyl-thiophosphonsäurechlorids in 50 ml of toluene is added a solution of sodium ethylate (0.04 mol) in 40 ml of ethanol. The addition is made dropwise and with stirring, keeping the reaction under nitrogen. Stirring is continued until the next day at ambient temperature, then about 80% of the solvents are removed in vacuo. 100 ml of toluene are added and the sodium chloride formed in the reaction is filtered. The toluene is stripped off in vacuo and the remaining liquid is distilled. The product (5.8 g = 69.5% yield) is distilled at 69 to 72 ° C under C, 2 mm Hg.

NMR proton analysis of this compound confirms the structure given above.

Examples 3 to 6

The procedure is analogous to that in Example 2 for the preparation of the following compounds of the formula:

235 018 Λ

SK ₂

the meaning of the radicals and the boiling point are given below:

At boiling point

4 R ₂

clearance RR ₁ R ₅ ⁰ C / mm Hg

• 3 C ₂ H ₅ CH ₃ ) ₂ CH tert-butyl 64-67 / 0, 7 4 C ₂ H ₅ ^C 3 ^H 7 tert-butyl   61-6 3/0, 05 5 C ₂ H ₅ (CH ₃ tert-butyl 42-43 / 0, 05 6 C ₂ H ₅ C ₂ H ₅ / ' tert-AmyI 56-58 / 0, 07 Example 7 manufacturing of O-phenyl-S-tert-butyl-ethyl-thiophosphonate

To a solution of 5.0 g (0.025 mol) of S-tert-butyl-ethylthiophosphonyl chloride, obtained according to Example 1, and of 2.35 g (0.025 mol) of phenol in 20 ml of acetone are added at once 2.5 g ( 0.025 mol) of triethylamine. The mixture is kept under nitrogen and with stirring at ambient temperature.

The reaction mixture is diluted with 100 ml of toluene and washed once with a 5% sodium hydroxide solution and twice with water. The solution is dried over anhydrous sodium sulfate and the solvent removed by stripping in vacuo. The remaining liquid is subjected to a high vacuum (0.2 mm Hg) at 60 ° C. for 15 minutes. The desired product is obtained, whose structure is confirmed by NMR proton spectroscopy in CDCl ₃ with tetramethylsilane as a reference substance.

Examples 8 to 15

The procedure is analogous to that in Example 7 for the preparation of the following compounds of the formula:

235018 A

R-P

OR,

SR.

the meaning of the radicals and their boiling points are given in the following table:

example R ^R l ^R 2 8th ^C 2 ^H 5 o-methyl-phenyl tert-butyl 9 ^C 2 ^H 5 p-chloro-phenyl tert-butyl IO C ₂ H ₅ phenyl tert-AmyI 11 C ₂ H ₅ m-trifluoromethyl- C. Z) phenyl tert-AmyI 12 ^C 2 ^H 5 p-fluoro-phenyl Tert-AmyI ' 13 ^C 2 ^H 5 p-chloro-phenyl tert-AmyI 14 ^C 2 ^H 5 o-chloro-phenyl tert-Amyl 15 C ₂ H ₅ phenyl tert-AmyI Example 16

4.6 g of m-cresol are dissolved in 100 ml of acetone and potassium carbonate is added. The mixture is kept under stirring at temperature for 30 minutes, then treated with 7.5 g of S-tert-butylmethyl-thiophosphonsäurechlorid. Stirring is continued until the next day, the medium filtered and the solvent evaporated.

After addition of 100 ml of water, the medium is subjected to extraction with 100 ml of ether. The extract is washed with 5% potassium hydroxide and then with water and finally dried and evaporated to dryness to give 4.0 g of O-3-tolyl-S-tert-butyl-methyl-thiophosphonate. The product is identified by NMR spectrography. Its purity is over 90%.

235018 k

Example 17

Efficacy test on Diabrotica (Corn root worm) and Bucher ( Southern army worm)

A) Actual effectiveness on Diabrotica (CRW)

The compound to be tested is placed in a 1% solution in acetone or ethanol. The mother liquor is then diluted with an aqueous solution of Tween-20 to the desired concentration (i.e., 100, 10, 1, 0.1, 0.005 ppm). Pipette 2 ml of this solution into a 9 cm Petri dish containing two layers of filter paper. Second stage larvae are introduced into the shell, which is then closed. After 2 days (48 hours) exposure one counts the dead and moribund larvae. The insecticidal activity is initially a contact and by steam and very little by digestion. The results are summarized in Table I.

B) Actual effectiveness on the box tensioner (Spodoptera eridania) (SAW)

A 1% mother solution of the compound to be tested is prepared in acetone and then diluted to the desired concentration with an aqueous solution containing 500 ppm Tween-20. Leaves of lima bean (Lima bean) are dipped in the solution and placed in petri dishes (100 x 15 mm) 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 third instar larvae of Beech Tree Caterpillar (Spodoptera Eridania) are placed on the leaves and the Petri dish is finally closed.

The insects are kept at 25 ° C for 72 hours, after which a mortality count is made. The results are summarized in Table I.

235018

- ίο -

Table I

mortality

I CRW 0.1 0.05 SAW ^^^^ s ^ osis in ppm ^^^^^ 1 95 75 500 100 Example No. ^ \ 100 100 2 100 70 - 100 100 3 100 45 100 90 4 100 95 100 100 15 5 80 100 90 80 15 6 100 100 , 15 100 50 7 100 35 40 100 95 8th 100 100 70 100 100 9 100 100 85 100 9 5 10 100 100 90 100 80 11 100 85 55 100 80 12 100 95 15 100 60 13 100 100 - 100 75 14 95 iop 80 16 100 _

These results demonstrate the excellent insecticidal activity of the compounds of the present invention which can be used to control many types of insects which are plant parasites, such as beetles (especially Diabrotica sp.) And butterflies (in particular book tensioners). In addition, no phytotoxicity was observed on the treated plants in these tests.

For their use in practice, the compounds of the invention are not used alone. Most commonly, they are part of compositions within the scope of the present invention, which generally include, in addition to the active material of the present invention, a carrier and / or surfactant coupled to the active material

235018 k

is compatible.

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

The term "carrier" as used herein means an organic or mineral; natural or synthetic material with which the active material is associated in order to facilitate its use or its transport or handling. This carrier should therefore be inert and acceptable in agriculture. The carrier can be solid (for example, clays, natural or synthetic silicates, calcium carbonate or magnesium carbonate, calcium sulfate) or liquid (for example water, alcohols, ketones, ether oxides, esters, aromatic or paraffinic hydrocarbons, halogenated hydrocarbons, petroleum fractions, liquefied gases, etc.).

When the carrier is water or a common organic solvent, the composition preferably comprises, in addition to the active material, another compound such as a surface-active agent, a pesticide (e.g., an insecticide or fungicide).

The surfactant or surfactant useful in the compositions of the present invention may be a wetting, dispersing or emulsifying agent which may be ionic or nonionic. For example, mention may be made of nonionic ones, such as condensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amides or amines, the alkylphenols, the esters of fatty acids and sorbitol, derivatives of sucrose; anionic ones, such as the salts of lignosulfonic acids, alkylarylsulfonic acids, alkylsulfosuccinates and sulfosuccinamates, amino acid derivatives, such as alkylamine or imidazoline acetates; amphoteric, such as alkyl betaines or sulfobetaines.

235018

In addition to the active material, carrier and surfactant, the compositions of the present invention may contain other additives such as non-surface-active dispersants, peptizers, protective colloids, thickeners, adhesives which increase resistance to rain, stabilizers, preservatives, corrosion inhibitors, dyes , Sequestering agents, anti-foaming agents, anti-lump agents, anti-gels etc.

The compositions of the invention may be prepared in the form of wettable powders, sputtering powders, granules, solutions, emulsifiable concentrates, emulsions, suspensions, concentrated or otherwise, and aerosols.

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

They are usually prepared by premixing ¹ the active material with a solid carrier and the thickening and dispersing agents. This premix is then ground either in a grinder, for example with pins, equipped with a powder sifter, or in an Air Jet grinder, the latter being preferred for low melting point active materials.

As an example, the following is the composition by weight of a wettable powder according to the invention:

235018 A

Active material (compound no. 1) 30%

Calcium lignosulfonate (deflocculant) 5%

Sodium isopropylnaphthalenesulfonate (wetting agent) 1%

Ariti lump silica 30%

Kaolin '' 34%

The powders for dusting can be prepared like the wettable powders, but without the surfactants or surfactants, dispersants, protective colloids, which are unnecessary for these formulations. In this case, the solid support is specially selected to facilitate comminution, to absorb when the active material is liquid, and to guarantee flow.

The granules and microgranules, generally with a low content of active material, can be prefabricated and then mass impregnated or produced, for example by sputtering or extrusion. In the latter case, they require the addition of binders and hygroscopic products to ensure their rapid disintegration in the soil. 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 in an aromatic hydrocarbon) and, if necessary, an auxiliary solvent or co-solvent, which may be a ketone, an ester, an ether oxide, etc. , Generally, they contain from 5 to 60% (w / v) of active material, from 2 to 20% (w / v) emulsifier, and can be prepared, for example, by dissolving the active material in the solvent or in the mixture Solvent and emulsifier, in a vessel or trough provided with a good agitator and a liquid circulation for heating or cooling.

235018

As an example, the composition of an emulsifiable concentrate is given below, the amounts being expressed in g / l:

Active material (Compound No. 1) 400 g / l

Alkalidodecylbenzenesulfonate 24 g / l

Nonylphenol, oxyethylated with 10 moles of ethylene oxide 16 g / l

Cyclohexanone 200 g / l aromatic hydrocarbons, make up to 11

The concentrated suspensions, so-called "flowables", which are also applicable after dilution in water for atomization, are prepared so as to obtain a fluid, stable, non-settling product. 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 various additives, such as Anti-foaming agents, thickening agents, stabilizers, adhesives, anti-gels, and as a carrier water or an organic liquid in which the active material is insoluble, or a mixture of the two. Certain solid organic materials or mineral salts may be dissolved in the carrier to retard sedimentation or as an anti-gel for the water.

These concentrated suspensions may be prepared, for example, by dispersing the active material premilled in a liquid carrier which may be water, a vegetable or mineral oil or the emulsified mixture of both, containing the auxiliary ingredients such as viscosity agents, preservatives and anti-gel, then grinding the dispersion in a ball mill.

Aqueous dispersions and emulsions, for example, compositions obtained by diluting a wettable powder or emulsifiable concentrate according to the invention with water, are within the general scope of the present invention. These emulsions can be of the type

235018

Water-in-oil or oil-in-water type, and they may have a tough texture like that of a "mayonnaise". For a so-called "very low volume" application, atomized into very fine droplets, solutions are prepared in organic solvents containing 70 to 99% active material.

In addition to the compounds of formula (I), the preparation of these compounds and the insecticidal and / or nematicidal compositions containing them, the present invention also relates to a method for controlling insects, which comprises treating the insects with an effective amount of an insect Brings the compound of formula (I) into contact. This insecticidal treatment may, if desired, be preventative, i.e., before insects are present, by applying the compound of the invention to the exposed parts of the plants to be protected or to the soil, or by incorporating the product into the soil.

However, the dose of active material to be used may vary depending on the compound used and the insect to be controlled. In general, dosages are active

4 -2/3

Material of 10 to 10 g / cm well suited. When used as nematicides, the compounds are effective at dosages of 0.5 to 5 kg / ha. In difficult cases, higher doses may be used.

Claims (3)

2 ** r A \ Q / - 16 - AP C 07 P / 235 018A <3 DUIO 4 60 128/11 invention claim 1. A process for the preparation of novel organophosphone derivatives of the formula OE ₁
EP "(I) E is an alkyl radical of 1 "to 8 carbon atoms, haloalkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, haloalkenyl of 2 to 8 carbon atoms, alkynyl of 2 to 8 carbon atoms or haloalkynyl of 2 to 8 carbon atoms, E _{1 is} an alkyl radical having 1 to 8 carbon atoms or an aryl radical and Ep is a tert-alkyl radical having 4 to 8 carbon atoms, characterized in that an alkyl thiophosphonsäurehalogenid with an alcohol or phenol according to the scheme: + E ₁ OH base _> EP ^ + base. HX where X is a halogen atom and the best E, E ₁ and E _? have the meanings given above, brings to the reaction. 2. The method according to item 1, characterized in that one brings an alkyl-thiophosphonsäurechlorid to Eeaktion. _ ^ 7 - ¹ ? - AP C 07 F / 235 018/4 60 128/11 3. The method according to any one of items 1 and 2, characterized in that one works between 0 and 100 ⁰ C in an organic solvent in the presence of a tertiary amine or a mineral base.