IL44641A - Phenoxyphenyl dialkyl esters of thiophosphoric and dithiophosphoric acids,their preparation and insecticidal and acaricidal compositions containing them - Google Patents

Description

AJ' The present invention provides phenoxyphenyl dialkyl esters of thiophosphoric and dithiophosphoric acids, processes for their manufacture, pesticidal compositions containing them and a method of using them in pest control.

The compounds of the present invention have the formula wherein R1 represents an alkyl group having from 3 to 7 carbon atoms , R2 represents an ethyl group ^3* ^4» ^5 anc ^ independently of one another represent a hydrogen or halogen atom or a nitro group and X represents an oxygen or sulphur atom.

The alkyl groups represented by R1 can be straight-chain or branched. Examples of such groups include: n-butyl, iso-butyl, sec. butyl and tert. butyl, n-pentyl, n-hexyl, n-heptyl and isomers thereof.

Preferred compounds on account of their action are those of the formula I wherein R1 represents n-propyl, sec. butyl, n-pentyl or n-heptyl, represents ethyl, R-j, R^, R^ and R^ each represents hydrogen, chlorine, bromine and/or nitro, and X represents oxygen or sulphur.

The compounds of the formula I can be manufactured by the following methods which are known per se: K ' (Illb) the formulae II to IV, the symbols R. to R,. and X 1 b have the same meanings as for the formula I and Me re- i^' presents an alkali metal, in particular sodium or potassium, or represents the group (R)<-jJlH, wherein R represents hydrogen or alkyl with 1 to 4 carbon atoms.

Suitable acid acceptors are: tertiary amines, e.g. trialkyl- amines, pyridine, dialkyl anilines; inorganic bases, e.g. hydrides, hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals.. It is sometimes necessary to use catalysts in the reactions, e.g. copper or copper chloride.

Processes la, lb and 2 are carried out at a reaction temperature between -2°C and +130°C, at normal pressure, and in solvents or diluents.

Examples suitable solvents or diluents are: ethers and ethereal compounds, e.g. diethyl ether, dipropyl ether, dioxan, tetra- hydrofuran; amides, e.g. Ν,Ν-dialkylated carboxy amides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylene, chloroform, chlorobenzene ; nitriles, e.g. acetonitrile ; dimethyl sulphoxide, ketones, e.g. acetone, methyl ethyl ketone; water.

The starting materials of the formulae II, III, IV and V are known and can be manufactured in analogous manner to known methods.

\. The compounds of the formula I exhibit a broad biocidal activity and can be used for the control of a variety of plant and animal pests.

In particular they are suitable for combating insects of the families: Acrididae, Blattidae, Gryllidae, Gry llotalpidae , Tettigoni- idae, Cimicidae, P^fyrrhocoridae , Reduviidae, Aphididae, Delphacddae, Diaspididae, Pseudococc idae , Chrysomelisae , Coccinellidae , Bruchidae, Scarabaeidae , Dermestidae, Tene-brionidae, Curulionidae , Tineidae, Noctuidae, Lymantriidae , Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae , Trypetidae, Pulicidae as well as Acaridae of the families: Ixodidae, Argasidae, Tetranchidae , Dermany ssidae .

By addition of other, indecticides and/or acaricides it is possible to improve substantially the insecticidal or acaricidal action and to adapt it to given circumstances.

Examples of suitable additives are: organic phosphorus compounds, nitrophenols and derivatives thereof; formamidines ; ureas; carbamates and chlorinated hydrocarbons.- - The compounds of the formula I may be used as pure active substance or together with suitable carriers and/or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technology, for example natural or regenerated substances, solvents, dispersants, wetting agents adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules,. dispersions, sprays, to solutions or suspensions, in the conventional formulation which is commonly employed in application technology. Mention is also to be made of cattle dips and spray races, in which aqueous preparations are used .

The agents according to the invention are manufactur in known manner by intimately mixing and/or grinding active substances of the formula I .with the suitable carriers, optionally with the addition of dispersants or solvents which are. inert towards the active substances. The active . substances can take, and be used in, the following forms: Solid forms: , ''. dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules. 1 Liquid forms: a) active substances which are dispersible in water: v?ettable powders, pasts, emulsions: b) solutions .

The content of active substance in the above described agents is between 0.1% to 95%, in which connection it should be mentioned that, in the case of application from aircraft or some. other suitable means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.

The active substances of the formula I can, for example, be formulated as follows: Dusts The following substances are used to manufacture a) a 5% and b) a 2% dust: '" · a) 5 parts of active substance . 95 parts of talcum b) 2 parts of active substance 1 part of highly disperse silicic acid 97 parts of talcum.

The active substances are mixed with the carriers and ground.

Granules - The following substances are used to produce 5% granules : 5 parts of active substance, 0.25 parts of epichlorohydrin, . 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3-0.8 ram).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The resulting solution is sprayed on kaolin, . and the acetone is subsequently evaporated in vacuo. lettable powder: The following constituents are used for the preparation of a) a 40%, b) and c) a 25%, and d) a 10% vettable powder: a) 40 parts of active substance, 5 . parts of sodium lignin sulphonate, 1 part of sodium dibutylrnaphthalene sulphonate, 54.. parts of silicic . acid . b) 25 parts of active substance, 4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene . sulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin. c) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxye thylene ethanol, 1.7 parts of Champagne chalk/hydroxyeth l cellulose mixture (1:1), 8.3 parts of sodiurn aluminium silicate, 16.6 parts of kieselguhr, 46 parts of kaolin. d) 10 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatt alcohol sulphates, 5 parts of naphthalenesulphonic acid/. formaldehyde condensate , 82 parts of kaolin.

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

Emulsifiable concentrates: The following substances are used to produce a) a 10% and b) a 25% emulsifiable concentrate: 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 13. parts of a combination emulsifier consistin of fatty alcohol polyglycol ether and alkyl aryl sulphonate calcium salt, 40 parts of dime hyIformamide , 43.2 parts of xylene, 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alk larylsulphonate/fatty alcoholglycol ether mixture, . 5 par s of dimethylformamide , 57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentra tion..

Spray: ■ The following constituents are used to prepared a 57o spray: 5 parts of active substance, 1 part of epichlorohydrin, 94 parts of benzene (boiling limits 160°C-190°C) .

E X AM P L E 1 With stirring, 41 g of O-ethyl-S-n-propylthiolphosphoric chloride in 60 ml of diethyl ether is added dropwise so rapidl to a solution, cooled to 10°C, of 37 g of 4-hydroxydiphenyl ether and 22 g of trie hylamine in 500 ml of absolute diethyl ether that the temperature does not rise above 30°C. The reaction mixture is stirred for a further 2 hours at 20°-30°G and treated, with continued stirring, with 300 ml of ice wate ; The organic phase is isolated, shaken once with water and twice with ice cold 570 sodium hydroxide solution and then washed neutral with water.

The ethereal phase is treated with activated charcoal, filtered, dried, and the solvent is evaporated off. The oily residue is dried for 3 hours at 70°C and 0.1 Torr to yield the compound of the formula as a yellowish, non-distillable , viscous oil with a refraction 20° of η υ = 1.5524.

The following compounds are also manufactured in analogous manner: Example 2 A) Insecticidal ingest poison, action Cotton and potato plants were sprayed with a 0.05% aqueous emuls ion (obtained from a 10% emulsifiable concentrate).

After the coating had dried, the cotton plants, were popu- . lated with Spodoptera littoralis or Heliothis virescens larvae and the potato plants with Colorado potato bettle larvae (Leptinotarsa decemlineata) . The test was carried out at 24°C and 60% relative humidity. In the above test, the compounds according to Example 1 displayed good ingest poiso action against Spodoptera littoralis, Heliothis and Leptinotarsa decemlineata larvae.', B) System insecticide! action To determine the systemic action, rooted bean plants (Vicia . fabae) were put into a 0.01% aqueous active substance solution (obtained from a 10% emulsifiable concentrate) . After 24 hours, aphide (Aphis fabae) were placed on the parts of the plant above the soil. The aphids were protected from contact and gas action by means of a special device. The test was carried out at 24°C and 70°C relative humidity. In the above test, the compounds according to Example 1 have systemic action against Aphis fabae.

. Example 3 '■; Action against Chilo suppressalis Six rice plants at a time of the. variety Caloro were transplanted into plastic pots (diameter at the top = 17 cm) arid reared to a height of about 60 cm. Infestation with Chilo suppressalis larvae (L, : 3-4 mm long) took place 2 days after the active substance had been applied in granule form to the paddy water (rate of application: 8 kg of actiive substance per hectare) . Evaluation of the insecticidal action took place 10 days afte application of the granules The compounds according to Example 1 v?ere active in the above test against Chilo suppressalis.

EXAMPLE 4 Sterilised compost earth was homogeneously mixed v/ith a wettable powder containing 25^ of active substance so that there resulted a rate of application of 8 kg of active substance per hectare. ' ; Young zucchetti plants .(Cucumis pepo) were put into plastic pots with the treated soil (3 plants per potj diameter of pot = 7 cm). Each pot was infected immediately afterwards with 5 Aulacophora femoralis and Pachmoda or Chortophila larvae. The control was carried out. 8, 16 and 32 days after depositing the larvae.

At 80-lOOfc kill after the first control, a fresh infestation with 5 larvae each was carried out in the same soil sample with new zucchetti plants. If the activity v/as less than' 8o$ , the remaining larvae remained in the soil sample until the control immediately following. If on active substance at a rate of application of 8 kg/ha still effected a lOO^ kill, a further control with h and 2 kg of active substance per hectare was carried out.

In. the above test, the compounds according to Example ί displayed action .against Aulacophora femoralis, Pachmoda and Chortophila larvae.

EXAMPLE 5 Action against ticks A) Rhipicephalus bursa Five adult ticks and 50 tick larvae were counted into a glass tube and immersed for 1 to 2 minutes in 2 ml of a aqueous emulsion from an emulsion series each containing 100, 10, 1 or 0.1 ppm of test subs ance. The tube was then sealed with a standardised cotton wool', plug and placed on its head, so that the active substance emulsion could be absorbed b the cotton wool.

In the case of the adults evaluation took place after 2 weeks, and in that of the larvae after 2 days. Each test-was repeated twice.

B) Boophilus microplus (larvae) Tests were carried out in each ca^e with 20 OP-sensitive larvae using a dilution series analogous to that of test A. (The resistance refers to the tolerability of Diazinon) . The compounds according to Example 1 acted in these tests against adults and larvae of Rhipicephalus bursa and sensitive and OP-resistant larvae of Boophilus microplus.

EXAMPLE 6 Acaricidal action Phaseolus vulgaris (dwarf beans) have an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test for the acaricidal action. The mobile stages which have migrated are sprayed v?ith the emulsified test preparations front a chromatography atomiser so that the spray broth does not run off. The number of liv5.ng and dead larvae, adults and eggs are evaluated after 2 to 7 days under a stereoscopic microscope and the result expressed in percentages. During the "interim", the treated plants are kept in greenhouse compartments at 25°C.

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

Claims (3)

1. 44641-2 We claim: 1. A compound of the formula I wherein R-^ represents an alkyl group having from 3 to 7 carbon atoms , R-2 represents an ethyl group R^, R^, R^ and R^ independently of one another represent a hydrogen or halogen atom or a nitro group and X represents an oxygen or sulphur atom.

2. A compound according to claim 1 wherein represents an n-propyl, sec. butyl, n-pentyl or n-heptyl group .

3. A compound according to claim 2 wherein R, represents an n-propyl group. A compound according to any one of claims 1 to 3 wherein , R^ and R^ independently of one another represent a hydrogen, chlorine or bromine atom or a nitro group. The compound according to claim 4t of the formula 0 44641- The. compound according to claim 4 of the formula 0 The compound according to claim 4 of the formula 0 (n) The compound according to claim 4 of the formula ) The compound according to claim 4 of the formula (n) The compound according to claim . 4 of the formula ,(n)X The compound according to claim ,4 of the formula The compound according to claim 4 of the formula The compound according to claim ;4 of the formula The compound according to claim 4 of the formula The compound according to claim 4 of the formula O c,0 -O- SC5U\Hn) 44641-2 . ' solid pesticidal composition which comprises a compound as claimed in any one of claims 1 to 9 as active ingredient, a solid extender and optionally a surface active agent. A liquid pesticidal composition which · comprises a compound as claimed in any one of claims 1 -to 9 as active ingredient, a liquid diluent and a surface ac ive agent. A method of combatting pests of the class Insecta or of the order Acarina at a locus, which method comprises applying to the locus a compound as claimed in any one o claims 1 to 9. A method .according to claim 18 wherein the locus comprises growing crops or plants. 20. A solid pesticidal composition which comprises a compound as claimed in any one of claims IQ to 15 as active ingredient, a solid extender and optionally a surface active agent. 21