GB2087891A - Alkylphosphonothioate insecticides and nematocides and intermediates therefor - Google Patents

Alkylphosphonothioate insecticides and nematocides and intermediates therefor Download PDF

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GB2087891A
GB2087891A GB8134877A GB8134877A GB2087891A GB 2087891 A GB2087891 A GB 2087891A GB 8134877 A GB8134877 A GB 8134877A GB 8134877 A GB8134877 A GB 8134877A GB 2087891 A GB2087891 A GB 2087891A
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carbon atoms
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butyl
alkyl
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Bayer CropScience SA
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Rhone Poulenc Agrochimie SA
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/38Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/42Halides thereof
    • C07F9/425Acid or estermonohalides thereof, e.g. RP(=X)(YR)(Hal) (X, Y = O, S; R = H, or hydrocarbon group)
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/22Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/38Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40Esters thereof
    • C07F9/4071Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075Esters with hydroxyalkyl compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/38Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40Esters thereof
    • C07F9/4071Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4084Esters with hydroxyaryl compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to compounds having the formula <IMAGE> in which R is alkyl 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; R1 is alkyl of 1 to 8 carbon atoms or aryl and, R2 is tertiary alkyl of 4 to 8 carbon atoms; which are useful as insecticides and nematocides, e.g., in controlling corn rootworm and Southern Army- worm, and to intermediates for their preparation.

Description

SPECiFICATION Alkylphosphonothioate insecticides and nematocides and intermediates therefor This invention relates to O-alkyl and O-aryl S-(tertiary alkyl) alkylphosphonothioate compounds, their preparation, insecticidal and nematocidal compositions containing them and intermediates for their preparation.
Certain alkylphosphonothioate insecticides are described in the prior art, for example, in U.S.
Patent No. 3,209,020. However, none of the species described in that patent or in other known prior art possess a tertiary alkyl group attached to the sulphur atom.
It has now been found that certain S-tertiary alkyl compounds possess particularly useful insecticidal or nematocidal activity.
The present invention accordingly provides compounds of the general formula:
wherein R represents alkyl 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 or 2 to 8 carbon atoms, R, represents alkyl of 1 to 8 carbon atoms or aryl and R2 represents tertiary alkyl or 4 to 8 carbon atoms, which exhibit a wide range of insecticidal and nematocidal activity and are of particular interest in controlling corn rootworm (Diabrotica sp) because of their excellent activity against this pest and their long residual soil activity.
It is to be understood that, in this specification and the accompanying claims, unless otherwise indicated, alkyl groups and moieties may be straight- or branched-chain.
In general formula I: R preferably represents alkyl of 1 to 4 carbon atoms, especially methyl or ethyl; R1 preferably represents alkyl of 1 to 4 carbon atoms (compounds in which R, represents phenyl or phenyl substituted by one or more (preferably one) atoms or radicals selected from the group consisting of alkyl of 1 to 4 carbon atoms (preferably methyl), alkoxy of 1 to 4 carbon atoms (preferably methoxy), alkylthio of 1 to 4 carbon atoms, alkylsulphinyl of 1 to 4 carbon atoms, alkylsulphonyl of 1 to 4 carbon atoms, chlorine, bromine, fluorine nitro, cyano and trifluoromethyl, are also preferred); and R2 preferably represents tert-butyl or tert-amyl.
Particularly preferred compounds of general formula I are those in which R represents methyl or ethyl, R, represents alkyl of 1 to 4 carbon atoms and R2 represents t-butyl or t-amyl. Other particularly preferred compounds are those in which R represents methyl or ethyl, R, represents phenyl or phenyl substituted by a chlorine or fluorine atom, or by a methyl, methoxy or trifluoromethyl group and R2 represents t-butyl or t-amyl.
The compounds of general formula I can be prepared by the application of known methods.
By the expression "known methods" as used in this specification is meant methods heretofore used or described in the literarture.
According to a feature of the invention the compounds of general formula I are prepared by the process which comprises reacting an S-alkyl alkylphosphonothioic halide of the general formula:
wherein R and R2 are as hereinbefore defined and X represents a halogen atom, preferably chlorine, with an alcohol or phenol of the general formula R,OH, wherein R, is as hereinbefore defined, in the presence of a base.
The process proceeds on accordance with the reaction scheme:
wherein R, R1, R2 and X are as hereinbefore defined.
The reaction is advantageously carried out at a temperature of about 0 C to 1 00 C in an organic solvent in the presence of a tertiary amine, or an alkali metal salt of the alcohol or the phenol R,OH, prepared from the alcohol or phenol and an alkali metal such as sodium.
Suitable organic solvents are, for example, benzene, toluene, cyclohexane and 2-butanone, or an alcohol RlOH.
Suitable tertiary amines includes trimethylamine, triethylamine, dimethylaniline, diethylaniline and pyridine.
The S-alkyl phosphonothioic of general formula II wherein R1, R2 and X are as hereinbefore defined also constitute a feature of the present invention.
The synthesis of S-alkyl alkylphosphonothioic halides is usually accomplished by methods other than the direct addition of thiols to alkylphosphonic dihalides because direct reaction is normally accompanied by an undesirable side reaction in which both halogen atoms in the phosphonic dihalide are substituted by an alkyl thiol. The side reaction is a particular problem when normal alkyl thiols are used. Thus, when the synthesis of normal S-alkyl alkylphosphonothioic chlorides is desired, alternative routes are selected.
It had been discovered that tertiary alkylthiols react smoothly with alkylphosphonic dihalides to give mono addition of one thiol in yield, according to the following equation:
wherein R, R2 and X are as hereinbefore defined. According to a feature of the present invention, the compounds of general formula 11 are prepared by reacting a compound of the general formula Ill wherein R and X are as hereinbefore defined with a compound of the general formula R2SH, wherein R2 is as herein before defined, in a solvent, in the presence of a base, at a temperature of about 20"C to 100"C. In the compounds of general formula II, preferably R represents alkyl of 1 to 4 carbon atoms, particularly methyl or ethyl; preferably R2 represents tert-butyl- or tert-amyl, and preferably X represents chlorine.
Suitably the reaction is carried out in an organic solvent, in the presence of a tertiary amine such as trimetylamine, triethylamine pyridine, dimethylaniline or diethylaninine.
Suitable organic solvents, which are preferred, include benzene, toluene, cyclohexane, acetone and 2-butanone.
Generally, the reaction is conducted at a temperature of about 20"C to 1 00"C, but the temperature is not critical except insofar as it is sufficient to make the reaction proceed at a reasonable rate and is not excessive. It has been found advantageous to add the terriary amine to the other reactants at a temperature of about 20"C to 30"C and then to heat the entire reaction mixture to a temperature of about 70"C to 80"C to complete the reaction.
The reaction is normally carried out with an approximately equal molar ratio of the alkyl phosphonic dihalide, thiol and the base. An excess of about 10 to 20% of the alkylphosphonic dihalide can be used relative to the other reactants. However, the use of a slight excess of the thiol and the base relative to the alkylphosphonic dihalide (5-10% excess) did not appreciably affect the yield.
Particularly preferred compounds of general formula II are S-tert-butyl ethylphosphonothioic chloride, S-tert-amyl ethylphosphonothioic chloride, S-tert-butyl methylphosphonothioic chloride, and S-tert-amyl methyl-phosphonothioic chloride which are used as intermediates in the following Examples 1 to 16.
The following Examples illustrate the preparation of compounds of general formulae I and II and the pesticidal properties of the former.
Example 1 S-tert-Butyl ethyiphosophonothinic chloride
To a solution of ethylphosphonic dichloride (32.0 g, 0.22 mol) in 300 ml toluene, was added 2-methyl-2- propanethiol (18 g, 0.2 mol). While stirring, triethylamine (22 g, 0.22 mol) was added dropwise; the temperature of the reaction mixture was maintained at 30-35"C during the addition of the amine. After addition of the amine the mixture was stirred overnight at room temperature. The amine hydrochloride which precipitated was filtered off and the toulene solution was concentrated under vacuum. Hexane (200 ml) was added and the solution obtained was filtered.
The solvents were stripped off under vacuum and the residual liquid was distilled. The product (25 g, 72.5% yield) distilled at 72-73"C/0.7 mmHg. Proton magnetic resonance spectroscopy in deuterochloroform (CDCl3) with Si(Me)4 as reference confirmed the structure of the title compound.
Example 2 Preparation of O-ethyl-S-tert-butyl ethylphosphonothioate To a solution of S-tert-butyl ethylphosphonothioic chloride (obtained as described in Example 1) (8.0 g, 0.048 mol) in toluene (50 ml) was added a solution of sodium ethoxide (0.04 mol) in ethanol (40 ml). The addition was carried out dropwise, with stirring under a nitrogen atmosphere. Stirring was continued overnight at room temperature, and then approximately 80% of the solvents were removed under vacuum. Toluene (100 ml) was added and the sodium chloride formed from the reaction was filtered off. Toluene was stripped off under vacuum and the residual liquid was distilled. The product (5.8 g, 69.6%b yield) distilled at 69-72"C/0.2 mmHg.
Analysis of the proton magnetic resonance sprectrum of this product confirmed the structure of the title compound.
Example 3 to 6 In the manner analogous to that of Example 2, the following compounds were prepared.
Example R R, R2 B.p. C/mmHg.
3 C2H5 CH3 t-butyl 64-67/0.7 4 C2H5 C3H7 t-butyl 61-63/0.05 5 QH5 (CH3)2CH t-butyl 42-43/0.05 6 C2H5 C2H5 t-amyl 56-58/0.07 Example 7 Preparation of O-phenyl-S-tert-butyl ethylphosphonothioate
To a solution of S-tert-butyl ethylphosphonothioic chloride (5 g, 0.025 mol), and phenol (2.35 g, 0.025 mol) in acetone (20 ml), was added, in one portion, triethylamine (2.5 g, 0.025 mol); the mixture was stirred overnight under nitrogen at room temperature. The reaction mixture was then diluted with toluene (100 ml) and washed once with 5% w/v sodium hydroxide solution, and twice with water. The solution was dried over anhydrous sodium sulphate and the solvent was stripped off under vacuum.The residual liquid was subjected to a high vacuum (0.2 mmHg) at 60"C for 1 5 minutes to yield the desired product as confirmed by its proton magnetic resonance spectrum in deuterochloroform (CDC1 3) with Si(Me)4 as reference.
Examples 8 to 15 In a manner analogous to that of Example 7, the following compounds were prepared.
Example R R, R2 8 C2H5 o-methyl-phenyl tert-butyl 9 C2H5 p-chloro-phenyl tert-butyl 10 C2H5 phenyl tert-amyl m-trifluoromethyi11 C2H5 phenyl tert-amyl 1 2 C2H5 p-fluoro-phenyl tert-amyl 1 3 C2H5 p-chloro-phenyl tert-amyl 1 4 C2H5 o-chloro-phenyl tert-amyl 1 5 CH3 phenyl tert-amyl Example 16 Meta-cresol (4.6 g) was dissloved in acetone (100 ml) and potassium carbonate was added.
The mixture was stirred at room temperature for 30 minutes, and S-tert-butyl methylphosothioic chloride (7.5 g) was than added.
Stirring was continued overnight, and the solution was then filtered and the solvent evaporated. Water (100 ml) was added and the mixture extracted with diethyl ether (100 ml).
The ethereal extract was washed once with 5% w/v potassium hydroxide solution, then with water and was finally dried and evaporated to give 4.0 g of 0-3-tolyl-S-tert-butyl methylphosphonothioate. The product was identified by its proton magnetic resonance spectrum. Its purity is higher than 90%.
Example 17 Testing for corn rootworm intrinsic activity, and activity against Southern Armyworm.
A. Corn Rootworm Intrinsic Activity (CRW) The test compound is prepared as a one percent w/v stock solution with acetone or ethanol.
The stock solution is then diluted with an aqueous solution of Tween-20 (500 ppm) and water to the appropriate concentration (i.e. 500, 100, 1, 0.1 or 0.05 ppm of test compound). Two ml of the test solution is pipetted into a 9 cm petri dish containing two layers of filter paper.
Second instar larvae are introduced and the dish closed. Observations for mortality and moribund larvae are made after two days (48 hours) exposure. Insecticidal activity is primarily by contact and vapour action with minimal ingestion.
B. Southern Armyworm Intrinsic Activity (SAW) Stock solution (1 % w/v) of test compound in acetone was prepared and diluted to the desired concentration using a 500 ppm Tween-20 aqueous solution. Lima bean leaves are dipped into the solution and transferred to petri dishes (100 X 15 mm) each containing two filter papers moistened with 2 ml water. Each petri dish contained one leaf and was left open to dry out the solution on the leaf. Five third instar larvae of Southern Armyworm (Spodoptera eridania) were added to the leaf and the dish was finally covered.
The dishes were kept at 78"F for 72 hours and percentage kill was recorded.
The resuits of Tests A and B are tabulated in Table 1 which shows the percentage kill obtained using compounds prepared in the indicated Examples.
Table 1 % Kill CRW SAW rate in ppm 1 0.1 0.05 500 100 Example No 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 12 100 100 90 100 60 13 100 85 55 100 75 14 95 95 15 100 80 16 100 100 100 - These results show the excellent insecticidal activity of the compounds according to the invention which can be used for combatting numerous insects such as coleotpera (e.g.
Diabrotica sp) or corn rootworm and lepidoptera.
For use in practice, the compounds of general formula I are generally employed in the form of compositions, which also constitute a feature of the invention, and which generally comprise, in addition to the active compound of general formula I, at least one agriculturally acceptable carrier and-or surface-active agent. The proportion of active ingredient in these compositions is generally from 0.001 % to about 95% by weight: the proportion of surface active agent is generally from 0 to 20% by weight.
In the present specification, the term "carrier" denotes an organic or inorganic, natural or synthetic material with which the active ingredient is associated in order to facilitate its application to the plants or to the soil. The carrier can be solid (e.g. clays, natural or synthetic silicates, silica, resins, waxes and solid fertilisers) or liquid (e.g. water, alcohols, petroleum fractions, aromatic or paraffinic hyxdrocarbons, chlorohydrocarbons and liquefied gases).
The surface-active agent can be an emulsifying, dispersing, deflocculating or wetting agent of the ionic or non-ionic type. Examples which may be mentioned are salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, condensates of ethylene oxide with fatty alcohols, fatty acids or fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyltaurates), and phosphoric acid esters of condensates of ethylene oxide with alcohols or with phenols.
The compositions can also contain other ingredients, e.g. thickeners, thixotropic agents, protective colloids, adhesives, penetrating agents and stabilisers, and also other known active ingredients having pesticidal properties (in particular herbicidal, fungicidal and insecticidal properties), properties which assist plant growth (in particular fertilisers) or properties which regulate plant growth. More generally, the compounds according to the invention can be combined with any of the solid or liquid additives used in the customary techniques for the preparation of pesticidal compositions.
The compositions according to the invention can be prepared in the form of wettable powders, dusting powders, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.
The wettable powders, or spraying powders, usually contain from 20 to 95% by weight of active ingredient and generally contain, in addition to a solid carrier, from 0 to 5% by weight of wetting agent, and from 0 to 10% by weight of one or more stabilisers and/or other additives, such as penetrating agents, adhesives or anti-caking agents and dyestuffs.
They are prepared by mixing the constituent in mixers and by grinding them in mills or other suitable grinders, e.g. air grinders, so as to obtain the desired particle size.
The composition of an 80% w/w wettable powder according to the invention is given below by way of example (in the following Examples percentages are by weight): Example 18 active ingredient 80% sodium alkylnaphthalenesulphonate 2% sodium lignosulphonate 2% anti-caking silica 3% kaolinite 13% Another example of a wettable powder according to the invention is given below: Example 19 active ingredient 50% sodium alkylnaphthalenesulphonate 2% low-viscosity methylcellulose 2% diatomaceous earth 46% Another example of a wettable powder according to the invention is given below: Example 20 active ingredient 90% sodium dioctylsulphosuccinate 0.2% synthetic silica 9.8% Granules, which are intended to be placed on the soil, are usually prepared so that they have dimensions of between 0. 1 and 2 mm, and they can be manufactured by agglomeration or impregnation.In general, the granules will contain from 0.5 to 25% of active ingredient and from 0 to 10% by weight of additives, such as stabilisers, slow-release modifiers, binders and solvents.
Emulsifiable concentrates, which can be applied after dilution, by spraying, usually contain from 10 to 50% by weight/v.olume of active ingredient. In addition to the active ingredient and the solvent, they can also contain, if necessary, from 2 to 20% by weight/volume of an emulsifying agent and from 2 to 20% by weight/volume of suitable additives, such as surfaceactive agents, stabilisers, penetrating agents, corrosion inhibitors, dyestuffs and adhesives.
Suspension concentrates, which can also be applied by spraying, are prepared so as to give a stable fluid product which does not settle out, and they usually contain from 10 to 75% by weight of active ingredient, from 0.5 to 15% by weight of surface-active agent, from 0.1 to 10% by weight of thixotropic agents, from 0 to 10% of suitable additives, such as anti-foam agents, corrosion inhibitors, stabilisers, penetrating agents and adhesives, and, as the carrier, water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids, or inorganic salts, can be dissolved in the carrier in order to assist in preventing sedimentation or to act as anti-freezing agents for water.
Aqueous dispersions and aqueous emulsions, which are obtained by diluting the abovementioned compositions with water, in particular the wettable powders and emulsifiable concentrates according to the invention, are also included in the general scope of the present invention. The emulsions thus obtained can be of the water-in-oil type or of the oil-in-water type and they can have a thick consistency such as that of a mayonnaise.
All these aqueous dispersions and emulsions, or spraying mixtures, can be applied by any suitable means to the crops in which weeds are to be destroyed, mainly by spraying, at doses which are generally of the order of 500 to 1 ,000 litres of spraying mixture per hectare.
As indicated above, the invention also relates to a method for the control of insects in crops, which comprises applying an effective amount of at least one of the compounds of general formula I to the aerial part of the crops and/or to the soil or incorporating the compound into the soil.
For the control of insects, the compounds of general formula I are used at concentrations of from 0.01 % to about 1 % by weight of the total formulation. As nematocides, the active component is effective within the range of about 0.5 to 5 kg/hectare. Under ideal conditions, depending on the pest to be controlled, the lower rate may offer adequate protection. On the other hand, adverse weather conditions, resistance of the pest and other factors may require that the active ingredient be used in higher proportions.
When the pest is soil-borne, the formulation containing the active ingredient is distributed evenly over the area to be treated in any convenient manner. The active component can be washed into the soil by spraying with water over the area or can be left to the natural action of rainfall. After application, the formulation can be distributed in the soil by ploughing or disking.
Application can be prior to planting or after planting but before sprouting has taken place or after sprouting.

Claims (30)

1. A compound of the general formula:
wherein R represents alkyl 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 or 2 to 8 carbon atoms, or haloalkynyl of 2 to 8 carbon atoms, R1 represents alkyl of 1 to 8 carbon atoms or aryl, and R2 represents tertiary alkyl of 4 to 8 carbon atoms.
2. A compound according to claim i wherein R represents alkyl of 1 to 4 carbon atoms.
3. A compound according to claim 1 or 2 wherein R1 represents alkyl of 1 to 4 carbon atoms.
4. A compound according to claim 1 or 2 wherein R1 represents phenyl or phenyl substituted by one or more atoms or radicals selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulphinyl of 1 to 4 carbon atoms, alkylsulphonyl of 1 to 4 carbon atoms, chlorine, bromine, fluorine, nitro, cyano, and trifluoromethyl.
5. A compound according to any one of the preceding claims, wherein R2 represents t-butyl or t-amyl.
6. A compound according to claim 1 wherein R represents methyl or ethyl, R, represents alkyl of 1 to 4 carbon atoms and R2 represents t-butyl or t-amyl.
7. A compound according to claim 1 wherein R represents methyl or ethyl, R, represents phenyl or phenyl substituted by a chlorine or fluorine atom, or by a methyl, methoxy or trifluoromethyl group and R2 represents t-butyl or t-amyl.
8. O-Ethyl-S-tert-butyl ethylphosphonothioate.
9. A compound according to claim 1 prepared in any one of Examples 3 to 6.
tO. O-Phenyl-S-tert-butyl ethylphosphonothioate.
11. A compound according to claim 1 prepared in any one of Examples 8 to 15.
12. O-3-Tolyi-S-tert-butyl methylphosphonothioate.
t 3. A process for the preparation of a compound of general formula I depicted in claim 1 wherein R, R1 and R2 are as defined in claim 1 which comprises reacting an S-alkyl alkylphosphonithioic halide of the general formula:
wherein R and R2 are as defined in claim 1 and X represents a halogen atom, with an alcohol or phenol of the general formula R,OIi wherein Rt is as defined in claim 1 in the presence of a base.
14. Process according to claim 13 in which the reaction is carried out at a temperature of about O"C to 100"C in an organic solvent in the presence of a tertiary amine or an alkali metal salt of the alcohol or phenol of general formula R,OH.
1 5. Process according to claim 1 3 substantially as hereinbefore described with especial reference to any one of Examples 2 to
1 6.
1 6. A compound of general formula I depicted in claim 1 wherein R, R, and R2 are as defined in claim 1, when prepared by the process claimed in any one of claims 13 to 15.
17. Insecticidal or nematocidal compositions which comprise a compound according to claim 1 in association with at least one agriculturally acceptable carrier and/or surface active agent.
18. Insecticidal or nematocidal compositions according to claim 1 7 substantially as hereinbefore described in any one of Examples 1 8 to 20.
19. A method for the control of insects in crops which comprises applying to the crops or to the soil in which they are growing a composition according to claim 17.
20. A method according to claim 1 9 substantially as hereinbefore described.
21. A compound of the general formula:
wherein R and R2 are as defined in claim 1 and X is as defined in claim 1 3.
22. A compound according to claim 21 wherein X represents a chlorine atom.
23. A compound according to claim 21 or 22 wherein R2 represents t-butyl or t-amyl.
24. A compound according to claim 21, 22 or 23 wherein R represents alkyl of 1 to 4 carbon atoms.
25. S-tert-Butyl ethylphosphonothioic chloride, S-tert-amyl ethylphosphonothioc chloride, Stert-amyl methylphosphonothioic chloride.
26. A process for the preparation of a compound of general formula ll depicted in claim 21 wherein R and R2 are as defined in claim 1 and X is as defined in claim 1 3 which comprises reacting a compound of the general formula:
(wherein R is as defined in claim 1 and X is as defined in claim 13) with a compound of the general formula R2SH wherein R2 is as defined in claim 1, in a solvent in the presence of a base at a temperature af about 20"C to 1 00'C.
27. A process according to claim 26 in which the solvent is benzene, toluene, cyclohexane, acetone or 2-butanone.
28. A process according to claim 26 or 27 in which the base is trimethylamine, triethylamine, pyridine, dimethylaniline or diethylaniline.
29. A process according to claim 26 substantially as hereinbefore described with especial reference to Example 1.
30. A compound of general formula II depicted in claim 21 wherein R is as defined in claim 1 and X is as defined in claim 1 3 when prepared by the process claimed in any one of claims 26 to 29.
GB8134877A 1980-11-21 1981-11-19 Alkylphosphonothioate insecticides and nematocides and intermediates therfor Expired GB2087891B (en)

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US20909380A 1980-11-21 1980-11-21
US20909480A 1980-11-21 1980-11-21
US06/221,642 US4391760A (en) 1980-12-31 1980-12-31 S-(Tertiary alkyl) alkylphosphonothioic halides

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GB08332398A Expired GB2140808B (en) 1980-11-21 1983-12-05 5-alkyl alkylphosphonothioc halides

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CH (2) CH651575A5 (en)
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ES (2) ES8307831A1 (en)
GB (2) GB2087891B (en)
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IT (1) IT1140285B (en)
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US4472391A (en) * 1980-11-21 1984-09-18 Rhone-Poulenc Agrochimie O-Aryl-s-(tertiary alkyl) alkylphosphonothioate insecticides and nematocides

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RO87258B (en) 1985-08-31
BR8107581A (en) 1982-08-17
RO90683B (en) 1987-01-31
IT1140285B (en) 1986-09-24
ES8400751A1 (en) 1983-11-01
MA19336A1 (en) 1982-07-01
ES507318A0 (en) 1983-02-16
DE3146056A1 (en) 1982-06-16
GB2140808A (en) 1984-12-05
AT380885B (en) 1986-07-25
RO87258A (en) 1985-08-31
PH18262A (en) 1985-05-14
CH651575A5 (en) 1985-09-30
NL8105228A (en) 1982-06-16
IT8125205A0 (en) 1981-11-20
CA1224474A (en) 1987-07-21
RO85049B (en) 1984-09-30
RO85049A (en) 1984-08-17
LU83780A1 (en) 1983-09-01
ES516464A0 (en) 1983-11-01
IL64186A0 (en) 1982-02-28
DD202167A5 (en) 1983-08-31
ATA501181A (en) 1985-12-15
ES8307831A1 (en) 1983-02-16
CH650002A5 (en) 1985-06-28
PH19084A (en) 1985-12-19
GB8332398D0 (en) 1984-01-11
GB2140808B (en) 1985-06-19
AU553581B2 (en) 1986-07-24
GB2087891B (en) 1985-02-06
BG36349A3 (en) 1984-10-15
AU7763181A (en) 1982-05-27
RO90683A (en) 1987-01-30
OA06955A (en) 1983-07-31
DK515181A (en) 1982-05-22

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