IL33781A - Indazole substituted thiophosphoric acid esters,process for the preparation thereof and insecticidal and acaricidal compositions containing the same - Google Patents

Description

NEW INDAZOIE SUBSTITUTED THIQPHOSPHORIO ACID ESTERS, PROCESS FOR THE PREPARATION THEREOF AND INSECT10IDAl AND ACARIC.IDAL COMPOSITIONS CONTAINING THE SAME THIS INVENTION relates to new phosphoric esters, to^ process for their preparation, and composit ons containing them, ϊ.. The new phosphoric esters of the present invention are those of the general formula: wherein _R-^ represents a halogen (preferably chlorine) atom or a cyano radical, IL, represents a hydrogen or halogen (preferably chlorine) atom, or a nitro radical, _and R^ and R^ are the same or different and each represents a hydrogen or halogen (preferably chlorine) atom.

According to a feature of the invention, these new phosphoric esters are obtained by reacting a phosphorus compound of the formula: (wherein M represents an-: alkali metal atom or an ammonium ion) with an indazole derivative of general formula: wherein R^, Rg, R^ and R^ are as hereinbefore defined, and Y represents the acid residue of a reactive ester such as' a halogen atom or a sulphuric or sulphonic ester residue. When the symbol M in formula II represents an alkali motal atom, the salt is generally prepared in situ.

The reaction is preferably carried out in an inert organic solvent and more particularly in an alcohol (e.g. ethanol) , acetate), a nitrile (e.g. acetonitrile) or an aromatic hydro--' carbon (e.g. benzene), at a temperature between normal temperature, i.e. 10-25°C, and 100°C.

The starting materials of general formula III can be obtained from indazole derivatives of the general formula: (wherein the various symbols are e.s hereinbefore defined) by N-hydroxymcthylation by means of formaldehyde, followed by conversion by methods known per se of the hydroxy radical into the acid residue of a reactive ester.

The indazole derivatives of general formula IV can be obtained according to one of the methods described in "The Chemistry of Heterocyclic Compounds (Pyrazoles, Pyrazolones, Pyrazolidines, Indazoles and Condensed Rings) , A. Weissbergor, Edit. Interscience Publishers, Part 3, 269-382 (1967)".

The phosphoric esters of general formula I have remarkable insecticidal and acaricidal properties; they are effective through contact and by direct ingestion. They have proved particularly active against dipteraT coleoptera, hemiptera. lepidop-tcra. orthoptera and acarides. Preferred esters are those in which R^ represents a halogen atom or a cyano radical, R2 represents a halogen atom and R^ and R^ represent hydrogen atoms, and in particular l-0,0-diethyldithiophosphorylmethyl-3,5-dichloroindazole and 1-0,0-diethyldithiophosphorylmethyl-3-cyano-5-chloroindazole .

According to a further feature of the present invention, there are provided insecticidal and acaricidal compositions containing} as the active ingredient, at least one phosphoric ester of formula I in association with one or more diluents or adjuvants com atible with the hos horic ester esters and suitable for use in the compositions contain between 0.005% and 80% by weight ϊ phosphoric ester.

The compositions may be solid if there is employed a powdered solid compatible diluent such as talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbent charcoal, or a clay such as kaolin or bcntonite. These solid compositions are preferably prepared by grinding the phosphoric ester with the solid diluent, or by impregnating the solid diluent with a solutio of the phosphoric ester in a volatile solvent, evaporating the solvent, and if necessary grinding the product so as to obtain a powder.

Instead of a solid diluent, there may be used a liquid in which the phosphoric ester is dissolved or dispersed. The compositions may thus take the form of suspensions, emulsions or solutions in organic or aqueous-organic media, for example aromatic hydrocarbons such as toluene or xylene or mineral, animal or vegetable oils, or mixtures of these diluents. The compositions in the form of suspensions, emulsions or solutions may contain wetting, dispersing or emulsifying agents of the ionic or non-ionic type, for example sulphoricinoleates , quaternary ammonium derivatives or products based on condensates of ethylene oxide, such as the condensates of ethylene oxide with octylphenol, or fatty acid esters of anhydrosorbitols which have been rendered soluble by etherificatior. of the free hydroxy! groups by condensation with ethylene oxide.

It is preferable to use agents of the non-ionic type because they are not sensitive to electrolytes. When emulsions are required, the phosphoric esters may be used in the form of self-emulsifying concentrates containing the active substance dissolved in the emulsifying agent or in a solvent containing an emulsifying agent compatible with the phosphoric ester and solvent, a simple addition of water to such concentrates producing compositions ready for use.

The following Examples illustrate the invention; EXAMPLE 1 Ammonium 0,0-diethyldithiophosphate (12.8 g.) is added to a solution of l-chloromethyl-3-chloro-5—nitroindazole (14 g.) in acetone (100 cc). The reaction mixture is stirred for 8 hours at about 25°0. The resulting precipitate is filtered off and the aco ono is evaporated under reduced pressure. The residual oil is taken up in methylene chloride ( 150 cc.) and the resulting solution is successively washed with distilled water (150 cc), a 10% (weight/volume) aqueous potassium "bicarbonate solution (150 cc.) and distilled water (150 cc). After drying over anhydrous sodium sulphate, treating with decolourising charcoal and concentrating under reduced pressure, l-0,0-dicthyldithiophosphorylmethyl-3-chloro-5-nitroindazole ( 19 g.), melting at 50°C,is obtained. l-Chloromothyl-3-chloro-5-nitroindazole , melting at 110°C, which is used as starting material is obtained by the reaction of thionyl chloride with l-hydroxymethyl-3-chloro-5-nitroindazole , melting at 180°0, prepared by the reaction of formaldehyde with 3-chloro-5-nitroindazole, melting at 222°G, which itself is prepared by nitration of 3-chloroindazolo . 3-Chloroindazolo , melting at 14-9°C, is prepared according to the process described by E. Stephenson Org. Synth., 2^, 55 (194-9) .

By following the procedure described above and employing appropriate starting materials of formula III, the following products conforming to formula I are obtained: l-0,0-diethyldithiophosphorylmethyl-3-chloroiiidazole, m.p. 28°G. ; l-0,0-diethyldithiophosphorylmethyl-3 , 5-dichloroindazole , m.p. 32°C. , and 1-0,0-diothyldithiophosphorylmethyl-3 , 5,6, ~tetrachloroindazole , m.p. 72°C.

EXAMPLE 2 Ammonium 0,0-diethyldithiophosphatc (16.56·) is added to The resulting precipitate is filtered off and the acetone is evaporated under reduced pressure. The residual solid, on rccrystallis^ ation from cthanol, yields 1-0,0-dicthyldithiophosphoryMethyl-3-cyanoindazole (22 g.) melting at 66°0, l-Chloromethyl-3-cyanoindazole used as starting material is ohtained "by the reaction of thionyl chloride with 1-hydroxymethyl-3-cyanoindazole, melting at 160°C, prepared by the reaction of formaldehyde with 3-cyanc-ir.dazole. 3-CyanoindazolG, melting at 140°C, is prepared according to the process described by J. Meisenheimer et al, Ber. ?B, 1715 (1924).

EXAMPLE 3 Ammonium 0,0-diethyldithiophosphatc (7.1 g.) is added to a solution of l-chloromethyl-3-cyano-5-chloroindazolo (8 g.) in acetone (150 cc.). The reaction mixture is stirred for 6 hours at about 25°C. The resulting precipitate is filtered off and the acetone is evaporated under reduced pressure. The residual oil is taken up in methylene chloride (200 cc.) and the resulting solution is successively washed with distilled water (100 cc.), a 0.4·% (weigh /volume) aqueous sodium hydroxide solution (100 cc.) and distilled water (100 cc.). After drying over anhydrous sodium sulphatc, treating with decolourising charcoal, concentrating under reduced pressure, and rccrystallisation from ethanol 1-0,0-diethyldithiophosphorylmethyl-3-cyano-5-chloroindazole (7 g.), melting at 70°C., is obtained. l-Chloromethyl-3-cyano-5-chloroiiidazolo, melting at 130°G, which is used as starting material, is obtained by the reaction of thionyl chloride with l-hydroxymethyl~3-cyano~5-chloro-indazolo, melting at 180°C, prepared by the reaction of formaldehyde with 3-cyano~5-chloroindazole, molting at 40°G, itself prepared by the reaction of sodium chlorate with 3-cyanoindazole. containing 10 moles of ethylene oxide per mole of octylphenol (10 parts by weight) is added to a solution of 1-0,0-diethyldi-thiophosphorylmethyl-3-chloro-5-nitroindazole (25 parts by weight) in a mixture of equal parts (by volume) of toluene and acetophenone (65 parts by volume). The resulting solution is used, after dilution with water in the ratio of 200 cc of this solution per 100 litres of water, to destroy aphids such as Aphis fabae or Magrosiphum pisi, caterpillars such as Plutella maculipennis or Tortrix sp. , or mites such as Tetranychus urticae or Panoaychus ulmiT on vegetable crops or fruit trees.

Claims (21)

■WE CLAIR

1, Phosphoric asters of general formula: heroin R^ represents a halogen atom or a cyano radical, I^ represents a hydrogen or halogen atom-or a nitro radical, and and R^ are the same or different and each represents a hydrogen or halogen atom.,

2. Phosphoric estors according to claim 1 wherein R-^ represents a halogen atom or a cyano radical, R represents a halogen atom, and R^ and R^ represent hydrogen atoms.

3* Phosphoric esters according to claim 1 or 2 wherein, the R symbols,, when halogen, represent chlorine atoms,

4·. 1-0,0-Diethyldithiophosphorylmethyl-3,5-dichlorο· indazole.

5. 1-0,0-Diethyldithiophospho:rylraethyl-3-cyano-5-chloroindazole.

6. 1-0,0-Diethyldithiophosphorylmethyl-3-chloro-indazole.

7. 1-0,0-Diethyldithiophosphorylmethyl-3,5,6,7-tQt achloroindazoleψ

8. l~0,0-Diethyldithiophosphorylmethyl-3-chloro-5-nitroindazole ,

9. 1-0,0-Diethyldithiophosphorylmctliyl-5-cyano- indazole .

10. Process for the preparation of phosphoric est as claimed in claim 1 which comprises reacting a phosphorus compound of the formula: (wherein M represents an alkali metal atom or an ammonium ion) with an indazole derivative of general formula: wherein ¾» R3 c,in(3- ¾ ^13 as hereinbefore defined, and Y represents the acid residue of a reactive oster.

11, Process according to claim 10 in which Y represents a halogen atom or a sulphuric or sulphonic ester residue.

12. Process accordin JO claim 10 or 11 in which , the reaction is carried out in an inert organic solvent medium at a temperature between 10° and 100°C.

15. Process according to claim 12 in which the solvent medium is an alcohol, ketone, ester, nitrile or aromatic hydrocarbon.

14. Process for the preparation of phosphoric esters of the formula specified in claim 1 substantially as described in Example 1 or 2.

15. Process for the preparation of phosphoric esters of the formula specified in claim 1 substantially as described in Example 3.

16. Phosphoric esters of the formula specified in claim 1 when prepared by the process claimed in any one of claims 10 to 15.

17. Insecticidal and acaricidal compositions comprising , as active ingredient , at least one phosphoric ester as claimed in any one of claims 1 to 9 in association with one or more diluents or adjuvants compatible with the phosphoric ester and suitable for use in agricultural insecticidal and acaricidal compositions .

18. Insecticidal and acaricidal compositions according to claim 17 wherein the quantity of phosphoric ostor is between 0,005%' and 80% by weight of the composition.

19. Insecticidal and acaricidal compositions according to claim 17 or 18 which contain a wetting, dispersing or emulsifying agent .

20. Insecticidal and acaricidal compositions according to claim 19 wherein the wetting , dispersing or emulsifying agent is a non-ionic compound.

21. Insecticidal and acaricidal compositions as claimed in any one of claims 17 to 20 substantially as described in Example 4. Attor