US3923932A - 3-Hydroxymethacrylic acid methyl ester dimethyl thionosphosphate - Google Patents

Abstract

The compound of the formula

its manufacture and use in pest control.

Description

United States Patent [191 Beriger et al.

[45] Dec.2,l97 5 3-I-IYDROXYMETHACRYLIC ACID METHYL ESTER DIMETHYL THIONOSPHOSPHATE [75] Inventors: Ernest Beriger, Neuallschwil;

Ladislaus Pinter, Basel. both of Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: Apr. 5, 1973 [21] Appl. No.: 348,426

Related US. Application Data [63] Continuation of Ser. No. 136,193 April 2|, l97l,

[56] References Cited UNITED STATES PATENTS 3,594.454 7/l9 7l Beriger ct al. 260/941 OTHER PUBLICATIONS Stothers et al., Canadian Journal of Chemistry, Vol. 39 (1961), pp. I389 to 1392.

Primary Examiner-Richard L. Raymond Attorney, Agent, or FirmFrederick H. Rabin; Karl F. Jorda [57] ABSTRACT The compound "of the formula its manufacture and use in pest control.

1 Claim, No Drawings 3-HYDROXYMETHACRYLIC ACID METHYL ESTER DIMETHYL THIONOSPHOSPHATE This is a continuation of application Ser. No. 136,193, filed on Apr. 21, 1971, now abandoned.

This invention relates to pest control agents.

The present invention relates to the compound of formula and its manufacture and use in pest control.

The compound according to the invention of formula I is manufactured in known fashion by reacting dimethylthiochlorophosphate with the methyl ester of a ahydroxymethylenepropionic acid, or preferably with a salt thereof, e.g. an alkali salt.

The reaction is carried out in an inert, preferably polar solvent such as dioxane, acetonitrile, dimethylsulfoxide, dimethylformamide, or for example benzene, toluene, xylene, chlorobenzene and others, at temperatures of 15 to 80C, especially 30 to 70C.

The compounds of fonnula I have a broad biocidal activity spectrum and can be used for combating various animal and vegetable pests.

They are suitable in particular for combating insect types of stored product and grain pests, since they fulfil all the necessary requirements of an insecticide for stored products, these being 1. low lethal minimum concentration for insects 2. low toxicity towards humans and domestic animals 3. an uniform action over many months 4. no residue problems 5. a faint characteristic smell.

Compared to the similarly consituted compounds of French Pat. No. 1530955, or the commercial product PHOSDRIN (Registered Trade Mark) of the formula warm blooded toxicity LD 3-7 mg/kg body weight orally (Rats) or DDVP (dimethyldichlorvinylphosphate): warm blooded toxicity LD 50 mg/kg body weight orally (Rats), the material of formula I only has a low toxicity of LD 500 mg/kg orally (Rats), but also has the advantages of stronger insecticidal action, very 'long effective life (more than 4 months), increased vapour pressure, lack of residue problems, and a faint characteristic smell. Furthermore it diffuses easily into the gaps between stored foodstuffs.

By virtue of these properties the following typical storage pests and crop pests can be combated with the active substance of formula I:

Oryzaeplzilus su rinamensis Trogoderma gra narium Lasioderma serricorne Clrrypmlesles ferrugineu: Stegabium puniceum Necrobia rufipes Simphilus grana rium Sirophilus aryzue Simpliilns Zen muix -continued Latin Name Common Name lesser grain borer dried bean beetle Angoumois grain moth Rhizoperlhu dominica Acanlhoscelides obtecrus Sitotroga cerealella Nemapagon granellus corn moth Tyrophagus putrescenliae copra mite Acarus .siro flour mite Ephestia kuclmiella Araecerus fasciculams Carpophilus hemiplerus Tenebrio malitor Tribolium caslaneum Tribalium destruclor Tribolium confusum BIaneI/a germanica Periplanela americana Blalla Orientalis The active substance of formula I can be used as pure concentrate or in admixture or conjunction with suitable carriers and/or adjuvants.

Suitable carriers and adjuvants can be solid or liquid and correspond to the substances conventionally used in formulation, technique, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilisers.

The active substance of formula I can be used in pure form, for example by treating warmed containers with the agent and allowing the contents to evaporate.

The active substance can also be formulated in customary solid or liquid fashion and can be used as an emulsion concentrate, spraying powder, ,dusting powder, granulate or spray. Of primary use are gas phase, fumigation or sprayed applications. In this way crops such as wheat, rye, barley, oats, millet, rice, maize and other dried fruits can be treated during filling into silo storage, for example on a conveyor belt, with a liquid formulation of the material of formula I.

Sprayable solutions suitable for direct application contain e.g. mineral oil fractions of high to medium boiling range, particularly over C, such as diesel oil or kerosene and furthermore coal tar oil or vegetable or animal oils, together with hydrocarbons such as alkylated naphthalene, tetrahydronaphthalene, xylene mixtures, cyclohexanols, and optionally in addition ketones, chlorinated hydrocarbons such as tetrachloroethane, trichloroethylene, or triand tetrachlorobenzenes.

For use in aqueous application forms, emulsion concentrates, pastes or wettable spraying powders are used with the addition of water. As emulsifiers or dispersants there can be used non-ionogenic products, e. g. condensation products of aliphatic alcohols, amines or carboxylic acids with a long chain hydrocarbon residue of from 10 to 30 carbon atoms with ethylene oxide, for example the condensation product of octadecyl alcohol and 25 to 30 mols ethyleneoxide, or that of soya fatty acid and 30 mols ethylene oxide or that of technical oleylamine and 15 mols ethyleneoxide or that of dodecylmercaptan and 12 mols ethyleneoxide. I-Iowever condensation products of ethyleneoxide with hydroaromatic-polycyclic carboxylic acids and amines can also be used. Amongst anionic emulsifying agents which may be used there should be mentioned: the sodium salt of dodecylalcoholsulphonate esters, the sodium salt of dodecylbenzenesulfonic acid, the potassium or triethanolamine salt of oleic acid or of abietic acid or of mixtures of these acids, or the sodium salt of a petroleum sulphonic acid. As cationic dispersing agents, there can be used quaternary ammonium and phosphonium compounds, e.g. cetylpyridiniumchloride or dioxyethylbenzyldodecylammonium chloride. If the active substance of the invention is to be used in the form of a dusting or scattering preparation, then it can contain talcum, kaolin, bentonite, sand, calcium car bonate, calcium phosphate or even coal as solid carrier materials. Evaporating agents can also be added to the stored goods such as, for example, porous clay bars impregnated with the active agent. The various preparations can contain in customary fashion the addition of materials which improve the distribution, the adhesive strength, or the penetration depth; among such materials should be mentioned fatty acids, resins, glues, casein, or e.g. alginates. The use of preparations in granulated form is also very useful. The compound of the invention can be present as sole active material in the pest control agents, or it may be in combination with other insecticides or acaricides.

The following Examples will serve to illustrate the invention:

EXAMPLE 1 27.6 parts of the sodium salt of a-hydroxymethylenepropionic acid methyl-ester,

were warmed in 200 parts by volume of acetonitrile to 40-50C. At this temperature, 33 parts of dimethylthiochlorophosphate were added dropwise and the mixture then maintained for 4 hours with stirring at 40-50C. After cooling, the salts were filtered off with suction and the solvent removed in vacuo at 50C bath temperature. The residue was taken up in methylene chloride and rinsed with N caustic soda. After the evaporation of the solvent in vacuo, the active substance according to the invention of the formula was obtained in the form of an oil.

The compound boiled at 80-90C (0.01 mm Hg).

EXAMPLE 2 A. Dusting agent Equal parts of the active agent according to the invention and precipitated silica were finely ground. By mixing with kaolin or talcum, it was possible to manufacture dusting agents with the preferred l6% content 5 of active substance.

B. Powder for spraying For the manufacture of a water soluble spraying powder, the following components were mixed and finely ground:

50 parts active agent of formula I 20 parts highly absorbent silica 25 parts Bolus alba (Kaolin) 1.5 parts sodium l-benzyl-2-stearyl-benzimidazol- 6,3-disulphonate.

3.5 parts of a reaction product of p-tert. octylphenol and ethyleneoxide.

C. Emulsion concentrates a. 40 parts of the active substance of formula I were mixed with 10 parts of a mixture of 'an anionic surface active compound, preferably the calcium or magnesium salt of monolaurylbenzenemonosulphonic acid, and a nonionic surface active compound, preferably a polyethyleneglycolether'of monosorbitollaureate, and

the whole dissolved in a little xylene. The solution was then made up with xylene to 100 ml and a clear solution was thus obtained which could be used as a spraying agent concentrate and which gave a stable emulsion on being poured into water;

b. it was also possible to formulate an emulsion concentrate according to the following instruction:

20 parts active agent parts xylene 10 parts of a mixture of a reaction product of an alkylphenol with ethyleneoxide and calciumdodecylbenzenesulphonate were mixed together. On dilution with water to the desired concentration, a spayable emulsion resulted.

D. Granulate 7.5 grams of the active agent of the formula were dis solved in ml acetone and the so obtained acetonic solution added to 92 grams of coarsely granulated attapulgite.

The whole was well mixed and the solvent was removed in a rotary evaporator. A granulate was obtained with 7.5% active substance content.

EXAMPLE 3 Gas Action against adult houseflies Mortality time for a Acute oral toxicity LD percentage of the houseflies (mg/kg) Active substance 10% 50% 100% (rats) Phosdrin (Registered v Trade Mark) 22' 25 30' 3-7 Compound I 5' 8' 25' 500 EXAMPLE 4 Ingestion test with one day old houseflies (Musca domestica) Dilution series were manufactured with water. As solvent for the test preparations and similarly as a nutrition agent for the flies, 30% sugar water was used which had been coloured with chlorantin light red (as an attractant). The dilutions were tested with one day old houseflies. The l, 2 and 4 hour controls enabled the speed of action to be determined. By means of the 24 hour control the limit concentration (action strength) could also be determined.

EXAMPLE 6 Diffusion action in wheat flies killed with active agent Active substance Concentration Phosdrin in 30% sugar water after all-exposure time (hours) Compound 1 PP'" l 2 4 24 I00 lOO -lOO I00 100 I00 lOO I00 I00 50 30 70 80 I00 60 99 I00 I00 25 20 40 60 100 40 70 100 I00 12 0 0 20 90 40 70 I00 I00 6 O 0 I0 80 I00 100 3 O O O 20 IO 20 5O 90 1.5 0 0 O 0 0 0 0 l0 0.8 0 0 0 0 0 0 0 0 0.4 0 0 0 0 0 0 0 0 EXAMPLE 5 D bili test between DDVP d C d 1 3O ggfszion of active substance in gas phase between the wheat Method Wheat was shaken up with 5% dusting agent and then (Test Animal Sit. Granarius) Distance in cm from the Mortality in after 7 days treated wheat layer exposure time with mixed again repeatedly with untreated wheat at half the DDVP Compound I poison concentration. In this way, a dilution series with 1 100 mu concentrations of 50 25 12 6 3 1.5 ppm 1 100 00 was obtained. In order to allow the duration differences 2 8 :88 between DDVP and Compound 1 to be demonstrated 5 0 90 even better, the containers filled with the treated wheat 6 O (sized for 500 grams of wheat) were stored unsealed. 40

Since the test is repeated once per month, the desired information is obtained concerning the residual effect. We clam: In the test, the important pests in storage protection The compound of formula were chosen, viz. the grain weevil (Sitophilus granarius) lesser grain borer (Rhizopertha dominica) 5 u and the larvae of the Khapra beetle (Trogoderma (CH:O)2P O CH COOCHS granarium), which are very resistant to insecticides. 20 test insects were tested per concentration and the re sults are expressed in the following table.

Table l Disinfection test with DDVP and Compound I on Wheat DDVP (Dimethyldichlorvinylphosphate) 20 test animals per concentration animals dead after one week exposure, at

Treated Silophilus granuriu: Rh izopertlm dominion Trogoderma granarium (L) Wheat concentration of active substance in wheat (ppm) Stored For 25 I2 6 3 1.5 50 25 25 12 6 3 1.5

fresh 100 I00 I00 I00 I00 100 I00 I00 I00 I00 100 95 100 I00 100 100 100 85 1 month 100 100 I00 25 5 0 I00 l5 l0 5 0 I00 5 0 O O 2 months 100 I00 55 0 0 0 95 40 2O 5 0 5 45 I0 0 O 0 0 3 months 95 50 0 0 0 0 15 0 0 O 0 0 0 O 0 0 0 Compound fresh I00 I00 I00 100 I00 I00 I00 100 I00 I00 20 100 I00 I00 I00 90 l month I00 I00 I00 I00 90 I00 I00 85 60 5 O 100 I00 95 85 I0 0 2 months 100 I00 I00 I00 I00 I00 I00 80 70 40 l0 I5 I00 I00 85 30 0 0 3 months 100 I00 100 I00 i 95 70 I00 75 35 l5 15 0 I00 I00 55 l0 0 0 Control fresh 0 O O l month 0 0 0 2 months 0 5 O 3 months 0 0 O

Claims (1)

1. THE COMPOUND OF FORMULA